WO2006112234A1 - Resin composition, cured film, and layered product - Google Patents

Abstract

A curable resin composition which comprises the following ingredients (A) to (C): (A) a fluoropolymer having a polymerizable group; (B) an organic compound which has a polymerizable group and, after curing, has a refractive index of 1.55 or higher; and (C) one or more organic solvents selected from the group consisting of ketones and esters and in which the one or more organic solvents (C) selected from the group consisting of ketones and esters account for 30 mass% or more of all solvents. Also provided is a cured film which has a structure composed of two or more layers and is obtained by curing the composition.

Description

 Specification

 Resin composition, cured film and laminate

 Technical field

 The present invention relates to a curable resin composition and a cured film comprising the same, and in particular, for example, a cured film having a multilayer structure of two or more layers such as a low refractive index layer and a high refractive index layer is applied as a single coating. The present invention relates to a curable resin composition that can be formed from a film and a cured film comprising the same.

 Background art

 In various display panels such as liquid crystal display panels, cold cathode ray tube panels, plasma displays, etc., in order to prevent reflection of external light and improve image quality, low refractive index properties, scratch resistance, coating properties, and There is a need for an antireflection film including a low refractive index layer that has a cured product having excellent durability. In these display panels, in order to remove attached fingerprints, dust, and the like, the surface is often wiped with gauze impregnated with ethanol or the like, and scratch resistance is required. In particular, in a liquid crystal display panel, the antireflection film is provided on the liquid crystal unit in a state of being bonded to a polarizing plate. In addition, for example, triacetyl cellulose is used as the base material. However, in an antireflection film using such a base material, an alkali is usually used in order to increase the adhesion when pasted to the polarizing plate. It is necessary to perform kenning with an aqueous solution. Therefore, in applications of liquid crystal display panels, there is a demand for an antireflection film excellent in alkali resistance, particularly in durability.

[0003] As a material for a low refractive index layer of an antireflection film, for example, a fluorine-based resin coating containing a hydroxyl group-containing fluorine-containing polymer is known. Patent Document 1, Patent Document 2, Patent Document 3, and the like It is disclosed. However, in such fluorocoating-based paints, in order to cure the coating film, it is necessary to bridge the hydroxyl group-containing fluoropolymer and a curing agent such as melamine coffin by heating under an acid catalyst. Depending on the heating conditions, there are problems that the curing time becomes excessively long and the types of base materials that can be used are limited. Also, the obtained coating film has a problem that it is excellent in weather resistance but poor in scratch resistance and durability.

[0004] Therefore, in order to solve the above problems, Patent Document 4 discloses that at least one isocyanate is used. An isocyanate group-containing unsaturated compound having an acrylate group and at least one addition-polymerizable unsaturated group and a hydroxyl group-containing fluoropolymer have a ratio of the number of isocyanate groups to the number of hydroxyl groups of 0.01 to 1.0. There has been proposed a coating composition containing an unsaturated group-containing fluorine-containing polymer obtained by reacting at a ratio of

 Patent Document 1: Japanese Patent Application Laid-Open No. 57-34107

 Patent Document 2: Japanese Patent Application Laid-Open No. 59-189108

 Patent Document 3: Japanese Patent Application Laid-Open No. 60-67518

 Patent Document 4: Japanese Patent Publication No. 6-35559

[0006] These conventional antireflection films made of a fluorine-based material require a low-refractive-index layer made of a fluorine-based material to be formed on a high-refractive index layer provided on a substrate, and these layers are formed. It was necessary to provide the coating process for this separately.

 Further, the scratch resistance of the low refractive index layer as the surface layer was insufficient.

 The present invention was made against the background described above, and its purpose is to efficiently produce a low refractive index layer and a high refractive index layer, and a curable resin composition that can be cured by ultraviolet rays. To provide things. Another object of the present invention is to provide a cured film having excellent scratch resistance with high adhesion to a substrate having high transparency and excellent environmental resistance.

 Disclosure of the invention

[0007] In order to achieve the above-mentioned object, the present inventors have intensively studied, blending a polymerizable group-containing organic compound having a high refractive index with a polymerizable group-containing fluoropolymer that is cured by irradiation with ultraviolet rays, When a composition in which a specific organic solvent is combined is applied to a substrate and the solvent is evaporated, a layer containing a high concentration of fluoropolymer and a high refractive index polymerizable group-containing organic compound are obtained. It has been found that it is separated into two or more layers with a layer present at a high concentration. In addition, when silica particles are blended into this composition, silica particles are present in a high density in a layer containing a high concentration of fluoropolymer, and high refractive index polymerizable group-containing organic compounds are present in a high concentration. It was found that the layer does not exist substantially. The cured films obtained by curing these compositions by irradiating them with ultraviolet rays were confirmed to have low reflection, excellent scratch resistance, chemical resistance, antifouling properties and transparency, and completed the present invention. . [0008] According to the present invention, the following curable resin composition, a cured film and a laminate thereof are provided.

 [1] The following components (A) to (C):

 (A) a fluorine-containing polymer having a polymerizable group,

 (B) an organic compound having a polymerizable group and having a refractive index after curing of 1.55 or more,

(C) one or more organic solvents selected from the group consisting of ketones and esters, and the group group consisting of the above-mentioned (C) ketones and esters A curable resin composition in which the ratio of one or more organic solvents selected from the above is 30% by mass or more.

 [2] The fluorine-containing polymer having a polymerizable group (A) is a compound (A-1) having one isocyanate group and one or more ethylenically unsaturated groups, and a fluorine-containing polymer having a hydroxyl group. The curable resin composition according to the above [1], which is a reaction product with the polymer (A-2).

[0009] [3] when the total 100 mol _^0/0 of the fluorine-containing polymer having a hydroxyl group (A- 2) forces the following structural units (a) ~ (c), (&) 20~70 mol%, (1)) 10 to 70 mol%, and (.) 5-70 mole _^0/0 contains, and gel permeation chromatography number average molecular weight in terms of polystyrene as measured by over 5, 000-50, 000 The curable resin composition according to the above [1] or [2].

 (a) A structural unit represented by the following general formula (1).

 (b) A structural unit represented by the following general formula (2).

 (c) A structural unit represented by the following general formula (3).

 [Chemical 1]

[Wherein R ¹ represents a fluorine atom, a fluoroalkyl group, or a group represented by OR ² (R ² represents an alkyl group or a fluoroalkyl group)]

[Chemical 2] HR ³

 — C-C― (2)

HR ⁴

[Wherein R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, (CH 3) —OR ⁵

 2

Or a group represented by OCOR ⁵ (R ⁵ represents an alkyl group or a glycidyl group, X represents a number of 0 or 1), a carboxyl group, or an alkoxycarbo group]

[Chemical 3]

HR ⁶

 C-C (3)

H (CH ₂ ) _a OR ⁷

[Wherein R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a hydroxyalkyl group, and a represents a number of 0 or 1]

[4] The fluoropolymer (A-2) having a hydroxyl group is derived from an azo group-containing polydimethylsiloxane compound with respect to a total of 100 mol parts of the structural units (a) to (c). The following structural unit (d) The curable resin composition according to the above [3], comprising 0.1 to 10 mole parts.

 (d) A structural unit represented by the following general formula (4).

[Chemical 4]

R ⁸

— Si— 0—— ( ⁴ )

R ⁹

[Wherein R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group, or an aryl group]

 [5] The curability according to the above [4], wherein the fluoropolymer (A-2) having a hydroxyl group contains the structural unit (d) as a part of the following structural unit (e). A rosin composition.

(e) A structural unit represented by the following general formula (5). _R 11 _R 14 _R 15 _R 10 One C— (CH ₂ ) bCONH (CH ₂ ) c— Si— (OSi) _d (CH ₂ ) _e NHOC (CH ₂ ) _f -C—— ( _{5) R} 13 _R 16 _R 17 _R 12

[Wherein R ^{1Q to} R ¹³ represent a hydrogen atom, an alkyl group, or a cyano group, R ″ to R ¹⁷ represent a hydrogen atom or an alkyl group, b and f are numbers 1 to 6, c, e Is a number from 0 to 6, and d is a number from 1 to 200.]

 [6] The fluorine-containing polymer (A-2) having a hydroxyl group has the following structural unit (f) 0 with respect to 100 mol parts of the total of the structural units (a) to (c). The curable resin composition according to any one of the above [2] to [5], which contains ~ 5 mol parts.

 (f) A structural unit represented by the following general formula (6).

 [Chemical 6]

[Wherein R ^ia represents a group having an emulsifying action. ]

 [7] The above-mentioned compound (A-1) having one isocyanato group and one or more ethylenically unsaturated groups is 2- (meth) ataloyloxetyl isocyanate [2] ~ V of [6], the curable resin composition according to any one of the above.

 [8] The curing according to any one of [1] to [7], wherein the organic compound (B) having a polymerizable group contains one or more (meth) acryloyl groups as the polymerizable group. Rosin composition.

[9] The organic compound (B) having a polymerizable group is characterized by having one or more of the following structural units (g) to (i) as a repeating unit. The curable resin composition according to any one of [1] to [8] above.

 (g) A structural unit represented by the following general formula (7).

 (h) A structural unit represented by the following general formula (8).

 (i) A structural unit represented by the following general formula (9).

[Chemical 7]

 [Wherein X represents a hydrogen atom or a halogen atom (excluding fluorine). ]

[10] The organic compound having a polymerizable group (B) is represented by the following structural formulas (j) to (! N), and any one of the structural units (g) to (i) or 2 The curable resin composition according to any one of claims 1 to 9, which is an organic compound (Ba) comprising at least one kind and having a (meth) atyl mouth group.

 (j) A structural unit represented by the following general formula (10).

 (k) A structural unit represented by the following general formula (11).

 (1) A structural unit represented by the following general formula (12).

 (m) A structural unit represented by the following general formula (13).

[Chemical 10]

[Wherein R ¹⁹ represents a methyl group or a hydrogen atom, R ² represents an alkyl group or a hydrogen atom having 3 or less carbon atoms, and X represents a hydrogen atom or a halogen atom (excluding fluorine). ]

[Chemical 11]

(1 1)

(1 1)

[Wherein ¹ is a methyl group or a hydrogen atom, X is a hydrogen atom or a halogen atom (excluding fluorine)

). ]

 [Chemical 12]

 [Wherein R represents a methyl group or a hydrogen atom, represents an alkyl group having 3 or less carbon atoms or a hydrogen atom. ]

[Chemical 13]

[Wherein R ²⁴ is a methyl group or a hydrogen atom, X is a hydrogen atom or a halogen atom (excluding fluorine) ). Three

 [0014] [11] Organic solvent (C) Acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl acetate, ethyl acetate, acetic acid The curable resin composition according to any one of [1] to 10, wherein the curable resin composition is selected from the group consisting of butyl and lactic acid ethers, which is one kind alone or a mixture of two or more kinds.

 [12] The method according to any one of claims 1 to 11, further comprising (D) a compound having 1 or more polymerizable groups and a fluorine-containing compound having Z or one or more (meth) attalyloyl groups. The curable resin composition of

 [13] The curable resin composition according to any one of [1] to [12], further comprising (E) silica particles.

 [14] The (E) silica particles are surface-treated with an organic compound (S) having a (meth) ataryloyl group! The curable resin composition according to [13] above.

[15] (S) The strength of the organic compound having a (meth) atalyloyl group In addition to the (meth) atalyloyl group, the curable composition according to the above [14] having a group represented by the following structural formula (n): Fat composition.

 (n) A structural unit represented by the following general formula (14).

 [Chemical 14]

—— U— C— N— (14)

 II

 V

 [In the formula, U represents NH, 0 (oxygen atom) or S (ion atom), and V represents O or S. ]

 [16] The curing according to the above [14] or [15], wherein the organic compound having the (S) (meth) atalyloyl group is a compound having a silanol group in the molecule or a compound which generates a silanol group by hydrolysis. Rosin composition.

 [17] The curable resin composition according to any one of [1] to [16], further comprising (F) a radical photopolymerization initiator.

[0016] [18] A cured film obtained by curing the curable resin composition according to any one of [1] to [17] and having a multilayer structure of two or more layers. [19] One or more layers made of a cured product mainly composed of (A) a fluoropolymer having a polymerizable group, and (B) a refractive index after curing having a polymerizable group of 1 The cured film according to the above-mentioned [18], which has a layer structure of two or more layers composed of one or more layers having a cured product strength mainly composed of an organic compound of 55 or more.

 [20] The above [19], wherein the (E) silica particles are substantially present in a layer made of a cured product mainly comprising the (A) a fluorine-containing polymer having a polymerizable group. Cured film.

 [21] A laminate having the cured film according to any one of [18] to [20].

 [0017] The curable resin composition of the present invention can form a cured film having a multilayer structure of any two or more layers, such as a low refractive index layer and a high refractive index layer, from one coating film. Therefore, the manufacturing process of the cured film having a multilayer structure can be simplified.

 [0018] Since the curable resin composition of the present invention does not undergo a curing reaction by heat, it can be cured in a short time and can provide a cured film excellent in productivity.

 [0019] The curable resin composition of the present invention can be used particularly advantageously for the formation of optical materials such as an antireflection film and a selective transmission film filter, and also utilizes the high fluorine content. Thus, it can be suitably used as a paint material, a weather resistant film material, a coating material, and the like for a substrate requiring weather resistance. In addition, since the cured film has excellent adhesion to the base material and provides a good antireflection effect with high scratch resistance, it is extremely useful as an antireflection film and can be applied to various display devices. By doing so, the visibility can be improved.

 Brief Description of Drawings

 FIG. 1 shows a schematic diagram of an antireflection film laminate comprising a cured film formed from the curable resin composition of the present invention.

 FIG. 2 is a schematic view of an antireflection film laminate including a cured film formed from the curable resin composition of the present invention containing silica particles.

 FIG. 3 is an electron micrograph showing a typical two-layer separation state of the cured film of the present invention.

FIG. 4 is an electron micrograph showing a typical two-layer separation state of the cured film of the present invention containing silica particles. BEST MODE FOR CARRYING OUT THE INVENTION

 [0021] Hereinafter, the curable resin composition, the cured film, and the laminate of the present invention will be specifically described.

 [0022] I. Curable resin composition

 The curable resin composition of the present invention is

 (A) Fluoropolymer having a polymerizable group

 (B) An organic compound having a polymerizable group and having a refractive index after curing of 1.55 or more

 (C) One or more organic solvents selected from the group consisting of ketones and esters

 (D) A compound having one or more polymerizable groups and a fluorine-containing compound (compound having Z or one or more (meth) ataryloyl groups)

 (E) Silica particles

 (F) Photoradical polymerization initiator

 (G) Other ingredients

 It contains. Of these, (A) to (C) are essential components, and (D) to (G) are non-essential components to be added as necessary.

[0023] 1. Each component of the chemical resin composition of the present invention will be specifically described.

 (A) Fluoropolymer having a polymerizable group

 The component (A) of the present invention is a fluoropolymer having a polymerizable group (hereinafter sometimes referred to as “polymerizable group-containing fluoropolymer”). The polymerizable group is not particularly limited, and examples thereof include an epoxy group, a bur group, and a (meth) atalyloyl group, and among them, a (meth) atallyloyl group is preferable.

 [0024] The polymerizable group-containing fluoropolymer (A) comprises a compound (A-1) having one isocyanate group and one or more ethylenically unsaturated groups, and a fluoropolymer having a hydroxyl group ( A product obtained by reacting with A-2) and obtained by reacting isocyanate group Z hydroxyl group at a ratio of 1.1 to 1.9 is preferable.

[0025] (A-1) Compound having one isocyanate group and one or more ethylenically unsaturated groups As compound (A-1), one isocyanate group and one or more are present in the molecule. If it is a compound which has this polymeric group, it will not restrict | limit in particular. Isocyanate group When there are two or more, there is a possibility of causing gelation when reacting with the hydroxyl group-containing fluoropolymer (A-2). In addition, as the ethylenically unsaturated group, a (meth) atallyloyl group is more preferable because the curable resin composition of the present invention can be more easily cured. Examples of such a compound include 2- (meth) atalylooxychetyl isocyanate and 2- (meth) atalylooxypropylisocyanate alone or in combination of two or more.

 [0026] The compound (A-1) can also be synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate. In this case, examples of diisocyanates include 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate, 1,3 xylylene diisocyanate, 1,4 xylylene diisocyanate, 1,5 naphthalene diisocyanate , M phenylene diisocyanate, p-phenol-diisocyanate, 3, 3, 1-dimethyl-4, 4, di-dimethane-dimethane diisocyanate, 4, 4'-diphenylmethane diisocyanate, 3, 3, 1-dimethylphenol-diisocyanate, 4, 4, -biphenyl-diisocyanate, 1, 6 hexane diisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate), 2, 2 , 4 Trimethylhexamethylene diisocyanate, bis (2 isocyanatoethyl) fumarate, 6 isopropyl 1,3 phenol diisocyanate 4 diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3 bis (isocyanatemethyl) cyclohexane, tetramethylxylylene diisocyanate, 2, 5 (Or 2, 6) -bis (isocyanate methyl) bicyclo [2.2.1] heptane, etc., alone or in combination of two or more. Among these, 2,4 tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexylenoisocyanate), 1,3 bis (isocyanate methyl) cyclohexane. Xan is particularly preferred.

[0027] Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, force prolatatone (meth) acrylate, polypropylene glycol (meth) acrylate, dipentaerythritol penta (meth) ) Atalylate, pentaerythritol tri (meth) atrelate, pentaerythritol di (meth) acrylate monostearate, isocyanuric acid EO modified One kind alone or a combination of two or more kinds such as di (meth) acrylate is included. Of these, 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are particularly preferred. Examples of commercially available hydroxyl group-containing polyfunctional (meth) atalylate include, for example, Osaka Organic Chemical Co., Ltd., trade name HEA, Nippon Kayaku Co., Ltd., trade name KAYAR AD DPHA, PET-30, Toagosei Product name Alonics M-215, M-233, M-305, M-400, etc.

 [0028] When synthesizing from diisocyanate and a hydroxyl group-containing polyfunctional (meth) acrylate, the amount of the hydroxyl group-containing polyfunctional (meth) acrylate is added to 1 to 1.2 mol with respect to 1 mol of diisocyanate. preferable.

 [0029] As a method for synthesizing such a compound, a method in which diisocyanate and a hydroxyl group-containing (meth) acrylate are charged together and reacted, a method in which the diisocyanate is reacted while dropping into a hydroxyl group-containing (meth) acrylate Etc.

 [0030] (A-2) Hydroxyl group-containing fluoropolymer

 The hydroxyl group-containing fluoropolymer (A-2) is preferably composed of the following structural units (a), (b), and (c), and further includes structural units (d) and (f). Is more preferable.

 [0031] Structural unit (a)

 The structural unit (a) is represented by the following general formula (1).

 [Chemical 15]

[Wherein R ¹ represents a fluorine atom, a fluoroalkyl group, or a group represented by OR ² (R ² represents an alkyl group or a fluoroalkyl group)]

In the above general formula (1), the fluoroalkyl group of R ¹ and R ² includes a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluoro mouth. Examples thereof include fluorinated alkyl groups having 1 to 6 carbon atoms such as xyl group and perfluorocyclohexyl group. In addition, the alkyl group of R ² includes an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclohexyl group. Is mentioned.

 [0033] The structural unit (a) can be introduced by using a fluorine-containing vinyl monomer as a polymerization component. Such a fluorine-containing butyl monomer is not particularly limited as long as it is a compound having at least one polymerizable unsaturated double bond and at least one fluorine atom. Examples of this include fluoroolefins such as tetrafluoroethylene, hexafluoropropylene, 3, 3, 3-trifluoropropylene; alkyl perfluoro oral ether or alkoxyalkyl perfluorobule. Ethers: Perfluoro (alkyl butyl ether) such as perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), (propyl vinyl ether), perfluoro (butinolevino reetenole), perfluoro (isobutino vinyl ether), etc. A single perfluoro (alkoxyalkyl butyl ether) such as perfluoro (propoxypropyl butyl ether) or a combination of two or more thereof. Among these, hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl butyl ether) are more preferable, and it is more preferable to use these in combination.

 [0034] The content of the structural unit (a) is 20 to 70 when the total of the structural units (a) to (c) of the hydroxyl group-containing fluoropolymer (A-2) is 100 mol%. Mol%. If the content of the structural unit (a) is less than 20 mol%, it is difficult to develop a low refractive index, which is an optical characteristic of the fluorine-containing material intended by the present application, while the content exceeds 70 mol%. In addition, the solubility of the hydroxyl group-containing fluoropolymer (A-2) in an organic solvent, transparency, or adhesion to a substrate may be reduced. For the above reasons, the content of the structural unit (a) is 25 to 65 mol% with respect to the total of the structural units (a) to (c) in the hydroxyl group-containing fluoropolymer (A-2). More preferably, it is more preferably 30 to 60 mol%.

 [0035] Structural unit (b)

 The structural unit (b) is represented by the following general formula (2).

[Chemical 16]

[Wherein R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, (CH 3) —OR ⁵ or

 2

A group represented by OCOR ⁵ (R ⁵ represents an alkyl group or a glycidyl group, X represents a number of 0 or 1), a carboxyl group, or an alkoxycarbo group]

[0036] In the general formula (2), the alkyl group of R ⁴ or R ⁵ includes carbon such as methyl group, ethyl group, propyl group, hexyl group, cyclohexyl group, lauryl group, etc. Examples thereof include alkyl groups of 1 to 12, and examples of the alkoxycarbonyl group include a methoxycarbon group and an ethoxycarbonyl group.

[0037] The structural unit (b) can be introduced by using the above-mentioned butyl monomer having a substituent as a polymerization component. Examples of such bur monomers include methyl vinyl ethere, ethino levinino le ethere, _n propino levinino ethere, isopropino levinino ether, n-butyl vinyl ether, isobutyl vinyl ether, tert- Butyl vinyl etherenole, n-pentinolevinoreethenore, n-hexenolevinoreethenore, n-year-old cutinorebi-noreethenore, n-dodecinolevinorenotere, 2-ethenorehexinolevenoreate, cyclohexyl vinyl ether, etc. Alkyl butyl ethers or cycloalkyl butyl ethers; arethyl ethers such as ethyl allyl ether and butyl allyl ether; butyl acetate, butyl propionate, butyl butyrate, pivalate, valproic acid, versatic acid Bull, Su Carboxylic acid butyl esters such as butyl acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxy ethyl (meth) acrylate , 2-Methacrylic acid esters such as 2-ethoxyethyl (meth) acrylate, 2- (n-propoxy) ethyl (meth) acrylate; (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid , Single type or a combination of two or more types of unsaturated carboxylic acids such as itaconic acid.

[0038] The content of the structural unit (b), hydroxyl group-containing fluoropolymer sum of (A- 2) Unit configuration of (a) ~ (c) is 100 mol _^0/0, 10 it is a 70 mole _^0/0. When the content of the structural unit (b) is less than 10 mol%, the hydroxyl group-containing fluoropolymer (A-2) becomes an organic solvent. On the other hand, if the content exceeds 70 mol%, the optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluoropolymer (A-2) may deteriorate. There is. For these reasons, the content of the structural unit (b) is 20 to 60 mol with respect to the total of the structural units (a) to (c) in the hydroxyl group-containing fluoropolymer (A-2). More preferably, it is 30 to 60 mol%.

[0039] structural unit (c)

 The structural unit (c) is represented by the following general formula (3).

 [Chemical 17]

HR ⁶

— C— C ( ³ )

H (CH ₂ ) _a OR ⁷

[Wherein R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a hydroxyalkyl group, and a represents a number of 0 or 1]

[0040] In the general formula (3), as the hydroxyalkyl group of R ⁷ , 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, Examples include 5-hydroxypentyl group and 6-hydroxyhexyl group.

 [0041] The structural unit (c) can be introduced by using a hydroxyl group-containing vinyl monomer as a polymerization component. Examples of such hydroxyl-containing butyl monomers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl. Hydroxyl-containing butyl ethers such as vinyl ether, 6-hydroxyhexyl vinyl ether, etc., hydroxyl-containing butyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether, allyl alcohol, etc. Can be mentioned. In addition to the above, hydroxyl group-containing vinyl monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and proprolacton. (Meth) acrylate, polypropylene glycol (meth) acrylate, etc. can be used.

[0042] The content of the structural unit (c) is determined by the structural unit (a) of the hydroxyl group-containing fluoropolymer (A-2). When the total of-(c) is 100 mol%, it is preferably 5-70 mol%. If the content rate is less than mol%, the solubility of the hydroxyl group-containing fluoropolymer (A-2) in an organic solvent may decrease. On the other hand, if the content rate exceeds 70 mol%, the hydroxyl group-containing fluorine-containing polymer is reduced. The optical properties such as transparency and low reflectivity of the base polymer (A-2) may deteriorate. For this reason, the content of the structural unit (c) is 5 to 40 mol with respect to the total of the structural units (a) to (c) in the hydroxyl group-containing fluoropolymer (A-2). _^0/0 more rather preferable is to, still more preferably from 5 to 30 mol%.

[0043] Structural unit (d) and structural unit (e)

 The hydroxyl group-containing fluoropolymer (A-2) preferably further comprises the following structural unit (d). Hereinafter, the structural unit (d) will be described.

 The structural unit (d) is represented by the following general formula (4).

 [Chemical 18]

R ⁸

 — Si— 0—— (4)

R ⁹

[Wherein R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group, or an aryl group]

[0044] In the general formula (4), the alkyl group represented by R ⁸ or R ^{9 is} an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, or a propyl group. As trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group and the like. , A naphthyl group, and the like.

 The structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the general formula (4). Examples of such azo group-containing polysiloxane compounds include compounds represented by the following general formula (15).

[0046] [Chemical 19]

 (15)

[Wherein R ^{1Q to} R ¹³ represent a hydrogen atom, an alkyl group, or a cyano group, R ″ to R ¹⁷ represent a hydrogen atom or an alkyl group, b and f are numbers 1 to 6, c, e Is a number from 0 to 6, d is a number from 1 to 200, and m is a number from 1 to 20.]

 [0047] When the compound represented by the general formula (15) is used, the structural unit (d) is the structural unit shown below.

 Included in the hydroxyl group-containing fluoropolymer as part of (e).

 The structural unit (e) is represented by the following general formula (5).

 [Chemical 20]

One ₍₅₎

[Wherein R ^{1G to} R ¹³ , R ″ to R ¹⁷ , b, c, d, e, and f are the same as those in the general formula (15).] [0048] Examples of the alkyl group of R ^{1G to} R ¹³ include alkyl groups having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, and a cyclohexyl group, and R

Examples of the alkyl group of ^{14 to} R ¹⁷ include an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group.

In the present invention, the azo group-containing polysiloxane compound represented by the general formula (15) is particularly preferably a compound represented by the following general formula (16). .

[0050] [Chemical 21]

(16)

 [Wherein d and m are the same as those in the general formula (15). ]

[0051] The content of the structural unit (d) depends on the structural unit of the hydroxyl group-containing fluoropolymer (A-2) (a ) To (c) is preferably 0.1 to 10 mole parts per 100 mole parts in total. When the content of the structural unit (d) is less than 0.1 mol part, the surface slipperiness of the cured coating film decreases and C Η Η I—

 The scratch resistance of the coating film may be reduced. On the other hand, if the content exceeds 10 parts by mole,

 RCHII

 The group-containing fluorine-containing polymer (A-2) is inferior in transparency, and when used as a coating material, repelling and the like are likely to occur during coating. For these reasons, the content of the structural unit (d) is set to 0. 0 with respect to a total of 100 mole parts of the structural units (a) to (c) of the hydroxyl group-containing fluoropolymer (A-2). It is more preferable to use 1 to 5 parts by mole. 0.1 to 3 parts by mole is even more preferable. For the same reason, it is desirable that the content of the structural unit (e) is determined so that the content of the structural unit (d) contained therein falls within the above range.

 [0052] structural unit (f)

 The hydroxyl group-containing fluoropolymer (A-2) preferably further comprises the above structural unit (f). Hereinafter, the structural unit (f) will be described.

 [0053] The structural unit (f) is represented by the following general formula (6).

 [Chemical 22]

[Wherein represents a group having an emulsifying action]

[0054] In the general formula (6), the group having an emulsifying action of R ¹⁸ has both a hydrophobic group and a hydrophilic group, and the hydrophilic group is a polyether structure such as polyethylene oxide or polypropylene oxide. The group is preferred.

 [0055] Examples of the group having such an emulsifying action include a group represented by the following general formula (17).

[0056] [Chemical 23]

[Where η is a number from 1 to 20, ρ is a number from 0 to 4, and q is a number from 3 to 50] [0057] The structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component. Examples of such reactive emulsifiers include compounds represented by the following general formula (18).

 [0058] [Chemical 24]

( ¹⁸⁾

 [Wherein n p and q are the same as those in the general formula (17)]

[0059] The content of the structural unit (f) is 0.15 mol with respect to 100 mol parts in total of the structural units (a) to (c) of the hydroxyl group-containing fluoropolymer (A-2). Part. When the content of the structural unit (f) is less than 0.1 mol part, the effect of improving the solubility of the hydroxyl group-containing fluoropolymer (A-2) in the solvent is small, but the content exceeds 5 mol parts. In addition, the tackiness of the curable resin composition increases excessively, making it difficult to handle, and when used as a coating material, the moisture resistance decreases. For this reason, the content of the structural unit (f) is set to 0.1 with respect to a total of 100 mole parts of the structural units (a) and (c) of the hydroxyl group-containing fluoropolymer (A-2). More preferred is 3 mole parts. 0.22 More preferred is 3 mole parts.

 [0060] Molecular weight of hydroxyl-containing fluoropolymer (A-2)

 The hydroxyl group-containing fluoropolymer (A-2) has a polystyrene equivalent number average molecular weight measured by gel permeation chromatography (hereinafter referred to as “GPC”) using tetrahydrofuran (hereinafter referred to as “THF”) as a solvent. Preferably it is 5,000 500,000. The reason for this is that when the number average molecular weight is less than 5,000, the mechanical strength of the hydroxyl group-containing fluoropolymer (A-2) may decrease, while the number average molecular weight is 500,000. This is because the viscosity of the curable resin composition of the present invention is increased, and thin film coating may be difficult. For these reasons, it is more preferable that the number average molecular weight in terms of polystyrene of the hydroxyl group-containing fluoropolymer (A2) is 10,000 300,000. Further preferred.

[0061] Reaction molar ratio between compound (A-1) and hydroxyl-containing fluoropolymer (A-2) The polymerizable group-containing fluoropolymer (A) used in the present invention includes the compound (A-1) containing one isocyanate group and one or more ethylenically unsaturated groups, as described above, It is preferably obtained by reacting the hydroxyl group-containing fluorine-containing polymer (A-2) with a molar ratio of isocyanate group Z hydroxyl group of 1.1 to 1.9. The reason for this is that if the molar ratio is less than 1.1, the scratch resistance and durability may be lowered. On the other hand, if the molar ratio exceeds 1.9, the application of the curable resin composition is not possible. This is because the scratch resistance of the membrane after immersion in an alkaline aqueous solution may decrease. For this reason, the molar ratio of the isocyanate group Z hydroxyl group is more preferably 1.1 to 1.5, and even more preferably 1.2 to 1.5.

 [0062] The content of the (A) polymerizable group-containing fluoropolymer in the curable resin composition of the present invention is usually 20 to 80% by mass with respect to 100% by mass of the total composition excluding the organic solvent. Is. The reason for this is that when the content is less than 20% by mass, the above two-layer separation is insufficient and the reflectance of the hardened coating film becomes high, or a layer containing a high concentration of fluoropolymer becomes an antireflection film. This is because it is difficult to obtain an appropriate film thickness and a sufficient antireflection effect may not be obtained. On the other hand, even if the added amount exceeds 80% by mass, the two-layer separation described above becomes insufficient and the reflectance of the cured coating film becomes high, or the layer containing a high refractive index polymerizable compound at a high concentration prevents reflection. This is because it is difficult to obtain an appropriate film thickness for the film, and a sufficient antireflection effect cannot be obtained, and scratch resistance may not be obtained. For this reason, it is more preferable to set the value of the component (A) in the range of 30 to 60% by mass, more preferably 30 to 70% by mass.

 [0063] (B) Organic compound having a polymerizable group and having a refractive index after curing of 1.55 or more

 The organic compound having a polymerizable group used in the present invention is a polymerizable organic compound (hereinafter referred to as “high refractive index”) having a refractive index measured by an Abbe refractometer of a cured film cured by itself of 1.55 or more. A polymerizable group-containing organic compound (B) ”.

 [0064] In order to increase the refractive index after curing, those containing an aromatic ring or a halogen element other than fluorine in the molecular structure are preferred. Further, as the polymerizable group, a vinyl group, a (meth) atalyloyl group, a cyclic ether group or the like that can be polymerized by a photo radical initiator or a photo acid generator can be used. Of these, the (meth) atalyloyl group is most preferred!

[0065] Among the components (B), as a compound having one (meth) atalyloyl group in the molecule, benzyl (Meth) Atalylate, N— (Meth) acryl morpholide, 1—Hydroxy— 3—Phenoxypropyl (Meth) acrylate, Pacamylyl phenol acrylate, 3— o—Phenol-phenol, —1— (Meth) Ataliloyl (1) 2-hydroxypropane and the like. These commercial products include M-110, 5700 manufactured by Toa Gosei, Biscoat # 160, 192 ゝ 220, manufactured by Osaka Organic Chemical Industry, PHE manufactured by Daiichi Kogyo, BZ, BZ-A, PO-A manufactured by Kyoeisha, M600, Nippon Kayaku R — 128H, Shin-Nakamura Igaku 401P, etc.

 In order to develop a high refractive index, a compound having one or more structural units (g) to (i) represented by the following general formulas (7) to (9) as a repeating unit is used. be able to.

 [Chemical 25]

 [Wherein X represents a hydrogen atom or a halogen atom (excluding fluorine)]

[Chemical 26]

[Wherein X represents a hydrogen atom or a halogen atom (excluding fluorine)] Furthermore, in the present invention, for the purpose of improving the mechanical properties of the cured coating film, it is more preferable to use a compound containing two or more (meth) atallyloyl groups in the molecule. The polymerizable organic compound (B) is preferably a compound represented by the following structural formulas (10) to (13).

[Chemical 28]

[Wherein R ¹⁹ represents a methyl group or a hydrogen atom, represents an alkyl group or a hydrogen atom having 3 or less carbon atoms, and X represents a hydrogen atom or a halogen atom (excluding fluorine). ]

[Chemical 29]

 [In the formula, represents a methyl group or a hydrogen atom, R represents an alkyl group having 3 or less carbon atoms, or a hydrogen atom. ]

[Chemical 31]

[Wherein, R ⁴ represents a methyl group or a hydrogen atom, and X represents a hydrogen atom or a halogen atom (excluding fluorine). Three

 [0068] Commercial products that can be used as these compounds include A-B PEF, A-BPE-4, BPE-200, BPE-500 manufactured by Shin-Nakamura & Co., Ltd., Neopol 8330, 8 332 manufactured by Nippon Pica. , 8335, Osaka Organic Chemical Co., Ltd. Biscoat 700, Showa Polymer VR60, 70, 90, V776, Sartoma I SR349, 348, 601, Nippon Kaiyaku Carrad R-551, 712, Toagosei M-208, 210, TO-904, TO-905, Kyoeisha BP-2EM, BR-MA, and the like.

 [0069] Considering the hardness of the cured coating film, it is preferable to use these bifunctional or higher functional organic compounds containing a high refractive index polymerizable group as the component (B). However, a small amount of a monofunctional high refractive index compound can improve the adhesion to the base substrate, and as a result, can improve the scratch resistance. Therefore, when the total amount of component (B) is 100% by mass, it is preferred that 50% by mass or more of a bifunctional or higher compound is used. When the bifunctional or higher bifunctional or higher refractive index polymerizable organic compound is less than 50% by mass in the component (B), sufficient hardness may not be obtained, and scratch resistance may deteriorate.

[0070] The content of the (B) high refractive index polymerizable group-containing organic compound in the curable resin composition of the present invention is usually 20 to 80% by mass with respect to 100% by mass of the total composition excluding the organic solvent. %. This is because when the content is less than 20% by mass, the above two-layer separation is insufficient and the reflectance of the cured coating film becomes high, or there is a layer in which a high refractive index polymerizable organic compound is present in a high concentration. This is because it is difficult to obtain a film thickness suitable as an antireflection film, and a sufficient antireflection effect may not be obtained, and the scratch resistance may be lowered. On the other hand, when the addition amount exceeds 80% by mass, the two-layer separation described above is insufficient and the reflectance of the cured coating film is increased, or the layer containing a high concentration of the low refractive index polymerizable fluoropolymer is reflected. It becomes difficult to obtain an appropriate film thickness for the anti-reflection film, and a sufficient anti-reflection effect cannot be obtained. Also, For these reasons, it is more preferable to set the added amount of the component (B) to 20 to 70% by mass, and it is more preferable to set the value within the range of 20 to 60% by mass.

[0071] (C) One or more organic solvents selected from the group consisting of ketones and esters

 The (C) organic solvent contained in the curable resin composition of the present invention is a highly soluble solvent with respect to the above (A) polymerizable group-containing fluoropolymer, and ketones or esters may be used. it can.

 [0072] As the organic solvent used as the component (C) in the present invention, specifically, ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetone, methyl amylken, methyl propyl ketone, methyl acetate, ethyl acetate, Examples thereof include esters such as butyl acetate, ethyl lactate, propylene glycol monomethyl acetate, and propylene glycol monoethyl acetate. Of these, methyl isobutyl ketone, butyl acetate, methyl amyl ketone, and propylene glycol monomethyl acetate are preferred. In the present invention, these solvents can be used alone or as a mixed solvent of two or more.

 [0073] Furthermore, in order to develop two-layer separation of the low refractive index polymerizable group-containing fluoropolymer (A) and the high refractive index polymerizable group-containing organic compound (B) in the present invention, an organic solvent ( C) needs to be contained in an amount of 30% by mass or more in 100% by mass of the total amount of the solvent in the composition of the present invention. If the proportion of the component (C) in the total solvent is less than 30% by mass, the separability of the components (A) and (B) may be insufficient and the reflectance may be increased. Therefore, these organic solvents (C) are preferably contained in an amount of 40% by mass or more in the solvent composition, and more preferably 50% by mass or more.

 [0074] The amount of the organic solvent containing the solvent (C) in the curable resin composition is usually 300 to 5000 parts by weight, preferably 300 to 4000 parts by weight, with the total amount of solid components being 100 parts by weight. More preferably, it is 300-3000 mass parts.

 [0075] (D) a compound having one or more polymerizable groups and a fluorine-containing compound having Z or one or more (meth) atalyloyl groups

In the present invention, (D) a compound having 1 or more polymerizable groups (hereinafter referred to as “polymerizable compound (D1)” or “compound” as long as it does not interfere with layer separation of component (A) and component (B) (D1) ”), and Z or fluorinated with one or more (meth) atalyloyl groups A compound (hereinafter, sometimes referred to as “fluorine-containing (meth) ataretoy compound (D2)” or “compound (D2)”) can be blended. (The compound (D1) and the compound (D2) may be collectively referred to as “polymerizable monomer (D)”.)

[0076] (1) (Meth) atare toy compound having one or more polymerizable groups

 Here, the polymerizable group is not particularly limited, and examples thereof include a bur group, an epoxy group, and a (meth) atalyloyl group. Among them, a (meth) attaloyl group and a buyl group are preferred (meth) attaroyl. The group is particularly preferred.

[0077] The polymerizable compound (D1) having one or more polymerizable groups is used for improving the scratch resistance of a cured product obtained by curing a curable resin composition and an antireflection film using the cured product. Used. As the compound (D1), a polyfunctional (meth) acrylate compound having two or more (meth) atalyloyl groups is preferable.

 [0078] The polymerizable compound (D1) having a bur group is not particularly limited as long as it is a compound having one or more bur groups in the molecule. Examples thereof include N-vinyl-2-pyrrolidone. It is done. Examples of the commercially available polymerizable compound (D1) having such a vinyl group include Alonics M-150 (manufactured by Toagosei Co., Ltd.).

[0079] The polymerizable compound (D1) having a (meth) atalyloyl group is not particularly limited as long as it is a compound having one or more (meth) acryloyl groups in the molecule. Examples of the monomer having one (meth) atrylyl group include acrylamide, (meth) atalyloyl morpholine, 7-amino-1,3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, -Luxetetyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, ethyl diethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) Acrylamide, dimethylaminoethyl (meth) acrylate, jetylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentagen (meth) acrylate, dicyclopente-loxychetyl (meth) acrylate, dicyclopentale (Meta) Ata , N, N—Dimethyl (meth) acrylamidotetrachromium (meth) acrylate, 2-tetrachlorophenoxyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenol Le (meth) tarylate, 2-tetrabromophenoxychetyl (meth) atalylate, 2-trichrome mouth Shetyl (meth) acrylate, tribromophenol (meth) acrylate, 2-tribromophenol ochichetil (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, birucaprolatatam , N-vinylpyrrolidone, phenoxycetyl (meth) acrylate, butoxychetil (meth) acrylate, pentachlorophenol (meth) acrylate, pentabromophenol (meth) acrylate, polyethylene glycol mono (meth) Examples thereof include compounds represented by acrylate, polypropylene glycol mono (meth) acrylate, borne (meth) acrylate, and methyltriethylene diglycol (meth) acrylate. Of these monofunctional monomers, isobornyl (meth) acrylate, lauryl (meth) acrylate, and phenoxychetyl (meth) acrylate are particularly preferred.

 [0080] Commercially available products of these monofunctional monomers include, for example, Alonics M-101, M-102, M-111, M-113, M-117, M-152, TO-1210 (above, Toagosei) KAYARAD TC-110S, R-564 (above, Nippon Kayaku Co., Ltd.), Biscote 2311 HP, Biscote 2000, Biscote 2100, Biscote 2150, Biscote 8F, Biscote 17F (above, Osaka Organic Chemical) Kogyo Co., Ltd.).

[0081] In addition, examples of the polyfunctional monomer having two or more (meth) atalyloyl groups include, for example, ethylene glycol di (meth) acrylate, dicyclopentadi (meth) acrylate, triethylene glycol dialate, Tetraethylene glycol di (meth) acrylate, trisic decandyldimethylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate Di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (Meth) acrylate, force prolatatatone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide (hereinafter referred to as “EO”). ) Modified trimethylolpropane tri (meth) acrylate, Lopylene oxide (hereinafter referred to as “Po”) modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl ether (Meth) acrylic acid adduct, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta erythritol tetra ( (Meta) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol Sa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, force prolatatone modified dipentaerythritol hexa (meth) acrylate, force prolatatone modified dipentaerythritol penta (meth) Atalylate, ditrimethylolpropane tetra (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, EO modified hydrogenated bisphenol A di (meth) attaly Examples thereof include rate, PO-modified hydrogenated bisphenol A di (meth) acrylate, EO-modified bisphenol F di (meth) acrylate, (meth) acrylate of phenol novolac polyglycidyl ether, and the like.

[0082] Commercially available products of these polyfunctional monomers include, for example, SA1002 (manufactured by Mitsubishi Chemical Corporation), biscoat 195, biscoat 230, biscoat 260, biscoat 215, biscoat 310, biscoat 214HP, biscoat 295. , Biscoat 300, Biscoat 360, Biscoat G PT, Biscoat 400, Biscoat 540, Biscoat 3000, Biscoat 3700 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), Carrad R-526, HDDA, NPGDA, TPGDA, MAND A, R — 604, R—684, PET—30, GPO—303, TMPTA, THE—330, DPHA, DPHA—2H, DPHA—2C, DPHA—21, D—310, D—330, DPCA—20, D PCA— 30, DPCA—60, DPCA—120, DN—0075, DN—2475, T—1420, T—2020, T—2040, TPA—320, TPA—330, RP—1040, RP—2040, R—01 1 , R—300, R—205 (above, manufactured by Enomoto Yakuyaku Co., Ltd.), Allonics M—220, M 233, M-240, M-215, M-305, M-309, M-310, M-315, M-325, M-400, M-6200, M-6400 (above, Toagosei Co., Ltd.) ), Light Atarylate BP—4EA, BP—4PA, BP—2EA, BP—2PA, DCP—A (from Kyoeisha Chemical Co., Ltd.), New Frontier BPE—4, BR-42M, GX—8345 ( Above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), ASF-400 (above, manufactured by Nippon Steel Chemical Co., Ltd.), Lipoxy SP-1506, SP-1507, SP-1509, VR-77, SP-4010 SP-4060 (manufactured by Showa Polymer Co., Ltd.) and the like.

[0083] The compound (D1) having a polymerizable group preferably contains a compound having two or more (meth) attalyloyl groups in the molecule. Further, a compound having 3 or more (meth) attalyloyl groups in the molecule is particularly preferred. 3 or more (meta) finished Examples of the compound having a acryloyl group include the above-described tri (meth) ataretoy compounds, tetra (meth) atalertoy compounds, penta (meth) ataretoy compounds, hexa (meta ) Atarilate® compounds and other medium strengths can also be selected, and among these, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate Particularly preferred are rate, dipentaerythritol penta (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate. Each of the above compounds may be used alone or in combination of two or more.

 [0084] (2) Fluorine-containing (meth) atareto toy compound having one or more (meth) attalyloyl groups

 The fluorine-containing (meth) ataretoy compound (D2) having one or more (meth) attalyloyl groups is used to lower the refractive index of the curable resin composition.

 [0085] The compound (D2) is not particularly limited as long as it is a fluorine-containing (meth) acrylate compound having one or more (meth) atalyloyl groups. For example, perfluorooctyl cetyl (meth) acrylate, octafluoropentyl (meth) acrylate, trifluoroethyl (meth) acrylate, etc., alone or in combination of two or more Is mentioned.

 Further, a compound obtained by modifying a fluorine alcohol having two or more hydroxyl groups with (meth) acrylic acid can also be used. Here, the fluoroalcohol having two or more hydroxyl groups specifically refers to ί or 2, 2, 3, 3, 4, 4, 5, 5—one-year-old Kutafunore, one, six-hexane-old, three, , 3, 4, 4, 5, 5, 6, 6-octafluorooctane-1,8-diol. These polyfunctional fluoroalcohols can be obtained by a general esterification method such as an acid chloride method, an acid-catalyzed dehydration condensation method, or a phase transfer catalyst method, to obtain a polyfunctional fluorine monomer having a (meth) atalyloyl group. . Further, a terminal acrylic fluorine oligomer (Cartoma Co., Ltd., CN4000) can also be used. These polyfunctional fluorine (meth) acrylates can be used as the compound (D2), and can reduce the refractive index and improve the strength of the low refractive index layer.

[0087] The content of the component (D) in the curable resin composition of the present invention is not particularly limited as long as it does not prevent layer separation of the components (i) and (ii). However, it is usually 0 to 30% by mass with respect to 100% by mass of the total composition excluding the organic solvent. Addition amount If it exceeds 30% by mass, the separability of components (A) and (B) will be impaired, the reflectance of the cured coating film will be high, and sufficient antireflection effect may not be obtained.

 [0088] (E) Silica particles

 In the curable resin composition of the present invention, particles containing silica as a main component can be blended. The silica particles are added to increase the hardness of the cured film and improve the scratch resistance. As the particles mainly composed of silica, known particles can be used, and if the shape is spherical, the particles are not limited to ordinary colloidal silica but are hollow particles, porous particles, and core-shell type. It may be a particle or the like. Moreover, it is not limited to a spherical shape, and may be an irregularly shaped particle. The particle size is preferably 1 to 200 nm, more preferably 1 to 100 nm. When the particle size is 200 nm or more, the transparency of the cured coating film may be impaired. Further, the silica particles (E) are preferably colloidal silica having a solid content of 10 to 40% by mass.

 [0089] The dispersion medium is water! /, And an organic solvent is preferred. Examples of the organic solvent include alcohols such as methanol, isopropyl alcohol, ethylene glycolate, butanol, ethylene glycol monopolypropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic carbonization such as toluene and xylene. Hydrogens; Amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; Esters such as ethyl acetate, butyl acetate, γ-butalate ratatones; Organic solvents such as ethers such as tetrahydrofuran and 1,4 dioxane Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in admixture of two or more as a dispersion medium.

 [0090] Commercially available particles of silica as a main component include, for example, colloidal silica, manufactured by Nissan Chemical Industries, Ltd., trade names: methanol silica sol, IPA-ST, MEK-ST, MEK-S T-S, ΜΕΚ— ST— L, IPA— ZL, NBA— ST, XBA— ST, DMAC— ST, ST— UP ゝ ST— OUP ゝ ST— 20, ST— 40, ST— C, ST— N, ST— 0, ST-50, ST-OL, etc. can be mentioned.

[0091] Further, the surface of the colloidal silica that has been subjected to a surface treatment such as chemical modification can be used. For example, it contains a hydrolyzable silicon compound having one or more alkyl groups in the molecule or a hydrolyzate thereof. Can be reacted. Such hydrolyzable The key compounds include trimethylmethoxysilane, tryptylmethoxysilane, dimethyldimethoxysilane, dibutinoresimethoxymethoxysilane, methyltrimethoxysilane, butinoretrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, 1, 1, 1-trimethoxy-1,2,2,2 trimethylmonodisilane, hexamethyl-1,3 disiloxane, 1,1,1-trimethoxy 3,3,3 trimethyl-1,3 disiloxane, α-trimethylsilyl ω-dimethylmethoxysilyl— Examples include polydimethylsiloxane, (X-trimethylsilyl-ω-trimethoxysilyl-polydimethylsiloxane hexamethyl-1,3 disilazane, etc. In addition, hydrolyzable silicon compounds having one or more reactive groups in the molecule. You can also use 1 in the molecule. Hydrolyzable Kei-containing compound having a reactive group of the above, as having a ΝΗ group as the reactive group In example embodiment, urea propyltrimethoxysilane, Nyu-

 2

 (2 aminoethyl) 3-aminopropyltrimethoxysilane and the like having a ΟΗ group, bis (2 hydroxyethyl) 3aminotripropylmethoxysilane and the like having an isocyanate group, 3-isocyanate propyltrimethyl Methoxysilane, etc., those with thiocyanate groups, 3-thiocyanatepropyltrimethoxysilane, etc., those with epoxy groups (3-glycidoxypropyl) trimethoxysilane, 2- (3, 4-epoxy compounds) Examples of those having a thiol group such as (xyl) ethyltrimethoxysilane include 3-mercaptopropyltrimethoxysilane. A preferred compound is 3-mercaptopropyltrimethoxysilane.

 [0092] The particles (主 成分) containing silica as the main component are those that have been surface-treated with an organic compound having a (meth) atallyloyl group (hereinafter sometimes referred to as "specific organic compound (S)"). It is preferable that Powerful surface treatment enables co-crosslinking with UV curable acrylic monomers, improving scratch resistance.

 [0093] (2) Specific organic compound (S)

 The specific organic compound used in the present invention is a polymerizable compound having a (meth) ataryloyl group in the molecule. This compound is preferably a compound further containing a group represented by the following formula (14) in the molecule, a compound having a silanol group in the molecule, or a compound that generates a silanol group by hydrolysis.

[0094] [Chemical 32] — UCN—— (14)

 II

 V

 [In the formula (14), X represents NH, 0 (oxygen atom) or S (ion atom), Y represents O or S o)

 [0095] (i) Polymerizable group

 The polymerizable unsaturated group contained in the specific organic compound is an allyloyl group or a methacryloyl group.

 This polymerizable group is a structural unit that undergoes addition polymerization with an active radical species.

[0096] (ii) a group represented by formula (14)

 The specific organic compound preferably further includes a group represented by the formula (14) in the molecule. Specifically, the group [—X—C (= Y) —NH—] represented by the above formula (m) specifically includes [—0—C (= 0) —NH—], [one O—C (= S ) —NH—], [One S—C (= 0) —NH—], [One NH One C (= 0) —NH—], [One NH—C (= S) —NH—], and [ One S—C (= S) —NH—]. These groups can be used alone or in combination of two or more. Among these, from the viewpoint of thermal stability, the [—O—C (= 0) —NH—] group, the [—O—C (= S) —NH—] group, and the [—S—C (= 0) — It is preferable to use in combination with at least one of the NH—] groups.

 The group [—X—C (= Y) —NH—] represented by the formula (14) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical strength when cured. It is thought to impart properties such as adhesion to the substrate and heat resistance.

(Iii) a silanol group or a group that generates a silanol group by hydrolysis

The specific organic compound is a compound having a silanol group in the molecule (hereinafter referred to as “silanol group-containing compound” t) or a compound that generates a silanol group by hydrolysis (hereinafter referred to as “silanol group-generating compound”). Is preferred). Examples of such a silanol group-generating compound include compounds having an alkoxy group, an aryloxy group, a acetoxy group, an amino group, a halogen atom, etc. on the silicon atom. An alkoxy group or an aryloxy group is formed on the silicon atom. A compound containing the compound, that is, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable. The silanol group-generating site of the silanol group or the silanol group-generating compound is a structural unit that binds to the silica particles by a condensation reaction or a condensation reaction that occurs after hydrolysis.

 [Iv] Preferred embodiment

 Preferable specific examples of the specific organic compound (S) include, for example, a compound represented by the following formula (19).

[0099] [Chemical 33]

(OR ²⁵ ) _r

_{^{. R 26 3 r -Si- R 27}} -S- C- N- R 28 -N- C- O- R29- (- 7, (19)

 I I II V

 0 0

[0100] R ²⁵ and R ²⁶ are the same or different hydrogen atom, or an alkyl group or aryl group having 1 to 8 carbon atoms, and r and s are each independently 1, 2 or 3 Indicates a number.

Examples of R ²⁵ and R ²⁶ include methyl, ethyl, propyl, butyl, octyl, phenol, xylyl group and the like.

[0101] Examples of the group represented by [(R ²⁵ 0) R ²⁶ Si—] include, for example, a trimethoxysilyl group, a triethoxy r 3-r

 Examples thereof include a silyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.

[0102] R ²⁷ is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms, linear, it may contain a branched or cyclic structure. Examples of such an organic group include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, and dodecamethylene. Among these, preferred examples are methylene, propylene, cyclohexylene, and phenylene.

[0103] R ²⁸ is a divalent organic group, and a medium force of a divalent organic group having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500 is also selected. For example, chain polyalkylene groups such as hexamethylene, otatamethylene, dodecamethylene, etc .; alicyclic or polycyclic divalent organic groups such as cyclohexylene, norvolylene, etc .; phenylene, naphthylene, biphenylene, Polyphere And divalent aromatic groups such as amines; and these alkyl group-substituted and aryl-substituted groups. In addition, these divalent organic groups may include a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, which may contain an atomic group containing an element other than carbon and hydrogen atoms, and further, in the above formula (14). Indicating groups can also be included.

R ²⁹ is a (s + 1) -valent organic group, preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.

 [0105] 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. For example, ataryloyl (oxy) group, meta-atallyloyl (oxy) group, bur (oxy) group, probe (oxy) group, butagel (oxy) group, styryl (oxy) group, ethur ( Oxy) group, cinnamoyl (oxy) group, maleate group, allylamido group, methacrylamide group and the like. Of these, an allyloyl (oxy) group and a methacryloyl (oxy) group are preferable. Further, b is preferably a positive integer of 1 to 20, more preferably 1 to 10, particularly preferably 1 to 5.

 [0106] For the synthesis of the specific organic compound used in the present invention, for example, a method described in JP-A-9-100111 can be used. That is, (i) it can be carried out by addition reaction of mercaptoalkoxysilane, polyisocyanate compound, and active hydrogen group-containing polymerizable unsaturated compound. Alternatively, the reaction can be carried out by a direct reaction between a compound having an alkoxysilyl group and an isocyanate group in the molecule and an active hydrogen-containing polymerizable unsaturated compound. Furthermore, (c) it can be synthesized directly by addition reaction of a compound having a polymerizable unsaturated group and isocyanate group in the molecule with mercaptoalkoxysilane or aminosilane.

 [0107] Of these methods, (i) is preferably used for synthesizing the compound represented by the formula (19). More specifically, for example,

Method (a): First, by reacting a mercaptoalkoxysilane with a polyisocyanate compound, an intermediate containing an alkoxysilyl group, [S—C (= 0) —NH] group and an isocyanate group in the molecule. And then reacting the isocyanate remaining in the intermediate with an active hydrogen-containing polymerizable unsaturated compound, the unsaturated compound is converted via the [Oc (= o) -NH] group. How to combine, Method (b): First, a polyisocyanate compound and an active hydrogen-containing polymerizable unsaturated compound are reacted to form a polymerizable unsaturated group, a [—0—C (= 0) —NH] group in the molecule, and Examples include a method of forming an intermediate containing an isocyanate group, reacting this with a mercaptoalkoxysilane, and bonding the mercaptoalkoxysilane via an [S—C (= 0) —NH] group. . Furthermore, among them, the method (a) is preferred in that the polymerizable unsaturated group is not reduced by the Michael addition reaction.

[0108] In the synthesis of the compound represented by the formula (19), by reaction with an isocyanate group, [—S

As an example of an alkoxysilane capable of forming a —C (= 0) NH] group, a compound having at least one alkoxysilyl group and one mercapto group in the molecule can be given. Examples of such mercaptoalkoxysilanes include mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyldimethoxymethylsilane, mercaptopropylmethoxydimethylsilane, mercaptopropyltriphenoxysilane, mercapto And propyltributoxysilane. Among these, mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane are preferable. Further, an addition product of an amino-substituted alkoxysilane and an epoxy group-substituted mercaptan, or an addition product of an epoxysilane and an α, _ω -dimethylcaptoy compound can also be used.

 [0109] The polyisocyanate compound used for synthesizing a specific organic compound should be selected from the polyisocyanate compounds composed of chain saturated hydrocarbons, cyclic saturated hydrocarbons, and aromatic hydrocarbons. Can do.

[0110] Examples of such polyisocyanate compounds include, for example, 2, 4 tolylene diisocyanate, 2, 6 tolylene diisocyanate, 1, 3 xylylene diisocyanate, 1, 4-kisylylene diisocyanate, 1,5 naphthalene diisocyanate, m-phenylene diisocyanate, ρ-ferylene diisocyanate, 3, 3, 1 dimethyl-4, 4, diphenylmethane diisocyanate 4,4'-diphenylmethane diisocyanate, 3,3, -dimethylphenol di-diisocyanate, 4,4'-biphenyl-diisocyanate, 1,6 hexanediisocyanate, isophorone diisocyanate, Methylene bis (4-cyclohexylenoisocyanate), 2, 2, 4 trimethylhexamethylene diisocyanate, bis (2-isocyanate) Chill) fumarate, 6-isopropyl-1,3 diisocyanate, 4 diphenyl propane diisocyanate, lysine diisocyanate, hydrogenated diphenol methane diisocyanate, 1, 3 Bis (isocyanatemethyl) cyclohexane, tetramethylxylylene diisocyanate, 2,5 (or 2,6) -bis (isocyanatemethyl) bicyclo [2.2.1] heptane, etc. . Among these, 2,4 tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexylenoisocyanate), 1,3 bis (isocyanate methyl) cyclohexane and the like are preferable. These can be used alone or in combination of two or more.

 [0111] In the synthesis of the specific organic compound, by addition reaction with the polyisocyanate compound.

 As an example of an active hydrogen-containing polymerizable unsaturated compound that can be bonded via a [one OC (= 0) —NH—] group, an addition reaction with an isocyanate group in the molecule [—0—C (= 0) —NH And compounds having at least one active hydrogen atom capable of forming a group and at least one polymerizable unsaturated group.

 [0112] These active hydrogen-containing polymerizable unsaturated compounds include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2 hydroxy mono 3 Phenyloxypropyl (meth) acrylate, 1, 4 Butanediol mono (meth) acrylate, 2 Hydroxyalkyl (meth) attaroyl phosphate, 4 Hydroxy cyclohexyl (meth) acrylate, 1, 6 hexanediol mono (meta ) Atarylate, neopentyl glycol mono (meth) acrylate, trimethylol propanedi (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) ate relay And the like can be given. In addition, a compound obtained by addition reaction of a glycidyl group-containing compound such as alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate, and (meth) acrylic acid can be used. Among these compounds, 2-hydroxyxetyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate and the like are preferable.

 These compounds can be used alone or as a mixture of two or more.

[0113] (3) Surface of particles mainly composed of silica by a specific organic compound (hereinafter also referred to as particles) Processing method

 The surface treatment method of the particles with the specific organic compound is not particularly limited, but it can also be produced by mixing the specific organic compound and particles, heating and stirring. The reaction is preferably carried out in the presence of water in order to efficiently combine the silanol group-generating site of the specific organic compound with the particles. However, when the specific organic compound has a silanol group, there is no need for water. Therefore, the surface treatment can be performed by a method including an operation of mixing at least the particles and the specific organic compound.

 [0114] The reaction amount of the particles and the specific organic compound is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably, with the total of the particles and the specific organic compound being 100% by mass. Is 1% by mass or more. If the content is less than 0.01% by mass, the transparency and scratch resistance of the resulting cured product may be insufficient due to insufficient dispersibility of the particles in the composition.

 [0115] Hereinafter, the alkoxysilyl group-containing compound represented by the formula (19) as the specific organic compound

 Taking the (alkoxysilane compound) as an example, the surface treatment method will be described in more detail. The amount of water consumed by hydrolysis of the alkoxysilane compound during the surface treatment should be such that at least one alkoxy group on the silicon in one molecule is hydrolyzed. Preferably, the amount of water added or present during hydrolysis is at least one third of the number of moles of all alkoxy groups on the silicon, more preferably two minutes of the number of moles of all alkoxy groups. 1 to less than 3 times. The product obtained by mixing the alkoxysilane compound and the particles in a completely moisture-free condition is a product in which the alkoxysilane compound is physically adsorbed on the particle surface. In the cured product of the composition containing the composed particles, the effect of developing high hardness and scratch resistance is low.

[0116] In the surface treatment, the alkoxysilane compound is separately subjected to a hydrolysis operation, and then mixed with powder particles or a solvent-dispersed sol of particles, followed by heating and stirring. A method of hydrolyzing the alkoxysilane compound in the presence of particles; or a method of surface-treating the particles in the presence of other components such as a polymerization initiator can be selected. Among these, a method in which the alkoxysilane compound is hydrolyzed in the presence of particles is preferable. During surface treatment, the temperature is preferably 0 ° C or higher and 150 ° C or lower. More preferably, it is 20 ° C or higher and 100 ° C or lower. The processing time is usually in the range of 5 minutes to 24 hours.

 [0117] When powder is used during the surface treatment, an organic solvent may be added for the purpose of smoothly and uniformly carrying out the reaction with the alkoxysilane compound. 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, Esters such as ethyl lactate and y-petite ratatotone; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Dimethylformamide, dimethylacetamide, N— Examples include amides such as methylpyrrolidone. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

 The amount of these solvents added is not particularly limited as long as it meets the purpose of carrying out the reaction smoothly and uniformly.

 [0118] When a solvent-dispersed sol is used as the particles, it can be produced by mixing at least a solvent-dispersed sol and a specific organic compound. Here, an organic solvent which is uniformly compatible with water may be added for the purpose of ensuring uniformity at the initial stage of the reaction and allowing the reaction to proceed smoothly.

 [0119] In order to promote the reaction during the surface treatment, acid, salt or base may be added as a catalyst.

Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, toluenesulfonic acid, phthalic acid, malonic acid, formic acid, acetic acid, and succinic acid; methacrylic acid, acrylic acid, Examples of unsaturated organic acids such as itaconic acid include salts such as ammonium salts such as tetramethyl ammonium hydrochloride and tetraptyl ammonium hydrochloride, and examples of bases include, for example, Ammonia water, jetylamine, triethylamine, dibutylamine, primary amines such as cyclohexylamine, secondary or tertiary aliphatic amines, aromatic amines such as pyridine, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, And quaternary ammonia hydroxides such as tetraptyl ammonium hydroxide. [0120] Among these, preferred examples of the acid are organic acids and unsaturated organic acids, and the base is tertiary amine or quaternary ammonium hydroxide. The amount of addition of these acids, salts or bases is preferably 0.001 to 1.0 parts by mass, more preferably 0.01 parts by mass and 0.1 parts by mass with respect to 100 parts by mass of the alkoxysilane compound.

 [0121] It is also preferable to add a dehydrating agent to accelerate the reaction.

 As the dehydrating agent, inorganic compounds such as zeolite, anhydrous silica and anhydrous alumina, and organic compounds such as methyl orthoformate, ethyl orthoformate, tetraethoxymethane, and tetrabutoxymethane can be used. Of these, orthoesters such as methyl orthoformate and ethyl orthoformate are preferred.

 The amount of the alkoxysilane compound bound to the particles is usually 110 ° C to 800 ° C in air as a constant value of mass loss% when the dry powder is completely burned in air. It can be obtained by thermal mass spectrometry.

 [0122] The amount of the component (E) in the resin composition is usually preferably less than 30% by mass, more preferably 20% by mass or less, based on the total amount of the composition other than the organic solvent. If the particle amount force is S30% by mass or more, the separability of the components (A) and (B) may be insufficient, and the reflectance of the cured coating film may be increased. The amount of particles means a solid content, and when the particles are used in the form of a solvent dispersion solution, the amount of the solvent does not include the amount of the solvent.

 [0123] (F) Photoradical polymerization initiator

 In the curable resin composition of the present invention, if necessary, (F) a photo radical polymerization initiator (radiation (photo) polymerization initiator) that generates active radical species by radiation (light) irradiation is used. Can be combined.

[0124] 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 benzil ketal, 1-hydroxycyclohexyl. Phenyl ketone, 2,2-dimethoxy-1,2-diphen-l-ethane 1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzobenzoenone 4, 4'-dimethoxybenzophenone, 4, 4'-diaminobenzopheno , Benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenol) 2 hydroxy-1-2-methylpropane-1-one, 2-hydroxy-2-methyl-1-phenylpropane 1-one, thixanthone, dimethylthioxanthone, 2-isopropylthixanthone, 2-chlorothiaxanthone, 2 methyl 1 [4 (methylthio) phenol] 2 morpholinopropane 1 on, 2-benzyl 1-2-dimethylamino 1 1- ( 4 morpholinophenol) butane 1-one, 1, 4 1 (2 hydroxyethoxy) felt (2 hydroxy-2 propyl) ketone, 2, 4, 6 — trimethylbenzoyldiphosphine oxide, bis 1 (2, 6 dimethoxybenzoyl) 2, 4, 4 trimethylpentylphosphine oxide, oligo (2 hydride) Carboxymethyl 2-methyl-1 one (4 one (1 Mechirubi - Le) Hue - Le) as possible out include propanone) and the like.

 [0125] Commercially available products of radiation (photo) polymerization initiator include, for example, Ciba 'Specialty' Chemicals Co., Ltd. trade names: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, Darocur 1116, 1173, manufactured by BAS F Company name: Lucyrin TPO, manufactured by UCB Product name: Nubekril P36, manufactured by Lamberti Company Product name: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KT046, ΚΙΡ75ΖΒ, etc.

 [0126] The amount of the radical photopolymerization initiator (F) used as needed in the present invention is usually 100 to 10% by mass of the composition excluding the organic solvent, and is usually compounded in an amount of 0 to 10% by mass, It is preferable to add 0.01 to 10% by mass, and more preferably 0.1 to 10% by mass. If it exceeds 10% by mass, the cured product may not be cured to the inside (lower layer).

 [0127] (G) Other ingredients

In the curable composition of the present invention, as long as the effects of the present invention are not impaired, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, and a surface active agent are used as necessary. Agents, plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, inorganic fillers, pigments, dyes, slip agents, and the like can be appropriately blended. In addition, for the purpose of improving coating properties, methanol, ethanol, isopropyl alcohol, t-butyl alcohol, 2-butyl alcohol, propylene glycol monomethyl ether are used within the range not impairing the layer separation in the present invention. In addition, organic solvents other than component (C) such as propylene glycol monoethyl ether can be used.

 [0128] 2. Method for producing curable resin composition

 The composition of the present invention is produced as follows.

 Polymerizable group-containing fluoropolymer (component (A)), high refractive index polymerizable group-containing organic compound (component (B)), organic solvent (component (C)), and polymerizable monomer ( (D) component), silica particles ((E) particles), photo radical polymerization initiator ((F) component), etc. are placed in a reaction vessel equipped with a stirrer and stirred at 35 ° C. to 45 ° C. for 2 hours. It is set as the curable resin composition of this.

[0129] 3. Application of curable resin composition (coating)

 The curable resin composition of the present invention is suitable for use as an antireflection film or a coating material. Examples of the base material to be used for 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 base materials may be plate-like, film-like or three-dimensionally formed by a usual coating method such as date coating, spray coating, flow coating, shower coating, ronore coating, spin coating, brush. For example, painting. The thickness of the coating film by these coatings is usually 0.01 to 0.5 / z m after drying and curing, and preferably 0.05 to 0.5.

[0130] 4. Method of curing curable resin composition

The curable resin composition of the present invention can be cured by 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, a laser, or the like is visible. Sun rays, lamps, fluorescent lamps, lasers, etc. as ray sources, mercury lamps, halide lamps, lasers, etc. as ultraviolet ray sources, and electron beam sources, generated from commercially available tungsten filaments Examples include methods that use hot electrons, cold cathode methods that generate high-voltage pulses in metals, and secondary electron methods that use secondary electrons generated by collisions between ionized gaseous molecules and metal electrodes. . In addition, as a source of alpha rays, beta rays and gamma rays, for example, fission materials such as ^6G Co For gamma rays, a vacuum tube or the like that causes accelerated electrons to collide with the anode can be used. These radiations can be used alone or in combination of two or more simultaneously or over a period of time.

[0131] When using radiation, have the preferred to a value within the range of exposure amount of 0. 01~10j / cm ^2. This is because if the exposure dose is less than 0. OljZcm ² , curing failure may occur. On the other hand, if the exposure dose exceeds lOjZcm ² , the curing time may become excessively long. . For this reason, it is more preferable to set the exposure amount to a value in the range of 0.05 to 5 j / cm ² , and more preferably to a value in the range of 0.3 to ³ jZcm ² .

 [0132] The curing reaction of the curable resin composition of the present invention may be performed under anaerobic conditions.

 This is because the inhibition of radical polymerization by oxygen is suppressed, the curing reaction further proceeds, and the mechanical properties of the cured coating film can be improved. As the gas used for anaerobic conditions, an inert gas such as nitrogen, carbon dioxide, or helium can be used. Of these, nitrogen is preferred.

 [0133] II. Cured film

 The cured film of the present invention is obtained by curing the curable resin composition of the present invention, and has a multilayer structure of two or more layers. In particular, the (A) one or more layers in which the polymerizable group-containing fluorine-containing polymer is present at a high concentration, and the (B) one or more layers in which the (B) high refractive index polymerizable group-containing organic compound is present at a high concentration. It is preferable to have a layer structure of two or more layers.

[0134] The cured film of the present invention can be obtained by coating and curing the curable resin composition on various substrates, for example, plastic substrates. Specifically, it is possible to obtain a coated molded body by coating the composition, and preferably drying the volatile component at 15 to 200 ° C. and then performing the curing treatment with the above-mentioned radiation. In such a case, the preferable irradiation amount of ultraviolet rays is 0.01 to 10 jZcm ² , and more preferably 0.1 to ² JZC m ² . Further, preferable electron beam irradiation conditions are a pressurization voltage of 10 to 300 KV, an electron density of 0.02 to 0.30 mAZcm ² , and an electron beam irradiation amount of 1 to: LOMrad.

[0135] After applying the curable resin composition, in the process of evaporating and drying the organic solvent (C) in the composition, the polymerizable group-containing fluorine-containing compound (A) is fluorine. Repeating organic groups contained Since it is included in the structure as a unit, it is unevenly distributed near the interface near the atmosphere where the surface free energy is low, so that the (A) component is concentrated at a high concentration near the atmosphere interface of the cured coating film. A fat layer is formed. On the other hand, on the coating base side opposite to the air interface, the component (B) is unevenly distributed, and a high refractive index resin layer concentrated to a high concentration is formed.

 [0136] Accordingly, a cured film having a layer structure of two or more layers can be obtained by curing one coating film having a curable resin composition strength. Each of these separately formed layers can be confirmed, for example, by calculating the refractive index of the cured film from the reflectance curve of the obtained cured film. The layer in which the component (A) is present at a high concentration is substantially a layer composed mainly of the component (A), but the component (B) may coexist in the layer. On the other hand, the layer in which the component (B) is present in a high concentration is substantially a layer composed mainly of the component (B), but the component (A) may coexist in the layer. The cured film of the present invention typically has a two-layer structure in which a layer in which the component (A) is present at a high concentration and a layer in which the component (B) is present at a high concentration form a continuous layer. When TAC resin is used as the base material, usually the base layer, (B) component is present in a high concentration, and (A) component is present in a high concentration in this order. Is formed.

 [0137] A typical configuration of an antireflection film using the cured film of the present invention will be described with reference to FIG.

 In the cured film of the present invention, a hard coat layer 2 is formed on the substrate 1 as necessary, and a coating film made of the curable resin composition of the present invention is formed on the hard coat layer 2 and cured. By doing so, the high refractive index layer 3 in which the component (B) is present at a high concentration and the low refractive index layer 4 in which the component (A) is present at a high concentration are formed from one coating film. Figure 3 shows a two-layer electron microscope photograph formed in this way. The right side of FIG. 3 is the air side, and the left side is the side close to the substrate. It can be seen that a layer in which the component (A) is present at a high concentration and a layer in which the component (B) is present at a high concentration form two continuous layers.

[0138] The (A) polymerizable group-containing fluoropolymer in the curable resin composition of the present invention has an antireflective property whose refractive index is lower than that of a thermosetting resin (for example, a melamine compound). It has favorable optical characteristics as a low refractive index layer of the film. By using a polymerizable group-containing organic compound having a high refractive index after curing as the constituent material of (B), an antireflection film having better antireflection properties can be obtained. [0139] The cured film of the present invention has a high hardness and can form a coating film (film) excellent in scratch resistance and adhesion to adjacent layers such as a substrate and a substrate or a hard coat layer. have. In addition, since no heat is used for the curing reaction, it does not involve a hydrolysis reaction caused by the thermosetting reaction, and thus the resulting cured film has excellent heat and heat resistance. Therefore, the cured film of the present invention is particularly suitably used for an antireflection film for film-type liquid crystal elements, touch panels, plastic optical parts and the like.

 [0140] The film thickness of the resulting cured film consisting of two or more continuous layers should be set as appropriate according to the purpose and application, but when used as a high refractive index layer and a low refractive index layer of an antireflection film In this case, the thickness of the entire cured film having a force of two or more layers is usually in the range of 0.1 to 1 μm, and preferably in the range of 0.15 to 0.

 In addition, the thickness of only the low refractive index layer in which the component (A) is present at a high concentration is usually in the range of 0.05 to 0.2 / zm, preferably in the range of 0.05-0.15 / zm. It is. The thickness of only the high refractive index layer in which the component (B) is present in a high concentration is usually in the range of 0.05 to 0.9 / zm, preferably in the range of 0.05 to 0.5 / zm. .

 [0141] The degree of change in reflectance of the cured film obtained can be adjusted by the content and type of components (A) and (B), the content and type of component (D) (polymerizable monomer), and the like. Furthermore, the reflectance of the cured film can also be adjusted by (C) the type and dilution of the organic solvent.

 Further, the refractive index in the low refractive index portion of the cured film is, for example, 1.30 to: L 50, and the refractive index in the high refractive index portion is 1.55 to: L 70.

 [0142] Further, when (E) silica particles are blended in the composition of the present invention, in the two-layer separation described above,

The component (E) is unevenly distributed in the layer in which the component (A) is present at a high concentration. In this case, the (E) component is unevenly distributed at a high density in the (A) low refractive index layer and the (E) component is substantially absent, while the (B) component is present in a high concentration layer. To separate. This layer separation can be confirmed by observing the cured coating film with a transmission electron microscope and by calculating the refractive index. The component (E) is unevenly distributed in the low refractive index layer in which the component (A) is present in a high concentration, thereby improving the hardness of the low refractive index layer and improving the scratch resistance. Furthermore, when the component (E) is surface-treated with an organic compound having a polymerizable group (specific organic compound (S)), the silica particles and the polymerizable fluoropolymer are chemically bonded, and the scratch resistance is further improved. The [0143] A typical structure of an antireflection film using the cured film of the present invention comprising the curable resin composition of the present invention containing the component (E) will be described with reference to FIG.

 In the cured film of the present invention, a hard coat layer 2 is formed on the substrate 1 as necessary, and a coating film made of the curable resin composition of the present invention is formed on the hard coat layer 2 and cured. As a result, a high refractive index layer 3 in which component (B) is present at a high concentration and a low refractive index layer 4 in which component (A) is present at a high concentration are formed from one coating film. The silica particles 5 as the component (E) are present in the low refractive index layer 4 where the component) is present at a high concentration. Fig. 4 shows an electron micrograph of the two layers thus formed. The left side of Fig. 4 is the air side, and the right side is the side close to the substrate. It can be seen that a layer containing (E) component silica particles and having a high concentration of component (A) and a layer having a high concentration of component (B) forms two continuous layers. Power.

 [0144] III. Laminate

 The laminate of the present invention is a laminate having a cured film having a layer structure of two or more layers obtained from the curable resin composition of the present invention as a part of the laminate structure. Any two or more adjacent layers other than the base material layer constituting the laminate of the present invention can be produced as a cured film of the curable resin composition of the present invention.

 For example, when the substrate is a transparent substrate, the laminate of the present invention is an excellent antireflection film by providing a low refractive index layer on the outermost layer (the layer farthest from the substrate). In addition to the antireflection film, the laminate of the present invention can be used for optical parts such as a lens and a selective transmission film filter.

 The specific layer configuration of the antireflection film is not particularly limited. Usually, at least a high-refractive index film and a low-refractive index film are laminated in this order on a base material to provide an antireflection function. In addition to this, a hard coat layer, an antistatic layer and the like can be included in a part of the layer structure of the laminate. Since the cured film obtained by curing the curable resin composition of the present invention can form a high refractive index layer and a low refractive index layer on a substrate in one step, the manufacturing process is simplified. I can do it.

[0145] The cured film of the present invention usually comprises two layers of a high refractive index layer and a low refractive index layer, and is formed on a base material to form a laminate suitable as an antireflection film. You can. An antireflection film as a typical example of the laminate of the present invention is shown in FIG. [0146] The antireflection film may further include layers other than these. For example, a plurality of combinations of a high refractive index film and a low refractive index film are provided, and the antireflection film is relatively uniform with respect to light in a wide wavelength range. An antistatic layer may also be provided that serves as a so-called wideband antireflection film having excellent reflectance characteristics.

 [0147] The substrate is not particularly limited, but when used as an antireflection film, for example, the above-mentioned plastics (polycarbonate, polymethylmetatalylate, polystyrene, polyesterol, polyolefin, epoxy resin, melamine resin) And triacetyl cellulose (TAC) resin, ABS resin, AS resin, norbornene resin, and the like.

 [0148] [Example]

 EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to the description of these examples. In Examples, unless otherwise specified, “parts” means parts by mass and “%” means mass% unless otherwise specified.

 [0149] Production Example 1: Production of hydroxyl-containing fluoropolymer (A-2)

 After replacing the stainless steel autoclave with a 1.5 L magnetic stirrer with nitrogen gas, 1200 g of ethyl acetate, 346.3 g of perfluoro (propyl butyl ether), 93.8 g of ethyl vinyl ether, hydroxyethyl vinyl ether 114. 6 g, “Adekalia Soap ER-30” as a nonionic reactive emulsifier (Asahi Denka Kogyo Co., Ltd., solid content concentration 15%) 427.8 g, “VPS-1001” as an azo group-containing polydimethylsiloxane (Wako Pure Chemical Industries, Ltd.) 20. Og and lauroyl peroxide 3. After adding Og and cooling to 50 ° C with dry ice-methanol, oxygen in the system was removed again with nitrogen gas.

[0150] Next, 214.8 g of hexafluoropropylene was added, and the temperature increase was started. The pressure when the temperature in the autoclave reached 60 ° C was 5.3 X 10 ⁵ Pa. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours, and when the pressure dropped to 1.7 × 10 ⁵ Pa, the autoclave was cooled with water to stop the reaction. After reaching room temperature, the unreacted monomer was released and the autoclave was released to obtain a polymer solution having a solid content of 29%. The obtained polymer solution was put into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 780 g of a fluoropolymer (A-2).

[0151] Production Example 2: Production of acryloyl group-containing fluoropolymer (A-3) In a separable flask with a capacity of 1 liter equipped with a magnetic stirrer, glass cooling tube and thermometer, 50.0 g of the hydroxyl group-containing fluoropolymer (A-2) obtained in Production Example 1 was used as a polymerization inhibitor. Di-t-butylmethylphenol 0. Olg and methylisobutylketone (hereinafter referred to as “MIBK”) 374 g were charged, and the hydroxyl group-containing fluoropolymer (A-2) was dissolved in MIBK at 20 ° C. Stirring was performed until the solution became clear and uniform. Next, 2-atallyloyloxetyl isocyanate (A-1) 16. Og was added to this system, and the mixture was stirred until the solution became homogeneous. Then, 0.1 lg of dibutyltin dilaurate was added and reacted. Then, the temperature of the system was maintained at 55 to 65 ° C. and stirring was continued for 5 hours to obtain a MIBK solution of the ethylenically unsaturated group-containing fluoropolymer (A-3). 2 g of this solution was weighed into an aluminum dish, dried on a hot plate at 150 ° C. for 5 minutes, and weighed to determine the solid content, which was 15.0%.

Production Example 3: Synthesis of specific organic compound (S-1) having a polymerizable group

To a solution consisting of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate in dry air, add 222 parts of isophorone diisocyanate at 50 ° C with stirring for 1 hour, then at 70 ° C. The mixture was heated and stirred for 3 hours. This new Nakamura I匕学Ltd. NK Ester A -. TMM- 3LM- N (consisting of 40 wt% pentaerythritol Atari rate 60 mass _^0/0 and pentaerythritol Lumpur tetra strike rate Among them, involved in the reaction It is only pentaerythritol tritalylate having a hydroxyl group.) After dropping 549 parts at 30 ° C over 1 hour, the organic compound containing a polymerizable group is heated and stirred at 60 ° C for 10 hours. Obtained. When the amount of isocyanate remaining in the reaction solution was analyzed by FT-IR, it was 0.1% or less, indicating that the reaction was almost quantitatively completed. In the infrared absorption spectrum of the product, the 2550 Kaiser absorption peak characteristic of the mercapto group in the raw material and the 2260 Kaiser absorption peak characteristic of the raw material isocyanate compound disappeared, and the urethane bond and S ( C = 0) A peak of 1660 Kaiser characteristic of NH group and a peak of 1720 Kaiser characteristic of atalyloxy group are observed, and atalyloxy group as polymerizable unsaturated group and S (C = O) NH-, It was shown that oxy-oxy group-modified alkoxysilane having both urethane bonds was produced. As described above, 773 parts of the compounds represented by the following formulas (20) and (21) are mixed, and 220 parts of pentaerythritol tetraatalylate which does not participate in the reaction are mixed. A composition (S-1) was obtained.

 [Chemical 34]

 [In the formula, Acryl represents an allyloyl group, Me represents a methyl group. ]

 [0153] Production Example 4: Production of silica particles (E-1) having a polymerizable group

 Composition containing a specific organic compound synthesized in Production Example 3 (S-1) 4.0 parts, methyl ethyl ketone silica sol (MEK-ST-L, manufactured by Nissan Chemical Industries, number average particle size 0.04 μm, silicic force concentration 30 %) 91.3 parts (solid content: 27.4 parts), 0.2 parts of isopropanol and 0.1 part of ion-exchanged water were stirred at 80 ° C for 3 hours, and then methyl orthoformate 1.4 parts Then, the mixture was further heated and stirred at the same temperature for 1 hour to obtain a colorless transparent particle dispersion (E-1). 2 g of the particle dispersion (E-1) was weighed in an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, and weighed to determine the solid content, which was 35% by mass.

 [0154] Production Example 5: Production of compound (D-1) having two or more (meth) atalyloyl groups

A solution consisting of 18.8 parts of isophorone diisocyanate and 0.2 part of dibutyltin dilaurate in a vessel equipped with a stirrer was added to NK Estel A-TMM-3LM-N (Shin Nakamura Chemical Co., Ltd.). (Only the pentaerythritol triatalylate having a hydroxyl group is added.) 93 parts are added dropwise at 10 ° C. for 1 hour, and then stirred at 60 ° C. for 6 hours. It was. The product in this reaction solution, that is, the amount of residual isocyanate was measured with FT-IR in the same manner as in Production Example 3, and was 0.1% by mass or less, indicating that the reaction was carried out almost quantitatively. confirmed. In addition, it was confirmed that the molecule contained a urethane bond and an allyloyl group (polymerizable unsaturated group).

 As a result, 75 parts of the compound represented by the following formula (22) was obtained, and 37 parts of pentaerythritol tetraatalylate that was not involved in the reaction were mixed to obtain a mixture (D-1). .

 [0155] [Chemical 36]

 [In the formula, Acryl represents an allyloyl group. ]

[0156] Production Example 6: Production of hydroxyl-containing fluoropolymer (A-4)

 After replacing the stainless steel autoclave with an internal volume of 1.5 L with nitrogen gas sufficiently with nitrogen gas, 1600 g of ethyl acetate, hexafluoropropene 405. Og, ethyl vinyl ether 32. Og, hydroxy ethyl vinyl ether 99. “VPS-1001” as Og and azo group-containing polydimethylsiloxane (Wako Pure Chemical Industries, Ltd.) 24. Og and lauryl peroxide 4. Add Og and dry ice—methanol at −50 ° C After cooling to 0, oxygen in the system was removed again with nitrogen gas.

Next, 1-bi-loxyheptafluorodecane 330. Og was added, and the temperature was raised. The pressure when the temperature inside the autoclave reached 60 ° C was 5.2 X 10 ⁵ Pa. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours, and when the pressure dropped to 1.7 × 10 ⁵ Pa, the autoclave was cooled with water to stop the reaction. After reaching room temperature, unreacted monomers were released and the autoclave was opened to obtain a polymer solution having a solid content of 30%. The obtained polymer solution was put into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 740 g of a fluoropolymer (A-4). [0157] Production Example 7: Production of fluorinated polymer (A-5) containing ataliloyl group

 In Production Example 2, the same operation was carried out except that (A-4) was used instead of the hydroxyl group-containing fluoropolymer (A-2), and the ethylenically unsaturated group-containing fluoropolymer (A — An Ml BK solution of 5) was obtained. The solid content was determined in the same manner as in Production Example 2 and found to be 15.0%.

[0158] Production Example 8: Production of hydroxyl-containing fluoropolymer (A-6)

 After replacing the stainless steel autoclave with an internal volume of 1.5L with a nitrogen stirrer sufficiently with nitrogen gas, ethyl acetate 2100g, ethyl vinyl ether 6 lg, hydroxyethyl butyl ether 186g, 1-bi-oxyl hepta 621 g of decafluorodecane, “Adekaria soap ER-30” (asahi Denka Kogyo Co., Ltd., solid concentration 15%) as a non-ionic reactive emulsifier, 1200 g, “VPS— 1001 ”(manufactured by Wako Pure Chemical Industries, Ltd.) and 8 g of lauroyl peroxide were cooled to 150 ° C. with dry ice / methanol, and oxygen in the system was removed again with nitrogen gas.

Next, 760 g of hexafluoropropylene was added, and the temperature was raised. The pressure when the temperature inside the autoclave reached 60 ° C was 5.3 X 10 ⁵ Pa. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours, and when the pressure dropped to 1.7 × 10 ⁵ Pa, the autoclave was cooled with water to stop the reaction. After reaching room temperature, the unreacted monomer was released and the autotarve was released to obtain a polymer solution with a solid content of 29%. The obtained polymer solution was poured into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 1500 g of a fluoropolymer (A-6).

[0159] Production Example 9: Production of hydroxyl-containing fluoropolymer (A-7)

After replacing the stainless steel autoclave with an internal volume of 1.5 L with nitrogen gas sufficiently with nitrogen gas, 1400 g of ethyl acetate, 506 g of perfluoro (propyl butyl ether), 15 lg of hydroxy stilbyl ether, 1-loxy-leptadecadeca Fluorodecane 93g, “Adekaria soap NE-30” (asahi Denka Kogyo Co., Ltd., solid content concentration 15%) 150g as a nonionic reactive emulsifier, “VPS-1001” as an azo group-containing polydimethylsiloxane (Wako Pure Chemical Industries, Ltd.) Add 23g and 4g lauroyl peroxide, cool to 50 ° C with dry ice and methanol, remove oxygen in the system again with nitrogen gas, and start heating did. The pressure when the temperature in the autoclave reaches 60 ° C is 5.3 X 10 ⁵ Pa It was. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours. When the pressure dropped to 1.7 × 10 ⁵ Pa, the autoclave was cooled with water to stop the reaction. After reaching room temperature, the unreacted monomer was released and the autoclave was opened to obtain a polymer solution having a solid content of 30%. The obtained polymer solution was poured into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 720 g of a fluoropolymer (A-7).

 [0160] Production Example 10: Production of polymerizable group-containing fluoropolymer (A-8)

 In a separable flask with a capacity of 10 liters equipped with a magnetic stirrer, a glass cooling tube and a thermometer, 680 g of the hydroxyl group-containing fluoropolymer (A-6) obtained in Production Example 8 was used as a polymerization inhibitor. Di-t-butylmethylphenol (0.1 lg) and MIBK4800g were charged, and the mixture was stirred at 20 ° C until the hydroxyl group-containing fluoropolymer (A-6) was dissolved in MIBK and the solution became clear and uniform. Next, 162 g of 2-Ataloyloxetyl isocyanate (A-1) was added and stirred until the solution became homogeneous, and then 1.7 g of dibutinoretin dilaurate was added to start the reaction. The MIBK solution of the ethylenically unsaturated group-containing fluoropolymer (A-8) was obtained by maintaining the temperature at 55 to 65 ° C and continuing stirring for 5 hours. 2 g of this solution was weighed in an aluminum dish, dried on a hot plate at 150 ° C. for 5 minutes, and weighed to obtain a solid content of 15%.

 [0161] Production Example 11: Production of polymerizable group-containing fluoropolymer (A-9)

A separable flask with a capacity of 1 liter equipped with a magnetic stirrer, glass cooling tube and thermometer was charged with 20 g of the hydroxyl group-containing fluoropolymer (A-7) obtained in Production Example 9, MIBK 180 g, and dimethylaline 5 g. The mixture was charged and stirred at room temperature until the solution was uniform. Next, 3.8 g of acrylic acid chloride was added and stirred until the solution became homogeneous, and then stirred for 12 hours while maintaining the temperature at 55 to 65 ° C. Then, it cooled to room temperature and 8g of 10% ammonia water was dripped. The reaction mixture solution thus obtained was poured into 1 liter of a mixed solution of methanol and water (mixing ratio methanol: water = 9: 1) to precipitate the polymer. The poor solvent was removed with decantation, and 200 g of MIBK was added and stirred until the solution became homogeneous. Then, 2 g of anhydrous magnesium sulfate was added, and the mixture was further stirred for 1 hour. After standing overnight, anhydrous magnesium sulfate was filtered off to obtain a MIBK solution of an ethylenically unsaturated group-containing fluoropolymer (A-9). Weigh 2g of this solution in an aluminum dish, dry on a hot plate at 150 ° C for 5 minutes, and weigh. The solid content was determined to be 10%.

 [0162] Example 1: Preparation of curable resin composition 1

 Hydroxyl group-containing fluoropolymer (A-2) obtained in Production Example 1 4.75 g (4.75 g as a polymerizable group-containing fluoropolymer), 9, 9-bis [4- (2-Ataliloyl) Oxyethoxy) phenol] fluorene (A—BPEF, Shin-Nakamura Chemical Co., Ltd.) 4. 75 g, 2-methyl-1- (4- (methylthio) phenol] -2 morpholinopropane-1-one ( (Irgacure 907, manufactured by Ciba “Specialty” Chemicals) 0.05 g and MIBK 115 g were stirred. The solid content concentration of the obtained curable resin composition was 8%.

 [0163] Example 2: Preparation of curable resin composition 2

 MIBK solution of Ataliloyl group-containing fluoropolymer (A-3) obtained in Production Example 2 31.7 g (4.75 g as a polymerizable group-containing fluoropolymer), 9, 9 Bis [4- (2-Ataliloylo) Xylethoxy) phenol] fluorene (A—BPEF, Shin-Nakamura Chemical Co., Ltd.) 4. 75 g, 2-methyl- 1 1 [4 (methylthio) phenol] 2 morpholinopropane 1-on (Irgacure 907, Chinoku ' (Specialty Chemicals) 0.05g and MIBK88.lg were stirred and stirred. The resulting curable resin composition had a solid content concentration of 8%.

 [0164] Examples 3 to 23, Comparative Examples 1 to 8

 A curable resin composition was obtained in the same manner as in Examples 1 to 2, except that each component was blended in the proportions shown in Tables 1 to 5. In Examples 7 to 13, Production Example 2 and Production Example 2 were used except that each dilution solvent listed in Table 3 was used instead of MIBK in Synthesis Example 2 to synthesize the alicyclic fluorinated polymer (A-3). A curable resin composition was obtained using the dilute solvent shown in each example by using the atalyloyl group-containing fluoropolymer (A-3) produced in the same manner.

[0165] A cured film was prepared using the curable resin composition produced in Examples 1 to 23 and Comparative Examples 1 to 8, and the characteristics of the cured film were evaluated. The method for producing the cured film is as follows: Silica particle sol (MEK-ST, manufactured by Nissan Chemical Industries, number average particle size 0.022 m, silica concentration 30%) 98.6 g, 2-methyl-1 [4 ( Methylthio) phenol] 2 Morpholinop Mouth pan 1-one (IRGACURE907, manufactured by Chinoku 'Specialty' Chemicals) 1. 2g, polyfunctional urethane acrylate oligomer (U-6HA, manufactured by Shin-Nakamura Chemical Co., Ltd.) 33. 2g, cyclo 7 g of hexanone was mixed and stirred to obtain a composition for a node coat layer containing silica particles. After coating this silica particle-containing composition for a node coat layer on a triacetyl cellulose film (LOFO, film thickness 80 μm) using a wire bar coater (# 12), it was heated in an oven at 80 ° C. Dried for 1 minute. Subsequently, a hard coat layer was formed by irradiating ultraviolet rays under a light irradiation condition of 0.3 jZcm ² using a high-pressure mercury lamp in the air. When the film thickness of the hard coat layer was measured with a stylus type film thickness meter, it was 5 μm.

[0166] Using the wire bar coater (# 3), each curable resin composition obtained in Examples 1 to 19 and Comparative Examples 1 to 8 was applied onto the obtained node coat layer. And dried at room temperature for 5 minutes. Then, a cured film layer having a total film thickness of 0.2; zm was formed by irradiating ultraviolet rays under a light irradiation condition of 0.9 jZcm ² using a high-pressure mercury lamp lamp in a nitrogen atmosphere.

 [0167] <Evaluation of cured film>

 The obtained cured film was evaluated for the following characteristics. The obtained results are shown in Tables 1-5. (1) Appearance

 The cured film obtained by the above-described method was visually observed under a fluorescent lamp, and appearance defects such as a rainbow pattern due to uneven coating of foreign matter due to foreign matters were evaluated according to the following criteria.

 A: No uneven coating is observed on the cured film.

 A: Although coating unevenness is slightly observed on the cured film, there is no problem in use. Δ: Application unevenness is observed in the cured film.

 X: Many uneven coatings are observed on the cured film.

[0168] (2) Haze

 Turbidity (Haze value) in the obtained laminate was measured using a Haze meter and evaluated according to the following criteria.

 : Haze value is 0.5% or less.

 ○: Haze value is 1% or less.

 Δ: Haze value is 3% or less.

 X: Haze value exceeds 3%.

[0169] (3) Reflectance

Spectral reflectance measurement device (large sample chamber) The reflectance was measured in the wavelength range of 340 to 700 nm using a self-recording spectrophotometer U-3410 equipped with an integrating sphere attachment device 150-09090 (manufactured by Hitachi, Ltd.) and evaluated. Specifically, the reflectance of the antireflection laminate (antireflection film) at each wavelength was measured using the reflectance of the deposited aluminum film as a reference (100%), and from the reflectance of light at a wavelength of 550 nm, The antireflection property was evaluated according to the following criteria.

 A: The reflectance is 1% or less.

 ○: Reflectance is 2% or less.

 Δ: Reflectance is 3% or less.

 X: Reflectance exceeds 3%.

[0170] (4) Meta-steel wool

 The steel wool resistance test of the cured film was performed by the following method. In other words, steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) is attached to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film is loaded. Scratching was repeated 10 times under the condition of 500 g, and the presence or absence of scratches on the surface of the cured film was visually evaluated according to the following criteria.

 A: No peeling or scratches are observed on the cured film.

 ◯: Almost no peeling or scratching of the cured film is observed.

 Δ: Fine and scratches are observed in the cured film.

 X: Peeling occurred on a part of the cured film, or streak scratches occurred on the surface of the cured film.

[0171] (5) Cloth resistance

 The cloth resistance test of the cured film was carried out by the following method. In other words, Bencott (S-2, manufactured by Asahi Kasei Co., Ltd.) was attached to a Gakushin friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film was loaded 100 times under the condition of load lkg. By rubbing repeatedly, the presence or absence of scratches on the surface of the cured film was visually evaluated according to the following criteria.

 A: No peeling or scratches are observed on the cured film.

 ◯: Almost no peeling or scratching of the cured film is observed.

 Δ: Fine and scratches are observed in the cured film.

X: Peeling occurred on a part of the cured film, or streak scratches occurred on the surface of the cured film. [0172] (6) Chemical resistance

 The chemical resistance test of the cured film was performed by the following method. A drop of 3% aqueous sodium hydroxide, 1% hydrochloric acid, ethanol, MEK and glass mypet (manufactured by Kao) was dropped on the resulting antireflection film and left at room temperature for 30 minutes. Thereafter, the chemical solution was wiped off with Bencott (S-2, manufactured by Asahi Kasei Co., Ltd.) and dried at room temperature for 3 minutes. Then, the dropped marks were visually evaluated according to the following criteria.

 ○: V, no peeling or scratches on the cured film is observed even with misaligned chemicals!

 Δ: One or more kinds of chemicals show peeling or scratches on the cured film.

 X: Exfoliation and scratches of the cured film are observed with all chemicals.

[0173] (7) Antifouling property

 The antifouling test of the cured film was carried out by the following method. A fingerprint was adhered on the obtained antireflection film, and the fingerprint was wiped with Bencot (S-2, manufactured by Asahi Kasei Co., Ltd.). The wiping trace was visually evaluated according to the following criteria.

 ○: Fingerprints can be completely wiped off.

 Δ: Fingerprints remain slightly.

 X: Fingerprints cannot be wiped off at all.

[0174] (8) Eye

 Based on the reflectance curve obtained from the above (3) reflectance measurement, the color space value (b *) from an angle of 10 ° with a C light source was used for evaluation according to the following criteria.

 ◎: b * is less than 5

 〇 ： b * is over 5 and under 8

 △: b * is more than -8 and less than 10

 X: b * is over 10

[0175] [Table 1] Table ^

3 S017 Table 2

Table 3

Table 4

[] [0179] [Table 5]

 Table 5

 In each table, “refractive index after curing” means a refractive index measured with an Abbe refractometer of a cured film cured with the component alone.

[0181] Details of the components described in each table are shown below.

 (Α) Ingredients:

 Hydroxyl group-containing fluoropolymer Α-2 (Manufactured in Production Example 1)

 Ataliloyl group-containing fluorine-containing polymer A-3 (Manufactured in Production Example 2)

 Ataliloyl group-containing fluoropolymer A-5 (manufactured in Production Example 7)

 (B) component:

 9, 9 Bis [4 (2-Atalyloxyethoxy) phenol] fluorene (Shin-Nakamura Chemical A-BPEF)

 Bisphenol A EO-modified diatalylate (Sartoma 1 SR—349)

Brominated bisphenol A epoxy diatalylate (Nippol, Nippon Pica 8330) Bisphenol A epoxy acrylate (Neopol 8332, Nippon Pica) Epoxy acrylate of copolymer of fluorene and bisphenol A (Nippa Oponole 8335)

Diluting solvent (including organic solvent of component (C)):

 All solvents were manufactured by Wako Pure Chemical.

 Component (D):

 Phenoxetyl Atylate (PHE)

 Dipentaerythritol Hexaatalylate (Nippon Kayaku DPHA)

 N-Bulu-2-pyrrolidone (Toagosei M-150)

 Compound (D— 1) (Manufactured in Production Example 5)

 CN4000 (Certoma's terminal acrylic fluorine oligomer)

 (E) component:

 Acrylic modified silica particles (E-1) (Manufactured in Production Example 3)

 Component (F):

 2-Methyl-1 4 (Methylthio) phenol] 2-Morpholinopropane 1-on (Chinok. Irgacure 907 from Specialty Chemicals)

 (G) component:

 Both ends methacryl-modified polydimethylsiloxane (Chisso FM7725, both ends methacrylic polydimethylsiloxane, slip agent)

Industrial applicability

 The curable resin composition of the present invention can form a cured film having a multilayer structure of two or more layers on a substrate from one coating film.

 The curable resin composition of the present invention and the cured product thereof may be damaged by, for example, plastic optical parts, touch panels, film-type liquid crystal elements, plastic containers, floor materials as building interior materials, wall materials, artificial marble, etc. Protective coating materials for preventing (scratching) and preventing contamination; antireflection films for film-type liquid crystal elements, touch panels, plastic optical parts, etc .; adhesives and sealing materials for various substrates; printing ink binder materials, etc. It can be suitably used as an antireflection film.

Claims

 The scope of the claims  [1] The following ingredients (A) to (C):  c F F——  (A) a fluorine-containing polymer having a polymerizable group,  RCFII  (B) an organic compound having a polymerizable group and having a refractive index after curing of 1.55 or more, (C) one or more organic solvents selected from the group consisting of ketones and esters, and the group group consisting of the above-mentioned (C) ketones and esters A curable resin composition in which the ratio of one or more organic solvents selected from the above is 30% by mass or more. [2] The (A) fluorine-containing polymer having a polymerizable group comprises a compound (A-1) having one isocyanate group and one or more ethylenically unsaturated groups, and a fluorine-containing polymer having a hydroxyl group. 2. The curable resin composition according to claim 1, which is a reaction product with the coalescence (A-2). [3] When the fluorine-containing polymer having a hydroxyl group (A- 2) is, with a total of 100 mole _^0/0 of the following structural units (a) ~ (c), (&) 20~70 mol%, (1)) 10 to 70 mol%, and (.) 5-70 Mo containing Le _^0/0, and polystyrene conversion arithmetic average molecular weight measured by gel permeation chromatography chromatography is 5, 000-50, is 000 Curable resin assembly according to claim 1 or 2,  Adult.  (a) A structural unit represented by the following general formula (1).  (b) A structural unit represented by the following general formula (2).  (c) A structural unit represented by the following general formula (3).  [Chemical 37]  1 — (1) [Wherein R ¹ represents a fluorine atom, a fluoroalkyl group, or a group represented by OR ² (R ² represents an alkyl group or a fluoroalkyl group)]  [Chemical 38] HR ³  — C-C—— (2) HR ⁴ [Wherein R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, (CH 3) —OR ⁵  2 Or a group represented by OCOR ⁵ (R ⁵ represents an alkyl group or a glycidyl group, X represents a number of 0 or 1), a carboxyl group, or an alkoxycarbo group]  [Chemical 39]

[Wherein R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a hydroxyalkyl group, and a represents a number of 0 or 1] [4] The fluoropolymer (A-2) having a hydroxyl group is converted into an azo group-containing polydimethylsiloxane compound with respect to a total of 100 mol parts of the structural units (a) to (c). The curable resin composition according to claim 3, comprising 0.1 to 10 mol parts of the following structural unit (d) derived from:  (d) A structural unit represented by the following general formula (4).  [Chemical 40] R ⁸  — Si-O— (4) R ⁹ [Wherein R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group, or an aryl group] [5] The curable resin according to claim 4, wherein the fluoropolymer (A-2) having a hydroxyl group contains the structural unit (d) as a part of the following structural unit (e). Composition.  (e) A structural unit represented by the following general formula (5).  [Chemical 41] R ¹¹ R ¹⁴ R ¹⁵ . —— C— (CH ₂ ) _b CONH (CH ₂ ) c— Si— (OSi) _d {CH ₂ ) _e NHOC (CH ₂ ) _f -C) _R 13 _R 16 _R 17 _R 12 [Wherein R ^{1Q to} R ¹³ represent a hydrogen atom, an alkyl group, or a cyan group, and R ″ to R ¹⁷ represent a hydrogen atom. A child or an alkyl group, b and f are numbers from 1 to 6, c and e are numbers from 0 to 6, and d is a number from 1 to 200. ]  [6] The fluorine-containing polymer (A-2) having a hydroxyl group has the following structural units (f) 0 to 5 mol parts with respect to 100 mol parts of the total of the structural units (a) to (c): The curable resin composition according to any one of claims 2 to 5, comprising  (f) A structural unit represented by the following general formula (6).  [Chemical 42]

[Wherein R ^ia represents a group having an emulsifying action. ] [7] The compound (A — 1) having one isocyanato group and one or more ethylenically unsaturated groups is 2- (meth) taroloyloxetyl isocyanate. 6. The curable resin composition according to 6.  [8] The curable composition according to any one of claims 1 to 7, wherein the organic compound (B) having a polymerizable group contains one or more (meth) attayl groups as the polymerizable group. A rosin composition.  [9] The organic compound (B) having a polymerizable group has one or more of the following structural units (g) to (i) as a repeating unit. The curable resin composition according to any one of -8.  (g) A structural unit represented by the following general formula (7).  (h) A structural unit represented by the following general formula (8).  (i) A structural unit represented by the following general formula (9).  [Chemical 43]

[Wherein X represents a hydrogen atom or a halogen atom (excluding fluorine). ] [Chemical 44]

 [Wherein X represents a hydrogen atom or a halogen atom (excluding fluorine). ]  (B) The organic compound having a polymerizable group is represented by the following structural formulas (j) to (! N), and the structural units (g) to (i) are either one kind or two kinds or more. The curable resin composition according to any one of claims 1 to 9, wherein the curable resin composition is an organic compound (Ba) which contains and has a (meth) atallyloyl group.  (j) A structural unit represented by the following general formula (10).  (k) A structural unit represented by the following general formula (11).  (1) A structural unit represented by the following general formula (12).  (m) A structural unit represented by the following general formula (13). [Chem 46]

[Wherein R ¹⁹ represents a methyl group or a hydrogen atom, represents an alkyl group or a hydrogen atom having 3 or less carbon atoms, and X represents a hydrogen atom or a halogen atom (excluding fluorine). ] [Chemical 47]

 [In the formula, represents a methyl group or a hydrogen atom, R represents an alkyl group having 3 or less carbon atoms, or a hydrogen atom. ] [Chemical 49]

 (13) [Wherein R ²⁴ represents a methyl group or a hydrogen atom, and X represents a hydrogen atom or a halogen atom (excluding fluorine). ] Organic solvent (C) Acetone, methyl ethyl ketone, methyl isobutyl ketone, methinoreaminoleketone, propylene glycol monomethino ethenore acetate, propylene glycol monoethyl ether acetate, methyl acetate, ethyl acetate, The curable resin composition according to claim 1, which is selected from the group consisting of butyl acetate and ethyl lactate, and is a single type or a mixture of two or more types. [12] The method according to any one of claims 1 to 11, further comprising (D) a compound having one or more polymerizable groups and a fluorine-containing compound having Z or one or more (meth) acryloyl groups. The curable resin composition according to 1.  [13] The curable resin composition according to any one of claims 1 to 12, further comprising (E) silica particles.  14. The curable resin composition according to claim 13, wherein the (E) silica particles are subjected to a surface treatment with an organic compound (S) having a (meth) atallyloyl group. [15] The organic compound having the (S) (meth) attalyloyl group is added to the (meth) attaroyl group. 15. The curable resin composition according to claim 14, which has a group represented by the following structural formula (n).  (n) A structural unit represented by the following general formula (14).  [Chemical 50] — U-C-N— (14)  II  V  [In the formula, U represents NH, 0 (oxygen atom) or S (ion atom), and V represents O or S. ]  [16] The curable resin composition according to claim 14 or 15, wherein the organic compound having a (meth) attalyloyl group is a compound having a silanol group in the molecule or a compound generating a silanol group by hydrolysis. object.  [17] The curable resin composition according to any one of claims 1 to 16, further comprising (F) a photoradical polymerization initiator.  [18] A cured film obtained by curing the curable resin composition according to any one of claims 1 to 17, and having a multilayer structure of two or more layers. [19] One or more layers made of a cured product mainly composed of the (A) polymerizable group-containing fluoropolymer, and the (B) polymerizable group having a refractive index after curing of 1. 19. The cured film according to claim 18, wherein the cured film has a layered structure of two or more layers composed of one or more layers. [20] The method according to claim 19, wherein the (E) silica particles are substantially present in a layer composed of a cured product mainly comprising the (A) a fluorine-containing polymer having a polymerizable group. Cured film. [21] A laminate having the cured film according to any one of claims 18 to 20.