CN113840882A - Inorganic fine particle dispersion, curable composition, and optical member - Google Patents

Inorganic fine particle dispersion, curable composition, and optical member Download PDF

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CN113840882A
CN113840882A CN202080034990.4A CN202080034990A CN113840882A CN 113840882 A CN113840882 A CN 113840882A CN 202080034990 A CN202080034990 A CN 202080034990A CN 113840882 A CN113840882 A CN 113840882A
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inorganic fine
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fine particle
acrylate
particle dispersion
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CN113840882B (en
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西田卓哉
伊藤正広
申东美
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability

Abstract

The present invention provides an inorganic fine particle dispersion containing inorganic fine particles (A) and a dispersant (B), characterized in that: 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 cured coating film having high refractive index properties and excellent bleeding resistance.

Description

Inorganic fine particle dispersion, curable composition, 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 the rapid development of display technologies of liquid crystal display devices and the like, demands for sheet-like or film-like optical members used for the same have been increasing for optical members having new functions or optical members of higher quality. Examples of such optical members include a prism sheet used for a backlight of a liquid crystal display device, and a brightness enhancement sheet such as a microlens sheet. These brightness enhancement sheets are generally those in which an optically functional layer having a fine uneven structure on the surface thereof is laminated on a substrate, and the luminance of the front surface of the display can be enhanced by refracting the backlight light by the fine uneven structure on the surface. The brightness enhancement sheet is mainly produced by shaping a resin material using a mold, and therefore the resin material is required to be free of a solvent and to have a low viscosity.
In order to improve the brightening effect, the cured product obtained is also required to have high refractive index performance and to be free from bleeding (bleedout) under high temperature and high humidity conditions.
As a conventionally known resin material for a brightness enhancement sheet, there is known a resin composition containing metal oxide nanoparticles, characterized in that: the metal oxide nanoparticles have a distribution in which the cumulative 10% particle diameter is 5nm to 25nm, the cumulative 50% particle diameter is 7nm to 30nm, the cumulative 90% particle diameter is 15nm to 50nm, and the cumulative 100% particle diameter is 50nm to 250nm in the particle size distribution, and contain a compound having two or more benzene skeletons as a resin component (for example, see patent document 1).
Therefore, a material having a low viscosity despite containing inorganic fine particles has been desired.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2013-249439
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing an inorganic fine particle dispersion having excellent dispersion stability, a curable composition containing the inorganic fine particle dispersion and having a low viscosity, and capable of forming a cured coating film having high refractive index performance and excellent bleed resistance, a cured product, and an optical member. The term "bleed-out" in the present invention means a phenomenon in which uncured components of the curable composition leak out over time under high temperature and high humidity conditions.
Means for solving the problems
The present inventors have made extensive 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.
That is, the present invention relates to an inorganic fine particle dispersion containing inorganic fine particles (a) and a dispersant (B) containing 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, a curable composition containing the same, a cured product, and an optical member.
ADVANTAGEOUS EFFECTS OF INVENTION
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, and therefore, the inorganic fine particle dispersion can be preferably used for optical members such as a brightness enhancement sheet such as a prism sheet and a microlens sheet.
Detailed Description
The inorganic fine particle dispersion of the present invention is characterized by containing 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, alumina, titanium oxide, niobium oxide, zinc oxide, tin oxide, tungsten oxide, and antimony. These inorganic fine particles may be used alone or in combination of two or more. Among these, zirconia is preferable in terms of the high refractive index property of the obtained hardened coating film.
When zirconia is used as the inorganic fine particles (a), generally known zirconia 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, and fibrous, and among these, spherical is preferable. The average primary particle diameter is preferably 1nm to 50nm, more preferably 1nm to 30 nm. Further, the crystal structure is also not particularly limited, but a monoclinic system is preferable.
The average primary particle size 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 (TEM). Examples of the measurement method include: the method of measuring the minor axis diameter and major axis diameter of the primary particles of each inorganic fine particle and determining the average value thereof as the average primary particle diameter of the primary particles.
As the dispersant (B), 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 are necessarily used.
In the present invention, the "(meth) acryloyl group" means an acryloyl group and/or a methacryloyl group. The "(meth) acrylate" means an acrylate and/or a methacrylate. Further, "(meth) acrylic acid-" means acrylic acid- "and/or methacrylic acid-" is used.
The phosphate compound (b1) is not particularly limited as long as it is a phosphate compound (b1) having at least one (meth) acryloyl group and at least one polyester chain, and the phosphate compound (b1) 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 a low viscosity and can form a cured coating film having high refractive index performance and excellent bleeding resistance.
[ solution 1]
Figure BDA0003346903840000031
(in the formula, R1Is a hydrogen atom or a methyl group, R2An 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 structural formula (1), x in the formula is preferably 4 or 5, and y is preferably an integer of 2 to 7, in the case 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. In addition, 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 (b2), a hydroxyl group-containing compound (b2) having a molecular weight of 250 or less was used.
Examples of the hydroxyl group-containing compound (b2) 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 (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.
As the hydroxyl group-containing compound (b2), there can be used: hydroxyl group-containing (meth) acrylate compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane (meth) acrylate, pentaerythritol acrylate, and the like; (poly) oxyalkylene group modifications in which a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain is introduced into the molecular structure of the hydroxyl group-containing (meth) acrylate compound; a lactone-modified product having a (poly) lactone structure introduced into the molecular structure of the hydroxyl group-containing (meth) acrylate compound.
Among these, the obtained inorganic fine particle dispersion is preferably a lactone-modified product obtained by introducing a (poly) lactone structure into the molecular structure of a hydroxyl group-containing (meth) acrylate compound, because the dispersion stability is excellent, and the curable composition containing the dispersion has a low viscosity and can form a cured coating film having high refractive index performance and excellent bleeding resistance. These hydroxyl group-containing compounds (b2) may be used alone or in combination of two or more.
The amount of the hydroxyl group-containing compound (b2) 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, based on 100 parts by mass of the phosphate compound (b1), in terms of the obtained inorganic fine particle dispersion having excellent dispersion stability and the curable composition containing the same having low viscosity and capable of forming a cured coating film having high refractive index performance and excellent bleeding resistance.
As the dispersant (B), other dispersants may be used in combination as necessary.
Examples of the other dispersants include: and 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 alone or in 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, per 100 parts by mass of the inorganic fine particles (a), in terms of the obtained inorganic fine particle dispersion having excellent dispersion stability, and the curable composition containing the same having low viscosity and capable of forming a cured coating film having high refractive index performance and excellent bleed 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) acryloyloxypropyltrimethylsilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane and 3- (meth) acryloyloxypropyltriethoxysilane;
vinyl silane coupling agents such as allyl trichlorosilane, allyl triethoxysilane, allyl trimethoxysilane, diethoxymethyl vinylsilane, trichloroethylsilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (2-methoxyethoxy) silane;
epoxy silane coupling agents such as diethoxy (glycidoxypropyl) methylsilane, 2- (3, 4 epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane;
styrene silane coupling agents such as p-styryltrimethoxysilane;
amino silane coupling agents such as N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylene) propylamine, and N-phenyl-3-aminopropyltrimethoxysilane;
urea-based silane coupling agents such as 3-ureidopropyltriethoxysilane;
chloropropyl silane coupling agents such as 3-chloropropyltrimethoxysilane;
mercapto silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane;
thioether silane coupling agents such as bis (triethoxysilylpropyl) tetrasulfide;
isocyanate silane coupling agents such as 3-isocyanatopropyltriethoxysilane;
aluminum coupling agents such as aluminum acetoacetoxy diisopropoxide. These silane coupling agents may be used alone or in combination of two or more. Among these, 3- (meth) acryloyloxypropyltrimethoxysilane is preferable in terms of good compatibility with the (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 per 100 parts by mass of the inorganic fine particles (a), in view of the fact that the obtained inorganic fine particle dispersion has excellent dispersion stability, the curable composition containing the same has low viscosity, and a cured coating film having high refractive index performance and excellent bleeding resistance can be formed.
The method for producing the inorganic fine particle dispersion of the present invention 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 particle dispersion is obtained by charging the inorganic fine particles (a) and the dispersant (B) into a stirrer, stirring the mixture for 0.5 to 2 hours, and then dispersing the mixture by a dispersing machine until the particle diameter of the inorganic fine particles (a) becomes 60nm or less.
Examples of the dispersion machine include a media-type wet dispersion machine, and examples of the media-type wet dispersion machine include a bead mill.
The medium used in the medium-type wet disperser 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 to 500. mu.m, more preferably in the range of 100 to 200. mu.m. When the particle size is 50 μm or more, the impact force on the raw material powder is appropriate, and an 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 on the raw material powder is appropriate, and therefore, the increase in surface energy of the dispersed particles can be suppressed, and reagglomeration can be prevented.
In addition, the time for the dispersion step can be shortened by a two-stage method using a medium having a large particle diameter and a medium having a small particle diameter, in which the impact force is large in the initial step of dispersion and re-aggregation is less likely to occur after the particle diameter of the dispersed particles is reduced.
The curable composition of the present invention contains the inorganic fine particle dispersion and a (meth) acryloyl group-containing compound (C).
Examples of the (meth) acryloyl group-containing compound (C) include monofunctional or polyfunctional (meth) acrylate compounds, epoxy (meth) acrylate compounds other than these, urethane (meth) acrylate compounds, and the like. In addition, the same (meth) acryloyl group-containing compound as the dispersant (B) may also 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, and octyl (meth) acrylate; alicyclic mono (meth) acrylate compounds such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl mono (meth) acrylate; 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 ester (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate, benzylbenzyl (meth) acrylate, and phenylphenoxyethyl (meth) acrylate; hydroxyl group-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);
[ solution 2]
Figure BDA0003346903840000071
Polyoxyalkylene-modified mono (meth) acrylate compounds in which a polyoxyalkylene chain such as a polyoxyethylene chain, a polyoxypropylene chain, or a polyoxytetramethylene chain is introduced into the molecular structure of each of the above 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 each of the above 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, hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate; alicyclic di (meth) acrylate compounds such as 1, 4-cyclohexanedimethanol di (meth) acrylate, norbornanedimethanol di (meth) acrylate, dicyclopentanyl di (meth) acrylate and tricyclodecanedimethanol di (meth) acrylate; aromatic di (meth) acrylate compounds such as biphenol di (meth) acrylate and bisphenol di (meth) acrylate; hydroxyl group-containing di (meth) acrylate compounds such as glycerol di (meth) acrylate and trimethylolpropane di (meth) acrylate; polyoxyalkylene-modified di (meth) acrylate compounds in which a polyoxyalkylene chain such as a polyoxyethylene chain, a polyoxypropylene chain, or a polyoxytetramethylene chain is introduced into the molecular structure of each of the above di (meth) acrylate compounds; lactone-modified di (meth) acrylate compounds in which a (poly) lactone structure is introduced into the molecular structure of each of the 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, and dipentaerythritol tri (meth) acrylate; polyoxyalkylene-modified tri (meth) acrylate compounds in which a polyoxyalkylene chain such as a polyoxyethylene chain, a polyoxypropylene chain, or a polyoxytetramethylene chain is introduced into the molecular structure of each of the above tri (meth) acrylate compounds; lactone-modified tri (meth) acrylate compounds in which a (poly) lactone structure is introduced into the molecular structure of each of the tri (meth) acrylate compounds;
tetrafunctional or higher aliphatic poly (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate; tetra-or higher-functional hydroxyl group-containing poly (meth) acrylate compounds such as dipentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate; a polyoxyalkylene group-modified poly (meth) acrylate compound in which a tetrafunctional or higher polyoxyalkylene chain such as a polyoxyethylene chain, a polyoxypropylene chain or a polyoxytetramethylene chain is introduced into the molecular structure of each of the above poly (meth) acrylate compounds; a lactone-modified poly (meth) acrylate compound having a tetrafunctional or higher lactone structure in which a (poly) lactone structure is introduced into the molecular structure of each of the poly (meth) acrylate compounds;
and a bicarbazole compound represented by the following structural formula (3).
[ solution 3]
Figure BDA0003346903840000081
(in the formula, X1And X2Are each independently hydrogenAn atom or a (meth) acryloyl group. )
The epoxy (meth) acrylate compound is obtained by reacting (meth) acrylic acid or an acid 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 diphenol compounds such as 3,3 '-biphenyldiol and 4,4' -biphenyldiol; bisphenol epoxy resins such as bisphenol a epoxy resin, bisphenol B epoxy resin, bisphenol F epoxy resin, and bisphenol S epoxy resin; polyglycidyl ethers of naphthol compounds such as 1, 4-naphthalenediol, 1, 5-naphthalenediol, 1, 6-naphthalenediol, 2, 7-naphthalenediol, binaphthol, bis (2, 7-dihydroxynaphthyl) methane and the like; triglycidyl ethers such as 4,4',4 ″ -methylenetrisphenol; novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac resins;
polyglycidyl ethers of polyether-modified aromatic polyols obtained by ring-opening polymerization of the above-mentioned biphenol compound, bisphenol compound, or naphthol compound and a cyclic ether compound such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, or allyl glycidyl ether;
and polyglycidyl ethers of lactone-modified aromatic polyols obtained by polycondensation of the above-mentioned biphenol compound, bisphenol compound, or naphthol compound with a lactone compound such as e-caprolactone.
These epoxy (meth) acrylate compounds may be used alone or in 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 modified uric acid esters, modified adducts, and modified biurets 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, and polyoxyalkylene-modified products and polylactone-modified products thereof. Examples of the polyol compound include: ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, biphenol, bisphenol, and the like.
These (meth) acryloyl group-containing compounds (C) may be used alone or in combination of two or more. Among these, the obtained inorganic fine particle dispersion is preferably a compound having an aromatic ring in the molecular structure, and more preferably a compound having a bisphenol structure in the molecular structure, in view of excellent dispersion stability, low viscosity of the curable composition containing the dispersion, and formation of 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, and more preferably 40 parts by mass or more, per 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 high refractive index performance and excellent bleed resistance.
The curable composition of the present invention may further contain a photopolymerization initiator.
Examples of the photopolymerization initiator include: 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2' -dimethoxy-1, 2-diphenylethan-1-one, diphenyl (2,4, 6-trimethoxybenzoyl) phosphine oxide, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and mixtures thereof, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, and the like.
Examples of commercially available products of the other photopolymerization initiators include: "Aunerad (Omnirad) -1173", "Aunerad (Omnirad) -184", "Aunerad (Omnirad) -127", "Aunerad (Omnirad) -2959", "Aunerad (Omnirad) -369", "Aunerad (Omnirad) -379", "Aunerad (Omnirad) -907", "Omnirad) -4265", "Aunerad (Omnirad) -1000", "Aunerad (Omnirad) -651", "Aunerad (Omnirad) -TPO", "Aunerad (Omnirad) -819", "Aunerad (Omnirad) -2022", "Aunerad (Omnirad) -2100", "Aunerad (Omnirad) -754", "Aunerad (Omnirad) -784", "Aunerad (Omnirad) -500", "Aunerad (Omnirad) -81" (manufactured by IGM); "Kaya library (Kayakure) -DETX", "Kaya library (Kayakure) -MBP", "Kaya library (Kayakure) -DMBI", "Kaya library (Kayakure) -EPA", "Kaya library (Kayakure) -OA" (manufactured by Nippon chemical Co., Ltd.); "Bara library (Vicure) -10", "Bara library (Vicure) -55" (manufactured by Stauffer Chemical Co.); "tokunox (Trigonal) P1" (manufactured by AKZO corporation); "Sandoray 1000" (manufactured by Sandorsi, Inc.); "pedicle (Deap)" (manufactured by APJOHN corporation); "Kuo Ora library (Quantacure) -PDO", "Kuo Ora library (Quantacure) -ITX", "Kuo Ora library (Quantacure) -EPD" (manufactured by Ward Bluensop); "Huati ya library (Runtecure) -1104" (manufactured by Huati (Runtec) Co., Ltd.), and the like. These photopolymerization initiators may be used alone or in 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% by mass, and more preferably in the range of 0.1 to 10% by mass.
Further, a photosensitizer may be added for the purpose of improving the curing properties.
Examples of the photosensitizer 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 alone or in combination of two or more. The amount of these photosensitizers added to the curable composition is preferably in the range of 0.01 to 10% by mass.
The curable composition of the present invention may optionally contain other additives. Examples of the other additives include: ultraviolet absorbers, antioxidants, silicone additives, fluorine additives, rheology control agents, defoamers, antistatic agents, antifogging agents, and the like. The addition amount of these other additives to the curable composition of the present invention is preferably in the range of 0.01 to 40% by mass.
The method for producing the curable composition of the present invention is not particularly limited, and examples thereof include: and a method of dispersing the raw materials including the inorganic fine particles (a), the dispersant (B), the (meth) acryloyl group-containing compound (C), and other additives.
As the disperser used in the above-mentioned method, a conventionally known disperser such as a media wet disperser can be used without limitation, and examples thereof include a bead Mill ("Star Mill (Star Mill) LMZ-015" manufactured by lugze fine technology (Ashizawa Finetech) corporation and "Ultra Apex Mill (Ultra Apex Mill) UAM-015" manufactured by shoddy industries, ltd.).
The medium used in the dispersing machine is not particularly limited as long as it is a generally known bead, and preferably includes zirconia, alumina, silica, glass, silicon carbide, and silicon nitride. The medium preferably has an average particle diameter of 50 to 500. mu.m, more preferably 100 to 200. mu.m. When the particle size is 50 μm or more, the impact force on the raw material powder is appropriate, and an 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 on the raw material powder is appropriate, and therefore, the increase in surface energy of the dispersed particles can be suppressed, and reagglomeration can be prevented.
In addition, the time for the dispersion step can be shortened by a two-stage method using a medium having a large particle diameter and a medium having a small particle diameter, in which the impact force is large in the initial step of dispersion and re-aggregation is less likely to occur after the particle diameter of the dispersed particles is reduced.
Examples of the method for curing the curable composition of the present invention include a method of heating and a method of irradiating with active energy rays such as ultraviolet rays.
The heating may be performed by heating at a temperature of 60 to 120 ℃ for 5 to 60 minutes to cure the resin.
In addition, as the method of irradiating the active energy rays, for example, in the case of ultraviolet rays, hardening may be performed by a method using an ultraviolet lamp 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, or a Light Emitting Diode (LED) as an ultraviolet ray generating source.
As the active energy ray, in addition to the ultraviolet ray, for example, ionizing radiation such as electron beam, α ray, β ray, and γ ray can be used.
The irradiation amount of the active energy ray is preferably 0.05J/cm2～5J/cm2More preferably 0.1J/cm2～3J/cm2Particularly preferably 0.1J/cm2～1J/cm2The range of (1). The ultraviolet irradiation dose is a value measured in a wavelength range of 300nm to 390nm using an ultraviolet inspector (UV Checker) UVR-N1 (manufactured by Nippon batteries Co., Ltd.).
The cured coating film of the curable composition of the present invention has high refractive index properties and can be preferably used for optical members.
Examples of the optical member include: plastic lenses, polarizing films, phase difference films, antireflection films, brightness enhancement films (prism sheets, microlens sheets, etc.), light diffusion films, hard coat films, film-type liquid crystal elements, touch panels, and the like.
Examples
The present invention will be specifically described below with reference to examples and comparative examples.
Example 1 production of inorganic Fine particle Dispersion (1)
The powder of zirconia nanoparticles (second order)166.5 parts by mass of "UEP-100" manufactured by Dilute element chemical industries, Ltd., primary particle diameter of 11nm), 33.0 parts by mass of 3- (meth) acryloyloxypropyltrimethoxysilane ("KBM-503" manufactured by shin-Etsu chemical industries, Ltd.), and a dispersant (B-1) [ R in the formula (1)1Is methyl, R2A mixture of a phosphoric acid ester compound (b1-1) 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 of hydroxyethyl methacrylate (b2-1) ("Plassel FM 1" manufactured by Daicel, Ltd., molecular weight: 244) in a ratio of (b1-1)/(b2-1) of 100/0.5]42.0 parts by mass and 415.5 parts by mass of methyl ethyl ketone (hereinafter, abbreviated as "MEK") were mixed and stirred by a disperser for 30 minutes to perform coarse dispersion. Subsequently, the obtained mixed solution was subjected to a dispersion treatment by a media wet disperser ("Star Mill (Star Mill) LMZ-015" manufactured by luziwa fine technology (Ashizawa Finetech) incorporated) and using zirconia beads having a particle size of 100 μm. While confirming the particle size in the middle, the dispersion treatment was performed for a retention time of 100 minutes to obtain an inorganic fine particle dispersion (1).
Example 2 production of inorganic Fine particle Dispersion (2)
Except that a dispersant (B-2) [ R in the formula (1) ] was used in place of the dispersant (B-1) used in example 11Is methyl, R2A mixture of a phosphate compound (b1-1) 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 (b2-2) (molecular weight: 130) in a ratio of (b1-1)/(b2-2) of 100/1.6]Except for this, the same procedure as in example 1 was carried out to obtain inorganic fine particle dispersion (2).
Example 3 production of inorganic Fine particle Dispersion (3)
Except that a dispersant (B-3) [ R in the formula (1) ] was used in place of the dispersant (B-1) used in example 11Is methyl, R2A phosphoric acid ester compound (b1-1) 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, andcaprolactone 1mol adduct of hydroxyethyl methacrylate (b2-1) (a mixture of "Placelel FM 1" manufactured by Daicel Corp., Ltd., "molecular weight: 244) in a ratio of (b1-1)/(b2-1) to 100/18]Except for this, an inorganic fine particle dispersion (3) was obtained in the same manner as in example 1.
Example 4 production of inorganic Fine particle Dispersion (4)
Except that a dispersant (B-4) [ R in the formula (1) ] was used in place of the dispersant (B-1) used in example 11Is methyl, R2A mixture of a phosphoric acid ester compound (b1-1) 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 of hydroxyethyl methacrylate (b2-1) ("Plassel FM 1" manufactured by Daicel, Ltd., molecular weight: 244) in a ratio of (b1-1)/(b2-1) being 100/27]Except for this, an inorganic fine particle dispersion (4) was obtained in the same manner as in example 1.
Example 5 production of inorganic Fine particle Dispersion (5)
Except that a dispersant (B-5) [ R in the formula (1) ] was used in place of the dispersant (B-1) used in example 11Is methyl, R2A mixture of a phosphoric acid ester compound (b1-1) 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 of hydroxyethyl methacrylate (b2-1) ("Plassel FM 1" manufactured by Daicel, Ltd., molecular weight: 244) in a ratio of (b1-1)/(b2-1) being 100/2]Except for this, an inorganic fine particle dispersion (5) was obtained in the same manner as in example 1.
Example 6 production of inorganic Fine particle Dispersion (6)
Except that a dispersant (B-6) [ R in the formula (1) ] was used in place of the dispersant (B-1) used in example 11Is methyl, R2A 1mol adduct of a phosphoric acid ester compound (b1-2) 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 caprolactone of hydroxyethyl methacrylate (b2-1) (xylonite (Dai)cel) manufactured by "plassel FM 1" by gmbh, molecular weight: 244) a mixture obtained by mixing (b1-2)/(b2-1) in a ratio of 100/0.5]Except for this, an inorganic fine particle dispersion (6) was obtained in the same manner as in example 1.
Example 7 production of inorganic Fine particle Dispersion (7)
Except that a dispersant (B-7) [ R in the formula (1) ] was used in place of the dispersant (B-1) used in example 11Is methyl, R2A mixture of a phosphoric acid ester compound (b1-3) 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 of hydroxyethyl methacrylate (b2-1) ("Plassel FM 1" manufactured by Daicel, Inc., molecular weight: 244) in a ratio of (b1-3)/(b2-1) of 100/0.5]Except for this, an inorganic fine particle dispersion (7) was obtained in the same manner as in example 1.
Example 8 production of inorganic Fine particle Dispersion (8)
Except that a dispersant (B-8) [ R in the formula (1) ] was used in place of the dispersant (B-1) used in example 11Is methyl, R2A mixture of a phosphoric acid ester compound (b1-1) 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 of hydroxyethyl methacrylate (b2-1) ("Plassel FM 1" manufactured by Daicel, Ltd., molecular weight: 244) in a ratio of (b1-1)/(b2-1) being 100/35]Except for this, an inorganic fine particle dispersion (8) was obtained in the same manner as in example 1.
Example 9 production of inorganic Fine particle Dispersion (9)
Except that a dispersant (B-9) [ R in the formula (1) ] was used in place of the dispersant (B-1) used in example 11Is methyl, R2A mixture of a phosphate compound (b1-1) 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 (b2-3) (molecular weight: 74) in a ratio of (b1-1)/(b2-3) of 100/0.5]Except that, the same procedure as in example 1 was repeated to obtainAn organic fine particle dispersion (9).
Example 10 production of inorganic Fine particle Dispersion (10)
Except that a dispersant (B-10) [ R in the formula (1) ] was used in place of the dispersant (B-1) used in example 11Is methyl, R2A mixture of a phosphate ester compound (b1-1) 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 (b2-4) (molecular weight: 62) in a ratio of (b1-1)/(b2-4) of 100/0.5]Except for this, an inorganic fine particle dispersion (10) was obtained in the same manner as in example 1.
Comparative example 1 production of inorganic Fine particle Dispersion (11)
Except that a dispersant (B-11) [ R in the formula (1) ] was used in place of the dispersant (B-1) used in example 11Is methyl, R2A phosphate compound 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 (b1-1)]Except for this, an inorganic fine particle dispersion (11) was obtained in the same manner as in example 1.
Comparative example 2 production of inorganic Fine particle Dispersion (12)
Except that a dispersant (B-12) [ R in the formula (1) ] was used in place of the dispersant (B-1) used in example 11Is methyl, R2A phosphate compound having an ethylene chain of 2 carbon atoms, x being 5, y being 1 (average value), and n being an integer of 1 to 3 (b1-4)]Except for this, an inorganic fine particle dispersion (12) was obtained in the same manner as in example 1.
Comparative example 3 production of inorganic Fine particle 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.
[ solution 4]
Figure BDA0003346903840000151
(wherein n is an integer of 1 to 3.)
Comparative example 4 production of inorganic Fine particle 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.
[ solution 5]
Figure BDA0003346903840000161
(wherein n is an integer of 1 to 3.)
Comparative example 5 production of inorganic Fine particle 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.
[ solution 6]
Figure BDA0003346903840000162
(wherein n is an integer of 1 to 3.)
Comparative example 6 production of inorganic Fine particle Dispersion (16)
Except that a dispersant (B-16) [ R in the formula (1) ] was used in place of the dispersant (B-1) used in example 11Is methyl, R2A mixture of a phosphoric acid ester compound (b1-1) 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 (molecular weight: 270) (b2-5) in a ratio of (b1-1)/(b2-5) to 100/2]Except for this, an inorganic fine particle dispersion (16) was obtained in the same manner as in example 1.
Example 11 preparation of curable composition (1)
Benzyl phenyl acrylate was added to the inorganic fine particle dispersion (1) obtained in example 1 at the ratio shown in table 1, and volatile components were removed under reduced pressure while heating the dispersion with an evaporator (evap ator). 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, except for 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, except that the compositions and blending ratios shown in table 2 were changed.
The following measurements and evaluations were carried out using the inorganic fine particle dispersions and curable compositions obtained in the above examples and comparative examples.
[ method for measuring refractive index ]
The curable compositions obtained in examples and comparative examples were applied onto a glass plate using an applicator (applicator) so that the film thickness at the time of curing became 50 μm, and a cured coating film of the curable composition was formed on the surface of the substrate by irradiation with active energy rays. The cured coating was peeled from the glass substrate, and the refractive index thereof was measured using an Abbe (abbe) refractometer ("NAR-3T" manufactured by Atago, Inc.).
[ method for evaluating viscosity stability ]
The viscosities of the curable compositions obtained in examples and comparative examples were measured using an E-type rotary viscometer ("RE 80U" manufactured by eastern engineeringpo ltd) at 25 ℃ immediately after the preparation of the curable compositions (hereinafter referred to as "initial viscosity") and at 40 ℃ x one month (hereinafter referred to as "one month viscosity"), and evaluated according to the following evaluation criteria.
Very good: the value obtained by dividing the viscosity by the initial viscosity after one month is 0% or more and less than 10%.
O: the value obtained by dividing the viscosity by the initial viscosity after one month is 10% or more and less than 15%.
And (delta): the value obtained by dividing the viscosity by the initial viscosity after one month is 15% or more and less than 20%.
X: the value obtained by dividing the viscosity by the initial viscosity after one month is 20% or more.
[ evaluation method of bleed-out resistance ]
The curable compositions obtained in examples and comparative examples were sandwiched between a polyethylene terephthalate film ("a 4300" manufactured by toyobo co., ltd., hereinafter, abbreviated as "pet (polyethylene terephthalate) film") and a brightness enhancement film (hereinafter, abbreviated as "bef (brightness enhancing film") manufactured by 3M), and passed through a film at 0.2J/cm2The high pressure mercury lamp of (1) is irradiated with UV, and the BEF film is peeled off, thereby producing a prism sheet having a prism shape transferred on the PET film. Then, the obtained prism sheet was attached to an acrylic plate and left to stand at a high temperature and high humidity of 65 ℃ and 95% humidity for 72 hours. The surfaces of the prism sheet and acrylic sheet after 72 hours were visually observed and evaluated according to the following evaluation criteria.
O: is completely unchanged
X: bleeding was observed 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, 10 parts by mass of bisphenol a ethylene oxide-modified diacrylate ("MIRAMER M2200") manufactured by miwoon corporation was added to and mixed with 100 parts by mass of the inorganic fine particle dispersions obtained in examples and comparative examples, and the resulting mixture was evaluated by appearance observation according to the following evaluation criteria.
O: no turbidity or agglomeration of the inorganic fine particle dispersion was observed.
And (delta): turbidity was observed in the inorganic fine particle dispersion.
X: the inorganic fine particle dispersion was 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]
Figure BDA0003346903840000191
The compositions of the curable compositions (C1) to (C6) prepared in comparative examples 7 to 12 and the evaluation results are shown in table 2.
[ Table 2]
Figure BDA0003346903840000201
In tables 1 and 2, "acrylic monomer 1" represents phenylbenzyl acrylate.
In Table 1, "acrylic monomer 2" represents m-phenoxybenzyl Acrylate ("Light Acrylate POB-A") manufactured by Kyoeisha chemical Co., Ltd.
In Table 1, "acrylic monomer 3" represents o-phenylphenoxyethyl acrylate ("Miramer M1142" manufactured by MIWON corporation).
In Table 1, "acrylic monomer 4" represents fluorene diacrylate ("OGSOL EA-0200") manufactured by 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 not having a 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 same was remarkably insufficient.
Comparative example 8 is an example of an inorganic fine particle dispersion not having a hydroxyl group-containing compound as a dispersant, and a curable composition containing the inorganic fine particle dispersion. It was confirmed that the curable composition was excellent in viscosity stability and bleeding resistance, but the dispersion stability of the inorganic fine particle dispersion was insufficient.
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 remarkably insufficient and the bleeding resistance was also remarkably 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 the viscosity stability and the bleeding resistance were also insufficient in the curable composition containing the inorganic fine particle dispersion.

Claims (7)

1. An inorganic fine particle dispersion comprising inorganic fine particles (A) and a dispersant (B), characterized in that:
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.
2. The inorganic fine particle dispersion according to claim 1, wherein the amount of the dispersant (B) used is in the range of 5 to 40 parts by mass per 100 parts by mass of the inorganic fine particles (A).
3. The dispersion of inorganic fine particles according to claim 1, wherein the phosphate ester compound (b1) is represented by the following structural formula (1),
[ solution 1]
Figure FDA0003346903830000011
(in the formula, R1Is a hydrogen atom or a methyl group, R2An 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).
4. The dispersion of inorganic fine particles according to claim 1, wherein the hydroxyl group-containing compound (b2) is used in an amount of 0.05 to 30 parts by mass per 100 parts by mass of the phosphate ester compound (b 1).
5. A curable composition characterized by: comprising the dispersion of inorganic fine particles according to any one of claims 1 to 4, and a (meth) acryloyl group-containing compound (C).
6. A cured product characterized by: is a curing reactant of the curable composition according to claim 5.
7. An optical member, characterized in that: has a cured coating film comprising the cured product according to claim 6.
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JPWO2020250721A1 (en) 2021-09-13
CN113840882B (en) 2023-08-11
TW202100587A (en) 2021-01-01
WO2020250721A1 (en) 2020-12-17

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