CN100543070C - The manufacture method of hollow resin particulate, organic-inorganic hybrid fine particles and hollow resin particulate - 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

The manufacture method of hollow resin particulate, organic-inorganic hybrid fine particles and hollow resin particulate

Technical field

The present invention relates to the manufacture method of a kind of hollow resin particulate, organic-inorganic hybrid fine particles and hollow resin particulate, when described hollow resin particulate is used as the particulate of the anti-reflection layer that constitutes low-refraction, dispersed good to the binding agent composition, the diffuse-reflectance of light can be prevented, the high anti-reflection layer of alkali resistance can be obtained simultaneously.

Background technology

Liquid-crystal display that uses in Personal Computer, word processor, the mobile phone etc. and other various commercial indicating meters etc. obtain utilizing in unusual extensive fields.These indicating meters use transparency carriers such as glass or plastics, by cognitive object of these transparency carriers and visual informations such as literal, figure.

Problem in these indicating meter practicalities for example has: the visuality that is caused by the reflection of display surface worsens.That is, no matter be indoor and outdoor, when incident environment such as light uses down outside,, cause being difficult to see the visual information of inside because incident lights such as outer light reflect on the surface of transparency carrier.

Prevent the method for the reflection of such transparency carrier, for example have: be formed with concavo-convex coating on the surface of transparency carrier, the irreflexive method of light outside this surface utilizes concavo-convex making.

For example, patent documentation 1 discloses a kind of antireflective film, it is in utilizing the formulated silicates coating-forming agent of sol-gel method, the mixed silica dispersion liquid, this mixed solution is coated in carries out on the glass substrate that roasting forms, the surface has concavo-convex that agglomeration by silicon dioxide granule or silicon dioxide granule causes.In addition, patent documentation 2 discloses a kind of antireflective film, it forms on transparent base film with the resin is the middle layer of main component, on this middle layer, have that to contain specific refractory power by coating be organic ultramicronized coating liquid concavo-convex top layer that form, that expose on organic ultramicronized surface below 1.45.

But, the irreflexive method of light outside the surface forms concavo-convex making, though visual dazzling lowered, catoptrical amount does not as a whole reduce, and has whole problem of turning white.In addition, the problem that also exists spots such as adhering to fingerprint, sebum, sweat, makeup on surface concavo-convex easily and stains attached to be not easy to remove owing to the existence of micro concavo-convex.

With respect to this, there is document to propose to form the method for the anti-reflection layer of low-refraction on the surface of transparency carrier.By form the anti-reflection layer of low-refraction on the surface of transparency carrier, can there be problems such as the diffuse-reflectance of light and spot, prevent the reflection of transparency carrier.

The anti-reflection layer of such low-refraction, used the material that constitutes by silicon class or fluorine class material, but because the adaptation of these and common transparency carrier is poor, therefore attempt using following antireflective film, promptly, the coating-forming agent that the microparticulate of low-refraction such as nano level silicon dioxide microparticle is for example formed has formed the antireflective film of coating on transparency carrier.For example, patent documentation 3 discloses a kind of low refractive index coating agent and has used the antireflective film of this low refractive index coating agent, and this low refractive index coating agent is to cooperate hollow silica particles to form with the polymerizable organosilicon compound thing with a fixed structure as binding agent.

But,, therefore,, then comprise the problem that the coating of silicon dioxide microparticle exists performance to reduce if use commercially available alkalis when wiping spot because silicon dioxide microparticle is poor to the patience of basic solution.

In addition, when using mineral-type polymerizable organosilicon compound thing etc. as the binding agent composition of low refractive index coating agent, the coating that obtains is enbrittled, the physical strength shortcoming.With respect to this, by the binding agent composition of organic class binding agents such as use transparent resin as the low refractive index coating agent, it is good to obtain film-forming properties, the coating that physical strength is good, but, though the favorable dispersity of silicon dioxide microparticle in the mineral-type binding agent composition of mineral-type silicoorganic compound etc., but its dispersed bad in organic class binding agent compositions such as transparent resin, as long as use silicon dioxide microparticle, owing to there is problem to the dispersiveness of resin, therefore, also existence is difficult to film-forming properties good, the transparent resin that physical strength is good is used as the problem of binding agent.

At this problem, also using voidage in research be that hollow resin particulate more than necessarily is as the low-refraction particulate.Because the alkali resistance of hollow resin particulate and relative binding agent is dispersed good, therefore, as long as use such hollow resin particulate, just can suppress the reflection of transparency carrier effectively, be expected to obtain anti-in spot and washing, antireflective film that physical strength is also good.

The manufacture method of such hollow resin particulate for example has: patent documentation 4, patent documentation 5 disclosed methods are, utilize letex polymerization to form the core-shell polymkeric substance, handle with alkali or alkali and acid, make the method for inner tool foraminous polymer particle; In addition, patent documentation 6, patent documentation 7 disclose the manufacture method of the hollow resin particulate that utilizes radical polymerization; In addition, patent documentation 8 discloses the manufacture method of the hollow resin particulate that utilizes seeding polymerization; In addition, patent documentation 9, patent documentation 10, patent documentation 11 disclose the manufacture method of utilizing the microcapsule with shell that surface reaction obtains.

But, in order to make the hollow resin particulate reach low-refraction fully, must realize high voidage, the particle that obtain with these methods this moment all is that particle diameter is micron-sized particle, can't obtain the hollow resin particulate that has nano level particle diameter, can obtain the high voidage of enough low specific refractory power.

[patent documentation 1] spy opens flat 9-101518 communique

[patent documentation 2] spy opens flat 7-092305 communique

[patent documentation 3] spy opens the 2002-317152 communique

[patent documentation 4] spy opens flat 1-185311 communique

[patent documentation 5] spy opens flat 6-248012 communique

[patent documentation 6] spy opens flat 2-255704 communique

[patent documentation 7] special fair 5-040770 communique

[patent documentation 8] spy opens flat 8-20604 communique

[patent documentation 9] spy opens flat 8-48075 communique

[patent documentation 10] spy opens flat 8-131816 communique

[patent documentation 11] spy opens flat 10-24233 communique

Summary of the invention

In view of above-mentioned present situation, present inventor's purpose is, 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.

Below, the present invention is described in detail.

Hollow resin particulate of the present invention is the hollow form with single hole structure.

So-called single hole structure in this specification sheets does not comprise the situation that vesicular etc. has a plurality of spaces, is meant only have a space.By forming the single hole structure, the stopping property of inside, space is good, for example, with hollow resin particulate of the present invention during as antireflective film, can prevent the reduction of the voidage that causes to the immersion of particle inside owing to binding agent or other composition.

There is gas in inside, space.The preferred air of such gas, but also can be other gas.Because the specific refractory power of air phase is roughly 1.00, therefore, by being set at hollow form, can realize low-down specific refractory power.

Hollow resin particulate of the present invention, the following 10nm of being limited to of its median size, on be limited to 100nm.When it is lower than 10nm, aggegation takes place between the hollow resin particulate, operability is poor.When it surpasses 100nm, with hollow resin particulate of the present invention during as antireflective film for example, produce on antireflective film surface by the hollow resin particulate cause concavo-convex, thereby smoothness is poor, or result from the Rayleigh scattering of hollow resin microparticle surfaces, thereby the transparency of antireflective film is reduced, the portrait whiting.Be limited to 70nm on preferred, be limited to 50nm on preferred.

Hollow resin particulate of the present invention is limited to 1.40 on its specific refractory power.When it surpasses 1.40, under with the situation of hollow resin particulate of the present invention, can not fully be prevented the effect of incident light reflections such as outer light as for example antireflective film, prevent to reflect the thickness of needed antireflective film, become necessary above thickness.Be limited to 1.35 on preferred, be limited to 1.30 on preferred.

Hollow resin particulate of the present invention, the preferred lower limit of its voidage are 30%.When it is lower than 30%, can't realize fully low specific refractory power sometimes.The upper limit of voidage is not particularly limited, but considers from the aspects such as intensity to a certain degree of keeping, guarantee that need shape, and it is limited to 95% on preferably, is limited to 70% on preferred.

Hollow resin particulate of the present invention, the preferred upper limit of the CV of its particle diameter are 20%.When it surpassed 20%, the ratio of the oversize particle that 100nm is above increased, and with hollow resin particulate of the present invention during as antireflective film for example, its transparency, smoothness are poor sometimes, was limited to 15% on preferred.

Hollow resin particulate of the present invention like this can suitably utilize the manufacture method of the hollow resin particulate that has used lipophilicity reacted constituent A described later and wetting ability reacted constituent B to make.The hollow resin particulate of the present invention that utilizes such method manufacturing to form has at least by lipophilicity reacted constituent A and wetting ability reacted constituent B and reacts the outermost layer that the resin that forms constitutes.

Above-mentioned lipophilicity reacted constituent A is not particularly limited, and for example has: polymeric polyisocyanate, epoxy prepolymer, acyl halide etc.

Above-mentioned polymeric polyisocyanate has lipophilicity, and the reaction of wetting ability reacted constituents such as itself and water, amine, polyvalent alcohol, polycarboxylic acid obtains resin.Above-mentioned polymeric polyisocyanate is not particularly limited, and for example has: buret (buret) type, adducts (adduct) type, isocyanuric acid ester type etc.

Need to prove that above-mentioned so-called polymeric polyisocyanate, polyvalent alcohol, polycarboxylic acid are meant that 1 intramolecularly has the compound of a plurality of these functional groups.

Above-mentioned epoxy prepolymer has lipophilicity, and itself and amine or polycarboxylic acid, acid anhydrides, polythiol, reactive modified phenolic resin obtain resin.

Above-mentioned epoxy prepolymer is not particularly limited, and for example has: bisphenol A-type, Resorcinol type, Bisphenol F type, tetraphenyl methane type, phenolic varnish type, polyvalent alcohol type, polyethylene glycol type, glycerine three ether types, glycidyl ether type, glycidyl ester type, glycidic amine type, aliphatics type, ester ring type type, amino-phenol type, hydantoin (ヒ ダ ト イ Application) type, isocyanuric acid ester type, bisphenol type, naphthalene type or these hydrogenation thing, fluorochemical etc.Wherein, preferred fluorinated thing.By using fluorochemical as above-mentioned epoxy prepolymer, can reduce the specific refractory power of hollow resin particulate of the present invention effectively, suppress the immersion to inside, space such as polarizable medium described later.

The epoxy equivalent (weight) of such epoxy prepolymer is not particularly limited, but is limited to 500 on preferred.By being limited to 500 epoxy prepolymer on the use epoxy equivalent (weight), can obtain the resin of the high thermotolerance solvent resistance good strength of degree of crosslinking.Be limited to 200 on preferred.

Be limited to 200 epoxy prepolymer on the epoxy equivalent (weight), be not particularly limited, for example have: エ Port ト-ト YD115, エ Port ト-ト YD127, エ Port ト-ト YD128 (trade(brand)name, all be that Dongdu changes into society's system), エ ピ コ-ト 825, エ ピ コ-ト 827, エ ピ コ-ト 828 (trade(brand)names, all be ジ ヤ パ Application エ Port キ シ レ ジ Application society system), EPICLON840, EPICLON850 bisphenol A type epoxy resins such as (trade(brand)name all are a big Japanese ink chemistry society system); エ Port ト-ト YDF-170, エ Port ト-ト YDF175S (trade(brand)name, all be that Dongdu changes into society's system), エ ピ コ-ト 806, エ ピ コ-ト 807 (trade(brand)names, all be ジ ヤ パ Application エ Port キ シ レ ジ Application society system), EPICLON830, EPICLON835 bisphenol f type epoxy resins such as (trade(brand)name all are a big Japanese ink chemistry society system); エ Port ト-ト YDPN-638, エ Port ト-ト YDCN-701, エ Port ト-ト YDCN-702, エ Port ト-ト YDCN-703, エ Port ト-ト YDCN-704, エ Port ト-ト YDCN-500 (trade(brand)name, all be that Dongdu changes into society's system), エ ピ コ-ト 152, エ ピ コ-ト 154 (trade(brand)names, all be ジ ヤ パ Application エ Port キ シ レ ジ Application society system), phenolic resin varnish type epoxy resin such as EPICLON N-655, EPICLON N-740, EPICLON N-770, EPICLON N-775, EPICLON N-865 (trade(brand)name all is a big Japanese ink society system); エ Port ト-ト YH-434, エ Port ト-ト YH434-L (trade(brand)name, all be that Dongdu changes into society's system), エ ピ コ-ト 1031S, エ ピ コ-ト 1032H60, エ ピ コ-ト 604, エ ピ コ-ト 630 (trade(brand)names, all be ジ ヤ パ Application エ Port キ シ レ ジ Application society system), EPICLON 430 (trade(brand)names, all be big Japanese ink chemistry society system), TETRAD-X, TETRAD-C special multifunctional types such as (trade(brand)name all are the ガ ス of a Mitsubishi chemistry society system); エ ピ コ-ト YX4000, エ ピ コ-ト YL6121H, エ ピ コ-ト YL6640, エ ピ コ-ト YL6677 biphenyl type epoxy resins such as (trade(brand)name all are a ジ ヤ パ Application エ Port キ シ レ ジ Application society system); エ Port ト-ト YH-300, エ Port ト-ト YH-301, エ Port ト-ト YH-315, エ Port ト-ト YH-324, エ Port ト-ト YH-325 aliphatic poly Racemic glycidol ether type epoxies such as (trade(brand)name all are that Dongdu changes into society's system); エ Port ト-ト YDC-1312, エ Port ト-ト YSLV-80XY crystallinity Resins, epoxy such as (trade(brand)name all are that Dongdu changes into society's system); EPICLONHP-4032, EPICLON EXA-4700 naphthalene type Resins, epoxy such as (trade(brand)name all are the chemical society of a big Japanese ink system); エ ピ コ-ト 191P, エ ピ コ-ト YX310 (trade(brand)name all is a ジ ヤ パ Application エ Port キ シ レ ジ Application society system), EPICLON HP-820 specific function type Resins, epoxy such as (trade(brand)name, the chemical society of big Japanese ink systems); EPICLON 725 (trade(brand)name, the chemical society of big Japanese ink system) isoreactivity thinner etc. or these fluorochemical etc.Wherein, preferred fluorinated thing.By using fluorochemical, can reduce the specific refractory power of hollow resin particulate of the present invention effectively, suppress the immersion to inside, space such as polarizable medium described later.

In addition, epoxy equivalent (weight) surpasses the epoxy prepolymer below 200 and 500, be not particularly limited, for example have: エ Port ト-ト YD134, エ Port ト-ト YD011 (trade(brand)name, all be that Dongdu changes into society's system), エ ピ コ-ト 801, エ ピ コ-ト 1001 (trade(brand)names, all be ジ ヤ パ Application エ Port キ シ レ ジ Application society system), EPICLON 860, EPICLON 1050, EPICLON 1055 bisphenol A type epoxy resins such as (trade(brand)name all are a big Japanese ink chemistry society system); エ Port ト-ト YDF-2001 bisphenol f type epoxy resins such as (trade(brand)name, Dongdu change into society's system); EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-695 phenolic resin varnish type epoxy resins such as (trade(brand)name all are the chemical society of a big Japanese ink system); エ ピ コ-ト 157S70 (trade(brand)name, ジ ヤ パ Application エ Port キ シ レ ジ Application society system), EPICLON5500 special multifunctional types such as (trade(brand)name, the chemical society of big Japanese ink systems); エ Port ト-ト YDB-360, エ Port ト-ト YDB-400, エ Port ト-ト YDB-405 (trade(brand)name all is that Dongdu changes into society's system), EPICLON 152, EPICLON 153 brominated epoxy resins such as (trade(brand)name all are the chemical society of a big Japanese ink system); エ Port ト-ト YD-171 (trade(brand)name, Dongdu changes into society's system), エ ピ コ-ト 871 (trade(brand)names, ジ ヤ パ Application エ Port キ シ レ ジ Application society system), EPICLONTSR-960, EPICLON TSR-601 flexible epoxy resins such as (trade(brand)name all are the chemical society of a big Japanese ink system); エ Port ト-ト ST-3000 (trade(brand)name, Dongdu change into society's system), エ ピ コ-ト YX8000, エ ピ コ-ト YX8034 hydrogenation type Resins, epoxy such as (trade(brand)name all are a ジ ヤ パ Application エ Port キ シ レ ジ Application society system); EPICLON HP-7200 dicyclopentadiene-type epoxy resin such as (trade(brand)name, the chemical society of big Japanese ink systems) etc. or these fluorochemical etc.Wherein, preferred fluorinated thing.By using fluorochemical, can reduce the specific refractory power of hollow resin particulate of the present invention effectively, suppress the immersion to inside, space such as polarizable medium described later.

These epoxy prepolymers can use separately, also can two or morely use simultaneously.

Need to prove, epoxy equivalent (weight) surpasses 500 epoxy prepolymer, for example have: エ Port ト-ト YD-012, エ Port ト-ト YD-013, エ Port ト-ト YD-014, エ Port ト-ト YD-017, エ Port ト-ト YD-019 (trade(brand)name, all be that Dongdu changes into society's system), エ ピ コ-ト 1002, エ ピ コ-ト 1003, エ ピ コ-ト 1055, エ ピ コ-ト 1004, エ ピ コ-ト 1007, エ ピ コ-ト 1009, エ ピ コ-ト 1010 (trade(brand)names, all be ジ ヤ パ Application エ Port キ シ レ ジ Application society system), EPICLON 3050, EPICLON 4050, EPICLON AM-020-P, EPICLON AM-030-P, EPICLON AM-040-P, EPICLON 7050, EPICLONHM-091, EPICLONHM-101 bisphenol A type epoxy resins such as (trade(brand)name all are the chemical society of a big Japanese ink system); エ Port ト-ト YDF-2004 (trade(brand)name, Dongdu changes into society's system), エ ピ コ-ト 4004P, エ ピ コ-ト 4007P, エ ピ コ-ト 4010P, エ ピ コ-ト 4110, エ ピ コ-ト 4210 bisphenol f type epoxy resins such as (trade(brand)name all are a ジ ヤ パ Application エ Port キ シ レ ジ Application society system); エ Port ト-ト YDB-405 (trade(brand)name, Dongdu change into society's system), EPICLON1123P-75M brominated epoxy resins such as (trade(brand)name, the chemical society of big Japanese ink systems); エ Port ト-ト YD-172 (trade(brand)name, Dongdu change into society's system), エ ピ コ-ト 872 (trade(brand)name, ジ ヤ パ Application エ Port キ シ レ ジ Application society system), EPICLON 1600-75X flexible epoxy resins such as (trade(brand)name, the chemical society of big Japanese ink systems); エ Port ト-ト ST-4000D hydrogenation type Resins, epoxy such as (trade(brand)name, Dongdu change into society's system); EPICLON 5800 multifunctional type Resins, epoxy such as (trade(brand)name, the chemical society of big Japanese ink systems) etc. or these fluorochemical etc.Wherein, preferred fluorinated thing.By using fluorochemical, can reduce the specific refractory power of hollow resin particulate of the present invention effectively, suppress the immersion to inside, space such as polarizable medium described later.

Above-mentioned acyl halide is not particularly limited, and for example has: dichloride hexanedioyl, dichloride (neighbour) phenyl-diformyl, dichloride paraphenylene terephthalamide, 1, binary acyl halides such as 4-hexanaphthene dicarbapentaborane muriate.

By using aforesaid material as above-mentioned lipophilicity reacted constituent A, hollow resin particulate of the present invention becomes good materials such as thermotolerance, solvent resistance, intensity.

Above-mentioned wetting ability reacted constituent B is not particularly limited, and cooperates with above-mentioned lipophilicity reacted constituent A to carry out suitably determining, so that it reacts the generation resin with above-mentioned lipophilicity reacted constituent A.

Specifically, for example, when using polymeric polyisocyanate as above-mentioned lipophilicity reacted constituent A, above-mentioned wetting ability reacted constituent B is suitable to be used and is selected from least a in one group that water, amine, polyvalent alcohol and polycarboxylic acid constitute.

At this moment, polymeric polyisocyanate and water and/or amine generate polyureas by reaction, and polymeric polyisocyanate and polyvalent alcohol generate urethane by reaction, and polymeric polyisocyanate and polycarboxylic acid generate polymeric amide by reaction.

In addition, for example, when using epoxy prepolymer as above-mentioned lipophilicity reacted constituent A, suitable amine and/or the polycarboxylic acid of using of above-mentioned wetting ability reacted constituent B.

At this moment, epoxy prepolymer and amine, polycarboxylic acid, polythiol and/or resol generate epoxy polymer by reaction.

In addition, for example, when using acyl halide as above-mentioned lipophilicity reacted constituent A, suitable amine, the polyvalent alcohol of using of above-mentioned wetting ability reacted constituent B.

At this moment, acyl halide and amine, polyvalent alcohol generate nylon, polyester by reaction.

Above-mentioned amine is not particularly limited, for example have: fatty amines such as quadrol and affixture thereof, Diethylenetriamine, dipropanetriamine, three second tetramines, tetraethylene-pentamine, dimethylaminopropylamine, diethyl amino propylamine, dibutyl amino propylamine, 1,6-hexanediamine and modification product thereof, N-aminoethyl piperazine, two-aminopropyl piperazine, trimethylhexamethylenediamine, two-hexa-methylene triamine, dicyano diamide, diacetyl acrylamide, various modified aliphatic polyamine, Polypropylene oxide diamine; 3,3 '-dimethyl 4,4 '-diamino-dicyclohexyl methane, 3-amino-1-cyclohexyl aminopropane, 4,4 '-diamino-dicyclohexyl methane, isophorone diamine, 1, cycloaliphatic amines and modifiers thereof such as 3-two (amine methyl) hexanaphthene, N-dimethylcyclohexylamine; 4,4 '-diaminodiphenylmethane (methylene dianiline (MDA)), 4,4 '-diaminodiphenyl oxide, diaminodiphenylsulfone(DDS), mphenylenediamine, 2, aromatic amine and modifiers thereof such as 4 '-tolylene diamine, toluylenediamine, ortho-toluene diamine, MXDP, xylylene diamines; Other special amine modifier, amino amides, polyaminoamides such as amino polyamide resin, the dimethyl amine methylphenol, 2,4,6-three (dimethyl amine methyl) phenol, the tertiary amines and the complex compounds thereof such as three-2 ethyl hexane salt of three (dimethyl amine methyl) phenol, ketoimine, glyoxal ethyline, 2-ethyl-4-methylimidazole, the 2-undecyl imidazole, 2-heptadecyl imidazoles, the 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, the 2-ethyl imidazol(e), 2 isopropyl imidazole, the 1-1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecyl imidazole, 1-cyanoethyl-2 isopropyl imidazole, 1-cyanoethyl-2-phenylimidazole, 1-1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-2-undecyl imidazole trimellitate, the 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2 '-Methylimidazole-(1) ']-ethyl-s-triazine, 2,4-diamino-6-[2 '-undecyl imidazole-(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-glyoxal ethyline muriate, 2 phenyl 4 methyl 5 hydroxy methylimidazole, 2-phenyl-4, the 5-hydroxymethyl-imidazole, 1-cyanoethyl-2-phenyl-4,5-two (cyanogen ethoxyl methyl) imidazoles, glyoxal ethyline and triazine mixture, imidazoles such as 2-phenylimidazole and triazine mixture; The amino affixture of hydrazides classes such as isophthalic dihydrazide, adipic dihydrazide, sebacic dihydrazide, Resins, epoxy etc. contains amino prepolymer etc.

Above-mentioned polyvalent alcohol is not particularly limited, for example have: ethylene glycol, 1,4-butyleneglycol, 2,3-butyleneglycol, catechol, Resorcinol, quinhydrones, neighbour-xylenediol, 4,4 '-dioxydiphenyl methane, 2,2-two (4-hydroxyphenyl)-propane, 1,1, hydroxyl polymer-containings such as 1-TriMethylolPropane(TMP), polyvinyl alcohol, poly-hydroxyl-metacrylate, polyoxyethylene glycol, poly-hydroxyl propylene glycol, poly-hydroxy alkylidene glycol etc.

Above-mentioned polycarboxylic acid is not particularly limited, for example can enumerate and contain 10 weight % above oxalic acid, hexanodioic acid, nonane diacid, sebacic acid, propanedioic acid, succsinic acid, 1, the 4-cyclohexyl dicarboxylic acid, (adjacent-,-, right-) any polymers copolymers etc. such as benzene dicarboxylic acid, toxilic acid, methylene-succinic acid, vinylformic acid, methyl methacrylate.

By using aforesaid material as above-mentioned wetting ability reacted constituent B, hollow resin particulate of the present invention becomes good materials such as thermotolerance, solvent resistance, intensity.

The outermost layer of hollow resin particulate of the present invention, according to the combination of above-mentioned lipophilicity reacted constituent A and above-mentioned wetting ability reacted constituent B, preferably contain at least a resin in a group that is selected from polyureas, urethane, polymeric amide, polyester, nylon and epoxy polymer formation.

And hollow resin particulate of the present invention preferably contains by the crosslinked resin that forms of inorganic components.Hollow resin particulate of the present invention like this has inorganic skeleton in its structure, and thermotolerance and solvent resistance are good, can effectively prevent the immersion of binding agent composition to the space simultaneously.

Like this by the crosslinked resin that forms of inorganic components, the silane coupling agent that functional group that for example can be by making the resin that contains in the hollow resin particulate of the present invention and inside configuration have epoxy group(ing), isocyanate group, urea groups, amino, sulfydryl, halogen reacts and obtains.

Hollow resin particulate of the present invention like this with single hole structure, can utilize following method to make aptly, this method has: in the polarizable medium that contains above-mentioned wetting ability reacted constituent B, the polymerizability drop that contains above-mentioned lipophilicity reacted constituent A is disperseed, the operation of preparation dispersion liquid; And the operation that above-mentioned lipophilicity reacted constituent A and above-mentioned wetting ability reacted constituent B are reacted.

The manufacture method of such hollow resin particulate also is one of the present invention.

The manufacture method of hollow resin particulate of the present invention has: in the polarizable medium that contains above-mentioned wetting ability reacted constituent B, the polymerizability drop that contains above-mentioned lipophilicity reacted constituent A is disperseed, the operation of preparation dispersion liquid.

In the manufacture method of hollow resin particulate of the present invention, also can in above-mentioned lipophilicity reacted constituent A, cooperate the non-polymerization compound.

Above-mentioned non-polymerization compound has following effect: form stable polymerizability drop or the speed of response of control lipophilicity reacted constituent A and wetting ability reacted constituent B in polarizable medium.In addition, by in above-mentioned lipophilicity reacted constituent A, cooperating the non-polymerization compound, in the resin particle that the aftermentioned operation prepares, wrap and state non-polymerization compound (and unreacted lipophilicity reacted constituent A), by from such resin particle, removing above-mentioned non-polymerization compound (and unreacted lipophilicity reacted constituent A), can make the hollow resin particulate of high voidage.

Above-mentioned non-polymerization compound, so long as under the temperature of reaction of above-mentioned lipophilicity reacted constituent A and wetting ability reacted constituent B, be aqueous, can mix with lipophilicity reacted constituent A, and discord lipophilicity reacted constituent A reaction, and by the materials that can easily evapotranspire such as heating, just be not particularly limited, for example have: butane, pentane, hexane, hexanaphthene, toluene, dimethylbenzene, octane, nonane, decane, undecane, dodecane, tridecane, the tetradecane, pentadecane, n-Hexadecane, heptadecane, octadecane, nonadecane, eicosane, ethyl acetate, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), Methyl amyl ketone, diisobutyl ketone, methyl chloride, methylene dichloride, chloroform, organic solvents such as tetracol phenixin etc.Above-mentioned non-polymerization compound can use separately, also can two or morely use simultaneously.

In above-mentioned non-polymerization compound, because the higher alkane hydrocarbon and the long-chain shape hydrophobic compound of carbon numbers about 8～20 such as octane, nonane, decane, undecane, dodecane, tridecane, the tetradecane, pentadecane, n-Hexadecane, heptadecane, octadecane, nonadecane, eicosane, can suppress effectively that the polymerizability drop integrates in the polarizable medium, therefore when suitably also with these non-polymerization compounds and the non-polymerization compound beyond these, can stably form nano level polymerizability drop.

The use level of above-mentioned non-polymerization compound is not particularly limited, above-mentioned relatively lipophilicity reacted constituent A90 weight part, and it preferably is limited to 10 weight parts down, is limited to 1000 weight parts on preferred.When it is lower than 10 weight parts; the voidage step-down of the hollow resin particulate that obtains sometimes; can't realize sufficient low-refraction; when it surpasses 1000 weight parts; can't keep particle shape when removing the non-polymerization compound sometimes, can not get the hollow resin particulate or the intensity extreme difference of the hollow resin particulate that obtains.

Above-mentioned polarizable medium is not particularly limited, and for example has: the material that uses in the common suspension polymerization such as water, ethanol, methyl alcohol, Virahol etc.Need to prove, when above-mentioned lipophilicity reacted constituent A is polymeric polyisocyanate, the function that water that uses as polarizable medium and/or ethanol self also play wetting ability reacted constituent B.

The compound method of above-mentioned dispersion liquid is not particularly limited, and can use existing known method, for example can use the emulsifier unit of high shear force and the dispersion liquid of preparation of nano level polymerizability drop aptly.The emulsifier unit of such high shear force for example has: omnidirectional's mixing tank, ultrasonic homogenizer, ultra micron dispersion, emulsifier unit (マ イ Network ロ Off Le イ ダ イ ザ-) etc.

When preparing above-mentioned dispersion liquid, can in above-mentioned polarizable medium, add various additives, for example have: anionic emulsifiers such as Sodium Lauryl Sulphate BP/USP, higher alcohol sulfate, triethanolamine lauryl sulfate, Texapon Special, polyethylene oxide bay ether sodium sulfate, polyethylene oxide alkyl ethers sodium sulfate, polyethylene oxide alkyl ethers sulfuric acid trolamine, Sodium dodecylbenzene sulfonate, sodium alkyl naphthalene sulfonate, dialkyl sodium sulfosuccinate, alkyl diphenyl ether disulphonic acid sodium, polyethylene oxide alkyl ethers potassiumphosphate, alkenyl succinic dipotassium, alkane sulfonate; Polyethylene oxide bay ether, the polyethylene oxide cetyl ether, polyethylene oxide octadecyl ether, polyethylene oxide oleyl ether, the polyethylene oxide myristyl ether, polyethylene oxide alkyl ethers, the senior alcohol ether of polyethylene oxide, polyethylene oxide alkylidene group alkyl oxide, polyethylene oxide toluylene phenyl ether, Span-20, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, the polyethylene oxide Span-20, polyethylene oxide sorbitan laurate, the polyethylene oxide sorbitan monopalmitate, the polyethylene oxide sorbitan monostearate, the polyethylene oxide sorbitan tristearate, the polyethylene oxide sorbitan monooleate, the polyethylene oxide sorbitan trioleate, Zerol, Zerol, non-ionic emulsifiers such as glyceryl monooleate; Cationic emulsifiers such as lauryl trimethyl ammonium chloride, stearyl-trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, stearyl-trimethyl ammonium chloride, distearyl acyl group alkyl dimethyl ammonium chloride, alkyl benzyl ammonio methacrylate; Amphoteric emulsifiers such as lauryl betaine, stearyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazole trimethyl-glycine, lauryl dimethyl amine oxide; Macromolecule dispersing agent such as partly-hydrolysed polyvinyl acetate, derivatived cellulose, poly-(methyl) vinylformic acid, poly-(methyl) acrylic copolymer, polyvinylpyrrolidone, polyacrylamide, マ リ ア リ system, polystyrolsulfon acid and cetyl alcohol etc. disperse auxiliary agent.

Above-mentioned so-called polymerizability drop instigates above-mentioned lipophilicity reacted constituent A uniform dissolution to form.The manufacture method of above-mentioned polymerizability drop is not particularly limited, and for example has: after other lipophilicity composition metering mixing such as additive with above-mentioned lipophilicity reacted constituent A and interpolation as required, be stirred to methods such as its uniform dissolution.

In order stably to form nano level polymerizability drop, when higher alkane hydrocarbon, long-chain shape hydrophobic compound and the non-polymerization compound beyond these with carbon number about 8～20 use simultaneously, total amount 100 weight parts of relative lipophilicity reacted constituent A and non-polymerization compound, the preferred lower limit of its proportioning is 0.1 weight part.When it is lower than 0.1 weight part, can not effectively suppress integrating of polymerizability drop sometimes.

The manufacture method of hollow resin particulate of the present invention has: the operation that makes above-mentioned lipophilicity reacted constituent A and above-mentioned wetting ability reacted constituent B reaction.

For example, make its temperature of reaction that becomes above-mentioned lipophilicity reacted constituent A and above-mentioned wetting ability reacted constituent B, above-mentioned lipophilicity reacted constituent A and the above-mentioned wetting ability reacted constituent B generation resin that reacts by heating above-mentioned dispersion liquid.At this moment, because comprising the above-mentioned polymerizability drop of above-mentioned lipophilicity reacted constituent A is separated with the above-mentioned polarizable medium that comprises above-mentioned wetting ability reacted constituent B, therefore, reaction only takes place at the near interface of above-mentioned polymerizability drop and above-mentioned polarizable medium, makes the hollow resin particulate of the present invention with the shell that is made of the resin that generates.

In the manufacture method of such hollow resin particulate of the present invention, the hollow resin particulate of manufacturing wraps unreacted above-mentioned lipophilicity reacted constituent A sometimes.At this moment, the manufacture method of hollow resin particulate of the present invention also preferably has the operation that the above-mentioned unreacted above-mentioned lipophilicity reacted constituent A with interior bag removes.

From the interior method of removing above-mentioned unreacted above-mentioned lipophilicity reacted constituent A the hollow resin particulate of stating unreacted above-mentioned lipophilicity reacted constituent A of wrapping, be not particularly limited, for example have: the method that in the dispersion liquid of the hollow resin particulate that obtains, is blown into gases such as nitrogen, air; Above-mentioned hollow resin particulate is heated to the method more than the boiling point of solvent of unreacted lipophilicity reacted constituent A and use; The method that total system is reduced pressure; With unreacted lipophilicity reacted constituent A with solvent-extracted method etc.

The above-mentioned solvent that uses during with solvent extraction, so long as can and the lipophilicity reacted constituent A blended solvent that suits, just be not particularly limited, for example, can suit to use aforesaid non-polymerization compound etc.

According to the manufacture method of such hollow resin particulate of the present invention, can make the following 10nm of being limited to single hole structure, median size aptly, be limited to 100nm and specific refractory power down is hollow resin particulate of the present invention below 1.40.

Have the single hole structure, having in the composite shell hollow resin particulate that is made of outermost layer and 2 layers of resin layer of la m at least, voidage is that the hollow resin particulate more than 30% also is one of content of the present invention.Below, the hollow resin particulate that will be referred to is called the hollow resin particulate of the present invention of the 2nd form.

The hollow resin particulate of the present invention of the 2nd form has the single hole structure, has the composite shell that is made of outermost layer and 2 layers of resin layer of la m at least.

By making the particle shell is the composite shell that is made of outermost layer and 2 layers of resin layer of la m at least, can make above-mentioned particle shell have multiple function, can obtain voidage height, hollow resin particulate that specific refractory power is low effectively.For example, though with by the specific refractory power height but the outermost layer that the resinous principle of thermotolerance, solvent resistance, good strength constitutes, though with by thermotolerance, solvent resistance, intensity difference but the hollow resin particulate that the la m that the low resinous principle of specific refractory power constitutes constitutes, can improve thermotolerance etc. and also can improve voidage, reduce the specific refractory power of hollow resin particulate integral body.In addition, by the resinous principle of suitable selection formation outermost layer, la m, can give specific refractory power, polarity, crystallinity, thermotolerance, solvent resistance, intensity, weathering resistance, the transparency etc. to the hollow resin particle arbitrarily.

The hollow resin particulate of the present invention of the 2nd form is the hollow form with single hole structure.

By forming the single hole structure, become the good material of the inner stopping property in space, for example, with the hollow resin particulate of the present invention of the 2nd form during, can prevent because the reduction of the voidage that binding agent and other composition cause to the immersion of particle inside as antireflective film.

In addition, there is gas in inside, space.The preferred air of such gas, but also can be other gas.Because the specific refractory power of air phase is roughly 1.00, therefore, by being set at hollow form, can realize low-down specific refractory power.

The hollow resin particulate of the present invention of the 2nd form, the following of its voidage is limited to 30%.When it is lower than 30%, can't fully realize low-refraction.The upper limit of voidage is not particularly limited, but keeps shape and guarantee that intensity aspect to a certain degree considers from needs, and it is limited to 95% on preferably, is limited to 70% on preferred.

The hollow resin particulate of the present invention of the 2nd form, the preferred lower limit of its median size are that 10nm, preferred upper limit are 100nm.When it is lower than 10nm, between the hollow resin particulate of the present invention of the 2nd form aggegation takes place sometimes, operability is poor.When it surpasses 100nm, with the hollow resin particulate of the present invention of the 2nd form during as antireflective film for example, sometimes surperficial at antireflective film owing to the hollow resin particulate causes concavo-convex generation, thereby smoothness is poor, or result from the Rayleigh scattering of hollow resin microparticle surfaces, thereby the transparency of antireflective film is reduced, the portrait whiting.Be limited to 70nm on preferred, be limited to 50nm on further preferred.

The hollow resin particulate of the present invention of the 2nd form, the preferred upper limit of its specific refractory power is 1.40.When it surpasses 1.40, the hollow resin particulate of the present invention of the 2nd form during as antireflective film for example, can not fully be prevented the effect of incident light reflections such as outer light, the thickness that prevents to reflect needed antireflective film becomes the thickness more than necessary.Be limited to 1.35 on preferred, be limited to 1.30 on further preferred.

The hollow resin particulate of the present invention of the 2nd form, the preferred upper limit of the CV of its particle diameter is 20%.When it surpassed 20%, the ratio of the oversize particle that 100nm is above increased, and with the hollow resin particulate of the present invention of the 2nd form during for example as antireflective film, its transparency, smoothness are poor sometimes.Be limited to 15% on preferred.

The hollow resin particulate of the present invention of the 2nd form like this can utilize and use lipophilicity reacted constituent A described later and wetting ability reacted constituent B and make aptly with the method for lipophilicity reacted constituent A and the nonreactive lipophilicity reacted constituent of wetting ability reacted constituent B C.Utilize the hollow resin particulate of the present invention of the 2nd form that such method manufacturing forms, its outermost layer is made of the resin that lipophilicity reacted constituent A and wetting ability reacted constituent B reaction forms, and its la m is made of the resin that forms with above-mentioned lipophilicity reacted constituent A and the nonreactive lipophilicity reacted constituent of above-mentioned wetting ability reacted constituent B C reaction.The hollow resin particulate of the present invention of the 2nd form of such structure by adjusting the formation of outermost layer and la m, can be realized above-mentioned median size, voidage and specific refractory power etc.

Above-mentioned lipophilicity reacted constituent A and above-mentioned wetting ability reacted constituent B are not special to be selected, and for example has: and the lipophilicity reacted constituent A and the same material of above-mentioned wetting ability reacted constituent B that in above-mentioned hollow resin particulate of the present invention, carried out explanation.

The outermost layer of the hollow resin particulate of the present invention of the 2nd form, according to the combination of above-mentioned lipophilicity reacted constituent A and above-mentioned wetting ability reacted constituent B, preferably contain at least a resin in a group that is selected from polyureas, urethane, polymeric amide, polyester, nylon and epoxy polymer formation.

In addition, the outermost layer of the hollow resin particulate of the present invention of the 2nd form preferably contains by the crosslinked resin that forms of inorganic components.The hollow resin particulate of the present invention of the 2nd form like this has inorganic skeleton in its outermost layer, and thermotolerance and solvent resistance are good, can effectively prevent the immersion of binding agent composition to the space simultaneously.

Like this by the crosslinked resin that forms of inorganic components, the silane coupling agent that unreacted functional group that can be by the resin that comprises in the hollow resin particulate of the present invention that for example makes the 2nd form and inside configuration have epoxy group(ing) or isocyanate group, urea groups, amino, sulfydryl, a halogen reacts and obtains.

Above-mentioned lipophilicity reacted constituent C, so long as and above-mentioned lipophilicity reacted constituent A and the nonreactive material of wetting ability reacted constituent B, just be not particularly limited, consider from aspects such as the selection of reacted constituent are extensive, easy and simple to handle, be fit to use free radical polymerization monomer.

Above-mentioned free radical polymerization monomer is not particularly limited, and for example has: (methyl) alkyl acrylates such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid myristin, (methyl) vinylformic acid palmityl ester, (methyl) stearyl acrylate acyl ester, (methyl) isobornyl acrylate; (methyl) vinyl cyanide, (methyl) acrylamide, (methyl) vinylformic acid, (methyl) glycidyl acrylate, 2-hydroxyethyl methacrylate, methacrylic acid-2-hydroxypropyl acrylate etc. contain polar group (methyl) acrylic monomer; Vinylbenzene, alpha-methyl styrene, p-methylstyrene, right-aromatic vinyl monomers such as chloro-styrene; Vinyl ester such as vinyl-acetic ester, propionate; Halogen such as vinylchlorid, vinylidene chloride monomer; Simple function monomers such as vinyl pyridine, phthalic acid 2-acryloyl hydroxyl ethyl ester, methylene-succinic acid, fumaric acid, ethene, propylene, the little monomer of polydimethylsiloxane; Ethylene glycol bisthioglycolate (methyl) acrylate, glycol ether two (methyl) acrylate, triglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, TriMethylolPropane(TMP) two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, oxyethane modification trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, Phthalic acid, diallyl ester, diallyl maleate, diallyl fumarate, the Succinic Acid diallyl, cyanacrylate, Vinylstyrene, multi-functional monomer such as divinyl etc.

These lipophilicity reacted constituents C can use separately, also can two or morely use simultaneously.

In addition, in the hollow resin particulate of the present invention of the 2nd form, above-mentioned lipophilicity reacted constituent C also can use the fluorinated monomer.By using the fluorinated monomer, can reduce the specific refractory power of the hollow resin particulate of the present invention of the 2nd form effectively, suppress the immersion to inside, space such as polarizable medium described later.

These fluorinated monomers are not particularly limited, and for example have: vinyl fluoride, vinylidene, tetrafluoroethylene, R 1216, perfluor-2,2-dimethyl-1, the luxuriant fluoroolefins hydro carbons that waits of 3-Er Evil; (methyl) acrylic acid part of following general formulas (1) such as trifluoroethyl methacrylate, (methyl) vinylformic acid perfluoro capryl ethyl ester expression or complete fluorinated alkyl esters derivatives class or (methyl) acrylic acid part or complete fluorinated vinyl ethers etc.

[changing 1]

In the formula, R ¹Expression hydrogen atom, methyl or fluorine atom, m, n represent natural number.

When using free radical polymerization monomer, preferably contain radical polymerization initiator as catalysts as above-mentioned lipophilicity reacted constituent C.

Above-mentioned radical polymerization initiator is not particularly limited, for example have: ditertiary butyl peroxide, dicumyl peroxide, ditertiary butyl peroxide, the di-tert-butyl peroxide carbonic ether, tert-butyl hydroperoxide lauroyl ester, tert butyl peroxy benzoate (ベ Application ゾ ネ-ト), tert-butyl hydroperoxide-2-ethylhexanoate, tert-butyl hydroperoxide sec.-propyl one carbonic ether, uncle's hexyl peroxide benzoate, 1,1-two (tert-butyl hydroperoxide)-3,5, the 5-trimethyl cyclohexane, 1,1-two (tert-butyl hydroperoxide)-2-methylcyclohexane, 1, various ketone peroxides such as 1-two (tert-butyl hydroperoxide) hexanaphthene and benzoyl peroxide, ketal peroxide, hydrogen peroxide, dialkyl peroxide, diacyl peroxide, peroxy dicarbonate, peroxycarbonates, organic class superoxide such as peroxy esters; 2,2 '-azo two (4-methoxyl group-2, the 4-methyl pentane nitrile), 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (2-methyl propionitrile), 2,2 '-azo two (2-methylbutyronitrile), 1,1 '-azo two (hexanaphthene-1-carbon nitrile), 2,2 '-azo two [N-(2-propenyl)-2-methyl propanamide], 2,2 '-azo two (N-butyl-2-methyl propanamide), 2,2 '-azo two (N-cyclohexyl-2-methyl propanamide), dimethyl-2,2 '-azo two (2 Methylpropionic acid ester), 2,2 '-azo two (2,4, the 4-trimethylpentane), VPS-0501 (trade(brand)name, with the pure pharmaceutical worker's industry of light society system), VPS-1001 azo-initiators such as (the pure pharmaceutical worker's industry of trade(brand)name and light society systems); Redox initiator etc.

By using aforesaid material as above-mentioned lipophilicity reacted constituent C, the hollow resin particulate of the present invention of the 2nd form becomes the material of low-refraction.

The use level of above-mentioned lipophilicity reacted constituent C is not particularly limited, above-mentioned relatively lipophilicity reacted constituent A100 weight part, and it preferably is limited to 1 weight part down, is limited to 1000 weight parts on preferred.When it is lower than 1 weight part; sometimes can't give stopping property as target, specific refractory power, polarity, crystallinity etc. fully to the hollow resin particulate that obtains; when it surpasses 1000 weight parts, can't keep particle shape sometimes, can not get the hollow resin particulate or the intensity extreme difference of the hollow resin particulate that obtains.

The hollow resin particulate of the present invention of the 2nd form, its above-mentioned outermost layer and above-mentioned la m are closed states.This can pass through electron microscope (NEC society system, " JEM-1200EXII ") and wait and confirm.

The hollow resin particulate of the present invention of the 2nd form like this, can utilize following method to make aptly, this method has: in the polarizable medium that contains above-mentioned wetting ability reacted constituent B, the polymerizability drop that contains lipophilicity reacted constituent A and lipophilicity reacted constituent C is disperseed, the operation of preparation dispersion liquid; Make the above-mentioned lipophilicity reacted constituent A on above-mentioned polymerizability drop surface and the above-mentioned wetting ability reacted constituent B reaction in the above-mentioned polarizable medium, form outermost operation on above-mentioned polymerizability drop surface; And the above-mentioned lipophilicity reacted constituent C of above-mentioned polymerizability drop inside is reacted, form the operation of la m.The manufacture method of the hollow resin particulate of the present invention of the 2nd form so also is one of the present invention.Below, such manufacture method is called the manufacture method of the hollow resin particulate of the present invention of the 2nd form.

The manufacture method of the hollow resin particulate of the present invention of the 2nd form has: in the polarizable medium that contains above-mentioned wetting ability reacted constituent B, the polymerizability drop that contains above-mentioned lipophilicity reacted constituent A and lipophilicity reacted constituent C is disperseed, the operation of preparation dispersion liquid.

Prepare the order of above-mentioned dispersion liquid, be not particularly limited, can in above-mentioned polarizable medium, add above-mentioned wetting ability reacted constituent B after, the polymerizability drop that contains above-mentioned lipophilicity reacted constituent A and lipophilicity reacted constituent C is disperseed; After the polymerizability drop that contains above-mentioned lipophilicity reacted constituent A and lipophilicity reacted constituent C is disperseed, add above-mentioned wetting ability reacted constituent B.

Above-mentioned polarizable medium is not particularly limited, the material that can use for example water, ethanol, methyl alcohol, Virahol etc. to use in the suspension polymerization etc. usually.Need to prove that when above-mentioned lipophilicity reacted constituent A was polymeric polyisocyanate, water that uses as polarizable medium and/or ethanol self is the function of possess hydrophilic property reacted constituent B also.

The compound method of above-mentioned dispersion liquid is not particularly limited, and for example can use the emulsifier unit of high shear force and the dispersion liquid of preparation of nano level polymerizability drop aptly.The emulsifier unit of such high shear force for example has: omnidirectional's mixing tank, ultrasonic homogenizer, ultra micron dispersion, emulsifier unit etc.

When preparing above-mentioned dispersion liquid, can in above-mentioned polarizable medium, add various additives, for example have: anionic emulsifiers such as Sodium Lauryl Sulphate BP/USP, higher alcohol sulfate, triethanolamine lauryl sulfate, Texapon Special, polyethylene oxide bay ether sodium sulfate, polyethylene oxide alkyl ethers sodium sulfate, polyethylene oxide alkyl ethers sulfuric acid trolamine, Sodium dodecylbenzene sulfonate, sodium alkyl naphthalene sulfonate, dialkyl sodium sulfosuccinate, alkyl diphenyl ether disulphonic acid sodium, polyethylene oxide alkyl ethers potassiumphosphate, alkenyl succinic dipotassium, alkane sulfonate; Polyethylene oxide bay ether, the polyethylene oxide cetyl ether, polyethylene oxide octadecyl ether, polyethylene oxide oleyl ether, the polyethylene oxide myristyl ether, polyethylene oxide alkyl ethers, the senior alcohol ether of polyethylene oxide, polyethylene oxide alkylidene group alkyl oxide, polyethylene oxide toluylene phenyl ether, Span-20, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, the polyethylene oxide Span-20, polyethylene oxide sorbitan laurate, the polyethylene oxide sorbitan monopalmitate, the polyethylene oxide sorbitan monostearate, the polyethylene oxide sorbitan tristearate, the polyethylene oxide sorbitan monooleate, the polyethylene oxide sorbitan trioleate, Zerol, Zerol, non-ionic emulsifiers such as glyceryl monooleate; Cationic emulsifiers such as lauryl trimethyl ammonium chloride, stearyl-trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, stearyl-trimethyl ammonium chloride, distearyl acyl group alkyl dimethyl ammonium chloride, alkyl benzyl ammonio methacrylate; Amphoteric emulsifiers such as lauryl betaine, stearyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazole trimethyl-glycine, lauryl dimethyl amine oxide; Macromolecule dispersing agent such as partly-hydrolysed polyvinyl acetate, derivatived cellulose, poly-(methyl) vinylformic acid, poly-(methyl) acrylic copolymer, polyvinylpyrrolidone, polyacrylamide, マ リ ア リ system, polystyrolsulfon acid and cetyl alcohol etc. disperse auxiliary agent.

Above-mentioned so-called polymerizability drop is the material of instigating above-mentioned lipophilicity reacted constituent A and lipophilicity reacted constituent C uniform dissolution to form.The manufacture method of above-mentioned polymerizability drop is not particularly limited, for example have: after other lipophilicity composition metering mixing such as above-mentioned radical polymerization initiator with above-mentioned lipophilicity reacted constituent A and lipophilicity reacted constituent C and interpolation as required, be stirred to methods such as its uniform dissolution.

In the above-mentioned polymerizability drop, the preferred interpolation cooperates the non-polymerization compound.Above-mentioned non-polymerization compound has following effect: form stable polymerizability drop or the speed of response of control lipophilicity reacted constituent A and wetting ability reacted constituent B in polarizable medium.In addition, by in above-mentioned polymerizability drop, adding the non-polymerization compound, in the resin particle of aftermentioned operation preparation, wrap and state non-polymerization compound (and unreacted lipophilicity reacted constituent A), by from such resin particle, removing non-polymerization compound (and unreacted lipophilicity reacted constituent A), can make the hollow resin particulate of high voidage.

As above-mentioned non-polymerization compound, so long as under the temperature of reaction of above-mentioned lipophilicity reacted constituent A and wetting ability reacted constituent B, be aqueous, can mix with lipophilicity reacted constituent A and lipophilicity reacted constituent C, and discord lipophilicity reacted constituent A and lipophilicity reacted constituent C reaction, and by the materials that can evapotranspire at an easy rate such as heating, just be not particularly limited, for example have: butane, pentane, hexane, hexanaphthene, toluene, dimethylbenzene, octane, nonane, decane, undecane, dodecane, tridecane, the tetradecane, pentadecane, n-Hexadecane, heptadecane, octadecane, nonadecane, eicosane, ethyl acetate, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), Methyl amyl ketone, diisobutyl ketone, methyl chloride, methylene dichloride, chloroform, organic solvents such as tetracol phenixin etc.

Above-mentioned non-polymerization compound can use separately, also can two or morely use simultaneously.

In above-mentioned non-polymerization compound, the polymerizability drop integrates in the polarizable medium because higher alkane hydrocarbon, the long-chain shape hydrophobic compound of carbon numbers about 8～20 such as octane, nonane, decane, undecane, dodecane, tridecane, the tetradecane, pentadecane, n-Hexadecane, heptadecane, octadecane, nonadecane, eicosane can effectively suppress, therefore when suitably also with these non-polymerization compounds and the non-polymerization compound beyond these, can stably form nano level polymerizability drop.

The use level of above-mentioned non-polymerization compound is not particularly limited, above-mentioned relatively lipophilicity reacted constituent A and above-mentioned lipophilicity reacted constituent C90 weight part, and it preferably is limited to 10 weight parts down, is limited to 1000 weight parts on preferred.When it is lower than 10 weight parts; the voidage step-down of the hollow resin particulate that obtains sometimes; can't realize sufficient low-refraction; when it surpasses 1000 weight parts; can't keep particle shape when removing the non-polymerization compound sometimes, can not get the hollow resin particulate or the intensity extreme difference of the hollow resin particulate that obtains.

In order stably to form nano level polymerizability drop, when higher alkane hydrocarbon, long-chain shape hydrophobic compound and the non-polymerization compound beyond these with carbon number about 8～20 use simultaneously, total amount 100 weight parts of relative lipophilicity reacted constituent A and lipophilicity reacted constituent C and non-polymerization compound, the preferred lower limit of its proportioning is 0.1 weight part.When it is lower than 0.1 weight part, can not effectively suppress integrating of polymerizability drop sometimes.

The manufacture method of the hollow resin particulate of the present invention of the 2nd form has: make the above-mentioned lipophilicity reacted constituent A on above-mentioned polymerizability drop surface and the above-mentioned wetting ability reacted constituent B reaction in the above-mentioned polarizable medium, form outermost operation on above-mentioned polymerizability drop surface.

Make its temperature of reaction that becomes above-mentioned lipophilicity reacted constituent A and above-mentioned wetting ability reacted constituent B by heating above-mentioned dispersion liquid, above-mentioned lipophilicity reacted constituent A and above-mentioned wetting ability reacted constituent B are reacted, generate resin.

At this moment, because comprising the above-mentioned polymerizability drop of above-mentioned lipophilicity reacted constituent A is separated with the above-mentioned polarizable medium that comprises above-mentioned wetting ability reacted constituent B, therefore, reaction only takes place at the near interface of above-mentioned polymerizability drop and above-mentioned polarizable medium, form have the outermost layer that constitutes by the resin that generates, in comprise the resin particle of lipophilicity reacted constituent C.

The manufacture method of the hollow resin particulate of the present invention of the 2nd form has: make the above-mentioned lipophilicity reacted constituent C reaction of above-mentioned polymerizability drop inside, form the operation of la m.

Make its temperature of reaction that becomes above-mentioned lipophilicity reacted constituent C by heating above-mentioned dispersion liquid, above-mentioned lipophilicity reacted constituent C is reacted.

As mentioned above, the reaction of above-mentioned lipophilicity reacted constituent A and above-mentioned wetting ability reacted constituent B, only the near surface at above-mentioned polymerizability drop and above-mentioned polarizable medium takes place, form outermost layer, event is by the resin formation la m of the reaction generation of above-mentioned lipophilicity reacted constituent C, and manufacturing has the hollow resin particulate of the composite shell that is made of outermost layer and 2 layers of resin layer of la m.

Need to prove, form the operation of above-mentioned la m, by utilizing control such as above-mentioned catalysts reaction conditions, can be before, during and after forming above-mentioned outermost operation arbitrary stage carry out.

In the manufacture method of the hollow resin particulate of the present invention of the 2nd such form, the hollow resin particulate of manufacturing sometimes in unreacted lipophilicity reacted constituent A of bag and unreacted lipophilicity reacted constituent C.At this moment, the manufacture method of the hollow resin particulate of the present invention of the 2nd form also preferably has the operation that above-mentioned unreacted lipophilicity reacted constituent A and unreacted lipophilicity reacted constituent C with interior bag remove.

The unreacted lipophilicity reacted constituent A of bag and the method for unreacted lipophilicity reacted constituent C are not particularly limited in removing in the above-mentioned resin particle, for example have: the method that is blown into gases such as nitrogen, air in the dispersion liquid of the hollow resin particulate that obtains; The hollow resin particulate is heated to the method more than the boiling point of unreacted lipophilicity reacted constituent A and unreacted lipophilicity reacted constituent C; The method that total system is reduced pressure; With unreacted lipophilicity reacted constituent A and unreacted lipophilicity reacted constituent C with solvent-extracted method etc.

The solvent that uses during above-mentioned extraction, so long as and the solvent that mixes of lipophilicity reacted constituent A and lipophilicity reacted constituent C, just be not particularly limited, be fit to use above-mentioned non-polymerization compound etc.

Need to prove, utilize this operation, also can remove the solvent of interior bag in the above-mentioned resin particle.

According to the manufacture method of the hollow resin particulate of the present invention of the 2nd such form, can make aptly that to have the composite shell, the voidage that are made of outermost layer and 2 layers of resin layer of la m at least be the hollow resin particulate of the present invention of the 2nd form more than 30%.

Having organic backbone and inorganic skeleton, specific refractory power and be organic-inorganic hybrid fine particles below 1.40 (below, be also referred to as hybrid fine particles of the present invention), also is one of the present invention.

Hybrid fine particles of the present invention like this is because the grid that organic backbone forms makes alkali resistance good.Therefore, for example, the antireflective film that uses such hybrid fine particles of the present invention to make is even use when the wiping spot under the situation of commercially available alkalis etc., the hybrid fine particles of the present invention that contains can not be dissolved in alkalis yet, can not reduce as the performance of antireflective film yet.In addition, hybrid fine particles of the present invention, by having inorganic skeleton, its thermotolerance and solvent resistance are good, when using hybrid fine particles of the present invention to make antireflective film, when when its film forming, using solvent etc., even the hybrid fine particles of the present invention hollow structure that has the space in inside described later also can effectively prevent because of solvent makes that the softening space that causes of particulate skeleton is shunk, the binding agent composition is to the immersion in space.And, because by making inside have air phase (specific refractory power=1.00), can reduce specific refractory power effectively, therefore, for example also can reduce the specific refractory power of the antireflective film that the coating-forming agent that uses the hybrid fine particles that contains such low-refraction forms.

Be limited to 1.40 on the specific refractory power of hybrid fine particles of the present invention.When it surpasses 1.40, when hybrid fine particles of the present invention for example is used as antireflective film, can not fully be prevented the effect of incident light reflections such as outer light, prevent that the thickness that reflects needed antireflective film from becoming necessary above thickness.Be limited to 1.35 on preferred, be limited to 1.30 on preferred.

Hybrid fine particles of the present invention like this, preferred inside has the hollow structure in space.Have the space by inside, the low-refraction of hybrid fine particles of the present invention can be lower.

When hybrid fine particles of the present invention inside had the space, the preferred lower limit of voidage was 30%.When it is lower than 30%, can't fully realize low-refraction sometimes.The preferred upper limit of voidage is not particularly limited, but from the keeping and must guarantee that its intensity aspect to a certain degree considers of shape, it is limited to 95% on preferably, is limited to 70% on preferred.

The synthetic method of the hybrid fine particles of such hollow structure, be not particularly limited, can use following suitable polymerization process to synthesize, for example have: use inside configuration to have the polymerizability silane coupling agent of vinyl and letex polymerization, the letex polymerization of dropping type, emulsifier-free emulsion polymerization, micro emulsion polymerization, miniemulsion polymerization, the microsuspension of non-polymerization organic solvent; Used inside configuration to have the surface aggregate etc. of the silane coupling agent of epoxy group(ing), isocyanate group, urea groups, amino, sulfydryl, halogen atom base.Can use suitable polymerization process synthetic.

Said structure inside has the polymerizability silane coupling agent of vinyl, be not particularly limited, for example have: vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, right-the styryl methoxy silane, 3-methacryloxypropyl dimethoxy silane, 3-methyl allyl acyloxypropyl trimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxyl silane, 3-acryloyl-oxy propyl trimethoxy silicane etc.The polymerizability silane coupling agent that these inside configuration have vinyl can use separately, also can use with the two or more mixing of any polymerizable monomer.

Above-mentioned polymerizable monomer is not particularly limited, and the simple function monomer for example has: (methyl) alkyl acrylates such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid myristin, (methyl) vinylformic acid palmityl ester, (methyl) stearyl acrylate acyl ester, (methyl) isobornyl acrylate; (methyl) vinyl cyanide, (methyl) acrylamide, (methyl) vinylformic acid, (methyl) glycidyl acrylate, 2-hydroxyethyl methacrylate, methacrylic acid-2-hydroxypropyl acrylate etc. contain polar group (methyl) acrylic monomer; Vinylbenzene, alpha-methyl styrene, p-methylstyrene, right-aromatic vinyl monomers such as chloro-styrene; Vinyl ester such as vinyl-acetic ester, propionate; Halogen atom such as vinylchlorid, vinylidene chloride monomer; Vinyl pyridine, phthalic acid 2-acryloyl hydroxyl ethyl ester, methylene-succinic acid, fumaric acid, ethene, propylene, the little monomer of polydimethylsiloxane etc.

Multi-functional monomer as above-mentioned polymerizable monomer is not particularly limited, and for example has: two (methyl) acrylate, three (methyl) acrylate, two or triallyl compound, divinyl compound.These can use separately, also can two or morely use simultaneously.Need to prove, above-mentioned multi-functional monomer for the second-order transition temperature (Tg) that improves above-mentioned hybrid fine particles, improve its thermotolerance and solvent resistance is added.

Above-mentioned two (methyl) acrylate is not particularly limited, for example have: ethylene glycol bisthioglycolate (methyl) acrylate, glycol ether two (methyl) acrylate, triglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, TriMethylolPropane(TMP) two (methyl) acrylate etc.

Above-mentioned three (methyl) acrylate is not particularly limited, and for example has: trimethylolpropane tris (methyl) acrylate, oxyethane modification trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate etc.

Above-mentioned two or the triallyl compound be not particularly limited, for example have: tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, Phthalic acid, diallyl ester, diallyl maleate, diallyl fumarate, Succinic Acid diallyl, cyanacrylate etc.

Above-mentioned divinyl compound is not particularly limited, and for example has: Vinylstyrene, divinyl etc.

As above-mentioned non-polymerization organic solvent, so long as have the polymerizability silane coupling agent mixing of vinyl and under polymerization temperature, be aqueous material with said structure inside, just be not particularly limited, for example have: butane, pentane, hexane, hexanaphthene, heptane, decane, n-Hexadecane, toluene, dimethylbenzene, ethyl acetate, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), 1, organic solvents such as 4-diox, methyl chloride, methylene dichloride, chloroform, tetracol phenixin etc. are suitable.

The silane coupling agent that said structure inside has epoxy group(ing) is not particularly limited, for example have: 2-(3,4 epoxy group(ing) cyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl-triethoxysilicane etc.

The silane coupling agent that said structure inside has isocyanate group is not particularly limited, and for example has: 3-isocyanic ester propyl-triethoxysilicane etc.

The silane coupling agent that said structure inside has urea groups is not particularly limited, and for example has: 3-urea groups propyl-triethoxysilicane etc.

Said structure inside has amino silane coupling agent and is not particularly limited, for example have: N-2 (aminoethyl) 3-aminopropyl methyl dimethoxysilane, N-2 (aminoethyl) 3-TSL 8330, N-2 (aminoethyl) 3-aminopropyltriethoxywerene werene, the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene) propyl group amine N-phenyl-3-aminopropyl trimethoxysilane, the hydrochloride of N-(vinyl benzyl)-2-aminoethyl-3-aminopropyl trimethoxysilane, special aminosilane etc.

The silane coupling agent that said structure inside has sulfydryl is not particularly limited, and for example has: 3-sulfydryl propyl group methyl dimethoxysilane, 3-sulfydryl propyl trimethoxy silicane etc.

The silane coupling agent that said structure inside has the halogen atom base is not particularly limited, and for example has: 3-r-chloropropyl trimethoxyl silane etc.

These can interfacial polymerization silane coupling agent, can use separately, also can with use as two or more mixing such as the epoxy group(ing) prepolymer of interface polymerization reaction material, isocyanic ester, amine, halogenide, polythiol, polychloride arbitrarily.

During with above-mentioned silane coupling agent and above-mentioned interface polymerization reaction material mixing use, above-mentioned silane coupling agent can add from the initial reaction stage of above-mentioned interface polymerization reaction material, also can add latter half in the reaction of above-mentioned interface polymerization reaction material.When above-mentioned silane coupling agent added in the reaction of above-mentioned interface polymerization reaction material latter half, the resin of the formation hybrid fine particles of the present invention that obtains became with the crosslinked structure that forms of above-mentioned silane coupling agent.

Above-mentioned epoxy prepolymer has lipophilicity, and itself and amine, polycarboxylic acid, acid anhydrides, multi-thiol, reactive modified phenolic resin form resin.

Above-mentioned epoxy prepolymer is not particularly limited, and for example has: bisphenol A-type, Resorcinol type, Bisphenol F type, tetraphenyl methane type, phenolic varnish type, polyvalent alcohol type, polyethylene glycol type, glycerine three ether types, glycidyl ether type, glycidyl ester type, glycidic amine type, aliphatics type, ester ring type type, amino-phenol type, hydantoin type, isocyanuric acid ester type, bisphenol type, naphthalene type or these hydrogenation thing, fluorochemical etc.

The epoxy equivalent (weight) of such epoxy prepolymer is not particularly limited, but is limited to 500 on preferred.By being limited to 500 epoxy prepolymer on the use epoxy equivalent (weight), can obtain the resin of the high thermotolerance solvent resistance good strength of degree of crosslinking.Be limited to 200 on preferred.

Be limited to 200 epoxy prepolymer on the epoxy equivalent (weight), be not particularly limited, for example have: エ Port ト-ト YD115, エ Port ト-ト YD127, エ Port ト-ト YD128 (trade(brand)name, all be that Dongdu changes into society's system), エ ピ コ-ト 825, エ ピ コ-ト 827, エ ピ コ-ト 828 (trade(brand)names, all be ジ ヤ パ Application エ Port キ シ レ ジ Application society system), EPICLON 840, EPICLON 850 bisphenol A type epoxy resins such as (trade(brand)name all are a big Japanese ink chemistry society system); エ Port ト-ト YDF-170, エ Port ト-ト YDF175S (trade(brand)name, all be that Dongdu changes into society's system), エ ピ コ-ト 806, エ ピ コ-ト 807 (trade(brand)names, all be ジ ヤ パ Application エ Port キ シ レ ジ Application society system), EPICLON 830, EPICLON 835 bisphenol f type epoxy resins such as (trade(brand)name all are a big Japanese ink chemistry society system); エ Port ト-ト YDPN-638, エ Port ト-ト YDCN-701, エ Port ト-ト YDCN-702, エ Port ト-ト YDCN-703, エ Port ト-ト YDCN-704, エ Port ト-ト YDCN-500 (trade(brand)name, all be that Dongdu changes into society's system), エ ピ コ-ト 152, エ ピ コ-ト 154 (trade(brand)names, all be ジ ヤ パ Application エ Port キ シ レ ジ Application society system), phenolic resin varnish type epoxy resin such as EPICLON N-655, EPICLON N-740, EPICLON N-770, EPICLON N-775, EPICLON N-865 (trade(brand)name all is a big Japanese ink society system); エ Port ト-ト YH-434, エ Port ト-ト YH434-L (trade(brand)name, all be that Dongdu changes into society's system), エ ピ コ-ト 1031S, エ ピ コ-ト 1032H60, エ ピ コ-ト 604, エ ピ コ-ト 630 (trade(brand)names, all be ジ ヤ パ Application エ Port キ シ レ ジ Application society system), EPICLON 430 (trade(brand)names, all be big Japanese ink chemistry society system), TETRAD-X, TETRAD-C special multifunctional types such as (trade(brand)name all are the ガ ス of a Mitsubishi chemistry society system); エ ピ コ-ト YX4000, エ ピ コ-ト YL6121H, エ ピ コ-ト YL6640, エ ピ コ-ト YL6677 biphenyl type epoxy resins such as (trade(brand)name all are a ジ ヤ パ Application エ Port キ シ レ ジ Application society system); エ Port ト-ト YH-300, エ Port ト-ト YH-301, エ Port ト-ト YH-315, エ Port ト-ト YH-324, エ Port ト-ト YH-325 aliphatic poly Racemic glycidol ether type epoxies such as (trade(brand)name all are that Dongdu changes into society's system); エ Port ト-ト YDC-1312, エ Port ト-ト YSLV-80XY crystallinity Resins, epoxy such as (trade(brand)name all are that Dongdu changes into society's system); EPICLONHP-4032, EPICLON EXA-4700 naphthalene type Resins, epoxy such as (trade(brand)name all are the chemical society of a big Japanese ink system); エ ピ コ-ト 191P, エ ピ コ-ト YX310 (trade(brand)name all is a ジ ヤ パ Application エ Port キ シ レ ジ Application society system), EPICLONHP-820 specific function type Resins, epoxy such as (trade(brand)name, the chemical society of big Japanese ink systems); EPICLON 725 (trade(brand)name, the chemical society of big Japanese ink system) isoreactivity thinner etc.

In addition, epoxy equivalent (weight) surpasses the epoxy prepolymer below 200 and 500, be not particularly limited, for example have: エ Port ト-ト YD134, エ Port ト-ト YD011 (trade(brand)name, all be that Dongdu changes into society's system), エ ピ コ-ト 801, エ ピ コ-ト 1001 (trade(brand)names, all be ジ ヤ パ Application エ Port キ シ レ ジ Application society system), EPICLON 860, EPICLON 1050, EPICLON 1055 bisphenol A type epoxy resins such as (trade(brand)name all are a big Japanese ink chemistry society system); エ Port ト-ト YDF-2001 bisphenol f type epoxy resins such as (trade(brand)name, Dongdu change into society's system); EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-695 phenolic resin varnish type epoxy resins such as (trade(brand)name all are the chemical society of a big Japanese ink system); エ ピ コ-ト 157S70 (trade(brand)name, ジ ヤ パ Application エ Port キ シ レ ジ Application society system), EPICLON5500 special multifunctional types such as (trade(brand)name, the chemical society of big Japanese ink systems); エ Port ト-ト YDB-360, エ Port ト-ト YDB-400, エ Port ト-ト YDB-405 (trade(brand)name all is that Dongdu changes into society's system), EPICLON 152, EPICLON 153 brominated epoxy resins such as (trade(brand)name all are the chemical society of a big Japanese ink system); エ Port ト-ト YD-171 (trade(brand)name, Dongdu changes into society's system), エ ピ コ-ト 871 (trade(brand)names, ジ ヤ パ Application エ Port キ シ レ ジ Application society system), EPICLONTSR-960, EPICLON TSR-601 flexible epoxy resins such as (trade(brand)name all are the chemical society of a big Japanese ink system); エ Port ト-ト ST-3000 (trade(brand)name, Dongdu change into society's system), エ ピ コ-ト YX8000, エ ピ コ-ト YX8034 hydrogenation type Resins, epoxy such as (trade(brand)name all are a ジ ヤ パ Application エ Port キ シ レ ジ Application society system); EPICLON HP-7200 dicyclopentadiene-type epoxy resin such as (trade(brand)name, the chemical society of big Japanese ink systems) etc.

These epoxy prepolymers can use separately, also can two or morely use simultaneously.

Need to prove, epoxy equivalent (weight) surpasses 500 epoxy prepolymer, for example have: エ Port ト-ト YD-012, エ Port ト-ト YD-013, エ Port ト-ト YD-014, エ Port ト-ト YD-017, エ Port ト-ト YD-019 (trade(brand)name, all be that Dongdu changes into society's system), エ ピ コ-ト 1002, エ ピ コ-ト 1003, エ ピ コ-ト 1055, エ ピ コ-ト 1004, エ ピ コ-ト 1007, エ ピ コ-ト 1009, エ ピ コ-ト 1010 (trade(brand)names, all be ジ ヤ パ Application エ Port キ シ レ ジ Application society system), EPICLON 3050, EPICLON 4050, EPICLON AM-020-P, EPICLON AM-030-P, EPICLON AM-040-P, EPICLON 7050, EPICLONHM-091, EPICLON HM-101 bisphenol A type epoxy resins such as (trade(brand)name all are the chemical society of a big Japanese ink system); エ Port ト-ト YDF-2004 (trade(brand)name, Dongdu changes into society's system), エ ピ コ-ト 4004P, エ ピ コ-ト 4007P, エ ピ コ-ト 4010P, エ ピ コ-ト 4110, エ ピ コ-ト 4210 bisphenol f type epoxy resins such as (trade(brand)name all are a ジ ヤ パ Application エ Port キ シ レ ジ Application society system); エ Port ト-ト YDB-405 (trade(brand)name, Dongdu change into society's system), EPICLON1123P-75M brominated epoxy resins such as (trade(brand)name, the chemical society of big Japanese ink systems); エ Port ト-ト YD-172 (trade(brand)name, Dongdu change into society's system), エ ピ コ-ト 872 (trade(brand)name, ジ ヤ パ Application エ Port キ シ レ ジ Application society system), EPICLON 1600-75X flexible epoxy resins such as (trade(brand)name, the chemical society of big Japanese ink systems); エ Port ト-ト ST-4000D hydrogenation type Resins, epoxy such as (trade(brand)name, Dongdu change into society's system); EPICLON 5800 multifunctional type Resins, epoxy such as (trade(brand)name, the chemical society of big Japanese ink systems) etc.

Above-mentioned isocyanic ester is not particularly limited, and for example has: buret type, adducts type, isocyanuric acid ester type etc.

Above-mentioned amine is not particularly limited, for example have: fatty amines such as quadrol and affixture thereof, Diethylenetriamine, dipropanetriamine, three second tetramines, tetraethylene-pentamine, dimethylaminopropylamine, diethyl amino propylamine, dibutyl amino propylamine, 1,6-hexanediamine and modification product thereof, N-aminoethyl piperazine, two-aminopropyl piperazine, trimethylhexamethylenediamine, two-hexa-methylene triamine, dicyano diamide, diacetyl acrylamide, various modified aliphatic polyamine, Polypropylene oxide diamine; 3,3 '-dimethyl 4,4 '-diamino-dicyclohexyl methane, 3-amino-1-cyclohexyl aminopropane, 4,4 '-diamino-dicyclohexyl methane, isophorone diamine, 1, cycloaliphatic amines and modifiers thereof such as 3-two (amine methyl) hexanaphthene, N-dimethylcyclohexylamine; 4,4 '-diaminodiphenylmethane (methylene dianiline (MDA)), 4,4 '-diaminodiphenyl oxide, diaminodiphenylsulfone(DDS), mphenylenediamine, 2, aromatic amine and modifiers thereof such as 4 '-tolylene diamine, toluylenediamine, ortho-toluene diamine, MXDP, xylylene diamines; Other special amine modifier, amino amides, polyaminoamides such as amino polyamide resin, the dimethyl amine methylphenol, 2,4,6-three (dimethyl amine methyl) phenol, the tertiary amines and the complex compounds thereof such as three-2 ethyl hexane salt of three (dimethyl amine methyl) phenol, ketoimine, glyoxal ethyline, 2-ethyl-4-methylimidazole, the 2-undecyl imidazole, 2-heptadecyl imidazoles, the 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, the 2-ethyl imidazol(e), 2 isopropyl imidazole, the 1-1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecyl imidazole, 1-cyanoethyl-2 isopropyl imidazole, 1-cyanoethyl-2-phenylimidazole, 1-1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-2-undecyl imidazole trimellitate, the 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2 '-Methylimidazole-(1) ']-ethyl-s-triazine, 2,4-diamino-6-[2 '-undecyl imidazole-(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-glyoxal ethyline muriate, 2 phenyl 4 methyl 5 hydroxy methylimidazole, 2-phenyl-4, the 5-hydroxymethyl-imidazole, 1-cyanoethyl-2-phenyl-4,5-two (cyanogen ethoxyl methyl) imidazoles, glyoxal ethyline and triazine mixture, imidazoles such as 2-phenylimidazole and triazine mixture; The amino affixture of hydrazides classes such as isophthalic dihydrazide, adipic dihydrazide, sebacic dihydrazide, Resins, epoxy etc. contains amino prepolymer etc.

Above-mentioned halogenide is not particularly limited, and for example has: dichloride hexanedioyl, dichloride phthalyl, dichloride paraphenylene terephthalamide, 1, binary acyl halides such as 4-hexanaphthene dicarbapentaborane muriate.

The hollow resin particulate of the present invention of the 2nd form by making the invention described above and hybrid fine particles of the present invention (below, these are generically and collectively referred to as particulate of the present invention) be scattered in the suitable binding agent, can make the antireflection resin combination that is used to make antireflective film etc.The antireflection resin combination that contains particulate of the present invention so also is one of the present invention.

Make the above-mentioned binding agent of microparticulate of the present invention, so long as transparent and can film forming material, just be not particularly limited, for example have: organic class material such as resin, mineral-type materials, can the polymeric monomer solution etc.

Above-mentioned organic class material is not particularly limited, and for example has: derivatived celluloses such as tri acetyl cellulose, diacetyl cellulose, propionyl Mierocrystalline cellulose, butyryl Mierocrystalline cellulose, ethanoyl propionyl cellulose ethanoate, soluble cotton; Polymeric amide, polycarbonate; Polyethylene terephthalate, poly terephthalic acid-1,4-hexanaphthene methylene radical ester, polyethylene 1,2-hexichol oxidative ethane-4, polyester such as 4-dicarboxylic ester, polybutylene terephthalate and PEN; The transparent resin that specific refractory poweres such as polystyrene, polypropylene, polyethylene, polymethylpentene, polysulfones, polyethersulfone, poly-virtueization resin, polyimide, polymethylmethacrylate or these various fluorine-containing bodies are lower etc.

Need to prove, when using transparent resin, preferably use its second-order transition temperature material lower than the second-order transition temperature of hollow resin particulate of the present invention as above-mentioned binding agent.Can obtain sufficient film toughness thus.

Above-mentioned mineral-type materials is not particularly limited, and for example has: the alkoxide of various elements, with the coordination compound of organic acid salt, coordination compound be combined into etc.Concrete example is if any metallic alkoxide compound such as purity titanium tetraethoxide, tetraisopropoxy titanium, four positive propoxy titaniums, four titanium n-butoxide, four sec-butoxy titaniums, four tert.-butoxy titaniums, aluminum ethylate, aluminium isopropoxide, aluminium butoxide, triethoxy antimony, three butoxy antimony, tetraethoxy zirconium, zirconium tetraisopropoxide, four n-propoxyzirconium, four n-butoxy zirconiums, four sec-butoxy zirconiums, four tert.-butoxy zirconiums; Two-isopropoxy diacetyl acetone network titanium, dibutoxy diacetyl acetone network titanium, diethoxy diacetyl acetone network titanium, diacetyl acetone zirconium, aluminium acetylacetonate, aluminum din-butoxide monoethylacetoacetate, diisopropoxy aluminium single acetyl methyl acetate, three-n-butoxy zirconium close inner complexs such as single acetyl ethyl acetate; Zirconium carbonate acyl ammonium or be active inorganic polymer of main component etc. with the zirconium.

Above-mentioned in can the polymeric monomer solution can the polymeric monomer, so long as transparent material, just be not particularly limited, for example have: (methyl) alkyl acrylates such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid myristin, (methyl) vinylformic acid palm ester, (methyl) stearyl acrylate alcohol ester, (methyl) isobornyl acrylate; (methyl) vinyl cyanide, (methyl) acrylamide, (methyl) vinylformic acid, (methyl) glycidyl acrylate, 2-hydroxyethyl methacrylate, methacrylic acid-2-hydroxypropyl acrylate etc. contain polar group (methyl) acrylic monomer; Vinylbenzene, alpha-methyl styrene, p-methylstyrene, right-aromatic vinyl monomers such as chloro-styrene; Vinyl ester such as vinyl-acetic ester, propionate; Halogen atom such as vinylchlorid, vinylidene chloride monomer; Vinyl pyridine, phthalic acid 2-acryloyl hydroxyl ethyl ester, methylene-succinic acid, fumaric acid, ethene, propylene etc.

These monomers can use separately, also can two or morely use simultaneously.

In order to improve film toughness, above-mentionedly can also can contain multifunctional monomer by the polymeric monomer solution.

Above-mentioned multifunctional monomer is not particularly limited, for example have: ethylene glycol bisthioglycolate (methyl) acrylate, glycol ether two (methyl) acrylate, triglycol two (methyl) acrylate, 1, two (methyl) acrylate such as 6-hexylene glycol two (methyl) acrylate, TriMethylolPropane(TMP) two (methyl) acrylate; Three (methyl) acrylate such as trimethylolpropane tris (methyl) acrylate, oxyethane modification trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate; Four (methyl) acrylate such as tetramethylolmethane four (methyl) acrylate; Six (methyl) acrylate such as tetramethylolmethane six (methyl) acrylate; Tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, Phthalic acid, diallyl ester, diallyl maleate, diallyl fumarate, Succinic Acid diallyl, triallyl isocyanuric acid ester etc. two or triallyl compound; Divinyl compound such as Vinylstyrene, divinyl etc.

These multifunctional monomers can use separately, also can two or morely use simultaneously.

The cooperation ratio of particulate of the present invention and above-mentioned binding agent is not particularly limited, and the preferred lower limit of the use level of particulate of the present invention is that 5 volume %, preferred upper limit are 95 volume %.When it is lower than 5 volume %, for example can not use the specific refractory power of the antireflective film that antireflection resin combination of the present invention makes low fully sometimes, when it surpasses 95 volume %, the bad mechanical strength of above-mentioned antireflective film sometimes.Be limited to 30 volume % under preferred, be limited to 90 volume % on more preferably, further preferably be limited to 50 volume % down, further preferred upper limit is 80 volume %.

When using the curing material as above-mentioned binding agent, antireflection resin combination of the present invention can be the latex that particle suspension of the present invention forms in binding agent, in addition, occasion in addition also can be the material that diluted with suitable volatile solvent.

Above-mentioned volatile solvent is not particularly limited, but considers from aspects such as the stability of composition, wettability, volatility, suitable use for example: alcohols such as methyl alcohol, ethanol, Virahol, butanols, 2-methyl cellosolve; Ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK); Ester classes such as methyl acetate, ethyl acetate, butylacetate; Ethers such as Di Iso Propyl Ether; Glycols such as ethylene glycol, propylene glycol, hexylene glycol; Glycol ethers such as ethyl cellosolve, ethylene glycol butyl ether, ethyl carbitol, diethylene glycol monobutyl ether; Aliphatic hydrocarbon classes such as hexane, heptane, octane; Halon; Aromatic hydrocarbons classes such as benzene,toluene,xylene; N-Methyl pyrrolidone, dimethyl formamide etc.These volatile solvents can use separately, also can two or morely use simultaneously.

In addition, above-mentioned antireflection resin combination of the present invention can be with acting on the antireflective film coating-forming agent of making antireflective film.By the antireflective film coating-forming agent that such antireflection resin combination of the present invention constitutes, also be one of the present invention.

And, use antireflective film of the present invention with the antireflective film that coating-forming agent forms, also be one of the present invention.

Make the method for antireflective film of the present invention, be not particularly limited, for example, antireflective film of the present invention is coated in after mould release film etc. goes up or directly be coated on the transparency carrier with coating-forming agent, carry out the exsiccant method.

Apply the method for antireflective film of the present invention with coating-forming agent, be not particularly limited, for example have: dip coating, spin-coating method, flow coat method, spraying method, rolling method, notch board coating process, air knife coating process, board-like coating process, Wound-rotor type scraper coating process, scraper coating process, oppositely coating process, transfer roller coating process, nick plate coating process, touch coating process, curtain coating coating process, slot orifice coating process, calendering coating process, mould coating process etc.

Utilize aforesaid method, antireflective film of the present invention is coated in after mould release film etc. goes up or directly be coated on the transparency carrier with coating-forming agent, film by formation such as heat dryings, then, by heat, humidification, uviolizing, electron beam irradiation etc., make above-mentioned curing of coating, obtain antireflective film of the present invention.

Antireflective film of the present invention, preferably its surface smoothing.Need to prove that so-called surface smoothing in this specification sheets is meant that the surfaceness Rz that the method for utilizing JIS B 0601 regulation is calculated is below the 0.2 μ m.

By making surface smoothing, antireflective film of the present invention can be because of the diffuse-reflectance of light on the surface do not cause integral body to be turned white, and in addition, spots such as fingerprint, sebum, sweat, makeup are difficult to adhere to, in case adhered to spot and also can remove at an easy rate.

Antireflective film of the present invention except having the layer of use antireflective film of the present invention with coating-forming agent formation, can also have substrate layer.By having substrate layer, the physical strength of antireflective film of the present invention improves, operability improves.

Above-mentioned substrate layer is so long as transparent just being not particularly limited, but considers from plasticity and physical strength aspect, the material of preference as constituting as the transparent resin of above-mentioned binding agent etc.

The thickness of antireflective film of the present invention is not particularly limited, and preferred is limited to 50nm down, is limited to 200nm on preferably.When it was lower than 50nm, its scuff resistance was insufficient sometimes, and when it surpassed 200nm, film split easily sometimes.

In addition, when antireflective film of the present invention had above-mentioned substrate layer, the thickness of substrate layer was not particularly limited, and preferably was limited to 3 μ m down, was limited to 7 μ m on preferably.When it is lower than 3 μ m, the intensity difference of antireflective film of the present invention sometimes, when it surpassed 7 μ m, the transparency of antireflective film of the present invention was poor sometimes, was difficult to see inner visual information.

According to the present invention, the manufacture method of a kind of hollow resin particulate, organic-inorganic hybrid fine particles and hollow resin particulate is provided, with described hollow resin 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.

Embodiment

Below, the present invention will be described in more detail to exemplify embodiment, but the present invention has more than and is defined in these embodiment.

Embodiment 1

(1) preparation of hollow resin particulate

To mix, stir as デ ユ ラ ネ-ト 21S (the ケ ミ カ of Asahi Chemical Industry Le ズ society system) 30 weight parts of polymeric polyisocyanate composition with as toluene 70 weight parts of non-polymerization compound, the mixing solutions total amount that forms thus is added into contains as in Sodium dodecylbenzene sulfonate 2 weight parts of water soluble emulsifier and ion exchanged water 400 weight parts as cetyl alcohol 2 weight parts of dispersing auxiliary, carried out forced emulsification 60 minutes with ultrasonic homogenizer, be mixed with and be dispersed with the dispersion liquid that median size is the polymerizability drop of 50nm.

Use has the 20L volumetrical polymerizer of stirrer, chuck, reflux exchanger and thermometer, decompression in the polymerizer is carried out in the container after the deoxidation, after nitrogen replacement makes its inside become nitrogen atmosphere, drop into the dispersion liquid that obtains, make polymerizer be warming up to 80 ℃ of beginning polymerizations.Polymerization 4 hours is left with then after ageing in 1 hour, makes polymerizer be cooled to room temperature.

The slurry that obtains is dialysed with the cellulose membrane of molecular weight cut-off 10,000, remove excessive tensio-active agent and inorganic salts, further remove by filter agglutination particle and insoluble composition.The resin particle that obtains is carried out vacuum-drying, obtain the hollow resin particulate.

During with the observable hollow resin particulate of electron microscope (the Ha イ テ of Hitachi Network ノ ロ ジ-ズ society system, " S-3500N "), its shape is roughly spherical shape.

(2) the antireflective film preparation of coating-forming agent and the formation of antireflective film

Relatively as polymethylmethacrylate 100 parts by volume of binding agent, mix with hollow resin particulate 100 parts by volume that obtain with as toluene 800 parts by volume of diluting solvent, be mixed with the antireflective film coating-forming agent.

The antireflective film that obtains is coated on tri acetyl cellulose (TAC) film with coating-forming agent, and 120 ℃ of dryings 10 minutes, forming thickness was the antireflective film of 100nm.

Embodiment 2

To mix as デ ユ ラ ネ-ト 21S (the ケ ミ カ of Asahi Chemical Industry Le ズ society system) 30 weight parts of polymeric polyisocyanate composition with as toluene 70 weight parts of non-polymerization compound, stir, the mixing solutions total amount that forms thus is added into ethylene glycol 10 weight parts that contain as polyhydroxy reactant, in Sodium dodecylbenzene sulfonate 2 weight parts of water soluble emulsifier and ion exchanged water 390 weight parts as cetyl alcohol 2 weight parts of dispersing auxiliary, carried out forced emulsification 60 minutes with ultrasonic homogenizer, be mixed with and be dispersed with the dispersion liquid that median size is the polymerizability drop of 60nm.

Use has the 20L volumetrical polymerizer of stirrer, chuck, reflux exchanger and thermometer, decompression in the polymerizer is carried out in the container after the deoxidation, after nitrogen replacement makes its inside become nitrogen atmosphere, drop into the dispersion liquid that obtains, make polymerization tank be warming up to 80 ℃ of beginning polymerizations.Polymerization 4 hours is left with then after ageing in 1 hour, makes polymerization tank be cooled to room temperature.

The slurry that obtains is dialysed with the cellulose membrane of molecular weight cut-off 10,000, remove excessive tensio-active agent and inorganic salts, further remove by filter agglutination particle and insoluble composition.

The resin particle that obtains is carried out vacuum-drying, obtain the hollow resin particulate.

During with the observable hollow resin particulate of electron microscope (the Ha イ テ of Hitachi Network ノ ロ ジ-ズ society system, " S-3500N "), its shape is roughly spherical shape.

The hollow resin particulate that use obtains, in addition, the method that all the other utilize and embodiment 1 is same, the preparation antireflective film is with coating-forming agent, formation antireflective film.

Embodiment 3

To mix as エ ピ コ-ト 828 (ジ ヤ パ Application エ Port キ シ レ ジ Application society system) 30 weight parts of epoxy prepolymer composition with as toluene 70 weight parts of non-polymerization organic solvent, stir, the mixing solutions total amount that forms thus is added into Diethylenetriamine 10 weight parts that contain as amine component, in Sodium dodecylbenzene sulfonate 2 weight parts of water soluble emulsifier and ion exchanged water 390 weight parts as cetyl alcohol 2 weight parts of dispersing auxiliary, carried out forced emulsification 60 minutes with ultrasonic homogenizer, be mixed with and be dispersed with the dispersion liquid that median size is the polymerizability drop of 65nm.

Use has the 20L volumetrical polymerizer of stirrer, chuck, reflux exchanger and thermometer, decompression in the polymerizer is carried out in the container after the deoxidation, after nitrogen replacement makes its inside become nitrogen atmosphere, drop into the dispersion liquid that obtains, make polymerizer be warming up to 80 ℃ of beginning polymerizations.Polymerization 4 hours is left with then after ageing in 1 hour, makes polymerizer be cooled to room temperature.

The slurry that obtains is dialysed with the cellulose membrane of molecular weight cut-off 10,000, remove excessive tensio-active agent and inorganic salts, further remove by filter agglutination particle and insoluble composition.

The resin particle that obtains is carried out vacuum-drying, obtain the hollow resin particulate.

With the observable hollow resin particulate of electron microscope (the Ha イ テ of Hitachi Network ノ ロ ジ-ズ society system, " S-3500N "), its shape is roughly spherical shape.

The hollow resin particulate that use obtains, in addition, the method that all the other utilize and embodiment 1 is same, the preparation antireflective film is with coating-forming agent, formation antireflective film.

Embodiment 4

To mix, stir as エ ピ コ-ト 828 (ジ ヤ パ Application エ Port キ シ レ ジ Application society system) 50 weight parts, toluene 50 weight parts of epoxy prepolymer composition, with the mixing solutions total amount that forms thus be added into Diethylenetriamine 10 weight parts that contain as amine component, as in Sodium dodecylbenzene sulfonate 2 weight parts of water soluble emulsifier and ion exchanged water 390 weight parts as cetyl alcohol 2 weight parts of dispersing auxiliary, carried out forced emulsification 60 minutes with ultrasonic homogenizer, be mixed with and be dispersed with the dispersion liquid that median size is the polymerizability drop of 72nm.

Use has the 20L volumetrical polymerizer of stirrer, chuck, reflux exchanger and thermometer, decompression in the polymerizer is carried out in the container after the deoxidation, after nitrogen replacement makes its inside become nitrogen atmosphere, drop into the dispersion liquid that obtains, make polymerization tank be warming up to 80 ℃ of beginning polymerizations.Polymerization 4 hours is left with then after ageing in 1 hour, makes polymerization tank be cooled to room temperature.

The slurry that obtains is dialysed with the cellulose membrane of molecular weight cut-off 10,000, remove excessive tensio-active agent and inorganic salts, further remove by filter agglutination particle and insoluble composition.

The resin particle that obtains is carried out vacuum-drying, obtain the hollow resin particulate.

With the observable hollow resin particulate of electron microscope (the Ha イ テ of Hitachi Network ノ ロ ジ-ズ society system, " S-3500N "), its shape is roughly spherical shape.

The hollow resin particulate that use obtains, in addition, the method that all the other utilize and embodiment 1 is same, the preparation antireflective film is with coating-forming agent, formation antireflective film.

Embodiment 5

To mix as エ ピ コ-ト 828 (ジ ヤ パ Application エ Port キ シ レ ジ Application society system) 30 weight parts of epoxy prepolymer composition with as toluene 65 weight parts and n-Hexadecane 5 weight parts of non-polymerization organic solvent, stir, the mixing solutions total amount that forms thus is added into Diethylenetriamine 10 weight parts that contain as amine component, in Sodium dodecylbenzene sulfonate 2 weight parts of water soluble emulsifier and ion exchanged water 390 weight parts as cetyl alcohol 2 weight parts of dispersing auxiliary, carried out forced emulsification 60 minutes with ultrasonic homogenizer, be mixed with and be dispersed with the dispersion liquid that median size is the polymerizability drop of 42nm.

Use has the 20L volumetrical polymerizer of stirrer, chuck, reflux exchanger and thermometer, decompression in the polymerizer is carried out in the container after the deoxidation, after nitrogen replacement makes its inside become nitrogen atmosphere, drop into the dispersion liquid that obtains, make polymerization tank be warming up to 80 ℃ of beginning polymerizations.Polymerization 4 hours is left with then after ageing in 1 hour, makes polymerization tank be cooled to room temperature.

The slurry that obtains is dialysed with the cellulose membrane of molecular weight cut-off 10,000, remove excessive tensio-active agent and inorganic salts, further remove by filter agglutination particle and insoluble composition.

The resin particle that obtains is carried out vacuum-drying, obtain the hollow resin particulate.

With the observable hollow resin particulate of electron microscope (the Ha イ テ of Hitachi Network ノ ロ ジ-ズ society system, " S-3500N "), its shape is roughly spherical shape.

The hollow resin particulate that use obtains, in addition, the method that all the other utilize and embodiment 1 is same, the preparation antireflective film is with coating-forming agent, formation antireflective film.

Comparative example 1

Covering median size with silicoorganic compound is that 60nm, specific refractory power are the surface of 1.36 porous silica particle, use the material that forms thus as the low-refraction particle, in addition, the method that all the other utilize and embodiment 1 is same, the preparation antireflective film is with coating-forming agent, formation antireflective film.

Embodiment 6

Will be as エ ピ コ-ト 828 (ジ ヤ パ Application エ Port キ シ レ ジ Application society system) 20 weight parts of epoxy prepolymer composition (lipophilicity reacted constituent A) with as methacrylic acid perfluoro capryl ethyl ester 10 weight parts of free radical polymerization monomer composition (lipophilicity reacted constituent C), Diisopropyl azodicarboxylate 1 weight part as polymerization starter, toluene 65 weight parts as the non-polymerization organic solvent, n-Hexadecane 5 weight parts mix, stir, the mixing solutions total amount that forms thus is added into Diethylenetriamine 10 weight parts that contain as amine component (lipophilicity reacted constituent B), in ion exchanged water 390 weight parts as Sodium dodecylbenzene sulfonate 2 weight parts of water soluble emulsifier, carried out forced emulsification 60 minutes with ultrasonic homogenizer, be mixed with and be dispersed with the dispersion liquid that median size is the polymerizability drop of 78nm.

Use has the 20L volumetrical polymerizer of stirrer, chuck, reflux exchanger and thermometer, decompression in the polymerizer is carried out in the container after the deoxidation, after nitrogen replacement makes its inside become nitrogen atmosphere, drop into the dispersion liquid that obtains, make polymerizer be warming up to 80 ℃ of beginning polymerizations.Polymerization 4 hours is left with then after ageing in 1 hour, makes polymerizer be cooled to room temperature.

The slurry that obtains is dialysed with the cellulose membrane of molecular weight cut-off 10,000, remove excessive tensio-active agent and inorganic salts, further remove by filter agglutination particle and insoluble composition.

The resin particle that obtains is carried out vacuum-drying, obtain the hollow resin particulate.

With the observable hollow resin particulate of electron microscope (the Ha イ テ of Hitachi Network ノ ロ ジ-ズ society system, " S-3500N "), its shape is roughly spherical shape.In addition, with the observable hollow resin particulate of electron microscope (electronics society of Hitachi system, " JEM-1200EXII "), it has dual structure.

The hollow resin particulate that use obtains, in addition, the method that all the other utilize and embodiment 1 is same, the preparation antireflective film is with coating-forming agent, formation antireflective film.

Embodiment 7

Will be as デ ユ ラ ネ-ト 21S (the ケ ミ カ of Asahi Chemical Industry Le ズ society system) 20 weight parts of polymeric polyisocyanate composition (lipophilicity reacted constituent A) with as methacrylic acid perfluoro capryl ethyl ester 10 weight parts of free radical polymerization monomer composition (lipophilicity reacted constituent C), Diisopropyl azodicarboxylate 1 weight part as polymerization starter, toluene 65 weight parts as the non-polymerization compound, n-Hexadecane 5 weight parts mix, stir, the mixing solutions total amount that forms thus is added into ethylene glycol 10 weight parts that contain as polyhydroxy reactant (lipophilicity reacted constituent B), in ion exchanged water 390 weight parts as Sodium dodecylbenzene sulfonate 2 weight parts of water soluble emulsifier, carried out forced emulsification 60 minutes with ultrasonic homogenizer, be mixed with and be dispersed with the dispersion liquid that median size is the polymerizability drop of 65nm.

Use has the 20L volumetrical polymerizer of stirrer, chuck, reflux exchanger and thermometer, decompression in the polymerizer is carried out in the container after the deoxidation, after nitrogen replacement makes its inside become nitrogen atmosphere, drop into the dispersion liquid that obtains, make polymerizer be warming up to 80 ℃ of beginning polymerizations.Polymerization 4 hours is left with then after ageing in 1 hour, makes polymerizer be cooled to room temperature.

The slurry that obtains is dialysed with the cellulose membrane of molecular weight cut-off 10,000, remove excessive tensio-active agent and inorganic salts, further remove by filter agglutination particle and insoluble composition.

The resin particle that obtains is carried out vacuum-drying, obtain the hollow resin particulate.

With the observable hollow resin particulate of electron microscope (the Ha イ テ of Hitachi Network ノ ロ ジ-ズ society system, " S-3500N "), its shape is roughly spherical shape.In addition, with the observable hollow resin particulate of electron microscope (NEC society system, " JEM-1200EX II "), it has dual structure.

The hollow resin particulate that use obtains, in addition, the method that all the other utilize and embodiment 1 is same, the preparation antireflective film is with coating-forming agent, formation antireflective film.

Embodiment 8

(1) making of organic-inorganic hybrid fine particles

In having the 20L volumetrical polymerizer of stirrer, chuck, reflux exchanger and thermometer, in the ion exchanged water of adjusting pH to 9, add emulsifying agent as polar solvent, begin to stir.

Decompression in the polymerizer is carried out in the container utilizing nitrogen to make pressure get back to normal atmosphere after the deoxidation, make its inside become nitrogen atmosphere.

After making polymerizer be warming up to 80 ℃, in polar solvent with polymerizability silane coupling agent and polymerizable monomer, as the ethyl acetate of non-polymerization organic solvent, as the Diisopropyl azodicarboxylate mixing solutions of polymerization starter, carry out emulsification to nano-scale with rotor stator type homogenizer, be mixed with and be dispersed with the dispersion liquid that median size is the polymerizability drop of 62nm, carry out the polymerization of polymerizability drop.

Then, adjust the pH to 5 of system once more, after the ageing in 4 hours, make polymerizer be cooled to room temperature, obtain slurry with acetate.

The slurry that obtains is dialysed with the cellulose membrane of molecular weight cut-off 10,000, remove excessive tensio-active agent and inorganic salts, further remove by filter agglutination particle and insoluble composition, make the organic-inorganic hybrid fine particles.

The organic-inorganic hybrid fine particles that use obtains, in addition, the method that all the other utilize and embodiment 1 is same, the preparation antireflective film is with coating-forming agent, formation antireflective film.

Embodiment 9

To stir as エ ピ コ-ト 828 (ジ ヤ パ Application エ Port キ シ レ ジ Application society system) 30 weight parts of epoxy prepolymer composition with as toluene 65 weight parts and the mixing of n-Hexadecane 5 weight parts of non-polymerization organic solvent, the mixing solutions total amount that forms thus is added into Diethylenetriamine 7 weight parts that contain as amine component, in Sodium dodecylbenzene sulfonate 2 weight parts of water soluble emulsifier and ion exchanged water 390 weight parts as cetyl alcohol 2 weight parts of dispersing auxiliary, carried out forced emulsification 60 minutes with ultrasonic homogenizer, be mixed with and be dispersed with the dispersion liquid that median size is the polymerizability drop of 63nm.

Use has the 20L volumetrical polymerizer of stirrer, chuck, reflux exchanger and thermometer, decompression in the polymerizer is carried out in the container after the deoxidation, after nitrogen replacement makes its inside become nitrogen atmosphere, drop into the dispersion liquid that obtains, make polymerizer be warming up to 80 ℃ of beginning polymerizations.Polymerization 4 hours adds the N-2 as amine component (aminoethyl) 3-aminopropyl trimethoxysilane 3 weight parts that are used for inorganic crosslinking, repolymerization 4 hours.Leave with then after ageing in 1 hour, make polymerizer be cooled to room temperature.

The slurry that obtains is dialysed with the cellulose membrane of molecular weight cut-off 10,000, remove excessive tensio-active agent and inorganic salts, further remove by filter agglutination particle and insoluble composition, make the organic-inorganic hybrid fine particles.

The organic-inorganic hybrid fine particles that use obtains, in addition, the method that all the other utilize and embodiment 1 is same, the preparation antireflective film is with coating-forming agent, formation antireflective film.

Comparative example 2

Open flat 1-185311 communique disclosed method according to the spy, making median size is the porous resin particle of 98nm.

Use the organic-inorganic hybrid fine particles of making in the porous resin particle alternate embodiment 8, in addition, the method that all the other utilize and embodiment 8 is same, the preparation antireflective film is with coating-forming agent, formation antireflective film.

Estimate

Utilize following method, the organic-inorganic hybrid fine particles that hollow resin particulate (low-refraction particle) that embodiment 1～7 and comparative example 1 are obtained and antireflective film and embodiment 8,9 and comparative example 2 obtain is estimated.The result is as shown in table 1.

(1) mensuration of the CV value of the median size of particulate and particle diameter

With dynamic light scattering formula particles distribution instrument (Particle Sizing Systems society system, " NICOMPmodel 380 ZLS-S "), measure the volume average particle size of the particulate that each embodiment and comparative example obtain and the CV value of particle diameter.

(2) mensuration of the reflectivity of antireflective film

Using the Sandpapering substrate surface, behind the blackwash of coating delustring, with spectrophotometer (society of Shimadzu Seisakusho Ltd. system, " UV-3101PC "), is that 550nm, angle of light are under 5 ° the condition in optical wavelength, measures the reflectivity of single face.

(3) mensuration of the specific refractory power of particulate and voidage

From the specific refractory power of the anti-reflection layer estimated by the value of the reflectivity of antireflective film, do not use the ratio of the particle that adds independent specific refractory power of the binding agent of particle and the anti-reflection layer, calculate the specific refractory power of particle.

With the specific refractory power of the particle that obtains and measured value, by the value of the specific refractory power of the resin part of forming the particle that calculates, calculate the voidage of the particulate that each embodiment and comparative example obtain.The voidage of calculating thus with from by electron microscope observation to the particle diameter of particulate and the voidage of the particle that calculates of thickness demonstrate good consistent.

(4) the alkali-proof evaluation of antireflective film

To antireflective film with impregnation the Mierocrystalline cellulose system non-woven fabrics of commercially available alkalis, carry out 100g/cm ²Increase the weight of, make it come and go 100 times after, the visual observations film appearance is judged with following standard.

Zero: good

△: roughly good

*: bad

Table 1

The possibility of commercial Application

According to the present invention, can provide a kind of hollow resin particulate, organic-inorganic hybrid fine particles and hollow The manufacture method of resin particle is at the particulate that described particulate is used as the anti-reflection layer that consists of low-refraction The time, can obtain dispersed good, the diffuse reflection that prevents light, alkali resistance simultaneously to Binder Composition High anti-reflection layer.

Claims (15)

1, a kind of hollow resin particulate is characterized in that, it has the single hole structure, and its median size is that 10～100nm and specific refractory power are 1.40 or less than 1.40,

And this hollow resin particulate has the wetting ability reacted constituent B reaction that is made of the lipophilicity reacted constituent A that constitutes with polymeric polyisocyanate and Yi Shui, amine, polyvalent alcohol or polycarboxylic acid and the outermost layer that resin was constituted that forms at least.

2, a kind of hollow resin particulate is characterized in that, it has the single hole structure, and its median size is that 10～100nm and specific refractory power are 1.40 or less than 1.40,

And this hollow resin particulate has the wetting ability reacted constituent B reaction that constitutes by the lipophilicity reacted constituent A that constitutes with epoxy prepolymer with amine, polycarboxylic acid, acid anhydrides, polythiol or resol and the outermost layer that resin was constituted that forms at least.

3, hollow resin particulate as claimed in claim 1 or 2 is characterized in that, its voidage is 30% or greater than 30%.

4, a kind of hollow resin particulate, it is characterized in that, it has the single hole structure, has the composite shell that constitutes by outermost layer and 2 layers of resin layer of la m at least, the voidage of described hollow resin particulate is 30% or greater than 30%, median size is that 10～100nm and specific refractory power are 1.40 or less than 1.40

The wetting ability reacted constituent B reaction that described outermost layer is made of the lipophilicity reacted constituent A that constitutes with polymeric polyisocyanate and Yi Shui, amine, polyvalent alcohol or polycarboxylic acid and the resin that forms constitutes, and described la m is made of the resin that the reaction with described lipophilicity reacted constituent A and the nonreactive lipophilicity reacted constituent of described wetting ability reacted constituent B C forms, and wherein this lipophilicity reacted constituent C is made of free-radical polymerised monomer.

5. hollow resin particulate, it is characterized in that, it has the single hole structure, has the composite shell that constitutes by outermost layer and 2 layers of resin layer of la m at least, the voidage of described hollow resin particulate is 30% or greater than 30%, median size is that 10～100nm and specific refractory power are 1.40 or less than 1.40

The wetting ability reacted constituent B reaction that described outermost layer constitutes by the lipophilicity reacted constituent A that constitutes with epoxy prepolymer with amine, polycarboxylic acid, acid anhydrides, polythiol or resol and the resin that forms constitutes, and described la m is made of the resin that the reaction with described lipophilicity reacted constituent A and the nonreactive lipophilicity reacted constituent of described wetting ability reacted constituent B C forms, and wherein this lipophilicity reacted constituent C is made of free-radical polymerised monomer.

6, as claim 1,2,4 or 5 described hollow resin particulates, it contains the fluorinated monomer.

7, as claim 1,2,4 or 5 described hollow resin particulates, it is characterized in that its outermost layer contains at least a resin that is selected from a group that is made of polyureas, urethane, polymeric amide, polyester, nylon and epoxy polymer.

As claim 1,2,4 or 5 described hollow resin particulates, it is characterized in that 8, it contains and utilizes the crosslinked resin that forms of inorganic components.

9, a kind of antireflection resin combination is characterized in that, it contains claim 1,2,4 or 5 described hollow resin particulates.

10, a kind of antireflective film Liniment is characterized in that, it is made of the described antireflection resin combination of claim 9.

11, a kind of antireflective film is characterized in that, it is to use the described antireflective film of claim 10 to make with Liniment.

12, a kind of manufacture method of hollow resin particulate is characterized in that, described hollow resin particulate has the single hole structure, and the manufacture method of described hollow resin particulate comprises:

Be formulated in the operation of the dispersion liquid that the polymerizability drop that contains the lipophilicity reacted constituent A that is made of polymeric polyisocyanate is disperseed and get; And

The operation that described lipophilicity reacted constituent A and described wetting ability reacted constituent B are reacted.

13, a kind of manufacture method of hollow resin particulate is characterized in that, described hollow resin particulate has the single hole structure, and the manufacture method of described hollow resin particulate comprises:

Be formulated in the operation of the dispersion liquid that the polymerizability drop that contains the lipophilicity reacted constituent A that is made of epoxy prepolymer is disperseed and get; And

The operation that described lipophilicity reacted constituent A and described wetting ability reacted constituent B are reacted.

14, a kind of manufacture method of hollow resin particulate is characterized in that, described hollow resin particulate has the single hole structure, and it has the composite shell that is made of outermost layer and 2 layers of resin layer of la m at least, and the manufacture method of described hollow resin particulate comprises:

Be formulated in that the polymerizability drop that makes the lipophilicity reacted constituent C that contains the lipophilicity reacted constituent A that is made of polymeric polyisocyanate and be made of free radical polymerization monomer in the polarizable medium that contains the wetting ability reacted constituent B that is made of water, amine, polyvalent alcohol or polycarboxylic acid disperses and the operation of dispersion liquid;

Make the described lipophilicity reacted constituent A on described polymerizability drop surface and the described wetting ability reacted constituent B reaction in the described polarizable medium, form outermost operation on described polymerizability drop surface; And

Make the described lipophilicity reacted constituent C reaction of described polymerizability drop inside, form the operation of la m.

15. the manufacture method of a hollow resin particulate is characterized in that, described hollow resin particulate has the single hole structure, and it has the composite shell that is made of outermost layer and 2 layers of resin layer of la m at least, and the manufacture method of described hollow resin particulate comprises:

Be formulated in that the polymerizability drop that makes the lipophilicity reacted constituent C that contains the lipophilicity reacted constituent A that is made of epoxy prepolymer and be made of free radical polymerization monomer in the polarizable medium that contains the wetting ability reacted constituent B that is made of amine, polycarboxylic acid, acid anhydrides, polythiol or resol disperses and the operation of dispersion liquid;

Make the described lipophilicity reacted constituent A on described polymerizability drop surface and the described wetting ability reacted constituent B reaction in the described polarizable medium, form outermost operation on described polymerizability drop surface; And

Make the described lipophilicity reacted constituent C reaction of described polymerizability drop inside, form the operation of la m.