KR100896123B1 - Liquid curable resin composition, cured film and multilayer body - Google Patents

Abstract

The present invention relates to (A) hydroxyl group-containing fluorine-containing polymer and / or ethylenically unsaturated group-containing fluorine-containing polymer, (B) curable compound, (C) curing catalyst, (D) silicon dioxide particles having a number average particle diameter of 100 nm or less, and (E) Applying a liquid curable resin composition containing a solvent with a sp value of greater than 8.5 and less than 12.8 to a substrate and removing the solvent, two layers of silicon dioxide and a layer substantially free of silicon dioxide When separated into layers and cured, it is possible to provide a cured film having excellent adhesion to a substrate, high scratch resistance and good antireflection effect.

Liquid curable resin composition, cured film

Description

Liquid curable resin composition, cured film, and laminated body {LIQUID CURABLE RESIN COMPOSITION, CURED FILM AND MULTILAYER BODY}

The present invention relates to a liquid curable resin composition, and in particular, a liquid curable resin composition having a high transparency and low refractive index and capable of forming a cured film having good scratch resistance, a cured film comprising the same, and a cured film thereof. It relates to a laminate to be made.

According to the development of multimedia, various developments have been made in various display devices (display devices). In addition, among various display devices, especially those that are used outdoors, especially in portable devices, the improvement of visibility thereof becomes more and more important, and even in large display devices, it is required from the consumer to make it easier to see. The matter became a technical task.

As a means for improving the visibility of a conventional display device, an antireflection film made of a low refractive index material is coated on a substrate of the display device. As a method of forming the antireflection film, for example, a thin film of a fluorine compound is deposited. The method of forming by is known. By the way, the technique which can form an anti-reflective film in low cost and large size display apparatus centering on a liquid crystal display device is calculated | required in recent years. However, in the case of the vapor deposition method, it is difficult to form a uniform antireflection film with high efficiency on a large-area substrate, and it is difficult to lower the cost because a vacuum device is required.

From these circumstances, a method of forming an antireflection film by dissolving a fluoropolymer having a low refractive index in an organic solvent to produce a liquid composition and applying it to the surface of a substrate has been studied. For example, it is proposed to apply fluorinated alkylsilane to the surface of a substrate (see Patent Document 1 and Patent Document 2, for example). Moreover, the method of apply | coating the fluoropolymer which has a specific structure was proposed (for example, refer patent document 3).

Patent Document 1: Japanese Patent Application Laid-Open No. 61-40845

Patent Document 2: Japanese Patent Application Laid-Open No. 6-98703

Patent Document 3: Japanese Unexamined Patent Publication No. 6-115023

In order to form two layers which are continuous on these base materials, these conventional anti-reflective films by the fluorine-type material needed to provide the application | coating process for forming these layers separately.

This invention is made on the background of the above situation, The objective is to provide the liquid curable resin composition which can manufacture arbitrary two or more layers efficiently. Another object of the present invention is to provide a cured film having high transparency, high adhesion to a substrate, and excellent scratch resistance (steel wool resistance).

In order to achieve the above object, the present inventors earnestly researched and obtained by hardening this by using the liquid curable resin composition containing the fluorine-containing polymer and silicon dioxide particle which have a specific structure, and the solvent which has a sp value of a specific range. The cured film was found to be layered into a layer in which silicon dioxide particles are present at a high density and a layer substantially free of silicon dioxide particles, and that the obtained two-layer film was excellent in scratch resistance, thereby completing the present invention.

<Start of invention>

That is, this invention provides a liquid curable resin composition, the cured film formed by hardening it, and a laminated body.

[1] (A) At least one fluorine-containing polymer selected from the group consisting of a fluorine-containing polymer having a hydroxyl group in the molecule and an ethylenically unsaturated group-containing fluorine-containing polymer,

(B) curable compound,

(C) curing catalyst,

(D) silicon dioxide particles having a number average particle diameter of 100 nm or less,

(E) Solvents with sp values greater than 8.5 and less than 12.8

Liquid curable resin composition comprising a.

[2] The liquid curable resin composition according to the above [1], wherein the sp value of the solvent (E) is from 8.9 to 10.

[3] A cured film having a two-layer structure composed of a layer in which silicon dioxide particles are present at a high density and a layer substantially free of silicon dioxide particles, obtained by curing the liquid curable resin composition according to the above [1].

[4] A method for producing a cured film having a step of curing the liquid curable resin composition according to the above [1] by heating or irradiating with radiation.

[5] A laminate having at least one or more layers on the substrate, the layer comprising the cured film according to the above [3].

[6] The laminate according to the above [5], wherein the laminate comprises a layer made of the cured film and another layer between the base material.

[7] The above [6] layer, wherein the other layer includes one or more layers selected from the group consisting of a hard coating layer, a layer having a refractive index of 1.5 to 1.7, and a layer having a refractive index of 1.3 to 1.5 and a layer having a refractive index of 1.6 to 2.2. Laminate.

[8] The laminate according to the above [5], wherein the substrate comprises triacetyl cellulose, polyethylene terephthalate resin, polycarbonate resin, acrylic resin, acrylic / styrene copolymer resin, polyolefin resin, norbornene-based resin, or glass.

[9] The laminate according to the above [5], which is an optical component.

[10] The laminate according to the above [5], which is for an antireflection film.

The liquid curable resin composition of this invention can be used advantageously for formation of optical materials, such as an anti-reflective film and an optical fiber sheath material, and also the paint material and weatherproof film with respect to the base material where weather resistance is requested | required using the thing with high fluorine content. It can be preferably used as a material for coating, a material for coating, and the like. Moreover, since the said cured film is excellent in adhesiveness with respect to a base material, high scratch resistance, and provides a favorable antireflection effect, it is very useful as an antireflection film, and its visibility can be improved by applying to various display apparatuses.

1 is an electron micrograph showing a typical two-layer separation state.

2 is an electron micrograph showing a uniform state without layer separation.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

1.Liquid curable resin composition

The liquid curable resin composition of this invention contains the following components (A)-(E).

(A) at least one fluorine-containing polymer selected from the group consisting of a fluorine-containing polymer having a hydroxyl group in the molecule and an ethylenically unsaturated group-containing fluorine-containing polymer

(B) curable compound

(C) curing catalyst

(D) Silicon dioxide particles having a number average particle diameter of 100 nm or less

(E) Solvents with sp values greater than 8.5 and less than 12.8

Hereinafter, each of these components is demonstrated.

(A) at least one fluorine-containing polymer selected from the group consisting of a fluorine-containing polymer having a hydroxyl group in the molecule and an ethylenically unsaturated group-containing fluorine-containing polymer

The fluorine-containing polymer is a polymer having a carbon-fluorine bond in a molecule, and in the present invention, a fluorine-containing polymer having a hydroxyl group in the molecule (hereinafter referred to as a "hydroxyl-containing fluorine-containing polymer") and an ethylenically unsaturated group-containing fluoropolymer At least one fluorine-containing polymer selected from the group consisting of is used. When thermosetting the liquid curable resin composition of this invention, since a hydroxyl group is needed as a reaction site with (B) component, a hydroxyl-containing fluorine-containing polymer is used. In the case of radiation curing, an ethylenically unsaturated group-containing fluorine-containing polymer is used. A hydroxyl group containing fluorine-containing polymer and ethylenically unsaturated group containing fluorine-containing polymer can also be used together.

(1) hydroxyl-containing fluorine-containing polymer

As an example of a preferable hydroxyl-containing fluorine-containing polymer, what has a polysiloxane segment in the main chain which contains 10 mol%-50 mol% of structural units derived from the monomer containing a hydroxyl group is mentioned. The hydroxyl group-containing fluorine-containing polymer preferably has a fluorine content of 30 mass% or more, more preferably 40 to 60 mass%, and the number average molecular weight in terms of polystyrene obtained by gel permeation chromatography is preferably 5000 or more. More preferably, it is 10000-500000. Here, a fluorine content is the value measured by the alizarin complexon method, and a number average molecular weight is a value when tetrahydrofuran was used as a developing solvent.

The hydroxyl group-containing fluorine-containing polymer is an olefin polymer having a polysiloxane segment represented by the following formula (1) in the main chain, and the proportion of the polysiloxane segment in the fluorine-containing polymer is usually 0.1 to 20 mol%.

In formula, R <^1> and R <^2> may be same or different and represents a hydrogen atom, an alkyl group, a halogenated alkyl group, or an aryl group.

The hydroxyl group-containing fluorine-containing polymer is (a) a fluorine-containing olefin compound (hereinafter referred to as "(a) component") and (b) a monomer compound containing a hydroxyl group copolymerizable with the (a) component (hereinafter "(b) component ) And (c) an azo group-containing polysiloxane compound (hereinafter referred to as "(c) component") and, if necessary, (d) a reactive emulsifier (hereinafter referred to as "(d) component") and / or (e It can obtain by making monomer compounds other than the (b) component copolymerizable with the said (a) component react.

Examples of the fluorine-containing olefin compound as the component (a) include compounds having at least one polymerizable unsaturated double bond and at least one fluorine atom. Specific examples thereof include (1) tetrafluoroethylene and hexafluoropropylene. Fluoroolefins such as 3,3,3-trifluoropropylene; (2) perfluoro (alkylvinylether) s or perfluoro (alkoxyalkylvinylether) s; (3) Perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether), etc. Perfluoro (alkyl vinyl ether) s; (4) perfluoro (alkoxyalkyl vinyl ether) such as perfluoro (propoxypropyl vinyl ether); And the like. These compounds can be used alone or in combination of two or more. Among the above, hexafluoropropylene, perfluoro (alkyl vinyl ether) or perfluoro (alkoxy alkyl vinyl ether) is particularly preferable, and it is more preferable to use these in combination.

As a monomer compound containing the hydroxyl group which is (b) component, it is (1) 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, for example. Hydroxyl group-containing vinyl ethers such as 3-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, and 6-hydroxyhexyl vinyl ether; (2) hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether; (3) allyl alcohol; (4) hydroxyethyl (meth) acrylic acid ester; And the like. These compounds can be used alone or in combination of two or more. Preferably they are hydroxyl-containing alkyl vinyl ethers.

As the azo group-containing polysiloxane compound as the component (c), a compound containing azo groups readily thermally decomposed as -N = N- and having a polysiloxane segment represented by the above formula (1), for example, It can manufacture by the method of Unexamined-Japanese-Patent No. 6-93100. As a specific example of (c) component, the compound represented by following General formula (2) is mentioned.

In formula, y is 10-500 and z is 1-50.

Preferred combinations of the above (a) component, (b) component and (c) component include, for example, (1) fluoroolefin / hydroxyl group-containing alkylvinylether / polydimethylsiloxane units, (2) fluoroolefin / perfluoro (Alkyl vinyl ether) / hydroxyl group-containing alkyl vinyl ether / polydimethylsiloxane unit, (3) fluoroolefin / perfluoro (alkoxyalkyl vinyl ether) / hydroxyl group-containing alkyl vinyl ether / polydimethylsiloxane unit, (4) fluoro Olefin / perfluoro (alkylvinylether) / hydroxyl group-containing alkylvinylether / polydimethylsiloxane unit, (5) fluoroolefin / perfluoro (alkoxyalkylvinylether) / hydroxyl group-containing alkylvinylether / polydimethylsiloxane unit. .

In this hydroxyl-containing fluorine-containing polymer, the structural unit derived from (a) component becomes like this. Preferably it is 20-70 mol%, More preferably, it is 25-65 mol%, Especially preferably, it is 30-60 mol%. When the ratio of the structural unit derived from (a) component is less than 20 mol%, the fluorine content in the fluorine-containing polymer obtained will become too small, and the hardened | cured material of the obtained liquid curable resin composition does not become low enough in refractive index. On the other hand, when the ratio of the structural unit derived from (a) component exceeds 70 mol%, the solubility to the organic solvent of the hydroxyl-containing fluorine-containing polymer obtained will fall remarkably, and the liquid curable resin composition obtained will have transparency and adhesiveness to a base material. Becomes smaller.

In the hydroxyl-containing fluorine-containing polymer, the structural unit derived from the component (b) is preferably 10 to 50 mol%. More preferably, the lower limit is 13 mol% or more, more preferably more than 20 mol%, 21 mol% or more, still more preferably the upper limit is 45 mol% or less, and still more preferably 35 mol% or less. . By constructing a liquid curable resin composition using a hydroxyl group-containing fluorine-containing polymer containing a predetermined amount of such a component (b), good two-layer separation, good scratch resistance and dust removal property can be realized in the cured product thereof. On the other hand, when the ratio of the structural unit derived from the component (b) is less than 10 mol%, the hydroxyl group-containing fluorine-containing polymer has poor solubility in an organic solvent, and when it exceeds 50 mol%, the cured product by the liquid curable resin composition is transparent. And low reflectance optical properties deteriorate.

The azo group-containing polysiloxane compound as the component (c) is itself a thermal radical generator, and acts as a polymerization initiator in the polymerization reaction for obtaining a hydroxyl group-containing fluorine-containing polymer, but other radical initiators may be used in combination. As for the ratio of the structural unit derived from (c) component in a hydroxyl-containing fluoropolymer, the polysiloxane segment represented by General formula (1) becomes like this. Preferably it is 0.1-20 mol%, More preferably, it is 0.1-15 mol%, Especially preferably, Preferably it is 0.1 to 10 mol%, Especially preferably, it is the ratio which becomes 0.1 to 5 mol%. When the ratio of the polysiloxane segment represented by General formula (1) exceeds 20 mol%, the obtained fluorine-containing polymer becomes inferior in transparency, and when used as a coating agent, cratering etc. generate | occur | produce easily at the time of application | coating.

It is preferable to use a reactive emulsifier as a monomer component other than the said (a)-(c) component as (d) component. By using this (d) component, when using a hydroxyl-containing fluorine-containing polymer as a coating agent, favorable applicability | paintability and spreadability can be obtained. Especially as this reactive emulsifier, it is preferable to use a nonionic reactive emulsifier. As a specific example of a nonionic reactive emulsifier, the compound represented by following formula (3) or (4) is mentioned, for example.

In formula, n is 1-20, m is 0-4, s is 3-50.

In the formula, m and s are the same as in the general formula (3). R <^3> is an alkyl group which may be linear or branched, Preferably it is a C1-C40 alkyl group.

In the hydroxyl-containing fluorine-containing polymer, the proportion of the structural unit derived from the component (d) is preferably 0 to 10 mol%, more preferably 0.1 to 5 mol%, particularly preferably 0.1 to 1 mol%. When this ratio exceeds 10 mol%, since the liquid curable resin composition obtained becomes adhesive, handling becomes difficult, and when used as a coating agent, moisture resistance falls.

As monomer compounds other than the (b) component copolymerizable with (a) component of (e) component, it is (1) methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, Isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, etc. Alkyl vinyl ethers or cycloalkyl vinyl ethers; (2) carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl versatate, and vinyl stearate; (3) methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (Meth) acrylic acid esters, such as (meth) acrylate and 2- (n-propoxy) ethyl (meth) acrylate; (4) It is carboxyl group-containing monomer compounds, such as (meth) acrylic acid, crotonic acid, a maleic acid, fumaric acid, and itaconic acid, and the thing which does not contain a hydroxyl group is mentioned. Preferably it is alkyl vinyl ether.

In the hydroxyl-containing fluorine-containing polymer, the proportion of the structural unit derived from the component (e) is preferably 0 to 70 mol%, more preferably 5 to 35 mol%. When this ratio exceeds 70 mol%, since the liquid curable resin composition obtained becomes adhesive, handling becomes difficult, and when used as a coating agent, moisture resistance falls.

Preferable combinations of (a) component, (b) component, (c) component, (d) component and (e) component in the case of containing (d) component are as follows.

(1) Fluoroolefin / hydroxyl group containing vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier / alkyl vinyl ether, (2) Fluoroolefin / perfluoro (alkyl vinyl ether) / hydroxyl group containing vinyl ether / polydimethylsiloxane Unit / nonionic reactive emulsifier / alkylvinylether, (3) fluoroolefin / perfluoro (alkoxyalkylvinylether) / hydroxyl group-containing vinylether / polydimethylsiloxane unit / nonionic reactive emulsifier / alkylvinylether, (4) Fluoroolefin / perfluoro (alkyl vinyl ether) / hydroxyl group containing vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier / alkyl vinyl ether, (5) fluoroolefin / perfluoro (alkoxy alkyl vinyl ether) / hydroxyl group Containing vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier / alkyl vinyl ether.

As a radical polymerization initiator which can be used together with (c) component, For example, (1) diacyl peroxides, such as acetyl peroxide and benzoyl peroxide; (2) ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; (3) hydroperoxides such as hydrogen peroxide, tert-butylhydroperoxide and cumene hydroperoxide; (4) dialkyl peroxides such as di-tert-butyl peroxide, dicumyl peroxide and dilauroyl peroxide; (5) peroxy esters such as tert-butyl peroxy acetate and tert-butyl peroxy pivalate; (6) azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile; (7) persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate; And the like.

As a specific example other than the said radical polymerization initiator, For example, perfluoro ethyl iodide, perfluoro propyl iodide, perfluoro butyl iodide, (perfluoro butyl) ethyl iodide, perfluoro Hexyl iodide, 2- (perfluorohexyl) ethyl iodide, perfluoroheptyl iodide, perfluorooctyl iodide, 2- (perfluorooctyl) ethyl iodide, perfluoro Decyl iodide, 2- (perfluorodecyl) ethyl iodide, heptafluoro-2-iodopropane, perfluoro-3-methylbutyl iodide, perfluoro-5-methylhexyl iodide Droid, 2- (perfluoro-5-methylhexyl) ethyl iodide, perfluoro-7-methyloctyl iodide, 2- (perfluoro-7-methyloctyl) ethyl iodide, perfluor Rho-9-methyldecyl iodide, 2- (perfluoro-9-methyldecyl) ethyl iodide, 2,2,3,3-tetrafluoropropyl iodide, 1H, 1H, 5 H-octafluoropentyl iodide, 1H, 1H, 7H-dodecafluoroheptyl iodide, tetrafluoro-1,2-diiodoethane, octafluoro-1,4-diiodobutane And iodine-containing fluorine compounds such as dodecafluoro-1,6-diiodohexane. The iodine-containing fluorine compound may be used alone or in combination with the organic peroxide, azo compound or persulfate.

As a polymerization mode for producing a hydroxyl group-containing fluorine-containing polymer, any of emulsion polymerization, suspension polymerization, block polymerization or solution polymerization using a radical polymerization initiator can be used, and also as a polymerization operation, it may be batchwise, semi-continuous or continuous. A suitable thing can be selected from operation of a formula, etc.

It is preferable to perform the polymerization reaction for obtaining a hydroxyl-containing fluorine-containing polymer in the solvent system using a solvent. Here, as a preferable organic solvent, For example, (1) Ester, such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, a cellosolve; (2) ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; (3) cyclic ethers such as tetrahydrofuran and dioxane; (4) amides such as N, N-dimethylformamide and N, N-dimethylacetamide; (5) aromatic hydrocarbons such as toluene and xylene; And the like. Alcohol, aliphatic hydrocarbons, etc. can also be mixed and used as needed.

Although the hydroxyl-containing fluorine-containing polymer obtained as mentioned above may use the reaction solution obtained by the polymerization reaction as it is as a liquid curable resin composition, it is also possible to perform appropriate post-processing with respect to a polymerization reaction solution. As this post-treatment, for example, a general reprecipitation treatment typified by a purification method in which the polymerization reaction solution is added dropwise to the insoluble solvent of the hydroxyl group-containing fluorine-containing polymer made of alcohol or the like to solidify the hydroxyl group-containing fluorine-containing polymer can be performed. The solution of the hydroxyl-containing fluorine-containing polymer can be manufactured by dissolving the solid copolymer obtained in the solvent next. Moreover, what removed the residual monomer from the polymerization reaction solution can also be used as it is as a solution of a hydroxyl-containing fluoropolymer.

(2) Ethylenic unsaturated group-containing fluorine-containing polymer

The ethylenically unsaturated group-containing fluorine-containing polymer used in the present invention is obtained by reacting a compound containing one isocyanate group and at least one ethylenically unsaturated group with the (1) hydroxyl group-containing fluorine-containing polymer. It is preferable that the molar ratio of an isocyanate group / hydroxyl group is obtained by making it react at 1.1 to 1.9 ratio.

The compound containing one isocyanate group and at least one ethylenically unsaturated group is not particularly limited as long as it is a compound containing one isocyanate group and at least one ethylenically unsaturated group in the molecule. Moreover, when 2 or more isocyanate groups are contained, there exists a possibility of gelatinization when making it react with the said (1) hydroxyl group containing fluorine-containing polymer. Moreover, as said ethylenically unsaturated group, since the liquid curable resin composition of this invention can be hardened more easily, a (meth) acryloyl group is more preferable. As such a compound, 1 type (s) or 2 or more types of combinations of 2- (meth) acryloyloxyethyl isocyanate and 2- (meth) acryloyloxypropyl isocyanate are mentioned.

Moreover, such a compound can also be synthesize | combined by making a diisocyanate and hydroxyl-containing (meth) acrylate react. In this case, examples of the diisocyanate 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-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3 ' -Dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexylisocyane art), 2,2,4- Trimethylhexamethylene diisocyanate, bis (2-isocyanate ethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, 1 , 3-bis (iso) 1 type single or 2 types or more combinations, such as a methyl acetate) cyclohexane, tetramethyl xylylene diisocyanate, and 2,5 (or 6) -bis (isocyanate methyl) -bicyclo [2.2.1] heptane, are mentioned. . Of these, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylenebis (4-cyclohexyl isocyanate), and 1,3-bis (isocyanate methyl) cyclohexane are particularly preferable. Do.

In addition, as an example of hydroxyl-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and caprolactone (meth) Acrylate, polypropylene glycol (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, isocyanuric acid Single 1 type, or 2 or more types of combinations, such as EO modified di (meth) acrylate, are mentioned. Among these, 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are particularly preferable. Moreover, as a commercial item of a hydroxyl-containing polyfunctional (meth) acrylate, for example, Osaka Yuki Kagaku Co., Ltd. brand name HEA, Nippon Kayaku Co., Ltd. brand name KAYARAD DPHA, PET-30, Toagosei Co., Ltd. brand name It is available as an Alonix M-215, M-233, M-305, M-400, etc.

When synthesize | combining from diisocyanate and hydroxyl group containing polyfunctional (meth) acrylate, it is preferable to make the addition amount of a hydroxyl group containing polyfunctional (meth) acrylate 1-1.2 mol with respect to 1 mol of diisocyanate.

As a synthesis | combining method of such a compound, the method of adding a diisocyanate and a hydroxyl group containing (meth) acrylate collectively, and making it react, the method of dripping diisocynet in a hydroxyl group containing (meth) acrylate and making it react etc. are mentioned.

<Reaction molar ratio of the compound containing one isocyanate group and one or more ethylenically unsaturated groups with the (1) hydroxyl group-containing fluorine-containing polymer>

The ethylenically unsaturated group-containing fluorine-containing polymer used in the present invention is obtained by reacting a compound containing one isocyanate group and at least one ethylenically unsaturated group with a hydroxyl group-containing fluorine-containing polymer, and the molar ratio of isocyanate group / hydroxyl group is It is preferable to react at the ratio of 1.1 to 1.9. This reason is because if the molar ratio is less than 1.1, the scratch resistance and durability may decrease. On the other hand, if the molar ratio exceeds 1.9, the scratch resistance after immersion of the aqueous alkali solution of the coating film of the ultraviolet curable resin composition may be lowered. to be. For this reason, the molar ratio of isocyanate group / hydroxyl group is preferably 1.1 to 1.5, and more preferably 1.2 to 1.5.

The content of at least one fluorine-containing polymer selected from the group consisting of a fluorine-containing polymer having a hydroxyl group and an ethylenically unsaturated group-containing fluorine-containing polymer in the (A) molecule in the liquid curable resin composition of the present invention is the whole composition except the organic solvent. It is preferable that it is 3-95 mass% with respect to 100 mass% of quantities. This reason is because, when content is less than 3 mass%, the refractive index of the cured coating film of an ultraviolet curable resin composition may become high, and sufficient antireflection effect may not be obtained. On the other hand, when addition amount exceeds 95 mass%, hardening of curable resin composition This is because the scratch resistance of the coating film may not be obtained. Moreover, for this reason, it is more preferable to make the addition amount of a component (A) into 5-90 mass%, and it is more preferable to set it as the value within the range of 10-80 mass%.

(B) curable compound

Although the curable compound which is (B) component is not specifically limited, It is a compound which has a thermosetting or radiation curable polymeric group, and it is necessary to include the compound which has at least 2 or more polymerizable groups as a part or all of (B) component. . This compound is preferably used in order to improve the film formability of a composition. In the liquid curable resin composition, the curable compound may be simply mixed with the fluorine-containing polymer of component (A), and the reaction product or part thereof reacts with all of the fluorine-containing polymer of component (A) and the curable compound. It may also include the one in the state.

(1) thermosetting compound

As a thermosetting curable compound, various hydroxyl compound containing compounds, such as various amino compounds, pentaerythritol, polyphenol, glycol, etc. are mentioned, for example.

The amino compound used as the curable compound is a compound containing two or more amino groups in total, which can react with hydroxyl groups present in the hydroxyl group-containing fluorine-containing polymer, for example, hydroxyalkylamino groups and alkoxyalkylamino groups in total. As a melamine type compound, a urea type compound, a benzoguanamine type compound, a glycoluril type compound etc. are mentioned, for example.

Melamine compounds are generally known as compounds having a skeleton in which a nitrogen atom is bonded to a triazine ring, and specific examples thereof include melamine, alkylated melamine, methylolmelamine, alkoxylated methylmelamine, and the like. It is preferable to have two or more of either or both of the alkoxylated methyl groups in total. Specifically, methylolated melamine, alkoxylated methylmelamine or derivatives thereof obtained by reacting melamine with formaldehyde under basic conditions are preferable, and particularly, good storage stability is obtained in the liquid curable resin composition, and good reactivity is obtained. Preferred is alkoxylated methylmelamine. There is no restriction | limiting in particular in the methylolation melamine and the alkoxylation methylmelamine used as a curable compound, For example, the various dendritic phases obtained by the method described in the literature [Plastic material course [8] urea-melamine resin (Nggan High School new injection)] The use of materials is also possible.

Examples of the urea-based compound include polymethylolated urea, alkoxylated methylurea which is a derivative thereof, methylolated uron having a uron ring, alkoxylated methyluron and the like. Moreover, also about compounds, such as a urea derivative, the use of the various dendritic materials described in the said document is possible.

As a commercial item of such a thermosetting curable compound, Mitsui Cytec Co., Ltd. Cymel series etc. are mentioned.

(2) radiation curable compounds

As a radiation curable compound, what has two or more polymerizable unsaturated groups is necessary, For example, melamine acrylates, (meth) acrylic esters, and vinyl compounds are mentioned. In this, the (meth) acrylic ester (henceforth a polyfunctional (meth) acryl compound) which has two or more (meth) acryloyl groups is preferable.

Specific examples of the polyfunctional (meth) acryl compound include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylic. Latex, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) arc relay , Ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) Cyanurate di (meth) acrylates and poly (meth) acrylates of ethylene oxide or propylene oxide adducts to these starting alcohols, oligoesters having two or more (meth) acryloyl groups in the molecule (meth) ) Acrylates, oligo ether (meth) acrylates, oligourethane (meth) acrylates and oligo epoxy (meth) acrylates. Among these, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate are preferable.

Divinyl benzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether etc. are mentioned as vinyl compounds.

As a commercial item of such a radiation curable compound, the acid and Chemicals make brand names: Nikarak MX-302, Toagosei Co., Ltd. make brand names: Alonics M-400, M-408, M-450, M -305, M-309, M-310, M-315, M-320, M-350, M-360, M-208, M-210, M-215, M-220, M-225, M-233 , M-240, M-245, M-260, M-270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221, M-203, TO-924, TO -1270, TO-1231, TO-595, TO-756, TO-1343, TO-902, TO-904, TO-905, TO-1330, Nippon Kayaku Co., Ltd.Product Name: KAYARAD D-310, D-330, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, SR-295, SR-355, SR-399E, SR-494, SR-9041, SR-368, SR-415, SR-444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR- 230, SR-259, SR-268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610, SR-9003, PET-30, T-1420, GPO-303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-551, R-712, R-167, R-526, R-551, R-712, R-604, R-684, TMPTA, THE-330, TPA-320, TPA -330, KS-HDDA, KS-TPGDA, KS-TMPTA, Kyoesha Chemical Co., Ltd. brand name: Lightacrylate PE-4A, DPE-6A, DTMP-4A, etc. are mentioned.

About content of (B) curable compound in the liquid curable resin composition of this invention, it is preferable that it is 3-95 mass% with respect to composition 100 mass% except the organic solvent. This reason is because when the addition amount is less than 3% by mass, the scratch resistance of the cured coating film of the curable resin composition may not be obtained. On the other hand, when the addition amount exceeds 95% by mass, the refractive index of the cured coating film of the curable resin composition is increased. This is because a sufficient antireflection effect may not be obtained. Moreover, for this reason, it is more preferable to make the addition amount of a component (B) into 5-90 mass%, and it is more preferable to set it as the value within the range of 10-80 mass%.

(C) curing catalyst

As a curing catalyst used by this invention, the radical radical generator which is a thermal acid generator and a photoinitiator is mentioned, for example.

(1) thermal acid generator

A thermal acid generator is a substance which can accelerate hardening reaction when the coating film etc. of the said liquid curable resin composition are heated and hardened | cured, and the substance which can improve the heating conditions to be more mild. There is no restriction | limiting in particular as this thermal acid generator, Various acids and its salts used as a hardening | curing agent for general urea resin, melamine resin, etc. can be used. Specific examples thereof include various aliphatic sulfonic acids and salts thereof, various aliphatic carboxylic acids such as citric acid, acetic acid and maleic acid, salts thereof, various aromatic carboxylic acids such as benzoic acid and phthalic acid, salts thereof, alkylbenzene sulfonic acids and ammonium salts thereof, various kinds The metal salt, phosphoric acid, phosphate ester of organic acid, etc. are mentioned.

(2) photoinitiator (photoradical generator)

As an example of a photoinitiator, for example, acetophenone, acetophenonebenzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, carbazole, xanthone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2,2-dimethol Methoxy-2-phenylacetophenone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2- Morpholinopropane-1-one, triphenylamine, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propylether, benzophenone, Michler's ketone, 3-methylacetophenone, 3,3 ', 4,4'-tetra (tert-butyl Peroxycarbonyl) benzophenone (BTTB), 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylme Til) -1-butanone, 4-benzoyl-4'-methyldiphenylsulfide, benzyl, or a combination of BTTB and xanthene, thioxanthene, coumarin, keto coumarin, and other dye sensitizers. have.

Among these photoinitiators, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2,4, 6-trimethylbenzoyldiphenylphosphineoxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -1- [4- ( Morpholinyl) phenyl] -2-phenylmethyl) -1-butanone and the like are preferred, and more preferably 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] 2-morpholino propane-1-one, 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl) -1-butanone, etc. are mentioned.

It is preferable that the usage-amount of the (C) hardening catalyst in the liquid curable resin composition of this invention is 0.1-20 mass% with respect to 100 mass% of composition total amounts except the organic solvent, More preferably, it is 0.1-10 mass%, Preferably it is 1-10 mass%. If the amount of the curing catalyst (C) is too small, sufficient mechanical strength is not obtained, which is not preferable. If this ratio is too large, it is not preferable because the storage stability of the liquid curable resin composition is inferior or sufficient mechanical strength is not obtained because the catalyst acts as a plasticizer in the cured film.

In the case of radiation curing, it can be performed based on light irradiation conditions of 0.001 to 10 J / cm ² using, for example, an ultraviolet irradiation device (metal halogen lamp, high pressure mercury lamp, etc.), but the irradiation conditions are not limited to this. Do not. 0.01-5 J / cm <^2> is more preferable, and 0.1-3 J / cm <^2> is more preferable.

(D) Silicon dioxide particles having a number average particle diameter of 100 nm or less

The silicon dioxide particle which is (D) component means particle | grains which have silicon dioxide (also called silica) as a main component. In addition, a number average particle diameter is measured by the dynamic light scattering method.

As a particle having a silica as a main component, a known one can be used, and if the shape thereof is also substantially spherical, the particle is not limited to ordinary colloidal silica and may be hollow particles, porous particles, core-shell particles, or the like. In addition, it is not limited to spherical form, Amorphous particle | grains may be sufficient. Colloidal silica having a number average particle diameter of 1 to 100 nm, a solid content of 10 to 40 mass%, and a pH of 2.0 to 6.5 determined by the dynamic light scattering method is preferable.

In addition, the dispersion medium of silica is preferably water or an organic solvent. As an organic solvent, Alcohol, such as methanol, isopropyl alcohol, ethylene glycol, butanol, ethylene glycol monopropyl ether; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Aromatic hydrocarbons such as toluene and xylene; Amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; Esters such as ethyl acetate, butyl acetate and γ-butyrolactone; Organic solvents, such as ethers, such as tetrahydrofuran and a 1, 4- dioxane, are mentioned, Among these, alcohol and ketones are preferable. These organic solvents can be used individually or in mixture of 2 or more types as a dispersion medium.

As a commercial item of the particle | grain which has a silica as a main component, Snowtex O (number average particle diameter 7nm, 20 mass% of solid content, pH 2.7) obtained by Nissan Chemical Industries, Ltd. make, Snowtex OL, for example. (Number average particle diameter: 15 nm, solid content: 20 mass%, pH 2.5) calculated | required by the dynamic light scattering method, etc. are mentioned.

Moreover, as particle | grains which have silica as a main component, the thing which surface-treated, such as a chemical formula, on the colloidal silica surface can be used. As a chemical formula, it contains the organic compound (Ab) which has the following polymerizable unsaturated group, the hydrolyzable silicon compound which has one or more alkyl groups, or its hydrolyzate, etc. (henceforth "organic compound (Ac)") in a molecule | numerator. A method of making it react is mentioned. However, the reaction here includes non-covalent bonds such as physical adsorption in addition to covalent bonds. In this case, silicon dioxide particles (hereinafter referred to as silicon dioxide particles (Aa) '' not bonded to the organic compound (Ab) and particles bonded to the organic compound (Ab) or (Ac) are formed into reactive particles (Dab) or (Dac Is called.

By having the silicon dioxide particles (Aa) as reactive particles (Dab) or (Dac) bonded to an organic compound (Ab) or (Ac) having a polymerizable unsaturated group, the (D) silicon dioxide particle component has a polymerizable unsaturated group To form a firm covalent bond with another polymerizable component, and to improve the scratch resistance of the resulting cured film.

(1) Chemical Formula by Organic Compound (Ab) Having Polymeric Unsaturation

It is preferable that the organic compound (Ab) used by this invention is a compound which has a polymerizable unsaturated group, and is also an organic compound containing the group represented by following formula (A-1). It also contains a [-0-C (= O) -NH-] group and also contains at least one of a [-OC (= S) -NH-] group and a [-SC (= O) -NH-] group. It is desirable to. Moreover, it is preferable that this organic compound (Ab) is a compound which has a silanol group in a molecule | numerator, or a compound which produces a silanol group by hydrolysis.

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

(i) polymerizable unsaturated groups

Although there is no restriction | limiting in particular as a polymerizable unsaturated group contained in an organic compound (Ab), For example, acryloyl group, methacryloyl group, vinyl group, propenyl group, butadiethyl group, styryl group, ethynyl group, cinnamoyl group, A maleate group and an acrylamide group are mentioned as a suitable example. This polymerizable unsaturated group is a structural unit which addition-polymerizes with an active radical species.

(ii) the group represented by the formula (A-1)

The group [-UC (= V) -NH-] represented by the formula (A-1) included in the organic compound is specifically [-OC (= O) -NH-], [-OC (= S) -NH -], [-SC (= O) -NH-], [-NH-C (= O) -NH-], [-NH-C (= S) -NH-], and [-SC (= S) -NH-] are 6 species. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, at least one of a [-OC (= O) -NH-] group, a [-OC (= S) -NH-] group and a [-SC (= O) -NH-] group is used in combination from the viewpoint of thermal stability. It is desirable to.

The group [-UC (= V) -NH-] represented by the above formula (A-1) generates a suitable cohesive force by hydrogen bonding between molecules, and when made into a cured product, excellent mechanical strength, such as a substrate or a high refractive index layer It is thought to impart characteristics such as adhesion to the adjacent layer and heat resistance.

(iii) silanol groups or groups that produce silanol groups by hydrolysis

It is preferable that an organic compound (Ab) is a compound which has a silanol group in a molecule | numerator, or a compound which produces a silanol group by hydrolysis. As a compound which produces | generates such a silanol group, The compound which the alkoxy group, the aryloxy group, the acetoxy group, the amino group, the halogen atom, etc. couple | bonded with the silicon atom is mentioned, The compound which the alkoxy group or the aryloxy group couple | bonded with the silicon atom, That is, an alkoxy silyl group containing compound or an aryloxy silyl group containing compound is preferable.

The silanol group generating site of the silanol group or the silanol group-producing compound is a structural unit that is bonded to the silicon dioxide particles (D) by a condensation reaction following a condensation reaction or hydrolysis.

(iv) preferred embodiments

As a preferable specific example of an organic compound (Ab), the compound represented by following formula (A-2) is mentioned, for example.

In formula, R <^24> , R <^25> may be same or different and is a hydrogen atom or a C1-C8 alkyl group or an aryl group, For example, methyl, ethyl, propyl, butyl, octyl, phenyl, xylyl group, etc. Can be mentioned. Here j is an integer of 1-3.

As a group represented by [(R ²⁴ O) _j R ²⁵ _{3 - j} Si-], for example, trimethoxysilyl group, triethoxysilyl group, triphenoxysilyl group, methyldimethoxysilyl group, dimethylmeth A oxysilyl group etc. are mentioned. Among these groups, trimethoxysilyl group, triethoxysilyl group, and the like are preferable.

R ²⁶ is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms, and may include a chain, branched or cyclic structure. Specific examples include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, dodecamethylene and the like.

R ²⁷ is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. As a specific example, Chain polyalkylene groups, such as hexamethylene, octamethylene, and dodecamethylene; Alicyclic or polycyclic divalent organic groups such as cyclohexylene and norbornylene; Divalent aromatic groups such as phenylene, naphthylene, biphenylene and polyphenylene; And alkyl group substituents and aryl group substituents thereof. Moreover, these divalent organic groups may contain the atomic group containing elements other than carbon and a hydrogen atom, and may also contain a polyether bond, a polyester bond, a polyamide bond, and a polycarbonate bond.

R ²⁸ is a (k + 1) valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.

Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule which undergoes an intermolecular crosslinking reaction in the presence of an active radical species. Further, k is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, particularly preferably an integer of 1 to 5.

Specific examples of the compound represented by the formula (A-2) include a compound represented by the following formula (A-4).

[In formula, "Acryl" represents acryloyl group. "Me" represents a methyl group.]

The synthesis | combination of the organic compound (Ab) used by this invention can use the method of Unexamined-Japanese-Patent No. 9-100111, for example. Preferably, mercaptopropyltrimethoxysilane and isophorone diisocyanate are mixed in the presence of dibutyltin dilaurate and reacted for several hours at 60 to 70 ° C, followed by addition of pentaerythritol triacrylate to 60 to It is made by further reacting for several hours at 70 ° C.

Reactive Particles (Dab)

An organic compound (Ab) having a silanol group or a group that generates a silanol group by hydrolysis is mixed with silicon dioxide particles (Aa) to be hydrolyzed to bind both. The ratio of the organic polymer component, ie, the hydrolyzate and condensate of the hydrolyzable silane, in the obtained reactive particles (Dab) is usually a drag value of the mass reduction% when the dry powder is completely burned in air, for example, at room temperature to air. Usually, it can obtain | require by thermal mass spectrometry to 800 degreeC.

The bonding amount of the organic compound (Ab) to the silicon dioxide particles (Aa) is 100% by mass of the reactive particles (Dab) (the sum of the silicon dioxide particles (Aa) and the organic compound (Ab)), preferably 0.01% by mass It is more than 0.1 mass%, More preferably, it is 1 mass% or more. When the amount of the organic compound (Ab) bonded to the silicon dioxide particles (Aa) is less than 0.01% by mass, the dispersibility of the reactive particles (Dab) in the composition is not sufficient, and the transparency and the scratch resistance of the cured product obtained are not sufficient. It may become. Moreover, the compounding ratio of the silicon dioxide particle (Aa) in the raw material at the time of manufacturing reactive particle (Dab) becomes like this. Preferably it is 5-99 mass%, More preferably, it is 10-98 mass%.

(2) Chemical modification by containing a hydrolyzable silicon compound which has one or more alkyl groups, or its hydrolyzate in a molecule | numerator (organic compound (Ac)), etc.

Moreover, as a thing containing a hydrolysable silicon compound which has one or more alkyl groups in a molecule | numerator, or its hydrolyzate, etc. (organic compound (Ac)), trimethylmethoxysilane, tributylmethoxysilane, dimethyldimethoxysilane, dibutyl dimeth Methoxysilane, methyltrimethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, 1,1,1-trimethoxy-2,2,2-trimethyl-disilane, hexa Methyl-1,3-disiloxane, 1,1,1-trimethoxy-3,3,3-trimethyl-1,3-disiloxane, α-trimethylsilyl-ω-dimethylmethoxysilyl-polydimethylsiloxane, α-trimethylsilyl-ω-trimethoxysilyl-polydimethylsiloxane hexamethyl-1,3-disilazane and the like. Moreover, the hydrolyzable silicon compound itself which has one or more reactive groups in a molecule | numerator can also be used. Hydrolyzable silicon compounds having one or more reactive in the molecule, for example as reaction with an NH ₂ group as a component trimethoxysilane, N- (2- aminoethyl) -3-aminopropyl trimethoxysilane or the like, 3-thiocyanate propyl tree as having thiocyanate groups, such as 3-isocyanate propyl trimethoxysilane, such as bis (2-hydroxyethyl) -3-aminotripropylmethoxysilane, etc., having an OH group 3-mercaptopropyl tree as having a thiol group, such as (3-glycidoxypropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, as having an epoxy group, such as methoxysilane Methoxysilane, etc. are mentioned. 3-mercaptopropyl trimethoxysilane is mentioned as a preferable compound.

In addition, the use ratio of the (D) silicon dioxide particle (including the case of reactive particle | grains (Aab) or (Aac)) contained in 100 mass% of liquid curable resin compositions of this invention is 100 mass of whole compositions of compositions except an organic solvent. It is preferable that it is 1-80 mass% with respect to%, More preferably, it is 10-60 mass%. Two or more kinds of (D) silicon dioxide particles which are different in particle size, surface modification, etc. can be mix | blended with the liquid curable resin composition of this invention.

The number average particle diameter of the silicon dioxide particles is 100 nm or less. When the number average particle diameter exceeds 100 nm, it may be difficult to uniformly disperse the silicon dioxide particles. In addition, silicon dioxide particles tend to settle, and the storage stability may be insufficient. Moreover, transparency of the cured film obtained may fall, or turbidity (haze value) may rise.

As for a number average particle diameter, 10-80 nm is more preferable, and 10-50 nm is further more preferable.

In addition, a "number average particle diameter" is a primary particle diameter when a silicon dioxide particle aggregates.

(E) Solvents with sp values greater than 8.5 and less than 12.8

The solvent of the component (E) used in the liquid curable resin composition of this invention is a thing whose sp value exceeds 8.5 and is less than 12.8, Preferably it is 8.9 or more and 10.0 or less, It will not specifically limit. By making sp value of the solvent used a specific range, the layer separation characteristic of the cured film obtained by hardening | curing the liquid curable resin composition of this invention is obtained, and transparency and abrasion resistance improve. Here, the layer separation property means that when the composition of the present invention is applied and the solvent is removed as described below, at least two layers, that is, at least (D) silicon dioxide particles are present at high density and (D) silicon dioxide particles are substantially present. It means that the two or more layers are formed separately by having a layer that does not exist.

Here, the sp value of a solvent is a solubility parameter (delta) and is a measure which shows the polarity value of a solvent. The sp value of the solvent is a value expressed by the negative square root of the aggregation energy density and the molecular capacity, as represented by the following formula.

Solubility Parameter (δ) = (ΔE _v / V) ^1/2

(Where ΔE _v is the cohesive energy density and V is the molecular capacity.)

The solubility parameter of each component of the specific organic solvent used by this invention is described in the literature [polymer handbook (3rd edition), J. BRANDRUP etc. (JOHN WILEY & SONS)] etc., for example.

As a solvent whose sp value used in the liquid curable resin composition of this invention exceeds 8.5 and is less than 12.8, for example, acetone (sp = 10.0), methyl ethyl ketone (sp = 9.3), methyl propyl ketone (sp = 8.9), etc. Can be mentioned.

Acetone, methyl ethyl ketone, methyl propyl ketone, etc. are mentioned as a solvent of the preferable component (E) used by the liquid curable resin composition of this invention.

The solvent of the liquid curable resin composition can normally contain the solvent used for manufacture of a fluorine-containing polymer as it is.

Moreover, it can mix | blend and add another solvent for improving the coating property etc. of a liquid curable resin composition, and other purposes. As a preferable solvent contained in the liquid curable resin composition of this invention, ketones, such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ester, such as ethyl acetate and butyl acetate, are mentioned. Moreover, in the solution of the liquid curable resin composition of this invention, the solvent which cannot dissolve a hydroxyl-containing fluorine-containing polymer or ethylenically unsaturated group containing fluorine-containing polymer, for example, poor solvents, such as water, alcohol, ethers, It can be used together in the range which does not precipitate containing fluorine-containing polymer or ethylenically unsaturated group containing fluorine-containing polymer. As a result, the solution of the hydroxyl group-containing fluorine-containing polymer or the ethylenically unsaturated group-containing fluorine-containing polymer may have good storage properties and preferable coatability. Ethyl alcohol, isopropyl alcohol, tert-butyl alcohol, ethyl cellosolve, butyl cellosolve, etc. are mentioned as such a poor solvent.

The blending amount of the solvent of the component (E) is preferably 25 to 9900 parts by mass, based on 100 parts by mass of the total amount of the solid product excluding the organic solvent (the solvent of the component (E) and other solvents) in the liquid curable resin composition of the present invention. Preferably it is 100-4900 mass parts, More preferably, 400-3300 mass parts is used.

(F) additive

In the liquid curable resin composition of the present invention, for example, various polymers, monomers, pigments or dyes having a hydroxyl group are used for the purpose of improving the applicability of the liquid curable resin composition and improving the physical properties of the thin film after curing and providing photosensitivity to a coating film. And various additives such as stabilizers such as colorants, antioxidants, ultraviolet absorbers, photosensitive acid generators, surfactants, and polymerization inhibitors. In particular, it is preferable to add a photoacid generator for the purpose of improving the hardness and durability of the cured film to be formed, and in particular, it is selected and used that is uniformly dissolved in the solution without lowering the transparency after curing of the liquid curable resin composition. It is preferable.

(i) a polymer having a hydroxyl group

As a polymer which has a hydroxyl group which can be mix | blended with the liquid curable resin composition of this invention, it is known as a polymer obtained by copolymerizing hydroxyl-containing copolymerizable monomers, such as hydroxyethyl (meth) acrylate, a novolak resin, or a resol resin, for example. The resin etc. which have the phenol skeleton which were made are mentioned.

(ii) coloring agents such as pigments or dyes

As a coloring agent which can be mix | blended with the liquid curable resin composition of this invention, For example, (1) extender pigments, such as alumina bag, clay, barium carbonate, barium sulfate; (2) inorganic pigments such as zinc oxide, lead white, sulfur lead, briquette, ultramarine blue, royal blue, titanium oxide, zinc chromate, iron group, carbon black and the like; (3) organic pigments such as brilliant carmine 6B, permanent red 6B, permanent red R, benzidine yellow, phthalocyanine blue and phthalocyanine green; (4) basic dyes such as magenta and rhodamine; (5) direct dyes such as direct scarlet and direct orange; (6) acid dyes such as loselin and methyl yellow; And the like.

(iii) stabilizers such as anti-aging agents and ultraviolet absorbers

A well-known thing can be used as an antioxidant and ultraviolet absorber which can be mix | blended with the liquid curable resin composition of this invention.

Specific examples of the anti-aging agent include, for example, di-tert-butylphenol, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone and n-butyl. Phenol, phenol, hydroquinone monopropylether, 4,4 '-[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] diphenol, 1,1, 3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, diphenylamines, phenylenediamines, phenothiazine, mercaptobenzimidazole, etc. are mentioned.

Moreover, as a specific example of a ultraviolet absorber, benzophenone type ultraviolet absorbers, such as the salicylic acid type ultraviolet absorber represented by phenyl salicylate, dihydroxy benzophenone, and 2-hydroxy-4- methoxy benzophenone, benzotria, for example. The ultraviolet absorber used as various plastic additives, such as a sol type ultraviolet absorber and a cyanoacrylate type ultraviolet absorber, can be used.

(iv) photosensitive acid generators

The photosensitive acid generator which can be blended into the liquid curable resin composition of the present invention imparts photosensitivity to the coating film of the liquid curable resin composition, and makes it possible to photocure the coating film by, for example, irradiating radiation such as light. It is a substance. As this photosensitive acid generator, it is (1) various onium salts, such as an iodonium salt, a sulfonium salt, a phosphonium salt, a diazonium salt, an ammonium salt, a pyridinium salt; (2) sulfone compounds such as β-ketoester and β-sulfonylsulfone and α-diazo compounds thereof; (3) sulfonic acid esters such as alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates; (4) sulfonimide compounds represented by the following formula (5); (5) diazomethane compounds represented by the following formula (6); And the like.

In formula, X represents bivalent groups, such as an alkylene group, an arylene group, and an alkoxylene group, and R <^4> represents monovalent groups, such as an alkyl group, an aryl group, a halogen substituted alkyl group, and a halogen substituted aryl group.

In formula, R <^5> and R <^6> may mutually be same or different, and represent monovalent groups, such as an alkyl group, an aryl group, a halogen substituted alkyl group, and a halogen substituted aryl group.

A photosensitive acid generator may be used individually or in combination of 2 or more types, and may be used together with the said thermal acid generator. The use ratio of the photosensitive acid generator in 100 mass parts of solid content of a liquid curable resin composition becomes like this. Preferably it is 0-20 mass parts, More preferably, it is 0.1-10 mass parts. If this ratio is too large, the strength of the cured film is inferior and transparency is also not preferable.

(v) surfactants

Surfactant can be mix | blended with the liquid curable resin composition of this invention for the purpose of improving the coating property of the said liquid curable resin composition. A well-known thing can be used as this surfactant, For example, various anionic surfactant, cationic surfactant, and nonionic surfactant can be used, but especially a cured film has the outstanding strength, and also the favorable optical characteristic In order to make it have, it is preferable to use cationic surfactant. Moreover, it is preferable that it is a quaternary ammonium salt, and especially a quaternary polyether ammonium salt is especially preferable at the point which further improves dust removal property. As cationic surfactant which is a quaternary polyether ammonium salt, Adekachol CC-15, CC-36, CC-42, etc. by Asahi Denka Kogyo Co., Ltd. are mentioned. The use ratio of surfactant is preferably 5 mass parts or less with respect to 100 mass parts of solid content of a liquid curable resin composition.

(vi) polymerization inhibitors

As a thermal polymerization inhibitor which can be mix | blended with the liquid curable resin composition of this invention, for example, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert- butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxy Hydroquinone, n-butylphenol, phenol, hydroquinone monopropylether, 4,4 '-[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] diphenol, 1 And 1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane. This thermal polymerization inhibitor is preferably used in an amount of 5 parts by mass or less with respect to 100 parts by mass of the liquid curable resin composition.

2. Cured film

When forming a cured film from the liquid curable resin composition of this invention, it is preferable to coat with respect to a base material (application member). As such a coating method, methods such as an immersion method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method or an ink jet method can be used.

When the liquid curable resin composition of the present invention is applied and the solvent is removed, two or more successive layers, that is, a layer in which at least (D) silicon dioxide particles are present at a high density and a layer in which substantially no (D) silicon dioxide particles are present Two or more layers having are formed separately. Each layer formed by these separation can be confirmed by observing the cross section of the obtained film | membrane with an electron microscope, for example. A layer in which silicon dioxide particles are present at a high density is a concept indicating a portion in which silicon dioxide particles are collected, and is a layer substantially composed of silicon dioxide particles, but the (A) component or (B) component Hardened | cured material may coexist. On the other hand, the layer in which the silicon dioxide particles are not substantially present is a concept indicating a portion where the aggregate of silicon dioxide particles is not observed, and in most cases, no silicon dioxide particles are observed. This layer is a layer comprised substantially from components other than silicon dioxide particles, such as hardened | cured material of (A) component and (B) component.

The film obtained in the process of apply | coating the liquid curable resin composition of this invention, and a solvent evaporating, in most cases forms the layer in which the layer which silicon dioxide particle exists in high density and the layer which is substantially free of silicon dioxide particle is continuous each. It has a two-layer structure. When a PET resin (including a PET resin having an easy bonding layer) is used as the substrate, a layer which is usually a substrate, a layer in which silicon dioxide particles are present at a high density, and silicon dioxide particles are substantially not present. Layers are formed adjacent to each other in this order.

Here, the layer structure of two or more layers may consist of two or more layers which respectively include a "layer in which silicon dioxide particles exist at a high density" and a "layer in which silicon dioxide particles do not substantially exist", and in addition, two or more "dioxides". Silicon particle may be two or more layers which consist only of the layer which exists in high density. "

When the liquid curable resin composition includes, for example, two or more kinds of silicon dioxide particles having different particle diameters or surface modifications, two or more layers of “layers in which silicon dioxide particles exist at a high density” may be formed. In addition, the "silicon dioxide particle" of the "layer in which a silicon dioxide particle exists in high density" means 1 or more types, ie, 1 or 2 or more types of "silicon dioxide particles". When the liquid curable resin composition contains two or more kinds of silicon dioxide particles, one "layer in which silicon dioxide particles exist at high density" may be composed of two or more kinds of silicon dioxide particles.

The means for curing the liquid curable resin composition is also not particularly limited, but heating is preferable, for example. In this case, it is preferable to heat at 30-200 degreeC for 1 to 180 minutes. By heating in this way, the cured film excellent in antireflection can be obtained more efficiently, without damaging a base material or the cured film formed. Preferably it is heated at 50-180 degreeC for 2 to 120 minutes, More preferably, it is heated at 80 to 150 degreeC for 2 to 60 minutes.

Moreover, it can harden | cure by irradiating radiation. In this case, although it can carry out under the light irradiation conditions of 0.001-10 J / cm <^2> using an ultraviolet irradiation device (metal halide lamp, a high pressure mercury lamp, etc.), for example, irradiation conditions are not limited to this. 0.01-5 J / cm <^2> is more preferable, and 0.1-3 J / cm <^2> is further more preferable.

In addition, when the melamine compound is used as the (B) curable compound, the degree of curing of the cured film is, for example, an infrared spectroscopic analysis of the amount of the methylol group or the alkoxylated methyl group of the melamine compound, or the gelation rate using a Soxhlet extractor. It can be confirmed quantitatively by measuring.

3. Laminate

The liquid curable resin composition of this invention can be apply | coated to various base materials in solution form, and a laminated body can be obtained by hardening the obtained coating film. For example, when the substrate is a transparent substrate, an excellent antireflection film can be formed.

The specific structure of the antireflection film is usually a laminate of a base material, a high refractive index film and a low refractive index film in this order.

Although the film thickness of the cured film of this invention in an antireflection film is 0.05 micrometer-50 micrometers, for example, it is not limited to this.

As a specific example of a transparent base material, For example, triacetyl cellulose, polyethylene terephthalate resin (Toray Co., Ltd. Lumiler etc.), glass, a polycarbonate resin, an acrylic resin, a styryl resin, an acrylate resin, norbornene type Various transparent plastic plates, films, etc., such as resin (JSR Corporation Aton etc.), methyl methacrylate / styrene copolymer resin, and polyolefin resin (Neonbon Xeon Corporation Zeonex etc.) are mentioned. Preferably, they are triacetyl cellulose, polyethylene terephthalate resin (Lumiler made by Toray Corporation etc.), and norbornene-type resin (Aton made by JSR Corporation etc.).

In addition, another layer may be interposed between the substrate and the cured film of the present invention, for example, a hard coating layer, a medium refractive index layer (refractive index 1.5 to 1.7), a low refractive index layer (1.3 to 1.5) and a high refractive index layer (1.6 to 1.5). Layers such as 2.2) may be provided. These layers may form only one layer, and may also form two or more other layers.

As a coating method of these layers, a well-known coating method can be used, In particular, various methods, such as an immersion method, a coating method, and a printing method, can be applied.

Moreover, in order to harden the coating film of the liquid curable resin composition formed by application | coating and to form the cured film which has the outstanding optical characteristic and durability, it is preferable to provide the heat history by heating especially. Of course, even when left at room temperature, the curing reaction proceeds with the passage of time to form a target cured film, but in practice, heating and curing are effective for shortening the required time. In addition, although the heating conditions for hardening reaction can be selected suitably, heating temperature needs to be below the heat-resistant limit temperature of the base material of application | coating.

The laminated body of this invention can be used for optical components, such as a lens and a selective permeable membrane filter, in addition to an antireflection film.

Hereinafter, although the Example of this invention is described, this invention is not limited at all by these Examples. In addition, in the following description, "part" or "%" shows a "mass part" or the "mass%", respectively, unless there is particular notice.

Preparation Example 1

Preparation of hydroxyl-containing fluorine-containing polymer

After fully replacing the autoclave made of stainless steel with an internal volume 1.5 L stirrer with nitrogen gas, 500 g of ethyl acetate, 75.4 g of perfluoro (propyl vinyl ether), 34 g of ethyl vinyl ether, and hydroxyethyl vinyl ether As 41.6 g, a nonionic reactive emulsifier, "Adeka Riaso NE-30" (made by Asahi Denka Kogyo Co., Ltd.) 50 g, as azo-containing polydimethylsiloxane "VPS-1001" (made by Wako Pure Chemical Industries, Ltd.) 7.5 g and 1.25 g of lauroyl peroxide were added, cooled to -50 DEG C with dry ice-methanol, and then oxygen in the system was removed again with nitrogen gas.

Then heating was started by adding 99.1 g of hexafluoropropylene. The pressure when the temperature in autoclave reached 60 degreeC showed 5.3x10 <^5> Pa. Thereafter, the reaction was continued under stirring at 70 ° C. for 20 hours, and the autoclave was water-cooled to stop the reaction when the pressure was lowered to 1.7 × 10 ⁵ Pa. After reaching room temperature, the unreacted monomer was released and the autocrab was opened to obtain a polymer solution having a solid content concentration of 31%. The obtained polymer solution was poured into a mixed solvent of methanol and water to precipitate a polymer, which was then washed with methanol and dried in vacuo at 50 ° C. to obtain 220 g of a hydroxyl group-containing fluorine-containing polymer.

In addition, the measurement of solid content concentration was performed as follows. Hereinafter, the measurement of solid content concentration was performed similarly.

That is, 1-1.5 g of samples were put into the aluminum dish previously weighed, and it dried for 5 minutes on a 150 degreeC hotplate, and solid content concentration was measured by weighing a residue.

Hereinafter, the manufacture example of the liquid curable resin composition of this invention is shown in Examples 1-3, and the comparative manufacture example is shown in Comparative Examples 1-8.

Example 1

Preparation of Liquid Curable Resin Composition 1

5.6 g of the hydroxyl group-containing fluorine-containing polymer obtained in Production Example 1, methoxylated methylmelamine `` cymel 303 '' of the thermosetting compound (manufactured by Mitsui Cytec Co., Ltd.) and `` catalyst 4050 '' which is a curing catalyst (Mitsui Scitec Co., Ltd.) ), Aromatic sulfonic acid compound active ingredient concentration 32%) 0.63 g, 1.3 g of hydrophobized colloidal silica having a number average particle diameter of 11 nm were dissolved in 211 g of acetone as a solvent to obtain a liquid curable resin composition 1. Solid content concentration in this liquid curable resin composition was 4.0 mass%.

Examples 2 and 3 and Comparative Examples 1 and 2

Preparation of Liquid Curable Resin Compositions 2 to 5

Liquid curable resin compositions 2 to 5 were prepared in the same manner as in Example 1, except that the solvent was changed to that shown in Table 1. Table 1 shows the solid content concentration of the obtained liquid curable resin composition.

Comparative Examples 3 and 4

Preparation of Liquid Curable Resin Compositions 6 and 7

Except having changed the solvent into what was shown in Table 1, liquid curable resin compositions 6 and 7 were manufactured like Example 1, but since the hydroxyl-containing fluorine-containing polymer was not dissolved in a solvent, solid content concentration could not be measured.

Comparative Example 5

Preparation of Liquid Curable Resin Composition 8

Liquid phase curability in the same manner as in Example 2, except that methoxylated methylmelamine "cymel 303" (manufactured by Mitsui Cytec Co., Ltd.) of the thermosetting compound was added to 170 g of methyl ethyl ketone as a solvent. Resin composition 8 was obtained. Solid content concentration in this liquid curable resin composition was 4.0 mass%.

Comparative Example 6

Preparation of Liquid Curable Resin Composition 9

Liquid curable resin composition 9 was obtained like Example 2 except not having added "catalyst 4050" which is a curing catalyst (32% of Mitsui Cytec Co., Ltd. product, aromatic sulfonic acid compound active ingredient concentration). Solid content concentration in this liquid curable resin composition was 4.0 mass%.

Comparative Example 7

Preparation of Liquid Curable Resin Composition 10

A liquid curable resin composition 10 was obtained in the same manner as in Example 2 except that hydrophobized colloidal silica having a number average particle diameter of 11 nm was not added and the amount of methyl ethyl ketone added as a solvent was changed to 180 g. Solid content concentration in this liquid curable resin composition was 4.0 mass%.

Comparative Example 8

Preparation of Liquid Curable Resin Composition 11

Kana ADS (manufactured by Elf Atochem Japan Japan Co., Ltd., which is a fluorine-containing polymer having a different structure in place of the hydroxyl group-containing fluorine-containing polymer obtained in Production Example 1. Copolymer of hexafluoropropylene, tetrafluoroethylene and difluoroethylene. And no polymerizable unsaturated group) was used in the same manner as in Example 2 to obtain a liquid curable resin composition 11. Solid content concentration in this liquid curable resin composition was 4.0 mass%.

Hereinafter, the manufacture example of the cured film of this invention is shown in Examples 4-6, and a comparative manufacture example is shown in Comparative Examples 9-16.

Examples 4-6, Comparative Examples 9, 10, 13-16

Polyethylene terephthalate film for easy adhesion to one side of liquid curable resin compositions 1 to 5 and 8 to 11 prepared in Examples 1 to 3 and Comparative Preparation Examples 1, 2 and 5 to 8 respectively using a wire bar coater (# 3) After coating on the easily treated surface or the untreated surface of A4100 (Toyo Bonde Co., Ltd. make, 188 micrometers in film thickness), the cured film layer of 0.1 micrometers in thickness was formed by heating at 140 degreeC in oven for 2 minutes.

In addition, since liquid curable resin compositions 6 and 7 (comparative examples 3 and 4) contained insoluble content, they could not be apply | coated and the cured film was not obtained.

<Evaluation of Curing Film>

The cured film obtained in Examples 4-6 and Comparative Examples 9, 10 and 13-16 was evaluated based on the following references | standards. The results are shown in Table 1.

(1) reflectance

The antireflection property of the obtained cured film was a range of wavelength 340-700 nm by the spectroscopic reflectance measuring apparatus (magnetic spectrophotometer U-3410 which manufactured the large sample chamber integrating apparatus attached to 150-09090, Hitachi Seisakusho Co., Ltd. product). The reflectance was measured and evaluated at. Specifically, the reflectance of the cured film was measured based on the reflectance in the aluminum vapor deposition film (100%).

(2) turbidity

The turbidity (haze value) in the obtained laminated body was measured using the haze meter, and the following references | standards evaluated.

○: The haze value is 1% or less.

(Triangle | delta): A haze value is 3% or less.

X: Haze value exceeds 5%.

(3) steel wool resistant

The steel wool tolerance test of the cured film was implemented by the method shown next. That is, a steel wool (Bonstar No.0000, manufactured by Nippon Steel Wool Co., Ltd.) is attached to a school-type friction fastness tester (AB-301, Tester Sangyo Co., Ltd.), and the surface of the cured film is loaded with a load of 500 g. Ten times was repeated under the conditions, and the presence or absence of scratches on the surface of the cured film was evaluated by the following criteria.

(Circle): Peeling of a cured film and generation | occurrence | production of a scratch are hardly confirmed.

(Triangle | delta): Fine scratches are recognized by a cured film.

X: Peeling generate | occur | produced in a part of cured film, or a string-shaped flaw generate | occur | produced on the surface of a cured film.

(4) layer separation

Whether the cured film was layer-separated, the cross section of the cured film was observed with the electron microscope, and the following references | standards evaluated. 1 and 2 show electron micrographs showing typical delamination and non-separation uniform states corresponding to the following evaluation criteria.

(Circle): It isolate | separates into the layer in which silicon dioxide particle exists in high density, and the layer in which a silicon dioxide particle does not exist substantially (layer separation state).

X: The thing separated into two layers was not confirmed (uniform state).

From the result of Table 1, when the sp value of the used solvent is 7.3 or less or 14.5 or more (Comparative Examples 3 and 4), it turns out that an insoluble content remains in the obtained liquid curable resin composition, and the target liquid curable resin composition is not obtained. Could.

When the sp value of the used solvent is 8.5 or less or 12.8 or more (Comparative Examples 1 and 2), although the liquid curable resin composition is obtained, it turns out that two layers are not separated and turbidity and steel wool resistance also fall.

Moreover, it turns out that scratch resistance falls even if any of components (B), (C), and (D) of the liquid curable resin composition of this invention fall out (Comparative Examples 5-7).

In addition, when using the fluorine-containing polymer which does not have a hydroxyl group and a polymerizable unsaturated group instead of the hydroxyl-containing fluorine-containing polymer obtained by the manufacture example 1 (comparative example 8), it turns out that turbidity and abrasion resistance fall, without separating two layers. Can be.

It can be seen that the cured film of the present invention, which has been separated in two layers, has a high reflectance, and has good turbidity and steel crying (Examples 4 to 6).

The liquid curable resin composition of this invention can be used advantageously for formation of optical materials, such as an anti-reflective film and an optical fiber sheath material, and also the paint material and weatherproof film with respect to the base material where weather resistance is requested | required using the thing with high fluorine content. It can be preferably used as a material for coating, a material for coating, and the like. Moreover, since the cured film obtained by hardening | curing the liquid curable resin composition of this invention is excellent in adhesiveness with respect to a base material, high scratch resistance, and gives favorable reflection prevention effect, it is very useful as an antireflection film, Visibility can be improved.

Claims (11)

(A) at least one fluorine-containing polymer selected from the group consisting of a fluorine-containing polymer having a hydroxyl group in the molecule and an ethylenically unsaturated group-containing fluorine-containing polymer, (B) at least one compound selected from a compound containing at least two of any one or both of a hydroxyalkylamino group and an alkoxyalkylamino group, and a compound containing two or more polymerizable unsaturated groups, (C) curing catalyst, (D) silicon dioxide particles having a number average particle diameter of 100 nm or less; and (E) Solvents with sp values greater than 8.5 and less than 12.8 The content of (A), (B), (C) and (D) is 3 to 95% by mass, 3 to 95% by mass, and 0.1 to 20% by mass relative to 100% by mass of the total component other than the organic solvent. % And 1 to 80 mass%, and content of [E] component is 25-9900 mass parts with respect to 100 mass parts of solids whole quantity except the organic solvent. Liquid curable resin composition of Claim 1 whose sp value of (E) solvent is 8.9 or more and 10 or less. The cured film which has a two-layered structure which consists of a layer which silicon dioxide particle exists by high density and the layer which a silicon dioxide particle does not exist substantially is obtained by hardening | curing the liquid curable resin composition of Claim 1. The manufacturing method of the cured film which has a process of hardening by heating the liquid curable resin composition of Claim 1, or irradiating a radiation. The laminated body which has at least one layer or more on the base material the layer containing the cured film of Claim 3. The laminated body of Claim 5 which has another layer between the layer containing a cured film, and a base material. The laminate of claim 6, wherein the other layer comprises at least one layer selected from the group consisting of a hard coating layer, a layer having a refractive index of 1.5 to 1.7, and a combination of a layer having a refractive index of 1.3 to 1.5 and a layer having a refractive index of 1.6 to 2.2. sieve. The laminate according to claim 5, wherein the substrate layer comprises triacetyl cellulose, polyethylene terephthalate resin, polycarbonate resin, acrylic resin, acrylic / styrene copolymer resin, polyolefin resin, norbornene-based resin or glass. The laminated body of Claim 5 which is an optical component. The laminate according to claim 5, which is for an antireflection film. The liquid curable resin composition according to claim 1, wherein the compound (B) is a compound containing two or more of either or both of a hydroxyalkylamino group and an alkoxyalkylamino group in total.

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