CN113840882B - Inorganic microparticle dispersion, curable composition, cured product, and optical member - Google Patents

Inorganic microparticle dispersion, curable composition, cured product, and optical member Download PDF

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CN113840882B
CN113840882B CN202080034990.4A CN202080034990A CN113840882B CN 113840882 B CN113840882 B CN 113840882B CN 202080034990 A CN202080034990 A CN 202080034990A CN 113840882 B CN113840882 B CN 113840882B
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西田卓哉
伊藤正広
申东美
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Abstract

The present invention provides an inorganic microparticle dispersion, a curable composition, a cured product, and an optical member, wherein the inorganic microparticle dispersion comprises inorganic microparticles (A) and a dispersant (B), and the dispersant (B) comprises a phosphate compound (B1) having at least one (meth) acryloyl group and at least one polyester chain, and a hydroxyl group-containing compound (B2) having a molecular weight of 250 or less. The inorganic fine particle dispersion has excellent dispersion stability, and can form a hardened coating film having high refractive index properties and excellent bleeding resistance.

Description

Inorganic microparticle dispersion, curable composition, cured product, and optical member
Technical Field
The present invention relates to an inorganic fine particle dispersion, a curable composition containing the same, a cured product, and an optical member.
Background
In recent years, with rapid development of display technology of liquid crystal display devices and the like, demands for optical members having new functions or optical members of higher quality have been increasing with respect to sheet-like or film-like optical members used therefor. Examples of such an optical member include a brightness enhancing sheet such as a prism sheet or a micro lens sheet used for a backlight of a liquid crystal display device. These brightness enhancing sheets are generally ones in which an optical functional layer having a fine uneven structure on the surface is laminated on a substrate, and backlight light is refracted by the fine uneven structure on the surface, whereby the brightness of the front surface of the display can be enhanced. The brightness enhancing sheet is mainly produced by a method of shaping a resin material using a mold, and therefore, the resin material is required to be free of a solvent and low in viscosity.
In order to improve the brightening effect, it is also required that the cured product obtained has a high refractive index property and does not bleed out (bleed out) at high temperature and high humidity.
As a conventionally known resin material for a brightness enhancing sheet, a resin composition is known which contains metal oxide nanoparticles having a distribution in which 10% of cumulative particle diameter is 5nm to 25nm, 50% of cumulative particle diameter is 7nm to 30nm, 90% of cumulative particle diameter is 15nm to 50nm, and 100% of cumulative particle diameter is 50nm to 250nm in its particle size distribution, and which contains a compound having two or more benzene skeletons as a resin component (for example, refer to patent document 1), and such an inorganic fine particle blended resin material has a high refractive index property, but has a tendency to become highly viscous due to blending of the inorganic fine particle.
Therefore, a material having low viscosity in spite of containing inorganic fine particles has been desired.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2013-249439
Disclosure of Invention
Problems to be solved by the invention
The object of the present invention is to provide an inorganic fine particle dispersion having excellent dispersion stability, a curable composition containing the same, which has low viscosity and can form a cured coating film having high refractive index performance and excellent bleeding resistance, a cured product, and an optical member. In the present invention, "bleeding" refers to a phenomenon in which uncured components of the curable composition leak over time under high temperature and high humidity.
Technical means for solving the problems
The present inventors have made diligent studies to solve the above problems, and as a result, have found that the above problems can be solved by using an inorganic fine particle dispersion containing inorganic fine particles and a dispersant having a specific structure, and have completed the present invention.
Specifically, the present invention relates to an inorganic fine particle dispersion, a curable composition, a cured product, and an optical member each containing the inorganic fine particle dispersion, wherein the inorganic fine particle dispersion contains an inorganic fine particle (A) and a dispersant (B), and the dispersant (B) contains a phosphate compound (B1) having at least one (meth) acryloyl group and at least one polyester chain, and a hydroxyl group-containing compound (B2) having a molecular weight of 250 or less.
ADVANTAGEOUS EFFECTS OF INVENTION
The inorganic fine particle dispersion of the present invention has excellent dispersion stability, and the curable composition containing the dispersion is low in viscosity and can form a cured coating film having high refractive index performance and excellent bleeding resistance, and therefore can be preferably used for optical members such as a brightness enhancing sheet such as a prism sheet and a micro lens sheet.
Detailed Description
The inorganic fine particle dispersion of the present invention contains inorganic fine particles (A) and a dispersant (B).
Examples of the inorganic fine particles (a) include zirconia, silica, barium sulfate, zinc oxide, barium titanate, cerium oxide, aluminum oxide, titanium oxide, niobium oxide, tin oxide, tungsten oxide, and antimony oxide. These inorganic fine particles may be used singly or in combination of two or more. Among these, zirconia is preferable in terms of the high refractive index property of the obtained cured coating film.
In the case of using zirconia as the inorganic fine particles (a), a generally known one can be used as the zirconia, and the shape of the particles is not particularly limited, and examples thereof include spherical, hollow, porous, rod-like, fibrous, and the like, and among these, spherical is preferable. The average primary particle diameter is preferably 1nm to 50nm, more preferably 1nm to 30nm. The crystal structure is not particularly limited, and is preferably monoclinic.
The average primary particle diameter of the present invention can be measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission electron microscope (transmission electron microscopy, TEM). Examples of the measurement method include: the method of measuring the minor axis diameter and the major axis diameter of the primary particles of each inorganic fine particle and taking the average value as the average primary particle diameter of the primary particles.
As the dispersant (B), it is necessary to use a phosphate compound (B1) having at least one (meth) acryloyl group and at least one polyester chain, and a hydroxyl group-containing compound (B2) having a molecular weight of 250 or less.
In the present invention, the term "(meth) acryl" means acryl and/or methacryl. In addition, the term "(meth) acrylate" refers to an acrylate and/or a methacrylate. The term "(meth) acrylic acid" means acrylic acid to/or methacrylic acid.
The phosphate compound (b 1) is not particularly limited as long as it is a phosphate compound (b 1) having at least one (meth) acryloyl group and at least one polyester chain, and the phosphate compound (b 1) represented by the following structural formula (1) is preferable in that the obtained inorganic fine particle dispersion has excellent dispersion stability, and the curable composition containing the same has low viscosity and can form a cured coating film having high refractive index performance and excellent bleeding resistance.
[ chemical 1]
(wherein R is 1 Is a hydrogen atom orMethyl, R 2 Is an alkylene chain having 2 to 4 carbon atoms. In addition, x is an integer of 4 to 10, y is an integer of 1 or more, and n is an integer of 1 to 3. )
In the phosphate compound represented by the above structural formula (1), x in the formula is preferably 4 or 5, and y is preferably an integer of 2 to 7, in terms of the obtained inorganic fine particle dispersion having excellent dispersion stability and the curable composition containing the same being low in viscosity and capable of forming a cured coating film having high refractive index performance and excellent bleeding resistance. The dispersant represented by the structural formula (1) may be a mixture in which n is 1, 2, and/or 3.
As the hydroxyl group-containing compound (b 2), a hydroxyl group-containing compound (b 2) having a molecular weight of 250 or less is used.
Examples of the hydroxyl group-containing compound (b 2) include: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, heptanol, hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, allyl alcohol, cyclohexanol, terpineol, dihydroterpineol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, and the like.
In addition, as the hydroxyl group-containing compound (b 2), it is also possible to use: hydroxy group-containing (meth) acrylate compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane (meth) acrylate, pentaerythritol acrylate, and the like; (poly) oxyalkylene group-modified products in which (poly) oxyalkylene groups such as (poly) oxyethylene chains, (poly) oxypropylene chains and (poly) oxytetramethylene chains are introduced into the molecular structure of the hydroxyl group-containing (meth) acrylate compound; a lactone modified product having a (poly) lactone structure, etc. is introduced into the molecular structure of the hydroxyl group-containing (meth) acrylate compound.
Among these, a lactone modified product in which a (poly) lactone structure is introduced into the molecular structure of a hydroxyl group-containing (meth) acrylate compound is preferable in that the obtained inorganic fine particle dispersion has excellent dispersion stability, and the curable composition containing the same has low viscosity and can form a cured coating film having high refractive index performance and excellent bleeding resistance. These hydroxyl group-containing compounds (b 2) may be used either singly or as a combination of two or more.
The amount of the hydroxyl group-containing compound (b 2) used is preferably in the range of 0.05 to 30 parts by mass, more preferably in the range of 0.1 to 20 parts by mass, per 100 parts by mass of the phosphate compound (b 1), in terms of the excellent dispersion stability of the obtained inorganic fine particle dispersion, and the low viscosity of the curable composition containing the same, and the capability of forming a cured coating film having high refractive index properties and excellent bleeding resistance.
As the dispersant (B), other dispersants may be used in combination as needed.
Examples of the other dispersant include: anionic dispersants having an acid group, such as carboxylic acid, sulfuric acid, sulfonic acid, and salts of these acid compounds. These other dispersants may be used either singly or as a combination of two or more.
The amount of the dispersant (B) used is preferably in the range of 5 to 40 parts by mass, more preferably in the range of 10 to 25 parts by mass, relative to 100 parts by mass of the inorganic fine particles (a), in terms of the excellent dispersion stability of the obtained inorganic fine particle dispersion, and the low viscosity of the curable composition containing the same, and the capability of forming a cured coating film having high refractive index properties and excellent bleeding resistance.
The inorganic fine particle dispersion of the present invention may optionally contain a silane coupling agent.
Examples of the silane coupling agent include: (meth) acryloyloxy silane coupling agents such as 3- (meth) acryloyloxy propyl trimethyl silane, 3- (meth) acryloyloxy propyl methyl dimethoxy silane, 3- (meth) acryloyloxy propyl trimethoxy silane, 3- (meth) acryloyloxy propyl methyl diethoxy silane, and 3- (meth) acryloyloxy propyl triethoxy silane;
Vinyl silane coupling agents such as allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (2-methoxyethoxy) silane;
epoxy silane coupling agents such as diethoxy (glycidoxypropyl) methylsilane, 2- (3, 4 epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, and 3-glycidoxypropyl triethoxysilane;
styrene silane coupling agents such as p-styryl trimethoxysilane;
amino silane coupling agents such as N-2- (aminoethyl) -3-aminopropyl methyldimethoxy silane, N-2- (aminoethyl) -3-aminopropyl trimethoxy silane, N-2- (aminoethyl) -3-aminopropyl triethoxy silane, 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylene) propylamine, and N-phenyl-3-aminopropyl trimethoxy silane;
urea silane coupling agents such as 3-ureidopropyltriethoxysilane;
A chloropropyl silane coupling agent such as 3-chloropropyl trimethoxysilane;
mercapto silane coupling agents such as 3-mercaptopropyl methyl dimethoxy silane and 3-mercaptopropyl trimethoxy silane;
sulfide silane coupling agents such as bis (triethoxysilylpropyl) tetrasulfide;
isocyanate silane coupling agents such as 3-isocyanatopropyl triethoxysilane;
aluminum coupling agents such as aluminum acetoacetyldiisopropyl acid. These silane coupling agents may be used either singly or as a combination of two or more. Among these, 3- (meth) acryloyloxy propyl trimethoxysilane is preferable in terms of good compatibility with a (meth) acryloyl group-containing compound (C) described later.
The amount of the silane coupling agent used is preferably in the range of 10 to 30 parts by mass based on 100 parts by mass of the inorganic fine particles (a), in terms of the excellent dispersion stability of the obtained inorganic fine particle dispersion, and the low viscosity of the curable composition containing the same, and the capability of forming a cured coating film having high refractive index properties and excellent bleeding resistance.
As a method for producing the inorganic fine particle dispersion of the present invention, the inorganic fine particles (a) can be obtained by dispersing the inorganic fine particles (a) with the dispersant (B). For example, the following methods can be mentioned: the inorganic fine particles (A) and the dispersant (B) are put into a stirrer and stirred for 0.5 to 2 hours, and then dispersed by a disperser until the particle diameter of the inorganic fine particles (A) is 60nm or less, thereby obtaining the inorganic fine particle dispersion.
Examples of the dispersing machine include a medium type wet dispersing machine, and examples of the medium type wet dispersing machine include a bead mill.
The medium used in the medium wet dispersion machine is not particularly limited as long as it is a generally known bead, and examples thereof include zirconia, alumina, silica, glass, silicon carbide, and silicon nitride. The average particle diameter of the medium is preferably in the range of 50 μm to 500. Mu.m, more preferably in the range of 100 μm to 200. Mu.m. When the particle diameter is 50 μm or more, the impact force to the raw material powder is appropriate, and excessive time is not required for dispersion. On the other hand, if the particle diameter of the medium is 500 μm or less, the impact force to the raw material powder is appropriate, so that the increase in the surface energy of the dispersed particles can be suppressed, and reagglomeration can be prevented.
In addition, the dispersing step time can be shortened by a two-stage method using a medium having a large particle diameter with a large impact force in the initial step of dispersing and using a medium having a small particle diameter, in which reagglomeration is less likely to occur after the particle diameter of the dispersed particles becomes smaller.
The curable composition of the present invention contains the inorganic fine particle dispersion and the (meth) acryloyl group-containing compound (C).
Examples of the (meth) acryl-containing compound (C) include monofunctional or polyfunctional (meth) acrylate compounds, epoxy (meth) acrylate compounds other than those, urethane (meth) acrylate compounds, and the like. In addition, the same (meth) acryl-containing compound as the dispersant (B) may be used.
Examples of the monofunctional or polyfunctional (meth) acrylate compound include: aliphatic mono (meth) acrylate compounds such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate; alicyclic mono (meth) acrylate compounds such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl mono (meth) acrylate, and the like; heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; aromatic mono (meth) acrylate compounds such as benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate, benzyl (meth) acrylate, phenylphenoxyethyl (meth) acrylate; hydroxy-containing mono (meth) acrylate compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate;
A mono (meth) acrylate compound such as a compound represented by the following structural formula (2);
[ chemical 2]
Polyoxyalkylene-modified mono (meth) acrylate compounds in which polyoxyalkylene chains such as polyoxyethylene chains, polyoxypropylene chains and polyoxytetramethylene chains are introduced into the molecular structures of the various mono (meth) acrylate compounds; lactone-modified mono (meth) acrylate compounds in which a structure derived from a (poly) lactone is introduced into the molecular structure of the various mono (meth) acrylate compounds;
aliphatic di (meth) acrylate compounds such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexylene glycol di (meth) acrylate, and neopentyl glycol di (meth) acrylate; alicyclic di (meth) acrylate compounds such as 1, 4-cyclohexanedimethanol di (meth) acrylate, norbornane dimethanol di (meth) acrylate, dicyclopentyl di (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate; aromatic di (meth) acrylate compounds such as bisphenol di (meth) acrylate and bisphenol di (meth) acrylate; hydroxy-containing di (meth) acrylate compounds such as glycerol di (meth) acrylate and trimethylolpropane di (meth) acrylate; polyoxyalkylene-modified di (meth) acrylate compounds in which polyoxyalkylene chains such as polyoxyethylene chains, polyoxypropylene chains and polyoxytetramethylene chains are introduced into the molecular structures of the various di (meth) acrylate compounds; lactone-modified di (meth) acrylate compounds in which a (poly) lactone structure is introduced into the molecular structures of the various di (meth) acrylate compounds;
Aliphatic tri (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate and glycerol tri (meth) acrylate; hydroxyl group-containing tri (meth) acrylate compounds such as pentaerythritol tri (meth) acrylate, di-trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, and the like; polyoxyalkylene-modified tri (meth) acrylate compounds in which polyoxyalkylene chains such as polyoxyethylene chains, polyoxypropylene chains and polyoxytetramethylene chains are introduced into the molecular structures of the various tri (meth) acrylate compounds; lactone-modified tri (meth) acrylate compounds in which a (poly) lactone structure is introduced into the molecular structure of the various tri (meth) acrylate compounds;
aliphatic poly (meth) acrylate compounds having four or more functions such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like; hydroxy group-containing poly (meth) acrylate compounds having four or more functions such as dipentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate; a polyoxyalkylene-modified poly (meth) acrylate compound having a molecular structure in which a polyoxyalkylene chain such as a polyoxyethylene chain, a polyoxypropylene chain, or a polyoxytetramethylene chain is introduced, and having four or more functions; a lactone-modified poly (meth) acrylate compound having a (poly) lactone structure and having four or more functions, wherein the molecular structures of the poly (meth) acrylate compounds are introduced;
And a dicarbazole compound represented by the following structural formula (3).
[ chemical 3]
(wherein X 1 X is X 2 Each independently is a hydrogen atom or a (meth) acryloyl group. )
The epoxy (meth) acrylate compound is obtained by reacting (meth) acrylic acid or an anhydride thereof with an epoxy resin, and examples of the epoxy resin include: diglycidyl ethers of dihydric phenols such as hydroquinone and catechol; diglycidyl ethers of bisphenol compounds such as 3,3 '-biphenyldiol and 4,4' -biphenyldiol; bisphenol a type epoxy resins, bisphenol B type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and other bisphenol type epoxy resins; polyglycidyl ethers of naphthol compounds such as 1, 4-naphthalenediol, 1, 5-naphthalenediol, 1, 6-naphthalenediol, 2, 7-naphthalenediol, binaphthol, and bis (2, 7-dihydroxynaphthyl) methane; triglycidyl ethers such as 4,4',4 "-methyltrisperidol; novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins;
polyglycidyl ethers of polyether-modified aromatic polyols obtained by ring-opening polymerization of the bisphenol compounds, or naphthol compounds with cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether;
And polyglycidyl ethers of lactone-modified aromatic polyols obtained by polycondensation of the above-mentioned bisphenol compounds, bisphenol compounds or naphthol compounds with a lactone compound such as epsilon-caprolactone.
These epoxy (meth) acrylate compounds may be used either singly or as a combination of two or more.
Examples of the urethane (meth) acrylate include those obtained by reacting a polyisocyanate compound, a hydroxyl group-containing (meth) acrylate compound, and optionally a polyol compound. Examples of the polyisocyanate compound include: diisocyanate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, xylene diisocyanate, and 4,4' -diphenylmethane diisocyanate, and urethane modified products, adduct modified products, biuret modified products, and the like thereof. Examples of the hydroxyl group-containing (meth) acrylate compound include: hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane diacrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, polyoxyalkylene-modified products of these, polylactone-modified products, and the like. Examples of the polyol compound include: ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, glycerol, trimethylolpropane, pentaerythritol, biphenol, bisphenol, and the like.
These (meth) acryl-containing compounds (C) may be used either singly or as a combination of two or more. Among these, the compound having an aromatic ring in the molecular structure is preferable, and the compound having a bisphenol structure in the molecular structure is more preferable, in that the obtained inorganic fine particle dispersion has excellent dispersion stability, and the curable composition containing the inorganic fine particle dispersion has low viscosity and can form a cured coating film having high refractive index performance and excellent bleeding resistance.
The amount of the (meth) acryloyl group-containing compound (C) used is preferably 10 parts by mass or more, more preferably 40 parts by mass or more, based on 100 parts by mass of the inorganic fine particle dispersion, in terms of the resulting curable composition having a low viscosity and capable of forming a cured coating film having a high refractive index property and excellent bleeding resistance.
The curable composition of the present invention may further contain a photopolymerization initiator.
Examples of the photopolymerization initiator include: 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2' -dimethoxy-1, 2-diphenylethane-1-one, diphenyl (2, 4, 6-trimethoxybenzoyl) phosphine oxide, 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, and the like.
Examples of the commercial products of the photopolymerization initiator include: "Ornidad (Omnidad) -1173", "Ornidad (Omnidad) -184", "Ornidad (Omnidad) -127", "Ornidad (Omnidad) -2959", "Ornidad (Omnidad) -369", "Ornidad (Omnidad) -379", "Ornidad (Omrad) -907", "Ornidad (Omrad) -4265", "Ornidad (Omrad) -1000", "Ornidad (Omrad) -651", "Ornidad (Omnidad) -TPO", "Ornidad (Omnidad) -819", "Ornidad (Omnidad) -2022", "Ornidad (Omnidad) -2100", "Ornidad (Omrad) -754", "Ornidad (Omnidad) -784", "Ornidad (Omnidad) -500", "Ornidad (Omnidad) -81" (manufactured by IGM); "Kayacht (Kayacure) -DETX", "Kayacht (Kayacure) -MBP", "Kayacht (Kayacure) -DMBI", "Kayacht (Kayacure) -EPA", "Kayacht (Kayacure) -OA" (manufactured by Nippon chemical Co., ltd.); "Barbary (Vicure) -10", "Barbary (Vicure) -55" (manufactured by Stoffer chemical (Stauffer Chemical)) Co., ltd; "Tocoporo (Trigonal) P1" (manufactured by Ackesu (AKZO)) company; "Sandoray 1000" (manufactured by SANDOZ corporation); "Diperot (Deap)" (manufactured by Apbolen (APJOHN) Co., ltd.); "kuda sub-library (Quantacure) -PDO", "kuda sub-library (Quantacure) -ITX", "kuda sub-library (Quantacure) -EPD" (Wo Debu lyne soprop (wasd BLENKINSOP) corporation); "Hua Taiya library (Runtecure) -1104" (Hua Tai (manufactured by Runtec)) and the like. These photopolymerization initiators may be used either singly or as a combination of two or more.
In the curable composition, the amount of the photopolymerization initiator added is, for example, preferably in the range of 0.05 to 20 mass%, and more preferably in the range of 0.1 to 10 mass%.
In addition, a photosensitizer may be further added for the purpose of improving hardenability.
Examples of the photosensitizing agent include: amine compounds such as aliphatic amines and aromatic amines; urea compounds such as o-tolylthiourea; sulfur compounds such as sodium diethyldithiophosphate and s-benzylisothiouronium-p-toluenesulfonate. These photosensitizers may be used either singly or as a combination of two or more. The addition amount of these photosensitizers in the curable composition is preferably in the range of 0.01 to 10 mass%.
The curable composition of the present invention may contain other additives as required. Examples of the other additives include: ultraviolet absorbers, antioxidants, silicone-based additives, fluorine-based additives, rheology control (rheology control) agents, deaerators, antistatic agents, antifogging agents, and the like. In the curable composition of the present invention, the amount of these other additives added is preferably in the range of 0.01 to 40 mass%.
The method for producing the curable composition of the present invention is not particularly limited, and examples thereof include: a method in which the raw materials including the inorganic fine particles (a), the dispersant (B), the (meth) acryl-containing compound (C), other additives, and the like are dispersed together.
As the dispersing machine used in the above-mentioned method, a conventionally known dispersing machine such as a medium wet dispersing machine can be used without limitation, and examples thereof include a bead Mill (Star Mill) LMZ-015 manufactured by Luze Fine technology (Ashizawa Finetech) Co., ltd.), and an Ultra Apex Mill (Ultra Apex Mill) UAM-015 manufactured by shou Industrial Co., ltd.).
The medium used in the dispersing machine is not particularly limited as long as it is a generally known bead, and examples thereof include zirconia, alumina, silica, glass, silicon carbide and silicon nitride. The average particle diameter of the medium is preferably 50 μm to 500. Mu.m, more preferably 100 μm to 200. Mu.m. When the particle diameter is 50 μm or more, the impact force to the raw material powder is appropriate, and excessive time is not required for dispersion. On the other hand, if the particle diameter of the medium is 500 μm or less, the impact force to the raw material powder is appropriate, so that the increase in the surface energy of the dispersed particles can be suppressed, and reagglomeration can be prevented.
In addition, the dispersing step time can be shortened by a two-stage method using a medium having a large particle diameter with a large impact force in the initial step of dispersing and using a medium having a small particle diameter, in which reagglomeration is less likely to occur after the particle diameter of the dispersed particles becomes smaller.
Examples of the method for curing the curable composition of the present invention include a method of heating and a method of irradiating an active energy ray such as ultraviolet rays.
As the method for heating, hardening can be performed by heating in a temperature range of 60 to 120℃for 5 to 60 minutes.
In addition, as a method of irradiating the active energy ray, for example, in the case of ultraviolet rays, ultraviolet lamps such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, a light emitting diode (Light Emitting Diode, LED) and the like can be used as an ultraviolet ray generating source to cure the active energy ray.
As the active energy beam, for example, an ionizing radiation such as an electron beam, an α ray, a β ray, or a γ ray may be used in addition to the ultraviolet ray.
The irradiation amount of the active energy ray is preferably 0.05J/cm 2 ～5J/cm 2 More preferably 0.1J/cm 2 ～3J/cm 2 Is particularly preferably 0.1J/cm 2 ～1J/cm 2 Is not limited in terms of the range of (a). The ultraviolet irradiation amount is based on a value measured at a wavelength range of 300nm to 390nm using an ultraviolet detector (UV Checker) UVR-N1 (manufactured by Japanese battery Co., ltd.).
The cured coating film of the curable composition of the present invention has high refractive index properties and is therefore preferably used for optical members.
Examples of the optical member include: plastic lenses, polarizing films, retardation films, antireflection films, brightness enhancement films (prism sheets, micro-lens sheets, etc.), light diffusion films, hard coating films, film-type liquid crystal elements, touch panels, etc.
Examples
Hereinafter, the present invention will be specifically described with reference to examples and comparative examples.
Example 1 production of inorganic microparticle Dispersion (1)
166.5 parts by mass of a powder of zirconia nanoparticles (UEP-100, primary particle diameter 11nm, manufactured by first dilute elements chemical industry Co., ltd.) 33.0 parts by mass of 3- (meth) acryloxypropyltrimethoxysilane (KBM-503, manufactured by Xinyue chemical industry Co., ltd.) and dispersant (B-1) [ R in the formula (1) 1 Is methyl, R 2 A mixture of a phosphoric acid ester compound (b 1-1) having an ethylene chain of 2 carbon atoms, x being 5, y being 2 (average value), and n being an integer of 1 to 3, and a caprolactone 1mol adduct (b 2-1) of hydroxyethyl methacrylate ("placel FM1", manufactured by Daicel Co., ltd.) and having a molecular weight of 244, which is mixed in a ratio of (b 1-1)/(b 2-1) of 100/0.5 ]42.0 parts by mass and 415.5 parts by mass of methyl ethyl ketone (hereinafter, abbreviated as "MEK (methyl ethyl ketone)") were mixed and stirred by a dispersing stirrer for 30 minutes to perform coarse dispersion. Subsequently, a medium wet dispersion machine (Star Mill) LMZ-015 manufactured by Luze Fine technology (Ashizawa Finetech) Co., ltd.) was usedThe obtained mixed solution was subjected to dispersion treatment with zirconia beads having a particle diameter of 100. Mu.m. While confirming the particle diameter in the middle, the dispersion treatment was performed for a residence time of 100 minutes to obtain an inorganic fine particle dispersion (1).
Example 2 production of inorganic microparticle Dispersion (2)
Except that dispersant (B-2) was used in place of dispersant (B-1) used in example 1 [ R in formula (1) 1 Is methyl, R 2 A mixture of a phosphate compound (b 1-1) having an ethylene chain of 2 carbon atoms, x being 5, y being 2 (average value), and n being an integer of 1 to 3, and hydroxyethyl methacrylate (b 2-2) (molecular weight: 130) in a ratio of (b 1-1)/(b 2-2) of 100/1.6]An inorganic fine particle dispersion (2) was obtained in the same manner as in example 1.
Example 3 production of inorganic microparticle Dispersion (3)
Except that dispersant (B-3) was used in place of dispersant (B-1) used in example 1 [ R in formula (1) 1 Is methyl, R 2 A mixture of a phosphoric acid ester compound (b 1-1) having an ethylene chain of 2 carbon atoms, x being 5, y being 2 (average value), and n being an integer of 1 to 3, and a caprolactone 1mol adduct (b 2-1) of hydroxyethyl methacrylate ("placel FM1", manufactured by Daicel Co., ltd.) and having a molecular weight of 244, which is mixed in a ratio of (b 1-1)/(b 2-1) of 100/18]An inorganic fine particle dispersion (3) was obtained in the same manner as in example 1.
Example 4 production of inorganic microparticle Dispersion (4)
Except that dispersant (B-4) was used in place of dispersant (B-1) used in example 1 [ R in formula (1) 1 Is methyl, R 2 A mixture of a phosphoric acid ester compound (b 1-1) having an ethylene chain of 2 carbon atoms, x being 5, y being 2 (average value), and n being an integer of 1 to 3, and a caprolactone 1mol adduct (b 2-1) of hydroxyethyl methacrylate ("placel FM1", manufactured by Daicel Co., ltd.) and having a molecular weight of 244, which is mixed in a ratio of (b 1-1)/(b 2-1) of 100/27]Inorganic fine particles were obtained in the same manner as in example 1Dispersion (4).
Example 5 production of inorganic microparticle Dispersion (5)
Except that dispersant (B-5) [ R in formula (1) was used in place of dispersant (B-1) used in example 1 ] 1 Is methyl, R 2 A mixture of a phosphoric acid ester compound (b 1-1) having an ethylene chain of 2 carbon atoms, x being 5, y being 2 (average value), and n being an integer of 1 to 3, and a caprolactone 1mol adduct (b 2-1) of hydroxyethyl methacrylate ("placel FM1", manufactured by Daicel Co., ltd.) and having a molecular weight of 244, the mixture being mixed in a ratio of (b 1-1)/(b 2-1) of 100/2]An inorganic fine particle dispersion (5) was obtained in the same manner as in example 1.
Example 6 production of inorganic microparticle Dispersion (6)
Except that dispersant (B-6) [ R in formula (1) was used in place of dispersant (B-1) used in example 1 ] 1 Is methyl, R 2 A mixture of a phosphoric acid ester compound (b 1-2) having an ethylene chain of 2 carbon atoms, x being 5, y being 3 (average value), and n being an integer of 1 to 3, and a caprolactone 1mol adduct (b 2-1) of hydroxyethyl methacrylate (placel FM1, manufactured by Daicel Co., ltd.) in a ratio of (b 1-2)/(b 2-1) of 100/0.5]An inorganic fine particle dispersion (6) was obtained in the same manner as in example 1.
Example 7 production of inorganic microparticle Dispersion (7)
Except that dispersant (B-7) was used in place of dispersant (B-1) used in example 1 [ R in formula (1) 1 Is methyl, R 2 A mixture of a phosphoric acid ester compound (b 1-3) having an ethylene chain of 2 carbon atoms, x being 5, y being 5 (average value), and n being an integer of 1 to 3, and a caprolactone 1mol adduct (b 2-1) ("placel FM1", manufactured by Daicel Co., ltd.) of hydroxy ethyl methacrylate, and a molecular weight 244, which were mixed in a ratio of (b 1-3)/(b 2-1) of 100/0.5]An inorganic fine particle dispersion (7) was obtained in the same manner as in example 1.
Example 8 production of inorganic microparticle Dispersion (8)
Except that dispersant (B-8) was used in place of dispersant (B-1) used in example 1 [ R in formula (1) 1 Is methyl, R 2 A mixture of a phosphoric acid ester compound (b 1-1) having an ethylene chain of 2 carbon atoms, x being 5, y being 2 (average value), and n being an integer of 1 to 3, and a caprolactone 1mol adduct (b 2-1) of hydroxyethyl methacrylate ("placel FM1", manufactured by Daicel Co., ltd.) and having a molecular weight of 244, which is mixed in a ratio of (b 1-1)/(b 2-1) of 100/35 ]An inorganic fine particle dispersion (8) was obtained in the same manner as in example 1.
Example 9 production of inorganic microparticle Dispersion (9)
Except that dispersant (B-9) [ R in formula (1) was used in place of dispersant (B-1) used in example 1 ] 1 Is methyl, R 2 A mixture of a phosphate compound (b 1-1) having an ethylene chain of 2 carbon atoms, x being 5, y being 2 (average value), and n being an integer of 1 to 3, and 1-butanol (b 2-3) (molecular weight: 74) in a ratio of (b 1-1)/(b 2-3) of 100/0.5]An inorganic fine particle dispersion (9) was obtained in the same manner as in example 1.
Example 10 production of inorganic microparticle Dispersion (10)
Except that dispersant (B-10) was used in place of dispersant (B-1) used in example 1 [ R in formula (1) 1 Is methyl, R 2 A mixture of a phosphoric acid ester compound (b 1-1) having an ethylene chain of 2 carbon atoms, x being 5, y being 2 (average value), and n being an integer of 1 to 3, and ethylene glycol (b 2-4) (molecular weight: 62) in a ratio of (b 1-1)/(b 2-4) of 100/0.5]An inorganic fine particle dispersion (10) was obtained in the same manner as in example 1.
Comparative example 1 production of inorganic microparticle Dispersion (11)
Except that dispersant (B-11) [ R in structural formula (1) ] was used in place of dispersant (B-1) used in example 1 1 Is methyl, R 2 A phosphate compound (b 1-1) which is an ethylene chain having 2 carbon atoms, x is 5, y is 2 (average value), and n is an integer of 1 to 3)]An inorganic fine particle dispersion (11) was obtained in the same manner as in example 1.
Comparative example 2 production of inorganic microparticle Dispersion (12)
Except that dispersant (B-12) [ R in structural formula (1) ] was used in place of dispersant (B-1) used in example 1 1 Is methyl, R 2 Phosphate ester compound (b 1-4) having 2-carbon-atom ethylene chain, x being 5, y being 1 (average value), and n being an integer of 1 to 3]An inorganic fine particle dispersion (12) was obtained in the same manner as in example 1.
Comparative example 3 production of inorganic microparticle Dispersion (13)
An inorganic fine particle dispersion (13) was obtained in the same manner as in example 1, except that a dispersant (B-13) represented by the following structural formula (4) was used in place of the dispersant (B-1) used in example 1.
[ chemical 4]
(wherein n is an integer of 1 to 3.)
Comparative example 4 production of inorganic microparticle Dispersion (14)
An inorganic fine particle dispersion (14) was obtained in the same manner as in example 1, except that a dispersant (B-14) represented by the following structural formula (5) was used in place of the dispersant (B-1) used in example 1.
[ chemical 5]
(wherein n is an integer of 1 to 3.)
Comparative example 5 production of inorganic microparticle Dispersion (15)
An inorganic fine particle dispersion (15) was obtained in the same manner as in example 1, except that a dispersant (B-15) represented by the following structural formula (6) was used in place of the dispersant (B-1) used in example 1.
[ chemical 6]
(wherein n is an integer of 1 to 3.)
Comparative example 6 production of inorganic microparticle Dispersion (16)
Except that dispersant (B-16) was used in place of dispersant (B-1) used in example 1 [ R in formula (1) 1 Is methyl, R 2 A mixture of a phosphate compound (b 1-1) having an ethylene chain of 2 carbon atoms, x being 5, y being 2 (average value), and n being an integer of 1 to 3, and 1-octadecanol (b 2-5) (molecular weight: 270) in a ratio of (b 1-1)/(b 2-5) to 100/2]An inorganic fine particle dispersion (16) was obtained in the same manner as in example 1.
EXAMPLE 11 preparation of curable composition (1)
Phenyl benzyl acrylate was added to the inorganic fine particle dispersion (1) obtained in example 1 in the ratio shown in table 1, and the volatile matter was removed under reduced pressure while heating the dispersion by an evaporator (evaprator). Further, a photopolymerization initiator was added to obtain a curable composition (1).
( Examples 12 to 22: preparation of curable compositions (2) to (12) )
Curable compositions (2) to (12) were obtained in the same manner as in example 11 with the compositions and blending ratios shown in table 1.
( Comparative examples 7 to 12: preparation of curable compositions (C1) to (C6) )
Curable compositions (C1) to (C6) were obtained in the same manner as in example 11 with the compositions and blending ratios shown in table 2.
The inorganic fine particle dispersion and the curable composition obtained in the examples and comparative examples were used to carry out the following measurement and evaluation.
[ method of measuring refractive index ]
The curable compositions obtained in examples and comparative examples were applied to a glass plate using an applicator (applicator) so that the film thickness at the time of curing became 50 μm, and an active energy ray was irradiated to form a cured coating film of the curable composition on the surface of the glass plate. The cured coating film was peeled off from the glass substrate, and the refractive index thereof was measured using an Abbe (abbe) refractive index meter ("NAR-3T" manufactured by Atago Co., ltd.).
[ evaluation method of viscosity stability ]
The viscosities of the curable compositions obtained in examples and comparative examples were measured using an E-type rotational viscometer (RE 80U manufactured by eastern machine industry Co., ltd.) and evaluated according to the following evaluation criteria, namely, the viscosity immediately after preparation of the curable composition at 25 ℃ (hereinafter referred to as "initial viscosity") and the viscosity after 40 ℃. Times.one month (hereinafter referred to as "one month post viscosity").
And (3) the following materials: the value obtained by dividing the initial viscosity by the viscosity after one month is 0% or more and less than 10%.
O: the value obtained by dividing the initial viscosity by the viscosity after one month is 10% or more and less than 15%.
Delta: the value obtained by dividing the initial viscosity by the viscosity after one month is 15% or more and less than 20%.
X: the value obtained by dividing the initial viscosity by the viscosity after one month is 20% or more.
[ evaluation method of exudation resistance ]
The curable compositions obtained in examples and comparative examples were interposed between a polyethylene terephthalate film (hereinafter, abbreviated as "A4300" manufactured by Toyo Co., ltd., hereinafter, abbreviated as "PET (polyethylene terephthalate) film") and a brightness enhancement film (hereinafter, abbreviated as "BEF (brightness enhancing film) film") manufactured by 3M Co., ltd., and passed through a film having a thickness of 0.2J/cm 2 The BEF film was peeled off by UV irradiation from a high-pressure mercury lamp of (a), thereby producing a prism sheet having a prism shape transferred onto the PET film. Then, the obtained prism sheet was attached to an acrylic plate, and left to stand at a high temperature and a high humidity of 95% at a temperature of 65℃for 72 hours. By visual observationThe surface of the prism sheet and the acrylic plate after 72 hours was observed and evaluated according to the following evaluation criteria.
O: completely unchanged
X: oozing was confirmed on the surface of the prism sheet or acrylic sheet.
[ evaluation method of Dispersion stability ]
The dispersion stability was evaluated by compatibility with a monomer containing a structure derived from ethylene oxide. Specifically, "Mi Laimei (MIRAMER) M2200" manufactured by Miluan (MIWON) was added to the inorganic fine particle dispersion obtained in examples and comparative examples in an amount of 10 parts by mass based on 100 parts by mass of the inorganic fine particle dispersion, and the mixture was mixed, and the mixture was evaluated by visual observation and according to the following evaluation criteria.
O: no turbidity or agglomeration of the inorganic fine particle dispersion was observed.
Delta: turbidity was observed in the inorganic microparticle dispersion.
X: inorganic fine particle dispersions were turbid, and aggregation of particles was observed.
The compositions and evaluation results of the curable compositions (1) to (12) prepared in examples 11 to 22 are shown in table 1.
TABLE 1
The compositions and evaluation results of the curable compositions (C1) to (C6) prepared in comparative examples 7 to 12 are shown in table 2.
TABLE 2
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In tables 1 and 2, "acrylate monomer 1" represents phenylbenzyl acrylate.
In Table 1, "Acrylate monomer 2" represents "Lai Tex Acrylate (Light Acrylate) POB-A" manufactured by Co., ltd.
In Table 1, "acrylate monomer 3" represents o-phenylphenoxyethyl acrylate (manufactured by Miwon corporation, "Mi Laimei (MIRAMER) M1142").
In Table 1, "acrylate monomer 4" represents fluorene diacrylate (OGsol) EA-0200 manufactured by Osaka gas chemistry (Osaka Gas Chemical) Co., ltd.).
Examples 11 to 22 shown in Table 1 are examples of curable compositions using the inorganic fine particle dispersion of the present invention. It was confirmed that the inorganic fine particle dispersion of the present invention has excellent dispersion stability, and the curable composition containing the same has low viscosity and can form a cured coating film having high refractive index performance and excellent bleeding resistance.
On the other hand, comparative example 7 is an example of an inorganic fine particle dispersion having no hydroxyl group-containing compound as a dispersant, and a curable composition containing the inorganic fine particle dispersion. It was confirmed that although the dispersion stability of the inorganic fine particle dispersion was excellent, the viscosity stability of the curable composition containing the dispersion was significantly insufficient.
Comparative example 8 is an example of an inorganic fine particle dispersion having no hydroxyl group-containing compound as a dispersant, and a curable composition containing the inorganic fine particle dispersion. It was confirmed that the dispersion stability of the inorganic fine particle dispersion was insufficient although the viscosity stability and bleeding resistance of the curable composition were excellent.
Comparative examples 9 to 11 are examples of inorganic fine particle dispersions using a phosphate compound having no (meth) acryloyl group as a dispersant, and curable compositions containing the inorganic fine particle dispersions. It was confirmed that the dispersion stability of the inorganic fine particle dispersion was significantly insufficient, and that the bleeding resistance was also significantly insufficient in the curable composition containing the inorganic fine particle dispersion.
Comparative example 12 is an example of an inorganic fine particle dispersion using a hydroxyl group-containing compound having a molecular weight of more than 250 as a dispersant, and a curable composition containing the inorganic fine particle dispersion. It was confirmed that the dispersion stability of the inorganic fine particle dispersion was insufficient, and that the viscosity stability and bleeding resistance were also insufficient in the curable composition containing the inorganic fine particle dispersion.

Claims (5)

1. An inorganic fine particle dispersion comprising inorganic fine particles (a) and a dispersant (B), the inorganic fine particle dispersion characterized in that:
the inorganic fine particles (A) are particles selected from the group consisting of zirconium oxide, silicon dioxide, barium sulfate, barium titanate, cerium oxide, aluminum oxide, titanium oxide, niobium oxide, tungsten oxide, and antimony oxide,
the dispersant (B) comprises a phosphate compound (B1) having at least one (meth) acryloyl group and at least one polyester chain, and a hydroxyl group-containing compound (B2) having a molecular weight of 250 or less, wherein
The hydroxyl group-containing compound (b 2) is used in an amount of 0.05 to 18 parts by mass per 100 parts by mass of the phosphate compound (b 1),
the phosphate compound (b 1) is represented by the following structural formula (1),
in the formula (1), R 1 Is a hydrogen atom or methyl group, R 2 An alkylene chain having 2 to 4 carbon atoms; in addition, x is an integer of 4 to 10, y is an integer of 1 or more, and n is an integer of 1 to 3.
2. The dispersion of inorganic fine particles according to claim 1, wherein the dispersant (B) is used in an amount ranging from 5 to 40 parts by mass per 100 parts by mass of the inorganic fine particles (a).
3. A curable composition characterized by: a compound (C) comprising the inorganic fine particle dispersion according to claim 1 or 2 and a (meth) acryloyl group.
4. A hardened material, characterized in that: a hardening reagent for a curable composition according to claim 3.
5. An optical component, characterized by: a cured coating film comprising the cured product according to claim 4.
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