JP5529320B2 - Hard coat layer forming composition, hard coat film, optical element and image display device - Google Patents

Description

  The present invention relates to a composition for forming a hard coat layer, a hard coat film, an optical element, and an image display device.

  Along with the advancement of technology in recent years, in addition to the conventional CRT (Cathode Ray Tube), liquid crystal displays (LCD), plasma displays (PDP), electroluminescent displays (ELD), etc. have been developed and put into practical use. ing. Among these, LCDs have been expanded from notebook personal computers and monitors to televisions due to technological innovations such as high viewing angles, high definition, high speed response, and color reproducibility. There are various uses. The basic structure of an LCD is that a glass substrate on a flat plate, each with a transparent electrode, is placed oppositely through a spacer so as to form a gap with a constant interval, and a liquid crystal material is injected between the glass substrates and sealed. The liquid crystal cell is further provided with polarizing plates on the outer surfaces of the pair of glass substrates. Conventionally, a cover plate made of glass or plastic is attached to the surface of the liquid crystal cell to prevent damage to the polarizing plate attached to the surface of the liquid crystal cell. However, when a cover plate is attached, it is disadvantageous in terms of cost and weight, and a hard coat treatment is gradually applied to the polarizing plate surface.

  In the hard coat treatment, a hard coat film in which a hard coat layer is formed on one side or both sides of a transparent plastic film substrate is generally used. The hard coat layer is usually formed using a hard coat layer forming composition such as a thermosetting resin or an ultraviolet curable resin.

  Hard coat films are required to have improved scratch resistance and antifouling properties. Therefore, in order to improve the scratch resistance and antifouling property of the hard coat layer, a hard coat layer using a curable composition containing a compound having either a fluorine atom or a silicon atom has been proposed. (For example, refer to Patent Document 1). It has also been proposed to add a silicon compound or fluorine compound to the hard coat layer so that the abundance ratio of silicon atoms or fluorine atoms on the outermost surface of the hard coat layer is within a specific range (for example, Patent Document 2). reference). However, as LCD applications are diversified, diversification of the chances of scratching or soiling the surface is also envisaged. With the diversification of the applications, there is a need for higher levels of scratch resistance and antifouling properties and to maintain these properties.

JP 2003-335984 A JP 2007-264281 A

  Accordingly, an object of the present invention is to provide a composition for forming a hard coat layer that has a sufficient hardness, is excellent in scratch resistance, and can provide a hard coat layer that is also excellent in antifouling property. . Furthermore, an object of the present invention is to provide a hard coat film having sufficient hardness, excellent scratch resistance, and excellent antifouling properties, an optical element using the hard coat film, and an image display device.

In order to achieve the above object, the composition for forming a hard coat layer of the present invention comprises:
A hard coat layer forming composition used for forming a hard coat layer,
The following (A) component, (B) component, (C) component, and (D) component are included, It is characterized by the above-mentioned.
(A) component: curable compound having at least one of acrylate group and methacrylate group (B) component: inorganic oxide particle surface is modified with an organic compound containing a polymerizable unsaturated group, and the weight average particle size (C) component: reactive fluorine compound (D) component: reactive silicon compound having a particle size of 200 nm or less

  The hard coat film of the present invention is a hard coat film having a hard coat layer on at least one surface of a transparent plastic film substrate, wherein the hard coat layer is formed from the hard coat layer forming composition of the present invention. It is formed.

  The optical element of the present invention is characterized in that the hard coat film of the present invention is laminated on at least one surface of an optical member.

  The image display device of the present invention comprises the hard coat film of the present invention or the optical element of the present invention.

  The hard coat film of the present invention formed from the composition for forming a hard coat layer of the present invention combines the functions of the four components, has sufficient hardness, has excellent scratch resistance, and is resistant to damage. Excellent soiling. According to the hard coat film of the present invention, it is difficult for dirt to adhere to the surface over a long period of time, and even if dirt is attached, the dirt can be easily wiped off. Since the hard coat film of the present invention is excellent in scratch resistance, it is difficult to be scratched even during the wiping. Therefore, the optical element and image display apparatus using the hard coat film of the present invention can maintain good characteristics.

FIG. 1 is a schematic cross-sectional view showing an example of the hard coat film of the present invention.

In the composition for forming a hard coat layer of the present invention, the component (C) may have, for example, a structure represented by the following general formula (1). In the following general formula (1), at least one R is a substituent having a fluoroalkyl group, and at least one R is a substituent having at least one of an acrylate group and a methacrylate group.

In the composition for forming a hard coat layer of the present invention, in R of the general formula (1), the substituent having the fluoroalkyl group may have, for example, a structure represented by the following general formula (2). Good. The structure represented by the following general formula (2) has a perfluoropolyether unit (—CF ₂ —CF ₂ — (O—CF ₂ —CF ₂ —CF ₂ ) _n —O—CF ₂ —CF at its end. ₃ ). In the perfluoropolyether unit, n is an integer of 1 or more.

In the composition for forming a hard coat layer of the present invention, in R of the general formula (1), the substituent having the acrylate group may have a substituent represented by the following general formula (3), for example. Good.

  The component (C) is represented by the general formula (1), and R in the general formula (1) has one substituent having a fluoroalkyl group having a structure represented by the general formula (2). And having two substituents having an acrylate group having a structure represented by the general formula (3).

In the composition for forming a hard coat layer of the present invention, the component (D) may have, for example, a structure represented by the following general formula (4). In the following general formula (4), R is a substituent selected from a substituent having a siloxane structure, a substituent having at least one of an acrylate group and a methacrylate group, and a substituent having an active hydrogen group. May be the same or different.

In the composition for forming a hard coat layer of the present invention, the component (D) may have, for example, a structure represented by the following general formula (9). Let the structure represented by following General formula (9) be 6-isocyanate hexyl isocyanuric acid unit (a).

In the composition for forming a hard coat layer of the present invention, in R of the general formula (4), the substituent having the siloxane structure may have, for example, a structure represented by the following general formula (5). . The structure represented by the following general formula (5) has a polydimethylsiloxane unit (c) at its end, and the unit (c) is bonded to a methylhydroxypropylsiloxane unit (b), In the unit (b), the hydroxy group is urethane-bonded to the terminal isocyanate group of 6-isocyanatohexylisocyanuric acid which is a part of the unit (a). In the polydimethylsiloxane unit (c), n is an integer of 1 or more, preferably 1-7.

In the composition for forming a hard coat layer of the present invention, in R of the general formula (4), the substituent having the active hydrogen group has, for example, a substituent represented by the following general formula (6). Also good. In the substituent represented by the general formula (6), the terminal isocyanate group of 6-isocyanatohexyl isocyanuric acid which is a part of the unit (a) is a carboxyl group. In the substituent represented by the general formula (6), the carboxyl group may be decarboxylated into an amino group.

In the composition for forming a hard coat layer of the present invention, in R of the general formula (4), the substituent having the acrylate group may have a structure represented by the following general formula (7), for example. . The structure represented by the general formula (7) has an aliphatic polyester unit (d) having an acrylate group at the terminal, and the unit (d) is a part of the unit (a). It is urethane-bonded to the terminal isocyanate group of hexyl isocyanuric acid. In the general formula (7), m and n are each an integer of 1 to 10, and may be the same or different. l is an integer of 1-5.

  The 6-isocyanate containing the component (D) containing the unit (a) having the structure represented by the general formula (9) and the substituents represented by the general formulas (5) to (7) In the case of a derivative of xylisocyanuric acid, the component ratio (molar ratio) of the unit (a): the unit (b): the unit (c): the unit (d) is 100 when the unit (a) is 100. The unit (b) is, for example, in the range of 1-80, preferably in the range of 1-60, and the unit (c) is, for example, in the range of 10-400, preferably 10 The unit (d) is, for example, in the range of 1 to 100, and preferably in the range of 5 to 50.

In the present invention, the ratio (molar ratio) of each component (unit) of the component (D) can be determined from, for example, an integral curve of ¹ H-NMR spectrum. The weight average molecular weight (Mw) of the said (D) component is the range of 500-150,000, for example, Preferably, it is the range of 2000-100000. The weight average molecular weight (Mw) can be measured by, for example, a gel permeation chromatograph (GPC) method.

  It is preferable to use a compound having a structure represented by the general formula (1) as the component (C) and a compound having a structure represented by the general formula (4) as the component (D). . By using a compound having a similar structure, it is presumed that the respective functions are easily expressed in the hard coat layer formed, but the present invention is not limited by this presumption.

  In the composition for forming a hard coat layer of the present invention, the weight average particle size of the component (B) is from 1 to 2 in terms of prevention of light scattering, prevention of transmittance reduction of the hard coat layer, prevention of coloring, transparency, and the like. A range of 100 nm is preferable. The said weight average particle diameter can be measured by the method as described in the below-mentioned Example, for example.

  In the composition for forming a hard coat layer of the present invention, examples of the component (B) include fine particles such as titanium oxide, silicon oxide, aluminum oxide, zinc oxide, tin oxide, and zirconium oxide. Among these, fine particles of titanium oxide, silicon oxide (silica), aluminum oxide, zinc oxide, tin oxide, and zirconium oxide are preferable. These may be used alone or in combination of two or more.

  In the composition for forming a hard coat layer of the present invention, the component (B) is preferably blended in the range of 100 to 200 parts by weight with respect to 100 parts by weight of the component (A).

  In the composition for forming a hard coat layer of the present invention, the component (C) is blended in the range of 0.05 to 0.4 parts by weight with respect to 100 parts by weight of the component (A), and the component (D). It is preferable that the component is blended in the range of 0.05 to 1 part by weight.

前記式（８）において、ｍおよびｎは、それぞれ、１以上の整数であり、同一でも異なっていてもよい。 It is preferable that the composition for forming a hard coat layer of the present invention further includes the following component (E).
(E) Component: Glycol compound represented by the following general formula (8)

In the formula (8), m and n are each an integer of 1 or more, and may be the same or different.

  In the composition for forming a hard coat layer of the present invention, the component (C) is blended in the range of 0.05 to 0.4 parts by weight with respect to 100 parts by weight of the component (A), and the component (D). It is preferable that the component and the component (E) are blended in a range of 0.1 to 1 part by weight in total.

  In the hard coat film of the present invention, the outermost layer of the hard coat layer has a fluorine atom intensity derived from a reactive fluorine compound in a range of 5 to 30% in an analysis by ESCA (Electron Spectroscopy for Chemical Analysis), And it is preferable that the silicon atom intensity | strength derived from a reactive silicon compound exists in the range of 0.2 to 10%. Within this range, both scratch resistance and antifouling properties can be achieved better.

  By the way, the addition amount of the reactive fluorine compound or the reactive silicon compound and the respective atomic strengths in the outermost layer tend not to coincide with each other or to have a proportional relationship. For example, even when a hard coat layer is formed using a hard coat layer forming composition having the same composition, when the thickness of the hard coat layer is different, the atomic strengths in the outermost layer are not the same. There is also. Therefore, when trying to obtain a hard coat film having better characteristics using the composition for forming a hard coat layer of the present invention, it is effective to perform characteristic evaluation focusing on each atomic strength.

  The fluorine atom intensity is more preferably in the range of 10 to 30%, and still more preferably in the range of 15 to 30%. The silicon atom intensity is more preferably in the range of 0.2 to 8%, and still more preferably in the range of 0.2 to 6%.

  In the hard coat film of the present invention, the thickness of the hard coat layer is not particularly limited, and an optimum thickness can be set according to the thickness of the transparent plastic film substrate, etc., for example, 12 to 50 μm It is a range. By setting the thickness in the above range, it is possible to more effectively prevent curling and folding of the hard coat film without causing a decrease in hardness. The thickness is more preferably in the range of 14 to 25 μm, and still more preferably in the range of 14 to 18 μm.

  In the hard coat film of the present invention, it is preferable that the pencil hardness of the hard coat layer surface with a weight of 500 g according to JIS K 5600-5-4 is 4H or more.

In the hard coat film of the present invention, the surface free energy on the surface of the hard coat layer is preferably in the range of 15 to 25 mJ / m ² . The surface free energy refers to a value calculated by calculation of two components of water / hexadecane according to Kaelble Uy theory. The surface free energy is more preferably in the range of 15~22mJ / ^{m 2,} further preferably in the range of 15~20mJ / ^{m 2.} The surface free energy value is calculated from the contact angle measured for each of water and hexadecane, and can be calculated automatically using the “Fully Automatic Contact Angle Meter DM700” manufactured by Kyowa Interface Science Co., Ltd.

  In the hard coat film of the present invention, it is preferable that the hard coat layer further contains fine particles.

  Next, the present invention will be described in detail. However, the present invention is not limited to the following description.

  The hard coat film of the present invention has a hard coat layer on one side or both sides of a transparent plastic film substrate.

  The transparent plastic film substrate is not particularly limited, but preferably has a visible light transmittance (preferably a light transmittance of 90% or more) and a transparency (preferably a haze value of 1% or less). For example, the transparent plastic film base material of Unexamined-Japanese-Patent No. 2008-90263 is mention | raise | lifted. As the transparent plastic film substrate, those having a small optical birefringence are preferably used. The hard coat film of the present invention can also be used for a polarizing plate as a protective film, for example. In this case, as the transparent plastic film substrate, triacetyl cellulose (TAC), polycarbonate, acrylic polymer, cyclic A film formed from a polyolefin having a norbornene structure or the like is preferable. In the present invention, the transparent plastic film substrate may be a polarizer itself. With such a configuration, a protective layer made of TAC or the like is not required, and the structure of the polarizing plate can be simplified. Therefore, the number of manufacturing steps of the polarizing plate or the image display device can be reduced, and the production efficiency can be improved. Moreover, if it is such a structure, a polarizing plate can be made thinner. In addition, when the said transparent plastic film base material is a polarizer, the said hard-coat layer will play the role as the conventional protective layer. Moreover, if it is such a structure, a hard coat film will serve as a cover plate with which the liquid crystal cell surface is mounted | worn.

  In the present invention, the thickness of the transparent plastic film substrate is not particularly limited. The thickness is preferably in the range of 10 to 500 μm, more preferably in the range of 20 to 300 μm, and most preferably 30 in consideration of, for example, workability such as strength and handleability and thin layer properties. It is in the range of ~ 200 μm. The refractive index of the transparent plastic film substrate is not particularly limited. The refractive index is, for example, in the range of 1.30 to 1.80, and preferably in the range of 1.40 to 1.70.

  The hard coat layer is formed using a hard coat layer forming composition containing the component (A), the component (B), the component (C), and the component (D).

  As said (A) component, the curable compound which has at least one group of the acrylate group and methacrylate group which harden | cure with a heat | fever, light (ultraviolet rays etc.) or an electron beam can be used, for example. Examples of the component (A) include acrylates of polyfunctional compounds such as silicone resins, polyester resins, polyether resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, and polyhydric alcohols. And oligomers or prepolymers such as methacrylate and the like. These may be used alone or in combination of two or more.

  As said (A) component, the reactive diluent which has at least one group of an acrylate group and a methacrylate group can also be used, for example. Examples of the reactive diluent include monofunctional acrylate, monofunctional methacrylate, polyfunctional acrylate, and polyfunctional methacrylate. Examples of the monofunctional acrylate include ethylene oxide-modified phenol acrylate, propylene oxide-modified phenol acrylate, ethylene oxide-modified nonylphenol acrylate, propylene oxide-modified nonylphenol acrylate, 2-ethylhexyl carbitol acrylate, isobornyl acrylate, Tetrahydrofurfuryl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyhexyl acrylate, diethylene glycol monoacrylate, triethylene glycol monoacrylate, tripropylene glycol monoacrylate and the like are included. Examples of the monofunctional methacrylate include ethylene oxide-modified phenol methacrylate, propylene oxide-modified phenol methacrylate, ethylene oxide-modified nonylphenol methacrylate, propylene oxide-modified nonylphenol methacrylate, 2-ethylhexyl carbitol methacrylate, isobornyl methacrylate, Tetrahydrofurfuryl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyhexyl methacrylate, diethylene glycol monomethacrylate, triethylene glycol monomethacrylate, tripropylene glycol monomethacrylate and the like are included. Examples of the polyfunctional acrylate include diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol diacrylate, 1,4-butanediol diacrylate, Neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, ethylene oxide modified neopentyl glycol diacrylate, ethylene oxide modified bisphenol A diacrylate, propylene oxide modified bisphenol A diacrylate, ethylene oxide modified hydrogenated bisphenol A Diacrylate, trimethylolpropane diacrylate, trimethyl Propane allyl ether diacrylate, trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane triacrylate, propylene oxide modified trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc. Including. Examples of the polyfunctional methacrylate include diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, Neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene oxide modified neopentyl glycol dimethacrylate, ethylene oxide modified bisphenol A dimethacrylate, propylene oxide modified bisphenol A dimethacrylate, ethylene oxide modified hydrogenated bisphenol A Dimethacrylate, trimethylol pro Dimethacrylate, trimethylolpropane allyl ether dimethacrylate, trimethylolpropane trimethacrylate, ethylene oxide modified trimethylolpropane trimethacrylate, propylene oxide modified trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexa Including methacrylate. The reactive diluent is preferably a trifunctional or higher acrylate or a trifunctional or higher methacrylate. This is because the hardness of the hard coat layer can be further improved. Examples of the component (A) include butanediol glycerin ether diacrylate, isocyanuric acid acrylate, isocyanuric acid methacrylate, and the like. As the component (A), one type may be used alone, or two or more types may be used in combination.

  The component (B) is as described above. In the component (B), examples of the inorganic oxide particles include fine particles such as silicon oxide (silica), titanium oxide, aluminum oxide, zinc oxide, tin oxide, and zirconium oxide. Among these, fine particles of silicon oxide (silica), titanium oxide, aluminum oxide, zinc oxide, tin oxide, and zirconium oxide are preferable. These may be used alone or in combination of two or more.

  In the composition for forming a hard coat layer of the present invention, the component (B) has a weight average particle diameter of 200 nm or less from the viewpoints of preventing light scattering, preventing the transmittance of the hard coat layer from being lowered, preventing coloring, and transparency. These are so-called nanoparticles. The said weight average particle diameter can be measured by the method as described in the below-mentioned Example, for example. The weight average particle diameter is preferably in the range of 1 nm to 100 nm.

  In the component (B), the inorganic oxide particles are bonded (surface modified) with an organic compound containing a polymerizable unsaturated group. The polymerizable unsaturated group is reactively cured with the component (A), thereby improving the hardness of the hard coat layer. As the polymerizable unsaturated group, for example, acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, maleate group, and acrylamide group are preferable. The organic compound containing a polymerizable unsaturated group is preferably a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis. It is also preferable that the organic compound containing a polymerizable unsaturated group has a photosensitive group.

  The blending amount of the component (B) is preferably in the range of 100 to 200 parts by weight with respect to 100 parts by weight of the component (A). By setting the blending amount of the component (B) to 100 parts by weight or more, curling and folding of the hard coat film can be more effectively prevented, and by setting it to 200 parts by weight or less, scratch resistance and pencil Hardness can be made high. The blending amount of the component (B) is more preferably in the range of 120 to 180 parts by weight with respect to 100 parts by weight of the component (A).

  By adjusting the blending amount of the component (B), for example, the refractive index of the hard coat layer can be adjusted. From the viewpoint of preventing interference fringes generated at the interface between the transparent plastic film substrate and the hard coat layer, it is preferable to reduce the refractive index difference between the transparent plastic film substrate and the hard coat layer. The interference fringes are a phenomenon in which reflected light of external light incident on the hard coat film exhibits a rainbow hue. Recently, in offices and the like, three-wavelength fluorescent lamps having excellent clarity are frequently used. The interference fringes appear prominently under the three-wavelength fluorescent lamp. From these points, in preparing the hard coat layer-forming composition, it is preferable to adjust the blending amount of the component (B) so that the refractive index difference is small.

  The refractive index difference is preferably 0.04 or less, and more preferably 0.02 or less. Specifically, for example, when a PET film (refractive index: about 1.64) is used as the transparent plastic film substrate, titanium oxide is used as the component (B), which is used as the hard coat layer forming composition. By blending about 30 to 40% by weight with respect to the entire resin component in the product, the refractive index difference can be controlled to 0.02 or less, and the occurrence of interference fringes can be suppressed. For example, when a TAC film (refractive index: about 1.48) is used as the transparent plastic film substrate, silicon oxide (silica) is used as the component (B), and this is used as the composition for forming the hard coat layer. By blending about 35 to 45% by weight with respect to the entire resin component in the product, the refractive index difference can be controlled to 0.02 or less, and the occurrence of interference fringes can be suppressed.

  The component (C) and the component (D) are as described above. By using the component (C), the surface free energy value of the obtained hard coat layer is lowered, and the antifouling property of the hard coat layer is improved. On the other hand, when the compounding amount of the component (C) is excessive, the scratch resistance of the obtained hard coat layer tends to be lowered. Further, by using the component (D), for example, the hard coat layer surface structure to be formed becomes rigid and the slipping property is improved, so that the scratch resistance is excellent. On the other hand, when the compounding amount of the component (D) becomes excessive, the antifouling property of the obtained hard coat layer tends to be lowered. From these points, the blending ratio of the component (C) and the component (D) is in the range of 0.05 to 0.4 parts by weight of the component (C) with respect to 100 parts by weight of the component (A). And the component (D) is preferably in the range of 0.05 to 1.0 part by weight, more preferably the component (C) is in the range of 0.1 to 0.3 part by weight. And the component (D) is in the range of 0.2 to 1.0 part by weight.

  The hard coat film of the present invention is prepared, for example, by preparing a hard coat layer forming composition in which the four components are dissolved or dispersed in a solvent, and the hard coat layer forming composition is at least one of the transparent plastic film substrates. It can be manufactured by forming a coating film by coating on the surface, and curing the coating film to form the hard coat layer.

  The solvent is not particularly limited. Examples of the solvent include dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, acetone, methyl ethyl ketone (MEK). , Diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, ethyl formate, propyl formate, n-pentyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, n-pentyl acetate, Acetylacetone, diacetone alcohol, methyl acetoacetate, ethyl acetoacetate, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, -Methyl-2-butanol, cyclohexanol, isobutyl acetate, methyl isobutyl ketone (MIBK), 2-octanone, 2-pentanone, 2-hexanone, 2-heptanone, 3-heptanone, ethylene glycol monoethyl ether acetate, ethylene glycol mono Including ethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and the like. These may be used alone or in combination of two or more.

  As described above, it is preferable that the composition for forming a hard coat layer further includes the component (E).

  When the component (E) is used, it is preferable to prepare the component (E) as a mixture with the component (D) in the preparation of the composition for forming a hard coat layer. As a material containing the said mixture, you may use a commercial item, for example. Examples of the commercial product include trade name “GRANDIC PC-4100” manufactured by Dainippon Ink & Chemicals, Inc. The weight average molecular weight (Mw) of the material containing the mixture is not particularly limited.

  By using the component (E), for example, the surface structure of the hard coat layer to be formed becomes rigid and the slipping property is improved, and the scratch resistance is improved. From the viewpoint of achieving both scratch resistance and antifouling property, the blending ratio of the component (E) is such that the component (C) is 0.05 to 0.4 weight with respect to 100 parts by weight of the component (A). It is preferable that the component (D) and the component (E) are in the range of 0.1 to 1 part by weight in total, and more preferably, the component (C) is 0. The range is from 0.1 to 0.3 parts by weight, and the component (D) and the component (E) are in the range of 0.2 to 1 part by weight in total.

  The hard coat layer forming composition may contain pigments, fillers, dispersants, plasticizers, ultraviolet absorbers, surfactants, antioxidants, thixotropic agents, etc., as necessary, as long as the performance is not impaired. May be included. These additives may be used alone or in combination of two or more.

  By adding fine particles to the composition for forming a hard coat layer, a hard coat film that also has antiglare properties can be obtained. The fine particles mainly have the function of providing an antiglare property by making the surface of the hard coat layer to be formed uneven, and controlling the haze value of the hard coat layer. The haze value of the hard coat layer can be designed by controlling the refractive index difference between the fine particles and the hard coat layer forming composition. Examples of the fine particles include inorganic fine particles and organic fine particles. The inorganic fine particles are not particularly limited, and examples thereof include silicon oxide fine particles, titanium oxide fine particles, aluminum oxide fine particles, zinc oxide fine particles, tin oxide fine particles, calcium carbonate fine particles, barium sulfate fine particles, talc fine particles, kaolin fine particles, calcium sulfate fine particles and the like. Can be given. The organic fine particles are not particularly limited. For example, polymethyl methacrylate resin powder (PMMA fine particles), silicone resin powder, polystyrene resin powder, polycarbonate resin powder, acrylic styrene resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin resin Examples thereof include powder, polyester resin powder, polyamide resin powder, polyimide resin powder, and polyfluorinated ethylene resin powder. These inorganic fine particles and organic fine particles may be used alone or in combination of two or more.

  In the composition for forming a hard coat layer, when the component (A) contains a photocurable compound, for example, a conventionally known photopolymerization initiator as described in JP-A-2008-88309 is used. Can do. The said photoinitiator may be used individually by 1 type, and may use 2 or more types together. The blending amount of the photopolymerization initiator is not particularly limited. The blending amount is, for example, in the range of 1 to 30 parts by weight and preferably in the range of 1 to 25 parts by weight with respect to 100 parts by weight of the component (A).

  Examples of a method for coating the composition for forming a hard coat layer on the transparent plastic film substrate include, for example, a fan ten coating method, a die coating method, a spin coating method, a spray coating method, a gravure coating method, and a roll coating method. A coating method such as a bar coating method can be used.

  The hard coat layer forming composition is applied to form a coating film on the transparent plastic film substrate, and the coating film is cured. Prior to the curing, the coating film is preferably dried. The drying may be, for example, natural drying, air drying by blowing air, heat drying, or a combination of these.

The means for curing the coating film of the hard coat layer forming composition is not particularly limited. The curing means is preferably ionizing radiation curing. Various active energies can be used for the curing means. The active energy is preferably ultraviolet light. As the energy ray source, for example, a high pressure mercury lamp, a halogen lamp, a xenon lamp, a metal halide lamp, a nitrogen laser, an electron beam accelerator, a radioactive element or the like is preferable. The irradiation amount of the energy ray source is preferably in the range of 50 to 5000 mJ / cm ² as an integrated exposure amount at an ultraviolet wavelength of 365 nm. When the irradiation amount is 50 mJ / cm ² or more, the curing becomes more sufficient, and the hardness of the hard coat layer to be formed becomes more sufficient. If the said irradiation amount is 5000 mJ / cm < ² > or less, the coloring of the said hard-coat layer formed can be prevented and transparency can be improved.

  As described above, the hard coat film of the present invention can be produced by forming the hard coat layer on at least one surface of the transparent plastic film substrate. In addition, you may manufacture the hard coat film of this invention with manufacturing methods other than the above-mentioned method.

  An example of the configuration of the hard coat film of the present invention is shown in the schematic cross-sectional view of FIG. In the figure, the size, ratio, and the like of each component are different from actual ones for easy understanding. As shown in the figure, in this hard coat film 10, a hard coat layer 12 is formed on one side of a transparent plastic film substrate 11. However, the present invention is not limited to this. The hard coat film of the present invention may have a structure in which hard coat layers are formed on both surfaces of a transparent plastic film substrate. Further, the hard coat layer 12 in this example is a single layer. However, the present invention is not limited to this. In the hard coat film of the present invention, the hard coat layer may have a multilayer structure in which two or more layers are laminated. In this case, at least the hard coat layer formed from the composition for forming a hard coat layer of the present invention may be on the outermost surface.

  In the hard coat film of the present invention, it is preferable to perform a surface treatment on at least one of the transparent plastic film substrate and the hard coat layer. If the surface of the transparent plastic film substrate is surface-treated, the adhesion with the hard coat layer, the polarizer or the polarizing plate is further improved. If the surface of the hard coat layer is surface-treated, the adhesion with the polarizer or polarizing plate is further improved. Examples of the surface treatment include low-pressure plasma treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, and acid or alkali treatment. As a surface treatment when a TAC film is used as the transparent plastic film substrate, an alkali treatment is preferable. This alkali treatment can be carried out, for example, by bringing the TAC film surface into contact with an alkali solution, washing with water and drying. As the alkaline solution, for example, potassium hydroxide solution and sodium hydroxide solution can be used. The specified concentration (molar concentration) of hydroxide ions in the alkaline solution is preferably in the range of 0.1 to 3.0 N (mol / L), more preferably 0.5 to 2.0 N (mol / L). Range.

  In a hard coat film including a transparent plastic film substrate, and the hard coat layer is formed on one surface of the transparent plastic film substrate, the other surface is treated with a solvent to prevent curling. You may go. The solvent treatment can be carried out by contacting a solvent capable of dissolving the transparent plastic film substrate or a solvent capable of swelling. The solvent treatment gives the transparent plastic film substrate a force to curl the other surface, thereby offsetting the force of the transparent plastic film substrate to curl due to the formation of the hard coat layer. By doing so, the occurrence of curling can be prevented. Similarly, in the hard coat film including the transparent plastic film substrate, and the hard coat layer is formed on one surface of the transparent plastic film substrate, in order to prevent the occurrence of curling, A transparent resin layer may be formed. Examples of the transparent resin layer include a layer mainly composed of a thermoplastic resin, a radiation curable resin, a thermosetting resin, and other reactive resins. Among these, a layer mainly composed of a thermoplastic resin is particularly preferable.

  In the hard coat film of the present invention, the transparent plastic film substrate side can usually be bonded to an optical member used in LCDs and ELDs via an adhesive or an adhesive. In the pasting, various surface treatments as described above may be performed on the surface of the transparent plastic film substrate.

  Examples of the optical member include a polarizer and a polarizing plate. Generally, the polarizing plate has a transparent protective film on one side or both sides of the polarizer. When providing a transparent protective film on both surfaces of a polarizer, the same material may be sufficient as the transparent protective film of front and back, and a different material may be sufficient as it. The polarizing plates are usually disposed on both sides of the liquid crystal cell. Further, the polarizing plates are arranged so that the absorption axes of the two polarizing plates are substantially orthogonal to each other.

  Next, the optical element on which the hard coat film of the present invention is laminated will be described by taking a polarizing plate as an example. A polarizing plate having the function of the present invention can be obtained by laminating the hard coat film of the present invention with a polarizer or a polarizing plate using an adhesive, a pressure sensitive adhesive or the like.

  The polarizer is not particularly limited, and various types can be used. Examples of the polarizer include hydrophilic polymer films such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene / vinyl acetate copolymer partially saponified film, and iodine and dichroic dyes. Examples thereof include a polyene-based oriented film such as a film obtained by adsorbing a chromatic substance and uniaxially stretched, a dehydrated polyvinyl alcohol product or a dehydrochlorinated polyvinyl chloride product.

  As the transparent protective film provided on one side or both sides of the polarizer, those having excellent transparency, mechanical strength, thermal stability, moisture shielding property, retardation value stability and the like are preferable. Examples of the material for forming the transparent protective film include the same materials as those for the transparent plastic film substrate.

  Examples of the transparent protective film include polymer films described in JP-A No. 2001-343529 (WO01 / 37007). The polymer film described in the publication includes, for example, (A) a thermoplastic resin having at least one imide group of a substituted imide group and an unsubstituted imide group on the side chain, and (B) a substituted phenyl group and a non-chain on the side chain. Examples thereof include a polymer film formed from a resin composition containing a thermoplastic resin having at least one phenyl group of a substituted phenyl group and a nitrile group. Examples of the polymer film formed from the resin composition include a polymer film formed from a resin composition containing an alternating copolymer composed of isobutylene and N-methylmaleimide and an acrylonitrile-styrene copolymer. can give. The polymer film can be produced by extruding the resin composition into a film. Since the polymer film has a small retardation and a small photoelastic coefficient, when applied to a protective film such as a polarizing plate, problems such as unevenness due to distortion can be solved. The polymer film is excellent in humidification durability because of its low moisture permeability.

  The transparent protective film is preferably a film made of cellulose resin such as TAC or a film made of norbornene resin from the viewpoints of polarization characteristics and durability. Examples of the commercial product of the transparent protective film include trade name “Fujitac” (manufactured by FUJIFILM Corporation), trade name “ZEONOR” (manufactured by ZEON Corporation), trade name “ARTON” (manufactured by JSR Corporation), and the like. .

  The thickness of the transparent protective film is not particularly limited. The thickness of the transparent protective film is, for example, in the range of 1 to 500 μm from the viewpoint of strength, workability such as handleability, and thin layer properties. When the thickness is within the above range, the polarizer is mechanically protected, and the polarizer does not shrink even when exposed to high temperature and high humidity, and stable optical characteristics can be maintained. The thickness is preferably in the range of 5 to 200 μm, and more preferably in the range of 10 to 150 μm.

  The configuration of the polarizing plate in which the hard coat film of the present invention is laminated is not particularly limited. For example, a transparent protective film, a polarizer and a transparent protective film may be laminated in this order on the hard coat film. And the structure which laminated | stacked the polarizer and the transparent protective film in this order on the hard coat film may be sufficient.

  The hard coat film of the present invention using the composition for forming a hard coat layer of the present invention and various optical elements such as a polarizing plate using the same can be preferably used for various image display devices such as a liquid crystal display device. The image display device of the present invention has the same configuration as the conventional image display device except that the hard coat film of the present invention is used. When the image display device of the present invention is a liquid crystal display device, for example, a liquid crystal cell, an optical element such as a polarizing plate, and various components such as an illumination system (backlight etc.) as needed are assembled as appropriate. It can manufacture by incorporating. The liquid crystal cell is not particularly limited. As the liquid crystal cell, various types such as a TN type, an STN type, and a π type can be used.

  In the present invention, the configuration of the liquid crystal display device is not particularly limited, and there are a liquid crystal display device in which the optical element is arranged on one side or both sides of a liquid crystal cell, a liquid crystal display device using a backlight or a reflector in an illumination system, and the like. Can be mentioned. In these liquid crystal display devices, the optical element of the present invention can be arranged on one side or both sides of the liquid crystal cell. When the optical elements are arranged on both sides of the liquid crystal cell, they may be the same or different. Furthermore, various optical members and optical components such as a diffusion plate, an antiglare layer, an antireflection layer, a protective plate, a prism array, a lens array sheet, a light diffusion plate, and a backlight may be disposed in the liquid crystal display device. Good.

  The image display device of the present invention is used for any appropriate application. Applications include, for example, OA equipment such as desktop personal computers, notebook personal computers, and copiers, mobile phones, watches, digital cameras, personal digital assistants (PDAs), portable devices such as portable game machines, video cameras, televisions, microwave ovens, etc. Household electrical equipment, back monitor, car navigation system monitor, car audio and other in-vehicle equipment, display equipment for commercial store information monitors, security equipment such as monitoring monitors, nursing care monitors, medical monitors, etc. Nursing care / medical equipment.

  Next, examples of the present invention will be described together with comparative examples. However, the present invention is not limited by the following examples and comparative examples. Various characteristics in the following examples and comparative examples were evaluated or measured by the following methods.

(Thickness of hard coat layer)
The total thickness of the hard coat film was measured using a micro gauge thickness meter manufactured by Mitutoyo Corporation, and the thickness of the hard coat layer was calculated by subtracting the thickness of the transparent plastic film substrate from the total thickness.

(Abrasion resistance)
The scratch resistance of the hard coat layer was evaluated by the following test contents.
(1) A 150 mm × 50 mm sample was cut out from the center of the hard coat film and placed on a glass plate with the surface on which the hard coat layer was not formed facing down.
(2) Scratches that entered the sample surface after steel wool # 0000 was uniformly attached to a smooth section of a cylinder having a diameter of 11 mm, and the sample surface was reciprocated 10 times at a speed of about 100 mm per second with a load of 1.5 kg. Were visually counted and judged according to the following indicators.
A: The number of scratches is 10 or less B: The number of scratches is 11 or more and 29 or less C: The number of scratches is 30 or more

(Pencil hardness)
A sample of 100 mm × 50 mm was cut out from the center of the hard coat film, placed on a glass plate with the surface on which the hard coat layer was not formed facing down, and then subjected to the pencil hardness test described in JIS K 5600-5-4. According to the regulations, the pencil hardness at a load of 500 g was measured. As the pencil, “Uni” manufactured by Mitsubishi Pencil Co., Ltd. (Nikkiso test for pencil scratch test) was used.

(Surface free energy)
Using “Fully Automatic Contact Angle Meter DM700” manufactured by Kyowa Interface Science Co., Ltd., the contact angles of water and hexadecane were measured, and the surface free energy was calculated using analysis software FAMAS. As a calculation method, two-component analysis based on Kaelble Uy theory was used.

(Measurement of atomic strength by ESCA)
The atomic strength was measured using “Quantum 2000” manufactured by ULVAC-PHI. The X-ray source was monochrome AlKα, the X-ray output was 30 W (15 kV), the measurement region was 200 μmφ, and the measurement angle was 45 ° with respect to the sample surface. The energy was corrected by correcting the peak due to the C—C bond of the C1s spectrum to 285.0 eV.
Qualitative analysis was performed by performing wide scan measurement at any two points of the sample at 0 to 1100 eV. Narrow scan was performed on the detected elements, and the element ratio (atomic%) was calculated. With respect to the Si2p spectrum, waveform analysis is performed at peaks attributed to each bond of bifunctional silicon and polyfunctional silicon and SiOx, and the silicon atom intensity derived from the reactive silicon compound is calculated.
Under the above conditions, each atomic intensity ratio in a region from the outermost surface of the sample to a depth of about 5 to 10 nm can be measured.

(Weight average particle diameter of particles (component (B)))
The resin raw material containing the component (B) is diluted with methyl ethyl ketone (MEK) to a solid content concentration of 10%, and a dynamic light scattering particle size distribution measuring device ("LB-500" manufactured by Horiba Ltd.) is used. Used to measure the particle size distribution. The weight average particle size was calculated from the obtained particle size distribution.

(Weight average molecular weight)
The weight average molecular weight was measured by a gel permeation chromatograph (GPC) method using polystyrene as a standard sample. Specifically, it measured with the following apparatus, instrument, and measurement conditions.
Analyzer: Tosoh Corporation, trade name “SC-8020”
Column: Showa Denko Co., Ltd., trade name “Shodex”
Column size: 20.0mmφ × 500mm
Column temperature: Room temperature Eluent: Chloroform flow rate: 3.5 mL / min Inlet pressure: 70 kgf / cm ² (6.9 MPa)

[Example 1]
(Preparation of composition for forming hard coat layer)
A resin raw material (manufactured by JSR Co., Ltd., trade name “OPSTAR”, in which nano silica particles (component (B)) modified with an organic compound containing a polymerizable unsaturated group on the particle surface are dispersed. Z7540 ”, solid content: 56% by weight, solvent: butyl acetate / methyl ethyl ketone (MEK) = 76/24 (weight ratio)).

  The resin raw material includes dipentaerythritol and isophorone diisocyanate polyurethane as the component (A) (ultraviolet curable compound), and silica fine particles whose surface is modified with organic molecules as the component (B) (weight average particle diameter: 100 nm). In the weight ratio of (A) component total: (B) component = 2: 3. The refractive index of the cured film of the resin raw material was 1.485.

  Reactive fluorine compound (manufactured by Daikin Industries, trade name "OPTOOL (registered trademark) DAC", solid content 20%, solvent: 1H, 1H, 3H-tetrafluoro with respect to 100 parts by weight of the solid content of the resin raw material 0.2 parts by weight of propanol), 0.5 parts by weight of a reactive silicon compound (manufactured by Dainippon Ink & Chemicals, Inc., trade name “GRANDIC PC-4100”), and a photopolymerization initiator (Ciba Specialty)・ Product number “Irgacure 127” manufactured by Chemicals Co., Ltd.) was added in an amount of 0.5 parts by weight, and diluted with butyl acetate so that the solid concentration was 50% by weight. Prepared. The reactive fluorine compound is represented by the general formula (1), and a substituent having a fluoroalkyl group having a structure represented by the general formula (2) in R of the general formula (1). The main component is a compound having one and two substituents having an acrylate group having a structure represented by the general formula (3). The reactive silicon compound is a mixture containing Component 1, Component 2 and a solvent shown below.

Component 1: Reactive silicone represented by the general formula (4) (the polydimethylsiloxane unit (X1) of the unit (c) of the general formula (5) and the unit (b) of the general formula (5) A methylhydroxypropylsiloxane unit (X2), a 6-isocyanatohexylisocyanuric acid unit (X3) of the general formula (9), and a substituent (X4) of the unit (d) of the general formula (7) are represented by X1 : X2: X3: X4 (molar ratio) = 187: 39: 100: 57) (6.85 parts by weight)
Component 2: Glycol compound represented by the general formula (8) (3.15 parts by weight)
Solvent: ethyl acetate (90 parts by weight)

(Preparation of hard coat film)
The composition for forming a hard coat layer is applied on a transparent plastic film substrate (TAC film having a thickness of 40 μm and a refractive index of 1.48, manufactured by Konica Minolta, trade name “KC4UY”) using a comma coater. A coating film was formed. After the coating, the coating film was dried by heating at 60 ° C. for 1 minute. The dried coating film was subjected to a curing treatment by irradiating ultraviolet rays with an integrated light quantity of 300 mJ / cm ² with a high-pressure mercury lamp to form a 7 μm thick hard coat layer. In this way, the hard coat film of this example was produced.

[Example 2]
A hard coat film of this example was obtained in the same manner as in Example 1 except that the hard coat layer was formed so as to have a thickness of 15 μm.

[Example 3]
A hard coat film of this example was obtained in the same manner as in Example 1 except that 0.1 parts by weight of the reactive fluorine compound and 0.5 parts by weight of the reactive silicon compound were used.

[Example 4]
A hard coat film of this example was obtained in the same manner as in Example 1 except that 0.2 parts by weight of the reactive fluorine compound and 0.2 parts by weight of the reactive silicon compound were used.

[Example 5]
A hard coat film of this example was obtained in the same manner as in Example 1 except that 0.1 parts by weight of the reactive fluorine compound and 1 part by weight of the reactive silicon compound were used.

[Example 6]
A hard coat film of this example was obtained in the same manner as in Example 1 except that 0.2 parts by weight of the reactive fluorine compound and 1 part by weight of the reactive silicon compound were used.

[Example 7]
A hard coat film of this example was obtained in the same manner as in Example 1 except that 0.1 parts by weight of the reactive fluorine compound and 0.2 parts by weight of the reactive silicon compound were used.

[Example 8]
A hard coat film of this example was obtained in the same manner as in Example 1 except that 0.1 parts by weight of the reactive fluorine compound and 0.1 parts by weight of the reactive silicon compound were used.

[Example 9]
A hard coat film of this example was obtained in the same manner as in Example 1 except that 0.2 parts by weight of the reactive fluorine compound and 0.1 parts by weight of the reactive silicon compound were used.

[Comparative Example 1]
A hard coat film of this comparative example was obtained in the same manner as in Example 1 except that the reactive fluorine compound and the reactive silicon compound were not added.

[Comparative Example 2]
A hard coat film of this comparative example was obtained in the same manner as in Example 1 except that the reactive fluorine compound was not added and the reactive silicon compound was changed to 0.2 parts by weight.

[Comparative Example 3]
A hard coat film of this comparative example was obtained in the same manner as in Example 1 except that the reactive fluorine compound was not added and that the reactive silicon compound was 1 part by weight.

[Comparative Example 4]
A hard coat film of this comparative example was obtained in the same manner as in Example 1 except that 0.2 part by weight of the reactive fluorine compound and the reactive silicon compound were not added.

[Comparative Example 5]
A hard coat film of this comparative example was obtained in the same manner as in Example 1 except that 1 part by weight of the reactive fluorine compound and the reactive silicon compound were not added.

  Various characteristics were measured or evaluated for the hard coat films of Examples and Comparative Examples thus obtained. The results are shown in Table 1 below.

  As shown in Table 1, the hard coat films of the examples had good antifouling properties represented by scratch resistance and surface free energy values. Particularly in Examples 1 to 6, extremely excellent scratch resistance was exhibited. Further, the hard coat films of the examples had high pencil hardness and good curl characteristics. In contrast, the hard coat film of the comparative example was not sufficiently scratch resistant. The hard coat films of Comparative Examples 1 to 3 have a large surface free energy value and cannot be said to have good antifouling properties. Although the hard coat films of Comparative Example 4 and Comparative Example 5 had a small surface free energy value, the scratch resistance was not sufficient.

  The hard coat film of the present invention using the composition for forming a hard coat layer of the present invention has sufficient hardness, excellent scratch resistance, and excellent antifouling property. Therefore, the hard coat film of the present invention can be suitably used for various image display devices such as optical elements such as polarizing plates, CRTs, LCDs, PDPs, and ELDs, for example. It is.

10 Hard Coat Film 11 Transparent Plastic Base Material 12 Hard Coat Layer

Claims (21)

A composition for forming a hard coat layer used for forming a hard coat layer of a hard coat film ,
The following (A) component, (B) component, (C) component and (D) component are included, and the following (B) component is the range of 120-200 weight part with respect to 100 weight part of the following (A) component. The composition for hard-coat layer formation characterized by being mix | blended by these.
(A) component: curable compound having at least one of acrylate group and methacrylate group (B) component: inorganic oxide particle surface is modified with an organic compound containing a polymerizable unsaturated group, and the weight average particle size (C) component: reactive fluorine compound (D) component: reactive silicon compound having a particle size of 200 nm or less The composition for forming a hard coat layer according to claim 1, wherein the component (C) has a structure represented by the following general formula (1).

In the general formula (1), at least one R is a substituent having a fluoroalkyl group, and at least one R is a substituent having at least one of an acrylate group and a methacrylate group. The composition for forming a hard coat layer according to claim 2, wherein, in R of the general formula (1), the substituent having the fluoroalkyl group has a structure represented by the following general formula (2).

In the general formula (2), n is an integer of 1 or more. The composition for forming a hard coat layer according to claim 2 or 3, wherein, in R of the general formula (1), the substituent having the acrylate group has a substituent represented by the following general formula (3).

The hard coat layer forming composition according to any one of claims 1 to 4, wherein the component (D) has a structure represented by the following general formula (4).

In the general formula (4), R is a substituent selected from a substituent having a siloxane structure, a substituent having at least one of an acrylate group and a methacrylate group, and a substituent having an active hydrogen group. May be the same or different. The composition for forming a hard coat layer according to claim 5, wherein, in R of the general formula (4), the substituent having the siloxane structure has a structure represented by the following general formula (5).

In the general formula (5), n is an integer of 1 or more. The composition for forming a hard coat layer according to claim 5 or 6, wherein, in R of the general formula (4), the substituent having the active hydrogen group has a substituent represented by the following general formula (6).

Hard coat layer formation as described in any one of Claim 5 to 7 in which the substituent which has the said acrylate group in R of the said General formula (4) has a substituent represented by following General formula (7). Composition.

In the general formula (7), m and n are each an integer of 1 to 10, and may be the same or different. l is an integer of 1-5. The composition for forming a hard coat layer according to any one of claims 1 to 8, wherein a weight average particle diameter of the component (B) is in a range of 1 to 100 nm. The component (B) includes at least one fine particle selected from the group consisting of titanium oxide, silicon oxide, aluminum oxide, zinc oxide, tin oxide, and zirconium oxide. Hard coat layer forming composition. With respect to 100 parts by weight of the component (A), the component (C) is blended in the range of 0.05 to 0.4 parts by weight, and the component (D) is in the range of 0.05 to 1 part by weight. The composition for hard-coat layer formation as described in any one of Claims 1-10 currently mix | blended. Furthermore, the composition for hard-coat layer formation as described in any one of Claim 1 to 11 containing the following (E) component.
(E) Component: Glycol compound represented by the following general formula (8)

In the general formula (8), m and n are each an integer of 1 or more and may be the same or different. The component (C) is blended in the range of 0.05 to 0.4 parts by weight with respect to 100 parts by weight of the component (A), and the component (D) and the component (E) are combined in total. The composition for forming a hard coat layer according to claim 12, which is blended in an amount of 0.1 to 1 part by weight. A hard coat film having a hard coat layer on at least one surface of a transparent plastic film substrate,
A hard coat film, wherein the hard coat layer is formed from the composition for forming a hard coat layer according to any one of claims 1 to 13. The outermost layer of the hard coat layer has a fluorine atom intensity derived from a reactive fluorine compound in the range of 5 to 30% in the analysis by ESCA, and a silicon atom intensity derived from the reactive silicon compound is 0.2. The hard coat film according to claim 14, which is within a range of -10%. The hard coat film according to claim 14 or 15, wherein the hard coat layer has a thickness in a range of 12 to 50 µm. The hard coat film according to any one of claims 14 to 16, wherein the hard coat layer has a pencil hardness of 4H or more at a weight of 500 g in accordance with JIS K 5600-5-4. 18. The hard coat film according to claim 14, wherein the surface free energy on the surface of the hard coat layer is in the range of 15 to 25 mJ / m ² . The hard coat film according to claim 14, wherein the hard coat layer further contains fine particles. An optical element, wherein the hard coat film according to any one of claims 14 to 19 is laminated on at least one surface of the optical member. An image display device comprising the hard coat film according to any one of claims 14 to 19 or the optical element according to claim 20.

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