CN100543070C - Hollow resin microparticles, organic-inorganic hybrid microparticles, and method for producing hollow resin microparticles - Google Patents

Abstract

The objective of the invention is to, the manufacture method of a kind of hollow resin particulate, organic-inorganic hybrid fine particles and hollow resin particulate is provided, with described particulate during, can obtain dispersed good, the diffuse-reflectance, the high anti-reflection layer of while alkali resistance that prevent light to the binding agent composition as the particulate of the anti-reflection layer that constitutes low-refraction.The present invention is the hollow resin particulate with single hole structure, is that median size is that 10～100nm and specific refractory power are 1.40 or less than 1.40 hollow resin particulate.

Description

Hollow resin microparticles, organic-inorganic hybrid microparticles, and method for producing hollow resin microparticles

technical field

The present invention relates to a method for producing hollow resin particles, organic-inorganic hybrid particles, and hollow resin particles. When the hollow resin particles are used as particles constituting a low-refractive index antireflection layer, the dispersion of the binder component It has excellent properties, can prevent diffuse reflection of light, and can obtain an anti-reflection layer with high alkali resistance.

Background technique

Liquid crystal displays used in personal computers, word processors, mobile phones, etc., and various other commercial displays are used in a very wide range of fields. These displays use transparent substrates such as glass or plastic, through which objects and visual information such as text and graphics are recognized.

Practical problems of these displays include, for example, degradation of visibility due to reflection on the display surface. That is to say, no matter indoors or outdoors, when using in an environment where external light and the like are incident, since incident light such as external light is reflected on the surface of the transparent substrate, it is difficult to see internal visual information.

As a method of preventing such reflection of a transparent substrate, there is, for example, a method of forming an uneven coating on the surface of the transparent substrate, and diffusely reflecting external light by utilizing the unevenness on the surface.

For example, Patent Document 1 discloses an antireflection film in which a silica dispersion is mixed with a silicate-based coating agent prepared by a sol-gel method, and the mixed solution is coated on a glass substrate. When fired, the surface has irregularities caused by silica particles or aggregates of silica particles. In addition, Patent Document 2 discloses an antireflection film in which an intermediate layer mainly composed of a resin is formed on a transparent base film, and an organic ultrafine particle having a refractive index of 1.45 or less is coated on the intermediate layer. The outermost layer of the irregularities exposed on the surface of the organic ultrafine particles formed by applying the liquid.

However, in the method of forming irregularities on the surface to diffusely reflect external light, although visual glare is reduced, the amount of reflected light as a whole does not decrease, and there is a problem that the entire body becomes white. In addition, there is also a problem that stains such as fingerprints, sebum, sweat, and cosmetics tend to adhere to the unevenness of the surface, and the once-adhered stains are difficult to remove due to the presence of fine unevenness.

In contrast, there are literatures that propose a method of forming an antireflection layer with a low refractive index on the surface of a transparent substrate. By forming an anti-reflection layer with a low refractive index on the surface of the transparent substrate, it is possible to prevent the reflection of the transparent substrate without problems such as diffuse reflection of light and stains.

Such a low-refractive index antireflection layer uses a material made of silicon or fluorine-based materials, but since these have poor adhesion to common transparent substrates, attempts have been made to use antireflection films that use, for example, nano A coating agent made by dispersing low-refractive index particles such as high-grade silicon dioxide particles forms a coated anti-reflection film on a transparent substrate. For example, Patent Document 3 discloses a low-refractive-index coating agent and an antireflection film using the low-refractive-index coating agent. The low-refractive-index coating agent uses an organic silicon compound polymer with a certain structure as an adhesive. The binder is made of hollow silica particles.

However, since the silica fine particles have poor resistance to alkaline solutions, if a commercially available alkaline detergent is used for wiping off stains, there is a problem that the performance of the coating containing the silica fine particles decreases.

In addition, when an inorganic organosilicon compound polymer or the like is used as a binder component of a low-refractive index coating agent, the resulting coating is brittle and lacks mechanical strength. On the other hand, by using an organic binder such as a transparent resin as a binder component of a low-refractive index coating agent, a coating with excellent film-forming properties and excellent mechanical strength can be obtained. The dispersibility in inorganic binder components such as organosilicon compounds is good, but its dispersibility in organic binder components such as transparent resins is poor. As long as silica particles are used, due to the dispersibility of the resin Therefore, there is also a problem that it is difficult to use a transparent resin excellent in film-forming property and excellent in mechanical strength as a binder.

In response to this problem, the use of hollow resin particles having a porosity of at least a certain level as low-refractive-index particles is still being studied. Since hollow resin particles have excellent alkali resistance and relative binder dispersibility, as long as such hollow resin particles are used, reflection of transparent substrates can be effectively suppressed, and resistance to stains and washing and mechanical strength are expected to be obtained. Excellent anti-reflection film.

The manufacturing method of such hollow resin microparticles includes, for example, the methods disclosed in Patent Document 4 and Patent Document 5, which utilize emulsion polymerization to form a core-shell polymer, and then process it with alkali or alkali and acid to produce a polymer with pores inside. In addition, Patent Document 6 and Patent Document 7 disclose a method for producing hollow resin particles utilizing radical polymerization; in addition, Patent Document 8 discloses a method for producing hollow resin particles utilizing seed polymerization; in addition, Patent Document 9. Patent Document 10 and Patent Document 11 disclose methods for producing microcapsules with shells obtained by surface reactions.

But, in order to make hollow resin microparticles fully reach low refractive index, must realize high porosity, the particle that obtains with these methods at this moment is particle diameter all is the particle of micron order, can't also obtain the particle diameter that can have nanometer order, can obtain. Hollow resin particles with sufficiently low refractive index and high porosity are obtained.

[Patent Document 1] JP-A-9-101518

[Patent Document 2] JP-A-7-092305

[Patent Document 3] JP-A-2002-317152

[Patent Document 4] Japanese Unexamined Patent Publication No. 1-185311

[Patent Document 5] JP-A-6-248012

[Patent Document 6] JP-A-2-255704

[Patent Document 7] Japanese Patent Publication No. 5-040770

[Patent Document 8] JP-A-8-20604

[Patent Document 9] JP-A-8-48075

[Patent Document 10] JP-A-8-131816

[Patent Document 11] JP-A-10-24233

Contents of the invention

In view of the above situation, the present inventors aim to provide a method for producing hollow resin particles, organic-inorganic hybrid particles, and hollow resin particles. An antireflection layer having excellent dispersibility to the binder component, preventing diffuse reflection of light, and high alkali resistance can be obtained.

The present invention is a hollow resin microparticle with a single hole structure, which is a hollow resin microparticle with an average particle diameter of 10-100 nm and a refractive index of 1.40 or less than 1.40.

Next, the present invention will be described in detail.

The hollow resin microparticles of the present invention are hollow and have a single-pore structure.

The term "monoporous structure" in this specification does not include a case where a porous structure has a plurality of voids, and means having only one void. By forming a single-hole structure, the airtightness of the inside of the void is excellent. For example, when the hollow resin particle of the present invention is used as an antireflection film, it is possible to prevent the loss of the void ratio due to the penetration of the binder or other components into the particle. reduce.

Gas is present inside the void. Such gas is preferably air, but other gases are also possible. Since the refractive index of the air phase is approximately 1.00, a very low refractive index can be realized by making it hollow.

The hollow resin fine particles of the present invention have an average particle diameter with a lower limit of 10 nm and an upper limit of 100 nm. When it is less than 10 nm, aggregation of hollow resin fine particles occurs, and handleability is poor. When it exceeds 100nm, when the hollow resin particles of the present invention are used as, for example, an antireflection film, unevenness caused by the hollow resin particles occurs on the surface of the antireflection film, resulting in poor smoothness, or due to Rayleigh scattering on the surface of the hollow resin particles , so that the transparency of the anti-reflection film is reduced and the image is whitened. A preferable upper limit is 70 nm, and a more preferable upper limit is 50 nm.

The upper limit of the refractive index of the hollow resin particles of the present invention is 1.40. When it exceeds 1.40, when the hollow resin particles of the present invention are used as, for example, an antireflection film, the effect of preventing reflection of incident light such as external light cannot be sufficiently obtained, and the thickness of the antireflection film required for preventing reflection becomes thicker than necessary. A preferable upper limit is 1.35, and a more preferable upper limit is 1.30.

The lower limit of the porosity of the hollow resin fine particles of the present invention is preferably 30%. When it is less than 30%, a sufficiently low refractive index may not be realized. The upper limit of the porosity is not particularly limited, but the upper limit is preferably 95%, more preferably 70%, from the viewpoint of maintaining the shape and ensuring a certain degree of strength.

The preferable upper limit of the CV of the particle size of the hollow resin fine particles of the present invention is 20%. When it exceeds 20%, the ratio of coarse particles of 100 nm or more increases, and when the hollow resin particles of the present invention are used as, for example, an antireflection film, the transparency and smoothness may be poor, and the more preferable upper limit is 15%.

Such hollow resin microparticles of the present invention can be produced appropriately by a method for producing hollow resin microparticles using the lipophilic reactive component A and the hydrophilic reactive component B described later. The hollow resin fine particles of the present invention produced by such a method have at least an outermost layer composed of a resin obtained by reacting the lipophilic reactive component A and the hydrophilic reactive component B.

The above-mentioned lipophilic reactive component A is not particularly limited, and examples include: polyisocyanate, epoxy prepolymer, acid halide, and the like.

The above-mentioned polyisocyanate has lipophilicity, and reacts with hydrophilic reactive components such as water, amine, polyhydric alcohol, and polycarboxylic acid to obtain a resin. The above-mentioned polyisocyanate is not particularly limited, and includes, for example, a buret type, an adduct type, and an isocyanurate type.

In addition, the said polyisocyanate, a polyol, and a polycarboxylic acid refer to the compound which has a plurality of said functional groups in 1 molecule.

The above-mentioned epoxy prepolymer has lipophilicity, and it reacts with amine or polycarboxylic acid, acid anhydride, polythiol and phenolic resin to obtain resin.

The above-mentioned epoxy prepolymer is not particularly limited, for example, there are: bisphenol A type, resorcinol type, bisphenol F type, tetraphenylmethane type, novolac type, polyol type, polyethylene glycol type, glycerin Triether type, glycidyl ether type, glycidyl ester type, glycidyl amine type, aliphatic type, alicyclic type, aminophenol type, caprolactone type, trimeric isocyanate type, bisphenol type, Naphthalene type, or these hydrogenated products, fluorides, etc. Among them, fluorides are preferable. By using a fluoride as the above-mentioned epoxy prepolymer, the refractive index of the hollow resin microparticles of the present invention can be effectively lowered, and the penetration of a polar medium or the like described later into the voids can be suppressed.

The epoxy equivalent of such an epoxy prepolymer is not particularly limited, but the upper limit is preferably 500. By using the epoxy prepolymer whose epoxy equivalent has an upper limit of 500, it is possible to obtain a resin excellent in heat resistance, solvent resistance, and strength with a high degree of crosslinking. A more preferable upper limit is 200.

The upper limit of epoxy equivalent is the epoxy prepolymer of 200, is not particularly limited, for example has: エポト-トYD115, エポト-トYD127, エポト-トYD128 (trade names, all are manufactured by Dongdu Chemical Industry Co., Ltd.), エピコ- Bisphenol A type epoxy resins such as ト825, エピコ-ト827, エピコ-ト828 (trade name, all are made by Japan エポロシレジン company), EPICLON840, EPICLON850 (trade name, all are made by Dainippon Ink Chemical Co., Ltd.); Epot-to YDF-170, Epot-to YDF175S (trade names, both manufactured by Tohto Kasei Co., Ltd.), Epico-to 806, Epico-to807 (trade names, all manufactured by Japan Epoch Resin Corporation), EPICLON830, EPICLON835 ( The trade names are bisphenol F-type epoxy resins such as Dainippon Ink Chemical Co., Ltd.; —トYDCN-704, エポト-トYDCN-500 (trade name, both manufactured by Tohto Kasei Co., Ltd.), Epiko-ト152, Epiko-ト154 (trade name, both manufactured by Japan Epoki Siresin Corporation), EPICLON N- 655, EPICLON N-740, EPICLON N-770, EPICLON N-775, EPICLON N-865 (trade names, all manufactured by Dainippon Ink Co., Ltd.);トYH434-L (trade name, all manufactured by Tohto Kasei Co., Ltd.), Epico-to 1031S, Epico-to 1032H60, Epico-to604, Epico-to630 (trade name, all manufactured by Japan-Epokisilesin Co., Ltd.), EPICLON 430 (trade name, both manufactured by Dainippon Ink Chemical Co., Ltd.), TETRAD-X, TETRAD-C (trade name, both manufactured by Mitsubishi Gas Chemical Co., Ltd.); Epico-to YL6640, Epico-to YL6677 (trade name, all are made by Japan Epokishiresin Corporation) and other biphenyl type epoxy resins; Aliphatic polyglycidyl ether type epoxy resins such as エポト-トYH-324, エポト-トYH-325 (trade names, all of which are manufactured by Dongdu Chemical Co., Ltd.); (trade names, both manufactured by Tohto Kasei Co., Ltd.); naphthalene-type epoxy resins such as EPICLON HP-4032, EPICLON EXA-4700 (trade names, both manufactured by Dainippon Ink Chemical Co., Ltd.); エピコ—ト191P, エピコ—ト YX310 (commodity Epoxy Resin Co., Ltd.), EPICLON HP-820 (trade name, Dainippon Ink Chemicals Co., Ltd.) and other special functional epoxy resins; EPICLON 725 (trade name, Dainippon Ink Chemicals Co., Ltd.) and other reactive epoxy resins Thinners, etc., or fluorides of these, etc. Among them, fluorides are preferable. By using fluoride, the refractive index of the hollow resin microparticles of the present invention can be effectively lowered, and the penetration of a polar medium or the like described later into the voids can be suppressed.

In addition, epoxy prepolymers with an epoxy equivalent of more than 200 and less than 500 are not particularly limited, for example: Epot-to YD134, Epot-to YD011 (trade names, all manufactured by Tohto Chemical Co., Ltd.), Epico-to 801 , Epico-to 1001 (trade name, both are made by Japan Epoki Shiresin Corporation), EPICLON 860, EPICLON 1050, EPICLON 1055 (trade name, all are made by Dainippon Ink Chemical Co., Ltd.) and other bisphenol A epoxy resins; Bisphenol F-type epoxy resin such as トYDF-2001 (trade name, manufactured by Tohto Kasei Co., Ltd.); EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N -695 (trade name, both manufactured by Dainippon Ink Chemical Co., Ltd.); Epico-to 157S70 (trade name, manufactured by Japan Ink Chemical Co., Ltd.), EPICLON 5500 (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.) and other special multi-functional types; エポト—トYDB-360, エポト—トYDB-400, エポト—トYDB-405 (trade name, all are manufactured by Dongdu Chemical Co.), EPICLON 152, EPICLON 153 (trade name, all are Brominated epoxy resins such as Dainippon Ink Chemical Co., Ltd.); Epico-to YD-171 (trade name, manufactured by Tohto Chemical Co., Ltd.), Epico-to 871 (trade name, manufactured by Japan Electronics Chemical Co., Ltd.), EPICLONT SR-960, Flexible epoxy resins such as EPICLON TSR-601 (trade name, both manufactured by Dainippon Ink Chemicals Co., Ltd.); エポト-トST-3000 (trade name, manufactured by Tohto Chemical Co.), エピコ-トYX8000, エピコ-トYX8034 Hydrogenated epoxy resins such as (trade name, both are manufactured by Japan Epoch Resin Co., Ltd.); dicyclopentadiene type epoxy resins such as EPICLON HP-7200 (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.), or these Fluoride etc. Among them, fluorides are preferable. By using fluoride, the refractive index of the hollow resin microparticles of the present invention can be effectively lowered, and the penetration of a polar medium or the like described later into the voids can be suppressed.

These epoxy prepolymers may be used alone or in combination of two or more.

It should be noted that epoxy equivalents exceeding 500 epoxy prepolymers, for example, include: エポト-トYD-012, エポト-トYD-013, エポト-トYD-014, エポト-トYD-017, エポト-トYD-019 (trade name, all manufactured by Tohto Kasei), Epiko-to1002, Epiko-to1003, Epiko-to1055, Epiko-to1004, Epiko-to1007, Epiko-to1009, Epiko-to 1010 (trade name, all made by Japan Epokishi Resin Corporation), EPICLON 3050, EPICLON 4050, EPICLON AM-020-P, EPICLON AM-030-P, EPICLON AM-040-P, EPICLON 7050, EPICLONHM-091, EPICLONHM- 101 (trade name, all are produced by Dainippon Ink Chemical Co., Ltd.); Epoto-to YDF-2004 (trade name, produced by Tohto Chemical Co., Ltd.), Epico-to 4004P, Epico-to 4007P, Epico-to 4010P, Epico-to 4110, Epico-to 4210 (trade name, all are made by Japan Epoki Siresin Co., Ltd.); ), EPICLON1123P-75M (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.); Flexible epoxy resins such as Resin Corporation), EPICLON 1600-75X (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.); hydrogenated epoxy resins such as Epot-toST-4000D (trade name, manufactured by Tohto Kasei Co., Ltd.) ; EPICLON 5800 (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.), etc., or polyfunctional epoxy resins, etc., or fluorides thereof, etc. Among them, fluorides are preferable. By using fluoride, the refractive index of the hollow resin microparticles of the present invention can be effectively lowered, and the penetration of a polar medium or the like described later into the voids can be suppressed.

The above-mentioned acid halides are not particularly limited, for example, dichloride adipyl dichloride, (phthaloyl dichloride) phthaloyl dichloride, dichloride terephthaloyl dichloride, 1,4-cyclohexanedicarbonyl chloride, etc. acid halide.

By using the above-mentioned substance as the above-mentioned lipophilic reactive component A, the hollow resin microparticles of the present invention are excellent in heat resistance, solvent resistance, strength, and the like.

The above-mentioned hydrophilic reactive component B is not particularly limited, and it is appropriately determined in combination with the above-mentioned lipophilic reactive component A so as to react with the above-mentioned lipophilic reactive component A to form a resin.

Specifically, for example, when polyisocyanate is used as the lipophilic reactive component A, at least one selected from the group consisting of water, amines, polyols, and polycarboxylic acids is preferably used for the hydrophilic reactive component B.

In this case, polyisocyanate reacts with water and/or amine to form polyurea, polyisocyanate and polyol reacts to form polyurethane, and polyisocyanate and polycarboxylic acid reacts to form polyamide.

In addition, for example, when an epoxy prepolymer is used as the lipophilic reaction component A, an amine and/or polyvalent carboxylic acid is suitably used for the hydrophilic reaction component B.

At this time, the epoxy prepolymer reacts with amine, polycarboxylic acid, polythiol and/or phenolic resin to form an epoxy polymer.

In addition, for example, when an acid halide is used as the above-mentioned lipophilic reaction component A, an amine or a polyhydric alcohol is preferably used for the above-mentioned hydrophilic reaction component B.

At this time, acid halides react with amines and polyols to produce nylon and polyester.

The above-mentioned amines are not particularly limited, for example, ethylenediamine and its adducts, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, Dibutylaminopropylamine, 1,6-hexanediamine and its modified products, N-aminoethylpiperazine, di-aminopropylpiperazine, trimethylhexamethylenediamine, di-hexamethylene Triamine, dicyanodiamide, diacetylacrylamide, various modified aliphatic polyamines, polypropylene oxide diamine and other aliphatic amines; 3,3'-dimethyl 4,4'-di Aminodicyclohexylmethane, 3-amino-1-cyclohexylaminopropane, 4,4'-diaminodicyclohexylmethane, isophoronediamine, 1,3-di(aminomethyl)cyclohexane, Alicyclic amines such as N-dimethylcyclohexylamine and their modified products; 4,4'-diaminodiphenylmethane (methylenediphenylamine), 4,4'-diaminodiphenyl ether, diamino Diphenylsulfone, m-phenylenediamine, 2,4'-toluenediamine, m-toluenediamine, o-toluenediamine, m-xylylenediamine, xylylenediamine and other aromatic amines and their modification Other special amine modified products, amino amides, amino polyamide resins and other polyamino amides, dimethylamine methylphenol, 2,4,6-tris(dimethylaminomethyl)phenol, tris(dimethylaminomethyl)phenol Tertiary amines such as tri-2-ethylhexane salt of amine methyl) phenol and their complexes, ketimine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecapitate Alkylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-ethylimidazole, 2-isopropyl Imidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-isopropylimidazole, 1-cyanoethyl-2- Phenyl imidazole, 1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-2-undecyl imidazole trimellitate, 1-cyanoethyl-2-phenyl Imidazole trimellitate, 2,4-diamino-6-[2'-methylimidazole-(1)']-ethyl-s-triazine, 2,4-diamino-6-[2' -Undecylimidazole-(1)']-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazole-(1)']- Ethyl-s-triazine, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1,3-dibenzyl-2-methylimidazolium chloride, 2-phenyl -4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dimethylolimidazole, 1-cyanoethyl-2-phenyl-4,5-bis(cyanoethoxymethyl base) imidazole, 2-methylimidazole and triazine complex, 2-phenylimidazole and triazine complex and other imidazoles; isophthalic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide Amino-containing prepolymers such as hydrazides, amino adducts of epoxy resins, etc.

The above-mentioned polyhydric alcohol is not particularly limited, for example, ethylene glycol, 1,4-butanediol, 2,3-butanediol, catechol, resorcinol, hydroquinone, o-dimethylolbenzene, 4,4'-dihydroxydiphenylmethane, 2,2-bis(4-hydroxyphenyl)-propane, 1,1,1-trimethylolpropane, polyvinyl alcohol, polyhydroxymethacrylate, poly Hydroxyl-containing polymers such as ethylene glycol, polyhydroxypropylene glycol, and polyhydroxyalkylene glycol, and the like.

The above-mentioned polycarboxylic acid is not particularly limited, for example, oxalic acid, adipic acid, azelaic acid, sebacic acid, malonic acid, succinic acid, 1,4-cyclohexyldicarboxylic acid, ( Polymer copolymers of o-, m-, p-) benzenedicarboxylic acid, maleic acid, itaconic acid, acrylic acid, methyl methacrylate, etc., etc.

By using the above-mentioned substance as the above-mentioned hydrophilic reaction component B, the hollow resin microparticles of the present invention are excellent in heat resistance, solvent resistance, strength, and the like.

The outermost layer of the hollow resin particle of the present invention preferably contains a compound selected from polyurea, polyurethane, polyamide, polyester, nylon, and epoxy polymer according to the combination of the above-mentioned lipophilic reaction component A and the above-mentioned hydrophilic reaction component B. Consists of at least one resin in the set.

Furthermore, the hollow resin fine particles of the present invention preferably contain a resin cross-linked with an inorganic component. Such hollow resin particles of the present invention have an inorganic skeleton in their structure, are excellent in heat resistance and solvent resistance, and can effectively prevent the binder component from penetrating into the voids.

The resin cross-linked by such inorganic components can be obtained, for example, by making the functional groups of the resin contained in the hollow resin particles of the present invention and silanes having epoxy groups, isocyanate groups, urea groups, amino groups, mercapto groups, and halogen groups inside the structure. Coupler reaction to get.

The hollow resin microparticles of the present invention having such a single-pore structure can be suitably produced by a method comprising: adding the above-mentioned lipophilic reactive component A to a polar medium containing the above-mentioned hydrophilic reactive component A a step of dispersing the polymerizable liquid droplets to prepare a dispersion; and a step of reacting the above-mentioned lipophilic reactive component A and the above-mentioned hydrophilic reactive component B.

A method for producing such hollow resin particles is also one of the present invention.

The method for producing hollow resin microparticles of the present invention includes the step of dispersing polymerizable liquid droplets containing the aforementioned lipophilic reactive component A in a polar medium containing the aforementioned hydrophilic reactive component B to prepare a dispersion.

In the method for producing hollow resin microparticles of the present invention, a non-polymerizable compound may be added to the above-mentioned lipophilic reactive component A.

The above-mentioned non-polymerizable compound functions to form stable polymerizable droplets in a polar medium, or to control the reaction rate of the lipophilic reactive component A and the hydrophilic reactive component B. In addition, by adding a non-polymerizable compound to the above-mentioned lipophilic reaction component A, the resin microparticles prepared in the later step contain the above-mentioned non-polymerizable compound (and unreacted lipophilic reaction component A), and by Removing the above-mentioned non-polymerizable compound (and unreacted lipophilic reaction component A) from the above can produce hollow resin particles with high porosity.

The above-mentioned non-polymerizable compound, as long as it is liquid at the reaction temperature of the above-mentioned lipophilic reactive component A and hydrophilic reactive component B, can be mixed with the lipophilic reactive component A without reacting with the lipophilic reactive component A, and can be heated by heating etc. Substances that can easily evaporate are not particularly limited, for example: butane, pentane, hexane, cyclohexane, toluene, xylene, octane, nonane, decane, undecane, dodecane, Tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl Amyl ketone, diisobutyl ketone, methyl chloride, methylene chloride, chloroform, carbon tetrachloride and other organic solvents. The above non-polymerizable compounds may be used alone or in combination of two or more.

Among the above-mentioned non-polymerizable compounds, since octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, Nonadecane, eicosane and other high-level alkanes and long-chain hydrophobic compounds with carbon numbers of 8 to 20 can effectively inhibit the aggregation of polymeric droplets in polar media, so these non-polymerizable droplets should be used in combination when appropriate. Compounds and non-polymerizable compounds other than these can stably form nanoscale polymerizable droplets.

The blending amount of the non-polymerizable compound is not particularly limited, but the lower limit is preferably 10 parts by weight and the upper limit is 1000 parts by weight relative to 90 parts by weight of the above-mentioned lipophilic reactive component A. When it is less than 10 parts by weight, the porosity of the obtained hollow resin particles may become low, and a sufficiently low refractive index cannot be realized. When it exceeds 1000 parts by weight, the shape of the particles may not be maintained when the non-polymerizable compound is removed, resulting in The strength of the obtained hollow resin fine particles is extremely poor or less than the hollow resin fine particles.

The aforementioned polar medium is not particularly limited, and examples include water, ethanol, methanol, and isopropanol, which are generally used in suspension polymerization and the like. In addition, when the said lipophilic reaction component A is polyisocyanate, the water and/or ethanol itself used as a polar medium also functions as the hydrophilic reaction component B.

The preparation method of the above-mentioned dispersion liquid is not particularly limited, and conventionally known methods can be used, for example, a dispersion liquid of nano-sized polymerizable liquid droplets can be prepared appropriately using a high-shear emulsification device. Such a high-shear emulsification device includes, for example, an omnidirectional mixer, an ultrasonic homogenizer, an ultrafine particle dispersion device, and an emulsification device (microfluidizer).

When preparing the above-mentioned dispersion liquid, various additives can be added to the above-mentioned polar medium, such as: sodium lauryl sulfate, sodium higher alcohol sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, polyethylene oxide lauryl ether sulfate Sodium, sodium polyethylene oxide alkyl ether sulfate, triethanolamine polyethylene oxide alkyl ether sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, Anionic emulsifiers such as sodium alkyl diphenyl ether disulfonate, potassium polyethylene oxide alkyl ether phosphate, dipotassium alkenyl succinate, sodium alkane sulfonate; polyethylene oxide lauryl ether, polycyclic Oxyethylene cetyl ether, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether, polyethylene oxide myristyl ether, polyethylene oxide alkyl ether, Polyethylene oxide higher alcohol ether, polyethylene oxide alkylene alkyl ether, polyethylene oxide distyrenated phenyl ether, sorbitan monolaurate, sorbitan monopalmitic acid Esters, Sorbitan Monostearate, Sorbitan Tristearate, Sorbitan Monooleate, Sorbitan Trioleate, Polyethylene Oxide Sorbitan Mono Laurate, polyethylene oxide sorbitan laurate, polyethylene oxide sorbitan monopalmitate, polyethylene oxide sorbitan monostearate, polyethylene oxide Alkyl sorbitan tristearate, polyethylene oxide sorbitan monooleate, polyethylene oxide sorbitan trioleate, glyceryl monostearate, glyceryl monostearate Non-ionic emulsifiers such as acid esters and glycerol monooleate; lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride Cationic emulsifiers such as ammonium chloride, distearoyl dimethyl ammonium chloride, alkyl benzyl methyl ammonium chloride; lauryl betaine, stearyl betaine, 2-alkyl-N-carboxylate Amphoteric emulsifiers such as methyl-N-hydroxyethylimidazolium betaine, lauryl dimethylamine oxide; partially saponified polyvinyl acetate, cellulose derivatives, poly(meth)acrylic acid, poly(meth) Polymer dispersants such as acrylic copolymer, polyvinylpyrrolidone, polyacrylamide, mariarim, and polystyrenesulfonic acid, and dispersing aids such as cetyl alcohol.

The above-mentioned polymerizable liquid droplets refer to those formed by uniformly dissolving the above-mentioned lipophilic reaction component A. The method for producing the above-mentioned polymerizable droplets is not particularly limited. For example, there is a method of measuring and mixing the above-mentioned lipophilic reactive component A and other lipophilic components such as additives as needed, and then stirring until they are uniformly dissolved.

In order to stably form nano-sized polymeric droplets, when high-level paraffins with about 8 to 20 carbon atoms and long-chain hydrophobic compounds are used together with non-polymerizable compounds other than these, the relative lipophilic reaction component A and non-polymeric The preferable lower limit of the compounding ratio is 0.1 weight part with respect to 100 weight part of total amounts of a polymeric compound. When it is less than 0.1 parts by weight, the coalescence of polymerizable liquid droplets may not be effectively suppressed.

The method for producing hollow resin microparticles of the present invention has a step of reacting the above-mentioned lipophilic reaction component A and the above-mentioned hydrophilic reaction component B.

For example, by heating the dispersion to a reaction temperature between the lipophilic reactive component A and the hydrophilic reactive component B, the lipophilic reactive component A and the hydrophilic reactive component B react to form a resin. At this time, since the above-mentioned polymerizable liquid droplets containing the above-mentioned lipophilic reaction component A and the above-mentioned polar medium containing the above-mentioned hydrophilic reaction component B undergo phase separation, the reaction occurs only between the above-mentioned polymerizable liquid droplets and the above-mentioned polar medium. occurs near the interface, and the hollow resin microparticles of the present invention having a shell made of the resulting resin are produced.

In such a method for producing hollow resin particles of the present invention, the produced hollow resin particles may contain the unreacted lipophilic reactive component A described above. In this case, the method for producing hollow resin microparticles of the present invention preferably further includes a step of removing the contained unreacted lipophilic reactive component A described above.

The method of removing the above-mentioned unreacted above-mentioned lipophilic reactive component A from the hollow resin particles containing the above-mentioned unreacted above-mentioned lipophilic reactive component A is not particularly limited, for example, blowing into the dispersion liquid of the obtained hollow resin particles The method of nitrogen, air and other gases; the method of heating the above-mentioned hollow resin particles to the boiling point of the unreacted lipophilic reaction component A and the solvent used; the method of depressurizing the entire system; the unreacted lipophilic reaction component A The method of solvent extraction, etc.

The solvent used for the above solvent extraction is not particularly limited as long as it can be properly mixed with the lipophilic reaction component A. For example, the above-mentioned non-polymerizable compounds and the like can be suitably used.

According to the production method of the hollow resin microparticles of the present invention, the hollow resin microparticles of the present invention having a single-pore structure, an average particle diameter with a lower limit of 10 nm to 100 nm, and a refractive index of 1.40 or less can be suitably produced.

Among the composite housing hollow resin particles having a single-hole structure and at least two resin layers consisting of an outermost layer and an inner layer, hollow resin particles with a porosity of 30% or more are also one of the contents of the present invention. Hereinafter, the hollow resin microparticles are referred to as the hollow resin microparticles of the present invention according to the second embodiment.

The hollow resin microparticles of the present invention according to the second aspect have a single-hole structure and have a composite shell composed of at least two resin layers, the outermost layer and the inner layer.

By making the particle shell a composite shell composed of at least two resin layers, the outermost layer and the inner layer, the particle shell can have multiple functions, and hollow resin particles with high porosity and low refractive index can be effectively obtained. For example, the outermost layer is composed of a resin component that has a high refractive index but is excellent in heat resistance, solvent resistance, and strength, and a resin component that is composed of a resin component that is poor in heat resistance, solvent resistance, and strength but has a low refractive index. The hollow resin particles constituted by the inner layer can improve the heat resistance, etc., and can also increase the porosity and lower the refractive index of the hollow resin particles as a whole. In addition, by appropriately selecting the resin components constituting the outermost layer and the inner layer, the hollow resin particles can be arbitrarily given refractive index, polarity, crystallinity, heat resistance, solvent resistance, strength, weather resistance, and transparency. wait.

The hollow resin microparticles of the present invention according to the second aspect are hollow and have a single-hole structure.

By forming a single-hole structure, it becomes a substance with excellent airtightness inside the void. For example, when the hollow resin particle of the present invention according to the second embodiment is used as an antireflection film, it is possible to prevent the penetration of the binder and other components into the particle. resulting in a decrease in porosity.

In addition, gas exists inside the void. Such gas is preferably air, but other gases are also possible. Since the refractive index of the air phase is approximately 1.00, a very low refractive index can be realized by making it hollow.

The hollow resin fine particles of the present invention according to the second aspect have a lower limit of porosity of 30%. When it is less than 30%, a low refractive index cannot be sufficiently realized. The upper limit of the porosity is not particularly limited, but the upper limit is preferably 95%, and more preferably 70%, from the viewpoint of maintaining the shape and ensuring a certain degree of strength.

The hollow resin fine particles of the present invention according to the second aspect have a preferable lower limit of the average particle diameter of 10 nm, and a preferable upper limit of 100 nm. When it is less than 10 nm, aggregation of the hollow resin fine particles of the second embodiment of the present invention may occur, resulting in poor handleability. When it exceeds 100nm, when the hollow resin particles of the present invention in the second aspect are used as, for example, an antireflection film, the surface of the antireflection film may have irregularities due to the hollow resin particles, resulting in poor smoothness, or it may be caused by hollow resin particles. Rayleigh scattering on the surface of the particles reduces the transparency of the anti-reflection film and causes whitening of the image. A more preferable upper limit is 70 nm, and an even more preferable upper limit is 50 nm.

The hollow resin fine particles of the present invention according to the second aspect have a preferable upper limit of the refractive index of 1.40. When it exceeds 1.40, when the hollow resin particle of the present invention of the second aspect is used as, for example, an antireflection film, the effect of preventing reflection of incident light such as external light cannot be sufficiently obtained, and the thickness of the antireflection film required for preventing reflection becomes thicker than necessary. A more preferable upper limit is 1.35, and an even more preferable upper limit is 1.30.

The preferred upper limit of the CV of the particle diameter of the hollow resin fine particles of the present invention according to the second aspect is 20%. When it exceeds 20%, the ratio of coarse particles of 100 nm or more increases, and when the hollow resin fine particles of the present invention according to the second aspect are used as an antireflection film, for example, the transparency and smoothness may be poor. A more preferable upper limit is 15%.

The hollow resin microparticles of the present invention in such a second form can utilize the lipophilic reaction component A and the hydrophilic reaction component B described later, and the lipophilic reaction component A and the hydrophilic reaction component B. The method of lipophilic reactive component C is suitably produced. The second embodiment of the hollow resin microparticles of the present invention produced by such a method has an outermost layer made of a resin formed by reacting lipophilic reactive component A and hydrophilic reactive component B, and an inner layer made of a resin that reacts with the above-mentioned hydrophilic reactive component B. A resin composition formed by reacting the oily reactive component A and the lipophilic reactive component C that does not react with the above-mentioned hydrophilic reactive component B. The hollow resin microparticles of the second aspect of the present invention having such a structure can realize the above-mentioned average particle diameter, porosity, refractive index, etc. by adjusting the configuration of the outermost layer and the inner layer.

The above-mentioned lipophilic reaction component A and the above-mentioned hydrophilic reaction component B are not particularly selected, for example, the same as the above-mentioned lipophilic reaction component A and the above-mentioned hydrophilic reaction component B described in the hollow resin particle of the present invention. substance.

The outermost layer of the hollow resin microparticles of the present invention according to the second aspect preferably contains a compound selected from polyurea, polyurethane, polyamide, polyester, nylon, and At least one resin from the group consisting of epoxy polymers.

In addition, the outermost layer of the hollow resin fine particles of the present invention according to the second aspect preferably contains a resin cross-linked with an inorganic component. The hollow resin fine particles of the present invention in the second aspect have an inorganic skeleton in the outermost layer, are excellent in heat resistance and solvent resistance, and can effectively prevent the binder component from penetrating into the void.

Such a resin cross-linked with inorganic components can be obtained by, for example, having an epoxy group, an isocyanate group, a urea group, or an amino group in the unreacted functional group and structure of the resin contained in the hollow resin microparticles of the second embodiment of the present invention. , mercapto, halogen silane coupling agent reaction to get.

The above-mentioned lipophilic reactive component C is not particularly limited as long as it is a substance that does not react with the above-mentioned lipophilic reactive component A and hydrophilic reactive component B. In view of wide selection of reactive components and easy operation, it is suitable to use free radicals. polymerizable monomer.

The above radical polymerizable monomer is not particularly limited, for example: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth) Amyl acrylate, cyclohexyl (meth)acrylate, myristyl (meth)acrylate, palmitoyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, etc. Alkyl (meth)acrylate; (meth)acrylonitrile, (meth)acrylamide, (meth)acrylic acid, glycidyl (meth)acrylate, 2-hydroxyethyl methacrylate, methyl Acrylic acid-2-hydroxypropyl ester and other polar group-containing (meth)acrylic monomers; styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene and other aromatic vinyl monomers ; Vinyl esters such as vinyl acetate and vinyl propionate; Halogenated monomers such as vinyl chloride and vinylidene chloride; Vinyl pyridine, 2-acryloyl hydroxyethyl phthalate, itaconic acid, fumaric acid, Monofunctional monomers such as ethylene, propylene, and polydimethylsiloxane micromonomers; ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate ) 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)acrylate, dipentaerythritol hexa(meth)acrylate, diallyl phthalate , diallyl maleate, diallyl fumarate, diallyl succinate, triallyl isocyanurate, divinylbenzene, butadiene and other polyfunctional monomers .

These lipophilic reactive components C may be used alone or in combination of two or more.

In addition, in the hollow resin fine particles of the present invention according to the second aspect, a fluorine-containing monomer may be used for the above-mentioned lipophilic reactive component C. By using a fluorine-containing monomer, the refractive index of the hollow resin microparticles of the second aspect of the present invention can be effectively lowered, and the penetration of a polar medium or the like described later into the voids can be suppressed.

These fluorine-containing monomers are not particularly limited, for example: vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxol and other fluorinated chains Olefins; partially or fully fluorinated alkyl ester derivatives of (meth)acrylic acid represented by the following general formula (1), such as trifluoroethyl methacrylate and perfluorooctylethyl (meth)acrylate, Or partially or fully fluorinated vinyl ethers of (meth)acrylic acid, etc.

[chemical 1]

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

When using a radical polymerizable monomer as the above-mentioned lipophilic reaction component C, it is preferable to contain a radical polymerization initiator as a reaction catalyst.

The above-mentioned radical polymerization initiator is not particularly limited, for example, there are: di-tert-butyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, di-tert-butyl peroxycarbonate, di-tert-butyl peroxide Lauroyl, tert-butylperoxybenzoate (Benzone-to), tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisopropyl monocarbonate, tert-hexylperoxybenzene Formate, 1,1-bis(tert-butyl peroxy)-3,5,5-trimethylhexane, 1,1-bis(tert-butyl peroxy)-2-methylcyclohexane, Various ketone peroxides, peroxyketals, hydrogen peroxide, dialkyl peroxides, diacyl peroxides, etc. , peroxydicarbonate, peroxycarbonate, peroxyester and other organic peroxides; 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, Ltd.), Azo-based initiators such as VPS-1001 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.); redox initiators, and the like.

By using the above-mentioned substance as the above-mentioned lipophilic reaction component C, the hollow resin fine particles of the present invention according to the second aspect have a low refractive index.

The blending amount of the above-mentioned lipophilic reactive component C is not particularly limited, but the lower limit is preferably 1 part by weight and the upper limit is preferably 1000 parts by weight relative to 100 parts by weight of the above-mentioned lipophilic reactive component A. When it is less than 1 part by weight, sometimes the target airtightness, refractive index, polarity, crystallinity, etc. cannot be sufficiently imparted to the obtained hollow resin microparticles, and when it exceeds 1000 parts by weight, the particle shape cannot be maintained, Hollow resin fine particles could not be obtained or the strength of the obtained hollow resin fine particles was extremely poor.

In the hollow resin particle of the present invention according to a second aspect, the outermost layer and the inner layer are in an adhesive state. This can be confirmed with an electron microscope (manufactured by JEOL Ltd., "JEM-1200EXII") or the like.

The hollow resin microparticles of the present invention in such a second aspect can be suitably produced by a method comprising: in a polar medium containing the above-mentioned hydrophilic reactive component B, making the lipophilic reactive component A and the hydrophilic reactive component A The process of dispersing the polymerizable liquid droplets of the oily reactive component C and preparing a dispersion liquid; reacting the above-mentioned lipophilic reactive component A on the surface of the above-mentioned polymerizable liquid droplet with the above-mentioned hydrophilic reactive component B in the above-mentioned polar medium, and reacting in the above-mentioned polymerization a step of forming an outermost layer on the surface of the polymerizable droplet; and a step of reacting the lipophilic reactive component C inside the polymerizable droplet to form an inner layer. Such a method for producing the hollow resin microparticles of the present invention according to the second aspect is also one of the present inventions. Hereinafter, such a production method is referred to as a production method of the hollow resin microparticles of the present invention according to the second aspect.

The method for producing hollow resin microparticles according to the second aspect of the present invention comprises: dispersing polymerizable liquid droplets containing the above-mentioned lipophilic reactive component A and lipophilic reactive component C in a polar medium containing the aforementioned hydrophilic reactive component B , The process of preparing the dispersion.

The order of preparing the above-mentioned dispersion liquid is not particularly limited. After adding the above-mentioned hydrophilic reaction component B to the above-mentioned polar medium, the polymerizable droplets containing the above-mentioned lipophilic reaction component A and lipophilic reaction component C are dispersed; The above-mentioned hydrophilic reaction component B may be added after dispersing the polymerizable liquid droplets containing the above-mentioned lipophilic reaction component A and lipophilic reaction component C in the above-mentioned polar medium.

The above-mentioned polar medium is not particularly limited, and for example, water, ethanol, methanol, isopropanol, etc., which are generally used in the suspension polymerization method and the like can be used. In addition, when the said lipophilic reaction component A is polyisocyanate, the water and/or ethanol itself used as a polar medium also has the function of the hydrophilic reaction component B.

The preparation method of the above-mentioned dispersion liquid is not particularly limited, for example, a dispersion liquid of nano-sized polymerizable liquid droplets can be prepared appropriately using a high-shear emulsification device. Such high-shear emulsification devices include, for example, omnidirectional mixers, ultrasonic homogenizers, ultrafine particle dispersion, emulsification devices, and the like.

When preparing the above-mentioned dispersion liquid, various additives can be added to the above-mentioned polar medium, such as: sodium lauryl sulfate, sodium higher alcohol sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, polyethylene oxide lauryl ether sulfate Sodium, sodium polyethylene oxide alkyl ether sulfate, triethanolamine polyethylene oxide alkyl ether sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, Anionic emulsifiers such as sodium alkyl diphenyl ether disulfonate, potassium polyethylene oxide alkyl ether phosphate, dipotassium alkenyl succinate, sodium alkane sulfonate; polyethylene oxide lauryl ether, polycyclic Oxyethylene cetyl ether, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether, polyethylene oxide myristyl ether, polyethylene oxide alkyl ether, Polyethylene oxide higher alcohol ether, polyethylene oxide alkylene alkyl ether, polyethylene oxide distyrenated phenyl ether, sorbitan monolaurate, sorbitan monopalmitic acid Esters, Sorbitan Monostearate, Sorbitan Tristearate, Sorbitan Monooleate, Sorbitan Trioleate, Polyethylene Oxide Sorbitan Mono Laurate, polyethylene oxide sorbitan laurate, polyethylene oxide sorbitan monopalmitate, polyethylene oxide sorbitan monostearate, polyethylene oxide Alkyl sorbitan tristearate, polyethylene oxide sorbitan monooleate, polyethylene oxide sorbitan trioleate, glyceryl monostearate, glyceryl monostearate Non-ionic emulsifiers such as acid esters and glycerol monooleate; lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride Cationic emulsifiers such as ammonium chloride, distearoyl dimethyl ammonium chloride, alkyl benzyl methyl ammonium chloride; lauryl betaine, stearyl betaine, 2-alkyl-N-carboxylate Amphoteric emulsifiers such as methyl-N-hydroxyethylimidazolium betaine, lauryl dimethylamine oxide; partially saponified polyvinyl acetate, cellulose derivatives, poly(meth)acrylic acid, poly(meth) Polymer dispersants such as acrylic copolymer, polyvinylpyrrolidone, polyacrylamide, mariarim, polystyrene sulfonic acid, and dispersing aids such as cetyl alcohol.

The above-mentioned polymerizable liquid droplets refer to those obtained by uniformly dissolving the above-mentioned lipophilic reaction component A and lipophilic reaction component C. The method for producing the above-mentioned polymerizable droplets is not particularly limited. For example, the above-mentioned lipophilic reaction component A and lipophilic reaction component C and other lipophilic components such as the above-mentioned radical polymerization initiator added as needed are measured and mixed, and then stirred. until it dissolves evenly.

A non-polymerizable compound is preferably added to the above-mentioned polymerizable liquid droplets. The above-mentioned non-polymerizable compound functions to form stable polymerizable droplets in a polar medium, or to control the reaction rate of the lipophilic reactive component A and the hydrophilic reactive component B. In addition, by adding a non-polymerizable compound to the above-mentioned polymerizable liquid droplets, the above-mentioned non-polymerizable compound (and unreacted lipophilic reaction component A) is included in the resin particles prepared in the process described later, and by removing Non-polymerizable compounds (and unreacted lipophilic reaction component A) can produce hollow resin particles with high porosity.

As the above-mentioned non-polymerizable compound, as long as it is liquid at the reaction temperature of the above-mentioned lipophilic reactive component A and hydrophilic reactive component B, it can be mixed with the lipophilic reactive component A and the lipophilic reactive component C without mixing with the lipophilic reactive component A and lipophilic reaction component C react, and the material that can evaporate easily by heating etc. is just not particularly limited, for example have: butane, pentane, hexane, hexanaphthene, toluene, xylene, octane, Nonane, Decane, Undecane, Dodecane, Tridecane, Tetradecane, Pentadecane, Hexadecane, Heptadecane, Octadecane, Nonadecane, Eicosane, Ethyl Acetate, Organic solvents such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone, methyl chloride, methylene chloride, chloroform, carbon tetrachloride, etc.

The above non-polymerizable compounds may be used alone or in combination of two or more.

Among the above-mentioned non-polymerizable compounds, since octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, Nonadecane, eicosane and other high-level alkanes and long-chain hydrophobic compounds with carbon numbers of about 8 to 20 can effectively inhibit the aggregation of polymeric droplets in polar media, so these non-polymeric compounds should be used in combination With non-polymerizable compounds other than these, nanoscale polymerizable droplets can be stably formed.

The compounding quantity of the said non-polymerizable compound is not specifically limited, The preferable minimum is 10 weight part, and the preferable upper limit is 1000 weight part with respect to the said lipophilic reaction component A and the said lipophilic reaction component C90 weight part. When it is less than 10 parts by weight, the porosity of the obtained hollow resin particles may become low, and a sufficiently low refractive index cannot be realized. When it exceeds 1000 parts by weight, the shape of the particles may not be maintained when the non-polymerizable compound is removed, resulting in The strength of the obtained hollow resin fine particles is extremely poor or less than the hollow resin fine particles.

In order to stably form nano-scale polymeric droplets, when high-level alkanes with 8 to 20 carbon atoms and long-chain hydrophobic compounds are used together with non-polymerizable compounds other than these, the relative lipophilic reaction component A and hydrophilic The preferred lower limit of the compounding ratio is 0.1 part by weight per 100 parts by weight of the total amount of the oily reaction component C and the non-polymerizable compound. When it is less than 0.1 parts by weight, the coalescence of polymerizable liquid droplets may not be effectively suppressed.

The production method of the hollow resin microparticles of the second aspect of the present invention comprises: reacting the above-mentioned lipophilic reaction component A on the surface of the above-mentioned polymerizable liquid droplet with the above-mentioned hydrophilic reaction component B in the above-mentioned polar medium; The process of forming the outermost layer on the drop surface.

By heating the dispersion liquid to the reaction temperature of the lipophilic reactive component A and the hydrophilic reactive component B, the lipophilic reactive component A and the hydrophilic reactive component B can be reacted to form a resin.

At this time, since the above-mentioned polymerizable liquid droplets containing the above-mentioned lipophilic reaction component A and the above-mentioned polar medium containing the above-mentioned hydrophilic reaction component B undergo phase separation, the reaction occurs only between the above-mentioned polymerizable liquid droplets and the above-mentioned polar medium. Occurs in the vicinity of the interface, forming resin particles having an outermost layer composed of the resulting resin and containing lipophilic reactive component C.

The method for producing hollow resin microparticles according to the second aspect of the present invention has a step of reacting the lipophilic reactive component C inside the polymerizable liquid droplet to form an inner layer.

By heating the above-mentioned dispersion liquid to the reaction temperature of the above-mentioned lipophilic reactive component C, the above-mentioned lipophilic reactive component C can be reacted.

As mentioned above, the reaction of the above-mentioned lipophilic reaction component A and the above-mentioned hydrophilic reaction component B occurs only near the surface of the above-mentioned polymerizable liquid droplet and the above-mentioned polar medium to form the outermost layer, so the reaction of the above-mentioned lipophilic reaction component The resin produced by the reaction of C forms the inner layer, and hollow resin particles having a composite outer shell composed of two resin layers, the outermost layer and the inner layer, are manufactured.

It should be noted that the step of forming the inner layer may be performed at any stage before, during, or after the step of forming the outermost layer by controlling the reaction conditions using the reaction catalyst or the like.

In the method for producing hollow resin microparticles of the present invention in such a second aspect, unreacted lipophilic reactive component A and unreacted lipophilic reactive component C may be contained in the produced hollow resin microparticles. In this case, the method for producing hollow resin fine particles according to the second aspect of the present invention preferably further includes a step of removing the contained unreacted lipophilic reactive component A and unreacted lipophilic reactive component C.

The method of removing the unreacted lipophilic reaction component A and the unreacted lipophilic reaction component C contained in the above-mentioned resin particles is not particularly limited, for example, gas such as nitrogen or air is blown into the dispersion liquid of the obtained hollow resin particles. The method; the method of heating the hollow resin particles to the boiling point of the unreacted lipophilic reaction component A and the unreacted lipophilic reaction component C; the method of decompressing the entire system; the unreacted lipophilic reaction component A And the method of extracting unreacted lipophilic reaction component C with a solvent, etc.

The solvent used in the above extraction is not particularly limited as long as it is compatible with the lipophilic reaction component A and the lipophilic reaction component C, and the above-mentioned non-polymerizable compounds and the like are suitably used.

In addition, this process can also remove the solvent contained in the said resin microparticles|fine-particles.

According to the method for producing hollow resin microparticles of the present invention in the second aspect, it is possible to suitably manufacture the second aspect having a composite shell composed of at least two resin layers, the outermost layer and the inner layer, and having a porosity of 30% or more. The hollow resin microparticles of the present invention.

Organic-inorganic hybrid fine particles having an organic skeleton and an inorganic skeleton and having a refractive index of 1.40 or less (hereinafter also referred to as the hybrid fine particles of the present invention) are also one of the present invention.

Such mixed fine particles of the present invention are excellent in alkali resistance due to the network formed by the organic skeleton. Therefore, for example, using such an antireflection film made of the mixed particles of the present invention, even when using a commercially available alkaline detergent or the like when wiping off stains, the contained mixed particles of the present invention will not dissolve in alkaline. Detergents do not degrade performance as an anti-reflection film. In addition, the mixed fine particles of the present invention have excellent heat resistance and solvent resistance due to having an inorganic skeleton. Even with a hollow structure having voids inside as described later, shrinkage of the voids and infiltration of the binder component into the voids due to the softening of the fine particle skeleton by the solvent can be effectively prevented. Moreover, since the refractive index can be effectively reduced by having an air phase (refractive index=1.00) inside, for example, the antireflection film using a coating agent containing such low refractive index mixed particles can also be reduced. refractive index.

The upper limit of the refractive index of the mixed fine particles of the present invention is 1.40. When it exceeds 1.40, when the mixed fine particles of the present invention are used as an antireflection film, for example, the effect of preventing reflection of incident light such as external light cannot be sufficiently obtained, and the thickness of the antireflection film required to prevent reflection becomes more than necessary. A preferable upper limit is 1.35, and a more preferable upper limit is 1.30.

Such mixed fine particles of the present invention preferably have a hollow structure having voids inside. By having voids inside, the low refractive index of the hybrid fine particles of the present invention will be even lower.

When the mixed fine particles of the present invention have voids inside, the lower limit of the porosity is preferably 30%. When it is less than 30%, a low refractive index cannot be fully realized in some cases. The upper limit of the porosity is not particularly limited, but it is preferably 95%, and more preferably 70%, from the viewpoint of maintaining the shape and ensuring a certain degree of strength.

The method of synthesizing such hollow-structure mixed particles is not particularly limited, and may be synthesized using the following suitable polymerization method, for example: emulsion polymerization using a polymerizable silane coupling agent having a vinyl group inside the structure and a non-polymerizable organic solvent , drop-in emulsion polymerization, emulsifier-free emulsion polymerization, microemulsion polymerization, microemulsion polymerization, and microsuspension polymerization; Surface polymerization of silane coupling agents, etc. It can be synthesized using a suitable polymerization method.

The polymeric silane coupling agent having a vinyl group inside the above-mentioned structure is not particularly limited, for example: vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styrylmethoxysilane , 3-methacryloxypropyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methyl Acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, etc. These polymerizable silane coupling agents having a vinyl group inside their structure may be used alone or in combination with two or more optional polymerizable monomers.

The above-mentioned polymerizable monomers are not particularly limited, and monofunctional monomers include, for example: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, ( Amyl Methacrylate, Cyclohexyl (Meth)acrylate, Myristyl (Meth)acrylate, Palmitoyl (Meth)acrylate, Stearyl (Meth)acrylate, Iso(meth)acrylate Alkyl (meth)acrylate such as bornyl ester; (meth)acrylonitrile, (meth)acrylamide, (meth)acrylic acid, glycidyl (meth)acrylate, 2-hydroxyethyl methacrylate , 2-hydroxypropyl methacrylate and other polar group-containing (meth)acrylic monomers; styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene and other aromatic vinyl monomers; vinyl esters such as vinyl acetate and vinyl propionate; halogen-containing monomers such as vinyl chloride and vinylidene chloride; vinyl pyridine, 2-acryloyl hydroxyethyl phthalate, itaconic acid, Fumaric acid, ethylene, propylene, polydimethylsiloxane micromonomer, etc.

The polyfunctional monomer as the polymerizable monomer is not particularly limited, and examples thereof include di(meth)acrylate, tri(meth)acrylate, di- or triallyl compounds, and divinyl compounds. These may be used alone or in combination of two or more. It should be noted that the above-mentioned multifunctional monomer is added in order to increase the glass transition temperature (Tg) of the above-mentioned mixed fine particles and to improve their heat resistance and solvent resistance.

The above-mentioned di(meth)acrylate 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, trimethylolpropane di(meth)acrylate, and the like.

The above-mentioned tri(meth)acrylates are not particularly limited, for example, trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, Meth)acrylate, etc.

The above-mentioned di- or triallyl compounds are not particularly limited, for example: pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, diallyl phthalate, diallyl maleate , diallyl fumarate, diallyl succinate, triallyl isocyanurate, etc.

The aforementioned divinyl compound is not particularly limited, and examples include divinylbenzene, butadiene, and the like.

The above-mentioned non-polymerizable organic solvent is not particularly limited as long as it is mixed with a polymerizable silane coupling agent having a vinyl group inside the above-mentioned structure and is liquid at the polymerization temperature, for example: butane, pentane, hexane, etc. alkane, cyclohexane, heptane, decane, hexadecane, toluene, xylene, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, 1,4-dioxane, methyl chloride, di Organic solvents such as methyl chloride, chloroform, and carbon tetrachloride are suitable.

Silane coupling agents with epoxy groups inside the above structure are not particularly limited, for example: 2-(3,4 epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane , 3-Glycidoxypropylmethyldiethoxysilane, 3-Glycidoxypropyltriethoxysilane, etc.

The silane coupling agent having an isocyanate group inside the structure is not particularly limited, for example, 3-isocyanatopropyltriethoxysilane and the like.

The silane coupling agent having a ureido group inside the structure is not particularly limited, for example, 3-ureidopropyltriethoxysilane and the like.

Silane coupling agents with amino groups inside the above structure are not particularly limited, for example: N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyl Trimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxy Methylsilyl-N-(1,3-dimethyl-butylene)propylamine N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl Hydrochloride of 3-aminopropyltrimethoxysilane, special aminosilane, etc.

The silane coupling agent having a mercapto group inside the above structure is not particularly limited, for example, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.

The silane coupling agent having a halogen atom group inside the above structure is not particularly limited, for example, 3-chloropropyltrimethoxysilane and the like.

These silane coupling agents that can be interfacially polymerized can be used alone, or with any epoxy-based prepolymer, isocyanate, amine, halide, polythiol, polychloride, etc. Mixed use.

When the above-mentioned silane coupling agent and the above-mentioned interfacial polymerization-reactive substance are mixed and used, the above-mentioned silane coupling agent may be added from the initial stage of the reaction of the above-mentioned interfacial polymerization-reactive substance, or may be added in the second half of the reaction of the above-mentioned interfacial polymerization-reactive substance. When the above-mentioned silane coupling agent is added in the second half of the reaction of the above-mentioned interfacial polymerization reactive substance, the obtained resin constituting the mixed fine particles of the present invention has a structure cross-linked by the above-mentioned silane coupling agent.

The above-mentioned epoxy prepolymer has lipophilicity, and it reacts with amines, polycarboxylic acids, acid anhydrides, polythiols, and phenolic resins to form resins.

The above-mentioned epoxy prepolymer is not particularly limited, for example, there are: bisphenol A type, resorcinol type, bisphenol F type, tetraphenylmethane type, novolac type, polyol type, polyethylene glycol type, glycerin Triether type, glycidyl ether type, glycidyl ester type, glycidyl amine type, aliphatic type, alicyclic type, aminophenol type, caprolactone type, trimeric isocyanate type, bisphenol type, naphthalene type, Or these hydrides, fluorides, etc.

The epoxy equivalent of such an epoxy prepolymer is not particularly limited, but the upper limit is preferably 500. By using the epoxy prepolymer whose epoxy equivalent has an upper limit of 500, it is possible to obtain a resin excellent in heat resistance, solvent resistance, and strength with a high degree of crosslinking. A more preferable upper limit is 200.

The upper limit of epoxy equivalent is the epoxy prepolymer of 200, is not particularly limited, for example has: エポト-トYD115, エポト-トYD127, エポト-トYD128 (trade names, all are manufactured by Dongdu Chemical Industry Co., Ltd.), エピコ- Bisphenol A-type epoxy such as ト825, Epico-ト827, Epiko-ト828 (trade names, all manufactured by Japan-Epokisilesin Co., Ltd.), EPICLON 840, EPICLON 850 (trade names, both manufactured by Dainippon Ink Chemical Co., Ltd.) Resin: Epot-to YDF-170, Epot-to YDF175S (trade names, both manufactured by Tohto Chemical Co., Ltd.), Epico-to 806, Epico-to 807 (trade names, both manufactured by Japan Epoch Resin Corporation), EPICLON 830 , EPICLON 835 (trade name, all manufactured by Dainippon Ink Chemical Co., Ltd.) and other bisphenol F epoxy resins; -703, Epoto-toYDCN-704, Epoto-toYDCN-500 (trade names, all manufactured by Tohto Kasei Co., Ltd.), Epico-to152, Epico-to154 (trade names, all manufactured by Japan Epoki Siresin Co., Ltd.) , EPICLON N-655, EPICLON N-740, EPICLON N-770, EPICLON N-775, EPICLON N-865 (trade names, all manufactured by Dainippon Ink Co., Ltd.) and other novolac epoxy resins; 434, Epico-to YH434-L (trade name, all manufactured by Dongdu Chemical Industry Co., Ltd.), Epico-to 1031S, Epico-to 1032H60, Epico-to604, Epico-to630 (trade name, all are Japan Epikisilesin Corporation EPICLON 430 (trade name, both manufactured by Dainippon Ink Chemical Co., Ltd.), TETRAD-X, TETRAD-C (trade name, both manufactured by Mitsubishi Gas Chemical Co., Ltd.); - biphenyl type epoxy resins such as -トYL6121H, エピコ-トYL6640, エピコ-トYL6677 (trade names, all made by Japan エポキシレジン Corporation); Aliphatic polyglycidyl ether type epoxy resins such as YH-315, エポト-トYH-324, エポト-トYH-325 (trade names, all of which are manufactured by Dongdu Chemical Co., Ltd.);トYSLV-80XY (trade name, both manufactured by Tohto Kasei Co., Ltd.) and other crystalline epoxy resins; EPICLON HP-4032, EPICLON EXA-4700 (trade name, both manufactured by Dainippon Ink Chemical Co., Ltd.) and other naphthalene-type epoxy resins ;Epico-to191P, Epiko-toYX31 0 (trade name, both manufactured by Japan Epoki Shiresin Co.), EPICLON HP-820 (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.); EPICLON 725 (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.), etc. Reactive diluents, etc.

In addition, epoxy prepolymers with an epoxy equivalent of more than 200 and less than 500 are not particularly limited, for example: Epot-to YD134, Epot-to YD011 (trade names, all manufactured by Tohto Chemical Co., Ltd.), Epico-to 801 , Epico-to 1001 (trade name, both are made by Japan Epoki Shiresin Corporation), EPICLON 860, EPICLON 1050, EPICLON 1055 (trade name, all are made by Dainippon Ink Chemical Co., Ltd.) and other bisphenol A epoxy resins; Bisphenol F-type epoxy resin such as トYDF-2001 (trade name, manufactured by Tohto Kasei Co., Ltd.); EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N -695 (trade name, both manufactured by Dainippon Ink Chemical Co., Ltd.); Epico-to 157S70 (trade name, manufactured by Japan Ink Chemical Co., Ltd.), EPICLON 5500 (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.) and other special multi-functional types; エポト—トYDB-360, エポト—トYDB-400, エポト—トYDB-405 (trade name, all are manufactured by Dongdu Chemical Co.), EPICLON 152, EPICLON 153 (trade name, all are Brominated epoxy resins such as Dainippon Ink Chemical Co., Ltd.); Epico-to YD-171 (trade name, manufactured by Tohto Chemical Co., Ltd.), Epico-to 871 (trade name, manufactured by Japan Electronics Chemical Co., Ltd.), EPICLONT SR-960, Flexible epoxy resins such as EPICLON TSR-601 (trade name, both manufactured by Dainippon Ink Chemicals Co., Ltd.); エポト-トST-3000 (trade name, manufactured by Tohto Chemical Co.), エピコ-トYX8000, エピコ-トYX8034 Hydrogenated epoxy resins such as Epiclon HP-7200 (trade name, both manufactured by Japan Electronics Co., Ltd.); dicyclopentadiene-type epoxy resins such as EPICLON HP-7200 (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.); and the like.

These epoxy prepolymers may be used alone or in combination of two or more.

It should be noted that epoxy equivalents exceeding 500 epoxy prepolymers, for example, include: エポト-トYD-012, エポト-トYD-013, エポト-トYD-014, エポト-トYD-017, エポト-トYD-019 (trade name, all manufactured by Tohto Kasei), Epiko-to1002, Epiko-to1003, Epiko-to1055, Epiko-to1004, Epiko-to1007, Epiko-to1009, Epiko-to 1010 (trade name, all made by Jaypan Epokishi Resin Corporation), EPICLON 3050, EPICLON 4050, EPICLON AM-020-P, EPICLON AM-030-P, EPICLON AM-040-P, EPICLON 7050, EPICLON HM-091, EPICLON HM Bisphenol A type epoxy resins such as -101 (trade name, both manufactured by Dainippon Ink Chemical Co., Ltd.); エポト-トYDF-2004 (trade name, manufactured by Tohto Chemical Co., Ltd.), エピコ-ト4004P, エピコ-ト4007P , Epico-to 4010P, Epico-to 4110, Epico-to 4210 (trade name, all are made by Japan Epoki Siresin Co.), etc.; brominated epoxy resins such as EPICLON1123P-75M (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.); Flexible epoxy resins such as Epokisilesin Co., Ltd.), EPICLON 1600-75X (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.); hydrogenated epoxy resins such as Epot-to ST-4000D (trade name, manufactured by Tohto Kasei Co., Ltd.) Resin: EPICLON 5800 (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.), etc.

The above-mentioned isocyanate is not particularly limited, and examples thereof include burette-type, adduct-type, isocyanurate-type, and the like.

The above-mentioned amines are not particularly limited, for example, ethylenediamine and its adducts, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, Dibutylaminopropylamine, 1,6-hexanediamine and its modified products, N-aminoethylpiperazine, di-aminopropylpiperazine, trimethylhexamethylenediamine, di-hexamethylene Triamine, dicyanodiamide, diacetylacrylamide, various modified aliphatic polyamines, polypropylene oxide diamine and other aliphatic amines; 3,3'-dimethyl 4,4'-di Aminodicyclohexylmethane, 3-amino-1-cyclohexylaminopropane, 4,4'-diaminodicyclohexylmethane, isophoronediamine, 1,3-di(aminomethyl)cyclohexane, Alicyclic amines such as N-dimethylcyclohexylamine and their modified products; 4,4'-diaminodiphenylmethane (methylenediphenylamine), 4,4'-diaminodiphenyl ether, diamino Diphenylsulfone, m-phenylenediamine, 2,4'-toluenediamine, m-toluenediamine, o-toluenediamine, m-xylylenediamine, xylylenediamine and other aromatic amines and their modification Other special amine modified products, amino amides, amino polyamide resins and other polyamino amides, dimethylamine methylphenol, 2,4,6-tris(dimethylaminomethyl)phenol, tris(dimethylaminomethyl)phenol Tertiary amines such as tri-2-ethylhexane salt of amine methyl) phenol and their complexes, ketimine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecapitate Alkylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-ethylimidazole, 2-isopropyl Imidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-isopropylimidazole, 1-cyanoethyl-2- Phenyl imidazole, 1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-2-undecyl imidazole trimellitate, 1-cyanoethyl-2-phenyl Imidazole trimellitate, 2,4-diamino-6-[2'-methylimidazole-(1)']-ethyl-s-triazine, 2,4-diamino-6-[2' -Undecylimidazole-(1)']-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazole-(1)']- Ethyl-s-triazine, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1,3-dibenzyl-2-methylimidazolium chloride, 2-phenyl -4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dimethylolimidazole, 1-cyanoethyl-2-phenyl-4,5-bis(cyanoethoxymethyl base) imidazole, 2-methylimidazole and triazine complex, 2-phenylimidazole and triazine complex and other imidazoles; isophthalic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide Amino-containing prepolymers such as hydrazides, amino adducts of epoxy resins, etc.

The above-mentioned halides are not particularly limited, for example, there are dibasic acyl groups such as adipyl dichloride, phthaloyl dichloride, terephthaloyl dichloride, 1,4-cyclohexanedicarbonyl chloride, etc. halogen.

By dispersing the hollow resin microparticles of the present invention according to the second aspect of the present invention and the mixed microparticles of the present invention (hereinafter, these are collectively referred to as the microparticles of the present invention) in an appropriate binder, it is possible to produce Anti-reflective resin composition for reflective film etc. Such an antireflective resin composition containing the fine particles of the present invention is also one of the present invention.

The above-mentioned binder for dispersing the fine particles of the present invention is not particularly limited as long as it is a transparent and film-forming material, and examples thereof include organic materials such as resins, inorganic materials, and polymerizable monomer solutions.

The above-mentioned organic materials are not particularly limited, for example: triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose acetate, nitrocellulose and other cellulose derivatives substances; polyamide, polycarbonate; polyethylene terephthalate, polyethylene terephthalate-1,4-cyclohexanemethylene ester, polyethylene 1,2-diphenoxyethane-4 , 4-dicarboxylate, polybutylene terephthalate and polyethylene naphthalate and other polyesters; polystyrene, polypropylene, polyethylene, polymethylpentene, polysulfone, poly Transparent resins with a low refractive index such as ether sulfone, polyarylate resin, polyetherimide, polymethyl methacrylate, or various fluorine-containing materials of these.

In addition, when using a transparent resin as the said binder, it is preferable to use the thing whose glass transition temperature is lower than the glass transition temperature of the hollow resin microparticle of this invention. Thereby, sufficient film strength can be obtained.

The above-mentioned inorganic materials are not particularly limited, and include, for example, alkoxides of various elements, salts of organic acids, coordination compounds formed by combining coordination compounds, and the like. Specific examples include: tetraethoxytitanium, tetraisopropoxytitanium, tetran-propoxytitanium, tetra-n-butoxytitanium, tetra-sec-butoxytitanium, tetra-tert-butoxytitanium, triethoxyaluminum , triisopropoxy aluminum, tributoxy aluminum, triethoxy antimony, tributoxy antimony, tetraethoxy zirconium, tetraisopropoxy zirconium, tetra-n-propoxy zirconium, tetra-n-butoxy Metal alkoxide compounds such as base zirconium, tetra-sec-butoxyzirconium, tetra-tert-butoxyzirconium and other metal alkoxide compounds; di-isopropoxy diacetylacetonate titanium, dibutoxy diacetylacetonate titanium, diethoxy diacetyl Titanium acetonate, zirconium diacetylacetonate, aluminum acetylacetonate, ethyl di-n-butoxyaluminum monoacetoacetate, methyl diisopropoxyaluminum monoacetoacetate, ethyl tri-n-butoxyzirconium monoacetoacetate Chelates such as esters; ammonium zirconium carbonate or active inorganic polymers with zirconium as the main component, etc.

The polymerizable monomer in the above-mentioned polymerizable monomer solution is not particularly limited as long as it is a transparent substance, for example: methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylic acid Propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, cyclohexyl (meth)acrylate, myristyl (meth)acrylate, palmityl (meth)acrylate, (meth)acrylic acid Alkyl (meth)acrylates such as stearyl alcohol and isobornyl (meth)acrylate; (meth)acrylonitrile, (meth)acrylamide, (meth)acrylic acid, glycidyl (meth)acrylate ester, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and other polar group-containing (meth)acrylic monomers; styrene, α-methylstyrene, p-methylbenzene Aromatic vinyl monomers such as ethylene and p-chlorostyrene; vinyl esters such as vinyl acetate and vinyl propionate; halogen-containing monomers such as vinyl chloride and vinylidene chloride; vinylpyridine and phthalic acid 2 - Acryloyl hydroxyethyl ester, itaconic acid, fumaric acid, ethylene, propylene, etc.

These monomers may be used alone or in combination of two or more.

In order to increase the film strength, the above-mentioned polymerizable monomer solution may also contain a multifunctional monomer.

The above-mentioned multifunctional monomers are not particularly limited, for example: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,6-hexane Diol di(meth)acrylate, trimethylolpropane di(meth)acrylate and other di(meth)acrylates; trimethylolpropane tri(meth)acrylate, ethylene oxide modified Tri(meth)acrylates such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate; tetra(meth)acrylates such as pentaerythritol tetra(meth)acrylate; pentaerythritol hexa( Hexa(meth)acrylate such as methacrylate; pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, diallyl phthalate, diallyl maleate, Di- or triallyl compounds such as diallyl fumarate, diallyl succinate, and triallyl isocyanurate; divinyl compounds such as divinylbenzene and butadiene, etc.

These multifunctional monomers may be used alone or in combination of two or more.

The compounding ratio of the fine particles of the present invention and the above-mentioned binder is not particularly limited, but the preferable lower limit of the blended amount of the fine particles of the present invention is 5% by volume, and the upper limit is preferably 95% by volume. When it is less than 5% by volume, for example, the refractive index of the antireflection film made using the antireflection resin composition of the present invention cannot be sufficiently low, and when it exceeds 95% by volume, the Poor mechanical strength. A more preferable lower limit is 30 volume %, a more preferable upper limit is 90 volume %, a still more preferable lower limit is 50 volume %, and a still more preferable upper limit is 80 volume %.

When a curable substance is used as the above-mentioned binder, the antireflection resin composition of the present invention may be a latex formed by suspending the fine particles of the present invention in the binder. Substance diluted in volatile solvents.

The above-mentioned volatile solvents are not particularly limited, but from the aspects of stability, wettability, and volatility of the composition, alcohols such as methanol, ethanol, isopropanol, butanol, and 2-methoxyethanol are suitable for use. Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate and butyl acetate; ethers such as diisopropyl ether; ethylene glycol, propylene glycol, hexyl Glycols such as glycols; ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol and other glycol ethers; hexane, heptane, octane and other aliphatic hydrocarbons; Halogenated hydrocarbons; aromatic hydrocarbons such as benzene, toluene, and xylene; N-methylpyrrolidone, dimethylformamide, etc. These volatile solvents may be used alone or in combination of two or more.

In addition, the above-mentioned antireflective resin composition of the present invention can be used as a coating agent for an antireflective film for producing an antireflective film. A coating agent for an antireflection film comprising such an antireflection resin composition of the present invention is also one of the present invention.

Furthermore, an antireflection film formed using the coating agent for an antireflection film of the present invention is also one of the present invention.

The method for producing the antireflection film of the present invention is not particularly limited. For example, the coating agent for the antireflection film of the present invention is coated on a release film or the like, or directly coated on a transparent substrate, and then dried. .

The method of coating the coating agent for anti-reflection film of the present invention is not particularly limited, for example, there are: dip coating method, spin coating method, pouring coating method, spray coating method, roll coating method, gravure coating method, air knife coating Coating method, plate coating method, wire-wound blade coating method, knife coating method, reverse coating method, transfer roller coating method, micro-gravure coating method, light touch coating method, tape coating method, slot orifice coating method, calender coating method, mold coating method, etc.

Utilize above-mentioned method, after coating agent for antireflection film of the present invention on release film etc., or directly on transparent substrate, form coating film by heat drying etc., then, by heating , humidification, ultraviolet irradiation, electron beam irradiation, etc., to cure the above-mentioned coating film to obtain the antireflection film of the present invention.

The antireflection film of the present invention preferably has a smooth surface. It should be noted that the so-called smooth surface in this specification means that the surface roughness Rz calculated by the method specified in JIS B 0601 is 0.2 μm or less.

By making the surface smooth, the anti-reflection film of the present invention does not cause overall whitening due to diffuse reflection of light on the surface. In addition, stains such as fingerprints, sebum, sweat, and cosmetics are difficult to adhere to, and once stains adhere, they can be easily removed. remove.

The antireflection film of the present invention may have a substrate layer in addition to the layer formed using the coating agent for an antireflection film of the present invention. By having a base material layer, the mechanical strength of the antireflection film of the present invention is improved, and the handleability is improved.

The above-mentioned base material layer is not particularly limited as long as it is transparent, but it is preferably composed of, for example, a transparent resin that can be used as the above-mentioned binder in terms of formability and mechanical strength.

The thickness of the antireflection film of the present invention is not particularly limited, but the lower limit is preferably 50 nm, and the upper limit is preferably 200 nm. When it is less than 50 nm, the scratch resistance may be insufficient, and when it exceeds 200 nm, the film may be easily cracked.

In addition, when the antireflection film of the present invention has the above-mentioned base layer, the thickness of the base layer is not particularly limited, but the lower limit is preferably 3 μm, and the upper limit is preferably 7 μm. When it is less than 3 μm, the strength of the antireflection film of the present invention may be poor, and when it exceeds 7 μm, the transparency of the antireflection film of the present invention may be poor, making it difficult to see internal visual information.

According to the present invention, there is provided a method for producing hollow resin particles, organic-inorganic hybrid particles, and hollow resin particles. It is an anti-reflection layer that has excellent dispersibility of the agent components, prevents diffuse reflection of light, and has high alkali resistance.

Detailed ways

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

Example 1

(1) Preparation of hollow resin particles

Mix and stir 30 parts by weight of Dulanet 21S (manufactured by Asahi Kasei Chemicals Co., Ltd.) as a polyisocyanate component and 70 parts by weight of toluene as a non-polymerizable compound. In 2 parts by weight of sodium dodecylbenzenesulfonate and 400 parts by weight of ion-exchanged water as a dispersing aid of 2 parts by weight of cetyl alcohol, use an ultrasonic homogenizer to perform forced emulsification for 60 minutes, and prepare to disperse with an average A dispersion of polymerizable droplets with a particle diameter of 50 nm.

Using a 20-L polymerizer equipped with a stirrer, jacket, reflux condenser, and thermometer, decompress the inside of the polymerizer to deoxidize the container, replace it with nitrogen to make the inside a nitrogen atmosphere, and throw in the obtained dispersion to make The temperature of the polymerizer was raised to 80° C. to start polymerization. Polymerization was carried out for 4 hours, and then after standing for 1 hour of aging, the polymerizer was allowed to cool to room temperature.

The obtained slurry was dialyzed with a cellulose membrane with a molecular weight cut off of 10,000 to remove excess surfactants and inorganic salts, and further filtered to remove aggregated particles and insoluble components. The obtained resin fine particles were vacuum-dried to obtain hollow resin fine particles.

When the obtained hollow resin microparticles were observed with an electron microscope (manufactured by Hitachi High Technologies, Inc., "S-3500N"), the shape was approximately spherical.

(2) Preparation of coating agent for anti-reflection film and formation of anti-reflection film

100 parts by volume of the obtained hollow resin particles were mixed with 100 parts by volume of polymethyl methacrylate as a binder, and 800 parts by volume of toluene as a diluting solvent to prepare a coating agent for an antireflection film.

The coating agent for the obtained anti-reflection film was coated on a triacetyl cellulose (TAC) film, and dried at 120° C. for 10 minutes to form an anti-reflection film with a thickness of 100 nm.

Example 2

Mix and stir 30 parts by weight of Dulanet 21S (manufactured by Asahi Kasei Chemicals Co., Ltd.) as a polyisocyanate component and 70 parts by weight of toluene as a non-polymerizable compound. 10 parts by weight of ethylene glycol, 2 parts by weight of sodium dodecylbenzenesulfonate as a water-soluble emulsifier, and 390 parts by weight of ion-exchanged water as 2 parts by weight of cetyl alcohol as a dispersion aid, homogenized with ultrasonic waves The emulsion was forcedly emulsified in a machine for 60 minutes to prepare a dispersion in which polymeric liquid droplets with an average particle diameter of 60 nm were dispersed.

Using a 20-L polymerizer equipped with a stirrer, jacket, reflux condenser, and thermometer, decompress the inside of the polymerizer to deoxidize the container, replace it with nitrogen to make the inside a nitrogen atmosphere, and throw in the obtained dispersion to make The temperature of the polymerization tank was raised to 80° C. to start polymerization. Polymerized for 4 hours, and then stored for 1 hour of aging, the polymerization tank was cooled to room temperature.

The obtained slurry was dialyzed with a cellulose membrane with a molecular weight cut off of 10,000 to remove excess surfactants and inorganic salts, and further filtered to remove aggregated particles and insoluble components.

The obtained resin fine particles were vacuum-dried to obtain hollow resin fine particles.

When the obtained hollow resin microparticles were observed with an electron microscope (manufactured by Hitachi High Technologies, Inc., "S-3500N"), the shape was approximately spherical.

A coating agent for an antireflection film was prepared in the same manner as in Example 1 except that the obtained hollow resin particles were used to form an antireflection film.

Example 3

30 parts by weight of Epico-to 828 (manufactured by Japan Epikisilesin Co., Ltd.) as an epoxy prepolymer component and 70 parts by weight of toluene as a non-polymerizable organic solvent were mixed and stirred, and the total amount of the mixed solution thus formed was added to the mixture containing 10 parts by weight of diethylenetriamine as an amine component, 2 parts by weight of sodium dodecylbenzenesulfonate as a water-soluble emulsifier, and 2 parts by weight of cetyl alcohol as a dispersion aid in 390 parts by weight of ion-exchanged water , using an ultrasonic homogenizer to perform forced emulsification for 60 minutes to prepare a dispersion liquid in which polymerizable liquid droplets with an average particle diameter of 65 nm are dispersed.

Using a 20-L polymerizer equipped with a stirrer, jacket, reflux condenser, and thermometer, decompress the inside of the polymerizer to deoxidize the container, replace it with nitrogen to make the inside a nitrogen atmosphere, and throw in the obtained dispersion to make The temperature of the polymerizer was raised to 80° C. to start polymerization. Polymerization was carried out for 4 hours, and then after standing for 1 hour of aging, the polymerizer was allowed to cool to room temperature.

The obtained slurry was dialyzed with a cellulose membrane with a molecular weight cut off of 10,000 to remove excess surfactants and inorganic salts, and further filtered to remove aggregated particles and insoluble components.

The obtained resin fine particles were vacuum-dried to obtain hollow resin fine particles.

The obtained hollow resin particles were observed with an electron microscope (manufactured by Hitachi High Technologies, Inc., "S-3500N"), and the shape was approximately spherical.

A coating agent for an antireflection film was prepared in the same manner as in Example 1 except that the obtained hollow resin particles were used to form an antireflection film.

Example 4

Mix and stir 50 parts by weight of Epicoat 828 (manufactured by Japan Epoxilesin Co., Ltd.) as an epoxy prepolymer component, and 50 parts by weight of toluene, and add the total amount of the resulting mixed solution to a mixture containing diethylene triethylene as an amine component. 10 parts by weight of amine, 2 parts by weight of sodium dodecylbenzenesulfonate as a water-soluble emulsifier, and 2 parts by weight of cetyl alcohol as a dispersion aid in 390 parts by weight of ion-exchanged water, using an ultrasonic homogenizer Forced emulsification was carried out for 60 minutes to prepare a dispersion in which polymerizable liquid droplets with an average particle diameter of 72 nm were dispersed.

Using a 20-L polymerizer equipped with a stirrer, jacket, reflux condenser, and thermometer, decompress the inside of the polymerizer to deoxidize the container, replace it with nitrogen to make the inside a nitrogen atmosphere, and throw in the obtained dispersion to make The temperature of the polymerization tank was raised to 80° C. to start polymerization. Polymerized for 4 hours, and then stored for 1 hour of aging, the polymerization tank was cooled to room temperature.

The obtained slurry was dialyzed with a cellulose membrane with a molecular weight cut off of 10,000 to remove excess surfactants and inorganic salts, and further filtered to remove aggregated particles and insoluble components.

The obtained resin fine particles were vacuum-dried to obtain hollow resin fine particles.

The obtained hollow resin particles were observed with an electron microscope (manufactured by Hitachi High Technologies, Inc., "S-3500N"), and the shape was approximately spherical.

A coating agent for an antireflection film was prepared in the same manner as in Example 1 except that the obtained hollow resin particles were used to form an antireflection film.

Example 5

30 parts by weight of Epicot 828 (manufactured by Japan Epikisilesin Co., Ltd.) as an epoxy prepolymer component, 65 parts by weight of toluene as a non-polymerizable organic solvent, and 5 parts by weight of hexadecane were mixed and stirred, and the thus formed The total amount of the mixed solution was added to a mixture containing 10 parts by weight of diethylenetriamine as an amine component, 2 parts by weight of sodium dodecylbenzenesulfonate as a water-soluble emulsifier, and 2 parts by weight of cetyl alcohol as a dispersing aid. 390 parts by weight of ion-exchanged water was forcibly emulsified with an ultrasonic homogenizer for 60 minutes to prepare a dispersion in which polymerizable liquid droplets with an average particle diameter of 42 nm were dispersed.

Using a 20-L polymerizer equipped with a stirrer, jacket, reflux condenser, and thermometer, decompress the inside of the polymerizer to deoxidize the container, replace it with nitrogen to make the inside a nitrogen atmosphere, and throw in the obtained dispersion to make The temperature of the polymerization tank was raised to 80° C. to start polymerization. Polymerized for 4 hours, and then stored for 1 hour of aging, the polymerization tank was cooled to room temperature.

The obtained slurry was dialyzed with a cellulose membrane with a molecular weight cut off of 10,000 to remove excess surfactants and inorganic salts, and further filtered to remove aggregated particles and insoluble components.

The obtained resin fine particles were vacuum-dried to obtain hollow resin fine particles.

The obtained hollow resin particles were observed with an electron microscope (manufactured by Hitachi High Technologies, Inc., "S-3500N"), and the shape was approximately spherical.

A coating agent for an antireflection film was prepared in the same manner as in Example 1 except that the obtained hollow resin particles were used to form an antireflection film.

Comparative example 1

The surface of porous silica particles with an average particle diameter of 60 nm and a refractive index of 1.36 was covered with an organosilicon compound, and the resulting material was used as a low refractive index particle. The same method as in Example 1 was used for the rest. , to prepare coating agents for anti-reflection films and to form anti-reflection films.

Example 6

20 parts by weight of Epicoat 828 (manufactured by Japan Epoch Resin Co., Ltd.) as an epoxy prepolymer component (lipophilic reaction component A) and methacrylic acid as a radically polymerizable monomer component (lipophilic reaction component C) 10 parts by weight of perfluorooctyl ethyl ester, 1 part by weight of azobisisobutyronitrile as a polymerization initiator, 65 parts by weight of toluene as a non-polymerizable organic solvent, and 5 parts by weight of hexadecane were mixed and stirred to form The total amount of the mixed solution was added to 390 parts by weight of ion-exchanged water containing 10 parts by weight of diethylenetriamine as an amine component (lipophilic reaction component B) and 2 parts by weight of sodium dodecylbenzenesulfonate as a water-soluble emulsifier. Parts were subjected to forced emulsification with an ultrasonic homogenizer for 60 minutes to prepare a dispersion in which polymerizable liquid droplets with an average particle diameter of 78 nm were dispersed.

Using a 20-L polymerizer equipped with a stirrer, jacket, reflux condenser, and thermometer, decompress the inside of the polymerizer to deoxidize the container, replace it with nitrogen to make the inside a nitrogen atmosphere, and throw in the obtained dispersion to make The temperature of the polymerizer was raised to 80° C. to start polymerization. Polymerization was carried out for 4 hours, and then after standing for 1 hour of aging, the polymerizer was allowed to cool to room temperature.

The obtained slurry was dialyzed with a cellulose membrane with a molecular weight cut off of 10,000 to remove excess surfactants and inorganic salts, and further filtered to remove aggregated particles and insoluble components.

The obtained resin fine particles were vacuum-dried to obtain hollow resin fine particles.

The obtained hollow resin particles were observed with an electron microscope (manufactured by Hitachi High Technologies, Inc., "S-3500N"), and the shape was approximately spherical. In addition, the obtained hollow resin microparticles were observed with an electron microscope (manufactured by Hitachi Electronics Co., Ltd., "JEM-1200EXII"), and it was found that they had a double structure.

A coating agent for an antireflection film was prepared in the same manner as in Example 1 except that the obtained hollow resin particles were used to form an antireflection film.

Example 7

20 parts by weight of Dulanet 21S (manufactured by Asahi Kasei Chemicals Co., Ltd.) as a polyisocyanate component (lipophilic reaction component A) and perfluorooctyl methacrylate as a radically polymerizable monomer component (lipophilic reaction component C) 10 parts by weight of ethyl ester, 1 part by weight of azobisisobutyronitrile as a polymerization initiator, 65 parts by weight of toluene as a non-polymerizable compound, and 5 parts by weight of hexadecane were mixed and stirred, and the total amount of the mixed solution thus formed Add to 390 parts by weight of ion-exchanged water containing 10 parts by weight of ethylene glycol as a polyol component (lipophilic reaction component B), and 2 parts by weight of sodium dodecylbenzenesulfonate as a water-soluble emulsifier, and use ultrasonic The homogenizer performed forced emulsification for 60 minutes to prepare a dispersion in which polymerizable liquid droplets with an average particle diameter of 65 nm were dispersed.

Using a 20-L polymerizer equipped with a stirrer, jacket, reflux condenser, and thermometer, decompress the inside of the polymerizer to deoxidize the container, replace it with nitrogen to make the inside a nitrogen atmosphere, and throw in the obtained dispersion to make The temperature of the polymerizer was raised to 80° C. to start polymerization. Polymerization was carried out for 4 hours, and then after standing for 1 hour of aging, the polymerizer was allowed to cool to room temperature.

The obtained slurry was dialyzed with a cellulose membrane with a molecular weight cut off of 10,000 to remove excess surfactants and inorganic salts, and further filtered to remove aggregated particles and insoluble components.

The obtained resin fine particles were vacuum-dried to obtain hollow resin fine particles.

The obtained hollow resin particles were observed with an electron microscope (manufactured by Hitachi High Technologies, Inc., "S-3500N"), and the shape was approximately spherical. In addition, the obtained hollow resin microparticles were observed with an electron microscope (manufactured by JEOL Ltd., "JEM-1200EX II") to have a double structure.

A coating agent for an antireflection film was prepared in the same manner as in Example 1 except that the obtained hollow resin particles were used to form an antireflection film.

Example 8

(1) Production of organic-inorganic hybrid particles

In a 20-L capacity polymerizer equipped with a stirrer, a jacket, a reflux condenser, and a thermometer, an emulsifier was added to ion-exchanged water as a polar solvent adjusted to pH 9, and stirring was started.

After decompressing the inside of the polymerizer to deoxidize the inside of the container, the pressure was returned to atmospheric pressure with nitrogen to make the inside a nitrogen atmosphere.

After raising the temperature of the polymerizer to 80°C, mix a polymerizable silane coupling agent, a polymerizable monomer, ethyl acetate as a non-polymerizable organic solvent, and azobisisobutyronitrile as a polymerization initiator in a polar solvent , using a rotor-stator type homogenizer to emulsify to a nanometer size, prepare a dispersion liquid in which polymerizable droplets with an average particle diameter of 62 nm are dispersed, and polymerize the polymerizable droplets.

Then, the pH of the system was adjusted to 5 again with acetic acid, and after aging for 4 hours, the polymerizer was cooled to room temperature to obtain a slurry.

Dialyze the obtained slurry with a cellulose membrane with a molecular weight cut-off of 10,000 to remove excess surfactants and inorganic salts, and further filter to remove aggregated particles and insoluble components to prepare organic-inorganic hybrid fine particles.

A coating agent for an antireflection film was prepared in the same manner as in Example 1 except that the obtained organic-inorganic hybrid fine particles were used to form an antireflection film.

Example 9

30 parts by weight of Epicoat 828 (manufactured by Japan Epikisilesin Co., Ltd.) as an epoxy prepolymer component, 65 parts by weight of toluene as a non-polymerizable organic solvent, and 5 parts by weight of hexadecane were mixed and stirred, and the thus formed The total amount of the mixed solution was added to a mixture containing 7 parts by weight of diethylenetriamine as an amine component, 2 parts by weight of sodium dodecylbenzenesulfonate as a water-soluble emulsifier, and 2 parts by weight of cetyl alcohol as a dispersing aid. 390 parts by weight of ion-exchanged water was forcibly emulsified with an ultrasonic homogenizer for 60 minutes to prepare a dispersion liquid in which polymerizable liquid droplets having an average particle diameter of 63 nm were dispersed.

Using a 20-L polymerizer equipped with a stirrer, jacket, reflux condenser, and thermometer, decompress the inside of the polymerizer to deoxidize the container, replace it with nitrogen to make the inside a nitrogen atmosphere, and throw in the obtained dispersion to make The temperature of the polymerizer was raised to 80° C. to start polymerization. After polymerization for 4 hours, 3 parts by weight of N-2(aminoethyl)3-aminopropyltrimethoxysilane as an amine component for inorganic crosslinking was added, and polymerization was continued for 4 hours. After standing for 1 hour of aging, the polymerizer was allowed to cool to room temperature.

Dialyze the obtained slurry with a cellulose membrane with a molecular weight cut-off of 10,000 to remove excess surfactants and inorganic salts, and further filter to remove aggregated particles and insoluble components to prepare organic-inorganic hybrid fine particles.

A coating agent for an antireflection film was prepared in the same manner as in Example 1 except that the obtained organic-inorganic hybrid fine particles were used to form an antireflection film.

Comparative example 2

According to the method disclosed in JP-A-1-185311, porous resin particles having an average particle diameter of 98 nm were produced.

Except for using porous resin particles instead of the organic-inorganic hybrid fine particles produced in Example 8, the same method as in Example 8 was used to prepare a coating agent for an antireflection film to form an antireflection film.

evaluate

The hollow resin particles (low refractive index particles) and antireflection film obtained in Examples 1 to 7 and Comparative Example 1, and the organic-inorganic hybrid particles obtained in Examples 8 and 9 and Comparative Example 2 were evaluated by the following methods. The results are shown in Table 1.

(1) Determination of the average particle size and the CV value of the particle size

The volume average particle diameter and the CV value of the particle diameter of the microparticles obtained in each Example and Comparative Example were measured with a dynamic light scattering particle size distribution analyzer (manufactured by Particle Sizing Systems, "NICOMPmodel 380 ZLS-S").

(2) Determination of reflectivity of anti-reflection film

After rubbing the surface of the base material with sandpaper and applying a matte black paint, use a spectrophotometer (manufactured by Shimadzu Corporation, "UV-3101PC") under the conditions of a light wavelength of 550 nm and a light incident angle of 5°. Measure the reflectance of one side.

(3) Determination of the refractive index and porosity of particles

The refractive index of the particles was calculated from the refractive index of the antireflection layer estimated from the value of the reflectance of the antireflection film, the refractive index of the binder alone without particles, and the ratio of particles added to the antireflection layer.

The porosity of the microparticles obtained in each of the Examples and Comparative Examples was calculated using the obtained refractive index of the particles, the measured value, and the value of the refractive index of the resin portion of the particles calculated from the composition. The porosity thus calculated shows good agreement with the porosity of the particles calculated from the particle diameter and film thickness of the fine particles observed with an electron microscope.

(4) Evaluation of alkali resistance of anti-reflection film

A cellulose nonwoven fabric impregnated with a commercially available alkaline detergent was used for the antireflection film, and a weight of 100 g/ ^cm2 was applied. After making it reciprocate 100 times, the appearance of the film was visually observed and judged by the following criteria.

○: Good

△: Generally good

×: Bad

Table 1

Possibility of industrial application

According to the present invention, it is possible to provide a method for producing hollow resin particles, organic-inorganic hybrid particles, and hollow resin particles. It is an anti-reflection layer that has excellent dispersibility of components, prevents diffuse reflection of light, and has high alkali resistance.

Claims (15)

1. A hollow resin particle, characterized in that it has a single-hole structure, its average particle diameter is 10-100 nm, and its refractive index is 1.40 or less than 1.40, And the hollow resin particles have at least an outermost layer composed of a resin formed by reacting lipophilic reactive component A composed of polyisocyanate and hydrophilic reactive component B composed of water, amine, polyhydric alcohol or polycarboxylic acid. 2. A hollow resin particle, characterized in that it has a single-hole structure, its average particle diameter is 10-100 nm, and its refractive index is 1.40 or less than 1.40. And the hollow resin particles have at least the resin formed by the reaction of the lipophilic reactive component A composed of epoxy prepolymer and the hydrophilic reactive component B composed of amine, polycarboxylic acid, acid anhydride, polymercaptan or phenolic resin. constitute the outermost layer. 3. The hollow resin particle according to claim 1 or 2, characterized in that its porosity is 30% or more. 4. A hollow resin particle, characterized in that it has a single-hole structure and has a composite shell composed of at least two resin layers, the outermost layer and the inner layer, and the porosity of the hollow resin particle is 30% or greater than 30%. %, the average particle size is 10-100nm, and the refractive index is 1.40 or less than 1.40, The outermost layer is composed of a resin formed by the reaction of lipophilic reactive component A composed of polyisocyanate and hydrophilic reactive component B composed of water, amine, polyhydric alcohol or polycarboxylic acid, and the inner layer is composed of and The lipophilic reactive component A and the lipophilic reactive component C which do not react with the hydrophilic reactive component B are formed by reacting the resin, wherein the lipophilic reactive component C is composed of a radically polymerizable monomer. 5. A hollow resin particle, characterized in that it has a single-hole structure and has a composite shell composed of at least two resin layers, the outermost layer and the inner layer, and the porosity of the hollow resin particle is 30% or greater than 30%. %, the average particle size is 10-100nm, and the refractive index is 1.40 or less than 1.40, The outermost layer is composed of a resin formed by the reaction of lipophilic reactive component A composed of epoxy prepolymer and hydrophilic reactive component B composed of amine, polycarboxylic acid, acid anhydride, polymercaptan or phenolic resin, And the inner layer is composed of a resin formed by reacting with the lipophilic reactive component C that does not react with the lipophilic reactive component A and the hydrophilic reactive component B, wherein the lipophilic reactive component C is composed of radical polymerizable single composition. 6. The hollow resin particles according to claim 1, 2, 4 or 5, which contain a fluorine-containing monomer. 7. The hollow resin particle according to claim 1, 2, 4 or 5, wherein the outermost layer contains a compound selected from polyurea, polyurethane, polyamide, polyester, nylon and epoxy polymer. At least one resin in the group. 8. The hollow resin microparticles according to claim 1, 2, 4 or 5, which contain a resin cross-linked with an inorganic component. 9. An antireflection resin composition comprising the hollow resin particles according to claim 1, 2, 4 or 5. 10. A coating agent for an antireflection film, comprising the antireflection resin composition according to claim 9. 11. An antireflection film, which is produced by using the coating agent for antireflection film according to claim 10. 12. A method for manufacturing hollow resin particles, characterized in that the hollow resin particles have a single-pore structure, and the method for manufacturing hollow resin particles includes: Preparation of a dispersion obtained by dispersing polymerizable droplets containing lipophilic reactive component A composed of polyisocyanate in a polar medium containing hydrophilic reactive component B composed of water, amine, polyol or polycarboxylic acid process; and A step of reacting the lipophilic reaction component A and the hydrophilic reaction component B. 13. A method for manufacturing hollow resin particles, characterized in that the hollow resin particles have a single-pore structure, and the method for manufacturing hollow resin particles includes: Prepare a polymeric liquid containing lipophilic reactive component A composed of epoxy prepolymer in a polar medium containing hydrophilic reactive component B composed of amine, polycarboxylic acid, acid anhydride, polythiol or phenolic resin the process of dropping the dispersed liquid; and A step of reacting the lipophilic reaction component A and the hydrophilic reaction component B. 14. A method for producing hollow resin particles, characterized in that the hollow resin particles have a single-hole structure, and have a composite shell composed of at least two resin layers, the outermost layer and the inner layer, and the hollow resin particles have Manufacturing methods include: Formulated in a polar medium containing a hydrophilic reactive component B composed of water, amines, polyols or polycarboxylic acids so that the lipophilic reactive component A composed of polyisocyanate and the hydrophilic reactive component A composed of free radical polymerizable monomers are formulated. The process of the dispersion obtained by dispersing the polymerizable droplets of the oily reaction component C; reacting the lipophilic reactive component A on the surface of the polymerizable droplet with the hydrophilic reactive component B in the polar medium to form an outermost layer on the surface of the polymerizable droplet; and A step of reacting the lipophilic reactive component C inside the polymerizable liquid droplet to form an inner layer. 15. A method for producing hollow resin particles, characterized in that the hollow resin particles have a single-hole structure, and have a composite shell composed of at least two resin layers, the outermost layer and the inner layer, and the hollow resin particles have a Manufacturing methods include: Formulated in a polar medium containing a hydrophilic reactive component B composed of amines, polycarboxylic acids, acid anhydrides, polythiols or phenolic resins to contain lipophilic reactive components A composed of epoxy prepolymers and free radicals The step of dispersing the polymerizable droplets of the lipophilic reaction component C composed of polymerizable monomers; reacting the lipophilic reactive component A on the surface of the polymerizable droplet with the hydrophilic reactive component B in the polar medium to form an outermost layer on the surface of the polymerizable droplet; and A step of reacting the lipophilic reactive component C inside the polymerizable liquid droplet to form an inner layer.