JP5218127B2 - Curable composition, cured film and laminate - Google Patents

Description

  The present invention relates to a curable composition, a cured film obtained by curing the curable composition, and a laminate. More specifically, the present invention relates to a curable composition containing a novel additive compound and suitable for forming a hard coat film, a cured film obtained by curing the composition, and a laminate.

  In recent years, plastics (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, etc.), metal, wood, paper, glass, slate, etc. As a protective coating material and anti-reflection coating material for preventing scratches (abrasion) on various substrate surfaces and preventing contamination, it has excellent coating properties, and the surface of each substrate has hardness, Curing composition capable of forming a cured film excellent in any of scratch resistance, antifouling property, abrasion resistance, surface slipperiness, low curling property, adhesion, transparency, chemical resistance and appearance of coating surface Things are requested.

In order to satisfy such a request, various compositions have been proposed, but have excellent coating properties as a curable composition, and when it is a cured film, has high hardness and scratch resistance, At present, no product with the characteristics of excellent transparency and antifouling properties has been obtained.
As a method for imparting antifouling properties, for example, Patent Document 1 describes a curable composition containing a polysiloxane having a (meth) acryloyl group. However, there is room for further improvement from the viewpoint of oil marker wiping. was there.

  Patent Document 2 discloses a composition for forming an antireflection film that can improve the slipperiness of the surface of the antireflection film, is soluble in a non-fluorine general-purpose solvent, and is easy to form a thin film. This composition for forming an antireflection film is a composition comprising a reactive surface modifier (I) and an antireflection film material (II), of which the reactive surface modifier (I) is (A A reactive group-containing composition comprising a reaction product of a triisocyanate trimerized from a diisocyanate and (B) at least two active hydrogen-containing compounds, wherein the component (B) is (B-1) The composition comprises a perfluoropolyether having at least one active hydrogen and (B-2) a monomer having an active hydrogen and a self-crosslinkable functional group. By adding such a reactive surface modifier (I), the surface properties of the antireflection film, especially surface slipperiness (lower coefficient of friction), surface hardness, wear resistance, chemical resistance, contamination wiping It is described that the surface property improved by improving the property, water repellency, oil repellency, solvent resistance, etc. can be imparted to the surface of the original coating film. The antireflection film material (II) combined with the reactive surface modifier (I) is for forming a low refractive index layer.

JP-A-2005-36018 JP 2006-37024 A

  This invention is made | formed in view of the above-mentioned problem, and it aims at providing the curable composition which gives the cured film which has outstanding transparency, antifouling property, and a coating-film external appearance.

  In order to achieve the above object, the present inventors have conducted intensive research and (A) oxide particles of a specific element having a polymerizable unsaturated group, (C) having two or more polymerizable unsaturated groups. By adding a compound containing (B) a perfluoropolyether group, a urethane group and 10 or more (meth) acryloyl groups to the curable composition containing the compound and (D) the photopolymerization initiator, The present inventors have found that a cured film that can satisfy the above characteristics can be obtained.

［式（１２）中、Ｕは、ＮＨ、Ｏ（酸素原子）又はＳ（イオウ原子）を示し、Ｖは、Ｏ又はＳを示す。］
７．さらに、（Ｄ）ラジカル重合開始剤を含有する上記１〜６のいずれかに記載の硬化性組成物。
８．さらに、（Ｅ）有機溶剤を含有する上記１〜７のいずれかに記載の硬化性組成物。
９．ハードコート形成用である上記１〜８のいずれかに記載の硬化性組成物。
１０．上記１〜９のいずれかに記載の硬化性組成物を硬化させてなる硬化膜。
１１．透明基材上に上記１０に記載の硬化膜を積層してなる積層体。 That is, this invention provides the following curable composition, the cured film and laminated body which harden it.
1. The following components (A) to (C):
(A) A group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony, and cerium bonded to an organic compound (Ab) having a polymerizable unsaturated group and hydrolyzable silyl group in the molecule Particles containing at least one element oxide selected from (B) a reaction product of perfluoropolyether diol and aromatic diisocyanate with a compound having 5 or more (meth) acryloyl groups. A compound having a perfluoropolyether group, a urethane group and 10 or more (meth) acryloyl groups (C), and two or more polymerizable unsaturated groups other than the above components (A) and (B). The curable composition containing the compound which has.
2. The aromatic diisocyanate compound is metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tolidine diisocyanate, 1,4-naphthalene. 2. The curable composition according to 1 above, selected from the group consisting of diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, and 2,7-naphthalene diisocyanate.
3. 3. The curable composition according to 2 above, wherein the aromatic diisocyanate is 2,4-tolylene diisocyanate.
4). 4. The curable composition according to any one of the above 1 to 3, wherein the compound having 5 or more (meth) acryloyl groups is dipentaerythritol penta (meth) acrylate.
5. Curing in any one of said 1-4 which is in the range of 0.1-5 mass% when the compounding quantity of the said (B) compound makes the total amount of the components except a solvent 100 mass%. Sex composition.
6). The curable composition according to any one of 1 to 5, wherein the organic compound (Ab) further has a structure represented by the following formula (12).

[In Formula (12), U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. ]
7). Furthermore, (D) The curable composition in any one of said 1-6 containing a radical polymerization initiator.
8). Furthermore, (E) The curable composition in any one of said 1-7 containing an organic solvent.
9. The curable composition according to any one of 1 to 8 above, which is used for forming a hard coat.
10. The cured film formed by hardening | curing the curable composition in any one of said 1-9.
11. A laminate obtained by laminating the cured film described in 10 above on a transparent substrate.

  According to the curable composition of this invention, the cured film excellent in transparency, antifouling property, and a coating-film external appearance can be manufactured.

2 is an IR chart of Compound 1. 1 is a ¹ H NMR chart of Compound 1. 2 is a ¹³ C { ¹ H} NMR chart of ¹³ C { ¹ H} of Compound 1. FIG.

Hereinafter, the present invention will be described in detail.
I. Curable composition The curable composition of this invention (henceforth "the composition of this invention") may contain the following component (A)-(F). Among these, components (A) to (C) are essential components, and components (D) to (G) are optional components that can be added as necessary.
(A) A group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony, and cerium bonded to an organic compound (Ab) having a polymerizable unsaturated group and hydrolyzable silyl group in the molecule Particles whose main component is an oxide of at least one element selected from (hereinafter referred to as “reactive particles”)
(B) Perfluoropolyether group, urethane group and 10 or more obtained by reacting a reaction product of perfluoropolyether diol and aromatic diisocyanate with a compound having 5 or more (meth) acryloyl groups (C) Compound having (meth) acryloyl group (C) Compound having two or more polymerizable unsaturated groups other than the above components (A) and (B) (hereinafter referred to as “polyfunctional polymerizable unsaturated group-containing compound”) Called)
(D) Radical polymerization initiator (E) Organic solvent (F) additive Hereinafter, each component is demonstrated.

(A) Reactive Particles The reactive particles (A) used in the present invention are oxidized of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. It is obtained by reacting particles (Aa) containing a product as a main component with an organic compound (Ab) having a polymerizable unsaturated group and a hydrolyzable silyl group in the molecule, and having a polymerizable unsaturated group. The particles are mainly composed of an oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium.

(1) Particles mainly composed of oxide (Aa)
The oxide particles (Aa) used for the production of the reactive particles (A) are silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin from the viewpoint of colorlessness of the cured film of the resulting curable composition. , Particles mainly composed of an oxide of at least one element selected from the group consisting of antimony and cerium.

  Examples of these oxide particles (Aa) include particles of silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, cerium oxide, and the like. Can be mentioned. Among these, silica, alumina, zirconia and antimony oxide particles are preferable from the viewpoint of high hardness. These may be used alone or in combination of two or more. Furthermore, the oxide particles (Aa) are preferably used as a powder or solvent-dispersed sol. When used as a solvent-dispersed sol, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such an organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone. , Esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide, dimethylacetamide, Examples thereof include amides such as N-methylpyrrolidone. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

  The number average particle diameter of the oxide particles (Aa) may be appropriately selected according to the use of the obtained cured film, but is preferably 0.001 μm to 2 μm, more preferably 0.003 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm is particularly preferable. When the number average particle diameter exceeds 2 μm, the transparency when cured is lowered or the surface state when cured is deteriorated. Various surfactants and amines may be added to improve the dispersibility of the particles.

  Commercially available products as silicon oxide particles (for example, silica particles) include, for example, colloidal silica, methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA- manufactured by Nissan Chemical Industries, Ltd. ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL and the like can be mentioned. As the powdered silica, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Silex H31, H32, H51, H52, H121, H122, Asahi Glass Co., Ltd., Nippon Silica Industry, Nippon Aerosil Co., Ltd. Examples include E220A and E220 manufactured by Fuji Electric, SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.

  Moreover, as an aqueous dispersion product of alumina, Nissan Chemical Industries, Ltd. alumina sol-100, -200, -520; As an alumina isopropanol dispersion product, Sumitomo Osaka Cement Co., Ltd. AS-150I; AS-150T manufactured by Sumitomo Osaka Cement Co., Ltd .; HXU-110JC manufactured by Sumitomo Osaka Cement Co., Ltd. as a toluene dispersion of zirconia; Nissan Chemical Industries, Ltd. as an aqueous dispersion of zinc antimonate powder ) Cellax: Alumina, titanium oxide, tin oxide, indium oxide, zinc oxide and other powders and solvent dispersion products are nanotech made by CI Kasei Co., Ltd .; Antimony-doped tin oxide water dispersion sol is Ishihara Sangyo ( SN-100D, manufactured by Mitsubishi Materials Corp .; cerium oxide The dispersion can be exemplified Taki Chemical Co., Ltd. Nidoraru like.

The oxide particles (Aa) have a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an indeterminate shape, and preferably a spherical shape. The specific surface area of the oxide particles (Aa) (by the BET specific surface area measurement method using nitrogen) is preferably 10 to 1000 m ² / g, and more preferably 100 to 500 m ² / g. These oxide particles (Aa) can be used in a dry state, or dispersed in water or an organic solvent. For example, a dispersion of fine oxide particles known in the art as a solvent dispersion sol of the above oxide can be used directly. In particular, the use of an organic solvent-dispersed sol of an oxide is preferable in applications where the cured product requires excellent transparency.

(2) Organic compound (Ab)
The organic compound (Ab) used in the present invention is not particularly limited as long as it is a compound having a polymerizable unsaturated group and a hydrolyzable silyl group. The hydrolyzable silyl group is a group that reacts with water to produce silanol (Si-OH). For example, one or more methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups, An n-butoxy group, an alkoxy group such as an aryloxy group, an acetoxy group, an amino group, or a halogen atom is bonded. Further, the organic compound (Ab) is preferably an organic compound containing a group represented by the following formula (12). Further, it includes a [—O—C (═O) —NH—] group, and further includes a [—O—C (═S) —NH—] group and a [—S—C (═O) —NH—] group. It is preferable that at least 1 of these is included.

［式（１２）中、Ｕは、ＮＨ、Ｏ（酸素原子）又はＳ（イオウ原子）を示し、Ｖは、Ｏ又はＳを示す。］

[In Formula (12), U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. ]

(I) Polymerizable unsaturated group The polymerizable unsaturated group contained in the organic compound (Ab) is not particularly limited, and examples thereof include acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, and ethynyl. Preferred examples include a group, a cinnamoyl group, a maleate group and an acrylamide group.
This polymerizable unsaturated group is a structural unit that undergoes addition polymerization with active radical species.

(Ii) The group represented by the formula (2) The group [—UC (═V) —NH—] represented by the formula (12) contained in the organic compound is specifically represented by [—O—C ( = O) -NH-], [-O-C (= S) -NH-], [-S-C (= O) -NH-], [-NH-C (= O) -NH-], Six types of [—NH—C (═S) —NH—] and [—S—C (═S) —NH—]. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, [—O—C (═O) —NH—] group, [—O—C (═S) —NH—] group and [—S—C (═O) — It is preferable to use in combination with at least one of the NH-] groups.
The group [—UC— (V) —NH—] represented by the formula (12) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical strength and group when cured. It is considered that it gives properties such as adhesion and heat resistance to adjacent layers such as materials and high refractive index layers.

(Iii) Hydrolyzable silyl group The organic compound (Ab) is a compound having a hydrolyzable silyl group in the molecule, that is, a compound that generates a silanol group by hydrolysis. Examples of the compound that generates such a silanol group include compounds in which an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen atom, and the like are bonded to a silicon atom. A compound having a group bonded thereto, that is, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.
The silanol group-generating site of the compound having a hydrolyzable silyl group is a structural unit that binds to the oxide particles (Aa) by a condensation reaction or a condensation reaction that occurs following hydrolysis.

(Iv) Preferred Embodiment As a preferred specific example of the organic compound (Ab), for example, a compound represented by the following formula (13) can be mentioned.

In the formula (13), R ⁶ and R ⁷ may be the same or different and each represents a hydrogen atom or an alkyl group or aryl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, Examples thereof include phenyl and xylyl groups. Here, j is an integer of 1 to 3.

Examples of the group represented by [(R ⁶ O) _j R ⁷ _3-j Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.
R ⁸ is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms and may contain a chain, branched or cyclic structure. Specific examples include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, dodecamethylene and the like.
R ⁹ is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. Specific examples include a chain polyalkylene group such as hexamethylene, octamethylene, and dodecamethylene; an alicyclic or polycyclic divalent organic group such as cyclohexylene and norbornylene; and 2 such as phenylene, naphthylene, biphenylene, and polyphenylene. Valent aromatic group; and these alkyl group-substituted and aryl group-substituted products. These divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and may contain a polyether bond, a polyester bond, a polyamide bond, and a polycarbonate bond.
R ¹⁰ is a (k + 1) -valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.
Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. K is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5.

  Specific examples of the compound represented by the formula (13) include compounds represented by the following formulas (14) and (15).

［式（１４）及び式（１５）中、「Ａｃｒｙｌ」は、アクリロイル基又はメタアクリロイル基を示す。］

[In Formula (14) and Formula (15), “Acryl” represents an acryloyl group or a methacryloyl group. ]

  For the synthesis of the organic compound (Ab) used in the present invention, for example, a method described in JP-A-9-100111 can be used. Preferably, mercaptopropyltrimethoxysilane and isophorone diisocyanate are mixed in the presence of dibutyltin dilaurate and reacted at 60 to 70 ° C. for several hours, then pentaerythritol triacrylate is added, and further at 60 to 70 ° C. for several hours. Produced by reacting to some extent.

(3) Preparation of Reactive Particles (A) An organic compound (Ab) having a silanol group or a group that generates a silanol group by hydrolysis is mixed with metal oxide particles (Aa), hydrolyzed, and bonded together. . The ratio of the organic polymer component, that is, the hydrolyzable silane hydrolyzate and condensate in the resulting reactive particles (A) is usually a mass loss% when the dry powder is completely burned in air. The constant value can be obtained, for example, by thermal mass spectrometry from room temperature to usually 800 ° C. in air.

  The amount of binding of the organic compound (Ab) to the oxide particles (Aa) is preferably 100% by mass of the reactive particles (A) (the total of the metal oxide particles (Aa) and the organic compound (Ab)), It is 0.01 mass% or more, More preferably, it is 0.1 mass% or more, Most preferably, it is 1 mass% or more. When the amount of the organic compound (Ab) bound to the metal oxide particles (Aa) is less than 0.01% by mass, the dispersibility of the reactive particles (A) in the composition is not sufficient, and the resulting curing is obtained. The transparency and scratch resistance of the object may not be sufficient. Moreover, the compounding ratio of the metal oxide particles (Aa) in the raw material during the production of the reactive particles (A) is preferably 5 to 99% by mass, and more preferably 10 to 98% by mass. The content of the oxide particles (Aa) constituting the reactive particles (A) is preferably 65 to 95% by mass of the reactive particles (A).

The content of the reactive particles (A) in the composition of the present invention is preferably in the range of 20 to 74% by mass, when the total of the components excluding the solvent is 100% by mass, More preferably, it is in the range of mass%. If the amount is less than 20% by mass, a film having a high hardness may not be obtained when cured, and if it exceeds 74% by mass, the film formability may be insufficient.
In addition, content of the reactive particle (A) means solid content, and when the reactive particle (A) is used in the form of a solvent-dispersed sol, the content does not include the amount of solvent.

(B) A perfluoropolyether group obtained by reacting a reaction product of a diol compound having a perfluoropolyether structure with an aromatic diisocyanate compound with a compound having a hydroxyl group and five or more (meth) acryloyl groups. , A compound having a urethane group and 10 or more (meth) acryloyl groups Component (B) in the composition of the present invention is a component that imparts excellent antifouling properties, particularly oily marker wiping properties, to the resulting cured film. .

  As aromatic diisocyanates, metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tolidine diisocyanate, 1,4-naphthalene diisocyanate 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,7-naphthalene diisocyanate, etc. are mentioned, and metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, preferable.

  Examples of the compound having 5 or more (meth) acryloyl groups include dipentaerythritol penta (meth) acrylate and tripentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate is preferable.

Furthermore, the compound of component (B) preferably has a structure represented by the following general formula (1).

In formula (1), R ¹ is a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
R ³ is a single bond, a methylene group or an ethylene group.
R ⁴ and R ⁵ each independently represent a methylene fluoride group (—CF ₂ —) or a C 2-4 perfluoroalkylene group, and are a methylene fluoride group, a perfluoroethylene group, or a perfluoropropylene group. Is preferred.
n is an integer of 5 to 50, preferably an integer of 10 to 30. When n is smaller than 5, there is a possibility that sufficient slipping property and oil marker wiping property may not be obtained when formed into a coating film, and when it is larger than 50, solubility in a solvent may be impaired.

  The molecular weight of the component (B) compound is usually in the range of 2000 to 6000, and preferably in the range of 2500 to 3500. Here, the molecular weight is measured by gel permeation chromatography.

The compound of a component (B) can be manufactured with the manufacturing method of the following this invention.
The production method of the present invention comprises (i) a step of reacting a diol compound having a perfluoropolyether structure with an aromatic diisocyanate compound,
(Ii) including a step of reacting a compound having a hydroxyl group and five or more (meth) acryloyl groups.

  More specifically, the perfluoropolyether compound having a hydroxyl group is mixed with a diisocyanate compound in a solvent such as methyl ethyl ketone or without solvent, and cooled in a 10-20 ° C. water bath. When the temperature of the solution reaches 10 to 20 ° C, a Lewis acid catalyst such as dibutyltin dilaurate is added, and the reaction solution is stirred in the range of 20 to 65 ° C for 1 to 3 hours. It can manufacture by mixing the compound which has 5 or more (meth) acryloyl groups and a hydroxyl group after that, and stirring for 3 to 6 hours at 45-65 degreeC.

The diol compound having a perfluoropolyether structure is not particularly limited as long as it is a compound having hydroxyl groups at both ends of the perfluoropolyalkylene oxide, but the terminal diol compound of perfluoropolyethylene oxide, the terminal diol compound of perfluoropolypropylene oxide Is preferred.
Examples of commercially available diol compounds having a preferred perfluoropolyether structure include Fluorolink D10H, Fluorolink D (manufactured by Solvay Solexis) and the like.

  The content of the compound (B) in the composition of the present invention is preferably in the range of 0.1 to 5% by mass, when the total of components excluding the solvent is 100% by mass, More preferably, it is in the range of ˜1% by mass. If it is less than 0.1% by mass, the effect of addition may not be exhibited. If it exceeds 5% by mass, the hardness of the coating film may be impaired.

(C) Polyfunctional polymerizable unsaturated group-containing compound The polyfunctional polymerizable unsaturated group-containing compound (C) used in the present invention is suitably used for enhancing the film-forming property of the composition. The polyfunctional polymerizable unsaturated group-containing compound (C) is not particularly limited as long as it contains two or more polymerizable unsaturated groups in the molecule, except for the components (A) and (B) described above. For example, (meth) acrylic esters and vinyl compounds can be mentioned. Of these, (meth) acrylic esters are preferred.

  (Meth) acrylic esters include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-butanediol di ( (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Hydroxyl-containing (meth) such as ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate Acrylates and poly (meth) acrylates of ethylene oxide or propylene oxide adducts to these hydroxyl groups, oligoesters (meth) acrylates having two or more (meth) acryloyl groups in the molecule, oligoether (meth) acrylates And oligoepoxy (meth) acrylates. Among these, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate and the like are preferable.

  Examples of vinyl compounds include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether.

  As a commercial item of such a polyfunctional polymerizable unsaturated group containing compound (C), Toagosei Co., Ltd. Aronix M-400, M-404, M-408, M-450, M-305, M-309, M-310, M-315, M-320, M-350, M-360, M-208, M-210, M-215, M-220, M-225, M-233, M- 240, M-245, M-260, M-270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221, M-203, TO-924, TO-1270, TO-1231, TO-595, TO-756, TO-1343, TO-902, TO-904, TO-905, TO-1330, Nippon Kayaku Co., Ltd. KAYARAD D-310, D-330, DPHA, DPC -20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, SR-295, SR-355, SR-399E, SR-494, SR-9041, SR-368, SR-415 SR-444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR -268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610, SR-9003, PET-30, T-1420, GPO-303, TC-120S, HDDA, NPGDA , TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-551, R-712, R-167, R-526, R-551, R-712, R-604, R-684, TMPTA, THE-330, TPA-320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA, Kyoeisha Chemical Co., Ltd. ) Light acrylate PE-4A, DPE-6A, DTMP-4A, and the like.

  The compounding amount of the polyfunctional polymerizable unsaturated group-containing compound (C) in the composition of the present invention is within the range of 20 to 70% by mass when the total of components excluding the solvent is 100% by mass. Preferably, it is in the range of 30 to 60% by mass. If it is less than 20% by mass, the curability of the coating film may be insufficient, and if it exceeds 70% by mass, the appearance of the coating film may be impaired.

(D) Radical polymerization initiator In addition to the components (A) to (C), the composition of the present invention preferably contains (D) a radical polymerization initiator.
Examples of such (D) radical polymerization initiator include a compound that thermally generates active radical species (thermal polymerization initiator) and a compound that generates active radical species by radiation (light) irradiation (radiation (light ) Polymerization initiators) and the like can be mentioned, and radiation (photo) polymerization initiators are preferred.

  The radiation (photo) polymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2 , 2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy Roxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2, 4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1- Methyl vinyl) phenyl) propanone) and the like.

  As a commercial item of a radiation (photo) polymerization initiator, for example, Ciba Specialty Chemicals Co., Ltd. Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG 24-61 Darocur 1116, 1173, Lucylin TPO manufactured by BASF, Ubekrill P36 manufactured by 8893UCB, Ezacure KIP150, KIP65LT, KIP100F manufactured by Fratelli Lamberti, KT37, KT55, KTO46, KIP75 / B, and the like.

  The blending amount of the radical polymerization initiator (D) in the composition of the present invention is preferably in the range of 0.01 to 20% by mass, when the total of components excluding the solvent is 100% by mass, More preferably, it is in the range of 0.1 to 10% by mass. If it is less than 0.01% by mass, the hardness of the cured product may be insufficient, and if it exceeds 20% by mass, the hardness of the coating film may be impaired.

(E) Organic solvent The composition of the present invention can be used after diluted with an organic solvent in order to adjust the thickness of the coating film. For example, the viscosity when used as an antireflection film or a coating material is usually 0.1 to 50,000 mPa · sec / 25 ° C., and preferably 0.5 to 10,000 mPa · sec / 25 ° C.
Examples of the organic solvent (E) include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone , Esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide, dimethylacetamide, Examples include amides such as N-methylpyrrolidone.

  The compounding amount of the organic solvent (E) used as necessary in the composition of the present invention is within the range of 50 to 10,000 parts by mass when the total of the components excluding the solvent is 100 parts by mass. Is preferred. The blending amount of the solvent can be appropriately determined in consideration of the coating film thickness, the viscosity of the composition, and the like.

(F) Additive In addition to the above components, a thermal polymerization initiator, an antioxidant, an ultraviolet absorber, a leveling agent, and the like can be added to the composition of the present invention as necessary.
Preferable thermal polymerization initiators include, for example, peroxides and azo compounds. Specific examples include benzoyl peroxide, t-butyl-peroxybenzoate, azobisisobutyronitrile, and the like. it can.

  The composition of the present invention can be prepared by adding the above components (A) to (F) and mixing at room temperature or under heating conditions. Specifically, it can be prepared using a mixer such as a mixer, a kneader, a ball mill, or a three roll. However, when mixing under heating conditions, it is preferable to carry out at a temperature lower than the decomposition start temperature of the polymerization initiator or polymerizable unsaturated group.

  The composition of the present invention obtained as described above can be cured by heat and / or radiation (light).

II. Cured film The cured film of the present invention can be obtained by coating and curing the curable composition on various substrates, for example, plastic substrates. Specifically, after coating the composition and preferably drying the volatile component at 0 to 200 ° C., it can be obtained as a coated molded body by performing a curing treatment with heat and / or radiation.
When using heat, as the heat source, for example, an electric heater, an infrared lamp, hot air, or the like can be used. The preferable curing conditions in the case of heat are 20 to 150 ° C., and are performed within a range of 10 seconds to 24 hours.

In the case of radiation (light), the radiation source is not particularly limited as long as the composition can be cured in a short time after coating. For example, as an infrared radiation source, a lamp, a resistance heating plate, Commercially available lasers, etc., as visible ray sources, sunlight, lamps, fluorescent lamps, lasers, etc., ultraviolet ray sources, mercury lamps, halide lamps, lasers, etc., and electron beam sources Using thermionic electrons generated from tungsten filaments, cold cathode method for generating metal through high voltage pulse, and secondary electron method using secondary electrons generated by collision between ionized gaseous molecules and metal electrode Can be mentioned. Examples of the source of alpha rays, beta rays, and gamma rays include fission materials such as ⁶⁰ Co. For gamma rays, a vacuum tube that collides accelerated electrons with the anode can be used. These radiations can be irradiated alone or in combination of two or more at a certain time. When using radiation, it is preferable to use ultraviolet rays or electron beams. In such a case, the preferable irradiation amount of ultraviolet rays is 0.01 to 10 J / cm ² , more preferably 0.1 to ² J / cm ² . Moreover, preferable irradiation conditions of the electron beam are an acceleration voltage of 10 to 300 kV, an electron density of 0.02 to 0.30 mA / cm ² , and an electron beam irradiation amount of 1 to 10 Mrad.

  The composition of the present invention is suitable for use as a coating material (hard coat) or an antireflection film. Examples of the base material to be subjected to antireflection or coating include plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin). , Epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, slate and the like. These substrates may be in the form of a plate, film or three-dimensional molded body, and the coating method may be a normal coating method such as dipping coating, spray coating, flow coating, shower coating, roll coating, spin coating, brush. A paint etc. can be mentioned. The thickness of the coating film in these coatings is usually 0.1 to 400 μm, preferably 1 to 200 μm after drying and curing.

  The cured film of the present invention has characteristics of being able to form a coating film (film) having excellent hardness and scratch resistance, and particularly excellent in oil marker wiping, and having excellent surface slippage depending on the composition. CD, DVD, MO and other recording disks, plastic optical components, touch panels, film-type liquid crystal elements, plastic containers, flooring materials for building interior materials, wall materials, artificial marble, etc. It is particularly preferably used as a protective coating material for preventing contamination, or as an antireflection film for film-type liquid crystal elements, touch panels, plastic optical components and the like.

III. Laminate The laminate of the present invention can be obtained by laminating the cured film of the present invention on a transparent substrate. A suitable transparent substrate and a laminated method of the cured film are as described above. Since the laminate of the present invention has high transparency and hardness, and is excellent in antifouling properties, in particular, oil marker wiping and sustainability, it is suitable as a surface protective film for various display devices. .

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

［式中、ｎ＝１０〜１５］ Synthesis example 1
Synthesis of Compound 1 (Compound (B))

[Where n = 10-15]

  In a reaction vessel equipped with a stirrer, a reflux pipe and a dry air introduction pipe, 2,6-di-t-butyl-p-cresol (Yoshinox BHT, manufactured by Yoshitomi Fine Chemical Co., Ltd.) (0.024 g, 0.1 mmol), Fluoropolyetherdiol (manufactured by Solvay Solexis, Fluorolink D10H) (37.00 g, 24.6 mmol), 2,4-tolylene diisocyanate (manufactured by Mitsui Chemicals Polyurethane Co., Ltd., TOLDY-100) (8.58 g, 49.2 mmol) ) And methyl ethyl ketone (manufactured by Maruzen Petrochemical Co., Ltd.) (45.58 g) are added and cooled in a water bath. After adding dibutyltin dilaurate (manufactured by Kyodo Yakuhin Co., Ltd., CASTIN-D) (0.080 g, 0.1 mmol) at 10 ° C. ± 5 ° C., the temperature was raised to 60 ° C. and heated for 1.5 hours. Next, the reaction mixture was cooled in a water bath, and dipentaerythritol pentaacrylate (Atotonix M403, manufactured by Toagosei Co., Ltd.) (108.84 g) diluted with methyl ethyl ketone to a solid content concentration of 50% was added thereto using a dropping funnel. Added. This was heated to 60 ° C. and heated for 4 hours. Thus, a methyl ethyl ketone solution (200 g) of Compound 1 represented by the above chemical structural formula was obtained.

The IR chart, ¹ H NMR chart, and ¹³ C { ¹ H} NMR chart of the obtained compound 1 are shown in FIGS.

［式中、ｎ＝６〜１０］ Synthesis example 2
Synthesis of Compound 2 (Comparative Example Compound)

[Where n = 6 to 10]

  In a three-necked flask equipped with a stirrer, 0.024 g of 2,6-di-t-butyl-p-cresol (Yoshitomi Fine Chemical, Yoshinox BHT), perfluoropolyether diol (manufactured by Solvay Solexis, Fluorolink D10H) 52.89 g, 12.4-tolylene diisocyanate (Mitsui Chemical Polyurethane Co., Ltd., TOLDY-100) 12.27 g and methyl ethyl ketone (Maruzen Petrochemical Co., Ltd.) were charged and cooled in a water bath. Then, 0.080 g of dibutyltin dilaurate (manufactured by Kyodo Yakuhin Co., Ltd., CASTIN-D) was added, and then the temperature was raised to 60 ° C. and heated for 1.5 hours. Next, the reaction mixture was cooled in a water bath, and 34.84 g of tetramethylolmethane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A-TMM-3LM-N) was added to the solid content concentration of 50% by mass with methyl ethyl ketone. Diluted material was added. The temperature was raised to 60 ° C. and heated for 4 hours. Thus, Compound 2 represented by the above chemical structural formula was obtained.

［式中、ｎ＝６〜１０］ Synthesis example 3
Synthesis of Compound 3 (Comparative Example Compound)

[Where n = 6 to 10]

  In a three-necked flask equipped with a stirrer, 0.024 g of 2,6-di-t-butyl-p-cresol (Yoshitomi Fine Chemical, Yoshinox BHT), perfluoropolyether diol (manufactured by Solvay Solexis, Fluorolink D10H) 51.16 g, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (Sumitomo Chemical Bayer Urethane Co., Ltd., Desmodur I) 15.14 g and methyl ethyl ketone 66.30 g (Maruzen Petrochemical Co., Ltd.) were charged. Cooled in a water bath. Then, 0.080 g of dibutyltin dilaurate (manufactured by Kyodo Yakuhin Co., Ltd., CASTIN-D) was added, and then the temperature was raised to 60 ° C. and heated for 1.5 hours. Next, the reaction mixture was cooled in a water bath, and 33.70 g of tetramethylolmethane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A-TMM-3LM-N) was added to the solid content concentration of 50% by mass with methyl ethyl ketone. Diluted material was added. The temperature was raised to 60 ° C. and heated for 4 hours. Thus, Compound 3 represented by the above chemical structural formula was obtained.

Production Example 1
Synthesis of organic compound (Ab) To a solution consisting of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate in dry air, 222 parts of isophorone diisocyanate was added dropwise at 50 ° C. over 1 hour, followed by 70 ° C. And stirred for 3 hours. This is composed of NK ester A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical Co., Ltd.) comprising 60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate. Of these, it is pentaerythritol having a hydroxyl group that is involved in the reaction. 549 parts were added dropwise at 30 ° C. over 1 hour, and then heated and stirred at 60 ° C. for 10 hours to obtain an organic compound (Ab) containing a polymerizable unsaturated group. When the amount of residual isocyanate in the product was analyzed by FT-IR, it was 0.1% or less, indicating that the reaction was almost quantitatively completed. Infrared absorption spectrum of the product disappeared absorption peaks characteristic 2260 cm ^-1 to the absorption peak and the raw material isocyanate compounds characteristic 2550 cm ^-1 mercapto group in the raw material, new urethane bond and S (C = O) NH- peaks characteristic 1720 cm ^-1 to a peak and an acryloxy group of characteristic 1660 cm ^-1 based on observed, acryloxy group and -S (C = O as a polymerization unsaturated group) NH-, It was shown that an acryloxy group-modified alkoxysilane having a urethane bond was formed. As a result, a total of 773 parts of organic compounds (Abs) represented by the formulas (14) and (15) and 220 parts of pentaerythritol tetraacrylate were obtained.

Production Example 2
Production of reactive particles 2.98 parts of composition produced in Production Example 1 (including 2.32 parts of organic compound (Ab)), silica particle dispersion (Aa) (solid content: 35% by mass, MEK-ST- L, number average particle size 0.022 μm, manufactured by Nissan Chemical Industries, Ltd.) 89.90 parts, ion-exchanged water 0.12 parts, and p-hydroxyphenyl monomethyl ether 0.01 parts, After stirring for 4 hours, 1.36 parts of orthoformate methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain a reactive particle dispersion. 2 g of this dispersion was weighed on an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour, and weighed to determine the solid content, which was 36.5%. Further, 2 g of the dispersion was weighed in a magnetic crucible, preliminarily dried on an 80 ° C. hot plate for 30 minutes, and calcined in a muffle furnace at 750 ° C. for 1 hour to obtain the inorganic content in the solid content. As a result, it was 95%.

<Manufacture of curable composition for hard coat formation>
Example 1
Reactive particles 178.3 parts by mass (solid content 65.08 parts by mass) produced in Production Example 2 were concentrated to a solid content of 70%, and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd .: KAYARAD DPHA). 31.52 parts by mass, photoinitiator (manufactured by Ciba Specialty Chemicals Co., Ltd .: Irgacure 184) and 0.3 part by mass of Compound 1 produced in Synthesis Example 1 and 70 parts by mass of methyl isobutyl ketone were added. Then, methyl ethyl ketone was added so that the solid content concentration was 50% by mass and stirred to obtain a curable composition.

Comparative Examples 1-3
Each curable composition was produced in the same manner as in Example 1 except that the composition shown in Table 1 was used.

  The ratio of each component is shown in Table 1 below when the total of the components excluding the solvent of each obtained curable composition is 100% by mass.

<Preparation of cured film>
Each curable composition produced in Examples, Comparative Examples and Reference Examples was coated on a TAC film substrate having a thickness of 80 μm using a bar coater (12 mil). After drying at 80 ° C. for 2 minutes, a cured film was prepared by irradiating with ultraviolet rays at an intensity of 1 J / cm ^{2 in} air using a high-pressure mercury lamp.

<Evaluation of physical properties of cured film>
The haze, total light transmittance, and contact angle of the obtained cured film were measured. Moreover, oil marker wiping property and coating film appearance were evaluated. The results are shown in Table 1.

(1) Measurement of haze The haze (%) of the cured film was measured according to JIS K7105 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.).

(2) Measurement of total light transmittance The total light transmittance (%) of the cured film was measured according to JIS K7105 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.).

(3) Oil marker wiping test An oil marker (Zebra Co., Ltd., Mackie MO-120-MC-BK) was attached to the cured film, and after 30 seconds, wiped with a non-woven fabric (trade name: Bencot S-2, manufactured by Asahi Kasei). It was. When completely wiped off, an oil marker was attached again, and wiping was repeated again. The number of possible wipings was counted and evaluated according to the following evaluation criteria.
A: Oil marker wiping possible 10 times or more B: Oil marker wiping oil marker wiping possible 5-10 times C: Oil marker wiping possible 1 to 4 times D: Oil marker wiping possible 0 times

(4) Measurement of contact angle The contact angle of the cured film with respect to water and hexadecane was measured according to JIS6768 using a contact angle meter Drop Master 500 manufactured by Kyowa Interface Chemical Co., Ltd.

(5) Appearance of coating film (face repellency)
The cured film was visually observed and evaluated according to the following evaluation criteria.
○: 10 or less repellants in the cured film 180 mm × 100 mm Δ: 10 to 30 repellants in the cured film 180 mm × 100 mm ×: More than 30 repellants in the cured film 180 mm × 100 mm

Abbreviations and the like in Table 1 represent the following.
Reactive particles: Reactive group-modified colloidal silica produced in Production Example 2 Compound 1 (DPPA-TDI-perfluoropolyether-TDI-DPPA): Compound (B) produced in Synthesis Example 1
Compound 3 (PETA-IPDI-perfluoropolyether-IPDI-PETA): Comparative compound produced in Synthesis Example 3 Compound 2 (PETA-TDI-perfluoropolyether-TDI-PETA): Reference compound produced in Synthesis Example 2 Dipentaerythritol hexaacrylate: Nippon Kayaku Co., Ltd .: KAYARAD DPHA
Irg. 184: Photopolymerization initiator manufactured by Ciba Specialty Chemicals Co., Ltd. Polydimethylsiloxane-containing urethane acrylate: manufactured by Chisso Corporation, (compound name) Silaplane FM0711

From the results shown in Table 1, the curable composition containing the compound of component (B) in the present invention has high transparency, excellent oil marker wiping properties, and excellent coating appearance. Recognize.
In Comparative Example 1 in which no surface modifier was blended, it was found that although the transparency was excellent, the oil marker wiping property was greatly inferior.
In Comparative Example 2 in which the compound of the component (B) in the present invention is not blended, the transparency and the oil marker wiping property are excellent, but the repelling occurs and the coating film appearance is greatly inferior.
In Reference Example 1, it can be seen that the coating film appearance is inferior although the transparency and oil marker wiping property are excellent.

The curable composition of the present invention is useful for producing a cured film excellent in transparency, antifouling property and coating film appearance.
The cured film of the present invention is particularly useful as a hard coat because it is excellent in transparency, antifouling property and coating film appearance. Moreover, since it is excellent in transparency and coating film appearance, it is suitable for optical applications.

Claims (11)

The following components (A) to (C):
(A) A group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony, and cerium bonded to an organic compound (Ab) having a polymerizable unsaturated group and hydrolyzable silyl group in the molecule Particles containing at least one element oxide selected from (B) a reaction product of perfluoropolyether diol and aromatic diisocyanate with a compound having 5 or more (meth) acryloyl groups. A compound having a perfluoropolyether group, a urethane group and 10 or more (meth) acryloyl groups (C), and two or more polymerizable unsaturated groups other than the above components (A) and (B). The curable composition containing the compound which has.   The aromatic diisocyanate compound is metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tolidine diisocyanate, 1,4-naphthalene. The curable composition of claim 1 selected from the group consisting of diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, and 2,7-naphthalene diisocyanate.   The curable composition according to claim 2, wherein the aromatic diisocyanate is 2,4-tolylene diisocyanate.   The curable composition according to any one of claims 1 to 3, wherein the compound having 5 or more (meth) acryloyl groups is dipentaerythritol penta (meth) acrylate.   The amount of the compound (B) is in the range of 0.1 to 5% by mass when the total amount of the components excluding the solvent is 100% by mass. The curable composition as described. The curable composition according to any one of claims 1 to 5, wherein the organic compound (Ab) further has a structure represented by the following formula (12).

[In Formula (12), U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. ]   Furthermore, (D) The curable composition of any one of Claims 1-6 containing a radical polymerization initiator.   Furthermore, (E) The curable composition of any one of Claims 1-7 containing an organic solvent.   It is an object for hard-coat formation, The curable composition of any one of Claims 1-8.   A cured film obtained by curing the curable composition according to claim 1. The laminated body formed by laminating | stacking the cured film of Claim 10 on a transparent base material.

Images