Composition

Abstract

The purpose of the present invention is to provide a composition which contains silica particles and a monomer and which has reduced viscosity. The present invention is a composition which contains silica particles (a), an ethylenically unsaturated group-containing monomer (b), and at least one additive (c) selected from the group consisting of phosphine, amine, nitrogen-containing heterocyclic compounds, and ammonium hydroxide salts, and which does not contain a solvent or contains 10 mass% or less of a solvent per 100 mass% of the composition.

Description

Technical Field

[0001] The present invention relates to a composition. Background Art

[0002] In the past, silica particles can impart various properties such as scratch resistance to resin products, and therefore have been usefully used. As an example, silica particles are used in a hard coating for improving the surface hardness and scratch resistance of a resin substrate, etc. The hard coating can be formed by applying a composition to which silica is added to a monomer constituting the hard coating to a resin substrate, etc. and curing it, but the composition to which silica particles are added sometimes has an increased viscosity and is difficult to handle.

[0003] For example, in Patent Document 1, it is necessary to reduce the viscosity by adding a solvent to a composition containing silica particles and a monomer. However, the hard coating composition disclosed in Patent Document 1 needs to dry the solvent after being applied to the substrate, so there is a problem of reduced productivity. In addition, from the perspective of environmental concern, a hard coating composition that does not contain a solvent is also desired.

[0004] In order to solve the technical problem of using the above-mentioned solvent, a composition without solvent is proposed. For example, Patent Document 2 discloses a method of preparing a composition without solvent. 29 A silica particle-containing composition in which silica particles having a specific peak in Si-solid NMR spectrum, that is, silica particles having a small number of residual silanol groups, are mixed with a viscous substance.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2017-48300

[0008] Patent Document 2: Japanese Patent Application Publication No. 2018-16502 Summary of the invention

[0009] Problem that the invention aims to solve

[0010] An object of the present invention is to provide a composition comprising silica particles and a monomer, wherein the viscosity of the composition is reduced by a method different from that of Patent Document 2.

[0011] Solutions for solving problems

[0012] The present invention which has achieved the above-mentioned technical problems is as follows.

[0013] [1] A composition comprising silica particles (a), a monomer containing an ethylenically unsaturated group (b), and at least one additive (c) selected from the group consisting of phosphines, amines, nitrogen-containing heterocyclic compounds, and ammonium hydroxide salts, wherein the composition does not contain a solvent or contains 10% by mass or less of a solvent in 100% by mass of the composition.

[0014] [2] The composition according to [1], wherein the amount of the additive (c) is 0.01 to 5 parts by mass based on 100 parts by mass of the silica particles (a).

[0015] [3] The composition according to [1] or [2], wherein the concentration of the silica particles (a) in 100% by mass of the composition is 10% by mass or more and 70% by mass or less.

[0016] [4] The composition according to any one of [1] to [3], wherein the silica particles (a) are surface-treated with a silane coupling agent containing a functional group selected from at least one of an aryl group, a (meth)acryloyl group, an alkyl group, a vinyl group, a styryl group, an epoxy group, a mercapto group, an amino group, an isocyanate group, and a halogenated alkyl group.

[0017] [5] The composition according to any one of [1] to [4], wherein the monomer (b) containing an ethylenically unsaturated group is at least one selected from the group consisting of a monomer (b-1), a monomer (b-2) and a monomer (b-3), the monomer (b-1) having a carbamate bond or having a (1-hydroxy, 2-oxy)ethylene structure, the monomer (b-2) being a monomer having neither a carbamate bond nor a (1-hydroxy, 2-oxy)ethylene structure, wherein the number of ethylenically unsaturated groups in one molecule of the monomer is 3 or more, and the concentration of ethylenically unsaturated groups is 4.8 mmol / g or more, and the monomer (b-3) being a monomer having neither a carbamate bond nor a (1-hydroxy, 2-oxy)ethylene structure, wherein at least one of the necessary conditions that the number of ethylenically unsaturated groups in one molecule of the monomer is less than 3 and the necessary condition that the concentration of ethylenically unsaturated groups is less than 4.8 mmol / g is satisfied.

[0018] [6] The composition according to [5], wherein the ethylenically unsaturated group-containing monomer (b) is composed of at least one of monomer (b-1) and monomer (b-2) and monomer (b-3), or is composed only of monomer (b-3).

[0019] [7] The composition according to any one of [1] to [6], wherein the viscosity of the ethylenically unsaturated group-containing monomer (b) at a temperature of 25° C. is 2000 mPa·s or less.

[0020] Effects of the Invention

[0021] According to the present invention, the viscosity of the monomer composition containing silica particles can be reduced even without using a large amount of solvent. DETAILED DESCRIPTION

[0022] The composition of the present invention comprises silica particles (a), a monomer containing an ethylenically unsaturated group (b), and at least one additive (c) selected from the group consisting of phosphines, amines, nitrogen-containing heterocyclic compounds, and ammonium hydroxide salts, wherein the composition does not contain a solvent or contains 10% by mass or less of a solvent in 100% by mass of the composition. Each of the above is described below.

[0023] 1. Composition

[0024] 1-1. Silica particles (a)

[0025] The silica particles (a) are preferably nanometer-scale particles, and the average primary particle size is, for example, 1 nm or more, preferably 5 nm or more, more preferably 10 nm or more, and for example, 100 nm or less, preferably 90 nm or less, and more preferably 70 nm or less (i.e., preferably 1 to 100 nm, more preferably 5 to 90 nm, and further preferably 10 to 70 nm). The average primary particle size can be obtained by observing with an electron microscope, and the arithmetic mean of the diameters measured for any 50 particles can be used. It should be noted that, in the case where the shape of the silica particles is not roughly spherical, the major diameter can be measured as the diameter. The average sphericity of the silica particles can be obtained by observing the silica particles with an electron microscope, measuring the major diameter and the minor diameter of one silica particle, calculating the sphericity ratio (major diameter / minor diameter), averaging the sphericity ratios measured for 50 silica particles, and the value is preferably 1.2 to 1, more preferably 1.1 to 1, and further preferably 1.05 to 1.

[0026] The silica particles (a) may be surface treated, preferably with a silane coupling agent containing the following functional groups, wherein the functional groups are at least one selected from the group consisting of aryl, (meth)acryloyl, alkyl, vinyl, styryl, epoxy, mercapto, amino, isocyanate and alkyl halide. The silica particles (a) surface treated with such a silane coupling agent have the functional groups on the surface. The silica particles (a) are preferably surface treated with a silane coupling agent containing at least a (meth)acryloyl group.

[0027] The silane coupling agent is preferably a compound having a hydrolyzable group (a group that can form a silanol group by hydrolysis) and a functional group bonded to the central silicon atom, and examples thereof include: aryl alkoxysilane compounds such as phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3 - Alkoxysilane compounds containing (meth)acryloyl groups, such as acryloxypropylmethyldimethoxysilane; alkylalkoxysilane compounds, such as methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane; vinylalkoxysilane compounds, such as vinyltrimethoxysilane and vinyltriethoxysilane; p-phenylenetrimethoxysilane 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxy-containing alkoxysilanes; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane and other mercapto-containing alkoxysilane compounds; 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane and other epoxy-containing alkoxysilanes; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane and other mercapto-containing alkoxysilane compounds; 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane Alkoxysilane compounds containing amino groups such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, and N-phenyl-3-aminopropyltrimethoxysilane; alkoxysilane compounds containing isocyanate groups such as 3-isocyanatopropyltriethoxysilane; halogenated alkylalkoxysilane compounds such as chloroalkylalkoxysilane compounds such as 3-chloropropylmethyldimethoxysilane and 3-chloropropyltrimethoxysilane, and fluoroalkylalkoxysilane compounds such as trifluoropropyltrimethoxysilane; etc. The silane coupling agent may be used alone or in combination of two or more.

[0028] The concentration of the silica particles (a) in 100% by mass of the composition is preferably 10% by mass or more and 70% by mass or less (i.e., 10 to 70% by mass). The concentration of the silica particles is more preferably 15% by mass or more, further preferably 20% by mass or more, further more preferably 65% ​​by mass or less, further preferably 60% by mass or less (i.e., more preferably 15 to 65% by mass, further preferably 20 to 60% by mass). When the silica particles (a) are surface treated, the concentration of the surface treated silica particles is preferably within the range.

[0029] In particular, when the ethylenically unsaturated group-containing monomer (b) consists only of (b-3), the concentration of the silica particles (a) in 100% by mass of the composition is preferably 20 to 70% by mass, more preferably 30 to 70% by mass, and even more preferably 40 to 70% by mass.

[0030] When the ethylenically unsaturated group-containing monomer (b) is composed of at least one of (b-1) and (b-2) and (b-3), the concentration of the silica particles (a) in 100% by mass of the composition is preferably 20 to 60% by mass.

[0031] 1-2. Ethylenically unsaturated group-containing monomer (b)

[0032] As the ethylenically unsaturated group-containing monomer (b), one or two or more kinds may be used, and any one of a monofunctional monomer having one ethylenically unsaturated group in one molecule and a crosslinking monomer having two or more ethylenically unsaturated groups in one molecule may be used.

[0033] Examples of the monofunctional monomer include: (meth)acrylates; vinyl monomers such as N-vinyl-2-pyrrolidone (NVP); styrene monomers (styrenes) such as styrene, p-tert-butylstyrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, and p-hydroxystyrene; carboxyl-containing monomers such as (meth)acrylic acid; hydroxyl-containing monomers such as 2-hydroxyethyl (meth)acrylate (HEA), 3-hydroxy-2-hydroxypropyl (meth)acrylate, and 3-phenoxy-2-hydroxypropyl (meth)acrylate; and cyclotrimethylolpropane formal acrylate (CTFA).

[0034] Specific examples of the (meth)acrylates include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate (BA), isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate; cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate (CHA); aryl (meth)acrylates such as 2,4-dibromo-6-sec-butylphenyl (meth)acrylate, 2,4-dibromo-6-isopropylphenyl (meth)acrylate, phenyl (meth)acrylate, 2,4,6-tribromophenyl (meth)acrylate, and pentabromophenyl (meth)acrylate; aryl (meth)acrylates such as benzyl (meth)acrylate and pentabromobenzyl (meth)acrylate; (Meth)acrylates having an aryloxy unit such as ethyl (meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, 2,4,6-tribromophenoxyethyl (meth)acrylate, 2,4-dibromophenoxyethyl (meth)acrylate, 2-bromophenoxyethyl (meth)acrylate, 1-naphthyloxyethyl (meth)acrylate, 2-naphthyloxyethyl (meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, and phenoxyethoxyethyl (meth)acrylate; (meth)acrylates having an arylthio group such as phenylthioethyl (meth)acrylate, 1-naphthylthioethyl (meth)acrylate, and 2-naphthylthioethyl (meth)acrylate; alkylene glycol mono(meth)acrylates such as methoxypolyethylene glycol (meth)acrylate and phenoxypolyethylene glycol (meth)acrylate; (meth)acrylates having a glycidyl group such as glycidyl (meth)acrylate, and the like.

[0035] As the monofunctional monomer, preferred are (meth)acrylates, N-vinyl-2-pyrrolidone (NVP), cyclotrimethylolpropane formal acrylate (CTFA), 2-hydroxyethyl (meth)acrylate (HEA), 3-hydroxy-2-hydroxypropyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate or styrene-based monomers (styrenes), and particularly preferred are n-butyl (meth)acrylate (BA), cyclohexyl (meth)acrylate (CHA) or N-vinyl-2-pyrrolidone (NVP).

[0036] Examples of the crosslinking monomer include tetramethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate (EGDA), diethylene glycol di(meth)acrylate (DEGDA), triethylene glycol di(meth)acrylate (TEGDA), tetraethylene glycol di(meth)acrylate (TeEGDA), polyethylene glycol di(meth)acrylate (PEGDA), propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate (DPGDA), tripropylene glycol di(meth)acrylate (TPGDA), polypropylene glycol di(meth)acrylate (PPGDA), 1,4-butylene glycol di(meth)acrylate (BDDA), polybutylene glycol di(meth)acrylate (PGEDA), and polybutylene glycol di(meth)acrylate. ) acrylate (PBGDA), 1,6-hexanediol di(meth)acrylate (HDDA) and other alkylene glycol poly(meth)acrylates; neopentyl glycol di(meth)acrylate (NPGDA), dineopentyl glycol di(meth)acrylate (DNPGDA) and other neopentyl glycol poly(meth)acrylates; trimethylolpropane tri(meth)acrylate (TMPTA), ethoxylated (3) trimethylolpropane tri(meth)acrylate (TMPTA-EO), propoxylated (3) trimethylolpropane tri(meth)acrylate (TMPTA-PO), ditrimethylolpropane tetra(meth)acrylate and other trimethylolpropane poly(meth)acrylates; tri(meth)acrylate glyceryl esters, poly(meth)acrylates such as ethoxylated glyceryl tri(meth)acrylate; pentaerythritol tri(meth)acrylate (PETA), pentaerythritol tetra(meth)acrylate (PETTA), ethoxylated pentaerythritol tri(meth)acrylate (PETA-EO), propoxylated pentaerythritol tri(meth)acrylate (PETA-PO), ethoxylated pentaerythritol tetra(meth)acrylate (PETTA-EO), propoxylated pentaerythritol tetra(meth)acrylate (PETTA-PO), ditrimethylolpropane tetra(meth)acrylate (DTMPTEA), dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate (DPTPEA), dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate (DPTPEA), dipentaerythritol tetra(meth)acrylate (DPTPEA), dipentaerythritol tetra(meth)acrylate (DPTPEA), dipentaerythritol tri(meth)acrylate (PETA-EO), propoxylated pentaerythritol tetra(meth)acrylate (PETTA-PO), dipentaerythritol tetra(meth)acrylate (DTMPTEA), dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate (DPTPEA), dipentaerythritol hexa(meth)acrylate (DPTPEA), dipentaerythritol tri(meth)acrylate (PETA-EO), propoxylated pentaerythritol tetra(meth)acrylate (PETTA-PO ... HA), ethoxylated dipentaerythritol hexa(meth)acrylate (DPHA-EO), propoxylated dipentaerythritol hexa(meth)acrylate (DPHA-PO) and other pentaerythritol poly(meth)acrylates; divinylbenzene (DVB) and other multifunctional styrene monomers; 2-(allyloxymethyl) methyl acrylate, 2-(allyloxymethyl) cyclohexyl acrylate, 2-(allyloxymethyl) acrylate derivatives and other allyl ester monomers; diallyl phthalate, diallyl isophthalate, triallyl cyanurate, triallyl isocyanurate and other multifunctional allyl ester monomers; 2-(2-vinyloxyethoxy) (meth) ethyl acrylate (VEEA);Urethane acrylate oligomers (e.g., Ziguang (registered trademark) series (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), CN series (manufactured by Sartomer Co., Ltd.), UNIDIC (registered trademark) series (manufactured by DIC Co., Ltd.), KAYARAD (registered trademark) UX series (manufactured by Nippon Kayaku Co., Ltd.), etc.); epoxy acrylate oligomers (e.g., EBECRYL series (manufactured by Daicel-Allnex Co., Ltd.), NK Oligo series (manufactured by Shin-Nakamura Chemical Co., Ltd.), Neopol series (manufactured by Japan U-PICA Co., Ltd.), Epoxyester series (manufactured by Kyoeisha Chemical Co., Ltd.)); acrylic resin acrylate oligomers (e.g., HA series (manufactured by Showa Denko Materials Co., Ltd.), EBECRYL series, and KRM series (all manufactured by Daicel-Allnex Co., Ltd.)), etc.;

[0037] In addition, the ethylenically unsaturated group-containing monomer (b) is used to include the above-mentioned oligomer.

[0038] As the crosslinking monomer, 1,4-butanediol di(meth)acrylate (BDDA), 1,6-hexanediol di(meth)acrylate (HDDA), ethylene glycol di(meth)acrylate (EGDA), diethylene glycol di(meth)acrylate (DEGDA), triethylene glycol di(meth)acrylate (TEGDA), dipropylene glycol di(meth)acrylate (DPGDA), tripropylene glycol di(meth)acrylate (TPGDA), tetraethylene glycol di(meth)acrylate (TeEGDA), polyethylene glycol di(meth)acrylate (PEGD A), polypropylene glycol di(meth)acrylate (PPGDA), polybutylene glycol di(meth)acrylate (PBGDA), tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate (TMPTA), ethoxylated (3) trimethylolpropane tri(meth)acrylate (TMPTA-EO), propoxylated (3) trimethylolpropane tri(meth)acrylate (TMPTA-PO), pentaerythritol tri(meth)acrylate (PETA), ethoxylated pentaerythritol tri(meth)acrylate (PETA-EO), propoxylated Pentaerythritol tri(meth)acrylate (PETA-PO), ethoxylated pentaerythritol tetra(meth)acrylate (PETTA-EO), propoxylated pentaerythritol tetra(meth)acrylate (PETTA-PO), ethoxylated dipentaerythritol hexa(meth)acrylate (DPHA-EO), propoxylated dipentaerythritol hexa(meth)acrylate (DPHA-PO), ditrimethylolpropane tetra(meth)acrylate (DTMPTEA), 2-(allyloxymethyl)methyl acrylate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate (V EEA), neopentyl glycol di(meth)acrylate (NPGDA) or dineopentyl glycol di(meth)acrylate (DNPGDA), dipentaerythritol hexa(meth)acrylate (DPHA), pentaerythritol tetra(meth)acrylate (PETTA), urethane acrylate oligomers, divinylbenzene (DVB), diallyl phthalate or diallyl isophthalate, cyclohexyl 2-(allyloxymethyl)acrylate, 2-(allyloxymethyl)acrylate derivatives, particularly preferably: 1,4-butanediol di(meth)acrylate (BDDA), 1,6-Hexanediol di(meth)acrylate (HDDA), ethylene glycol di(meth)acrylate (EGDA), diethylene glycol di(meth)acrylate (DEGDA), triethylene glycol di(meth)acrylate (TEGDA), dipropylene glycol di(meth)acrylate (DPGDA), tripropylene glycol di(meth)acrylate (TPGDA), tetraethylene glycol di(meth)acrylate (TeEGDA), polyethylene glycol di(meth)acrylate (PEGDA), polypropylene glycol di(meth)acrylate (PPGDA), polybutylene glycol di(meth)acrylate (PBGDA), tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate (TMPTA), ethoxylated (3) trimethylolpropane tri(meth)acrylate (TMPTA-EO), propylene glycol di(meth)acrylate (EPGDA), polypropylene glycol di(meth)acrylate (PPGDA), polybutylene glycol di(meth)acrylate (PBGDA), tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate (TMPTA), ethoxylated (3) trimethylolpropane tri(meth)acrylate (TMPTA-EO), Oxylated (3) trimethylolpropane tri(meth)acrylate (TMPTA-PO), pentaerythritol tri(meth)acrylate (PETA), ethoxylated pentaerythritol tri(meth)acrylate (PETA-EO), propoxylated pentaerythritol tri(meth)acrylate (PETA-PO), ethoxylated pentaerythritol tetra(meth)acrylate (PETTA-EO), propoxylated pentaerythritol tetra(meth)acrylate (PETTA-PO), ethoxylated dipentaerythritol hexa(meth)acrylate (DPHA-EO), propoxylated dipentaerythritol hexa(meth)acrylate (DPHA-PO), ditrimethylolpropane tetra(meth)acrylate (DTMPTEA), methyl 2-(allyloxymethyl)acrylate, ethyl 2-(2-vinyloxyethoxy)(meth)acrylate.

[0039] The ethylenically unsaturated group-containing monomer (b) can be classified into any of the following (b-1) to (b-3). The monomer classified into (b-1) or (b-2) is a monomer having a relatively high viscosity, and the monomer classified into (b-3) is a monomer having a relatively low viscosity.

[0040] Monomer (b-1) is a monomer having a urethane bond (-OC(=O)NH-) or a (1-hydroxy, 2-oxy)ethylene structure (-O-CH 2 -C(OH)- structure).

[0041] Examples of the monomer having a urethane bond include the urethane acrylate oligomers described above.

[0042] The (1-hydroxy, 2-oxy)ethylene structure is a structure formed by ring-opening polymerization of an epoxy group and a carboxyl group. Examples of monomers having such a structure include epoxy acrylate oligomers and acrylic resin acrylate oligomers.

[0043] Monomer (b-2) is a monomer having neither a urethane bond nor a (1-hydroxy, 2-oxy)ethylene structure, wherein the number of ethylenically unsaturated groups in one molecule of the monomer is 3 or more, and the concentration of ethylenically unsaturated groups is 4.8 mmol / g or more.

[0044] As the monomer (b-2), a monomer having the requirements of the monomer (b-2) can be selected from the above-mentioned crosslinking monomers, and for example, trimethylolpropane tri(meth)acrylate (TMPTA), ethoxylated (3) trimethylolpropane tri(meth)acrylate, ethoxylated (3) trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate (DPHA-EO), dimethylolpropane tetra(meth)acrylate (DTMPTEA), dipentaerythritol hexa(meth)acrylate (DPHA), pentaerythritol tetra(meth)acrylate (PETTA) or ethoxylated pentaerythritol tri(meth)acrylate (PETA-EO) correspond to the monomer (b-2).

[0045] Monomer (b-3) is a monomer that does not have a carbamate bond and a (1-hydroxy, 2-oxy)ethylene structure, and satisfies at least one of the necessary conditions that the number of ethylenically unsaturated groups in one molecule of the monomer is less than 3 and the necessary conditions that the concentration of ethylenically unsaturated groups is less than 4.8 mmol / g.

[0046] As monomer (b-3), a monomer having the necessary conditions of monomer (b-3) can be selected from the above-mentioned monofunctional monomers and cross-linking monomers, for example, 2-(allyloxymethyl) methyl acrylate (AOMA), 1,4-butanediol di(meth)acrylate (BDDA), 1,6-hexanediol di(meth)acrylate (HDDA) or cyclotrimethylolpropane formal acrylate (CTFA) is equivalent to the monomer (b-3).

[0047] The monomer (b) containing an ethylenically unsaturated group may be only monomer (b-1), only monomer (b-2) or only monomer (b-3), or two or more of (b-1), (b-2) and (b-3) may be used. From the viewpoint of facilitating application of the composition of the present invention to a substrate, the monomer (b) containing an ethylenically unsaturated group is preferably composed of at least one of monomer (b-1) and monomer (b-2) and monomer (b-3), or is composed of only monomer (b-3).

[0048] From the viewpoint of facilitating application of the composition of the present invention on a substrate, the viscosity of the ethylenically unsaturated group-containing monomer (b) at a temperature of 25° C. is preferably 2000 mPa·s or less. When two or more ethylenically unsaturated group-containing monomers (b) are used, it is preferred that the viscosity of the two or more monomers (b) be mixed to satisfy the above range.

[0049] It should be noted that the viscosity of the monomer can be measured as shown in the examples described below. When a monomer corresponding to (b-1) or (b-2) is used and when at least one of (b-1) and (b-2) and (b-3) are used, the viscosity can be measured using TVE-22H manufactured by Toki Sangyo Co., Ltd. under the conditions of a rotor diameter of 1.9 cm, a rotation speed of 20 rpm, and a range of "H".

[0050] In addition, when only the monomer equivalent to (b-3) is used, the measurement can be performed using TV-100EL manufactured by Toki Sangyo Co., Ltd., with a rotor diameter of 4.7 cm, a rotation speed of 5 rpm, and a range of "M" when the viscosity is ~100 mPa·s, "2.5M" when the viscosity is 100 to 200 mPa·s, and "5M" when the viscosity is above 200 mPa·s.

[0051] The viscosity of the monomer (b) containing an ethylenically unsaturated group at a temperature of 25° C. is preferably 1000 mPa·s or less, more preferably 500 mPa·s or less, and the lower limit is not particularly limited, for example, it can be 0.5 mPa·s (that is, preferably 1000 to 0.5 mPa·s, more preferably 500 to 0.5 mPa·s).

[0052] 1-3. Additives (c)

[0053] The composition of the present invention contains at least one additive (c) selected from the group consisting of phosphines, amines, nitrogen-containing heterocyclic compounds and ammonium hydroxide salts. The composition containing such an additive (c) can suppress the increase in viscosity of the composition (usually a liquid composition).

[0054] Phosphine refers to pH 3 A compound in which at least one hydrogen atom is replaced by an organic group. Examples of the organic group replacing at least one hydrogen atom include aliphatic hydrocarbon groups or aromatic hydrocarbon groups, preferably aliphatic saturated hydrocarbon groups having 1 to 10 carbon atoms or aromatic hydrocarbon groups having 6 to 10 carbon atoms, and more preferably aliphatic saturated hydrocarbon groups having 3 to 8 carbon atoms or aromatic hydrocarbon groups having 6 to 8 carbon atoms. 3 In the case of a compound in which two or more hydrogen atoms are replaced by organic groups, the two or more organic groups replacing the hydrogen atoms may be the same or different, but are preferably the same. 3All hydrogen atoms of the amine are replaced by organic groups, and in this case, the three organic groups are preferably the same.

[0055] As the phosphine, tributylphosphine, trioctylphosphine or triphenylphosphine is preferred, and triphenylphosphine is particularly preferred.

[0056] Examples of the amine include aliphatic amines such as methylamine, ethylamine, propylamine, n-butylamine, dimethylamine, dibutylamine, trimethylamine, triethylamine, and tributylamine; alicyclic amines such as cyclohexylamine; and aromatic amines such as aniline and benzylamine. The amine is preferably an aliphatic amine, and triethylamine is particularly preferred.

[0057] Examples of the nitrogen-containing heterocyclic compound include nitrogen-containing aromatic heterocyclic compounds such as pyridine, quinoline, 2,2-bipyridine, imidazole, and 1-methylimidazole, and nitrogen-containing polycyclic heterocyclic compounds such as diazabicycloundecene (DBU), diazabicyclononene (DBN), methyltriazabicyclodecene (MTBD), triazabicyclodecene (TBD), and diazabicyclooctane (DABCO). Nitrogen-containing aromatic heterocyclic compounds are more preferred, and pyridine is particularly preferred.

[0058] Examples of the ammonium hydroxide salt include tetraalkylammonium hydroxide, trialkylarylammonium hydroxide, dialkyldiarylammonium hydroxide, alkyltriarylammonium hydroxide, tetraarylammonium hydroxide, cyclic ammonium hydroxide, and dicyclic ammonium hydroxide, and tetraalkylammonium hydroxide is preferred.

[0059] Examples of the tetraalkylammonium hydroxides include tetraalkylammonium hydroxides having four short-chain (having about 1 to 6 carbon atoms) alkyl groups, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, dimethyldibutylammonium salt, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, and tetrahexylammonium hydroxide; and tetraalkylammonium hydroxides having short-chain (having about 1 to 6 carbon atoms) and medium-chain or long-chain (having about 7 to 30 carbon atoms) alkyl groups, such as lauryltrimethylammonium hydroxide, stearyltrimethylammonium hydroxide, cetyltrimethylammonium hydroxide, and distearyldimethylammonium hydroxide. The tetraalkylammonium hydroxides having four short-chain alkyl groups are preferred, and tetramethylammonium hydroxide, tetraethylammonium hydroxide, or tetrabutylammonium hydroxide is particularly preferred.

[0060] The additive (c) may be used alone or in combination of two or more.

[0061] The amount of the additive (c) relative to 100 parts by mass of the silica particles (a) is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and further preferably 0.05 parts by mass or more, and is further preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and further preferably 1 part by mass or less (i.e., preferably 0.01 to 5 parts by mass, more preferably 0.02 to 3 parts by mass, and further preferably 0.05 to 1 part by mass).

[0062] In addition, the amount of the additive (c) relative to 100 mass % of the composition is preferably 0.001 mass % or more, more preferably 0.005 mass % or more, further preferably 0.01 mass % or more, and is further preferably 3 mass % or less, more preferably 2 mass % or less, further preferably 1 mass % or less (i.e., preferably 0.001 to 3 mass %, more preferably 0.005 to 2 mass %, further preferably 0.01 to 1 mass %).

[0063] When the monomer (b) containing an ethylenically unsaturated group consists only of (b-3), the amount of the additive (c) is preferably 0.001% by mass or more and 1% by mass or less (i.e., 0.001 to 1% by mass), and preferably 0.001% by mass or more and 0.5% by mass or less (i.e., 0.001 to 0.5% by mass), relative to 100% by mass of the composition.

[0064] When the monomer (b) containing an ethylenically unsaturated group is composed of at least one of (b-1) and (b-2) and (b-3), the amount of the additive (c) is preferably 0.001 mass % or more and 2 mass % or less (i.e., 0.001 to 2 mass %), and more preferably 0.001 mass % or more and 1 mass % or less (i.e., 0.001 to 1 mass %), relative to 100 mass % of the composition.

[0065] Among the additives (c), phosphine is particularly preferred, and triphenylphosphine is most preferred. When the additive (c) is triphenylphosphine and the ethylenically unsaturated group-containing monomer (b) consists only of (b-3), the amount of triphenylphosphine is preferably 0.001% by mass or more and 0.5% by mass or less relative to 100% by mass of the composition. Furthermore, when the additive (c) is triphenylphosphine and the ethylenically unsaturated group-containing monomer (b) consists of at least one of (b-1) and (b-2) and (b-3), the amount of triphenylphosphine is preferably 0.001% by mass or more and 1% by mass or less (i.e., 0.001 to 1% by mass), and more preferably 0.05% by mass or more and 1% by mass or less (i.e., 0.05 to 1% by mass) relative to 100% by mass of the composition.

[0066] In addition, when using 2 or more types as an additive (c), what is necessary is just to adjust the total amount to the said range.

[0067] 1-4. Polymerization initiator

[0068] The composition of the present invention may include a polymerization initiator. As the polymerization initiator, for example, a photopolymerization initiator, a thermal polymerization initiator, etc. can be listed, which can be used alone or in combination. It should be noted that there are substances that act as thermal polymerization initiators in the photopolymerization initiator, and in addition, there are substances that act as photopolymerization initiators in the thermal polymerization initiator, so the substances with two properties can cure the active energy ray-curable resin composition by light irradiation or heating. Among the polymerization initiators, from the perspective of not imparting thermal experience to the formed film, the substrate to which the active energy ray-curable resin composition is applied, etc., a photopolymerization initiator is preferred.

[0069] Examples of thermal polymerization initiators include: 2,2'-azobis-(2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4'-dimethylvaleronitrile), benzoyl peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butylperoxy-2-ethylhexanoate and other oil-soluble initiators; persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; water-soluble peroxides such as hydrogen peroxide; water-soluble azo compounds such as 2,2'-azobis(2-amidinopropane) dihydrochloride, etc., but the present invention is not limited to the examples described above. These thermal polymerization initiators may be used alone or in combination of two or more.

[0070] Examples of the photopolymerization initiator include benzophenone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-[2-oxo-2-phenylacetoxyethoxy]ethyl hydroxyphenylacetate, 2-[2-hydroxyethoxy]ethyl hydroxyphenylacetate, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-Hydroxy-2-methyl-1-phenylpropane-1-one, 1-(4-isopropylphenyl)2-hydroxy-2-methylpropane-1-one, 2-methyl-1-[4-(methylthio)phenyl]2-morpholinopropane-1-one, 2-morpholinopropane-1-one, iodonium, sulfonium salt, diazonium salt, (4-methylphenyl [4-(2-methylpropyl)phenyl]) hexafluorophosphate, diethylthioxanthone, isopropylthioxanthone, etc., but the present invention is not limited to the above examples. These photopolymerization initiators can be used alone or in combination of two or more.

[0071] The amount of the polymerization initiator is, for example, 1 part by mass or more and 25 parts by mass or less relative to 100 parts by mass of the ethylenically unsaturated group-containing monomer (b).

[0072] 1-5. Solvent

[0073] The composition of the present invention contains no solvent, or when containing a solvent, the amount of the solvent is 10% by mass or less in 100% by mass of the composition. The amount of the solvent is more preferably 5% by mass or less, and further preferably 1% by mass or less in 100% by mass of the composition.

[0074] The amount of the solvent can be quantified by a calibration curve method (internal standard) using gas chromatography as shown in the examples described below.

[0075] 1-6. Other ingredients

[0076] The composition of the present invention may contain other additives in addition to the silica particles (a), the monomer containing an ethylenically unsaturated group (b), the additive (c), the polymerization initiator and the solvent, and the amount of the other additives is preferably 3% by mass or less, more preferably 2% by mass or less, and further preferably 0% by mass in 100% by mass of the composition.

[0077] 1-7. Viscosity of the composition

[0078] Since the composition of the present invention contains the additive (c), the viscosity increase is suppressed. The ratio of the viscosity of the composition to the viscosity of the monomer (b) containing an ethylenically unsaturated group (the viscosity of the mixture when two or more are used) is preferably 35 or less, more preferably 30 or less, and further preferably 20 or less. The lower limit is not particularly limited, for example, it can be 3 or more, or 5 or more (that is, preferably 35 to 3, more preferably 30 to 5, and further preferably 20 to 5). It should be noted that the viscosity of the composition can be determined according to the type of the monomer (b) containing an ethylenically unsaturated group contained in the composition, and the above-mentioned determination method suitable for the monomer (b) containing an ethylenically unsaturated group can be directly used.

[0079] 1-8. Scratch resistance of cured product of composition

[0080] Since the composition of the present invention contains the additive (c), the particles can be uniformly dispersed in the coating film formed from the composition of the present invention (cured film of the composition of the present invention), and the coating film can be expected to have scratch resistance.

[0081] 2. Manufacturing method

[0082] The composition of the present invention can be prepared by a production method comprising a synthesis step (A) of silica particles (a), an ultrafiltration step (C), an ion exchange step (D), and an additive (c) addition and a monomer replacement step (E). The production method may further include a surface treatment step (B) between step (A) and step (C).

[0083] 2-1. Synthesis step (A) of silica particles (a)

[0084] In the synthesis step (A) of the silica particles (a) (hereinafter also simply referred to as step (A)), the silica particles are produced by hydrolyzing and condensing alkoxysilane in the presence of a basic catalyst and water.

[0085] The alkoxysilane is a compound having an alkoxy group as a substituent of a silicon atom, and as a substituent of a silicon atom, in addition to the alkoxy group, an alkyl group having 2 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms may be present. In addition, the hydrogen atom of the alkyl group may be substituted by a halogen atom, a vinyl group, a glycidyl group, a mercapto group, an amino group, or the like.

[0086] Examples of the alkoxysilane include compounds in which an alkoxy group and an unsubstituted or substituted alkyl group are bonded to a silicon atom. Mono- to tetrafunctional alkoxysilanes can be used, and tetrafunctional alkoxysilanes such as tetramethoxysilane and tetraethoxysilane are particularly preferred.

[0087] In the reaction solution for hydrolyzing and condensing alkoxysilane, the concentration of alkoxysilane is, for example, 0.1 mmol / g to 3 mmol / g. When the concentration of alkoxysilane in the reaction solution is within this range, the reaction rate can be easily controlled and the particle size can be made uniform.

[0088] The concentration of water in the reaction solution is preferably 2 mmol / g to 25 mmol / g based on the amount at the time of charging (before hydrolysis / condensation starts), and the molar ratio of water to alkoxysilane (water / alkoxysilane) is preferably 4 to 10.

[0089] As the basic catalyst, ammonia, amines, quaternary ammonium compounds, etc. can be listed, among which ammonia and amines are preferred from the viewpoint of easy control of particle size and improvement of the purity of the obtained silica particles. Ammonia is preferred from the viewpoint of both catalytic effect and ease of removal, and ammonia is particularly preferred.

[0090] The concentration of the basic catalyst in the reaction solution is preferably 0.8 mmol / g to 2 mmol / g. The mass ratio of the basic catalyst to the sum of the basic catalyst and water (basic catalyst / (basic catalyst+water)) is preferably 0.2 to 0.32.

[0091] When the alkoxysilane is hydrolyzed / condensed, a diluent may be coexistent. As the diluent, a water-soluble organic solvent is preferred, and as the water-soluble organic solvent, an alcohol solvent is preferred, and monohydric alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, and amyl alcohol are more preferred, and methanol is particularly preferred.

[0092] The diluent in the reaction solution is preferably 40% by mass or more and 90% by mass or less. In addition, the diluent is preferably 120 parts by mass or more and 500 parts by mass or less relative to 100 parts by mass of the total of alkoxysilane and water. However, due to the hydrolysis / condensation of the alkoxysilane, the amount of alcohol changes, so the amount of the diluent is based on the amount at the time of loading (before the start of hydrolysis / condensation).

[0093] The reaction solution may also contain ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; alkanes such as isooctane and cyclohexane; ethers such as dioxane and diethyl ether; aromatic hydrocarbons such as benzene and toluene; and other hydrophobic organic solvents. When using these hydrophobic organic solvents, a surfactant may be added to improve dispersibility.

[0094] The above components may be mixed in an appropriate order. For example, the components other than the alkoxysilane may be mixed in advance by preparing a premixed liquid, and then adding the alkoxysilane to the premixed liquid.

[0095] When the alkoxysilane is hydrolyzed / condensed, the reaction temperature is preferably 20 to 70° C., and the duration of the hydrolysis / condensation is preferably 30 minutes to 100 hours.

[0096] 2-2. Surface treatment process (B)

[0097] The preferred production method of the present invention preferably includes a surface treatment step (B) (hereinafter also referred to as step (B)). In step (B), the above-mentioned silane coupling agent is preferably mixed with the reaction liquid after hydrolysis / condensation of the alkoxysilane obtained in step (A). During mixing, the silane coupling agent is preferably added to the reaction liquid after hydrolysis / condensation of the alkoxysilane obtained in step (A), and it is particularly preferred to add the silane coupling agent by dropping in equal portions a plurality of times.

[0098] Preferably, the silane coupling agent is used in an amount of about 1 to 30 parts by mass, preferably 7 to 15 parts by mass, relative to 100 parts by mass of the amount (charged amount) of the alkoxysilane used in step (A). After the total amount of the silane coupling agent is mixed with the reaction solution of step (A), it is preferably stirred for about 10 to 30 hours. Step (B) is preferably carried out at a temperature of 30 to 60°C.

[0099] 2-3. Ultrafiltration step (C)

[0100] By performing an ultrafiltration step (C) (hereinafter also referred to as step (C)) using an ultrafiltration membrane after step (A) or after step (B), water, alkaline catalyst, diluent added as needed, ketones, etc. contained in the reaction solution after hydrolysis / condensation can be removed, and the remaining surface treatment agent that cannot cover the surface of the silica particles in the step (B) can be removed. In step (C), a dispersion medium such as an alcohol solvent different from the dispersion medium (reaction solvent) of the reaction solution can be added while filtering with an ultrafiltration membrane. In the solvent replacement, it is preferred to concentrate the silica particles (surface-treated silica particles in the case of surface treatment) to a concentration of about 5 to 20% by mass to prepare a silica particle dispersion.

[0101] 2-4. Ion exchange step (D)

[0102] It is preferred that the silica particle dispersion after step (C) is further subjected to an ion exchange step (D) (hereinafter also referred to as step (D)) in which a cation exchange resin is used to treat the silica particle dispersion. By step (D), the alkaline catalyst adsorbed on the particle surface can be removed. The cation exchange resin can use a cation exchange resin known in the past, and any of a weakly acidic cation exchange resin and a strongly acidic cation exchange resin can be used. As the weakly acidic cation exchange resin, for example, AMBERLITE IRC-76 (Organo (Strain) system), DIAION WK10, WK20 (Mitsubishi Chemical (Strain) system), LEWATITCNP80 (Bayer (Strain) system), etc. can be cited. Examples of the strongly acidic cation exchange resin include AMBERLYST 16, AMBERLITE IR-120B (manufactured by Organo Co., Ltd.), DIAION PK-208, PK-228, PK-216 (manufactured by Mitsubishi Chemical Corporation), DUOLITE C-26, DUOLITE ES-26 (manufactured by Sumitomo Chemical Co., Ltd.), and MSC-1, 88 (manufactured by Dow Chemical).

[0103] 2-5. Additive (c) addition and monomer replacement step (E)

[0104] In the additive (c) addition and monomer replacement step (E) (hereinafter also referred to as step (E)), the silica particle dispersion obtained in the ion exchange step (D) is mixed with the additive (c) and the ethylenically unsaturated group-containing monomer (b), and the dispersion medium of the silica particle dispersion obtained in the step (D) is distilled off to obtain a composition containing silica particles (a), the ethylenically unsaturated group-containing monomer (b) and the additive (c).

[0105] The additive (c) is preferably used in an amount of 0.001 to 1 part by mass per 100 parts by mass of the silica particles contained in the silica particle dispersion obtained in step (D). The ethylenically unsaturated group-containing monomer (b) is preferably used in an amount of 50 to 150 parts by mass per 100 parts by mass of the silica particles.

[0106] In step (E), the solvent contained in the silica particle dispersion obtained in the ion exchange step (D) may be removed by a solid-liquid separation method such as centrifugal separation or solvent distillation removal by reduced pressure distillation. As a result, the dispersion medium is replaced by the ethylenically unsaturated group-containing monomer (b) from the solvent in the silica particle dispersion obtained in step (D), and the amount of solvent in the composition can be adjusted.

[0107] The composition of the present invention can suppress the increase in viscosity and is therefore useful as a coating composition (composition for coating) for use in forming precise microstructures such as adhesives, dental materials, optical parts, coating materials (for hard coating, anti-glare), nanocomposites, polishing materials, nanoimprinting, inkjet, and resists.

[0108] This application claims the benefit of priority based on Japanese Patent Application No. 2022-117480 filed on July 22, 2022. The entire contents of the specification of Japanese Patent Application No. 2022-117480 filed on July 22, 2022 are incorporated herein by reference.

[0109] Example

[0110] The present invention is not limited to the following embodiments, and can be implemented by appropriately changing the embodiments within the scope of the above and the following descriptions, which are all included in the technical scope of the present invention.

[0111] The following Examples and Comparative Examples were evaluated by the following methods.

[0112] (1) Measurement of particle size of silica particles

[0113] The silica particles were photographed using a scanning electron microscope JSM-7600F manufactured by JEOL Ltd., and the diameter (long diameter) of any 50 particles in the photographed SEM image was measured with a vernier caliper, and the arithmetic mean of the 50 diameters was taken as the average primary particle size. In addition, the long diameter and short diameter of one silica particle were measured, and the sphericity ratio (long diameter / short diameter) was calculated. The sphericity ratios measured for 50 silica particles were averaged to obtain the average sphericity ratio. It should be noted that in the photographing using a scanning electron microscope, the measurement magnification was set so that there were 50 to 100 particles in the field of view of one photograph.

[0114] (2) Monomer viscosity measurement

[0115] Among the monomers (2-1), the monomer corresponding to the above-mentioned (b-1) or (b-2), the monomer consisting of at least one of (b-1) and (b-2) and (b-3) is measured by the following method. A predetermined amount of sample is placed on a stage, and the viscosity is recorded 1 minute after the start of rotation under the following conditions.

[0116] Device: TVE-22H manufactured by Toki Industry Co., Ltd.

[0117] Measurement temperature: 25℃.

[0118] Rotor diameter: 1.9cm in diameter.

[0119] Rotation speed: 20rpm.

[0120] Range: H.

[0121] Sample volume: 0.2mL.

[0122] (2-2) The monomer corresponding to the above-mentioned (b-3) was measured by the following method: A predetermined amount of sample was placed on a stage, and the viscosity was recorded 1 minute after the start of rotation under the following conditions.

[0123] Device: TV-100EL manufactured by Toki Industry Co., Ltd.

[0124] Measurement temperature: 25℃.

[0125] Rotor diameter: 4.7cm in diameter.

[0126] Rotation speed: 5rpm.

[0127] Range: M (~100mPa·s);

[0128] 2.5M (100~200mPa·s);

[0129] 5M(200mPa·s~).

[0130] Sample volume: 1.1 mL.

[0131] (3) Viscosity measurement of monomer dispersion of silica particles

[0132] The viscosity of the monomer dispersion of silica particles is measured from the viscosity value by the same method as in the above (2).

[0133] (4) Determination of solvent (methanol) content

[0134] In a glass vial, 0.2 g of the monomer dispersion, 0.02 g of diethylene glycol diethyl ether as an internal standard, and 5 g of n-butanol were mixed. The mixed solution was filtered with a filter having a pore size of 0.45 μm, and the content of the solvent in the filtrate was determined by a gas chromatography standard curve method (internal standard). The conditions of the gas chromatography were as follows.

[0135] Apparatus: GC-2014 (manufactured by Shimadzu Corporation).

[0136] Chromatographic column: capillary column InertCap Pure-WAX (manufactured by GL Sciences, column length: 30 m, column inner diameter: 0.25 mm, capillary inner film thickness: 0.25 μm).

[0137] Carrier gas: Helium.

[0138] Column temperature: maintained at 50°C for 5 minutes, increased at 10°C / min, and maintained at 240°C for 6 minutes.

[0139] Injection temperature: 280℃.

[0140] Detector temperature: 280°C (FID).

[0141] Examples of detectable substances and retention times: methanol (2.5 minutes), diethylene glycol diethyl ether (12.3 minutes).

[0142] (5) Appearance evaluation of monomer dispersion cured product

[0143] The composition was applied onto a polyethylene terephthalate film (COSMOSHINE A4300#100 manufactured by Toyobo Co., Ltd.) using a bar coater and irradiated with a metal halide lamp at a single irradiation energy of 2000 mJ / cm 2 The irradiation was performed in a manner of , and a cured coating film was produced. The produced coating film was evaluated according to the following criteria to determine the appearance.

[0144] 0:There is a foreign object.

[0145] ×: No foreign matter.

[0146] Example 1

[0147] Process 1A Particle synthesis process

[0148] 16500 g of methanol, 4200 g of water, and 2000 g of 25% ammonia water were added to a 50 L SUS container equipped with a stirrer, a dropping port, and a thermometer, and stirred for 30 minutes to obtain a uniform mixed solution. While adjusting the liquid temperature of the mixed solution to 49-51° C. and stirring, 5700 g of tetramethyl orthosilicate (TMOS) was added dropwise from the dropping port over a period of 90 minutes. After the addition was completed, stirring was continued for 30 minutes while maintaining the liquid temperature, thereby obtaining an alcoholic solution suspension of silica particles (suspension 1A).

[0149] Process 1B Surface treatment process

[0150] The suspension 1A obtained in the step A was heated to 50°C again while stirring, and 660 g of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise from the dropping port over a period of 120 minutes while maintaining the liquid temperature and stirring. After the addition was completed, stirring was continued for 15 hours while maintaining the liquid temperature, thereby obtaining an alcoholic solution suspension of silica particles having methacryloyl groups on the particle surface (suspension 1B).

[0151] Process 1C Ultrafiltration Process

[0152] The suspension 1B obtained in the above step B was subjected to solvent replacement at room temperature while adding appropriate amounts of methanol using a commercially available ultrafiltration membrane equipped with a ceramic tubular ultrafiltration membrane having a molecular weight cutoff of about 10,000, and concentrated to a concentration of SiO 2 The concentration was about 11%, thereby obtaining a methanol suspension of silica particles having methacryloyl groups on the particle surfaces (suspension 1C).

[0153] Process 1D Ion Exchange Process

[0154] The suspension 1C was passed through a column filled with hydrogen-type strongly acidic cation exchange resin AMBERLITE IR-120B (Organo) at room temperature at a space velocity of 3 per hour to obtain a methanol suspension of silica particles having methacryloyl groups (suspension 1D).

[0155] Process 1E Additive Addition and Monomer Replacement Process

[0156] 1800 g of the suspension 1D was weighed, and an amount of 1,6-hexanediol diacrylate (HDDA) (monomer (b-3)) equal to the amount of silica particles contained and 1000 ppm of triphenylphosphine (additive (c)) relative to the silica particles were added, and the solvent was distilled off using a rotary evaporator at a reduced pressure of 30 to 300 hPa and 40° C., thereby obtaining a HDDA dispersion of silica particles having a methacryloyl group (dispersion E1).

[0157] Example 2

[0158] The addition amounts of methanol, water, and 25% ammonia water in step 1A were changed to 1700 g, 3200 g, and 1400 g, respectively, the addition amount of KBM-503 in step 1B was changed to 1600 g, and trimethylolpropane triacrylate (TMPTA) was used instead of 1,6-hexanediol diacrylate (HDDA) in step 1E. A monomer dispersion of silica particles having a methacryloyl group (dispersion E2) was obtained in the same manner as in Example 1, except that the above-mentioned amounts were changed to 1700 g, 3200 g, and 1400 g, respectively; the addition amount of KBM-503 in step 1B was changed to 1600 g; and trimethylolpropane triacrylate (TMPTA) was used instead of 1,6-hexanediol diacrylate (HDDA) in step 1E.

[0159] Embodiments 3 to 12

[0160] Except having changed the monomer added in step 1E, the kind of additive, and the amount of additive as described in Table 1, it carried out similarly to Example 1, and obtained the monomer dispersion of the silica particle which has a methacryloyl group (dispersion E3-E12).

[0161] Comparative Examples 1 to 3

[0162] In Examples 1 to 3, except that the additive (c) was not added, the same procedures as in Examples 1 to 3 were carried out to obtain monomer dispersion C1 (Comparative Example 1), monomer dispersion C2 (Comparative Example 2), and monomer dispersion C3 (Comparative Example 3), respectively.

[0163] The results of the measurements of Examples 1 to 12 and Comparative Examples 1 to 3 according to the above (1) to (4) are shown in Table 1. In Table 1, TMAH refers to tetramethylammonium hydroxide, TEAH refers to tetraethylammonium hydroxide, and TBAH refers to tetrabutylammonium hydroxide.

[0164] [Table 1]

[0165]

[0166] It should be noted that, in Examples 1 to 12, the average sphericity ratio of the silica particles was in the range of 1.05 to 1.

[0167] Embodiment 13

[0168] 5 g of the dispersion E1, 5 g of DPHA (monomer (b-2)), and 0.5 g of Omnirad184 (photoradical polymerization initiator, manufactured by IGM RESINS) were placed in a transparent glass bottle, and stirred until uniform using a stirring / defoaming device (ARE-310, manufactured by THINKY) to obtain a silica particle-containing composition (1).

[0169] Embodiment 14

[0170] The same operation was performed except that the suspension 1D of step 1E was changed to 900 g, the amount of 1,6-hexanediol diacrylate (HDDA) added was changed to the same amount as the contained silica particles, and 200% of DPHA (dipentaerythritol hexaacrylate) was added relative to the contained silica particles, to obtain a silica particle dispersion. In addition, 10 g of the present dispersion and 0.5 g of Omnirad184 (photoradical polymerization initiator, manufactured by IGM RESINS) were placed in a transparent glass bottle, and stirred until uniform using a stirring / defoaming device (ARE-310, manufactured by THINKY Co., Ltd.) to obtain a silica particle-containing composition (2).

[0171] Embodiment 15

[0172] After adding 1,6-hexanediol diacrylate (HDDA) and silica particles in the same manner as in step 1E, the same operation was performed except that 50% of UV series UV7650B (manufactured by Mitsubishi Chemical Corporation) was added based on the silica particles to obtain a silica particle-containing composition (3).

[0173] Comparative Example 4

[0174] The same operation was carried out as in Example 14 except that triphenylphosphine was not added to obtain a silica particle-containing composition (4).

[0175] Table 2 shows the results of measurements of Examples 13 to 15 and Comparative Example 4 according to the above (2), (3) and (5).

[0176] [Table 2]

[0177]

Claims

1. A composition comprising silica particles (a) and a monomer (b) containing an ethylenically unsaturated group, further comprising at least one additive (c) selected from the group consisting of phosphines, amines, nitrogen-containing heterocyclic compounds and ammonium hydroxide salts, The composition contains no solvent or contains 10% by mass or less of a solvent in 100% by mass of the composition.

2. The composition according to claim 1, wherein The amount of the additive (c) is 0.01 to 5 parts by mass based on 100 parts by mass of the silica particles (a).

3. The composition according to claim 1 or 2, wherein The concentration of the silica particles (a) in 100% by mass of the composition is 10% by mass or more and 70% by mass or less.

4. The composition according to claim 1 or 2, wherein The silica particles (a) are surface-treated with a silane coupling agent containing a functional group selected from at least one of an aryl group, a (meth)acryloyl group, an alkyl group, a vinyl group, a styryl group, an epoxy group, a mercapto group, an amino group, an isocyanate group, and a halogenated alkyl group.

5. The composition according to claim 1 or 2, wherein The monomer (b) containing an ethylenically unsaturated group is at least one selected from the group consisting of monomer (b-1), monomer (b-2) and monomer (b-3), The monomer (b-1) has a urethane bond or a (1-hydroxy, 2-oxy)ethylene structure, The monomer (b-2) is a monomer having neither a carbamate bond nor a (1-hydroxy, 2-oxy)ethylene structure, wherein the number of ethylenically unsaturated groups in one molecule of the monomer is 3 or more, and the concentration of the ethylenically unsaturated groups is 4.8 mmol / g or more, The monomer (b-3) is a monomer that does not have a carbamate bond and a (1-hydroxy, 2-oxy)ethylene structure, and satisfies at least one of the necessary conditions that the number of ethylenically unsaturated groups in one molecule of the monomer is less than 3 and the necessary conditions that the concentration of ethylenically unsaturated groups is less than 4.8 mmol / g.

6. The composition according to claim 5, wherein The ethylenically unsaturated group-containing monomer (b) is composed of at least one of the monomer (b-1) and the monomer (b-2) and the monomer (b-3), or is composed of only the monomer (b-3).

7. The composition according to claim 1 or 2, wherein The viscosity of the ethylenically unsaturated group-containing monomer (b) at a temperature of 25° C. is 2000 mPa·s or less.

Images