JP4866074B2 - Anti-reflection coating agent and anti-reflection film - Google Patents

Description

The present invention relates to an antireflection coating agent capable of obtaining an antireflection film excellent in scratch resistance, and an antireflection film.

Liquid crystal displays used for personal computers, word processors, mobile phones, and other various commercial displays are used in a very wide range of fields. These displays use transparent substrates such as glass and plastic, and recognize visual information such as objects, characters, and figures through these transparent substrates.
As a practical problem of these displays, deterioration of visibility due to reflection of the display surface can be mentioned. That is, when used in an environment in which external light is incident regardless of whether it is indoors or outdoors, the incident light such as external light is reflected on the surface of the transparent substrate, so that the internal visual information becomes difficult to see.

As a method for preventing such reflection of the transparent substrate, conventionally, a coating agent layer containing transparent fine particles is formed on the surface of glass or plastic, and irregular light is reflected by the uneven surface, or glass And a method of forming an antireflection layer having a low refractive index on the surface of plastic.

For example, in Patent Document 1, a silica dispersion is mixed in a silicate coating agent prepared by a sol-gel method, and the mixture is applied to a glass substrate and baked to form silica particles or silica particles on the surface. It is described that an antireflection film having irregularities due to aggregates can be obtained.

Further, for example, in Patent Document 2, it is possible to form an antireflection layer having a porous structure by dispersing independent micropores in a transparent material so that the refractive index is lower than the refractive index of the transparent material itself. Is described.

However, such a conventional antireflection film having an uneven surface or a low-refractive index layer formed as a single layer can prevent reflection of the transparent substrate, but the surface is scratched by rubbing or the like. There is a problem that the display image is easily scratched when the antireflection film is attached to the display screen or when the antireflection film is wiped off.
JP 09-101518 A JP 2002-317152 A

In view of the above situation, the present inventors have aimed to provide an antireflection coating agent and an antireflection film capable of obtaining an antireflection film having excellent scratch resistance.

The present invention is an antireflection coating agent comprising an average particle size of 50 to 200 nm , a refractive index of 1.40 or less, and containing at least a fine particle comprising a polyorganosiloxane compound and a binder component. The fine particles have a hollow structure and have a single-hole structure.
The present invention is described in detail below.

As a result of intensive studies, the present inventors use an antireflection coating agent containing fine particles made of a specific substance having an average particle diameter in a specific range and a low surface tension, and a binder component. Thus, an antireflection film having excellent scratch resistance can be obtained, and by adjusting the refractive index of the fine particles and the binder component within a predetermined range, a sufficiently low refractive index is exhibited and an excellent antireflection effect is exhibited. The present inventors have found that an antireflection film exhibiting the above can be obtained, and have completed the present invention.

The antireflection coating agent of the present invention contains fine particles (hereinafter also referred to as slipperiness-imparting fine particles) having an average particle diameter of 50 to 200 nm and at least a surface comprising a polyorganosiloxane compound or a fluorine compound.
The slipperiness-imparting fine particles are fine particles that impart excellent scratch resistance to the antireflection film using the antireflection coating agent of the present invention, and the lower limit of the average particle diameter is 50 nm, and the upper limit is 200 nm.
The slipperiness-imparting particles have an average particle size that is the same or slightly larger than the typical antireflection film thickness of about 100 nm. Therefore, the antireflection coating agent of the present invention is used for antireflection. When the film is formed, the slipperiness-imparting particles made of a polyorganosiloxane compound or a fluorine compound having a low surface tension are partially exposed on the surface of the antireflection film. As a result, the antireflection film using the antireflection coating agent of the present invention has a high surface slipperiness and an excellent scratch resistance effect.

When the antireflection film is formed when the average particle size of the slipperiness-imparting fine particles is less than 50 nm, the slipperiness-imparting fine particles are buried inside the antireflection film, or the slip-giving fineness polyorganosiloxane compound or If the surface of the fluorine compound does not exhibit the scratch resistance effect and exceeds 200 nm, the antireflection film formed using the antireflection coating agent of the present invention may cause a whitening phenomenon due to Rayleigh scattering. It becomes inconvenient when it is necessary. A preferred lower limit is 70 nm and a preferred upper limit is 150 nm.

The upper limit of the CV value of the particle diameter of the slipperiness-imparting fine particles is 20%. When the CV value exceeds 20%, the ratio of coarse particles having a particle diameter exceeding 200 nm increases, and the haze of the antireflection film using the antireflection coating agent of the present invention may increase.

The slipperiness-imparting fine particles preferably have an upper limit of refractive index of 1.40. When it exceeds 1.40, the refractive index of the entire antireflection film using the antireflection coating agent of the present invention is increased, and as a result, a sufficient antireflection effect may not be obtained. A more preferred upper limit is 1.35, and a more preferred upper limit is 1.30.

In the present specification, “refractive index” means a value obtained as follows.
First, a thin film is prepared using fine particles whose refractive index is to be obtained and a polymerizable compound having a known refractive index. At this time, it is preferable to produce a thin film having a minimum reflectance at a light wavelength of 550 nm.
About the obtained thin film, the single-sided reflection spectrum in the incident angle of 5 degrees of light with a light wavelength of 380-770 nm is measured.
About the obtained reflection spectrum, the refractive index of a thin film is estimated using optical characteristic analysis software (for example, "WVASE32" by JA Woollam Japan).
Using the refractive index value of the obtained thin film at a light wavelength of 550 nm and the refractive index value of the polymerizable compound having a known refractive index, the refractive index of the fine particle is determined from the volume ratio of the fine particles to the polymerizable compound having the known refractive index. Is calculated.

The internal shape of the slipperiness-imparting fine particles is not particularly limited as long as the average particle diameter is within the above-mentioned range. For example, solid fine particles having no voids or hollow fine particles having voids may be used. However, since it is easy to achieve a low refractive index, hollow fine particles are preferable.

When the slipperiness-imparting fine particles are hollow fine particles, it is preferable to have a single-pore structure. Due to the single-hole structure, the inside of the voids has excellent sealing properties, and in the case of an antireflection film, other components such as a binder enter the void and the porosity of the slipperiness-imparting fine particles decreases. Can be prevented. In addition, the strength of the entire antireflection film can be improved. In the present specification, “having a single pore structure” does not include the case of having a plurality of voids such as a porous shape, and means having an outer shell layer and only one void.

When the slipperiness-imparting fine particles are hollow fine particles, the preferable lower limit of the porosity is 10%. If it is less than 10%, the refractive index may not be sufficiently lowered. A more preferred lower limit is 30%, and a still more preferred lower limit is 50%. Although the upper limit of the porosity is not particularly limited, the preferable upper limit is 90% and the more preferable upper limit is 80% from the viewpoint of maintaining the shape of the fine particles and securing a certain degree of strength.

Further, the structure of the slipperiness-imparting fine particles is not particularly limited as long as at least the surface is made of a polyorganosiloxane compound or a fluorine compound. For example, the fine particles themselves are made of a polyorganosiloxane compound or a fluorine compound. Alternatively, the surface of fine particles (hereinafter also referred to as substrate particles) other than the polyorganosiloxane compound and the fluorine compound may be surface-treated with the polyorganosiloxane compound or the fluorine compound.

When the above-mentioned slipperiness-imparting fine particles themselves comprise a polyorganosiloxane compound or a fluorine compound, the synthesis method is not particularly limited. For example, an organosiloxane compound having a vinyl group or (meth) acryl group inside the structure, or Emulsion polymerization using fluorine-based monomer and non-polymerizable organic solvent, drop-type emulsion polymerization, soap-free polymerization, microemulsion polymerization, miniemulsion polymerization, microsuspension polymerization; epoxy group, isocyanate group, ureido group inside the structure And interfacial polymerization using an organosiloxane compound having an amino group, mercapto group, or halogen group, and the like, and can be synthesized using an appropriate polymerization method.
In addition, the slipperiness | fine-particles provision fine particle obtained can be made into a solid structure or a hollow structure by adjusting suitably the compounding quantities of the said organosiloxane compound, a fluorine-containing monomer, a nonpolymerizable organic solvent, etc.

The organosilane compound having a vinyl group or (meth) acryl group inside the structure is not particularly limited. For example, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styrylmethoxysilane, 3- Methacryloxypropyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyl group or (meth) Acrylic group-modified polydimethylsiloxane compounds (commercially available products include, for example, X-22-164A, X-22-164B, X-22-164C, X-22-174DX, X-24-8201, X-22-2426. , X-22-2 04 (above, all manufactured by Shin-Etsu Chemical Co., Ltd.), Silaplane FM-7711, FM-7721, FM-7725, FM-0711, FM-0721, FM-0725, FM-0701, FM-0701T (above, any From the viewpoint of slipperiness, a vinyl group or a (meth) acrylic group-modified polydimethylsiloxane compound is preferable, and a vinyl group having a number average molecular weight of 3000 or more, or ( It is a (meth) acrylic group-modified polydimethylsiloxane compound.

The fluorine-containing monomer is not particularly limited. For example, fluoroolefins such as fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole; Part of (meth) acrylic acid or fully fluorinated alkyl ester derivatives represented by the following general formula (1) such as fluoroethyl methacrylate and perfluorooctylethyl (meth) acrylate; part of (meth) acrylic acid or complete fluorine Vinyl ethers and the like.

式中、Ｒ^１は水素原子、メチル基、又は、フッ素原子を表し、ｍ、ｎは自然数を表す。

In the formula, R ¹ represents a hydrogen atom, a methyl group, or a fluorine atom, and m and n represent natural numbers.

The non-polymerizable organic solvent is not particularly limited as long as it is mixed with an organosiloxane compound having a vinyl group or a (meth) acryl group in the structure or a fluorine-containing monomer and is liquid at the polymerization temperature. For example, but not limited to, butane, pentane, hexane, cyclohexane, heptane, decane, hexadecane, toluene, xylene, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, 1,4-dioxane, methyl chloride, methylene chloride, chloroform, carbon tetrachloride An organic solvent such as is suitable.

The organosilane compound having an epoxy group inside the structure is not particularly limited, and examples thereof include 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyl. Methyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, epoxy group-modified polydimethylsiloxane compound (commercially available products include, for example, KF-1001, KF-101, KF-102, KF-105 manufactured by Shin-Etsu Chemical Co., Ltd. X-22-2000, X-22-163A, X-22-163B, X-22-163C, X-22-169AS, X-22-169B, X-22-173-DX, X-22-3667 X-22-4741) and the like, but from the viewpoint of slipperiness, an epoxy group-modified polymer Le siloxane compounds are preferred, and more preferably the number average molecular weight of 3000 or more epoxy group-modified polydimethylsiloxane compounds.

The organosilane compound having an isocyanate group inside the structure is not particularly limited, and examples thereof include 3-isocyanatopropyltriethoxysilane.

The organosilane compound having a ureido group in the structure is not particularly limited, and examples thereof include 3-ureidopropyltriethoxysilane.

The organosilane compound having an amino group in the structure is not particularly limited. For example, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, special aminosilane, amino group-modified polydimethylsiloxane compound (as commercial products For example, KF-393, KF-858 KF-859, KF-860, KF-861, KF-864, KF-865, KF-867, KF-868, KF-869, KF-880, KF-8003, KF-8002, KF-8004, KF- 8005, KF-8008, KF-8010, KF-8012, X-22-3939A, X-22-3908A, X-22-161A, X-22-161B, X-22-1660B-3, KF-857, KF-862, KF-8001 (all are manufactured by Shin-Etsu Chemical Co., Ltd.), Silaplane FM-3311, FM-3321, FM-3325 (all are manufactured by Chisso)) and the like. From the viewpoint, an amino group-modified polydimethylsiloxane compound is preferable, and an epoxy group-modified polydimethyl having a number average molecular weight of 3000 or more is more preferable. It is a Rokisan compound.

The organosilane compound having a mercapto group in the structure is not particularly limited. For example, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, mercapto group-modified polydimethylsiloxane compound (commercially available products include, for example, , KF-2002, KF-2004, X-22-167B (all of which are manufactured by Shin-Etsu Chemical Co., Ltd.) and the like, and a mercapto group-modified polydimethylsiloxane compound is preferable from the viewpoint of slipperiness, more preferably a number. It is a mercapto group-modified polydimethylsiloxane compound having an average molecular weight of 3000 or more.

The organosilane compound having a halogen group in the structure is not particularly limited, and examples thereof include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.

The said organosilane compound may be used independently and may use 2 or more types together. Especially, the organosilane compound which has a vinyl group or a (meth) acryl group, the organosilane compound which has an epoxy group, or the organosilane compound which has an amino group is preferable. This is because, by containing such an organosilane compound, it is possible to produce slipperiness-imparting fine particles having excellent slipperiness and strength.

Moreover, when synthesizing the slipperiness imparting fine particles having the above structure, a resin component may be used in combination. By using the resin component in combination, the resulting slip imparting fine particles are excellent in alkali resistance.

The resin component is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cumyl (meth) acrylate, cyclohexyl (meth) acrylate, myristyl ( (Meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, (meth) acrylic acid, glycidyl (meth) acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1.6 Hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( (Meth) acrylic resins, (meth) acrylic resins such as dipentaerythritol hexa (meth) acrylate, vinyl ester resins such as vinyl acetate and vinyl propionate, halogen-containing vinyl resins such as vinyl chloride and vinylidene chloride, allyl methacrylate, diallyl phthalate, Allyl resins such as diallyl malate, diallyl fumarate, diallyl succinate, triallyl isocyanurate, styrene, α-methylstyrene, p-methyls Examples include aromatic divinyl resins such as tylene, p-chlorostyrene, divinylbenzene, polyurethane resins, polyurea resins, polyamide resins, polyimide resins, polyester resins, nylon resins and epoxy resins, or complete or partially fluorinated products thereof. . Of these, a complete or partially fluorinated product is preferable. By using a completely or partially fluorinated product, it is possible to satisfactorily express the slipperiness of the above-mentioned slipperiness-imparting fine particles, and in the case of a hollow structure, penetration of pores such as a polar medium to be described later It is because it becomes possible to suppress suitably.

When using the said resin component together, the compounding quantity is although it does not specifically limit, A preferable minimum is 1 weight part and a preferable upper limit is 90 weight part with respect to 100 weight part of said organosiloxane compounds or fluorine compounds. When the amount is less than 1 part by weight, the above-mentioned slipperiness-imparting fine particles may not be provided with sufficient alkali resistance. When the amount exceeds 90 parts by weight, the anti-scratch film of the antireflection film using the antireflection coating of the present invention has scratch resistance. May be insufficient. A more preferred lower limit is 10 parts by weight, and a more preferred upper limit is 50 parts by weight.

When the structure of the slipperiness-imparting fine particles is obtained by surface-treating the surface of the base material particle with the polyorganosiloxane compound or the fluorine compound, the structure of the base material particle is not particularly limited, for example, a solid structure Although it may have a hollow structure, a hollow structure is preferable because the slipperiness-imparting particles can easily achieve a low refractive index.

As said base material particle, it consists of other than the above-mentioned polyorganosiloxane compound or a fluorine compound, for example, may be an inorganic type fine particle and an organic type fine particle.

When the substrate particles are inorganic fine particles, the raw material is not particularly limited, and various inorganic components can be used, and examples thereof include silica and alumina. Among these, silica is preferable from the viewpoint of heat resistance, solvent resistance, strength, and refractive index, and hollow silica is particularly preferable.

When the substrate particles are organic fine particles, the raw material is not particularly limited, and examples thereof include the same resin components as described above.
When the organic fine particles have a hollow structure, the outer shell layer is preferably a resin obtained by reacting a lipophilic reaction component and a hydrophilic reaction component described later among the resin components. By forming the outer shell layer from a resin obtained by reacting a lipophilic reaction component and a hydrophilic reaction component, organic particles having voids inside (hereinafter also referred to as hollow substrate particles) can be suitably prepared. it can. The outer shell layer may be a single layer or a structure in which a plurality of layers are stacked.

Although it does not specifically limit as a manufacturing method of the hollow base material particle which has the outer shell layer which consists of resin which makes the above-mentioned lipophilic reaction component and the hydrophilic reaction component react, Lipophilic reaction component and hydrophilic reaction component which are mentioned below It can be suitably produced by a method for producing fine particles using. By using such a production method, it is possible to suitably produce hollow substrate particles having a single-pore structure, and it is possible to suitably achieve a desired porosity.

The lipophilic reaction component is not particularly limited, and examples thereof include polyisocyanate, epoxy prepolymer, and acid halide. Among these, an epoxy prepolymer is preferable. When an epoxy prepolymer is used as the lipophilic reaction component, the hollow base particle contains an epoxy resin. By containing an epoxy resin, the hollow base material particles have excellent heat resistance, solvent resistance, and strength, and the present invention contains slipperiness-imparting fine particles obtained by using such hollow base material particles. The antireflection coating agent is difficult to be destroyed when the antireflection layer is formed.

Among the above epoxy resins, cresol novolac type, phenol novolac type, dicyclopentadiene type, naphthalene type, bisnaphthol type, fluorene type, triphenolmethane type, tetraphenolethane type, glycidylamine type, special multifunctional type, etc. When used, the heat resistance can be improved.

The epoxy prepolymer has lipophilic properties and reacts with amines, polycarboxylic acids, and acid anhydrides to give resins. The epoxy prepolymer is not particularly limited. For example, bisphenol A type, resorcin type, bisphenol F type, tetraphenylmethane type, novolac type, polyalcohol type, polyglycol type, glycerin triether type, glycidyl ether type, glycidyl type. Ester type, glycidylamine type, aliphatic type, alicyclic type, aminophenol type, hydatoin type, isocyanurate type, biphenol type, biphenylene type, naphthalene type, bisnaphthol type, or their water additives, fluorinated products , Bromide, phosphorus-containing material, silicon-containing material and the like.

Among the above-mentioned epoxy prepolymers, halogenated epoxy prepolymers such as bromides and fluorinated compounds, phosphorus-containing epoxy prepolymers, silicon-containing epoxy prepolymers, phenol biphenylenes, etc. A type epoxy prepolymer or the like is preferably used.

Among the epoxy prepolymers, when an epoxy prepolymer having an upper limit of epoxy equivalent of 500 is used, a resin layer having a high degree of crosslinking is obtained, and the hollow resin fine particles are excellent in heat resistance, solvent resistance, and strength. Can be obtained. A more preferred upper limit is 200.

The epoxy prepolymer having an upper limit of the above epoxy equivalent of 200 is not particularly limited. For example, Epototo YD115, Epototo YD127, Epototo YD128 (trade name, manufactured by Toto Kasei Co., Ltd.), Epicoat 825, Epicoat 827, Epicoat 828 (trade name Japan Epoxy) Resin Co., Ltd.), EPICLON 840, EPICLON 850 (trade name, Dainippon Ink Chemical Co., Ltd.) and other bisphenol A type epoxy resins; Epototo YDF-170, Epototo YDF-175S (trade name, manufactured by Toto Kasei), Epicoat 806, Epicoat Bisphenol F type epoxy resins such as 807 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 (trade name, manufactured by Dainippon Ink and Chemicals); Epotot YDPN-638, Epot YDCN-701, Epototo YDCN-702, Epotot YDCN-703, Epotot YDCN-704, Epotot YDCN-500 (trade name, manufactured by Toto Kasei Co., Ltd.), Epicoat 152, Epicoat 154 (trade name, manufactured by Japan Epoxy Resin), EPICLON Novolac type epoxy resins such as N-655, EPICLON N-740, EPICLONN-770, EPICLON N-775, EPICLON N-865 (trade name, manufactured by Dainippon Ink and Chemicals); Epotot YH-434, Epotot YH434-L (Product) Name Toto Kasei Co., Ltd.), Epicoat 1031S, Epicoat 1032H60, Epicoat 604, Epicoat 630 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 430 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) Special multifunctional types such as TETRAD-X, TETRAD-C (trade name, manufactured by Mitsubishi Gas Chemical Company); biphenyl type epoxy resins such as Epicoat YX4000, Epicoat YL6121H, Epicoat YL6640, Epicoat YL6677 (trade name, manufactured by Japan Epoxy Resin); Aliphatic polyglycidyl ether type epoxy resins such as Epototo YH-300, Epototo-YH301, Epototo YH-315, Epototo YH-324, Epototo YH-325 (trade name, manufactured by Toto Kasei Co., Ltd.); Epototo YDC-1312, Epototo YSLV- Crystalline epoxy resins such as 80XY (trade name, manufactured by Toto Kasei Co., Ltd.); Naphthalene type epoxy resins such as EPICLON HP-4032 and EPICLON EXA-4700 (trade names, manufactured by Dainippon Ink and Chemicals); Epico 191P, Epicote YX310 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON HP-820 (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.), etc .; EPICLON 725 (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.), etc. Reactive diluents and the like.
In addition, naphthalene type epoxy resins such as EXA4701 (trade name, all manufactured by Dainippon Ink Chemical Co., Ltd.), ESN355, ESN375 (trade name, both manufactured by Nippon Steel Chemical Co., Ltd.), and the like can also be suitably used.

The epoxy prepolymer having an epoxy equivalent of more than 200 is not particularly limited. Examples of the epoxy prepolymer having an epoxy equivalent of more than 200 and not more than 500 include, for example, Epototo YD134, Epototo YD011 (trade names, all of which are Toto Kasei Co., Ltd.) ), Epicoat 801, Epicoat 1001 (trade names, all manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 860, EPICLON 1050, EPICLON 1055 (trade names, both manufactured by Dainippon Ink and Chemicals), etc .; Epototo YDF- Bisphenol F type epoxy resin such as 2001 (trade name, manufactured by Toto Kasei Co., Ltd.); EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EP Novolak type epoxy resins such as CLON N-680 and EPICLON N-695 (trade names, both manufactured by Dainippon Ink and Chemicals); Epicoat 157S70 (trade name, manufactured by Japan Epoxy Resin), EPICLON 5500 (trade names, Dainippon Ink) Epototo YDB-360, Epototo YDB-400, Epototo YDB405 (trade names, all manufactured by Tohto Kasei Co., Ltd.), EPICLON 152, EPICLON 153 (trade names, both manufactured by Dainippon Ink Chemical Co., Ltd.) Brominated epoxy resins such as Epototo YD-171 (trade name, manufactured by Tohto Kasei Co., Ltd.), Epicoat 871 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLONTSR-960, EPICLON TSR-601 (trade names, both large) Nippon Ink Chemical Flexible epoxy resins such as Epototo ST-3000 (trade name, manufactured by Tohto Kasei Co., Ltd.), hydrogenated epoxy resins such as Epicoat YX8000, Epicoat YX8034 (trade names, both manufactured by Japan Epoxy Resin Co., Ltd.); Dicyclopentadiene type epoxy resins such as EPICLON HP-7200 (trade name, manufactured by Dainippon Ink and Chemicals), etc., or fluorinated products thereof; ESN165, SN175, ESN185, ESN195 (trade names, all of which are Nippon Steel Chemical Co., Ltd.) And naphthalene type epoxy resins. Of these, a fluorinated product is preferable. By using the fluoride, it is possible to suppress the penetration of the polar medium or the like described later into the pores.

Moreover, as an epoxy prepolymer exceeding epoxy equivalent 500, for example, Epototo YD-012, Epototo YD-013, Epototo YD-014, Epototo YD-017, Epototo YD-019 (trade names, all manufactured by Toto Kasei Co., Ltd.) , Epicoat 1002, Epicoat 1003, Epicoat 1055, Epicoat 1004, Epicoat 1007, Epicoat 1009, Epicoat 1010 (trade names, all manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 3050, EPICLON 4050, EPICLON AM-020-P, EPICLON AM-030- P, EPICLON AM-040-P, EPICLON 7050, EPICLON HM-091, EPICLON HM-101 (trade names, all made by Dainippon Ink Epototo YDF-2004 (trade name, manufactured by Tohto Kasei Co., Ltd.), Epicoat 4004P, Epicoat 4007P, Epicoat 4010P, Epicoat 4110, Epicoat 4210 (trade names, all manufactured by Japan Epoxy Resin Co., Ltd.) Brominated epoxy resins such as Epototo YDB-405 (trade name, manufactured by Toto Kasei Co., Ltd.), EPICLON 1123P-75M (trade name, manufactured by Dainippon Ink &Chemicals); Epototo YD-172 (product) Name, manufactured by Toto Kasei Co., Ltd.), Epicoat 872 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 1600-75X (trade name, manufactured by Dainippon Ink & Chemicals), etc .; Epototo ST-4000D (trade name) , Manufactured by Toto Kasei) -Contained epoxy resin; EPICLON5800 (trade name, manufactured by Dainippon Ink and Chemicals Incorporated) polyfunctional epoxy resins such as, or, these fluoride and the like. Of these, a fluorinated product is preferable. By using the fluoride, it is possible to suppress the penetration of the polar medium or the like described later into the pores.
These epoxy prepolymers may be used alone or in combination of two or more.

The polyisocyanate has lipophilicity and reacts with hydrophilic reaction components such as water, amine, polyol, polycarboxylic acid to give a resin. The polyisocyanate is not particularly limited, and examples thereof include a burette type, an adduct type, and an isocyanurate type.
In addition, the said polyisocyanate, polyol, and polycarboxylic acid mean the compound which has multiple this functional group in 1 molecule.

The acid halide is not particularly limited, and examples thereof include dibasic acid halides such as adipoyl dichloride, phthaloyl dichloride, terephthaloyl dichloride, and 1,4-cyclohexanedicarbonyl chloride.

By using the above-mentioned lipophilic reaction component, the hollow substrate particles are excellent in heat resistance, solvent resistance, strength, and the like.

It does not specifically limit as said hydrophilic reaction component, It determines suitably according to the said lipophilic reaction component so that resin may be produced | generated by reacting with the said lipophilic reaction component.
Specifically, for example, when polyisocyanate is used as the lipophilic reaction component, the hydrophilic reaction component is at least one selected from the group consisting of water, amines, polyols, and polycarboxylic acids. Are preferably used.
In this case, a polyurea is produced by reacting polyisocyanate with water and / or amine, a polyurethane is produced by reacting polyisocyanate and polyol, and a polyamide is produced by reacting polyisocyanate and polycarboxylic acid. Is generated.

When an epoxy prepolymer is used as the lipophilic reaction component, amine, polycarboxylic acid, polythiol and the like are preferably used as the hydrophilic reaction component.
An epoxy polymer is formed by the reaction of the epoxy compound with amine, polycarboxylic acid, polythiol and the like.

The amine is not particularly limited. For example, polyamines such as ethylenediamine, tetramethylenediamine, hexamethylenediamine, phenylenediamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenepentamine; 2-methylimidazole, 2- Undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1- Anoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino- 6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2 , 4-diamino-6- [2′-methyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, etc. Imidazole; piperazine such as piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine Compounds; amino group-containing prepolymer of amino adducts of epoxy resins.

The polycarboxylic acid is not particularly limited. For example, oxalic acid, adipic acid, azelaic acid, sebacic acid, malonic acid, succinic acid, 1,4-cyclohexyldicarboxylic acid, (o-, m-, p-) Examples thereof include a polymer copolymer containing 10% by weight or more of any of benzenedicarboxylic acid, maleic acid, itaconic acid, acrylic acid, methylmethacrylic acid and the like.

The polyol is not particularly limited, and examples thereof include ethylene glycol, 1,4-butanediol, 2,3-butanediol, catechol, resorcinol, hydroquinone, o-dihydroxymethylbenzene, 4,4′-dihydroxydiphenylmethane, 2, 2-bis (4-hydroxyphenyl) -propane, 1,1,1-trimethylolpropane; hydroxyl group-containing polymers such as polyvinyl alcohol, polyhydroxy methacrylate, polyethylene glycol, polyoxypropylene glycol, and polyoxyalkylene glycol It is done.

Further, for example, when an acid halide is used as the lipophilic reaction component, an amine or a polyol is preferably used as the hydrophilic reaction component.
In this case, nylon and polyester are produced by the reaction of the acid halide with the amine and polyol.

The method for producing the hollow substrate particles is not particularly limited, but is preferably a production method in which the lipophilic reaction component and the hydrophilic reaction component are reacted, and specifically includes the lipophilic reaction component. One of a step of preparing a lipophilic reaction solution, a step of preparing a hydrophilic reaction solution containing the hydrophilic reaction component, a step of adding an emulsifier, and the lipophilic reaction solution and the hydrophilic reaction solution. A hollow substrate particle is preferably produced by a method comprising a step of preparing a dispersion in which the reaction solution of 1 is dispersed in the other reaction solution and a step of reacting the lipophilic reaction component and the hydrophilic reaction component. Can do.

As the step of preparing the lipophilic reaction liquid, it is preferable to mix the above-described lipophilic reaction component and other lipophilic components. Examples of the other lipophilic reaction component include non-polymerizable compounds.

The non-polymerizable compound has a role of forming a stable polymerizable droplet in a polar medium and controlling a reaction rate between the lipophilic reaction component and the hydrophilic reaction component. In addition, when resin fine particles containing unreacted lipophilic reaction components are prepared by the steps described later by blending non-polymerizable compounds with the lipophilic reaction components, the resin fine particles also contain non-polymerizable compounds. The resin fine particles are made hollow by removing the non-polymerizable compound and the unreacted lipophilic reaction component from the resin fine particles encapsulating the non-polymerizable compound and the unreacted lipophilic reaction component. Have a role.

The non-polymerizable compound is liquid at the reaction temperature between the lipophilic reaction component and the hydrophilic reaction component, can be mixed with the lipophilic reaction component, does not react with the lipophilic reaction component, and can be easily heated. Is not particularly limited as long as it can be evaporated, for example, butane, pentane, hexane, cyclohexane, toluene, xylene, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, heptadecane, hexadecane, heptadecane, Preferred are organic solvents such as octadecane, nonadecane, eicosane, ethyl acetate, methyl chloride, methylene chloride, chloroform, carbon tetrachloride, stearyl (meth) acrylate, and the like. The said nonpolymerizable compound may be used independently and 2 or more types may be used together.

Among the non-polymerizable compounds, higher alkanes having about 8 to 20 carbon atoms such as octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, heptadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, stearyl (meth) acrylate, etc. And long-chain hydrophobic compounds can effectively suppress the coalescence of polymerizable droplets in a polar medium, so when used in combination with these non-polymerizable compounds as appropriate, Nanometer order polymerizable droplets can be formed stably.

As a blending amount of the non-polymerizable compound. A preferable lower limit is 10 parts by weight and a preferable upper limit is 1000 parts by weight with respect to 90 parts by weight of the lipophilic reaction component. If the amount is less than 10 parts by weight, the void ratio of the obtained hollow base material particles may be low and a sufficiently low refractive index may not be realized. If the amount exceeds 1000 parts by weight, the particle shape may be reduced when the non-polymerizable compound is removed. However, the hollow base particles may not be obtained, or the strength of the obtained hollow base particles may be extremely inferior.

In the case of using higher alkanes having about 8 to 20 carbon atoms or long-chain hydrophobic compounds in combination with other non-polymerizable compounds for the purpose of stably forming nanometer-order polymerizable droplets. As for the compounding ratio, a preferable minimum is 0.1 weight part with respect to 100 weight part of total amounts of a lipophilic reaction component and a nonpolymerizable compound. If it is less than 0.1 part by weight, coalescence of polymerizable droplets may not be effectively suppressed.

As the step of preparing the hydrophilic reaction solution, it is preferable to mix the above-described hydrophilic reaction component with a polar medium. The polar medium is not particularly limited, and examples thereof include water, ethanol, methanol, isopropyl alcohol, and the like.

Among the hydrophilic reaction solution and the lipophilic reaction solution, in the step of preparing a dispersion of polymerizable droplets in which one reaction solution is dispersed in the other reaction solution, the lipophilic reaction solution is converted into the hydrophilic reaction solution. It is preferable to disperse in a solution.
The method for preparing the dispersion is not particularly limited, and a conventionally known method can be used. For example, a nanometer-order dispersion can be prepared by using a high shearing emulsifier. Examples of the high elasticity emulsifying device include an omni mixer, an ultrasonic homogenizer, and a microfluidizer.

As the step of adding the emulsion, it may be added to the hydrophilic reaction solution, may be added to the lipophilic reaction solution, and one of the hydrophilic reaction solution and the lipophilic reaction solution. It may be added when preparing the dispersion in the step of preparing a dispersion of polymerizable droplets in which the reaction solution is dispersed in the other reaction solution.

Examples of the emulsifier include sodium lauryl sulfate, sodium higher alcohol sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, polyethanol ethylene alkyl ether sulfate triethanolamine. Sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium alkyldiphenyl ether disulfonate, potassium polyoxyethylene alkyl ether phosphate, dipotassium alkenyl succinate, sodium alkanesulfonate, polyoxyethylene alkyl ether phosphate Anionic emulsifiers such as esters, polyoxyethylene la Ryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene myristyl ether, polyoxyethylene alkyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene diether Styrenated phenyl ether, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan laurate, poly Oxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate Nonionic emulsifiers such as polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, glycerol monostearate, glycerol monostearate, glycerol monooleate, lauryltrimethylammonium chloride, Stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, palm alkyl ammonium chloride, beef tallow alkyl ammonium chloride, behenyl ammonium chloride, tetradecyldimethylbenzen ammonium chloride, octadecyldimethylbenzylammonium chloride, N, N-diacyloxyethyl N -Hydroxye N-methylammonium methosulfate, N, N-dipolyoxyethylene chloride-N-stearyl-N-methylammonium, N-chloride beef tallow alkyl N, N, N ′, N ′, N-pentamethylpropylenediammonium dichloride N-didecyltrimethylammonium chloride chloride, di-alkyl alkyl ammonium chloride, di-cured tallow alkyl ammonium chloride, dioleyl ammonium chloride, coconut alkyl polyethylene oxide addition ammonium chloride, oleyl alkyl polyethylene oxide addition ammonium chloride, distearyl dimethyl ammonium Chloride, benzalkonium chloride, stearamidepropyldimethylamide, alkylbenzylmethylammonium chloride, 1- Cationic emulsifiers such as loxyethyl 2-alkyl imidazoline, amphoteric emulsifiers such as lauryl betaine, stearyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, lauryl dimethylamine oxide, partially saponified polyvinyl acetate , Cellulose derivatives, poly (meth) acrylic acid, poly (meth) acrylic acid copolymers, polymer dispersants such as polyvinylpyrrolidone, polyacrylamide, marialim, polystyrene sulfonic acid, and dispersion aids such as cetyl alcohol. .

When the emulsifier is blended with the hydrophilic reaction solution or the lipophilic reaction solution, the blending amount is not particularly limited, but a preferable lower limit with respect to 100 parts by weight of the hydrophilic reaction solution is 0.01 parts by weight, A preferred upper limit is 10% by weight.

In the step of preparing a dispersion in which one of the lipophilic reaction solution and the hydrophilic reaction solution is dispersed in the other reaction solution, the blending ratio of the lipophilic reaction solution and the hydrophilic reaction solution is as follows. Although there is no particular limitation, the preferred lower limit of the lipophilic reaction solution is 1 part by weight and the preferred upper limit is 100 parts by weight with respect to 100 parts by weight of the hydrophilic reaction solution.

In the step of reacting the hydrophilic reaction component and the lipophilic reaction component, the outer shell layer containing the resin component is formed by reacting the lipophilic reaction component and the hydrophilic reaction component at the interface of the dispersion. Can be formed.

The method for reacting the hydrophilic reaction component and the lipophilic reaction component is not particularly limited. For example, the dispersion liquid is heated to the reaction temperature of the lipophilic reaction component and the hydrophilic reaction component described above to cause the reaction. And a method of forming an outer shell layer. At this time, the reaction occurs only in the vicinity of the interface of the dispersion, and fine resin particles are formed that have a generated outer shell and encapsulate an unreacted oil component (and the non-polymerizable organic solvent or the like).

Thereafter, unreacted oil components and the like encapsulated in the resin fine particles are removed to synthesize hollow base particles.

The method for removing unreacted oil components contained in the resin fine particles is not particularly limited. For example, a method of blowing a gas such as nitrogen or air into the obtained dispersion of resin fine particles; a method of depressurizing the entire system A method of extracting and removing the oil component in a solvent that can be mixed with the encapsulated oil component.
Furthermore, by making the temperature condition equal to or higher than the boiling point of the unreacted oil component inside the fine particles, the encapsulated unreacted oil component can be removed from the resin fine particles.

The hollow base particle may be one in which the outer shell layer of the particle has a two-layer structure. Such hollow base particles having an outer shell having a two-layer structure can have various functions.
In such hollow base particles, the outer shell layer is preferably composed of two layers of an outermost layer and an inner layer, and the outermost layer and the inner layer are preferably in close contact with each other. This can be confirmed with an electron microscope (“JEM-1200EXII” manufactured by JEOL Ltd.).

The hollow base particle having the outer shell layer having a two-layer structure uses a lipophilic reaction component, a hydrophilic reaction component, and a lipophilic reaction component and another lipophilic reaction component that does not react with the hydrophilic reaction component. Can be suitably produced by the conventional method. The outermost layer of the hollow base particles produced by such a method is constituted by the reaction between the lipophilic reaction component and the hydrophilic reaction component, and the inner layer comprises the lipophilic reaction component and the hydrophilic reaction component. Is constituted by the reaction of other lipophilic reaction components that do not react. The hollow base particle having such a structure can achieve both a low refractive index and a particle strength by adjusting the configuration of the outermost layer and the inner layer.

It does not specifically limit as said lipophilic reaction component and said hydrophilic reaction component, For example, the thing similar to the lipophilic reaction component and hydrophilic reaction component demonstrated in the manufacturing method of the hollow base particle mentioned above is mentioned.

The other lipophilic reaction component is not particularly limited as long as it does not react with the lipophilic reaction component and the hydrophilic reaction component, but radical polymerization is performed from the viewpoint of the wide selection of reaction components and the ease of handling. Sex monomers are preferably used.

The radical polymerizable monomer is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cumyl (meth) acrylate, cyclohexyl (meth) acrylate , Myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, alkyl (meth) acrylate such as isobornyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, (meth) acrylic acid, glycidyl ( Polar group-containing (meth) acrylic monomers such as (meth) acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, styrene, α-methylstyrene, p-methylstyrene, -Aromatic vinyl monomers such as chlorostyrene, vinyl esters such as vinyl acetate and vinyl propionate, halogen-containing monomers such as vinyl chloride and vinylidene chloride, vinyl pyridine, 2-acryloyloxyethylphthalic acid, itaconic acid, fumaric acid, ethylene Monofunctional monomer such as propylene, polydimethylsiloxane macromonomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate , Trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol Li (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, diallyl phthalate, diallyl malate, diallyl fumarate, diallyl succinate, triallyl isocyanurate, divinylbenzene, butadiene, etc. A functional monomer etc. are mentioned.
These other lipophilic reaction components may be used alone or in combination of two or more.

When using a radically polymerizable monomer as said other lipophilic reaction component, it is preferable to contain a radical polymerization initiator as a reaction catalyst.
The radical polymerization initiator is not particularly limited, and examples thereof include di-t-butyl peroxide, dicumyl peroxide, di-t-butyl peroxide, di-sec-butyl peroxycarbonate, and t-butyl peroxylaur. Rate, t-butylperoxybenzoate, t-butylperoxy-2-ethylhexanate, t-butylperoxyisopropylmonocarbonate, t-hexylperoxybenzoate, 1,1-bis (t-butylperoxy ) -3,5,5-trimethylhexane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, benzoyl peroxide, and the like Ketone peroxide, peroxyketal, hydroperoxide Organic peroxides such as dialkyl peroxide, diacyl peroxide, peroxydicarbonate, peroxycarbonate, peroxyester; 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2, 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (Cyclohexane-1-carbonitrile), 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), 2 , 2′-azobis (N-cyclohexyl-2-methylpropionamide), dimethyl-2,2′-azobis (2-methylpropionate) 2,2′-azobis (2,4,4-trimethylpentane), VPS-0501 (trade name, manufactured by Wako Pure Chemical Industries), VPS-1001 (trade name, manufactured by Wako Pure Chemical Industries) System initiators; redox initiators and the like.

Moreover, you may use a fluorine-containing monomer as said other lipophilic reaction component. By using a fluorine-containing monomer, it is possible to suppress the penetration of the above-described polar medium or the like into the gap.
The fluorine-containing monomer is not particularly limited, and examples thereof include the same ones as described above.

The surface treatment of the substrate particle surface with a polyorganosilane compound or a fluorine compound is not particularly limited, and an epoxy group, an isocyanate group, or a ureido can be used depending on the functional group of the substrate particle on the surface. A silane coupling agent having a group, an amino group, a mercapto group, a vinyl group, a (meth) acryl group, an organosiloxane compound such as a modified silicone oil, a fluorine compound, or the like can be appropriately used as a surface treatment agent. Especially, the modified silicone oil which has an epoxy group, an amino group, a vinyl group, and a (meth) acryl group is used suitably.

Although it does not specifically limit as molecular weight of the modified silicone oil which has the said epoxy group, an amino group, a vinyl group, and a (meth) acryl group, A preferable minimum is 400 and a preferable upper limit is 100,000. When the molecular weight is less than 400, the slipperiness imparting effect of the slipperiness imparting particles obtained by the surface treatment may not be sufficient, and when the molecular weight exceeds 100,000, the viscosity may increase and the handling property may be poor. A more preferred lower limit is 1000, a more preferred upper limit is 50,000, a still more preferred lower limit is 3000, and a still more preferred upper limit is 10,000.

In the anti-reflection coating agent of the present invention, the blending amount of the slipperiness-imparting fine particles is not particularly limited, but a preferable lower limit is 1 part by volume and a preferable upper limit is 900 parts by volume with respect to 100 parts by volume of the binder component described later. . When the amount is less than 1 part by volume, the antireflection film obtained by using the antireflection coating agent of the present invention may not be provided with sufficient scratch resistance. When the amount exceeds 900 parts by volume, the antireflection film is obtained. The film strength may be inferior, and the refractive index of the film may be high if the slipperiness-imparting fine particles are not sufficiently low.

The antireflection coating agent of the present invention contains a binder component.
By containing the binder component, for example, in the case of producing an antireflection film using the antireflection coating agent of the present invention, the antireflection coating agent of the present invention is molded into a desired shape and simply antireflective. A film can be made.

The binder component is not particularly limited as long as it is transparent and can be formed into a film, and examples thereof include various organic materials, inorganic materials, and polymerizable monomer solutions.
The organic material is not particularly limited. For example, cellulose derivatives such as triacetylcellulose, diacetylcellulose, propionylcellulose, butanoylcellulose, acetylpropionylcellulose acetate, nitrocellulose; polyamide, polycarbonate; polyethylene terephthalate, poly-1, Polyesters such as 4-cyclohexanedimethylene terephthalate, polyethylene 1,2-diphenoxyethane-4,4-dicarboxylate, polybutylene terephthalate and polyethylene naphthalate; polystyrene, polypropylene, polyethylene, polymethylpentene, polysulfone, polyether Sulphone, polyarylate, polyetherimide, polymethyl methacrylate, or various fluorine-containing materials thereof Relatively transparent resin having a low refractive index and the like.
In addition, when using transparent resin as the said binder, it is preferable to use a glass transition temperature lower than the glass transition temperature of the said slipperiness | lubricity provision fine particle. Thereby, sufficient film strength can be obtained.

The inorganic material is not particularly limited, and examples thereof include alkoxides of various elements, salts of organic acids, and coordination compounds bonded to coordination compounds. Specifically, for example, titanium tetraethoxide, titanium Tetra-i-propoxide, titanium tetra-n-propoxide, titanium tetra-n-butoxide, titanium tetra-sec-butoxide, titanium tetra-tert-butoxide, aluminum triethoxide, aluminum tri-i-propoxide, aluminum Tributoxide, antimony triethoxide, antimony riboxide, zirconium tetraethoxide, zirconium tetra-i-propoxide, zirconium tetra-n-propoxide, zirconium tetra-n-butoxide, zirconium tetra-sec-butoxide, zirco Metal alcoholate compounds such as um tetra-tert-butoxide; di-isopropoxytitanium bisacetylacetonate, dibutoxytitanium bisacetylacetonate, diethoxytitanium bisacetylacetonate, bisacetylacetone zirconium, aluminum acetylacetonate, aluminum di- Chelating compounds such as n-butoxide monoethyl acetoacetate, aluminum di-i-propoxide monomethyl acetoacetate, tri-n-butoxide zirconium monoethyl acetoacetate; active inorganic polymers mainly composed of zirconyl ammonium carbonate or zirconium Can be mentioned.

The polymerizable monomer in the polymerizable monomer solution is not particularly limited as long as it is transparent. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate , Alkyl (meth) acrylates such as cumyl (meth) acrylate, cyclohexyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate; (meth) acrylonitrile, ( Polar group-containing (meth) acrylic monomers such as (meth) acrylamide, (meth) acrylic acid, glycidyl (meth) acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; styrene Aromatic vinyl monomers such as α-methylstyrene, p-methylstyrene, and p-chlorostyrene; vinyl esters such as vinyl acetate and vinyl propionate; halogen-containing monomers such as vinyl chloride and vinylidene chloride; vinyl pyridine, 2-acryloyloxy Examples include ethylphthalic acid, itaconic acid, fumaric acid, ethylene, propylene and the like.
These monomers may be used independently and 2 or more types may be used together.

The polymerizable monomer solution may contain a polyfunctional monomer for the purpose of improving the film strength of an antireflection film using the antireflection coating agent of the present invention.
The polyfunctional monomer is not particularly limited. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tri Di (meth) acrylates such as methylolpropane di (meth) acrylate; Tri (meth) acrylates such as trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate A tetra (meth) acrylate such as pentaerythritol tetra (meth) acrylate; a hexa (meth) acrylate such as pentaerythritol hexa (meth) acrylate; a pentaerythritol Di- or triallyl compounds such as rutetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, diallyl phthalate, diallyl malate, diallyl fumarate, diallyl succinate, triallyl isocyanurate; divinyl compounds such as divinylbenzene, butadiene, etc. Is mentioned.
These polyfunctional monomers may be used independently and 2 or more types may be used together.

When a polymerizable monomer solution is used as the binder component, a polymerization initiator is preferably contained.
The polymerization initiator is not particularly limited, and may be a thermosetting type or a photocurable type. As such a polymerization initiator, examples of the thermosetting type include di-t-butyl peroxide, dicumyl peroxide, di-t-butyl peroxide, di-sec-butyl peroxycarbonate, t -Butyl peroxylaurate, t-butyl peroxybenzoate, t-butyl peroxy-2-ethyl hexanate, t-butyl peroxyisopropyl monocarbonate, t-hexyl peroxybenzoate, 1,1-bis ( t-butylperoxy) -3,5,5-trimethylhexane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, and benzoyl Various peroxides such as peroxides, peroxyketals, hydropero Organic peroxides such as side, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, peroxycarbonate, peroxyester; 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1 ′ -Azobis (cyclohexane-1-carbonitrile), 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2'-azobis (N-butyl-2-methylpropionamide) 2,2′-azobis (N-cyclohexyl-2-methylpropionamide), dimethyl-2,2′-azobis (2-methylpropiamide) Nate), 2,2′-azobis (2,4,4-trimethylpentane), VPS-0501 (trade name, manufactured by Wako Pure Chemical Industries), VPS-1001 (trade name, manufactured by Wako Pure Chemical Industries), etc. Azo initiators; redox initiators and the like can be used.

Examples of the photo-curing type include acetophenones, benzophenones, α-amyloxime esters, tetramethylchuram monosulfide, thioxanthones, and the like. Moreover, when using the said photocurable hardening | curing agent, n-butylamine, a triethylamine, poly- n-butylsulfine etc. can be mixed and used as a photosensitizer. These polymerization initiators may be used alone or in combination of two or more.

The blending amount of the polymerization initiator is not particularly limited, but a preferable lower limit is 0.1 parts by weight and a preferable upper limit is 100 parts by weight with respect to 100 parts by weight of the monomer component in the polymerizable monomer solution. If the amount is less than 0.1 part by weight, curing may be insufficient when an antireflection film is formed. If the amount exceeds 100 parts by weight, the antireflection obtained by decomposition by-products of the polymerization initiator is present. The strength and solvent resistance of the film may decrease.

The binder component can be obtained by blending and mixing each predetermined amount of the monomer component in the polymerizable monomer component and the polymerization initiator.
The mixing method is not particularly limited, and for example, an appropriate mixing method such as a disper, a homogenizer, a stirrer, a ball mill, or an ultrasonic wave can be used.

The binder component may contain a solvent as appropriate. Such a solvent is not particularly limited, for example, alcohols such as methanol, ethanol, isopropanol, butanol, 2-methoxyethanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl acetate, ethyl acetate , Esters such as butyl acetate, ethers such as diisopropyl ether, glycols such as ethylene glycol, propylene glycol, hexylene glycol, glycol ethers such as ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, hexane, heptane Aliphatic hydrocarbons such as chloroform, halogenated hydrocarbons such as chloroform, aromatic hydrocarbons such as benzene, toluene, xylene, N-methylpyrrolidone, dimethylformia De, steady Rusuru sulfoxide, 1,4-dioxane, tetrahydrofuran and the like. These solvents may be used alone or in combination of two or more.

The antireflection coating agent of the present invention may contain low refractive fine particles having an average particle diameter of 100 nm or less and a refractive index of 1.35 or less in addition to the slipperiness-imparting fine particles.
By using such low refractive fine particles, even when the refractive index of the slipperiness-imparting particles is not sufficiently low, the refractive index of the antireflection film using the coating agent of the present invention can be kept low.

The low refractive fine particles are not particularly limited as long as they satisfy the above particle diameter and refractive index, but hollow silica and the above hollow resin particles are preferable.

The blending amount of the low refractive particles is not particularly limited, but the preferred lower limit is 10 parts by weight and the preferred upper limit is 900 parts by weight with respect to 100 parts by weight of the binder component. If the amount is less than 10 parts by weight, the effect of adding the low refractive particles may not be sufficiently obtained. If the amount exceeds 900 parts by weight, the strength of the resulting antireflection film may be inferior. A more preferred lower limit is 50 parts by weight, and a more preferred upper limit is 400 parts by weight.

The antireflection coating agent of the present invention is a mixture of the above-mentioned slipperiness-imparting fine particles, the above-mentioned binder component, and the predetermined amounts of the above-mentioned low-refractive fine particles having an average particle diameter of 100 nm or less and additives described later, which are added as necessary. Can be obtained at

The antireflective coating agent of the present invention is a light diffusing agent, an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, a colorant, an antioxidant, as necessary, in addition to the above-described slipperiness-imparting fine particles and binder component. You may contain additives, such as a flame retardant.
Although it does not specifically limit as a compounding quantity in the case of containing the said additive, From a viewpoint which does not inhibit antireflection performance, a preferable upper limit is 100 weight part with respect to 100 weight part of said binder components.

The additive may be added when preparing the binder component, or may be added when preparing the antireflection coating agent of the present invention.

The antireflective coating agent of the present invention may be in an emulsion state in which the slipperiness-imparting fine particles are suspended in the binder component, or may be appropriately diluted in a volatile solvent.
Although it does not specifically limit as said volatile solvent, For example, alcohol, such as methanol, ethanol, isopropanol, butanol, 2-methoxyethanol; acetone, methyl ethyl ketone, methyl isobutyl from stability of a composition, wettability, volatility, etc. Ketones such as methyl acetate, ethyl acetate and butyl acetate; ethers such as diisopropyl ether; glycol ethers such as ethylene glycol, propylene glycol and hexylene glycol; aliphatic carbonization such as hexane, heptane and octane Hydrogens; halogenated hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; N-methylpyrrolidone, dimethylformamide and the like are preferably used. These volatile solvents may be used alone or in combination of two or more.

In the antireflection coating agent of the present invention, the preferable upper limit of the refractive index of the film-formed body is 1.40. When it exceeds 1.40, when an antireflection film is produced, a sufficiently low refractive index cannot be obtained, and as a result, a sufficient antireflection effect may not be obtained. A more preferred upper limit is 1.37, and a more preferred upper limit is 1.35. Although it does not specifically limit as a minimum, A preferable minimum is 1.25.
In the present specification, the refractive index of the film-formed body refers to a light incident angle of 5 ° using a spectrophotometer (“UV-3101PC” manufactured by Shimadzu Corporation) for the film formed on the substrate. By measuring the reflectance spectrum of one side at a light wavelength of 380 to 780 nm, and estimating the obtained reflection spectrum using optical characteristic analysis software (for example, “WVASE32” manufactured by JA Woollam Japan) Means the value obtained.
The film forming method of the film forming body is not particularly limited. For example, the film forming body can be formed by the same method as the manufacturing method of the antireflection film described later.

An antireflection film comprising a matrix resin and fine particles having an average particle diameter of 50 to 200 nm dispersed in the matrix resin and at least a surface comprising a polyorganosiloxane compound or a fluorine compound is also included in the present invention. One.

An antireflection film can be produced using the antireflection coating agent of the present invention. Such an antireflection film using the antireflection coating agent of the present invention is also one aspect of the present invention.

That is, the antireflection film of the present invention can be obtained by forming the above-described antireflection coating agent of the present invention into a film.
The structure of the antireflection film of the present invention is not particularly limited. For example, the antireflection film of the present invention may have a single-layer structure consisting of only the layer made of the antireflection coating agent of the present invention. The laminated structure in which the layer which consists of coating agents for coatings was formed may be sufficient. Especially, it is preferable that it is a laminated structure in which the layer which consists of the coating agent for antireflection of this invention was formed on the said base material layer. This is because by having the base material layer, the mechanical strength of the antireflection film of the present invention is improved and the handleability is excellent.

The method for producing the antireflection film of the present invention is not particularly limited. For example, in the case of the single-layer structure, after coating and curing the antireflection coating agent of the present invention on a release film or the like, Examples include a method of peeling the release film, and in the case of the laminated structure, after directly coating the antireflection coating agent of the invention on the base material layer described later, Examples thereof include a method of attaching a film made of an antireflection coating agent on a substrate.
In addition, the thickness of the coating agent of the present invention applied on the release film or the base material layer is equal to or smaller than the average particle diameter of the slipperiness-imparting fine particles contained in the coating agent of the present invention. preferable. By using such a thickness, the surface of the antireflection film of the present invention to be produced has irregularities made of slipperiness-imparting fine particles as described later, and the antireflection film of the present invention has excellent scratch resistance. Because it becomes.

The method for coating the antireflection coating agent of the present invention on the release film or substrate layer is not particularly limited, and examples thereof include dip coating, spin coating, flow coating, spray coating, and roll coating. Method, gravure roll coating method, air doctor coating method, blade coating method, wire doctor coating method, knife coating method, reverse coating method, transfer roll coating method, micro gravure coating method, kiss coating method, cast coating method, slot orifice coating method , Calendar coating method, die coating method and the like.

As a method of curing the antireflection coating agent of the present invention coated on the release film or substrate layer, the polymerization initiator contained in the polymerizable compound is activated and the polymerizable composition is cured. However, for example, when the polymerization initiator is a thermosetting initiator, it may be heated, and when the polymerization initiator is a thermosetting initiator, light irradiation is performed. Just do it.
The heating method or the light irradiation method is not particularly limited, and a conventionally known method can be used.

Although it does not specifically limit as a material which comprises the said base material layer, It is preferable that it is transparent, As such a material, for example, triacetylcellulose, diacetylcellulose, propionylcellulose, butanoylcellulose, acetylpropionylcellulose acetate, Cellulose derivatives such as nitrocellulose; polyamides, polycarbonates, polyesters described in JP-B-48-40414 (in particular, polyethylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene 1,2-diphenoxyethane-4, 4-dicarboxylate, polybutylene terephthalate, polyethylene naphthalate, etc.), polystyrene, polypropylene, polyethylene, polymethylpentene, polysulfone, polyether Rusurufon, polyarylate, polyetherimide, polymethyl methacrylate, or a transparent resin having a relatively low refractive index, such as these various fluorinated products thereof.

Although it does not specifically limit as thickness of the said base material layer, A preferable minimum is 40 micrometers and a preferable upper limit is 200 micrometers. If it is less than 40 μm, the antireflection film of the present invention may have poor mechanical strength, and if it exceeds 200 μm, the antireflection film of the present invention may have poor transparency, making it difficult to see internal visual information. .

When the antireflection film of the present invention has the base material layer, a layer using the antireflection coating agent may be directly formed on the base material layer, or a layer using the antireflection coating agent. May be prepared separately and laminated on the base material by various conventionally known methods.

Further, the thickness (d) nm of the antireflection layer of the present invention is not particularly limited, but when the refractive index of the antireflection film is n and the light wavelength (λ) nm used for measurement is n · d = It is desirable that the relationship of λ / 4 holds.
The thickness (d) of the antireflection film is obtained by measuring the reflectance spectrum of one surface having a light wavelength of 380 to 780 nm obtained by measuring the reflectance of the antireflection film with optical characteristic calculation software (JA Woollam Japan). It can measure by analyzing using "WVASE32" by Corporation | KK.

It is preferable that the antireflection film of the present invention has a concavo-convex shape whose surface is made of a polyorganosiloxane compound or a fluorine compound derived from the slipperiness-imparting fine particles. By having a concavo-convex shape made of polyorganosiloxane or fluorine compound on the surface, excellent scratch resistance can be obtained. This is because the surface of the polyorganosiloxane compound or fluorine compound having a low surface tension is exposed on the surface of the antireflection film, thereby reducing the frictional resistance against abrasion.

The number of surface irregularities made of a polyorganosiloxane compound or a fluorine compound on the surface of the antireflection film of the present invention is not particularly limited, but the preferred lower limit of the number of irregularities per 1 μm ^{2 of the} antireflection film is 1, and the preferred upper limit is 500. Less than When the number is less than 1, the intended scratch resistance effect due to imparting slipperiness may not be sufficiently obtained, and when it is 500 or more, the ratio of slipperiness imparting particles is too large and slipperiness is imparted. However, the strength of the film itself may be inferior. A more preferred lower limit is 10 and a more preferred upper limit is less than 100.

The height of the slipperiness-imparting fine particles protruding from the surface of the antireflection film of the present invention is not particularly limited, but the preferred lower limit is 1% of the particle diameter of the slip-providing fine particles, and the preferred upper limit is the particles of the slip-giving fine particles. 50% of the diameter. If it is less than 1%, sufficient anti-scratch resistance may not be imparted to the antireflection film of the present invention, and if it exceeds 50%, the slipperiness-imparting fine particles are likely to fall off. A more preferred lower limit is 2%, and a more preferred upper limit is 20%.
In addition, the surface of the antireflection film of the present invention referred to herein means the surface of the antireflection layer of the present invention between the irregularities of the polyorganosiloxane compound or fluorine compound derived from the slipperiness-imparting fine particles.

The antireflection film of the present invention preferably has a static friction coefficient and a dynamic friction coefficient of 0.3 or less. When the static friction coefficient and the dynamic friction coefficient exceed 0.3, the antireflection film of the present invention is likely to be damaged by rubbing. A more preferred upper limit is 0.1, and a still more preferred upper limit is 0.05.

In the antireflection film of the present invention, the lower limit of the contact angle of ultrapure water is preferably 100 °. When the contact angle of ultrapure water is less than 100 °, the antireflection film surface of the present invention has a high polarity, resulting in high frictional resistance and inferior scratch resistance, and the antireflection film of the present invention. There is a problem that the surface is easily soiled.

In the antireflection film of the present invention, the upper limit of the falling angle of ultrapure water and n-hexadecane is preferably 30 °. When the falling angle exceeds 30 °, contaminants tend to adhere to the surface of the antireflection film of the present invention. A more preferred upper limit is 20 °.

In the antireflection film of the present invention, the upper limit of the refractive index of light having a wavelength of 550 nm is preferably 1.40. If it exceeds 1.40, the antireflection film of the present invention may not have a sufficient antireflection effect. A more preferred upper limit is 1.37, and a more preferred upper limit is 1.35.

In the antireflection film of the present invention, the preferable upper limit of haze is 1.0%. When the haze exceeds 1.0%, the appearance of the antireflection film of the present invention may become whitish. A more preferred upper limit is 0.5%, and a still more preferred upper limit is 0.3%. Although it does not specifically limit as a preferable minimum, It is preferable that it is a detection limit.

Since the present invention contains fine particles made of a polyorganosiloxane compound or fluorine compound having a low surface tension at least on the surface, when the antireflection film is formed, a part of the fine particles protrudes from the surface to form irregularities. By doing so, it is possible to provide an antireflection coating agent and an antireflection film that can have excellent scratch resistance.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
(1) Preparation of slipperiness imparting fine particles 40 parts by weight of Silaplane FM-7721 (manufactured by Chisso) as a reactive silicone component and 50 parts by weight of toluene and 10 parts by weight of hexadecane as non-polymerizable organic solvents were mixed and stirred. The total amount of the mixed solution is added to 390 parts by weight of ion-exchanged water containing 2 parts by weight of sodium dodecylbenzenesulfonate as a water-soluble emulsifier, 6 parts by weight of cetyl alcohol, and 2 parts by weight of ammonium persulfate as an initiator, and is added to an ultrasonic homogenizer. The mixture was forcibly emulsified for 60 minutes to prepare a dispersion in which polymerizable droplets having an average particle diameter of 108 nm were dispersed.

Using a 20 L polymerization vessel equipped with a stirrer, jacket, reflux condenser and thermometer, the inside of the vessel was depressurized and deoxygenated in the vessel, and then purged with nitrogen to make the inside a nitrogen atmosphere. The dispersion was charged, and the polymerization vessel was heated to 80 ° C. to initiate polymerization. Polymerization was performed for 4 hours, and after a aging period of 1 hour, the polymerization vessel was cooled to room temperature. The resulting slurry was dialyzed using a cellulose membrane having a molecular weight cut off of 10,000 to remove excess surfactant and inorganic salts, and further filtered to remove aggregated particles and insoluble matter, thereby obtaining silicone resin fine particles. .
The obtained silicone resin fine particles were vacuum-dried to obtain slipperiness-imparting fine particles having an average particle diameter of 112 nm.

(2) Preparation of anti-reflection coating agent and preparation of anti-reflection film Dipentaerythritol hexaacrylate was used as 100 parts by volume of the polymerizable compound, 100 parts by volume of the resulting slipperiness-imparting fine particles, and methyl ethyl ketone as the diluent solvent 800 parts by volume and Irgacure 814 (trade name: manufactured by Ciba Specialty Chemicals) as an initiator were added to prepare a coating agent for an antireflection film.
The obtained anti-reflection coating agent was applied onto a triacetyl cellulose film using a bar coater so that the reflectance of the polymerized cured product had a minimum value of 550 nm, and then a 120 W high-pressure mercury lamp was irradiated with ultraviolet rays from a distance of 20 cm. Was irradiated for 180 seconds to obtain an antireflection film. The thickness of the antireflection film was 98 nm, and surface irregularities derived from the slipperiness-imparting fine particles were present on the surface of the antireflection film.

(Example 2)
The total amount of a mixed solution obtained by mixing and stirring 40 parts by weight of Epicoat 828 (manufactured by Japan Epoxy Resin Co.) as an epoxy prepolymer component and 60 parts by weight of toluene as a non-polymerizable organic solvent, 10 parts by weight of ethylenediamine as an amine component, water-soluble Add to 390 parts by weight of ion-exchanged water containing 2 parts by weight of lauryltrimethylammonium chloride as an emulsifier, and forcibly emulsify with an ultrasonic homogenizer for 60 minutes to prepare a dispersion in which polymerizable droplets having an average particle size of 92 nm are dispersed. did.
Using a 20 L polymerization vessel equipped with a stirrer, jacket, reflux condenser and thermometer, the inside of the vessel was depressurized and deoxygenated in the vessel, and then purged with nitrogen to make the inside a nitrogen atmosphere. The dispersion was charged, and the polymerization vessel was heated to 80 ° C. to initiate polymerization. Polymerization was performed for 4 hours, and after a aging period of 1 hour, the polymerization vessel was cooled to room temperature. The obtained slurry was dialyzed using a cellulose membrane having a molecular weight cut off of 10,000, excess surfactant and inorganic salts were removed, and further filtered to remove aggregated particles and insoluble matter to obtain base particles. .

The obtained base particles were vacuum dried to obtain resin fine particles, and then 10 parts by weight were redispersed in 90 parts by weight of methyl ethyl ketone to prepare a methyl ethyl ketone dispersion of resin fine particles.
5 parts by weight of one-end epoxy-modified silicone oil (“X-22-173DX” manufactured by Shin-Etsu Chemical Co., Ltd.) as a surface treatment agent was added to 95 parts by weight of the obtained dispersion of base particles, and the mixture was stirred at 60 ° C. while stirring. Time reaction was performed. The obtained particles were washed by centrifugation and unreacted silicone oil was removed, followed by vacuum drying to obtain slipperiness-imparting fine particles in which the surface of the base material particles having an average particle diameter of 98 nm was coated with silicone.

An antireflection coating agent was prepared by the same method as in Example 1 except that the resulting base particle surface was coated with silicone-coated slipperiness-imparting fine particles. The thickness of the obtained antireflection film was 94 nm, and surface irregularities derived from the slipperiness-imparting fine particles were present on the surface of the antireflection film.

( Reference Example 1 )
(1) Preparation of slipperiness-imparting microparticles The total amount of a mixed solution obtained by mixing and stirring 90 parts by weight of Silaplane FM-7721 (manufactured by Chisso) as a reactive silicone component and 10 parts by weight of hexadecane as a non-polymerizable organic solvent, It is added to 390 parts by weight of ion-exchanged water containing 2 parts by weight of sodium dodecylbenzenesulfonate as a water-soluble emulsifier, 6 parts by weight of cetyl alcohol and 2 parts by weight of ammonium persulfate as an initiator, and forcibly emulsified with an ultrasonic homogenizer for 60 minutes. Thus, a dispersion liquid in which polymerizable droplets having an average particle diameter of 120 nm were dispersed was prepared.
Using a 20 L polymerization vessel equipped with a stirrer, jacket, reflux condenser and thermometer, the inside of the vessel was depressurized and deoxygenated in the vessel, and then purged with nitrogen to make the inside a nitrogen atmosphere. The dispersion was charged, and the polymerization vessel was heated to 80 ° C. to initiate polymerization. Polymerization was performed for 4 hours, and after a aging period of 1 hour, the polymerization vessel was cooled to room temperature. The resulting slurry was dialyzed using a cellulose membrane having a molecular weight cut off of 10,000 to remove excess surfactant and inorganic salts, and further filtered to remove aggregated particles and insoluble matter, thereby obtaining silicone resin fine particles. .
The obtained silicone resin fine particles were vacuum-dried to obtain slipperiness-imparting fine particles having an average particle diameter of 132 nm.

(2) Preparation of anti-reflection coating agent and preparation of anti-reflection film Dipentaerythritol hexaacrylate was used as 100 parts by volume of the polymerizable compound, and 20 parts by volume of slipperiness-imparting fine particles thus obtained and averaged as low refractive particles. Antireflective coating agent by adding particle size 60 nm, refractive index 1.30 hollow silica fine particle 80 volume part, methyl ethyl ketone 800 volume part as diluent solvent, and Irgacure 814 (trade name: manufactured by Ciba Specialty Chemicals) as initiator. Was prepared.
The obtained anti-reflection coating agent was applied onto a triacetyl cellulose film using a bar coater so that the reflectance of the polymerized cured product had a minimum value of 550 nm, and then a 120 W high-pressure mercury lamp was irradiated with ultraviolet rays from a distance of 20 cm. Was irradiated for 180 seconds to obtain an antireflection film. The thickness of the antireflection film was 98 nm, and surface irregularities derived from the slipperiness-imparting fine particles were present on the surface of the antireflection film.

(Comparative Example 1)
The same as in Example 1, except that no slipperiness-imparting particles were added, and 100 parts by weight of low-refractive particles having an average particle diameter of 60 nm and a refractive index of 1.30 hollow silica particles were used with respect to 100 parts by weight of the polymerizable compound. An antireflection coating agent was prepared by the above method to obtain an antireflection film. The thickness of the film was 103 nm, and surface irregularities derived from the hollow silica fine particles were not formed on the surface of the antireflection film.

(Evaluation)
Examples 1-2, fine particles imparted with slipperiness obtained in Reference Example 1 , hollow silica used in Comparative Example 1, and anti-reflective coating obtained in Examples 1-2, Reference Example 1 and Comparative Example 1 The agent and the antireflection film were evaluated by the following methods. The results are shown in Table 1.

(1) Measurement of reflectance of antireflection film The surface of the antireflection film prepared in Examples 1 and 2, Reference Example 1 and Comparative Example 1 was roughened with # 400 sandpaper, and then a matte black paint was applied. Then, using a spectrophotometer (manufactured by Shimadzu Corporation, “UV-3101PC”), the reflectance spectrum of one side at a light wavelength of 380 to 780 nm at an incident angle of light of 5 ° was measured. The reflectance value of the obtained reflectance spectrum at a light wavelength of 550 nm was used as the reflectance of the antireflection film.

(2) Measurement of refractive index of antireflection film One side reflectance spectrum of light wavelength of 380 to 780 nm obtained by measuring the reflectance of the antireflection film is obtained by optical property calculation software (manufactured by JA Woollam Japan). The refractive index of the antireflection film was calculated using “WVASE32”).

(3) Measurement of transmittance and haze of antireflection film The total light transmittance and haze of the antireflection film were measured using a haze meter (“TC-H3PDK” manufactured by Tokyo Denshoku Co., Ltd.).

(4) Scratch resistance of the antireflection film The surface of the antireflection film was rubbed 20 times with steel wool “Nihon Steel Wool Co., Ltd. (Bonster # 0000 :)” at 250 g / cm ² and the presence or absence of scratches was visually observed. The determination was made according to the following criteria.
○: No scratch △: Slightly scratched ×: Scratched

(5) Measurement of friction coefficient of anti-reflection film Using an automatic friction / wear analyzer (DFPM-SS type: manufactured by Kyowa Interface Science Co., Ltd.), point contact using sapphire according to JIS K 7125, load 200 g, speed The static friction coefficient and the dynamic friction coefficient of each antireflection film under the conditions of 1.7 mm / s and a stroke of 50.0 mm were measured.

(6) Contact angle measurement of antireflection film Using a contact angle meter (CA-X type: manufactured by Kyowa Interface Science Co., Ltd.), a droplet of 1.8 μL at 20 ° C. and 65% RH was formed and contacted with the sample surface. The contact angle when measured was measured. As the measurement liquid, ultrapure water “Milli-Q Gradient manufactured by Nihon Millipore” was used.

(7) Measurement of falling angle of antireflection film Using a falling angle meter (CA-X type: manufactured by Kyowa Interface Science Co., Ltd.), a droplet of 63 μL at 20 ° C. and 65% RH was formed on the needle tip, Droplets were made by contacting the sample surface. The sample was then tilted and the angle at which the droplet began to slide was measured. As the measurement liquid, ultrapure water “Milli-Q Gradient manufactured by Nihon Millipore” was used.

(8) Measurement of average particle diameter of fine particles and CV value of particle diameter Using a dynamic light scattering particle size distribution meter (manufactured by Particle Sizing Systems, "Nicomp model 380ZLS-S") in each example and comparative example The volume average particle diameter and the CV value of the particle diameter of the obtained fine particles were measured.

(9) Measurement of refractive index and hollowness of fine particles In the same manner as the method for measuring the refractive index value of an antireflection film, the refractive index of only a polymerizable compound that does not use fine particles is measured, and polymerization added to the antireflection film The refractive index of each fine particle was calculated from the volume addition ratio of the functional compound and the fine particles.
Further, the hollowness of the fine particles was calculated using the calculated refractive index value of the fine particles and the refractive index value of the fine particles calculated from the composition excluding the hollow portion. The hollowness calculated in this manner showed good agreement with the particle hollowness calculated from the particle diameter of the fine particles and the film thickness observed with an electron microscope (manufactured by JEOL Ltd., “JEM-1200EXII”).

ADVANTAGE OF THE INVENTION According to this invention, the coating agent for antireflection which can obtain the antireflection film excellent in abrasion resistance, and an antireflection film can be provided.

Claims (6)

An antireflective coating agent comprising an average particle size of 50 to 200 nm , a refractive index of 1.40 or less , and at least a surface comprising fine particles composed of a polyorganosiloxane compound, and a binder component, wherein the fine particles are An antireflection coating agent having a hollow structure and a single-hole structure. Further, the average particle diameter is not more 100nm or less, and, for preventing coatings reflection of claim 1 Symbol placement refractive index is characterized in that it contains 1.35 microparticles. An antireflective film comprising the antireflective coating agent according to claim 1 or 2 . 4. The antireflection film according to claim 3, wherein the surface has irregularities made of a polyorganosiloxane compound derived from fine particles. 5. The antireflection film according to claim 3, wherein the dynamic friction coefficient and the static friction coefficient are 0.3 or less. 6. The antireflection film according to claim 3 , wherein the contact angle of water is 100 ° or more.