JP2007254650A - Hardened film, antireflection film, polarizing plate using them, and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hardened film having sufficient film strength, prevented from curling, and having good brittleness, and an antireflection film using the hardened film; further to provide a hardened film, an antireflection film, a polarizing plate and an image display device subjected to reflection-preventing treatment by a proper means, having excellent physical strength, inexpensive, and excellent in productivity. <P>SOLUTION: The hardened film is obtained by coating/hardening a coating composition containing the following components (A) and (B) on a transparent supporter to form a hardcoat layer: (A) a hardenable multibranched polymer (RHB) obtained by binding a photohardenable reactive group and/or a thermosetting reactive group to 10-90 mol% of (a) a reactive group present at the branched terminals of a multibranched polymer (HB); and (B) at least one kind of a hardening agent and a hardening accelerator. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a cured film, an antireflection film, a polarizing plate in which an antireflection film is provided on a protective film of a polarizing film, and an image display device in which these antireflection film or polarizing plate is disposed on an image display surface.

  The antireflection film is provided in various image display devices such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), and a cathode ray tube display device (CRT). In an image display device, an antireflection film (antireflection film) that reduces the reflectance by using the principle of optical interference in order to prevent a decrease in contrast and image reflection due to reflection of external light on the surface of the display device Is generally disposed on the outermost surface of the display device. In addition, anti-reflection films are provided on the glasses and camera lenses.

  As the antireflection film, a multilayer film obtained by laminating a transparent thin film of metal oxide has been conventionally used. The reason for using a plurality of transparent thin films is to prevent reflection of light in a wavelength range as wide as possible in the visible range. The transparent thin film of metal oxide is formed by a chemical vapor deposition (CVD) method or a physical vapor deposition (PVD) method, particularly a vacuum vapor deposition method or a sputtering method which is a kind of physical vapor deposition method. However, the metal oxide transparent thin film has low productivity and is not suitable for mass production by a deposition method or a sputtering method.

  Therefore, a method of forming an antireflection film by a coating method instead of the vapor deposition method has been proposed. An antireflection film is produced with high productivity by continuously producing an antireflection film by a coating method.

Since the antireflection film is disposed on the outermost surface of the display device, it is required to impart high film hardness and scratch resistance to the cured film constituting the antireflection film. In order to improve the film hardness, it is useful to increase the thickness of the cured film, but there is a problem that curling of the cured film increases as the film thickness increases, and handling of the formed film deteriorates. Furthermore, as the film hardness increases, the brittleness of the film deteriorates, and problems such as generation of cracks occur when the film is bent by handling or the like.
On the other hand, a cured film using a curable resin composition containing a vinyl group-containing dendrimer is disclosed as a cured film that can suppress the occurrence of curling and can impart good film hardness (Patent Document 1 and Patents). Literature 2 etc.). However, Patent Documents 1 and 2 also fail to provide an antireflection film that achieves both curl and brittleness and is excellent in productivity.
JP 2005-76005 A JP 2006-10929 A

Accordingly, an object of the present invention is to provide a cured film having sufficient film hardness, curling of the film and good brittleness of the film, and an antireflection film using the cured film.
Another object of the present invention is to provide a cured film, an antireflection film, a polarizing plate, and an image display that are antireflection treated by appropriate means, excellent in physical strength, inexpensive and excellent in productivity. Is to provide a device.

The present invention is as follows.
(1) A cured film characterized in that a hard coat layer is formed by applying and curing a coating composition containing the following (A) and (B) on a transparent support.
(A) Curability in which a photocurable reactive group and / or a thermosetting reactive group are bonded to 10 mol% to 90 mol% of the reactive group (a) present at the branched end of the multi-branched polymer (HB). Multi-branched polymer (RHB)
(B) At least one of the curing agent and the curing accelerator (2) The multi-branched polymer (HB) is centered on a polyvalent base nucleus bonded to two or more branched chain extension units. Is a compound having at least two reactive groups (a) for forming a linking group, and the branched chain extension unit is chemically bonded to the reactive group (a) to form a linking group. Item 2. The cured film according to Item 1, wherein the cured film is formed by a chemical bond between one reactive group (b), a branched chain extending compound having at least two reactive groups (a), and the nucleus.
(3) The cured film according to item 2, wherein the branched chain extension unit contains at least one ring structure selected from an alicyclic ring and an aryl ring, and an alkylene chain structure.
(4) The curable reactive group of the curable multi-branched polymer (RHB) contains at least one polymerizable group selected from a radical polymerizable group, a cationic polymerizable group, and a hydrolyzable group-substituted silyl group. The cured film as described in any one of claim | item 1 -3.
(5) The cured film is a cured film formed by applying and curing a curable composition containing a polymerizable compound copolymerizable with a curable reactive group of a curable hyperbranched polymer (RHB). The cured film in any one of claim | item 1 -4.
(6) The cured film is applied and cured with a curable composition containing a polymerizable compound copolymerizable with the remaining reactive group (a) of the curable multi-branched polymer (RHB) and a polymerization initiator. Item 6. The cured film according to any one of Items 1 to 5, which is a cured film formed as described above.
(7) The cured film according to any one of Items 1 to 6, wherein the reactive group (a) is a hydroxyl group.
(8) The curing according to any one of Items 1 to 7, wherein the hard coat layer contains at least one kind of translucent resin fine particles having an average particle diameter of 0.5 to 10 μm. film.
(9) The curing according to any one of Items 1 to 8, wherein after forming the hard coat layer, one or more optical functional layers having a refractive index different from that of the hard coat layer are further laminated. film.
(10) The cured film according to any one of Items 1 to 9, wherein the uppermost layer of the optical functional layer is a low refractive index layer having a lower refractive index than other optical functional layers.
(11) The inorganic having a hollow structure in which the low refractive index layer has an average particle size of 30 to 100% of the film thickness of the low refractive index layer and a refractive index of 1.17 to 1.37. Item 11. The cured film according to Item 10, containing at least one kind of fine particles.
(12) The antireflection film, wherein the cured film according to any one of items 1 to 11 has an antireflection function.
(13) A polarizing plate, wherein the cured film according to item 1 to 11 or the antireflection film according to item 12 is provided on at least one of the protective films of the polarizing film.
(14) The cured film according to item 1 to 11, or the antireflection film according to item 12 is provided on one of the protective films of the polarizing film, and the optical compensation film having optical anisotropy is provided on the other side of the protective film of the polarizing film. A polarizing plate characterized by being provided in the above.
(15) An image in which the cured film according to item 1 to 11, the antireflection film according to item 12, or the polarizing plate according to item 13 or item 14 is arranged on an image display surface. Display device.
(16) The image display according to item 15, wherein the image display device is a transmissive, reflective, or transflective liquid crystal display device in any one of TN, STN, IPS, VA, and OCB modes. apparatus.

  According to the present invention, it is possible to obtain a cured film that is optically transparent, has sufficient film strength, suppresses curling of the film, and has good brittleness of the film, and has such a cured film. An antireflection film can be obtained. Further, according to the present invention, a cured film having sufficient film strength, curling of the film and having good film brittleness, and an antireflection film provided with such a cured film are inexpensive and excellent in productivity. Manufacturing methods can be provided. Further, by using the cured film or antireflection film, a polarizing plate having film strength (elastic modulus), high durability, and high hardness can be obtained, and a liquid crystal display excellent in durability using such a polarizing plate. A device can be obtained.

  The use of the cured film of the present invention and the antireflection film using such a cured film is not particularly limited, but it can be used as a protective film for polarizing plates used in liquid crystal display devices, and other functional films, For example, it can be used in combination with a retardation film, a field-of-view expansion film, and the like. In addition, the cured film of the present invention and the antireflection film using such a cured film are also preferably used as an antireflection film used in image display devices other than liquid crystal display devices, such as plasma displays and organic EL displays. Can do.

Hereinafter, the present invention will be described in detail.
The antireflection film of the present invention is an antireflection film having a multilayer structure in which at least two hardened layers having light transmittance and different refractive indexes (light transmission layers) are laminated. Specifically, (1) an antireflection film comprising at least two layers having different refractive indexes, preferably three or more layers (medium refractive index layer / high refractive index layer / low refractive index layer), (2) at least A light-scattering antireflection film formed by sequentially laminating a light-scattering layer containing translucent particles and a low-refractive-index layer, (3) an anti-glare layer forming at least surface irregularities, and a low-refractive-index layer A preferable example is an antiglare antireflection film formed by sequentially laminating. Hereinafter, the antireflection film and the antireflection film are treated as synonymous.

The embodiment of the antireflection film of the present invention is not limited to these. In order to achieve the object of the present invention, it is preferable to provide at least one hard coat layer on the surface (hereinafter sometimes referred to as the back surface) opposite to the viewing side of these antireflection films.
In the present specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”. . In addition, in this specification, for example, descriptions of “(meth) acryloyl”, “(meth) acrylate”, “(meth) acrylic acid” and the like are “acryloyl and / or methacryloyl”, “acrylate and / or methacrylate”, respectively. ”,“ Acrylic acid and / or methacrylic acid ”.

<Antireflection film>
[Layer structure of antireflection film]
The antireflection film according to the present invention is formed of a multilayer antireflection film in which at least two layers (light transmission layers) having light transmittance and different refractive indexes are laminated. Usually, the antireflection film is provided on a transparent substrate film. The antireflection film comprising two layers has a layer structure in the order of a high refractive index layer and a low refractive index layer (outermost layer) on the base film. The transparent substrate film, the high refractive index layer, and the low refractive index layer have a refractive index that satisfies the following relationship.
Refractive index of high refractive index layer> Refractive index of transparent substrate film> Refractive index of low refractive index layer

  A hard coat layer may be provided between the transparent substrate film and the high refractive index layer. Furthermore, it may be composed of a high refractive index hard coat layer, a light scattering layer or an antiglare high refractive index layer, and a low refractive index layer.

The antireflection film comprising at least three layers has a layer structure in the order of a medium refractive index layer, a high refractive index layer, and a low refractive index layer (outermost layer) on the transparent substrate film. The transparent substrate film, the middle refractive index layer, the high refractive index layer, and the low refractive index layer have a refractive index that satisfies the following relationship.
The refractive index of the high refractive index layer> The refractive index of the medium refractive index layer> The refractive index of the transparent substrate film> The refractive index of the low refractive index layer

  A hard coat layer may be provided between the transparent substrate film and the medium refractive index layer. Further, it may comprise a medium refractive index hard coat layer, an antiglare high refractive index layer and a low refractive index layer.

  Such an antireflection film having a three-layer structure has an optical film thickness of each of the medium refractive index layer, the high refractive index layer, and the low refractive index layer, that is, the product of the refractive index and the film thickness with respect to the design wavelength λ. JP-A-59-50401 describes that it is preferably around λ / 4 or a multiple thereof.

  Further, for the design wavelength λ (400 to 680 nm), the medium refractive index layer represents the following formula (1), the high refractive index layer represents the following formula (2), and the low refractive index layer represents the following formula (3). Satisfying each is preferable in that an antireflection film having more excellent antireflection performance can be produced.

Formula (1): (m ₁ λ / 4) × 0.60 <n ₁ d ₁ <(m ₁ λ / 4) × 0.80
Formula (2): (m ₂ λ / 4) × 1.00 <n ₂ d ₂ <(m ₂ λ / 4) × 1.50
Formula (3): (m ₃ λ / 4) × 0.85 <n ₃ d ₃ <(m ₃ λ / 4) × 1.05
Wherein, m ₁ is 1, n ₁ is the refractive index of the medium refractive index layer, and, d ₁ is at a layer thickness of the medium refractive index layer (nm); m ₂ is 2, n ₂ is the refractive index of the high refractive index layer, and d ₂ is the layer thickness (nm) of the high refractive index layer; m ₃ is 1, n ₃ is the refractive index of the low refractive index layer; D ₃ is the thickness (nm) of the low refractive index layer]

  Further, by using the principle of an equivalent film in which a layer having a refractive index higher than a set refractive index and a plurality of layers having a low refractive index are combined, a medium refractive index layer or a high refractive index layer substantially It is known that an optically equivalent layer can be formed, and can be applied to realize the reflectance characteristics of the present invention. The “substantially three layers” of the present invention means that four or five antireflection layers using such an equivalent film are also included.

  By satisfying each of the above formulas (1) to (3), the color of the reflected light of the antireflection film becomes a neutral approximation, and the visibility of the display image of the display device becomes excellent.

  The antireflection layer having a multilayer structure according to the present invention is formed by coating the antireflection film so that the thickness of the antireflection film is “substantially uniform”, and the thickness of the antireflection film is “substantially uniform”. Is preferably within a range of ± 6% of the variation in the total thickness of the antireflection layer. More preferably ± 5%, particularly preferably ± 3%. For example, in the case of a three-layer design in which a low refractive index layer, a high refractive index layer, and a medium refractive index layer are laminated in this order with a thickness of nλ / 4 from the air interface side (n is a natural number), The uniformity of the film thickness is preferably in the range of ± 3%, and if it is within this range, problems such as a significant decrease in antireflection performance are unlikely to occur. In particular, it is most preferable to be within ± 2%.

  If desired, the thickness of the anti-reflective coating can be as high as that of a transmission electron microscope (TEM), scanning electron microscope (SEM), atomic force microscope (AFM), and X-ray photoelectron spectrometer (ESCA). It can be analyzed by various surface analysis means well known in the field.

  In the antireflection film of the present invention having the above layer structure, at least a cured film formed using the curable composition improved according to the present invention is used.

<Curing film>
The cured film of the present invention is used for at least one layer constituting the antireflection film. The curable composition of the present invention is preferably used for a hard coat layer, and more preferably used for at least one of a hard coat layer, a medium refractive index layer, a high refractive index layer, and a low refractive index layer.

(Curable composition)
The curable composition of the present invention comprises a curable multi-branched polymer (RHB) having a multi-branched polymer (HB) as a core and a photocurable and / or thermosetting reactive group bonded to a branch branch end, and a curing agent. And at least one of curing accelerators. Furthermore, the photocurable and / or thermosetting reactive group contained in the curable multi-branched polymer (RHB) is selected from a radical polymerizable group, a cationic polymerizable group, and a hydrolyzable group-substituted silyl group. It is preferably a curable reactive group (hereinafter sometimes simply referred to as a curable group). It is preferable to further contain a polymerizable compound copolymerizable with these polymerizable groups and a polymerization initiator. Moreover, it is also preferable to contain inorganic compound fine particles having a predetermined refractive index in order to adjust the refractive index of the cured film, if necessary.

[Curable multi-branched polymer (RHB)]
[Multi-branched polymer (HB) as core]
The photo-curing and / or thermosetting multi-branched polymer (RHB) of the present invention has a multi-branched polymer (HB) as a core (core) and 10 mol% to 90 mol% of hydroxyl groups present at the branch branch ends. It is a highly “branched (dendritic)” macromolecule having a photocurable and / or thermosetting reactive group attached to it.
For example, it is a compound represented by the following schematic diagram (1) or schematic diagram (2).

  As shown in the schematic diagram (1), the compound includes a portion having branches extending from a central portion in a three-dimensional radial shape and further having a branch from its end. In addition, as shown in the schematic diagram (2), the dendritic compound that can be used in the present invention can be used as long as the branched portion is radially expanded even if it does not grow uniformly in all directions. is there.

  Further, the multi-branched polymer (HB) serving as a nucleus is a compound that is bonded to a branched chain extension unit that is two or more regular dendritic branches with a multivalent base nucleus as a center. The polyvalent group nucleus is a compound having at least two reactive groups (a) that form a linking group, and the linking group is chemically bonded to the reactive group (a) of the compound serving as the group nucleus. A hyperbranched polymer having a structure extended by repeating a chemical reaction between one reactive group (b) that forms a compound and a compound having at least two reactive groups (a) (branched chain extension compound) Preferably there is.

  Specific examples of the multi-branched polymer (HB) include multi-branched polyurea, multi-branched polyurethane, multi-branched polyamide amine, multi-branched polyamide, multi-branched polyester, multi-branched polycarbonate, multi-branched polycarbosilane, multi-branched polycarbosiloxane, Examples include multi-branched polycarbosilazenes, multi-branched polyethers, multi-branched poly (ether ketones), multi-branched poly (propylene imines), multi-branched polyalkylamines, and copolymers thereof.

  Such multi-branched polymers are, for example, edited by Yasuhiko Okada, “Science and Function of Dendrimers” pp 29-31 (IPC Co., Ltd., 2000), ibid, Chapter 2, edited by Koji Ishizu, “ Nanotechnology ”Chapter 6 (IPC Co., Ltd., 2000), COMPREHENSIVE SUPERMOLECULAR 10, Chapter 26 (PeramonPress, New York, 1995), and the like can be mentioned.

  Preferred examples include multi-branched polyamidoamines, multi-branched polyamides, multi-branched polyesters, multi-branched polycarbosilanes, multi-branched polycarbosiloxanes, multi-branched polyethers, multi-branched poly (ether ketones), and multi-branched polyalkylamines.

  Examples of the multi-branched polymer (HB) that serves as a nucleus include D.I. A. Tomalia, et al., “Angew. Chem. Int. Ed. Engl.”, 29, 138 (1990); , “Advanceds in Polymer Science”, Volume 143, 1 (Springer, New York) (1999); C. Salamone, Ed. , “Polymeric Materials Encyclopedia,” Volume 30, page 4949 (CRC Press, published by New York (1996); Masaaki Enomoto, “Polymer”, Volume 47, page 804 (1998), and references cited in the above-mentioned books, etc. The contents described in.

  As a specific example of the core multi-branched polymer (HB), for example, as a polyamino-based multi-branched polymer, for example, a reaction in which butylene diamine and acrylonitrile are reacted and a terminal nitrile group is reduced to an amine is performed in one step. Propyleneimine multibranched polymer obtained by repeating (WO093 / 14147, US5,530,092 specification, Japanese Examined Patent Publication No.7-330631); Ring opening using amine as nucleophilic component and palladium catalyst Amine-based multibranched polymer {M. Suzuki, et al. , “Macromolecules”, Vol. 31, p. 1716 (1998)}; Michael addition of methyl acrylate to ammonia or ethylenediamine, and further introducing a secondary amino group at the terminal by ester amide exchange reaction as one step, if necessary And an amidoamine-based multibranched polymer obtained by repeated reaction (WO0884705, JP-B-6-70132); polyamide-based multibranched polymer {S. C. E. Backson, et al. , “Macromol. Symp.”, Vol. 77, p. 1 (1994), JP-A No. 2000-86758, JP-A No. 2000-256659, etc.}; polyphenylene ester-based multibranched polymer {K. L. Wooley, et al. , “Polymer Journal”, 26, 187 (1994)}; polyetherketone-based multibranched polymer {C. J. et al. Hawker, “Macromolecules”, 29, 4370 (1996)}; polyurethane or polyurea multibranched polymers {R. Spindler, “Macromolecules”, 26 4809 (1993), A.M. Kumar, “Chem. Commun.”, 1629 (1998), etc.}; polyether-based multibranched polymers {V. Percec et al. “Macromolecules”, 27, 4441 (1994), C.I. J. et al. Hawker, et al. “J. Am. Chem. Soc.”, 112, 7638 (1990), JP-A-2001-206886, JP-A-2002-37823, etc.}; polyester-based multibranched polymer terminated with a hydroxyl group (US5) 418,301, WO096 / 12754, JP 03-522266, and the like; polyester-based multibranched polymers terminated with carboxyl groups (SR Turner, et al. “Macromolecules”, Vol. 27) 1611 (1994), JP-A-11-60540, etc.); polyester-based multibranched polymers terminated with a group containing an epoxy group (US Pat. No. 5,663,247, WO096 / 13558, etc.) it can. The present invention is not limited to these.

  In the present invention, the multi-branched polymer (HB) serving as a nucleus is preferably composed of at least one selected from the group consisting of dendrimers, hyperbranched polymers and starburst polymers described below. Specifically, as the core multi-branched polymer (HB), for example, “BOLTORN” (trade name, manufactured by Perstorp) of aliphatic polyester-based multi-branched polymers, polypropylamino-based multi-branched polymers (DSM) Available), poly (amidoamine) multi-branched polymers such as “STARBURRST” (manufactured by PAMAN), “Dendrimer” (trade name, manufactured by Aldrich) and the like can be used.

  The polyvalent group nucleus of the multi-branched polymer (HB) serving as a nucleus (core) is not particularly limited as long as it is a polyfunctional compound having an organic residue, nitrogen atom, silicon atom or phosphorus atom as a nucleus. The organic residue includes a single ring containing at least one heteroatom selected from carbon atoms, aromatic hydrocarbon rings (benzene ring, naphthalene ring, biphenyl ring, phenanthrene ring, triphenylene ring, etc.), oxygen, nitrogen, and sulfur. Heterocyclic rings having a cyclic or polycyclic ring structure (eg, pyrazine ring, hydropyrazine ring, piperazine ring, triazine ring, hydrotriazine ring, phenazine ring, xanthene ring, thioxanthene ring, etc.), calixarene structure, azacryptant structure , Crown ether structure, porphyrin structure and the like. These are also not particularly limited.

  The multibranched polymer (HB) serving as the core of the present invention is preferably a molecule prepared by a polycondensation cycle. Each cycle involves reacting all of the reactive functional groups of the core with one equivalent of a branched chain extending compound. Depending on the number of cycles (n), it is referred to as the “nth generation” multi-branched molecule. In the present invention, the first to sixth generations are preferred. The second generation to the fourth generation are particularly preferable.

  In the multi-branched polymer (HB) serving as the core of the present invention, it is preferable that the branched chain extension unit contains a cyclic structure. Further, it preferably contains a cyclic structure (also referred to as a ring structure) and an alkylene chain structure.

  The cyclic structure is selected from an alicyclic ring structure and an aromatic ring structure. Examples of the alicyclic ring structure include monocyclic, polycyclic and bridged cyclic C5-C22 aliphatic cyclic hydrocarbons, and specific examples thereof include cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, Cyclohexene, cyclohexadiene, cycloheptane, cycloheptene, cycloheptadiene, cyclooctane, cyclooctene, cyclooctadiene, cyclooctatriene, cyclosonane, cyclosonene, cyclodecane, cyclodecane, cyclodecanediene, cyclodecanetriene, cycloundecane, cyclododecane, Rings such as bicycloheptane, bicyclohexane, bicyclohexene, tricyclohexene, norcaran, norpinane, norbornane, norbornene, tricycloheptane, tricycloheptene, decalin, adamantane Concrete hydrocarbons, etc.).

  As the aromatic ring, an aryl ring (for example, benzene, naphthalene, dihydronaphthalene, indene, fluorene, acenaphthylene, acenaphthene, biphenylene, etc.), a monocyclic ring containing at least one of an oxygen atom, a sulfur atom, and a nitrogen atom or Heterocyclic group having a polycyclic ring structure (for example, a furanyl group, a tetrahydrofuranyl group, a pyranyl group, a pyroyl group, a chromenyl group, a phenoxathiinyl group, an indazoyl group, a pyrazoyl group, a pyridiyl group , Pyrazinyl group, pyrimidinyl group, indoyl group, isoindoyl group, quinoniyl group, pyrrolidinyl group, pyrrolinyl group, imidazolinyl group, pyrazolidinyl group, piperidinyl group, piperazinyl group, morpholinyl group, thienyl group, benzothienyl group and the like. The aryl ring is preferably an aryl ring having 6 to 18 carbon atoms.

The alkylene chain contained in the branched chain extension unit is preferably an alkylene group having 1 to 22 carbon atoms, and more preferably an alkylene group having 1 to 12 carbon atoms. The cyclic structure and the alkylene chain may be directly bonded or may be bonded via another divalent linking group. Examples of the divalent linking group include —O—, —S—, —COO—, —OCO—, —NHCOO—, —NHCONH—, —SO ₂ —, —CO—, —CON (Q ¹ ) —, — SO ₂ N (Q ¹ ) — and the like can be mentioned. (Where Q ¹ is a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, 2-chloroethyl group) 2-bromoethyl group, 2-cyanoethyl group, 2-methoxyethyl group, etc.).

  The branched chain extending unit constituted by the reaction of the multi-branched polymer (HB) serving as the nucleus with the branched chain extending compound is preferably an embodiment selected from a polyester structure, a polyamide structure, and a polyamine amide structure. A curable multi-branched polymer containing these branched chain extension units is preferable because the strength of the cured film to be formed is further improved. Furthermore, these multi-branched polymers (HB) are preferable because they can be easily synthesized by a sequential polymerization reaction and are supplied as an inexpensive material.

  The branched branch of the multi-branched polymer (HB) serving as the nucleus has a terminal structure of the reactive group (a) having reactivity with the branched extension compound as described above. Examples of the reactive group (a) at the branched branch end include a carboxy group, a hydroxyl group, an amino group, and an epoxy group. In the present invention, a hydroxyl group is preferred from the viewpoint of dispersibility of the translucent resin fine particles. Further, the multi-branched polymer serving as the core of the present invention preferably has 6 to 128 groups of reactive groups (a) at the ends of the branched branches, and more preferably has 8 to 64 groups.

  The mass average molecular weight of the multi-branched polymer (HB) is generally about 1,000 to about 50,000, preferably about 1500 to about 20,000. Within this range, the curing reaction proceeds sufficiently and the film strength of the obtained cured film can be maintained.

  The average degree of branching (DB) of the multi-branched polymer (HB) is the number average ratio of branching groups per molecule, that is, “terminal group + the total number of terminal groups, branching groups and linear groups”. It is defined in the literature as the proportion of “branched groups”. For ideal dendrons and dendrimers, the degree of branching is 1. For an ideal linear polymer, the degree of branching is close to zero. The degree of branching was determined by Hawker C.I. J. et al. Lee, R .; Frechet, J .; M.M. J. et al. , “J. Am. Chem. Soc.”, (1991) 113, 4583, it is mathematically expressed as the following formula (4).

(Here, Nt represents the number of terminal groups, Nb represents the number of branch groups, and NI represents the number of linear groups.)

  The degree of branching (DB) of the multibranched molecule used in the present invention ranges from dendrimers (ideally having a degree of branching of 1) to 0.25. More typically, multi-branched polymers having a degree of branching (DB) of 0.25 to 0.80 can be easily produced and are relatively inexpensive compared to dendrimers. In short, it is preferable that the multibranched molecules form a radially expanded form. A more preferable degree of branching (DB) is 0.3 to 0.8.

[Curable multi-branched polymer (RHB)]
The curable multibranched polymer (RHB) of the present invention is characterized in that it contains a curable group that undergoes a crosslinking reaction by light and / or heat at least at a part of the branched branch ends of the multibranched polymer (HB). To do.

  Examples of the curable group that can participate in the crosslinking reaction include a group having an active hydrogen atom (for example, a hydroxyl group, a carboxyl group, an amino group, a carbamoyl group, a mercapto group, a β-ketoester group, a hydrosilyl group, and a silanol group). A group having an unsaturated double bond capable of radical polymerization, a group capable of cationic polymerization, an acid anhydride-containing group, a hydrolyzable silyl group (eg, alkoxysilyl group, acyloxysilyl group, etc.), a group that can be substituted by a nucleophile (Active halogen atoms, sulfonate esters, etc.), isocyanate groups (which are protected and may be block isocyanate groups which generate isocyanate groups upon heating), and the like. In particular, it is preferably selected from a radical polymerizable group, a cationic polymerizable group, and a hydrolyzable silyl group. In particular, it is most preferably selected from radically polymerizable groups.

  10 mol% to 90 mol% of the total number of branches of the multi-branched polymer (HB) (hereinafter sometimes simply referred to as “core molecule”) as a core contains a curable group. preferable. Thereby, sufficient strength of the cured film is expressed, curling is suppressed, and a film having a cured film excellent in brittleness can be obtained. Further, when the cured film has translucent resin fine particles, the dispersibility of the fine particles is improved, and a cured film having excellent productivity can be obtained. The ratio containing a curable group is more preferably 50 mol% to 90 mol%, still more preferably 70 mol% to 90 mol%, particularly preferably 80 mol% to 90 mol%.

  Further, the curable groups in the molecule may be the same or different. For example, at least one kind of polymerizable group selected from a radical polymerizable group and a cationic polymerizable group may be contained.

(Radical polymerizable group)
Examples of the radical polymerizable group include a curable group represented by the following general formula (1).
General formula (1)

Wherein (1), V ¹¹ is -COO -, - OCO -, - CH 2 OCO -, - CH 2 COO -, - O -, - CONHCOO -, - CONHCO -, - SO 2 -, - CO-, —CON (Q ¹¹ ) —, —SO ₂ N (Q ¹¹ ) — or a phenylene group (hereinafter, the phenylene group may be represented by Ph.
However, Ph represents 1,2-, 1,3- and 1,4-phenylene groups). Here, Q ¹¹ is a hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxyethyl group, benzyl group, fluorobenzyl group, methylbenzyl group, cyclohexylmethyl group, 2-ethoxyethyl group, 3-methoxypropyl group, etc.). In a preferred embodiment of the ^{V 11, -COO -, - OCO} -, - CONH -, - CH 2 OCO -, - CH 2 COO -, - O-, include a phenylene group. a ¹¹ and a ¹² may be the same or different, and may be a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.) or -CH ₂ COOR ¹¹ group (R ¹¹ represents an alkyl group. for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, etc.) representing the.

  These polymerizable groups may be directly bonded to the organic residue chemically reacted (described later) with the reactive group (a) at the end of the branched branch of the core molecule, or may be bonded via a linking group. Also good. Here, the linking group represents a linking group having 1 to 22 total atoms (the total number of atoms herein excludes a hydrogen atom bonded to a carbon atom, a nitrogen atom or a silicon atom). As the linking group, a carbon atom-carbon atom bond (single bond or double bond), a carbon atom-heteroatom bond (such as an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom), a heteroatom-hetero It is composed of any combination of atomic groups composed of atomic bonds. For example, the following are mentioned as atomic groups. A direct bond or a linking group having 1 to 12 total atoms is preferable.

Here, z ¹¹ and z ¹² are a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxyl group, and an alkyl group (for example, a methyl group, an ethyl group, and a propyl group). Etc.) z ¹³ and z ¹⁴ are each a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, benzyl group, phenethyl group). , Phenyl group, tolyl group, etc.). z ¹⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms (for example, the same as z ¹³ described above).

(Cationically polymerizable group)
Examples of the cationically polymerizable group in the present invention include a functional group containing a polymerizable group that causes a polymerization reaction and / or a crosslinking reaction when irradiated with an active energy ray in the presence of an active energy ray-sensitive cationic polymerization initiator. Specific examples include an epoxy group, a cyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester compound, and a vinyloxo group. More specifically, those having the chemical structure exemplified in the cationically polymerizable monomer (M _A2 ) described later can be mentioned.

  These photocationically polymerizable groups may be bonded directly to the branched branch of the core molecule or may be bonded via a linking group, as described above.

(Hydrolyzable silyl group)
Examples of the hydrolyzable group-substituted silyl group having the performance as a curable reactive group include those having the structure of the following general formula (2). Such a hydrolyzable group-substituted silyl group may be either directly bonded to the branched branch of the core molecule or bonded via a linking group, as described above.
Formula (2): (R ²¹ O) _3-a (R ²² ) _a Si—

In the general formula (2), the (R ²¹ O) group represents an alkoxy group (when R ²¹ is an aliphatic group) or an acyloxy group (when R ²¹ is —COR ²⁰ ), and is hydrolyzed to form a silanol group. [typically _{(HO) 3-a -Si (} R 22) a -] next polycondensation reaction proceeds. When R ²¹ is an aliphatic group, a linear or branched aliphatic group having 1 to 8 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, Trifluoroethyl group, methoxymethyl group, benzyl group, phenethyl group, cyclohexyl group, cyclohexylmethyl group, etc.). When R ²¹ is —COR ²⁰ , R ²⁰ represents a hydrocarbon group, preferably a linear or branched aliphatic group having 1 to 6 carbon atoms which may be substituted (specifically, the aliphatic group represented by R ²¹ above). Synonymous with group groups, and the same specific examples can be given), and optionally substituted phenyl groups (for example, phenyl group, methoxyphenyl group, fluorophenyl group, tolyl group, xylyl group, etc.). Among them, preferred (R ²¹ O) groups include hydrolysis reactivity of the (R ²¹ O) group, and drying properties of alcohols or carboxylic acids generated by elimination as a by-product in the coating drying process. To an alkoxy group having 1 to 4 carbon atoms or an acyloxy group having 1 to 3 carbon atoms. R ²² represents a hydrocarbon group, preferably an aliphatic group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms. These hydrocarbon groups may be substituted. Specific examples include those having the same contents as the substituent R ⁰¹ of the non-polymerizable linking group described later.

The curable multi-branched polymer (RHB) of the present invention has a structure in which a non-polymerizable hydrocarbon group is bonded to a part of all branched branches, that is, a structure chemically modified with another non-polymerizable linking group. There may be. Examples of such a terminal linking group include —OR ⁰¹ , —OCOR ⁰¹ , —COOR ⁰¹ , —CONHR ⁰¹ , —NHCOR ⁰¹ , —NHSO ₂ R ⁰¹ , —N (R ⁰¹ ) (R ⁰² ), —OOCNHR ⁰¹ , -NHCONHR ⁰¹ etc. are mentioned.

Here, R ⁰¹ and R ⁰² represent a hydrocarbon group having 1 to 32 carbon atoms. The hydrocarbon group represents an aliphatic group, an aryl group or a heterocyclic group. As the aliphatic group, a linear or branched alkyl group having 1 to 32 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group) Decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nanodecyl group, eicosanyl group, heneicosanyl group, docosanyl group, etc.), straight chain having 2 to 32 carbon atoms Or branched alkenyl groups (for example, vinyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, dodecenyl, tridecenyl, tetradecenyl, hexadecenyl, octadecenyl, eicosenyl, dococenyl, butadienyl Group, pentadienyl group, hexadienyl group Octadienyl group, etc.), linear or branched alkynyl group having 2 to 22 carbon atoms (for example, ethynyl group, propynyl group, butynyl group, hexynyl group, octanyl group, decanyl group, dodecanyl group, etc.); 22 alicyclic hydrocarbon groups (the alicyclic hydrocarbon groups include monocyclic, polycyclic, and bridged cyclic aliphatic hydrocarbon groups, and specific examples thereof include cyclopentane and cyclopentene. , Cyclopentadiene, cyclohexane, cyclohexene, cyclohexadiene, cycloheptane, cycloheptene, cycloheptadiene, cyclooctane, cyclooctene, cyclooctadiene, cyclooctatriene, cyclosonane, cyclosonene, cyclodecane, cyclodecene, cyclodecanediene, cyclodecanetriene, Cycloundecane, Cyclod Kang, bicycloheptane, bicyclohexane, bi- cyclohexene, tri-cyclohexene, norcarane, norpinane, norbornane, norbornene, norbornadiene, tricyclo heptane, tricyclo-heptene, decalin, cyclic structures hydrocarbons such adamantane, etc.).

  Among these, a linear aliphatic group having 1 to 18 carbon atoms, a branched chain having 3 to 18 carbon atoms, and a cyclic aliphatic group having 5 to 16 carbon atoms are more preferable.

The aliphatic group may have a substituent, and as the substituent that can be introduced, a monovalent nonmetallic atomic group excluding hydrogen is used. Specific examples of the nonmetallic atomic group include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, —OH group, —OR ⁰¹¹ , —SR ⁰¹¹ , —COR ⁰¹¹ , -COOR ⁰¹¹ , -OCOR ⁰¹¹ , -SO ₂ R ⁰¹¹ , -NHCONHR ⁰¹¹ , -N (R ⁰¹² ) COR ⁰¹¹ , -N (R ⁰¹² ) SO ₂ R ⁰¹¹ , -N (R ⁰¹³ ) (R ⁰¹⁴ ),- CON (R ⁰¹³ ) (R ⁰¹⁴ ), —SO ₂ N (R ⁰¹³ ) (R ⁰¹⁴ ), —P (═O) (R ⁰¹⁵ ) (R ⁰¹⁶ ), —OP (═O) (R ⁰¹⁵ ) (R ⁰¹⁶ ), ^-Si (R ⁰¹⁷ ) (R ⁰¹⁸ ) (R ⁰¹⁹ ), an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, and 5 to 10 carbon atoms An alicyclic hydrocarbon group, an aryl group having 6 to 18 carbon atoms (the aryl ring includes benzene, naphthalene, dihydro A heterocyclic group having a monocyclic or polycyclic ring structure containing at least one of phthalene, indene, fluorene, acenaphthylene, acenaphthene, biphenylene, etc.), oxygen atom, sulfur atom, nitrogen atom (heterocyclic group) As, for example, furanyl group, tetrahydrofuranyl group, pyranyl group, pyroyl group, chromenyl group, phenoxathiinyl group, indazoyl group, pyrazoyl group, pyridiyl group, pyrazinyl group, pyrimidinyl group, indoyl group, isoindoyl group, quinoniyl group Pyrrolidinyl group, pyrrolinyl group, imidazolinyl group, pyrazolidinyl group, piperidinyl group, piperazinyl group, morpholinyl group, thienyl group, benzothienyl group and the like.

  These alkenyl group, alkynyl group, alicyclic hydrocarbon group, aryl group, and heterocyclic group may further have a substituent, and the substituent may be a group that can be introduced into the aliphatic group. The thing similar to what was illustrated as is mentioned.

Here, R ⁰¹¹ represents an aliphatic group having 1 to 22 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a heterocyclic group. The aliphatic group for R ^{011 has the same meaning as} the aliphatic group represented by R ⁰¹ . As the aryl group for R ^011, the same aryl groups as those exemplified above as the substituent which can be introduced into the aliphatic group represented by R ⁰¹ can be mentioned. Such an aryl group may further have a substituent, and examples of the substituent include those exemplified as the substituents that can be introduced into the aliphatic group in R ⁰¹ . R ⁰¹² represents a hydrogen atom or the same as the R ⁰¹¹ group.

R ⁰¹³ and R ⁰¹⁴ each independently represents a hydrogen atom or the same as R ^011, and R ⁰¹³ and R ⁰¹⁴ are bonded to each other to form a 5-membered or 6-membered ring containing an N atom. It may be formed.

R ⁰¹⁵ and R ⁰¹⁶ each independently represents an aliphatic group having 1 to 22 carbon atoms, an aryl group having 6 to 14 carbon atoms, or —OR ⁰¹¹ . The aliphatic group for R ⁰¹⁵ and R ⁰¹⁶ has the same ^{meaning as} the aliphatic group represented by R ⁰¹ . Examples of the aryl group in R ⁰¹⁵ and R ⁰¹⁶ include the same aryl groups as those exemplified as the substituent that can be introduced into the aliphatic group in R ⁰¹ . Such an aryl group may further have a substituent, and examples of the substituent include those exemplified as the substituents that can be introduced into the aliphatic group in R ⁰¹ .

R ⁰¹⁷ , R ⁰¹⁸ and R ⁰¹⁹ each independently represents a hydrocarbon group having 1 to 22 carbon atoms or —OR ^020, and at least one of these substituents represents a hydrocarbon group. The hydrocarbon group represents the same aliphatic group and aryl group represented by R ⁰¹ , and —OR ⁰²⁰ represents the same content as —OR ⁰¹¹ .

Examples of the aryl group of R ⁰¹ and R ⁰² in the polar group include the same aryl groups as those exemplified as the substituent that can be introduced into the aliphatic group in R ⁰¹ . Such an aryl group may further have a substituent, and examples of the substituent that can be introduced include the same substituents as those exemplified as the substituent that can be introduced into the aliphatic group in R ⁰¹ . .

Examples of the heterocyclic group represented by R ⁰¹ and R ⁰² in the polar group include the same heterocyclic groups as those exemplified as the substituent that can be introduced into the aliphatic group in R ⁰¹ . The heterocyclic group may further have a substituent, and the substituent that can be introduced is the same as that exemplified as the substituent that can be introduced into the aliphatic group represented by R ⁰¹ . Things.

When the terminal linking group is [—N (R ⁰¹ ) (R ⁰² )], R ⁰² represents a hydrogen atom or the same content as R ⁰¹ described above.

  The curable multi-branched polymer (RHB) of the present invention is obtained by synthesizing a multi-branched polymer as a core by a synthesis method such as a conventionally known stepwise synthesis method (Divergent method) or polycondensation reaction of an ABx type compound The polar group at the end of the branched branch can be obtained by modifying with a specific substituent according to a conventionally known synthesis method. The curable multi-branched polymer (RHB) of the present invention can also be obtained by a synthesis method according to the description in Japanese Patent No. 2574201.

  As the antireflection film of the optical film for image display, the curable multi-branched polymer (RHB) is preferably non-absorbing in the wavelength range of 400 nm to 650 nm from the viewpoint of maintaining transparency without being colored. . The light transmittance in the wavelength range of 400 nm to 650 nm as a film is preferably 85% or more and 100%, more preferably 90% or more and 100%.

[Curing agent and curing accelerator]
In the curable composition of the present invention, at least one of a curing agent and a curing accelerator is used in combination. These can be used by appropriately selecting conventionally known ones according to the curing reaction of the curable reactive group (a) in the curable multi-branched polymer (RHB) of the present invention.

  As such a curing agent and a curing accelerator, for example, Shinzo Yamashita, Tosuke Kaneko “Crosslinking Agent Handbook” published by Taiseisha (1981) “Polymer Data Handbook Fundamental” edited by Taiseisha (1986) Etc.) can be used. Also, for example, organic silane compounds, polyisocyanate compounds, polyol compounds, polyamine compounds, acid anhydride compounds, polyepoxy group-containing compounds, epoxy resins {eg, “New Epoxy Resins” written by Hiroshi Horiuchi (Published in 1985), “epoxy resins” written by Kuniyuki Hashimoto, published by Nikkan Kogyo Shimbun (1969), etc., melamine resins {eg, “Yulia Melamine Resin” edited by Ichiro Miwa and Hideo Matsunaga, Nikkan Kogyo Shimbun (Compounds described in (1969)) and poly (meth) acrylate compounds {for example, Nobu Okawara, Takeo Saegusa, Toshinobu Higashimura "Oligomer" Kodansha (1976), Eizo Omori "Functional acrylics" Resins "compounds described in Techno System (published in 1985), etc.}.

  For example, as the curing agent used when the curable reactive group of the curable multi-branched polymer (RHB) is a group having an active hydrogen such as a hydroxyl group or an amino group, for example, a polyisocyanate-based, aminoplast, polybasic acid or The anhydride etc. can be mentioned.

Examples of polyisocyanates include m-xylylene diisocyanate, toluene-2,4-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and other polyisocyanate compounds, silyl isocyanate compounds such as methylsilyl triisocyanate, and partial condensates of these isocyanate compounds. And adducts with multimers, polyhydric alcohols and low molecular weight polyesters, and blocked polyisocyanate compounds in which isocyanate groups are blocked with a blocking agent such as phenol.

  As the aminoplast, melamine-formaldehyde, guanamine-formaldehyde, urea-formaldehyde and the like are employed. Among them, methylol melamine which is at least partially etherified with one or more of lower alcohols such as methanol, ethanol, propanol and butanol (for example, hexamethyletherified methylolmelamine, hexabutyletherified methylolmelamine, methylbutyl mixed etherification) Methylol melamine, methyl etherified methylol melamine, butyl etherified methylol melamine, etc.), or their condensates.

  As polybasic acid or its anhydride, pyromellitic acid, pyromellitic anhydride, trimellitic acid, trimellitic anhydride, phthalic acid, phthalic anhydride and other aromatic polyvalent carboxylic acids or anhydrides thereof, maleic acid, Examples thereof include aliphatic polycarboxylic acids such as maleic anhydride, succinic acid, and succinic anhydride, or anhydrides thereof.

  On the other hand, when the curable group of the curable multi-branched polymer (RHB) is an epoxy group or oxetanyl group, a reactive group having an active hydrogen (for example, a hydroxyl group, a carboxyl group, an amino group, a mercapto group, etc.) or a cyclic acid It can be cured by a chemical reaction with an anhydride-containing group.

  In the present invention, an organosilane compound can be used in the curable composition. The organosilane is preferably an organosilane compound having at least one functional group capable of providing a silanol group by hydrolysis in the molecule. In the composition of the present invention, hydrolysis obtained by hydrolysis and condensation is preferred. And / or a partial condensate, and serves as a binder in the composition.

Preferably, it is an organosilane compound represented by the following general formula (3) and / or a derivative compound thereof.
Formula (3): R ³¹ _4-b —Si (X ³¹ ) _b

In the general formula (3), R ³¹ represents a substituted or unsubstituted aliphatic group or aryl group. X ³¹ represents a halogen atom (a chlorine atom, a bromine atom, etc.), an OH group, an OR ³² group, or an OCOR ³² group. R ³² represents a substituted or unsubstituted alkyl group. b represents an integer of 1 to 4;

In the general formula (3), R ³¹ is preferably a substituted or unsubstituted aliphatic group having 1 to 30 carbon atoms or an aryl group having 6 to 14 carbon atoms.
The aliphatic group is preferably a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkenyl group having 2 to 22 carbon atoms, or a linear or branched group having 2 to 22 carbon atoms. -Like alkynyl group, alicyclic hydrocarbon group having 5 to 22 carbon atoms (the alicyclic hydrocarbon group includes monocyclic, polycyclic, and bridged cyclic aliphatic cyclic hydrocarbon groups, Specific examples thereof include those exemplified for the substituent R ⁰¹ of the non-polymerizable linking group, and the aliphatic group preferably has 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms. In addition, examples of the aryl group include phenyl, naphthyl, anthranyl, and the like, and a phenyl group is preferable.

There is no restriction | limiting in particular as a substituent of the said aliphatic group. Specific examples include those having the same contents as the substituent that can be introduced into the aliphatic group represented by R ⁰¹ .

In the general formula (3), examples of b = 4 (hereinafter referred to as tetrafunctional organosilane) include tetraalkoxysilane (alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, etc.), tetraacetoxysilane, and the like. it can.

  Specific compounds of b = 3 (hereinafter referred to as trifunctional organosilane) and b = 2 (hereinafter referred to as bifunctional organosilane) include, for example, paragraph number [0021] of JP-A-9-169951. And compounds described in paragraphs [0016] to [0021] of JP-A No. 2000-275403.

  The organosilane compound used in the present invention preferably has a substituent containing an active energy ray reactive group. Such a substituent is preferably an organic group having 2 to 10 carbon atoms. Examples of the active energy ray reactive group include radically polymerizable ethylenically unsaturated groups and cationic polymerizable groups.

  Examples of the radical polymerizable group or the cationic polymerizable group as the reactive group include the same as the polymerizable group described above.

The organosilane compound is more preferably an organosilane compound represented by the following general formula (3-1) and / or a derivative compound thereof.
General formula (3-1): (R ³¹¹ ) _(4-cd) (R ³¹² ) _c Si (X ³¹¹ ) _{d In} general formula (3-1), R ³¹¹ and X ³¹¹ are each the above general formula (3 ) Represents the same contents as R ³¹ and X ^{31 in FIG} .

R ³¹² represents an organic group containing an active energy ray-reactive group having 2 to 22 total atoms. However, hydrogen atoms substituted with carbon atoms, nitrogen atoms, silicon atoms, etc. are excluded. c is 1 or 2, d is an integer of 1-3.

The active energy ray reactive group in R ³¹² is preferably a radical polymerizable group or a cationic polymerizable group, and examples thereof include those having the same contents as the above reactive group.

  Specific examples of the organosilane compound represented by the general formula (3-1) include, for example, those described in JP-A 2000-275403, paragraph numbers [0023] to [0025] and paragraph numbers [0041] to [0042]. Compounds and the like.

  These curing agents are preferably added in an amount of about 0.5 to 300 parts by mass per 100 parts by mass of the curable multi-branched polymer (RHB), in particular, per 100 parts by mass of the curable multi-branched polymer (RHB). The addition amount is preferably about 5.0 to 100 parts by mass.

[Curing accelerator]
As the curing accelerator that accelerates the curing, a known acid, base catalyst, or metal chelate compound can be used as a reaction catalyst. As the acid, Bronsted acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or the like, or organic acid such as acetic acid, formic acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, dibutyltin dilaurate, Examples thereof include Lewis acids such as dibutyltin diacetate, dibutyltin dioctate, triisopropoxyaluminum, tetrabutoxyzirconium, and tetrabutoxytitanate.

  The curing catalyst varies greatly depending on the basicity and boiling point of the organic base combined with the acid. The curing catalyst preferably used in the present invention is described below from each viewpoint.

  The lower the basicity of the organic base, the higher the acid generation efficiency during heating, which is preferable from the viewpoint of curing activity. However, if the basicity is too low, the storage stability becomes insufficient. Therefore, it is preferable to use an organic base having an appropriate basicity. When expressed using pKa of a conjugate acid as a basic index, the pKa of the organic base used in the present invention is preferably 5.0 to 11.0, and more preferably 6.0 to 10.5. 6.5 to 10.0 is more preferable. The value of pKa of organic base in aqueous solution is described in Chemical Handbook Fundamentals (5th revised edition, edited by The Chemical Society of Japan, Maruzen, 2004) Volume II, pages II-334 to 340. An organic base having an appropriate pKa can be selected. In addition, a compound that can be presumed to have a pKa that is structurally appropriate even if not described in this document can be preferably used. Although the compound which has suitable pKa described in this literature in the following table | surface is shown, the compound which can be preferably used for this invention is not limited to these.

  The lower the boiling point of the organic base, the higher the acid generation efficiency during heating, which is preferable from the viewpoint of curing activity. Therefore, it is preferable to use an organic base having an appropriate boiling point. The boiling point of the base is preferably 120 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 70 ° C. or lower.

Examples of the organic base that can be preferably used in the present invention include, but are not limited to, the following compounds. Figures in parentheses indicate boiling points.
b-3: pyridine (115 ° C), b-14: 4-methylmorpholine (115 ° C), b-20: diallylmethylamine (111 ° C), b-19: triethylamine (88.8 ° C), b-21 : T-butylmethylamine (67-69 ° C), b-22: dimethylisopropylamine (66 ° C), b-23: diethylmethylamine (63-65 ° C), b-24: dimethylethylamine (36-38 ° C) ), B-18: trimethylamine (3-5 ° C.).

  In addition, when the curable group of the curable multi-branched polymer (RHB) contains a silyl group substituted with a hydrolyzable group as a site involved in the curing reaction, a known acid or base as a catalyst for the sol / gel reaction It is preferable to use a catalyst or a metal chelate compound as a curing accelerator.

In addition, from the viewpoint of storage stability of the curable composition, a compound that generates a curing accelerator such as an acid or a base by the action of light and / or heat may be used. When these compounds are used, the coating film can be cured by irradiation with active energy rays or heat irradiation.

  As the compound that generates a base, known compounds can be used, and specific examples thereof include nitrobenzyl carbamates and dinitrobenzyl carbamates. As the compound that generates an acid, known compounds can be used, and specific examples include those described in the polymerization initiator described later.

  The amount of these curing accelerators used varies depending on the type of compound and the curing reactive site, but is generally preferably about 0.1 to 15% by mass relative to the total solid content of the curable composition. Preferably it is about 0.5-5 mass%.

[Polymerizable compound (M _A )]
The curable composition of the present invention can be copolymerized with the curable group of the curable multibranched polymer (RHB) when the curable group of the curable multibranched polymer (RHB) contains a polymerizable group. It is preferable to use a polymerizable compound (M _A ) and a polymerization initiator in combination. The polymerizable compound (M _A ) is preferably a compound containing at least one polymerizable group selected from a radical polymerizable group and a cationic polymerizable group and having no absorption at a wavelength of 400 nm or longer. Thereby, it becomes an antireflection film with good transparency without coloring as an optical film. Specifically, it is a radical polymerizable compound or a cationic polymerizable compound, and may be either a monomer or an oligomer.

{Radically polymerizable monomer (M _A1 )}
Examples of the radical polymerizable group include ethylenically unsaturated groups such as a (meth) acryloyl group, a vinyloxy group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable. Further, the radical polymerizable group preferably contains a polyfunctional monomer containing two or more radical polymerizable groups in the molecule.

  The radical polymerizable polyfunctional monomer is preferably selected from compounds having at least two terminal ethylenically unsaturated bonds. Preferably, it is a compound having 2 to 6 terminal ethylenically unsaturated bonds in the molecule. Such a compound group is widely known in the polymer material field, and these can be used without particular limitation in the present invention. These can have chemical forms such as, for example, monomers, prepolymers, ie dimers, trimers or oligomers, or mixtures or copolymers thereof.

Examples of the radical polymerizable monomer (M _A1 ) include unsaturated carboxylic acids (for example, (meth) acrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof and amides. Preferably, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound can be used. In addition, unsaturated carboxylic acid esters having nucleophilic substituents such as hydroxyl group, amino group, mercapto group, amides, monofunctional or polyfunctional isocyanates, addition products of epoxies, polyfunctional A dehydration condensation reaction product with a carboxylic acid is also preferably used. A reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent, such as an isocyanate group or an epoxy group, and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. . As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene or the like instead of the unsaturated carboxylic acid.

Examples of the aliphatic polyhydric alcohol compound include alkanediol, alkanetriol, cyclohexanediol, cyclohexanetriol, inositol, cyclohexanedimethanol, pentaerythritol, sorbitol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin and the like. Polymerizable ester compounds (monoesters or polyesters) of these aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids, for example, compounds described in JP-A No. 2001-139663, paragraph numbers [0026] to [0027]. .

  Examples of other polymerizable esters include, for example, vinyl (meth) acrylate, allyl (meth) acrylate, JP-B-46-27926, JP-B-51-47334, and JP-A-57-196231. The aliphatic alcohol esters described above, those having an aromatic skeleton described in JP-A-2-226149, and those having an amino group described in JP-A-1-165613 are also preferably used.

  Specific examples of polymerizable amides formed from an aliphatic polyvalent amine compound and an unsaturated carboxylic acid include methylene bis- (meth) acrylamide, 1,6-hexamethylene bis- (meth) acrylamide, diethylenetriamine tris ( Examples include meth) acrylamide, xylylene bis (meth) acrylamide, and those having a cyclohexylene structure described in JP-B No. 54-21726.

In addition, a vinylurethane compound containing 2 or more polymerizable vinyl groups in one molecule (Japanese Patent Publication No. 48-41708), urethane acrylates (Japanese Patent Publication No. 2-16765), ethylene oxide skeleton Urethane compound (Japanese Examined Patent Publication No. 62-39418, etc.), polyester acrylates (Japanese Examined Patent Publication No. 52-30490, etc.), and further described in “Journal of Japan Adhesion” Vol. 20, No. 7, pages 300-308 (1984). These photocurable monomers and oligomers can also be used.
These radical polymerizable polyfunctional monomers may be used in combination of two or more.

{Cationically polymerizable monomer (M _A2 )}
Next, the compound (cation polymerizable monomer) (M _A2 ) containing a cationic polymerizable group will be described.

The cationically polymerizable monomer (M _A2 ) used in the present invention is any compound that causes a polymerization reaction and / or a crosslinking reaction when irradiated with an active energy ray in the presence of an active energy ray-sensitive cationic polymerization initiator. Representative examples include epoxy compounds, cyclic thioether compounds, cyclic ether compounds, spiro orthoester compounds, vinyl ether compounds, and the like. In the present invention, one or more of the above cationic polymerizable organic compounds may be used.

As the cationic polymerizable monomer (M _A2 ), the number of cationic polymerizable groups in one molecule is preferably 2 to 10, particularly preferably 2 to 5. The molecular weight of the compound is preferably 3000 or less, more preferably in the range of 200 to 2000, particularly preferably in the range of 400 to 1500. If it is this range, volatilization in a film formation process does not become a problem, and there is no problem also in the point of compatibility with a curable composition, and it is preferable.

Examples of the epoxy compound that is one of the cationic polymerizable monomers (M _A2 ) include aliphatic epoxy compounds and aromatic epoxy compounds.

  Examples of the aliphatic epoxy compound include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers and copolymers such as glycidyl (meth) acrylate, and the like. be able to. In addition to the above epoxy compounds, for example, monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, butyl epoxide stearate, octyl epoxide stearate, epoxidized linseed oil, epoxidized polybutadiene, etc. Can be mentioned. Examples of the alicyclic epoxy compound include polyglycidyl ether of polyhydric alcohol having at least one alicyclic ring, or unsaturated alicyclic ring (for example, cyclohexene, cyclopentene, dicyclooctene, tricyclodecene, etc. ) Cyclohexene oxide or cyclopentene oxide-containing compound obtained by epoxidizing the containing compound with a suitable oxidizing agent such as hydrogen peroxide or peracid.

  Examples of the aromatic epoxy compound include mono- or polyglycidyl ethers of mono- or polyhydric phenols having at least one aromatic nucleus or alkylene oxide adducts thereof. As these epoxy compounds, for example, compounds described in paragraphs [0084] to [0086] of JP-A No. 11-242101, paragraph numbers [0044] to [0046] of JP-A No. 10-158385, and the like. And the compounds described.

  Among these epoxy compounds, aromatic epoxides and alicyclic epoxides are preferable, and alicyclic epoxides are particularly preferable in consideration of rapid curability. In the present invention, one of the above epoxy compounds may be used alone, but two or more may be used in appropriate combination.

  Examples of the cyclic thioether compound include compounds in which the epoxy ring is a thioepoxy ring.

  Specific examples of the compound containing an oxetanyl group as a cyclic ether include compounds described in paragraph numbers [0024] to [0025] in JP-A No. 2000-239309. These compounds are preferably used in combination with an epoxy group-containing compound.

  Examples of the spiro orthoester compound include compounds described in JP-A No. 2000-506908.

Examples of the vinyl hydrocarbon compound include a styrene compound, a vinyl group-substituted alicyclic hydrocarbon compound (vinyl cyclohexane, vinyl bicycloheptene, etc.), a vinyloxy compound (same as described in the above radical polymerizable compound), a propenyl compound. {"J. Polymer Science: Part A: Polymer Chemistry", Vol. 32, page 2895 (1994), etc.}, alkoxyallene compounds {"J. Polymer Science: Part A: Polymer Chemistry", Vol. 1995), etc.}, vinyl compounds {"J. Polymer Science: Part A: Polymer Chemistry", 34, 1015 (1996), Japanese Patent Application Laid-Open No. 2002-29162 Etc. according}, isopropenyl compound { "J.Polymer Science: Part A: Polymer Chemistry", 34 vol, may be mentioned p. 2051 (1996) described the like} and the like.
You may use these in combination of 2 or more types as appropriate.

  Moreover, it is preferable that the polyfunctional compound used by this invention uses the compound which contains at least 1 type of each group chosen from the said radically polymerizable group and cation polymerizable group at least in a molecule | numerator. Examples of such compounds include compounds described in paragraphs [0031] to [0052] in JP-A-8-277320, compounds described in paragraph No. [0015] in JP-A-2000-191737, and the like. The compounds used in the present invention are not limited to these examples.

M _A polymerizable compound, the curable hyperbranched polymer (RHB) 100 parts by weight per preferably added amount of about 1 to 300 parts by weight, in particular, curable hyperbranched polymer (RHB) 100 parts by weight per 5 It is preferable to make it an addition amount of about ~ 100 parts by mass.
The radical polymerizable compound and the cationic polymerizable compound described above are preferably contained in a mass ratio of radical polymerizable compound: cation polymerizable compound in a ratio of 90:10 to 20:80, and 80:20 to More preferably, it is contained at a ratio of 30:70.

[Polymerization initiator]
Next, the polymerization initiator will be described in detail.
Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator. The polymerization initiator (L) of the present invention is a compound that generates radicals or acids by light and / or heat irradiation.

  The photopolymerization initiator (L) used in the present invention preferably has a maximum absorption wavelength of 400 nm or less. Thus, the handling can be performed under a white light by setting the absorption wavelength to the ultraviolet region. A compound having a maximum absorption wavelength in the near infrared region can also be used.

First, the compound (L ₁ ) that generates radicals will be described in detail.
The compound (L ₁ ) that generates radicals preferably used in the present invention refers to a compound that generates radicals by irradiation with light and / or heat, and initiates and accelerates polymerization of a compound having a polymerizable unsaturated group. . A known polymerization initiator or a compound having a bond with a small bond dissociation energy can be appropriately selected and used. Moreover, the compound which generate | occur | produces a radical can be used individually or in combination of 2 or more types.

Examples of the compound (L ₁ ) that generates radicals include conventionally known organic peroxides, thermal radical polymerization initiators such as azo polymerization initiators, and organic peroxides (described in JP-A-2001-139663, etc.). Amine compounds (described in JP-B-44-20189), metallocene compounds (described in JP-A-5-83588, JP-A-1-304453, etc.), hexaarylbiimidazole compounds (US Pat. No. 3,479,185). Photo radical polymerization initiators such as disulfone compounds (described in JP-A-5-239015, JP-A 61-166544, etc.), organic halogen compounds, carbonyl compounds, and organic boric acid compounds. It is done.

Specific examples of the organic halogen compound include Wakabayashi et al. “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, M.M. P. The compounds described in Hutt, “J. Heterocyclic Chemistry”, Vol. 1 (No. 3), (1970) and the like are mentioned, and in particular, an oxazole compound substituted with a trihalomethyl group: an s-triazine compound.
The following initiators are preferred as initiators for the active halogens.

  Examples of the curable compound having an ethylenically unsaturated group and the self-polymerization initiating curable compound in which the polymerization initiation site is linked and bonded in the molecule are shown below.

  Further, specific compounds of the initiator that can be used in the present invention are shown below.

  Examples of the carbonyl compound include, for example, “Latest UV Curing Technology”, pages 60 to 62 {published by Technical Information Association, 1991}, Japanese Patent Laid-Open No. 8-134404, paragraph numbers [0015] to [0016], And the compounds described in paragraphs [0029] to [0031] of JP-A No. 11-217518, and benzoin compounds such as acetophenone, hydroxyacetophenone, benzophenone, thioxan, benzoin ethyl ether, and benzoin isobutyl ether, p -Benzoic acid ester derivatives such as ethyl dimethylaminobenzoate and ethyl p-diethylaminobenzoate, benzyldimethyl ketal, acylphosphine oxide and the like.

  Examples of the organic borate compound include organic compounds described in JP-A-2002-116539 and the like, and Kunz, Martin, “Rad Tech '98. Proceeding April 19-22, 1998, Chicago”. Borate salts include the compounds described. Examples thereof include compounds described in paragraph numbers [0022] to [0027] of JP-A-2002-116539. Specific examples of other organic boron compounds include organic boron transition metal coordination complexes described in JP-A-6-348011 and JP-A-7-292014.

  These radical generating compounds may be used alone or in combination of two or more. As addition amount, it is 0.1-30 mass% with respect to the whole quantity of a radically polymerizable monomer, Preferably it is 0.5-25 mass%, Most preferably, it can add at 1-20 mass%. Within this range, the temporal stability of the curable composition becomes highly polymerizable without problems.

Next, the photoacid generator (L ₂ ) that can be used as the photopolymerization initiator (L) will be described in detail.
Examples of the acid generator (L ₂ ) include known compounds such as a photo-initiator for photocationic polymerization, a photo-decoloring agent for dyes, a photo-discoloring agent, or a known acid generator used in a microresist. And mixtures thereof. Examples of the acid generator (L ₂ ) include onium compounds, organic halogen compounds, and disulfone compounds. Specific examples of these organic halogen compounds and disulfone compounds are the same as those described for the compound generating a radical.

  Examples of the onium compounds include diazonium salts, ammonium salts, iminium salts, phosphonium salts, iodonium salts, sulfonium salts, arsonium salts, selenonium salts, and the like, for example, paragraph numbers [0058] to [0059] of JP-A-2002-29162. And the like.

In the present invention, the acid generator (L ₂ ) that is particularly preferably used includes onium salts, among which diazonium salts, iodonium salts, sulfonium salts, and iminium salts are used for photopolymerization initiation photosensitivity, compound materials. It is preferable from the viewpoint of stability and the like.

  Specific examples of onium salts that can be suitably used in the present invention include, for example, an amylated sulfonium salt described in paragraph [0035] of JP-A-9-268205, and JP-A-2000-71366. A diaryl iodonium salt or a triarylsulfonium salt described in paragraphs [0010] to [0011], a sulfonium salt of thiobenzoic acid S-phenyl ester described in paragraph [0017] of JP-A-2001-288205, Examples thereof include the onium salts described in paragraph numbers [0030] to [0033] of JP-A-2001-133696.

  Other examples of the acid generator include organometallic / organic halides described in JP-A-2002-29162, paragraphs [0059] to [0062], and a photoacid generator having an o-nitrobenzyl type protecting group. And compounds such as compounds that generate photosulfonic acid to generate sulfonic acid (iminosulfonate, etc.).

  These acid generators may be used alone or in combination of two or more. These acid generators are preferably in a proportion of 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and particularly preferably 1 to 10% by mass with respect to 100 parts by mass of the total mass of the cationically polymerizable monomer. % Can be added. When the addition amount is in the above range, it is preferable from the viewpoint of stability of the curable composition, polymerization reactivity, and the like.

  The curable composition used in the present invention is 0.5 to 10% by mass of the radical polymerization initiator and 1 to 10% by mass of the cationic polymerization initiator based on the total mass of the radical polymerizable compound and the cationic polymerizable compound. It is preferable to contain in the ratio. More preferably, it contains 1 to 5% by mass of a radical polymerization initiator and 2 to 6% by mass of a cationic polymerization initiator.

  In the curable composition of the present invention, when a polymerization reaction is performed by ultraviolet irradiation, a conventionally known ultraviolet spectral sensitizer or chemical sensitizer may be used in combination. Examples include Michler's ketone, amino acids (such as glycine), and organic amines (such as butylamine and dibutylamine).

  Moreover, when performing a polymerization reaction by near infrared irradiation, it is preferable to use a near infrared spectral sensitizer together. The near-infrared spectral sensitizer used in combination may be a light-absorbing substance having an absorption band in at least a part of the wavelength range of 700 nm or more, and a compound having a molecular extinction coefficient of 10,000 or more is preferable. Moreover, it is more preferable that there is a trough of absorption in the visible light wavelength region of 420 nm to 700 nm, and it is optically transparent.

  As the near-infrared spectral sensitizer, various pigments and dyes known as near-infrared absorbing pigments and near-infrared absorbing dyes can be used. Among these, it is preferable to use a conventionally known near-infrared absorber.

  Commercial dyes and literature {For example, “Chemical Industry”, May 1986, pages 45-51, “Near-infrared absorbing dyes”, “Development and market trends of functional dyes in the 90s”, Chapter 2, Section 2.3 ( 1990) issued by CMC, J.C. FABIAN, “Chem. Rev.”, Vol. 92, pages 1197 to 1226 (1992), known dyes described in a catalog issued in 1995 by the Japan Photosensitive Pigment Research Institute can be used.

[Other additive of curable composition]
Other compounds can be appropriately added to the cured film of the present invention depending on the application and purpose. For example, in each refractive index layer of the middle / high refractive index layer to be described later, high refractive index inorganic fine particles are used for adjusting the refractive index higher than that of the transparent substrate film, and colloidal is used for further improving the film strength or coating property. Inorganic particles can be added.

  As such colloidal inorganic particles, those having a particle size of 5 to 50 nm are used, preferably those having a particle size of 5 to 30 nm, and particularly preferably those having a particle size of 8 to 20 nm. Examples of the inorganic particles include silica, alumina, magnesium fluoride and the like. Colloidal silica is preferred. Such colloidal silica is, for example, I.V. M.M. Hydrolysis and polycondensation using tetraalkoxysilane as a raw material and a catalyst such as aqueous ammonia in accordance with the method described in Thomas, “Appl. Opt.”, 1986, 25, 1481 Can be adjusted. Among the commercially available products, “Snowtex IPA-ST” and “Snowtex MEK-ST” manufactured by Nissan Chemical Industries, Ltd .; “AEROSIL300”, “AEROSIL130” and “AEROSIL50” manufactured by Nippon Aerosil Co., Ltd. It is also possible to use a product name). The addition amount of the colloidal inorganic particles is preferably in the range of 1 to 70% by mass, particularly preferably 5 to 60% by mass of the total solid content of the curable composition after the coating film is cured.

  Furthermore, surfactants, antistatic agents, coupling agents, thickeners, anti-coloring agents, coloring agents (pigments, dyes), antifoaming agents, leveling agents, flame retardants, ultraviolet absorbers, infrared absorbers, and adhesion imparting An agent, a polymerization inhibitor, an antioxidant, a surface modifier, conductive metal fine particles and the like can also be added.

[Curing composition solvent]
The curable composition of the present invention is usually prepared by dissolving or colloidally dispersing the curable multi-branched polymer (RHB) of the present invention in an appropriate solvent. At this time, the concentration of the curable multi-branched polymer (RHB) is appropriately selected according to the use, but is generally about 0.1 to 60% by mass, preferably 0.5 to 50% by mass, particularly Preferably, it is about 1% to 20% by mass.

  The solvent is not particularly limited as long as the composition containing the curable multi-branched polymer (RHB) of the present invention is uniformly dissolved or dispersed without causing precipitation, and two or more kinds of solvents are used in combination. You can also Preferable examples of the dispersion medium include alcohols, ketones, esters, amides, ethers, ether esters, hydrocarbons, halogenated hydrocarbons and the like. Specifically, alcohol (for example, methanol, ethanol, propanol, butanol, benzyl alcohol, ethylene glycol, propylene glycol, ethylene glycol monoacetate, etc.), ketone (for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, etc.), ester ( For example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl formate, propyl formate, butyl formate, ethyl lactate, etc.), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, methyl chloroform, etc.) ), Aromatic hydrocarbons (eg, toluene, xylene, etc.), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone, etc.), ethers (eg Dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc.), ether alcohols (eg 1-methoxy-2-propanol, ethyl cellosolve, methyl carbinol etc.), fluoroalcohols (eg JP-A-8-143709). No. paragraph [0020], and the compound described in paragraph No. [0037] of JP-A-11-60807.

  These solvents can be used alone or in admixture of two or more. Preferred solvents include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, isopropanol, and butanol. A coating solvent system mainly comprising a ketone solvent (for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) is also preferably used, and the content of the ketone solvent is 10% by mass or more of the total solvent contained in the curable composition. It is preferable. More preferably, it is 30 mass% or more, More preferably, it is 60 mass% or more.

(Formation of cured film layer)
At least one cured film of the light-transmitting layer contained in the antireflection film is formed by applying the above-described curable composition coating liquid directly on the transparent substrate film described later or via another layer. To construct. The coating solution for a cured film of the present invention comprises a matrix binder solution (containing a curable composition), and, if necessary, an ultrafine particle dispersion of a specific inorganic compound and an additive as a coating dispersion medium (solvent). Each is adjusted by mixing and diluting to a predetermined concentration.

  It is preferable to filter the coating solution before coating. As a filter for filtration, it is preferable to use a filter having a pore diameter as small as possible within a range in which components in the coating solution are not removed. For filtration, a filter having an absolute filtration accuracy of 0.1 to 100 μm is used, and a filter having an absolute filtration accuracy of 0.1 to 25 μm is preferably used. The thickness of the filter is preferably 0.1 to 10 mm, and more preferably 0.2 to 2 mm. In that case, the filtration pressure is preferably 1.5 MPa or less, more preferably 1 MPa or less, and further preferably 200 kPa or less.

  The filtration filter member is not particularly limited as long as it does not affect the coating solution. Specifically, the same thing as the filtration member of the wet dispersion of an inorganic compound mentioned above is mentioned. Further, it is also preferable that the filtered coating solution is ultrasonically dispersed immediately before coating to assist defoaming and dispersion holding of the dispersion.

In the present invention, the cured film layer is a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, and a coating solution containing the curable composition of the present invention on a transparent substrate film described later. It can be produced by applying by a known thin film forming method such as a gravure coating method, a micro gravure coating method, a die coating method (extrusion coating method, slide coating method, etc.), drying, light and / or heat irradiation. Preferably, it is advantageous from the viewpoint of thin film coating and rapid uniform curing to employ a gravure coating method, a micro gravure coating method, a coating method by a die coating method, and curing by light irradiation. Furthermore, it is also preferable to perform heat treatment in the latter half of the photocuring treatment. As for the coating method, it is particularly preferable to use the coating methods described in JP2003-200097A and JP2003-211052A. The specification is particularly preferably used in a region where the wet coating amount is small (20 cm ³ / m ² or less), but in this patent, it is also preferably used in a region where the wet coating amount is 20 cc / m ² or more.

  The light source for light irradiation may be any one in the ultraviolet light region or near infrared light region, and as a light source for ultraviolet light, ultrahigh pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, metal halides. Lamp, xenon lamp, sunlight, and the like. Various available laser light sources having a wavelength of 350 to 420 nm may be irradiated as a multi-beam. Further, examples of the near-infrared light source include a halogen lamp, a xenon lamp, and a high-pressure sodium lamp. Various available laser light sources having a wavelength of 750 to 1400 nm may be irradiated in a multi-beam form.

  When using a near-infrared light source, it may be used in combination with an ultraviolet light source, or may be irradiated from the substrate surface side opposite to the high refractive index layer coating side. As a result, film curing in the depth direction in the coating layer proceeds without delay with the vicinity of the surface, and a cured film having a uniform cured state is obtained.

In the case of radical photopolymerization by light irradiation, it can be carried out in air or in an inert gas, but in order to shorten the polymerization induction period of the radically polymerizable monomer or sufficiently increase the polymerization rate, etc. It is preferable that the atmosphere has a reduced oxygen concentration. The irradiation intensity of the irradiated ultraviolet rays is preferably about 0.1 to 100 mW / cm ² , and the light irradiation amount on the coating film surface is preferably 100 to 1000 mJ / cm ² . Further, the temperature distribution of the coating film in the light irradiation step is preferably as uniform as possible, preferably within ± 3 ° C., and more preferably controlled within ± 1.5 ° C. In this range, the polymerization reaction in the in-plane and in-layer depth directions of the coating film proceeds uniformly, which is preferable.

  It is preferable that it is 3H or more in the pencil hardness test according to JIS K-5400 of a cured film layer. Further, in the Taber test according to JIS K-5400, it is preferable that the amount of wear of the test piece coated with the cured film before and after the test is smaller.

(High refractive index layer)
When the cured film of the present invention forms a high-refractive-index layer of an antireflection film, the above-mentioned curable composition contains a high-refractive-index inorganic compound fine particle (hereinafter sometimes referred to as inorganic fine particle). It is preferable to consist of a cured film having a refractive index of 1.55 to 2.50, which is formed by coating a conductive composition. The refractive index is preferably 1.65 to 2.40, more preferably 1.70 to 2.20.

  Further, the surface of the high refractive index layer forms a fine surface irregularity shape having a size that does not optically affect, and the arithmetic average roughness of the surface irregularity of the high refractive index layer based on JIS B-0601-1994. (Ra) is 0.001 to 0.03 [mu] m, further 0.001 to 0.015 [mu] m, particularly 0.001 to 0.010 [mu] m; ten-point average roughness (Rz) is 0.001 to 0.03 [mu] m. It is in the range of 06 μm, further 0.002 to 0.05 μm, particularly 0.002 to 0.025 μm, and the maximum height (Ry) is 0.09 μm or less, further 0.05 μm or less, particularly preferably 0.2 mm. The thickness is preferably 04 μm or less.

  Further, in the above-described fine surface irregularity having a size that does not affect optically, the ratio (Ra / Rz) of arithmetic average roughness (Ra) to ten-point average roughness (Rz) is 0.15 or more. And it is preferable that the average space | interval (Sm) of the surface unevenness | corrugation of this high refractive index layer based on JISB-0601-1994 is 0.01-1 micrometer. Here, the relationship between Ra and Rz indicates the uniformity of surface irregularities. More preferably, the (Ra / Rz) ratio is 0.17 or more, and the average interval (Sm) is 0.01 to 0.8 μm. Within these ranges, the coated surface of the layer coated on the high refractive index layer is excellent in that there is no unevenness or streaks, and the adhesion between the two layers can be improved. It becomes. The concave and convex shapes on the surface of the layer can be evaluated by an atomic force microscope (AFM).

  In order to make the high refractive index layer a high refractive index cured film having a refractive index of 1.55 to 2.50 in which inorganic fine particles having a high refractive index are dispersed in the matrix binder of the cured film, a matrix binder is usually used. Since the refractive index of the fine particles is 1.4 to 1.5, the proportion of the fine particles used is determined by the refractive index of the fine particles used, but is 40 to 80% by mass in the total mass of the cured film. Preferably, it is 45-75 mass%.

  As described above, the high refractive index layer designed by increasing the ratio of the inorganic fine particles increases its own film strength, and after providing an upper layer such as a low refractive index layer, the adhesiveness with the upper layer is strengthened. To achieve this, together with the effects of the curable multi-branched polymer of the present invention, and further, the curing agent itself as a polymerizable compound, as described later, inorganic fine particles having a super fine particle size and a uniform particle size are used, and It is preferable that this is uniformly dispersed in the high refractive index layer and that the surface of the layer forms an uneven state as described above. By setting the shape and distribution of surface irregularities on the entire surface of the high refractive index layer within a specific range, even when an upper layer is provided continuously on a long film, the entire surface of the upper layer exhibits an anchoring effect evenly. Therefore, it is preferable because adhesion is maintained. Further, it is preferable because the adhesion is maintained without change even after storage for a long period of time.

  The adhesion between the cured film of the high refractive index layer in the present invention and the upper layer (such as the low refractive index layer) coated on the high refractive index layer is determined by the amount of wear in the Taber abrasion test based on JIS K-6902. It is preferably 50 mg or less, more preferably 40 mg or less. The Taber abrasion test is specifically the amount of abrasion after 500 revolutions with a load of 1 kg. Within this range, scratch resistance as an antireflection film is sufficiently maintained, which is preferable.

  Further, in the antireflection film including the high refractive index layer formed with the surface shape, the number of luminance defects having a diameter of 100 μm or more that is easily noticeable as a foreign object is 1 or less per square meter. It is preferable to become.

[Composition for forming a high refractive index layer]
(Inorganic fine particles with high refractive index)
The high refractive index inorganic fine particles contained in the high refractive index layer in the present invention have a refractive index of 1.80 to 2.80, more preferably 1.90 to 2.80; an average primary particle size of 3 to 150 nm, Furthermore, it is preferable that it is 3-100 nm, especially 5-80 nm. If the refractive index of the inorganic fine particles is 1.80 or more, the refractive index of the layer can be effectively increased, and if the refractive index is 2.80 or less, there is no inconvenience such as coloring of the particles, which is preferable. Further, if the average particle size of the primary particles of the inorganic fine particles is 150 nm or less, the haze value of the high refractive index layer to be formed is high, and there is no inconvenience such as impairing the transparency of the layer. It is preferable because a high refractive index is maintained.

  Specific examples of preferable high refractive index inorganic fine particles include oxides or composite oxides such as Ti, Zr, Ta, In, Nd, Sn, Sb, Zn, La, W, Ce, Nb, V, Sm, Y, and sulfide. The particle | grains which have an object as a main component are mentioned. Here, the main component refers to a component having the largest content (% by mass) among the components constituting the particles. More preferable inorganic fine particles in the present invention are particles mainly composed of an oxide or composite oxide containing at least one metal element selected from Ti, Zr, Ta, In, and Sn.

The inorganic fine particles may contain various elements in the particles (hereinafter, such elements may be referred to as containing elements). Examples of the contained element include Li, Si, Al, B, Ba, Co, Fe, Hg, Ag, Pt, Au, Cr, Bi, P, and S. In the case of tin oxide and indium oxide, it is preferable to contain an element such as Sb, Nb, P, B, In, V, or halogen in order to increase the conductivity of the particles, and in particular, about 5 to 20 mass of antimony oxide. % Is most preferable.

  Particularly preferred inorganic fine particles in the present invention are inorganic fine particles mainly composed of titanium dioxide containing at least one element selected from Co, Zr, and Al as contained elements (hereinafter sometimes referred to as “specific oxide”). ). A particularly preferable element is Co. The total content of Co, Al, and Zr is preferably 0.05 to 30% by mass with respect to Ti, more preferably 0.1 to 10% by mass, still more preferably 0.3 to 5% by mass, most preferably Preferably it is 0.5-3 mass%. The contained elements Co, Al, and Zr are present inside or on the surface of inorganic fine particles mainly composed of titanium dioxide. It is more preferable that it exists inside the inorganic fine particles mainly composed of titanium dioxide, and most preferable that it exists both inside and on the surface. Among these contained elements, the metal element may exist as an oxide.

  As another preferable inorganic fine particle, a composite oxide of titanium element and at least one metal element (hereinafter also abbreviated as “Met”) selected from metal elements having an oxide having a refractive index of 1.95 or more. And the composite oxide includes inorganic fine particles doped with at least one metal ion selected from Co ions, Zr ions, and Al ions (sometimes referred to as “specific multi-oxide”). It is done. Here, Ta, Zr, In, Nd, Sb, Sn, and Bi are preferable as the metal element whose refractive index of the oxide is 1.95 or more. In particular, Ta, Zr, Sn, and Bi are preferable. The content of the metal ions doped in the composite oxide is preferably within a range not exceeding 25 mass% with respect to the total amount of metal [Ti + Met] constituting the composite oxide from the viewpoint of maintaining the refractive index. More preferably, it is 0.05-10 mass%, More preferably, it is 0.1-5 mass%, Most preferably, it is 0.3-3 mass%.

  The doped metal ion may be present as a metal ion or in any form of metal atom, and may be appropriately present from the surface to the inside of the composite oxide. It is preferably present both on the surface and inside.

  The inorganic fine particles preferably have a crystal structure. The crystal structure is preferably composed mainly of rutile, a mixed crystal of rutile / anatase, and anatase, and particularly preferably a rutile structure. Accordingly, the inorganic fine particles of the specific oxide or the specific composite oxide are preferable because the refractive index thereof is 1.90 to 2.80. The refractive index is more preferably 2.10 to 2.80, and still more preferably 2.20 to 2.80. In addition, this can suppress the photocatalytic activity of titanium dioxide, and can significantly improve the weather resistance of the high refractive index layer itself and the upper / lower layers in contact with the high refractive index layer in the present invention. Therefore, it is preferable.

  As a method for doping a specific metal element or metal ion as described above, a conventionally known method can be used. For example, JP-A-5-330825, JP-A-11-263620, and JP-A-11-512336. , Published in European Patent No. 0335773, etc .; ion implantation method [for example, edited by Shunichi Gonda, Junzo Ishikawa, Eiji Kamijo “Ion Beam Applied Technology” CMC Co., Ltd., 1989, Yasushi Aoki "Surface Science" 18 (5), 262, 1998, Shoichi Anbo etc., "Surface Science" 20 (2), 60, 1999, etc.] etc.].

The inorganic fine particles may be surface-treated. Surface treatment is a modification of the particle surface using an inorganic compound and / or an organic compound, whereby the wettability of the surface of the inorganic fine particles is adjusted to form fine particles in an organic solvent, and a high refractive index layer. Dispersibility and dispersion stability in the forming composition are improved. Examples of inorganic compounds that are physicochemically adsorbed on the particle surface include inorganic compounds containing silicon (such as SiO ₂ ), inorganic compounds containing aluminum [such as Al ₂ O ₃ and Al (OH) ₃ ], and cobalt. Inorganic compounds containing (CoO ₂ , Co ₂ O ₃ , Co ₃ O ₄ etc.), inorganic compounds containing zirconium [ZrO ₂ , Zr (OH) ₄ etc.], inorganic compounds containing iron (Fe ₂ O ₃ etc.) ) And the like.

  As examples of organic compounds used for the surface treatment, conventionally known surface modifiers of inorganic fillers such as metal oxides and inorganic pigments can be used. For example, it is described in “Pigment Dispersion Stabilization and Surface Treatment Technology / Evaluation”, Chapter 1 (Technical Information Association, published in 2001).

  Specifically, an organic compound having a polar group having an affinity for the surface of the inorganic fine particles and a coupling compound can be mentioned. Examples of the polar group having affinity with the surface of the inorganic fine particles include a carboxy group, a phosphono group, a hydroxy group, a mercapto group, a cyclic acid anhydride group, an amino group, and the like, and a compound containing at least one kind in the molecule is preferable. . For example, long-chain aliphatic carboxylic acids (eg, stearic acid, lauric acid, oleic acid, linoleic acid, linolenic acid, etc.), polyol compounds (eg, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, ECH (epichlorohydrin) modified glycerol triacrylate Etc.), phosphono group-containing compounds {for example, EO (ethylene oxide) -modified phosphoric acid triacrylate, etc.}, alkanolamines {ethylenediamine EO adducts (5 mol), etc.}.

As a coupling compound, a conventionally well-known organometallic compound is mentioned, A silane coupling agent, a titanate coupling agent, an aluminate coupling agent, etc. are contained. Silane coupling agents are most preferred. Specific examples include compounds described in paragraph numbers [0011] to [0015] in JP-A-2002-9908 and 2001-310423.
Two or more kinds of compounds used for these surface treatments can be used in combination.

  The inorganic fine particles are also preferably fine particles having a core / shell structure in which a shell made of another inorganic compound is formed using the inorganic fine particles as a core. The shell is preferably an oxide composed of at least one element selected from Al, Si, and Zr. Specifically, for example, the contents described in JP-A-2001-166104 can be mentioned.

  The shape of the inorganic fine particles is not particularly limited, but is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, or an indefinite shape. The inorganic fine particles may be used singly or in combination of two or more.

(Dispersant)
In order to use the inorganic fine particles as stable predetermined ultrafine particles, it is preferable to use a dispersant in combination. The dispersant is preferably a low molecular compound or a high molecular compound having a polar group having affinity for the surface of the inorganic fine particles.

Examples of the polar group include a hydroxy group, a mercapto group, a carboxyl group, a sulfo group, a phosphono group, an oxyphosphono group, a -P (= O) (OR ⁹¹ ) (OH) group, and a -OP (= O) (OR ⁹¹ ) (OH) group, amide group (—CONHR ⁹² , —SO ₂ NHR ⁹² ), cyclic acid anhydride-containing group, amino group, quaternary ammonium group and the like.

Here, R ⁹¹ represents a hydrocarbon group having 1 to 18 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group,
Chloroethyl group, methoxyethyl group, cyanoethyl group, benzyl group, methylbenzyl group, phenethyl group, cyclohexyl group, etc.). R ⁹² represents a hydrogen atom or the same content as R ⁹¹ .

In the polar group, the group having a dissociable proton may be a salt thereof. The amino group and quaternary ammonium group may be any of primary amino group, secondary amino group or tertiary amino group, and more preferably tertiary amino group or quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is an aliphatic group having 1 to 12 carbon atoms (having the same contents as the above R ⁹¹ or R ⁹² group, etc. ) Is preferable. The tertiary amino group may be a ring-forming amino group containing a nitrogen atom (for example, a piperidine ring, a morpholine ring, a piperazine ring, a pyridine ring, etc.), and the quaternary ammonium group is a cyclic amino group. Or a quaternary ammonium group. In particular, an alkyl group having 1 to 6 carbon atoms is more preferable.

The counter ion of the quaternary ammonium group is a halide ion, PF ₆ ion, SbF ₆ ion, BF ₄ ion, B (R ⁹³ ) ₄ ion (R ⁹³ represents a hydrocarbon group, for example, butyl group, phenyl group, tolyl Group, naphthyl group, butylphenyl group, etc.), sulfonate ions and the like are preferable.

  The polar group of the dispersant is preferably an anionic group having a pKa of 7 or less or a salt of these dissociating groups. In particular, a carboxyl group, a sulfo group, a phosphono group, an oxyphosphono group, or a salt of these dissociating groups is preferable.

The dispersant preferably further contains a crosslinkable or polymerizable functional group. As the crosslinkable or polymerizable functional group, an ethylenically unsaturated group capable of addition reaction / polymerization reaction by radical species {for example, (meth) acryloyl group, allyl group, styryl group, vinyloxy group carbonyl group, vinyloxy group, etc.}, And cationically polymerizable groups (epoxy groups, thioepoxy groups, oxetanyl groups, vinyloxy groups, spiroorthoester groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups) and the like, preferably ethylene. An unsaturated group, an epoxy group, or a hydrolyzable silyl group.
Specific examples include the compounds described in paragraph numbers [0013] to [0015] in JP-A No. 2001-310423.

The dispersant used in the present invention is preferably a polymer dispersant. In particular, a polymer dispersant containing an anionic group and a crosslinkable or polymerizable functional group is preferable. The mass average molecular weight (Mw) of the polymer dispersant is not particularly limited, but is preferably 1 × 10 ³ or more as a polystyrene equivalent value measured by GPC method. More preferable Mw is 2 × 10 ³ to 1 × 10 ⁶ , further preferably 5 × 10 ³ to 1 × 10 ⁵ , and particularly preferably 8 × 10 ³ to 8 × 10 ⁴ . Those within this range are preferred because inorganic fine particles are easily dispersed and stable dispersions free from aggregates and precipitates can be obtained. Specific examples include the contents described in paragraph numbers [0024] to [0041] in JP-A-11-153703.

(Dispersion medium)
The dispersion medium used for wet dispersion of the inorganic fine particles can be appropriately selected from water and organic solvents, and is preferably a liquid having a boiling point of 50 ° C. or higher, and an organic solvent having a boiling point in the range of 60 ° C. to 180 ° C. More preferably, it is a solvent. Specifically, the thing similar to the solvent of said curable composition is mentioned.

  The dispersion medium is preferably used in such a ratio that the total components for forming a high refractive index layer containing inorganic fine particles and a dispersant are 5 to 50% by mass. Furthermore, 10-30 mass% is preferable. In this range, the dispersion easily proceeds, and the resulting dispersion is preferable because it has a viscosity range with good workability.

(Inorganic fine particles)
When the curable composition for forming a high refractive index layer used in the present invention is an ultrafine particle dispersion of an inorganic compound having an average particle size of 100 nm or less, the stability of the liquid of the composition is improved. The high refractive index layer, which is a cured film formed from a conductive composition, is a transparent high refractive index layer in which inorganic fine particles are uniformly dispersed in an ultrafine particle state in the matrix of the cured film, and the optical properties are uniform and transparent Is formed. The size of the ultrafine particles present in the matrix of the cured film is preferably in the range of an average particle size of 3 to 100 nm, more preferably 5 to 80 nm. Furthermore, it is preferable that large particles having an average particle diameter of 500 nm or more are not included, and it is particularly preferable that large particles having an average particle diameter of 300 nm or more are not included. Thereby, the cured film surface can form the above-mentioned specific uneven | corrugated shape, and is preferable.

  In order to disperse the high refractive index inorganic fine particles in the size of ultrafine particles not containing coarse particles in the above range, a wet dispersion method using a medium having an average particle diameter of less than 0.8 mm together with the dispersant is used. Can be achieved in a distributed manner.

  Examples of the wet disperser include conventionally known ones such as a sand grinder mill (for example, a bead mill with a pin), a dyno mill, a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. In particular, a sand grinder mill, a dyno mill, and a high-speed impeller mill are preferable for dispersing the inorganic fine particles used in the present invention in ultrafine particles.

  As the media used with the disperser, the average particle size is preferably less than 0.8 mm, and when the media has an average particle size within this range, the inorganic fine particle diameter is 100 nm or less, and the particle diameter is Uniform ultrafine particles can be obtained. The average particle size of the media is more preferably 0.5 mm or less, and even more preferably 0.05 to 0.3 mm. Moreover, as a medium used for wet dispersion, beads are preferable. Specific examples include zirconia beads, glass beads, ceramic beads, steel beads, etc., and 0.05 to 0.2 mm from the viewpoint of durability and ultrafine particle formation such that the beads are not easily broken during dispersion. Zirconia beads are particularly preferred.

  The dispersion temperature in the dispersion step is preferably 20 to 60 ° C, more preferably 25 to 45 ° C. This is preferable because dispersion in the ultrafine particles at a temperature in this range does not cause re-aggregation or precipitation of the dispersed particles. This is presumably because adsorption of the dispersant to the inorganic compound particles is appropriately performed and dispersion stability is not deteriorated due to desorption of the dispersant from the particles at room temperature. By carrying out the dispersion step in such a range, it is possible to form a high refractive index film excellent in refractive index uniformity, film strength, adhesion to an adjacent layer, etc. without impairing transparency.

  Moreover, you may implement a preliminary dispersion process before the said wet dispersion | distribution process. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

  Furthermore, in order that the dispersed particles in the dispersion satisfy the above-mentioned range of the average particle diameter and the monodispersibility of the particle diameter, separation treatment with beads is performed in order to remove coarse aggregates in the dispersion. It is also preferable to arrange the filter medium so that it is microfiltered in The filter medium for fine filtration preferably has a filtration particle size of 25 μm or less. The type of filter medium for microfiltration is not particularly limited as long as it has the above performance, and examples thereof include a filament type, a felt type, and a mesh type. The material of the filter medium for microfiltration of the dispersion is not particularly limited as long as it has the above performance and does not adversely affect the obtained composition for forming a high refractive index layer. For example, stainless steel, polyethylene, polypropylene , Nylon and the like.

  The film thickness of the high refractive index layer is preferably 30 to 500 nm, and more preferably in the range of 50 to 300 nm. When the high refractive index layer also serves as the hard coat layer, 0.5 to 10 μm is preferable, more preferably 1 to 7 μm, and particularly preferably 2 to 5 μm. The haze of the high refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less.

(Medium refractive index layer)
The antireflection film of the present invention preferably has a laminated structure in which the high refractive index layer is composed of two layers having different refractive indexes. That is, on the transparent substrate film, the lower refractive index layer (medium refractive index layer) of the two high refractive index layers, and the higher refractive index layer (high refractive index layer) of the two high refractive index layers. ) And a three-layer structure in the order of a low refractive index layer (outermost layer). The middle refractive index layer has a refractive index intermediate between the refractive index of the transparent substrate film and the refractive index of the high refractive index layer. Thus, the refractive index of each refractive index layer is relative. The medium refractive index layer is formed by coating the medium refractive index layer forming composition in the same manner as the high refractive index layer.

  The material constituting the middle refractive index layer in the present invention may be any conventionally known material, but it is preferable to use the same material as the high refractive index layer. The refractive index is easily adjusted by the kind and amount of inorganic fine particles, and the film thickness is preferably 0.03 to 5 μm, more preferably 0.05 to 0.5 μm, in the same manner as described in the high refractive index layer. Furthermore, 0.05 to 0.3 μm is preferable. The haze of the medium refractive index layer is preferably as low as possible. It is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.

(Low refractive index layer)
The refractive index of the low refractive index layer in the present invention is preferably in the range of 1.31 to 1.48 for the purpose of imparting antireflection properties.

  The low refractive index layer in the present invention is preferably constructed as an outermost layer having scratch resistance and antifouling properties. The low refractive index layer contains at least one hollow structure inorganic fine particle having an average particle size of 30% to 100% of the thickness of the low refractive index layer and a refractive index of 1.17 to 1.37. It is preferable that If the average particle diameter of the inorganic fine particles is in the range of 30% to 100% of the thickness of the low refractive index layer, the strength of the low refractive index layer film is sufficiently exhibited, which is preferable. In addition, by using inorganic fine particles having such a refractive index in the low refractive index layer, while suppressing an increase in the refractive index of the layer itself, there are also restrictions such as a long-time thermosetting and a saponification treatment for providing a polarizing film. Without both, a low refractive index and high film strength can be achieved at the same time.

[Material for forming cured film of low refractive index layer]
Further, the low refractive index layer realizes a low refractive index, can effectively impart slipperiness to the surface, and is a conventionally known silicone resin and / or fluorine-containing means as a means for greatly improving scratch resistance. It is preferable to appropriately apply a material for forming a cured film into which a compound is introduced. More preferably, it contains a fluorine-containing compound. In particular, the low refractive index layer in the present invention is composed of a thermosetting and / or light or radiation (for example, ionizing radiation) curable cross-linkable fluorine-containing compound as a main component and is composed of a cured fluorine-containing polymer. Is preferred.

  Furthermore, it is preferable that the low refractive index layer of the present invention is used in combination with a curable multi-branched polymer (RHB). The curable hyperbranched polymer (RHB) preferably provided contains a fluorine-containing hydrocarbon structure in the molecule as described above. In particular, those containing a fluorine-containing alkyl group as a non-polymerizable chemical modification group at the branch branch terminal can be preferably used. At the same time, it is preferable that the curable multi-branched polymer (RHB) does not contain a nitrogen atom or an aromatic ring (aryl ring or heterocyclic ring) in the molecule. By these, since the usage-amount of the inorganic fine particle for low refractive index adjustment (it mentions later) in a low refractive index layer can be suppressed, it becomes much more effective for the intensity | strength improvement of a low refractive index layer membrane | film | coat.

  In the present invention, the low refractive index layer is a hydrolyzate of an organosilane represented by the following general formula (4), which is produced in the presence of inorganic fine particles, a fluorinated polymer having a curable reactive group, and an acid catalyst. It is preferably a cured film formed by applying and curing a curable composition for forming a low refractive index layer containing at least one partial condensate thereof.

Formula _{^{(4) :( R 41) 4}} -e -Si (X 41) e
(In the formula, R ⁴¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X ⁴¹ represents a hydroxyl group or a hydrolyzable group. E represents an integer of 1 to 3)

The curable composition for forming a low refractive index layer further comprises a polyfunctional polymerizable compound containing at least two polymerizable groups selected from a radical polymerizable group and / or a cationic polymerizable group and a polymerization initiator. It is preferable to contain.
Hereinafter, the curable composition for forming a low refractive index layer will be described.

[Composition for forming a low refractive index layer]
(Inorganic fine particles with hollow structure)
The low refractive index layer preferably uses hollow inorganic fine particles (hereinafter sometimes referred to as hollow particles) in order to further reduce the increase in the refractive index. The hollow particles preferably have a refractive index of 1.17 to 1.40, more preferably 1.17 to 1.37, and still more preferably 1.17 to 1.35. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell forming the hollow particle. The refractive index of the hollow particles is preferably 1.17 or more from the viewpoint of the strength of the particles and the scratch resistance of the low refractive index layer containing the hollow particles.
The refractive index of these hollow particles can be measured with an Abbe refractometer [manufactured by Atago Co., Ltd.].

When the radius of the cavity in the hollow particle is r _i and the radius of the particle outer shell is r _o , the void ratio w (%) of the hollow particle is calculated according to the following formula (5).
Formula (5): w = (r _i / r _o ) ³ × 100
The void ratio of the hollow particles is preferably 10 to 60%, more preferably 20 to 60%, and most preferably 30 to 60%.

  The average particle diameter of the hollow particles is preferably 30 to 100%, more preferably 35 to 80%, particularly preferably 40 to 60% of the thickness of the low refractive index layer. That is, if the thickness of the low refractive index layer is 100 nm, the particle size of the hollow particles is preferably 30 to 100 nm, more preferably 35 to 80 nm, and particularly preferably 40 to 60 nm. When the average particle size is in the above range, the strength of the film is sufficiently expressed, which is preferable.

As the inorganic fine particles used in the low refractive index layer, particles such as silicon dioxide (silica) and fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride) are preferable. Particularly preferred are silicon dioxide (silica) particles.
The shape of the inorganic fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a short fiber shape, a ring shape, or an indefinite shape.

(Inorganic fine particles of small size)
In addition, at least one kind of inorganic fine particles having an average particle size of less than 25% of the thickness of the low refractive index layer (hereinafter sometimes referred to as “small size particles”) is used. Hereinafter, it may be referred to as “large size particles”). The small size particles may not have a hollow structure.
The small-sized particles are preferable because they can exist in the gaps between the large-sized particles and can contribute as a retaining agent for the large-sized particles. Moreover, it is preferable also in terms of raw material costs.

  When the film thickness of the low refractive index layer is 100 nm, the average particle size of the small size particles is preferably 1 to 20 nm, more preferably 5 to 15 nm, and particularly preferably 10 to 15 nm.

  5-100 mass parts is preferable with respect to 100 mass parts of large size particles (preferably hollow particles), and more preferably 10-80 mass parts.

  Specific compounds constituting the small size particles include the same compounds as exemplified for the hollow particles. Particularly preferred is an oxide of silicon.

(Dispersion of inorganic fine particles)
Any of the above-mentioned hollow particles (large-size particles) and small-size particles may be dispersed in a dispersion or a curable composition for forming a low refractive index layer, or may be a binder. In order to enhance affinity and binding properties with components, physical surface treatment such as plasma discharge treatment or corona discharge treatment, and chemical surface treatment with a surfactant or a coupling agent may be performed. The use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (for example, a titanium coupling agent or a silane coupling agent) is preferably used. Of these, treatment with a silane coupling agent is particularly preferred.

The above coupling agent is used as a surface treatment agent for the inorganic fine particles of the low refractive index layer in order to perform surface treatment in advance before preparing the coating liquid for forming the curable low refractive index layer. It is preferable to add it as an additive at the time of preparation to be contained in the layer.
The inorganic fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.

  The blending ratio of the inorganic fine particles is preferably 5 to 90 parts by mass with respect to 100 parts by mass of the composition for forming a low refractive index layer, from the viewpoint of transparency, strength, etc. of the low refractive index layer film. More preferably, it is 60 mass parts. Moreover, when mix | blending a hollow particle and another particle, 5-95 mass parts is preferable, and, as for the hollow particle in all the particles, More preferably, it is 10-90 mass parts, Most preferably, it is 30-80 mass parts.

(Fluoropolymer)
As described above, the low refractive index layer in the present invention is composed of a fluorine-containing polymer formed and cured mainly of a thermosetting and / or light or radiation (for example, ionizing radiation) -curable crosslinkable fluorine-containing compound. Is preferred.

  In the present invention, “mainly containing a fluorine-containing compound” means that the fluorine-containing compound contained in the low refractive index layer is 50% by mass or more based on the total mass of the low refractive index layer. More preferably, it is contained in an amount of at least mass%.

  The refractive index of the fluorine-containing compound is preferably 1.35 to 1.50. More preferably, it is 1.36-1.47. Moreover, it is preferable that a fluorine-containing compound contains a fluorine atom in 35-80 mass%.

  Examples of the fluorine-containing compound include a fluorine-containing polymer, a fluorine-containing surfactant, a fluorine-containing ether compound, and a fluorine-containing silane compound. Specifically, for example, Japanese Patent Application Laid-Open No. 9-222503, paragraph numbers [0018] to [0026], Japanese Patent Application Laid-Open No. 11-38202, paragraph numbers [0019] to [0030], Japanese Patent Application Laid-Open No. 2001-40284, paragraph number [0027]. To [0028] and the like.

  The fluorine-containing polymer used in the low refractive index layer includes a repeating structural unit containing a fluorine atom, a repeating structural unit containing a crosslinkable or polymerizable functional group, or a co-polymer consisting of a repeating structural unit comprising other substituents. Coalescence is preferred. That is, a copolymer of a fluorinated monomer and a monomer for imparting a crosslinkable group, that is, a fluorinated polymer having a curable reactive group that is a crosslinkable or polymerizable functional group is preferred, and other monomers are also co-polymerized. A polymerized fluorine-containing polymer may be used. The crosslinkable or polymerizable functional group may be any conventionally known functional group.

  Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition. These compounds having a crosslinkable functional group can form a crosslinked structure by heating after coating.

  Examples of the polymerizable functional group include a radical polymerizable group and a cationic polymerizable group. Preferably, radically polymerizable groups {for example, (meth) acryloyl group, styryl group, vinyloxy group, etc.} and cationic polymerizable groups (for example, epoxy group, thioepoxy group, oxetanyl group, etc.) can be mentioned.

  As the other repeating structural unit, a repeating structural unit formed by a hydrocarbon-based copolymer component for solubilization of a solvent is preferable, and a fluorine-based polymer in which such a structural unit is introduced in an amount of about 50% by mass in the whole polymer is preferable. . In this case, it is preferable to combine with a silicone compound.

  The silicone compound is preferably a compound having a polysiloxane structure, containing a curable functional group or a polymerizable functional group in the polymer chain, and having a crosslinked structure in the film of the low refractive index layer. Examples thereof include reactive silicones such as “Silaplane” (manufactured by Chisso Corporation), commercially available products, and compounds containing silanol groups at both ends of the polysiloxane structure described in JP-A-11-258403.

  The crosslinking or polymerization reaction of the fluorine-containing polymer having a crosslinking or polymerizable group is carried out by irradiating or heating the curable composition for forming the outermost layer of the low refractive index layer simultaneously with or after coating. It is preferable. In this case, the polymerization initiator that can be used is the same as that described in the above curable composition.

  When the polymerization reaction is performed by ultraviolet irradiation, a conventionally known ultraviolet spectral sensitizer or chemical sensitizer may be used in combination. Examples include Michler's ketone, amino acids (such as glycine), and organic amines (such as butylamine and dibutylamine).

Other monomers that may be copolymerized are not particularly limited. For example, olefins, (meth) acrylic acid esters, styrene derivatives, vinyl ethers (such as methyl vinyl ether), vinyl esters, (meth) acrylamides, ( And (meth) acrylonitrile derivatives. Examples thereof include compounds described in paragraph No. [0038] of JP-A-2004-45462.

  As described in JP-A-10-25388 and JP-A-10-147739, a curing agent may be appropriately used in combination with the above polymer.

  The low refractive index layer is a sol-gel cured film formed by curing an organometallic compound such as a silane coupling agent and a specific fluorine-containing hydrocarbon group-containing silane coupling agent in the presence of a catalyst in a condensation reaction. Are also preferably used.

  For example, polyfluoroalkyl group-containing silane compounds or partially hydrolyzed condensates thereof (compounds described in JP-A-58-142958, JP-A-58-147483, JP-A-58-147484, etc.), JP-A-9-157582 And a silyl compound containing a poly "perfluoroalkyl ether" group which is a fluorine-containing long chain group (Japanese Patent Laid-Open Nos. 2000-117902, 2001-48590, 2002) -53804), and the like.

  Examples of the catalyst to be used in combination include conventionally known compounds, and those described in the above documents are preferably exemplified.

(Fluorine-containing polymer having a curable reactive group)
Examples of the fluorine-containing polymer having a curable reactive group particularly useful in the present invention include copolymers of perfluoro compounds selected from perfluoroolefins, perfluorocycloolefins and non-conjugated perfluorodienes and vinyl ethers or vinyl esters. In particular, it preferably has a group capable of undergoing crosslinking reaction alone {a radical reactive group such as a (meth) acryloyl group, a ring-opening polymerizable group such as an epoxy group or an oxetanyl group}. These cross-linking reactive group-containing polymer units preferably occupy 5 to 70 mol%, particularly preferably 30 to 60 mol% of the total polymerized units of the polymer.

A preferred embodiment of the copolymer used in the present invention is a compound represented by the following general formula (5).
General formula (5)

  In general formula (5), component [F] represents the following component (pf1), component (pf2), or component (pf3).

In the component (pf1), R ⁵¹ represents an F atom or a perfluoroalkyl group having 1 to 3 carbon atoms.

In the component (pf2), R ⁵² and R ⁵³ may be the same or different and each represents a fluorine atom or a —C _j F _{2j + 1} group, j is an integer of 1 to 4 (preferably j is 1 or 2). ). f1 represents 0 or 1, and f2 represents an integer of 2 to 5. f3 represents 0 or 1. When f1 and / or f3 is 0, each represents a single bond.

In the component (pf3), R ⁵⁴ and R ⁵⁵ each represent a fluorine atom or a —CF ₃ group. f1 and f3 represent 0 or 1 like the component (pf2). f4 represents 0 or an integer of 1 to 4, f5 represents 0 or 1, and f6 represents 0 or an integer of 1 to 5. When f3, f4, f5 and / or f6 are 0, each represents a single bond. (F4 + f5 + f6) is an integer in the range of 1-6.

In the above general formula (5), X ⁵² represents a linking group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms. It may have a ring structure. Further, it may have a heteroatom selected from O, N and S. Preferred examples of the linking group X ⁵² include * — (CH ₂ ) ₂ —O — **, * — (CH ₂ ) ₂ —NH — **, * — (CH ₂ ) ₄ —O — **, * _{- (CH 2) 6 -O -} **, * - (CH 2) 2 -O- (CH 2) 2 -O - **, * - CONH- (CH 2) 3 -O - **, * - CH ₂ CH (OH) CH ₂ —O — **, * —CH ₂ CH ₂ OCONH (CH ₂ ) ₃ —O — ** (where * represents a connecting site on the polymer main chain side, and ** represents (Represents a linking site on the (meth) acryloyl group side). u represents 0 or 1;

In the general formula (5), Z ⁵¹ represents a hydrogen atom or a methyl group. From the viewpoint of curing reactivity, a hydrogen atom is more preferable.

Further, in the general formula (5), X ⁵¹ represents a repeating unit derived from an arbitrary vinyl monomer, and is not particularly limited as long as it is a constituent component of a monomer copolymerizable with the monomer corresponding to the component [F]. From various viewpoints such as adhesion to the lower layer of the low refractive index layer, for example, the high refractive index layer, Tg of the polymer (contributing to film hardness), solubility in solvents, transparency, slipperiness, dustproof / antifouling properties, etc. It can select suitably and may be comprised by the single or several vinyl monomer according to the objective.

Preferred examples of X ⁵¹ in the general formula (5) include vinyl ethers (for example, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether, Allyl vinyl ether, etc.), carboxylic acid vinyl esters (eg, vinyl acetate, vinyl propionate, vinyl butyrate, etc.), (meth) acrylic acid alkyl esters {eg, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) Acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ( ) Acrylate, allyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, etc.}, styrene or styrene derivatives (eg styrene, p-hydroxymethylstyrene, etc.), unsaturated carboxylic acids such as crotonic acid, maleic acid, itaconic acid, etc. Acids and derivatives thereof can be mentioned, and more preferred are vinyl ethers and vinyl esters, and particularly preferred are vinyl ethers.

  x, y, and z represent the mol% of each constituent component, and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65. Preferably, 35 ≦ x ≦ 55, 30 ≦ y ≦ 60, and 0 ≦ z ≦ 20, and particularly preferably 40 ≦ x ≦ 55, 40 ≦ y ≦ 55, and 0 ≦ z ≦ 10. However, x + y + z = 100.

  Particularly preferably, in the general formula (5), the component [F] is the component (pf1), specifically, compounds described in paragraph numbers “0043” to “0047” of JP-A-2004-45462. Etc.

(Organosilane compound)
It is preferable to further add a hydrolyzate of organosilane represented by the general formula (6) and / or a partial condensate thereof to the fluoropolymer.
The organosilane hydrolyzate and / or its partial condensate represented by the general formula (6) will be described.
Formula _{^{(6) :( R 61) 4}} -h -Si (X 61) h

In the general formula (6), R ⁶¹ represents a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aryl group. The aliphatic group is preferably an aliphatic group having 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 6 carbon atoms, such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, decyl, Hexadecyl etc. are mentioned. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.

X ⁶¹ represents a hydroxyl group or a hydrolyzable group. For example, an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group), a halogen atom (for example, Cl, Br, I and the like), and R ⁶² COO (R ⁶² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as CH ₃ COO, C ₂ H ₅ COO, etc.). An alkoxy group is preferable, and a methoxy group or an ethoxy group is particularly preferable.
h represents an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 2 or 3, and particularly preferably 3.

When R ⁶¹ or the X ⁶¹ there are a plurality, a plurality of R ⁶¹ or X ⁶¹ may be different even in the same, respectively.

There are no particular restrictions on the substituents contained in R ⁶¹ , but halogen atoms (fluorine, chlorine, etc.), hydroxyl groups, mercapto groups, carboxyl groups, epoxy groups, alkyl groups (methyl, ethyl, propyl, butyl, etc.), aryl Groups (phenyl, naphthyl, etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl, etc.), acyloxy groups {acetoxy, (meth) acryloyloxy, etc.}, alkoxycarbonyl groups (methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl Groups (phenoxycarbonyl, etc.), carbamoyl groups (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc.), acid amide groups {acetamide, benzamide, (meth) acrylamide, etc.}, etc. And this Substituents may be further substituted.

When there are a plurality of R ^{61 s} , at least one is preferably a substituted alkyl group or a substituted aryl group.

Specific examples of the organosilane compound represented by the general formula (6) include compounds described in paragraph numbers [0021] to [0025] of JP-A 2000-275403. Furthermore, an organosilane compound having a vinyl polymerizable substituent is particularly preferable, and examples thereof include compounds represented by the general formula (1) described in JP-A-2004-42278. Examples include the compounds described in the numbers [0026] to [0028].
Two or more compounds of the general formula (6) may be used in combination.

  The hydrolyzate and / or partial condensate of an organosilane compound is generally produced by treating the organosilane compound in the presence of a catalyst. Specifically, the same catalyst as the curing accelerator organosilane compound can be used.

  5-100 mass% is preferable, the usage-amount of the sol component of the organosilane with respect to a fluorine-containing polymer in a low refractive index layer has more preferable 5-40 mass%, 8-35 mass% is still more preferable, 10-30 mass % Is particularly preferred. If the amount used is too small, it is difficult to obtain the effect of the present invention. However, if the amount used is less than or equal to the upper limit value, the refractive index increases excessively, or the film shape or surface shape of the low refractive index layer deteriorates. Therefore, it is preferable to use an appropriate amount within the above range because the excellent effects of the present invention can be exhibited.

(Other additives)
In addition to the components described above, the low refractive index layer in the present invention is provided with an anti-fouling property of a known silicone compound or fluorine compound for the purpose of imparting antifouling properties, water resistance, chemical resistance, slipping properties and the like. It is preferable that a soiling agent, a slipping agent and the like are appropriately added. When these additives are added, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the curable composition for forming the low refractive index layer, more preferably 0.05 to It is a case where it is added in the range of 10% by mass, and particularly preferably 0.1 to 5% by mass.

  Preferable examples of the silicone compound include those having a substituent at the end of the compound chain and / or the side chain, containing a plurality of dimethylsilyloxy units as repeating units. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include (meth) acryloyl groups, vinyl groups, aryl groups, cinnamoyl groups, epoxy groups, oxetanyl groups, hydroxyl groups, fluoroalkyl groups, polyoxyalkylene groups, carboxyl groups, amino groups, and the like. Is mentioned.

  Although there is no restriction | limiting in particular in the molecular weight of a silicone type compound, It is preferable that it is 100,000 or less, It is especially preferable that it is 50,000 or less, It is most preferable that it is 3000-30000. Although there is no restriction | limiting in particular also in silicone atom content of a silicone type compound, It is preferable that it is 18.0 mass% or more, It is especially preferable that it is 25.0-37.8 mass%, 30.0-37. Most preferably, it is 0.0 mass%.

  Examples of preferable silicone compounds include compounds of the trade name “X-22” series manufactured by Shin-Etsu Chemical Co., Ltd., and compounds of the trade name “FM” series manufactured by Chisso Corporation. It is not limited.

As the fluorine compound, a compound having a fluoroalkyl group is preferable. The fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and a straight chain [eg, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H, etc.], even branched structures [eg, —CH (CF ₃ ) ₂ , —CH ₂ CF (CF ₃ ) ₂ , —CH (CH ₃ ) CF ₂ CF ₃ , —CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.], an alicyclic structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group, A perfluorocyclopentyl group or an alkyl group substituted with these, and may have an ether bond (for example, —CH ₂ OCH ₂ CF ₂ CF ₃ , —CH ₂ CH ₂ OCH ₂ C ₄ F). _{8 H, -CH 2 CH 2 OCH} 2 CH 2 C 8 F 17, -CH 2 CH 2 OCF ₂ CF ₂ OCF ₂ CF ₂ H, etc.). A plurality of the fluoroalkyl groups may be contained in the same molecule.

  It is preferable that the fluorine-based compound further has a substituent that contributes to bond formation or compatibility with the film of the low refractive index layer. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include (meth) acryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like.

  The fluorine-based compound may be a polymer or an oligomer with a compound not containing a fluorine atom, and the molecular weight is not particularly limited. Although there is no restriction | limiting in particular in fluorine atom content of a fluorine-type compound, It is preferable that it is 20 mass% or more, It is especially preferable that it is 30-70 mass%, It is most preferable that it is 40-70 mass%. Examples of preferred fluorine-based compounds include “R-2020”, “M-2020”, “R-3833”, “M-3833” {trade name: manufactured by Daikin Chemical Industries, Ltd.}; "F-171", "Megafuck F-172", "Megafuck F-179A", "Defenser MCF-300" {trade name: manufactured by Dai Nippon Ink Co., Ltd.} It is not something.

  The low refractive index layer in the present invention is further provided with a dustproof agent, an antistatic agent, etc., such as a known cationic surfactant or polyoxyalkylene compound, for the purpose of imparting properties such as dustproofness and antistatic properties. It can also be added as appropriate. As for these dustproof agent and antistatic agent, the structural unit may be included as a part of the function in the above-described silicone compound or fluorine compound. When adding these as an additive, it is preferable to add in the range of 0.01-20 mass% of curable composition total solid, More preferably, it is a case of 0.1-5 mass%. . Examples of preferable compounds include “Megafac F-150” {trade name: manufactured by Dainippon Ink Co., Ltd.}, “SH-3748” {trade name: manufactured by Toray Dow Corning Co., Ltd.}, and the like. It is not limited to these.

  The low refractive index layer may also contain microvoids. Specific examples include the contents described in JP-A-9-222502, JP-A-9-288201, JP-A-11-6902, and the like.

  Furthermore, in the present invention, organic fine particles can also be used. Examples of the organic fine particles include compounds described in paragraphs [0020] to [0038] of JP-A No. 11-3820, and the shape thereof is The same as the above-mentioned inorganic fine particles.

  The thickness of the low refractive index layer is preferably 0.03 to 0.2 μm, more preferably 0.05 to 0.15 μm.

[Properties of low refractive index layer]
The low refractive index layer in the present invention preferably has a surface energy of 26 mN / m or less, more preferably in the range of 15 to 25.8 mN / m. It is preferable from the viewpoint of antifouling property to make the surface energy within this range.

  In addition, the low refractive index layer exhibits an antifouling effect as long as it is a cured film made of a fluorine-containing polymer containing a thermosetting or crosslinkable fluorine-containing compound of light or radiation (for example, ionizing radiation). Therefore, it is preferable. In particular, if the fluorine-containing compound contained in the low refractive index layer that is the outermost layer is 50% by mass or more with respect to the total mass of the outermost layer, the entire surface of the low refractive index layer film has uniform and stable characteristics. This is preferable.

  The surface energy of a solid can be determined by a contact angle method, a wet heat method, and an adsorption method as described in “Basics and Applications of Wetting” (issued by Realize 1989.12.10). In the case of the antireflection film of the present invention, the contact angle method is preferably used. Specifically, two types of solutions having known surface energies are dropped on the surface of a film provided with an antireflection film, such as the transparent protective film of the polarizing plate of the present invention, and the surface of the droplet and the film surface The surface energy of the film can be calculated by calculating the angle between the tangent line drawn on the droplet and the angle formed by the film surface and defining the angle containing the droplet as the contact angle. The contact angle of the outermost layer surface with water is preferably 90 ° or more, more preferably 95 ° or more, and particularly preferably 100 ° or more.

  The dynamic friction coefficient on the surface of the low refractive index layer is preferably 0.25 or less, more preferably 0.05 to 0.25, and particularly preferably 0.03 to 0.15. The dynamic friction coefficient described here refers to a dynamic friction coefficient between a surface and a stainless steel hard sphere having a diameter of 5 mm when a load of 0.98 N is applied to a stainless steel hard sphere having a diameter of 5 mm and the surface is moved at a speed of 60 cm / min. .

  The hardness of the low refractive index layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K-5400. The scratch resistance of the low refractive index layer is preferably as the wear amount in the Taber test according to JIS K-6902 is smaller.

[Anti-glare function (anti-glare)]
The antireflection film may have an antiglare function that scatters external light. The antiglare function is obtained by forming irregularities on the surface of the antireflection film. When the antireflection film has an antiglare function, the haze of the antireflection film is preferably 3 to 50%, more preferably 5 to 40%, and most preferably 7 to 20%.

The antiglare property correlates with the average surface roughness (Ra) of the surface. It is preferable that the surface roughness is 1 mm ² randomly taken out from an area of 100 cm ² , and the average surface roughness (Ra) is 0.01 to 0.4 μm per 1 mm ² area of the extracted surface. More preferably, it is 0.03-0.3 micrometer, More preferably, it is 0.07-0.2 micrometer.
The average surface roughness (Ra) is measured according to JIS B-0601-1994.

  The concave and convex shapes on the surface of the antireflection film used in the present invention can be evaluated by an atomic force microscope (AFM).

  As a method for forming irregularities on the surface of the antireflection film, any method can be applied as long as these surface shapes can be sufficiently maintained. For example, fine particles are used in the low refractive index layer, thereby forming irregularities on the film surface (for example, JP 2000-271878 A), lower layers of the low refractive index layer (high refractive index layer, medium refractive index) The surface irregularity film is formed by adding a small amount (0.1 to 50% by mass) of relatively large particles (particle size 0.05 to 5 μm) to the rate layer or hard coat layer), and these shapes are maintained thereon. Then, a method of providing a low refractive index layer (for example, JP 2000-281410 A, JP 2000-95893 A, etc.), a method of physically transferring a concavo-convex shape to the surface after coating a low refractive index layer { For example, an embossing method (for example, JP-A-63-278839, JP-A-11-183710, JP-A-2000-275401, etc.), release paper transfer method (for example, JP No. 3332534), Particle sp Over transfer method (e.g., JP-A 6-87632 Patent Publication)} and the like.

[Anti-glare layer (AGL)]
When particles are contained in any layer of the antireflection film of the present invention to form an antiglare layer, the antiglare layer particles used in the antiglare layer have an average particle size in the range of 0.2 to 10 μm. Particles are preferred. The average particle diameter here is the mass average diameter of secondary particles (or primary particles when the particles are not aggregated). Examples of the antiglare layer particles include inorganic fine particles and organic particles. Specific examples of inorganic fine particles include particles such as silicon dioxide, titanium dioxide, zirconium oxide, aluminum oxide, tin oxide, ITO (antimony-containing tin oxide), zinc oxide, calcium carbonate, barium sulfate, talc, kaolin and calcium sulfate. Is mentioned. Silicon dioxide and aluminum oxide are preferred.

  The organic particles are preferably resin particles. Specific examples of the resin particles include particles made from silicone resin, melamine resin, benzoguanamine resin, polymethyl methacrylate resin, polystyrene resin, and polyvinylidene fluoride resin. Preferred are particles made from melamine resin, benzoguanamine resin, polymethyl methacrylate resin, polystyrene resin, and particularly preferred are particles made from polymethyl methacrylate resin, benzoguanamine resin, polystyrene resin.

  The particles for the antiglare layer used for the antiglare layer in order to form irregularities are preferably resin particles. The average particle size of the particles is preferably 0.5 to 10.0 μm, more preferably 0.5 to 9.0 μm, still more preferably 1.0 to 8.0 μm, and particularly preferably 1.5 to 7.0 μm. is there. The refractive index of the particles is preferably 1.35 to 1.80, more preferably 1.40 to 1.75, and still more preferably 1.45 to 1.75. The narrower the particle size distribution, the better. The S value indicating the particle size distribution of the particles is represented by the following mathematical formula (6), preferably 2 or less, more preferably 1.0 or less, and particularly preferably 0.7 or less.

Formula (6): S = (D _0.9 −D _0.1 ) / D _0.5 D _0.1 : Particle diameter equivalent to 10% of the integrated value of the volume converted particle diameter D _0.5 : Particle diameter equivalent to 50% of the integrated value of the volume converted particle diameter D _0.9 : Particle size equivalent to 90% of the integrated value of volume-converted particle size

  Further, as the particles for the antiglare layer, it is preferable to use translucent particles, and the refractive index is not particularly limited, but is almost the same as the refractive index of the antiglare layer (the difference in refractive index is 0.00. 005) or 0.02 or more. By making the refractive index of the particles and the refractive index of the antiglare layer substantially the same, the contrast when the antireflection film is mounted on the image display surface is improved. Furthermore, by adding a refractive index difference between the refractive index of the particle and the refractive index of the antiglare layer, the visibility (glare failure, viewing angle characteristics, etc.) when the antireflection film is mounted on the liquid crystal display surface is improved. Is done.

  In the case of adding a difference in refractive index between the refractive index of the particles and the refractive index of the antiglare layer, it is preferably 0.02 to 0.5, more preferably 0.03 to 0.4, and particularly preferably 0. 0.05 to 0.3.

  As the translucent particles, two or more different translucent particles may be used in combination. When two or more kinds of translucent particles are used, the translucent particles having the highest refractive index and the translucent particles having the lowest refractive index are used to effectively exert the refractive index control by mixing a plurality of types of particles. The difference in refractive index with the active particles is preferably 0.02 or more and 0.10 or less, and particularly preferably 0.03 or more and 0.07 or less. Further, it is possible to impart an antiglare property with a light-transmitting particle having a larger particle diameter and to impart another optical characteristic with a light-transmitting particle having a smaller particle diameter. For example, when an antireflection film is attached to a high-definition display of 133 ppi or higher, it is required that there is no problem in optical performance called glare. Glare is derived from the fact that the unevenness of the film surface (which contributes to antiglare properties) causes the pixels to be enlarged or reduced and loses brightness uniformity, but is smaller than the light-transmitting particles that impart antiglare properties. The diameter can be greatly improved by using translucent particles different from the refractive index of the translucent resin as the matrix binder.

  The use amount of the particles for the antiglare layer is preferably 3 to 75% by mass in the solid content of the layer imparting the antiglare property.

  The particles imparting antiglare properties can be contained in any layer constructed in the antireflection film, preferably a hard coat layer, a low refractive index layer, or a high refractive index layer, particularly preferably a hard coat layer. A high refractive index layer. It may be added to a plurality of layers.

(Light scattering layer)
The antireflection film of the present invention has a light scattering layer corresponding to the high refractive index layer in the present invention, which has a higher refractive index than the transparent substrate film on the transparent substrate film, and a lower refractive index than the transparent substrate film. It may be an embodiment in which the low refractive index layers are laminated at least sequentially. Furthermore, the light-scattering layer or the light-scattering hard coat layer, and the antireflective film composed of two or three layers of the medium refractive index layer and / or the high refractive index layer and the low refractive index layer are also included.

  The light scattering layer is preferably formed by dispersing at least one kind of translucent particles having an average particle diameter of 0.1 to 5 μm in a translucent resin. High refraction with no surface irregularities formed of a layer in which the difference in refractive index is 0.02 to 0.2 and the light-transmitting particles are contained in 3 to 30% by mass in the total solid content of the light scattering layer The rate layer is preferred. That is, the translucent particles dispersed in the high refractive index layer are those whose particle diameter is smaller than the film thickness of the high refractive index layer. It is preferable that The average particle diameter of the translucent particles is more preferably 0.5 to 5 μm. As the translucent particles used for the light scattering layer, inorganic fine particles and organic particles mentioned above in the description of the antiglare layer are preferable.

  The thickness of the light scattering layer is usually about 0.5 μm to 50 μm, preferably 1 μm to 20 μm, and more preferably 2 μm to 10 μm. The refractive index of the translucent resin is preferably 1.51 to 2.00, more preferably 1.51 to 1.90, still more preferably 1.51 to 1.85, and particularly preferably. 1.51-1.80. In addition, the refractive index of translucent resin is the value measured without including translucent particle | grains.

  The difference in refractive index between the translucent particles and the translucent resin is usually about 0.02 to 0.20, and particularly preferably 0.04 to 0.10. If the difference is 0.20 or less, problems such as cloudiness of the film do not occur, and if it is 0.02 or more, an excellent light scattering effect can be exhibited, which is preferable. The amount of translucent particles added to the translucent resin is as important as the refractive index, and in order to maintain the transparency of the film and obtain an excellent light scattering effect, the content of the translucent particles is light. It is preferable that it is 3-30 mass% in a scattering layer total solid, and also 5-20 mass%.

  When the above-described light-transmitting particles are added, the light-transmitting particles easily settle in the light-transmitting resin, and therefore an inorganic filler such as silica may be added to prevent sedimentation. In addition, although the amount of the inorganic filler added is more effective in preventing the translucent particles from settling, it adversely affects the transparency of the light scattering layer. Therefore, it is preferable that an inorganic filler having a particle size of 0.5 μm or less is contained in an amount of less than 0.1% by mass so as not to impair the transparency of the light scattering layer with respect to the translucent resin.

  Further, the antireflection film having the light scattering layer of the present invention preferably has an average reflectance of 2.5% or less at a wavelength of 380 nm to 680 nm and a haze of 10 to 40%. More preferably, the average reflectance is 1.8% or less and the haze is 10 to 35%.

  By specifying the optical characteristics of the antireflection film in such a range, when used as an antireflection film in an image display device, the image does not look whitish or blurs the image display. In addition, it is possible to achieve excellent image display quality with excellent anti-reflection properties, no reflection of external light, no screen glare, and the like, in which contrast reduction and hue change due to viewing angle change are sufficiently suppressed.

  Specific contents of the matrix, translucent particles, and other additives used in the light scattering layer of the present invention are the same as those described in the high refractive index layer and the antiglare layer. Can be mentioned.

[Hard coat layer]
The hard coat layer is provided on the surface of the transparent substrate film (or the transparent protective film in the case of a polarizing plate) as necessary to impart physical strength to the antireflection film. In particular, it is preferably provided between the transparent substrate film and the high refractive index layer.

  The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of a photocurable and / or thermosetting compound. The curable functional group is preferably a photopolymerizable functional group, and the hydrolyzable functional group-containing organometallic compound is preferably an organic alkoxysilyl compound. Specific examples of these compounds include those described in JP-A Nos. 2002-144913, 2000-9908 and WO00 / 46617.

  What comprises the matrix binder of the hard-coat layer in this invention has a preferable thing hardened | cured from what contains the curable composition of this invention.

  The hard coat layer preferably contains inorganic fine particles having an average primary particle size of 300 nm or less. More preferably, it is 10-150 nm. The inorganic fine particles have functions of increasing the hardness of the hard coat layer and suppressing curing shrinkage of the coating layer. It is also added for the purpose of controlling the refractive index of the hard coat layer.

  As described above, each of the high refractive index layer, the antiglare layer, and the light scattering layer can also serve as the hard coat layer. When each of these layers also serves as a hard coat layer, it is preferable that fine particles are dispersed finely and contained in the hard coat layer using the method described for the high refractive index layer.

  The film thickness of the hard coat layer can be appropriately designed depending on the application. The film thickness of the hard coat layer is preferably 0.2 to 25 μm, more preferably 2 to 15 μm, still more preferably 4 μm to 15 μm.

[Other layers]
[Transparent antistatic layer]
In the present invention, a transparent antistatic layer containing a conductive material can be provided between the transparent substrate film and the light scattering layer. This is preferable because an antistatic effect on the surface of the antireflection film can be exhibited. Note that it is preferable to provide a conductive layer as a transparent antistatic layer in order to protect the polarizing plate on the viewing side provided in the display device in which the liquid crystal mode is the IPS mode or the VA mode from the outer surface energy.

  The method for forming the transparent antistatic layer is, for example, a method of applying a conductive antistatic layer coating solution containing conductive fine particles and a reactive curable resin, a method of forming a conductive polymer cured film, or a transparent A conventionally known method such as a method of forming a conductive thin film by vapor deposition or sputtering of a metal or metal oxide that forms a film can be exemplified. The transparent antistatic layer can be formed directly on the transparent substrate film or via a primer layer that strengthens adhesion to the transparent substrate film.

  A transparent antistatic layer can also be used as part of the antireflection film. In this case, when used in a layer close to the outermost layer, sufficient antistatic properties can be obtained even if the film is thin. The coating method is not particularly limited, and an optimum method is selected from known methods such as roll coating, gravure coating, bar coating, extrusion coating, etc., depending on the characteristics and coating amount of the coating solution for forming the antistatic layer. You can do it.

  As the transparent antistatic layer, a conventionally known antistatic layer can be appropriately adjusted and used. As the transparent antistatic layer, for example, edited by Toray Research Center Co., Ltd. “Current Status and Prospects of Transparent Conductive Films” {Toray Research Center Co., Ltd., published in 1997}, Yutaka Toyoda “New Development of Transparent Conductive Films” "{CMC Co., Ltd., published in 1999}" and the like.

  The thickness of the transparent antistatic layer is preferably 0.01 to 10 μm, and more preferably 0.05 to 5 μm.

The surface resistance of the transparent antistatic layer is preferably 2 × 10 ¹² Ω / □ or less, more preferably 10 ⁵ to 10 ¹² Ω / □, and still more preferably 10 ⁵ to 10 ⁸ Ω / □. □. The surface resistance of the transparent antistatic layer can be measured by a four probe method.

  The transparent antistatic layer is preferably substantially transparent. Specifically, the haze of the transparent antistatic layer is preferably 10% or less, more preferably 3% or less, and most preferably 1% or less. The transmittance of light having a wavelength of 550 nm is preferably 50% or more, more preferably 60% or more, further preferably 65% or more, and most preferably 70% or more.

  Furthermore, it is preferable that the transparent antistatic layer has excellent surface strength, and the specific surface hardness of the transparent antistatic layer is 2H or more with a pencil hardness of 1 kg (as defined in JIS-K-5400). Is preferable, and 3H or more is more preferable.

(Conductive inorganic fine particles of transparent antistatic layer)
The transparent antistatic layer is preferably a cured resin layer containing conductive inorganic fine particles. The specific surface area of the conductive inorganic fine particles is preferably from 10 to 400 m ² / g, more preferably from 30 to 150 m ² / g.

  Examples of conductive inorganic fine particles include “Current Status and Prospects of Transparent Conductive Films”, Chapters 3 to 4, edited by Technical Information Association “Development and Application of Conductive Fillers” (Technical Information Association, published in 1997), etc. Inorganic compounds described; metal particles described in paragraph No. [0027] of JP 2001-330702 A; compounds described in paragraph No. [0046] of JP 2001-255403 A, and the like. Specifically, for example, it is preferably formed from a metal, a metal oxide or a nitride, and tin oxide (ATO) containing antimony (Sb) and indium oxide (ITO) containing Sn are particularly preferable. The ratio of Sb in ATO is preferably 3 to 20% by mass. The ratio of Sn in ITO is preferably 5 to 20% by mass.

  The average primary particle diameter of the conductive inorganic fine particles used in the transparent antistatic layer is preferably 1 to 150 nm, more preferably 3 to 100 nm. The average particle diameter of the conductive inorganic fine particles in the formed transparent antistatic layer is 1 to 200 nm, and more preferably 10 to 80 nm. The average particle diameter of the conductive inorganic fine particles is an average diameter weighted by the mass of the particles and can be measured by a light scattering method or an electron micrograph.

  The conductive inorganic fine particles may be subjected to a surface treatment. The surface treatment is performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina and silica. Silica treatment is particularly preferred. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Silane coupling agents are most preferred. Two or more types of surface treatments may be combined.

  The shape of the conductive inorganic fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape. Two or more kinds of conductive inorganic fine particles may be used in combination in the antistatic layer.

  The proportion of the conductive inorganic fine particles in the transparent antistatic layer is preferably 20 to 90% by mass, preferably 25 to 85% by mass, and more preferably 30 to 80% by mass.

(Binder for transparent antistatic layer)
In the transparent antistatic layer, a crosslinked polymer, that is, a cured resin can be used as a binder. The crosslinked polymer preferably has an ionic group. The ionic group may be any of cationic, anionic and betaine, but an anionic group is preferred.

In the crosslinked polymer having an anionic group, the main chain of the polymer having an anionic group preferably has a crosslinked structure. The anionic group has a function of maintaining the dispersion state of the conductive inorganic fine particles. The crosslinked structure has a function of strengthening the transparent antistatic layer by imparting a film forming ability to the polymer.
Specific examples of these ionic polymers include, for example, those described in the publication technique 2001-1745 page 36.

  For these binders, for example, reactive organic silicon compounds (1) to (3) described in JP-A No. 2003-39586 can be used in combination. The reactive organosilicon compound is used in the range of 10 to 100% by mass based on the total amount of the binder and the reactive organosilicon compound.

  The laminated antireflection film may further be provided with a moisture proof layer, a primer layer, an undercoat layer, a protective layer, a shield layer, and a sliding layer. The shield layer is provided to shield electromagnetic waves and infrared rays.

[Transparent substrate film used for antireflection film]
The light transmittance of the transparent substrate film serving as the base material of the antireflection film of the present invention is preferably 80% or more, and more preferably 86% or more. The haze of the transparent substrate film is preferably 2.0% or less, and more preferably 1.0% or less. The refractive index of the transparent substrate film is preferably 1.4 to 1.7.

  In the present invention, it is preferable to use a plastic film as the transparent substrate film. Examples of plastic film materials include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate). , Poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, Polypropylene, polyethylene, polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyether De include polymethyl methacrylate and polyether ketone.

  In these plastic film materials, those containing known additives (for example, antistatic agents, ultraviolet absorbers, plasticizers, slip agents, colorants, antioxidants, flame retardants, etc.) can also be used. . For these details, materials described in detail on pages 16 to 22 of the invention association disclosure technique (public technical number 2001-1745, issued on March 15, 2001, invention association) are preferably used. The amount of these additives added is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, based on the base material.

  In particular, when a polarizing plate in which the antireflection film of the present invention is provided on a transparent protective film of a polarizing plate is used for a liquid crystal display device, an organic EL display device, or the like, cellulose acylate is preferably used as the transparent protective film, that is, the transparent substrate film. It is done. As a method for producing a cellulose acylate film, a method disclosed in published technical report No. 2001-1745 is preferably used. In addition, polyethylene terephthalate or polyethylene naphthalate is preferable when it is used by being attached to a glass substrate or the like for use in a flat CRT or PDP.

  The thickness of the transparent substrate film is preferably 5 to 200 μm, more preferably 10 to 150 μm, still more preferably 20 to 120 μm.

<Polarizing plate>
The polarizing plate with an antireflection film of the present invention is formed by coating the antireflection film described above on the transparent protective film, and applying a polarizing film, which will be described later, to the opposite surface of the transparent protective film with an adhesive. A mode of using and laminating is preferable. As a result, the thickness of the entire polarizing plate can be reduced, and the weight of the image display device provided with the polarizing plate can be reduced.

  As a preferred transparent protective film for use in such a polarizing plate, the hydrophobic / hydrophilic balance of the film, the bonding property of the polarizing film with the vinyl alcohol film, and the uniformity of the optical properties throughout the film plane are important. Especially preferred is a cellulose acylate film. In particular, a fatty acid ester (cellulose acylate) film of cellulose is preferable, and a film containing cellulose acylate, a plasticizer, and fine particles is more preferable.

[Polarizing film]
The polarizing film used for the polarizing plate with the antireflection film of the present invention is preferably composed of polyvinyl alcohol (PVA) and a dichroic molecule. However, as described in JP-A-11-248937, A polyvinylene polarizing film in which a polyene structure is produced by dehydrating and dechlorinating vinyl chloride and oriented can also be used.

  PVA is a polymer material obtained by saponifying polyvinyl acetate, but may contain components copolymerizable with vinyl acetate such as unsaturated carboxylic acids, unsaturated sulfonic acids, olefins, and vinyl ethers. . In addition, modified PVA containing an acetoacetyl group, a sulfonic acid group, a carboxyl group, an oxyalkylene group, or the like can also be used.

  The degree of saponification of PVA is not particularly limited, but is preferably 80 to 100 mol%, particularly preferably 90 to 100 mol% from the viewpoint of solubility and the like. The number average degree of polymerization of PVA is not particularly limited, but is preferably 1000 to 10,000, and particularly preferably 1500 to 5000.

  PVA is preferably formed into a film and then a dichroic molecule is introduced to form a polarizing film. As a method for producing a PVA film, a method of forming a film by casting a stock solution in which a PVA resin is dissolved in water or an organic solvent is generally preferably used. The concentration of the polyvinyl alcohol-based resin in the stock solution is usually 5 to 20% by mass, and a PVA film having a thickness of 10 to 200 μm can be produced by forming this stock solution by casting. The PVA film can be produced with reference to Japanese Patent No. 3342516, Japanese Patent Application Laid-Open No. 09-328593, Japanese Patent Application Laid-Open No. 13-302817, Japanese Patent Application Laid-Open No. 14-144401, and the like.

In addition, the polarizing plate of the present invention includes a PVA film having a 1,2-glycol bond amount of 1.5 mol% or less described in Japanese Patent No. 3021494; described in JP-A No. 13-316492. PVA film having 500 or less optical foreign matters of 5 μm or more per 100 cm ² ; PVA having hot water cutting temperature spots in the TD direction of 1.5 ° C. or less of the film described in JP-A No. 14-030163 From a solution in which 1 to 100 parts by mass of a tri- or 6-valent polyhydric alcohol such as glycerin or a plasticizer described in JP-A No. 06-289225 is further mixed. PVA film formed into a film; etc. can be used preferably.

As the dichroic molecule, higher-order iodine ions such as I ₃ ⁻ and I ₅ ^— or dichroic dyes can be preferably used. In the present invention, higher-order iodine ions are particularly preferably used. Higher-order iodine ions can be obtained by converting iodine into potassium iodide as described in “Application of Polarizing Plate” by Nagata Ryohen (CMC Publishing) and “Industrial Materials” Vol. 28, No. 7, pages 39-45. PVA can be immersed in a solution dissolved in an aqueous solution and / or a boric acid aqueous solution, and can be produced in a state of being adsorbed and oriented in PVA.

  When a dichroic dye is used as the dichroic molecule, an azo dye is preferable, and a bisazo dye and a trisazo dye are particularly preferable. The dichroic dye is preferably a water-soluble dye. For this reason, a hydrophilic substituent such as a sulfonic acid group, an amino group, or a hydroxyl group is introduced into the dichroic molecule, and a free acid or an alkali metal salt, an ammonium salt, an amine is introduced. It is preferably used as a salt.

Specific examples of such dichroic dyes include, for example, “Application of Polarizing Film” (published by CMC, published on February 10, 1986), “COLOUR INDEX”, 3rd edition, Volume 2 (The Society of Dyers and Cololists, The American Association of Textile Chemists and Collists, published in 1971). I. Direct dyes (direct dyes) and the like can be mentioned.
In order to produce dichroic molecules having various hues, two or more of these dichroic dyes may be blended. When a dichroic dye is used, the adsorption thickness may be 4 μm or more as described in JP-A No. 14-082222.

  If the content of the dichroic molecule in the film is too small, the degree of polarization is low, and if it is too large, the single-plate transmittance is lowered. Therefore, the polyvinyl alcohol polymer constituting the film matrix is usually used. On the other hand, it is adjusted in the range of 0.01% by mass to 5% by mass.

  Further, from the viewpoint of increasing the heat resistance and moisture resistance of the polarizing film, it is preferable to perform hardening in combination with a crosslinking agent in the manufacturing process of the polarizing film. As the cross-linking agent, the one described in US Reissue Patent No. 232897 can be used, and as described in Japanese Patent No. 3357109, a polyvalent aldehyde is used as the cross-linking agent in order to improve dimensional stability. However, boric acids are most preferably used.

  When boric acid is used as the crosslinking agent, metal ions may be added to the boric acid-potassium iodide aqueous solution. Zinc chloride is preferable as the metal ion. However, as described in JP-A No. 2000-35512, zinc halide such as zinc iodide, zinc sulfate such as zinc acetate is used instead of zinc chloride. It can also be used.

  The thickness of the polarizing film is preferably 5 to 40 μm, more preferably 10 to 30 μm, and particularly preferably 5 to 22 μm. Even when the thickness of the polarizing film is reduced to 5 to 22 μm, the transmittance at 700 nm when the polarizing film is crossed Nicol is 0.001% or more and 0.3% or less, and the transmittance at 410 nm is 0. The aspect which makes it 0.001% or more and 0.3% or less is preferable. The upper limit of the 700 nm transmittance during crossed Nicols is preferably 0.3% or less, and preferably 0.2%. The upper limit of the transmittance at 410 nm is preferably 0.3% or less, more preferably 0.08% or less, and further preferably 0.05% or less. This improves the light leakage failure (picture frame failure) from the peripheral part of the image display device caused by the contraction of the polarizing film due to the change over time, shows a neutral gray color with less bluishness, and exhibits a good display image quality. Can be achieved.

  When the thickness of the polarizing film is reduced to 5 to 22 μm, as a means for reducing the transmittance at 700 nm and the transmittance at 410 nm at the time of crossed Nicols, in addition to the dichroic substance such as iodine, the polarizing film can be used. It is effective to add the above-mentioned dichroic dye having absorption in the wavelength range to be used as a hue adjusting agent, and to add a hardening agent such as boric acid when adding a dichroic substance such as iodine. . It is also effective to combine these.

〔Polarizer〕
The polarizing film is provided as a polarizing plate by attaching a transparent protective film on both sides. The two transparent protective films may be the same or different. The polarizing film and the transparent protective film are preferably bonded together with a pair of rolls so that the adhesive liquid is supplied immediately before the bonding and the polarizing film and the transparent protective film are overlapped. The thickness of the adhesive layer after drying is preferably 0.001 to 5 μm, and more preferably 0.005 to 3 μm.

  The adhesive between the polarizing film and the transparent protective film is not particularly limited, but PVA-based resins (including modified PVA into which an acetoacetyl group, a sulfonic acid group, a carboxyl group, an oxyalkylene group, etc. are introduced), an aqueous boron compound solution, etc. Among them, PVA resin is preferable.

[Polarizing plate with antireflection function]
The polarizing plate of the present invention is formed by laminating a transparent protective film provided with the antireflection film of the present invention on the viewing side of the polarizing film. As the protective film on the lower side of the polarizing plate (the side opposite to the viewing side), it is preferable that the transparent substrate film, particularly the cellulose acylate film, is bonded. The polarizing film generally contains polyvinyl alcohol as a main component, and it is preferable to make the surface of the transparent protective film hydrophilic in order to improve adhesiveness with the polarizing film.

  As a method of hydrophilizing the transparent protective film with an antireflection film, (1) a method of coating each layer constituting the antireflection film on one surface of a protective film that has been previously hydrophilized; (2) protection There are two possible methods: coating and forming the antireflection film on one side of the film and then hydrophilizing the side to be bonded to the polarizing film. (1) is to coat the antireflection film. Since the surface to be made is hydrophilic and it is difficult to ensure the adhesion between the protective film and the antireflection film, the method (2) is preferable. Hereinafter, although the hydrophilic treatment of the transparent protective film with an antireflection film will be described, the transparent protective film as the protective film on the lower side of the polarizing plate can also be hydrophilized using the same treatment method.

(Hydrophilic treatment)
The hydrophilic treatment of the surface of the transparent protective film can be performed by a known method. Examples thereof include a method for modifying the film surface by corona discharge treatment, glow discharge treatment, ultraviolet irradiation treatment, flame treatment, ozone treatment, acid treatment, alkali saponification treatment, and the like. These are described in detail in the aforementioned public technical number 2001-1745, pages 30-32.

(Saponification treatment)
Among these, it is particularly preferable to treat the surface of the cellulose acylate film with an alkali saponification treatment.

(1) Immersion method This is a technique in which a protective film with an antireflection film is immersed in an alkaline solution under appropriate conditions to saponify all surfaces that are reactive with alkali on the entire surface of the film. Since it is not necessary, it is preferable from the viewpoint of cost. Examples of the alkali saponification solution include potassium hydroxide solution and sodium hydroxide solution, and the prescribed concentration of hydroxide ions is preferably in the range of 0.1 to 3.0 mol / L. Furthermore, as an alkali treatment liquid, it contains a solvent (for example, isopropyl alcohol, n-butanol, methanol, ethanol, etc.) having good wettability with respect to the film, a surfactant, a wetting agent (for example, diols, glycerin, etc.). Thus, the wettability of the saponification solution to the transparent substrate film, the aging stability of the saponification solution, and the like are improved. The liquid temperature of a preferable alkali liquid is 20-70 degreeC, Most preferably, it is 30-60 degreeC.

  After being immersed in the alkaline solution, it is preferable that the film is sufficiently washed with water so that the alkali component does not remain in the film, or is immersed in a dilute acid to neutralize the alkali component.

  By performing the saponification treatment, the main surface on the side having the antireflection film of the transparent protective film and the opposite main surface are hydrophilized. The polarizing film is usually used by being adhered to the hydrophilic surface of the transparent protective film.

  The saponification treatment is preferable in that the lower the contact angle with water on the surface of the transparent protective film opposite to the side having the antireflection film, the better the adhesion to the polarizing film, whereas in the dipping method, The surface of the antireflection film may be damaged by alkali, and it is important to set the reaction conditions to the minimum necessary. As an index of damage received by the antireflection film due to alkali, when the contact angle to the water of the main surface on the side having no antireflection film of the transparent protective film is used, particularly if the transparent protective film is a cellulose acylate film, Is in the range of 20 to 50 °, more preferably 30 to 45 °. Within this range, the damage received by the antireflection film is not harmful, and the adhesiveness to the polarizing film can be maintained, which is preferable.

(2) Alkaline liquid coating method As a means for avoiding damage to the antireflection film in the above immersion method, an alkaline liquid is applied only to the main surface opposite to the main surface having the antireflection film under appropriate conditions. An alkaline solution coating method in which heating, washing, and drying are preferably used. Examples of the alkaline solution and treatment include those described in JP-A No. 2002-82226, WO 02/46809 pamphlet, and JP-A No. 2003-313326.

  By using the polarizing plate configured as described above, a polarizing plate having an antireflection function excellent in physical strength and weather resistance can be manufactured, and the cost can be reduced and the display device can be thinned.

[Optical compensation film]
The viewing side polarizing plate of the present invention is preferably formed by providing an optical compensation film on the protective film on the side opposite to the side having the antireflection film of the polarizing plate. This enables a wide viewing angle of the display image of the liquid crystal display device.

  Examples of the optical compensation film include a birefringent film obtained by uniaxially or biaxially stretching a polymer film, and a liquid crystal alignment having an optically anisotropic layer made of a liquid crystalline material exhibiting birefringence on a support film. Examples include films. The thickness of the optical compensation film is not particularly limited, but is generally about 5 to 100 μm. Among these optical compensation films, a liquid crystal alignment film having an optically anisotropic layer on a support film is preferable.

  Examples of the polymer film material to be the birefringent film include polyvinyl alcohol, polyvinyl butyral, polymethyl vinyl ether, polyhydroxyethyl acrylate, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, polycarbonate, polyarylate, polysulfone, and polyethylene terephthalate. , Polyethylene naphthalate, polyethersulfone, polyphenylene sulfide, polyphenylene oxide, polyallylsulfone, polymethyl methacrylate, polyamide, polyimide, polyolefin, polyvinyl chloride, cellulosic polymer, norbornene resin, or binary of these, three Examples thereof include various copolymers, graft copolymers, and blends. These polymer materials become oriented products (stretched films) by stretching or the like.

[Liquid crystal alignment film]
The optically anisotropic layer is preferably designed so as to compensate for the liquid crystal compound molecules in the liquid crystal cell in the black display of the liquid crystal display device. The alignment state of the liquid crystal compound molecules in the liquid crystal cell in black display varies depending on the mode of the liquid crystal display device. The alignment state of the liquid crystal compound molecules in this liquid crystal cell is described in IDW'00, FMC 7-2, pages 411 to 414.

(Liquid crystal compound)
The liquid crystal compound used for the optically anisotropic layer may be a rod-like liquid crystal or a discotic liquid crystal, and these are high molecular liquid crystals or low molecular liquid crystals, and those in which low molecular liquid crystals are crosslinked and no longer exhibit liquid crystallinity. Including. Most preferred is a discotic liquid crystal.

  Examples of rod-like liquid crystalline molecules include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines. , Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. These low-molecular liquid crystalline molecules preferably have a polymerizable group in the molecule (for example, described in paragraph No. [0016] of JP-A No. 2000-304932). In addition to the above low-molecular liquid crystalline molecules, high-molecular liquid crystalline molecules can also be used. The high-molecular liquid crystalline molecule is a polymer having a side chain corresponding to the above low-molecular liquid crystalline molecule. Examples of the optical compensation sheet using polymer liquid crystalline molecules include compounds described in JP-A-5-53016.

  Examples of discotic liquid crystals include C.I. A benzene derivative described in a research report of Destrade et al., “Mol. Cryst.”, 71, 111 (1981); Destrode et al., “Mol. Cryst.”, 122, 141 (1985), “Physics lett, A”, 78, 82 (1990); The cyclohexane derivative described in the research report of Kohne et al., “Angew. Chem.”, 96, 70 (1984); M.M. Lehn et al., “J. Chem. Commun.”, P. 1794 (1985), J. Chem. Examples include azacrown and phenylacetylene macrocycles described in the research report of Zhang et al., “J. Am. Chem. Soc.”, 116, 2655 (1994).

  The discotic liquid crystal generally has a structure in which these are used as a mother nucleus at the center of a molecule, and a linear alkyl group, an alkoxy group, a substituted benzoyloxy group, etc. are radially substituted as the linear chain, and the liquid crystallinity is improved. Show. However, the molecule itself is not limited to the above description as long as the molecule itself has negative uniaxiality and can give a certain orientation. Further, in the present invention, the term “formed from a discotic compound” does not require that the final substance is the above-mentioned compound, for example, a low molecular discotic liquid crystal has a group that reacts with heat, light, or the like. As a result, it may be polymerized or cross-linked by reaction with heat, light, etc., resulting in high molecular weight and loss of liquid crystallinity. Preferred examples of the discotic liquid crystal include those described in JP-A-8-50206.

  The optically anisotropic layer is generally formed by applying a solution obtained by dissolving a discotic compound and other compounds (for example, a plasticizer, a surfactant, a polymer, etc.) in a solvent onto the alignment film, drying, and then discotic nematic. It is obtained by heating to the phase formation temperature and then cooling while maintaining the orientation state (discotic nematic phase). Alternatively, the optically anisotropic layer is formed by applying a solution obtained by dissolving a discotic compound and another compound (for example, a polymerizable monomer, a photopolymerization initiator) in a solvent onto the alignment film, drying, and then discotic It is obtained by heating to the nematic phase formation temperature, polymerizing (by irradiation with UV light or the like), and further cooling.

  The thickness of the optically anisotropic layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm, and most preferably 0.7 to 5 μm. However, depending on the mode of the liquid crystal cell, it may be thickened (3 to 10 μm) in order to obtain high optical anisotropy.

[Alignment film]
The alignment film is usually used because it has a function of defining the alignment direction of the liquid crystal compound molecules. However, if the alignment state is fixed after the liquid crystal compound is aligned, the alignment film plays its role. It is not necessarily essential as a component of the invention. For example, it is possible to produce the polarizing plate of the present invention by transferring only the optically anisotropic layer on the alignment film in which the alignment state is fixed onto the polarizing film.

  The alignment film is an organic compound (eg, ω-tricosanoic acid) formed by rubbing treatment of an organic compound (preferably polymer), oblique deposition of an inorganic compound, formation of a layer having a microgroove, or Langmuir-Blodgett method (LB film). , Dioctadecylmethylammonium chloride, methyl stearylate). Furthermore, an alignment film in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known.

  The alignment film is preferably formed by polymer rubbing treatment. In principle, the polymer used for the alignment film has a molecular structure having a function of aligning liquid crystal molecules.

  In the present invention, in addition to the function of aligning liquid crystal molecules, a crosslinkable functional group having a function of binding a side chain having a crosslinkable functional group (for example, a double bond) to the main chain or aligning liquid crystal molecules. Is preferably introduced into the side chain.

  As the polymer used in the alignment film, either a polymer that can be crosslinked by itself or a polymer that is crosslinked by a crosslinking agent can be used, and a plurality of combinations thereof can be used.

  Examples of the polymer used in the alignment film include, for example, methacrylate copolymers, styrene copolymers, polyolefins, polyvinyl alcohols and modified polyvinyl alcohols described in paragraph No. [0022] of JP-A-8-338913. (N-methylolacrylamide), polyester, polyimide, vinyl acetate copolymer, carboxymethylcellulose, polycarbonate and the like. Most preferred are polyvinyl alcohol and modified polyvinyl alcohol. Specific examples of the alignment film forming composition such as the modified polyvinyl alcohol compound and the crosslinking agent include those described in JP-A Nos. 2000-155216 and 2002-62426.

  The alignment film can basically be formed by applying the above polymer, which is an alignment film forming material, on a support film, followed by heat drying (crosslinking) and rubbing treatment. As described above, the crosslinking reaction may be carried out at any time after coating on the support film.

  The alignment film is preferably applied by spin coating, dip coating, curtain coating, extrusion coating, rod coating, or roll coating. In particular, the extrusion coating method and the rod coating method are preferable.

  The alignment film may be provided directly on the support film, or a method of providing an undercoat layer on the support film and then providing it on the undercoat layer. When providing directly on a support body film, the said surface hydrophilization treatment is mentioned.

  When providing an undercoat layer, for example, a method using an undercoat layer described in JP-A-7-333433 or a resin layer such as gelatin containing both a hydrophobic group and a hydrophilic group is only one layer. A single layer method to be applied, and further, a layer that adheres well to the polymer film as the first layer (hereinafter abbreviated as the undercoat first layer), and a hydrophilic layer such as gelatin that adheres well to the alignment film as the second layer thereon For example, a so-called multi-layer method (for example, described in JP-A No. 11-248940) in which an adhesive resin layer (hereinafter abbreviated as an undercoat second layer) is applied.

  The alignment film can be obtained by rubbing the surface after crosslinking the polymer layer as described above. Next, the alignment film functions to align the liquid crystal molecules of the optically anisotropic layer provided on the alignment film. Thereafter, as necessary, the alignment film polymer and the polyfunctional monomer contained in the optically anisotropic layer are reacted, or the alignment film polymer is crosslinked using a crosslinking agent. The thickness of the alignment film is preferably in the range of 0.1 to 10 μm.

[Support film for coating optically anisotropic layer made of liquid crystal compound]
The support film for coating the optically anisotropic layer is not particularly limited as long as it is a plastic film having a high light transmittance, but a protective film for a polarizing plate is preferably used. That is, it is preferable that an alignment film (not necessarily essential as described above) and an optically anisotropic layer are formed directly on the protective film of the polarizing plate.

  Since the support on which the optically anisotropic layer is coated itself plays an optically important role, the Re retardation value of the support is adjusted to 0 to 200 nm, and the Rth retardation value is adjusted to 0 to 400 nm. It is preferred that

  The cellulose acylate film of the support preferably contains, as a retardation adjusting agent, a compound that absorbs ultraviolet rays having a wavelength (λmax) shorter than 400 nm that gives the absorption maximum of the ultraviolet absorption spectrum of the solution. Examples of such compounds include ultraviolet absorbing compounds such as phenyl salicylic acids, 2-hydroxybenzophenones, benzotriazoles, and triphenyl phosphate. In addition, an aromatic compound having at least two aromatic rings (for example, JP-A No. 2000-1111914), a triphenylene compound (for example, JP-A No. 2000-275434), and a rod-like compound (for example, JP-A No. 2002-363343). No. 2003-35821), a discotic compound (a compound containing a 1,3,5-triazine skeleton, porphyrin skeleton in a molecule, etc .: for example, JP-A No. 2001-166144) and the like are preferable. These compounds preferably have substantially no absorption in the visible light region. These compounds preferably have substantially no absorption in the visible light region.

  The birefringence (Δn: nx−ny) of the support film is preferably 0 to 0.002. The birefringence {(nx + ny) / 2−nz} in the thickness direction of the film is preferably 0.04 or less.

The front retardation value (Re) and the retardation value (Rth) in the film thickness direction of the support film are calculated according to Equations (23) and (24).
Formula (7): Re = (nx−ny) × d
Formula (8): Rth = {(nx + ny) / 2−nz} × d
Where nx is the refractive index in the slow axis direction in the plane of the support film (maximum refractive index in the plane); ny is the refraction in the direction perpendicular to the slow axis in the plane of the support film. Nz is the refractive index in the thickness direction of the film. d is the thickness of the film whose unit is nm.

  The thickness of the cellulose acylate film used for the optical compensation film is preferably 20 to 200 μm, and more preferably 30 to 120 μm.

  When an optical compensation film is used as a protective film for a polarizing film, that is, when an optically anisotropic layer is formed on a transparent protective film and then bonded to the polarizing film, the surface to be bonded to the polarizing film is saponified. It is preferable to carry out according to the saponification treatment described above.

  The configuration of the viewing side polarizing plate is a laminated film of “antireflection film / transparent protective film / polarizing film / transparent protective film”, and further “antireflection film / transparent protective film / polarizing film / optical compensation film (transparent protective film / (Alignment film) / optically anisotropic layer) ", and further thinning, weight reduction and cost reduction are achieved. The upper side (viewing side) transparent protective film of the viewing side polarizing plate serves as an antireflection film, and the lower transparent protective film serves as a support film (that is, an optical compensation film) coated with an optically anisotropic layer. A thin and light polarizing plate having excellent physical strength and weather resistance, an antireflection function, and excellent visibility can be obtained.

<Image display device>
The image display device of the present invention is characterized in that at least one of the above-described antireflection film, antireflection film and polarizing plate (polarizing plate with antireflection ability) is disposed on the image display surface. The antireflection film, antireflection film, and polarizing plate of the present invention can be applied to an image display device such as a liquid crystal display device (LCD) or an organic EL display. The image display device of the present invention is preferably applied to a transmissive, reflective, or transflective liquid crystal display device in any one of TN, STN, IPS, VA, and OCB modes. This will be further described below.

  Any conventionally known liquid crystal display device can be used. For example, supervised by Tatsuo Uchida, “Reflective color LCD integrated technology” {CMC, published in 1999}, “New development of flat panel display” {Research Division, Toray Research Center, published in 1996}, “Liquid crystal related market” And the future prospects (first volume), (second volume) "{Fuji Chimera Research Institute, Inc., published in 2003}, and the like.

  Specifically, for example, a transmissive type, a reflective type, such as twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optically compensated bend cell (OCB), etc. It can be preferably used for a liquid crystal display device of a type or a transflective type.

  In addition, the polarizing plate of the present invention realizes a good contrast and a wide viewing angle even when the size of the attached liquid crystal display device display image is 17 inches or more, and prevents hue change and transfer of external light. This is preferable because it has good durability.

[TN mode liquid crystal display]
The TN mode liquid crystal cell is most frequently used as a color TFT liquid crystal display device, and many publications are cited. The alignment state in the liquid crystal cell in the TN mode black display is an alignment state in which the rod-like liquid crystalline molecules rise at the center of the cell and the rod-like liquid crystalline molecules lie in the vicinity of the cell substrate.

[OCB mode liquid crystal display]
The OCB mode liquid crystal cell is a bend alignment mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned in a substantially opposite direction (symmetrically) between an upper portion and a lower portion of the liquid crystal cell. Since the liquid crystal display device using the bend alignment mode liquid crystal cell is aligned symmetrically between the upper part and the lower part of the liquid crystal cell, the devices disclosed in the specifications of US Pat. Nos. 4,583,825 and 5,410,422 are provided. The bend alignment mode liquid crystal cell has a self-optical compensation function. For this reason, this liquid crystal mode is also called an OCB (Optically Compensatory Bend) liquid crystal mode.

  Similarly to the TN mode, the liquid crystal cell in the OCB mode is in a black display, and the alignment state in the liquid crystal cell is such that the rod-like liquid crystalline molecules rise at the center of the cell and the rod-like liquid crystalline molecules lie near the cell substrate. .

[VA mode liquid crystal display]
In a VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied.

The VA mode liquid crystal cell includes (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). (2) Liquid crystal cell (SID97, “Digest of Tech. Papers” (Proceedings) 28 (1997) in which the VA mode is converted into a multi-domain (MVA mode) in order to expand the viewing angle. 845], (3) a liquid crystal cell in a mode (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied, and twisted multi-domain alignment is applied when a voltage is applied. -59 (1998) description] and (4) SURVAVAL mode liquid crystal cells (announced at LCD International 98).

[IPS mode liquid crystal display]
In the IPS mode liquid crystal cell, the liquid crystal molecules are always rotated in a horizontal plane with respect to the substrate, and are aligned so as to have a slight angle with respect to the longitudinal direction of the electrode when no electric field is applied. When an electric field is applied, the liquid crystal molecules change direction in the direction of the electric field. The light transmittance can be changed by arranging the polarizing plates sandwiching the liquid crystal cell at a predetermined angle. As the liquid crystal molecules, nematic liquid crystal having a positive dielectric anisotropy Δε is used. The thickness (gap) of the liquid crystal layer is more than 2.8 μm and less than 4.5 μm. This is because when the retardation Δn · d is more than 0.25 μm and less than 0.32 μm, a transmittance characteristic having almost no wavelength dependency within the visible light range can be obtained. By combining the polarizing plates, the maximum transmittance can be obtained when the liquid crystal molecules are rotated 45 ° from the rubbing direction to the electric field direction. The thickness (gap) of the liquid crystal layer is controlled by polymer beads. Of course, the same gap can be obtained with glass bead fiber or resin columnar spacers. The liquid crystal molecules are not particularly limited as long as they are nematic liquid crystals. When the value of the dielectric anisotropy Δε is large, the driving voltage can be reduced, and when the refractive index anisotropy Δn is small, the thickness (gap) of the liquid crystal layer can be increased, the liquid crystal sealing time is shortened, and the gap Variation can be reduced.

[Other LCD mode]
For the ECB mode and STN mode liquid crystal display devices, the polarizing plate of the present invention can be provided in the same manner as described above.

[Display device]
The liquid crystal display device can be formed according to the conventional method. That is, a liquid crystal display device is generally formed by incorporating a drive circuit by appropriately combining liquid crystal cells, an optical film, and, if necessary, components such as an illumination system. In this invention, there is no limitation in particular except the point which uses the liquid crystal display element by this invention, and it can apply according to the former.

  In forming the liquid crystal display device, for example, appropriate components such as a prism array, a lens array sheet, a light scattering plate, a light guide plate, and a backlight can be arranged in one or more layers at appropriate positions. Further, by combining with a λ / 4 plate, it can be used to reduce the reflected light from the surface and inside as a polarizing plate for reflective liquid crystal or a surface protective plate for organic EL display.

Although the specific Example about the cured film of this invention is described below, this invention is not limited to these.
Curable multi-branched polymer (RHB)
Synthesis Example 1: Synthesis of curable multi-branched polymer (RHB-1) According to the description in Japanese Patent No. 2574201, a reactor equipped with a reflux condenser, a stirrer, a thermometer, a temperature controller, and a water separator, As the multi-branched polymer (HB-1), 55.0 g of BOLTORN H20 (OH value: 510 mg KOH / g) manufactured by Perstor Puer Beh, 39.6 g (0.55 mol) of acrylic acid, 63.4 g of toluene as a reaction solvent, 0.143 g of hydroquinone as a polymerization inhibitor and 0.953 g of methanesulfonic acid as an acid catalyst were charged, and the reaction was performed while removing the produced water azeotropically with the solvent at a reaction temperature of 100 to 115 ° C., and the produced water reached 1.35 ml. By the way, the reaction was finished. The reaction mixture was dissolved in 40 g of toluene, neutralized with 25% aqueous sodium hydroxide solution, and then washed 3 times with 20 g of 15% brine. The solvent was distilled off under reduced pressure to obtain a curable multi-branched polymer (RHB-1). The OH value of the curable multi-branched polymer (RHB-1) was 434 mgKOH / g, and the conversion rate from the reactive hydroxyl group to the curable reactive group was 15 mol%.

Synthesis Example 2: Synthesis of curable multi-branched polymer (RHB-2) A curable multi-branched polymer (RHB-2) was prepared in the same manner as in Synthetic Example 1 except that the reaction was terminated when the produced water reached 6.3 ml. Got. The OH value of the curable multi-branched polymer (RHB-2) was 153 mgKOH / g, and the conversion rate from the reactive hydroxyl group to the curable reactive group was 70 mol%.

Synthesis Example 3: Synthesis of curable multi-branched polymer (RHB-3) A curable multi-branched polymer (RHB-3) was prepared in the same manner as in Synthetic Example 1 except that the reaction was terminated when the amount of generated water reached 7.8 ml. Got. The OH value of the curable multi-branched polymer (RHB-3) was 68 mgKOH / g, and the conversion rate from the reactive hydroxyl group to the curable reactive group was 87 mol%.

Synthesis Example 4: Synthesis of curable multi-branched polymer (RHB-4) Instead of multi-branched polymer (HB-1), BOLTORN H30 (OH value: 500 mgKOH / A curable multi-branched polymer (RHB-4) was obtained in the same manner as in Synthesis Example 1 except that the reaction was terminated when the generated water reached 7.2 ml using g). The OH value of the curable multi-branched polymer (RHB-4) was 100 mgKOH / g, and the conversion rate from the reactive hydroxyl group to the curable reactive group was 80 mol%.

Synthesis example 5: Synthesis of curable multi-branched polymer (RHB-5) BOLTORN H40 (OH value: 480 mgKOH / manufactured by Perstorpure Baie) as multi-branched polymer (HB-3) instead of multi-branched polymer (HB-1) A curable multi-branched polymer (RHB-5) was obtained in the same manner as in Synthesis Example 1 except that the reaction was terminated when the generated water reached 6.3 ml using g). The OH value of the curable multi-branched polymer (RHB-5) was 144 mgKOH / g, and the conversion rate from the reactive hydroxyl group to the curable reactive group was 70 mol%.

Synthesis Example 6: Synthesis of curable multi-branched polymer (RHB-6) According to the description in Japanese Patent No. 2574201, a reactor equipped with a reflux condenser, a stirrer, a thermometer, a temperature control device, and a water separator, Sodium hydride 3 while stirring at room temperature in a mixed solution of 10.0 parts by mass of BOLTORN H20 (OH value: 510 mgKOH / g) manufactured by Perstorpure Bee as a multi-branched polymer (HB-1) and 23 parts by mass of tetrahydrofuran 3 parts by weight were added. A mixed solution of 10.0 parts by mass of epibromohydrin and 43.4 parts by mass of tetrahydrofuran was added dropwise thereto over 1 hour, and the mixture was further stirred at a temperature of 50 ° C. for 6 hours. After cooling to room temperature, the reaction mixture was poured into 1 liter of water, extracted with 500 ml of toluene, thoroughly washed, and dried over magnesium sulfate. Toluene was distilled off under reduced pressure to obtain a curable multi-branched polymer (RHB-6). The OH value of the curable multi-branched polymer (RHB-5) was 102 mgKOH / g, and the conversion rate from the reactive hydroxyl group to the curable reactive group was 80 mol%.

Synthesis example 7: Synthesis | combination of curable multibranched polymer (RHB-7) The following compound A0.1 mol was prepared to the flask as a compound used as a base nucleus, and it heated at temperature 120 degreeC, replacing nitrogen with stirring. To this, 0.9 mol of Compound B and 0.01 mol of p-toluenesulfonic acid were added as branched chain extending compounds, and reacted at a temperature of 140 ° C. for 2 hours while removing generated water. Furthermore, after making it react for 1 hour, depressurizing at 2.0 kPa of decompression, 0.4 mol of acetic acid was added and reacted for 2 hours. The obtained reaction product {multi-branched polymer (HB-4)} was cooled and dissolved in tetrahydrofuran to obtain a 30% by mass mixture. The OH value of HB-4 was 320 mgKOH / g.

  To the mixture containing the multi-branched polymer (HB-4), 0.85 mol of Compound C was added and stirred at a temperature of 40 ° C. for 4 hours, and then a 50 mass% aqueous formic acid solution was added and stirred for 1 hour. The precipitated insoluble material was filtered and poured into water. The precipitate was extracted with ethyl acetate, washed thoroughly with alkaline water, and dried over magnesium sulfate. Ethyl acetate was distilled off under reduced pressure to obtain a curable multi-branched polymer (RHB-8). The OH value of the curable multi-branched polymer (RHB-8) was 96 mgKOH / g, and the conversion rate from the reactive hydroxyl group to the curable reactive group was 70 mol%.

Synthesis Example 8: Synthesis of curable multi-branched polymer (RHB-8) A curable multi-branched polymer (RHB-8) was prepared in the same manner as in Synthetic Example 1 except that the reaction was terminated when the produced water reached 0.45 ml. Got. The OH value of the curable multi-branched polymer (RHB-8) was 485 mgKOH / g, and the conversion rate from the reactive hydroxyl group to the curable reactive group was 5 mol%.

Synthesis Example 9: Synthesis of curable multi-branched polymer (RHB-9) A curable multi-branched polymer (RHB-9) was prepared in the same manner as in Synthetic Example 1 except that the reaction was terminated when the water produced reached 8.55 ml. Got. The OH value of the curable multi-branched polymer (RHB-9) was 26 mgKOH / g, and the conversion rate from the reactive hydroxyl group to the curable reactive group was 95 mol%.

Synthesis Example 10: Synthesis of curable multi-branched polymer (RHB-10) A curable multi-branched polymer (RHB-10) was prepared in the same manner as in Synthetic Example 1 except that the reaction was terminated when the produced water reached 9.0 ml. Got. The OH value of the curable multi-branched polymer (RHB-10) could not be detected, and the hydroxyl group that was a reactive group was completely converted to a curable reactive group.

  Preparation of coating solution for hard coat layer

The hard coat layer coating solutions HC-1 to HC-8 were prepared by filtering each well mixed solution through a polypropylene filter having a pore size of 30 μm according to Table 2 above. The numbers in the table mean parts by mass. The notations in the table are as follows.
DPHA: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate [manufactured by Nippon Kayaku Co., Ltd.]
“MEK-ST”: silica sol, average particle size 15 nm, solid content concentration 30% by mass, “SX-350HL” manufactured by Nissan Chemical Co., Ltd .: average particle size 3.5 μm crosslinked acrylic-styrene particles (refractive index 1.55) 30% by weight MiBK dispersion, manufactured by Soken Chemical Co., Ltd. "MX-600" used after dispersion at 10,000 rpm for 20 minutes in a Polytron disperser: Cross-linked polymethyl methacrylate particles having an average particle size of 6.0 μm (refractive index 1.49), 30% by mass MiBK dispersion, manufactured by Soken Chemical Co., Ltd. . Used after dispersion for 20 minutes at 10,000 rpm in a Polytron disperser
Irg.907: Polymerization initiator [Ciba Specialty Chemicals Co., Ltd.]
b-14 salt compound of p-toluenesulfonic acid: As an organic base of p-toluenesulfonic acid, b-14 (N-methylmorpholine) in Table 3 described in the section of [curing accelerator] in the text was combined. thing.

(1) Coating of hard coat layer A triacetyl cellulose film (Fujitac TDY80UL, manufactured by Fuji Photo Film Co., Ltd., Re = 2 nm, Rth = 48 nm) having a thickness of 80 μm is unwound in a roll form and described in FIG. The coating liquid HC-1 to HC-23 for hard coat layer is applied by the die coating method shown in the following coating conditions and the following coating conditions, dried at 30 ° C. for 15 seconds and 90 ° C. for 20 seconds, and further under nitrogen purge Using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), the coating layer was cured by irradiating with an ultraviolet ray with an irradiation amount of 60 mJ / cm ² to form a hard coat layer having the thickness shown in Table 1. After forming and winding, hard coat films HCL-1 to HCL-23 were prepared. However, when preparing HCL-13 and HCL-15, instead of drying at 30 ° C. for 15 seconds and 90 ° C. for 20 seconds, they were dried at 120 ° C. for 150 seconds and further dried at 100 ° C. for 8 minutes. In preparing HCL-14, instead of drying at 30 ° C. for 15 seconds and 90 ° C. for 20 seconds, drying was performed at 120 ° C. for 150 seconds, followed by further drying at 100 ° C. for 1 minute.

Basic conditions: The slot die 13 has an upstream lip land length I _UP of 0.5 mm, a downstream lip land length I _LO of 50 μm, a length of the opening of the slot 16 in the web running direction of 150 μm, and a length of the slot 16 The one with a length of 50 mm was used. The gap between the upstream lip land 18a and the web W was made 50 μm longer than the gap between the downstream lip land 18b and the web W, and the gap _GL between the downstream lip land 18b and the web W was set to 70 μm. Further, the gap _{G B} between the gap _{G S,} and the back plate 40a and the web W between the side plate 40b and the web W in the vacuum chamber 40 were both 200 [mu] m. Application was performed at an application rate of 30 m / min and an application amount of 30.0 ml / m ² . The application width was 1300 mm and the effective width was 1280 mm.

Evaluation of Hard Coat Film The following evaluation was performed on the prepared hard coat films HCL-1 to HCL-23.

(Evaluation of point defects)
After the back surface of each film was painted black with magic ink or the like, the number of bright spot defects on the coating film was visually determined. The size of the bright spot defect that can be visually observed is 50 μm or more. Bright spot defects were counted by the average number of point defects per 1 m ² when observed at 20 m ² . When 2 or more were observed per 1 m ^2, it was marked with ×, and when less than 2 were observed, it was marked with ○.

(Pencil hardness evaluation)
The hardness of the antireflection film of the present invention was evaluated by a pencil hardness test according to JIS K-5400. When the pencil hardness was 2H or less, x was marked when it was 3H or more, and ◎ when it was 4H or more.

[Curl evaluation]
The curl is measured using the curl measurement template of Method A in “Measuring Method of Curling of Photographic Film” of JIS K-7619-1988.
The curl size of the film after conditioning for 10 hours under the conditions of 25 ° C. and 60% RH is expressed by the following formula (6).
Formula (6): Curl = 1 / R
R represents a radius of curvature (m).
Here, the curl “+” means a curl in which the coating side of the film is inside the curve, and “−” means a curl in which the coating side is outside the curve.
In the present invention, when the curl is expressed by the following formula (6), the value is ◯ when it is within the range of −7 to +7, and × when it is not.

[Integral reflectance evaluation]
An adapter ILV-471 is attached to a spectrophotometer V-550 (manufactured by JASCO Corporation), and the integrated reflectance at an incident angle of 5 degrees is measured in a wavelength range of 380 to 780 nm, and an average reflection of 450 to 650 nm. The rate was calculated. When the integrated reflectance is 3% or less, the antireflection effect is remarkable, which is preferable.

[Evaluation of brittleness (cracking resistance)]
A film sample is cut into 35 mm x 120 mm, left at a temperature of 25 ° C and a relative humidity of 60% for 2 hours, and then measured for the diameter of curvature at which cracks start to occur when rolled up into a cylindrical shape to evaluate surface cracks. can do.
The crack resistance of the film of the present invention is preferably 50 mm or less, more preferably 40 mm or less (◯), and the curvature diameter at which cracking occurs when the coating layer side is rolled outward. The thickness is most preferably 30 mm or less (◎). A level of △ or higher was regarded as acceptable.

  The evaluation results are shown in Table 1. The hard coat film of the present invention is preferable because of good film hardness, curl and brittleness. A prescription in which silica sol is added is preferable because brittleness is particularly improved. Surprisingly, it can also be seen that the hard coat film in which the light-transmitting resin fine particles are added to the formulation containing the curable multi-branched polymer (RHB) of the present invention shows a good point defect. The reason for this is not clear, but it is expected that the dispersibility of the translucent fine particles is improved by using the curable multi-branched polymer of the present invention. Further, the hard coat film of the present invention is preferable because the film hardness can be secured even when the film thickness is reduced, and conversely, curl and brittleness are within the allowable range even when the film thickness is increased.

[Preparation of coating solution for low refractive index layer]
[Preparation of Sol Solution (b-1)]
In a reactor equipped with a stirrer and a reflux condenser, 119 parts by mass of methyl ethyl ketone, 3-acryloyloxypropyltrimethoxysilane “KBM-5103” {manufactured by Shin-Etsu Chemical Co., Ltd.} 101 parts by mass, diisopropoxyaluminum ethylacetate After adding 3 parts by mass of acetate and mixing, 30 parts by mass of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain a sol solution (b-1).

  The mass average molecular weight of the sol liquid (b-1) was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100% by mass. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

  The low refractive index layer coating liquids LN-1 to LN-26 were adjusted according to Table 2 above. The numbers in the table are parts of mass. In addition, the b-14 salt compound of p-toluenesulfonic acid in the table represents a salt (curing catalyst) composed of the acid and the organic base described above.

The compounds used for the preparation of each of the above coating solutions are shown below.
“JTA-113”: Thermally crosslinkable silicone-containing fluorine-containing polymer solution, refractive index 1.44, solid content concentration 6% by mass, solvent methyl ethyl ketone, solid-containing fluorine-containing silicone-containing fluorine-containing solution 78% by mass of polymer, 20% by mass of melamine-based crosslinking agent, 2% by mass of paratoluene sulfonate, manufactured by JSR Corporation,
“P-3”: fluorine-containing copolymer (P-3) described in JP-A No. 2004-45462, mass average molecular weight of about 50000, solid content concentration of 23.8% by mass, solvent methyl ethyl ketone,
“MEK-ST-L”: Silica particle dispersion, average particle size 45 nm, solid content concentration 30% by mass, dispersion solvent methyl ethyl ketone, manufactured by Nissan Chemical Co., Ltd.
Hollow silica dispersion: CS-60 IPA (Catalyst Chemical Industries, Ltd.) Refractive index 1.31, average particle size 60 nm, shell thickness 10 nm, solid content concentration 18.2% “KBM-5103” surface modified hollow silica sol (surface (Modification rate vs. 30% silica by mass)
“1C-1 compound solution”: solid content concentration 2 mass%, solvent methyl ethyl ketone,
“MP-triazine”: photopolymerization initiator, manufactured by Sanwa Chemical Co., Ltd.
“RMS-033”: Reactive silicone resin, manufactured by Gelest.

  Each of the above coating liquids is filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a low refractive index layer coating liquid. The low refractive index layer is coated on the hard coat film shown in Table 3 under the following conditions to reflect The prevention films LR-1 to LR-26 were completed.

(2) Coating of low refractive index layer The specified hard coat film described in Table 3 was unwound again, and the coating solution for low refractive index layer was applied under the following basic conditions, followed by drying at 120 ° C for 150 seconds. Then, after further drying at 100 ° C. for 8 minutes, an irradiation amount of 300 mJ / cm using a 240 W / cm air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) in an atmosphere with an oxygen concentration of 0.1% by nitrogen purge. ² was irradiated to form a low refractive index layer having a thickness of 95 nm and wound up to prepare antireflection films LR-1 to LR-26. However, when preparing LR-5, after drying at 120 ° C. for 150 seconds, further drying at 100 ° C. for 8 minutes was performed at 30 ° C. for 15 seconds and at 90 ° C. for 20 seconds.

Basic conditions: The slot die 13 has an upstream lip land length I _UP of 0.5 mm, a downstream lip land length I _LO of 50 μm, a length of the opening of the slot 16 in the web running direction of 150 μm, and a length of the slot 16 The one with a length of 50 mm was used. The gap between the upstream lip land 18a and the web W was made 50 μm longer than the gap between the downstream lip land 18b and the web W, and the gap _GL between the downstream lip land 18b and the web W was set to 50 μm. Further, the gap _{G B} between the gap _{G S,} and the back plate 40a and the web W between the side plate 40b and the web W in the vacuum chamber 40 were both 200 [mu] m. Application was performed at an application rate of 30 m / min and an application amount of 5.0 ml / m ² . The application width was 1300 mm and the effective width was 1280 mm.

Evaluation of antireflection film About the created antireflection films LR-1 to LR-22, the same evaluation as the contents performed in the evaluation of the hard coat film and the following evaluation were performed.
(Steel wool scratch resistance evaluation)
Using a “rubbing tester”, a rubbing test was performed under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH.
Rubbing material: steel wool {made by Nippon Steel Wool Co., Ltd. 0000} is wound around the rubbing tip (1 cm × 1 cm) of a tester that comes into contact with the sample, and the band is fixed.
Travel distance (one way): 13 cm.
Rubbing speed: 13 cm / sec.
Load: 500 g / cm ²
Tip contact area: 1 cm × 1 cm.
Number of rubbing: 10 round trips.
Oil-based black ink was applied to the back side of the rubbed sample, the scratches on the rubbed portion were visually observed with reflected light, and the number of scratches on the rubbed portion was evaluated according to the following criteria.
A: Scratches are not observed at all.
○: 3 or less fine scratches are observed.
Δ: Within 10 scratches are observed.
X: The grade more than (circle) in which 10 or more cracks are recognized was set as the pass.

  The evaluation results are shown in Table 3. From the results of Table 3, the antireflection film of the present invention is preferable because of good film hardness, curl and brittleness. Furthermore, it is an excellent antireflection film by laminating a low refractive index layer. Surprisingly, it can be seen that the antireflection film of the present invention is superior in scratch resistance as compared with the antireflection film of the comparative example. The reason for this is not clear, but it is expected that the remaining reactive group (a) of the curable multibranched polymer (RHB) contributes to interfacial adhesion with the low refractive index layer.

Claims (16)

A cured film characterized in that a hard coat layer is formed by coating and curing a coating composition containing the following (A) and (B) on a transparent support.
(A) Curability in which a photocurable reactive group and / or a thermosetting reactive group are bonded to 10 mol% to 90 mol% of the reactive group (a) present at the branched end of the multi-branched polymer (HB). Multi-branched polymer (RHB)
(B) At least one of a curing agent and a curing accelerator   The multi-branched polymer (HB) is centered on a polyvalent group nucleus bonded to two or more branched chain extension units, and the group nucleus contains a reactive group (a) for forming a linking group. A reactive group (a) having at least two reactive groups (b) in which the branched chain extension unit is chemically bonded to the reactive group (a) to form a linking group. The cured film according to claim 1, wherein the cured film is formed by a chemical bond between the branched chain extending compound having at least two or more and the base nucleus.   The cured film according to claim 2, wherein the branched chain extension unit contains at least one ring structure selected from an alicyclic ring and an aryl ring, and an alkylene chain structure.   The curable reactive group of the curable multi-branched polymer (RHB) contains at least one polymerizable group selected from a radical polymerizable group, a cationic polymerizable group, and a hydrolyzable group-substituted silyl group. The cured film as described in any one of -3.   The cured film is a cured film formed by applying and curing a curable composition containing a polymerizable compound copolymerizable with a curable reactive group of a curable hyperbranched polymer (RHB). Item 5. The cured film according to any one of Items 1 to 4.   A cured film is formed by applying and curing a curable composition containing a polymerizable compound copolymerizable with the remaining reactive group (a) of the curable multi-branched polymer (RHB) and a polymerization initiator. The cured film according to claim 1, which is a cured film.   Reactive group (a) is a hydroxyl group, The cured film as described in any one of Claims 1-6 characterized by the above-mentioned.   The cured film according to claim 1, wherein the hard coat layer contains at least one kind of translucent resin fine particles having an average particle diameter of 0.5 to 10 μm.   The cured film according to any one of claims 1 to 8, wherein after forming the hard coat layer, one or more optical functional layers having a refractive index different from that of the hard coat layer are further laminated.   The cured film according to claim 1, wherein the uppermost layer of the optical functional layer is a low refractive index layer having a lower refractive index than other optical functional layers.   The low refractive index layer has at least hollow inorganic fine particles having an average particle diameter of 30 to 100% of the thickness of the low refractive index layer and a refractive index of 1.17 to 1.37. The cured film of Claim 10 containing 1 type.   The cured film as described in any one of Claims 1-11 has an antireflection function, The antireflection film characterized by the above-mentioned.   A polarizing plate comprising the cured film according to claim 1 or the antireflection film according to claim 12 provided on at least one of the protective films of the polarizing film.   The cured film according to claim 1 or the antireflection film according to claim 12 is provided on one of the protective films of the polarizing film, and an optical compensation film having optical anisotropy is provided on the other of the protective films of the polarizing film. A polarizing plate provided.   The cured film according to claim 1, the antireflection film according to claim 12, or the polarizing plate according to claim 13 or 14 is disposed on an image display surface. Image display device.   16. The image display device according to claim 15, wherein the image display device is a transmissive, reflective, or transflective liquid crystal display device in any one of TN, STN, IPS, VA, and OCB modes.