Resin composition

Abstract

The present invention pertains to a curable resin composition or the like having excellent transparency, coating properties, and workability. Specifically, the present invention pertains to a resin composition or the like containing (A) a polymer having two or more (meth)acryloyl groups per molecule, (B) a silica powder that has been surface treated with an alkylsilane, and (C) boric acid or a boric acid ester.

Description

[Technical Field]

[0001] The present invention relates to a resin composition having excellent transparency, coatability and workability. [Background technology]

[0002] In adhesives, sealants, coatings, and the like, the viscosity and thixotropy of resins are commonly adjusted to improve workability during application. In particular, increasing thixotropy to enable application to vertical surfaces and adjusting flowability to prevent problems caused by overflowing beyond the required range are essential techniques when using adhesives and sealants. Common methods for increasing thixotropy include adding fillers to adhesives and sealants, and adding compounds that are poorly compatible with the base binder resin to the adhesive or sealant, thereby causing chemical repulsion with the base resin and resulting in high thixotropy (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-221893 Summary of the Invention

[0004] However, conventional methods of improving thixotropy by adding fillers result in a decrease in the light transmittance of the resin as the amount of filler added increases, and methods of improving thixotropy by adding compounds that are poorly compatible with the binder have the problem of the resin becoming cloudy.

[0005] As a result of intensive research to achieve the above object, the present inventors have discovered a method for effectively imparting thixotropy while maintaining transparency, thereby obtaining a resin composition with excellent coatability and workability, and have arrived at the present invention. Thixotropy is also called thixotropy or thixotropic properties, and the better the thixotropy, the lower the viscosity at high shear rates, such as when applying a coating material, but the higher the viscosity at low shear rates, such as after application, so that the coating material does not flow (drip) downward after application, and proper application can be completed.

[0006] The present invention can be any of the following [1] to

[13] . Appropriate combinations of the specific elements described in [1] to

[13] are also within the scope of the present invention. [1] (A) a polymer having two or more (meth)acryloyl groups in one molecule; (B) Silica powder surface-treated with alkylsilane, and (C) boric acid or boric acid ester, A resin composition comprising: [2] The component (C) is represented by the following general formula (1): B-(OR)3(1) (In formula (1), R may be the same or different and represent hydrogen or a functional group selected from an alkyl group having 1 to 6 carbon atoms, an aryl group, a carbonyl group, and an acetyl group, which may have a substituent.) The resin composition according to [1] above, wherein the compound is a compound represented by the formula: [3] The resin composition according to [1] or [2] above, wherein the silica powder of the component (B) is fumed silica powder. [4] The resin composition according to any one of [1] to [3] above, wherein the alkyl group of the component (B) has 3 to 15 carbon atoms. [5] The resin composition according to any one of [1] to [3] above, wherein the alkyl group of the component (B) is an octyl group. [6] The resin composition according to any one of [1] to [5] above, wherein the average particle size of the primary particles of the component (B) is 1 to 300 nm. [7] The resin composition according to any one of [1] to [6] above, wherein the mass ratio of the component (B) to the component (C) is 9:1 to 1:9. [8] A curable resin composition comprising the resin composition according to any one of [1] to [7] above and a radical polymerization initiator. [9] A cured product obtained by curing the curable resin composition described in [8] above.

[10] An adhesive comprising the curable resin composition according to [8] above.

[11] A sealant comprising the curable resin composition according to [8].

[12] (A) a polymer having two or more (meth)acryloyl groups in one molecule; (B) Silica powder surface-treated with alkylsilane, and (C) boric acid or boric acid ester, A method for producing a resin composition, comprising mixing the above components.

[13] (A) a polymer having two or more (meth)acryloyl groups in one molecule; (B) Silica powder surface-treated with alkylsilane, and (C) boric acid or boric acid ester, to produce a resin composition; and (D) mixing a radical polymerization initiator with the resin composition; and a step of curing the resin composition by light or heat to produce a cured product; A method for producing a cured product, comprising:

[0007] The resin composition of the present invention allows adjustment of thixotropy without impairing transparency, and is therefore extremely useful for improving coatability and workability in a wide range of fields where transparency is required. DETAILED DESCRIPTION OF THE INVENTION

[0008] The details of the present invention are described below. Note that the preferred and more preferred embodiments exemplified below can be used in appropriate combination with each other regardless of expressions such as "preferable" or "more preferred." Furthermore, the descriptions of numerical ranges are merely examples, and ranges obtained by appropriately combining the upper and lower limits of each range and the numerical values ​​of the examples can also be preferably used regardless of expressions such as "preferable" or "more preferred." Furthermore, terms such as "contain" or "comprise" may be interpreted as "essentially consisting of" or "consisting only of," as appropriate.

[0009] <Resin composition> One aspect of the present invention is a resin composition containing (A) a polymer having two or more (meth)acryloyl groups in one molecule, (B) silica powder surface-treated with an alkylsilane, and (C) boric acid or a borate ester. [Component (A)] The component (A) used in the present invention is a polymer having two or more (meth)acryloyl groups, and two or more (meth)acryloyl groups are attached to the molecular terminal or molecular chain. The main chain of the polymer is not particularly limited, and various types can be used, but a (meth)acrylic copolymer is preferred because it has excellent transparency and can effectively impart thixotropy. The polymer of component (A) has two or more (meth)acryloyl groups per molecule. The (meth)acryloyl group, also called a (meth)acrylic group, encompasses both acryloyl and / or methacryloyl groups, and can be expressed, for example, as -C(=O)-CR=CH2 (where R is hydrogen or a methyl group). Specifically, the polymer of component (A) has two or more (meth)acryloyl groups per molecule as side chains of the polymer constituting the main chain, e.g., three or more, four or more, or five or more, more preferably one (meth)acryloyl group at each end, for a total of two. The (meth)acryloyl groups may be the same or different, substituted or unsubstituted, and may be present as a side chain in the middle of the main chain or at the end of the main chain.

[0010] The polymerizable monomer that becomes the structural unit of the polymer that forms the main chain of the component (A) is not particularly limited, and various monomers can be used. For example, the polymerizable monomer includes (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, and methyl (meth)acrylate. n-Octyl, (meth)acrylate-2-ethylhexyl, (meth)acrylate nonyl, (meth)acrylate decyl, (meth)acrylate dodecyl, (meth)acrylate phenyl, (meth)acrylate toluyl, (meth)acrylate benzyl, (meth)acrylate-2-methoxyethyl, (meth)acrylate-3-methoxybutyl, (meth)acrylate-2-hydroxyethyl, (meth)acrylate-2-aminoethyl, γ-(methacryloyloxypropyl)trimethoxysilane, (meth)acrylate p) (meth)acrylic acid monomers such as ethylene oxide adducts of acrylic acid, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethylmethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate; styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and its salts; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, and monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid;Examples of suitable monomers include maleimide monomers such as maleimide, methylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. These monomers may be used alone or in combination. Among these, styrene-based monomers and (meth)acrylic acid-based monomers are preferred in terms of the physical properties of the resulting product. More preferred are acrylic acid ester monomers and methacrylic acid ester monomers, particularly preferred are acrylic acid ester monomers, and most preferred is butyl acrylate. In the present invention, the above-mentioned monomers may be copolymerized with other monomers, or even block copolymerized. In such cases, the content of the above-mentioned polymerizable monomers other than the other monomers is preferably 40% or more, preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more by mass. In the above expression, for example, (meth)acrylic acid represents acrylic acid and / or methacrylic acid.

[0011] The number-average molecular weight of component (A) is preferably 3,000 to 100,000, and particularly preferably 5,000 to 50,000. A number-average molecular weight of 3,000 or more results in a flexible cured product, while a number-average molecular weight of 100,000 or less prevents excessive viscosity and suppresses stringiness when the resin composition is applied. Unless otherwise specified, the number-average molecular weight in this specification was calculated using size exclusion chromatography (SEC) in terms of standard polystyrene.

[0012] The polymer of the present invention can be obtained by various polymerization methods, and the method is not particularly limited, but radical polymerization is preferred from the viewpoint of versatility of monomers and ease of control. Among radical polymerization methods, controlled radical polymerization is preferred, living radical polymerization is more preferred, and atom transfer radical polymerization is particularly preferred.

[0013] Commercially available products of component (A) include, but are not limited to, RC200C, RC210C, RC220C, RC100C, and RC120C (manufactured by Kaneka Corporation). Component (A) may be used singly or in combination of two or more types.

[0014] [(B) Component] The component (B) used in the present invention is a silica powder surface-treated with an alkylsilane. When used in combination with the component (C) described below, the component (B) of the present invention can exhibit remarkable thixotropy. The alkylsilane may be a silane represented by the general formula (2): Si(R 1 From the viewpoint of the effect of exhibiting compatibility and dispersibility with the component (A) and a very high thixotropy with the component (B), alkylsilane compounds represented by the general formula (2) are preferred. 1 are preferably alkyl groups having 3 to 15 carbon atoms, more preferably alkyl groups having 5 to 10 carbon atoms, and most preferably alkyl groups having 8 to 10 carbon atoms. 1 Specific examples of the alkyl group include a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, an octyl group, an isooctyl group, a nonyl group, an isononyl group, a decyl group, and an isodecyl group, with an octyl group being preferred.

[0015] The silica powder of component (B) is preferably fumed silica powder. Fumed silica powder is made of silicon dioxide obtained by flame hydrolysis, and is formed into spherical particles, with multiple particles agglomerating and fusing together like beads to form bulky aggregates.

[0016] The average particle size of the primary particles of the alkylsilane-surface-treated silica powder (B) is preferably 1 to 300 nm, more preferably 3 to 100 nm, and most preferably 5 to 50 nm. The average particle size of the primary particles referred to in the present invention is measured or calculated by common methods such as centrifugal sedimentation light transmission, laser diffraction, or measurement using a transmission electron microscope, but the average particle size of the primary particles referred to here is a value calculated by measuring the major and minor axes of two-dimensional projection images of each primary particle using a transmission microscope in accordance with JIS H 7804:2005 and averaging the measurements. In addition, the BET specific surface area of ​​the silica powder surface-treated with alkylsilane (component (B)) is 300 m from the viewpoint of the packing ratio with component (A). 2 / g or less, and more preferably 250m 2 The lower limit of the BET specific surface area is not particularly limited, but is, for example, 100 m 2 / g or more, preferably 150m 2 / g or more is appropriate.

[0017] To prevent the settling of component (B) over time, the apparent specific gravity of the alkylsilane-surface-treated silica powder (B) is preferably 1 g / L or more and less than 100 g / L, more preferably 10 g / L or more and less than 80 g / L. Note that the apparent specific gravity referred to in this specification is a value measured by measuring the apparent density after sufficient tapping in accordance with DIN ISO 787-11. The content of component (B) is preferably 0.01 to 100 parts by mass, more preferably 0.1 to 50 parts by mass, and most preferably 0.5 to 30 parts by mass, per 100 parts by mass of component (A). By using 0.01 to 100 parts by mass, the viscosity of the resin composition can be controlled while maintaining its performance.

[0018] Commercially available products of component (B) include AEROSIL R805 (manufactured by Evonik) and CAB-O-SIL TS-530 (manufactured by CABOT).

[0019] [(C) component] The component (C) that can be used in the present invention is boric acid or a boric acid ester. Component (C) is a major component that suppresses an increase in the viscosity of the resin composition and enhances the thixotropy-imparting effect. From the viewpoints of the thixotropy-imparting effect and compatibility with component (A), boric acid esters are particularly preferred.

[0020] Any boric acid ester can be used as the boric acid ester, but in the present invention, a compound having one boric acid ester in the molecule and represented by the following general formula (1) is more preferred. B-(OR)3(1) In formula (1), R represents hydrogen or a functional group selected from an alkyl group having 1 to 6 carbon atoms, which may have a substituent, an aryl group, a carbonyl group, and an acetyl group, and all three may be the same or different. Examples of the compound include borate trialkyl ester compounds such as trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, tripentyl borate, trihexyl borate, triphenyl borate, tri-o-tolyl borate, triisopropyl borate, tri-n-octyl borate, tridecyl borate, and tetradecyl borate, with tributyl borate being preferred from the viewpoint of storage stability of the resin composition.

[0021] The amount of component (C) is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and most preferably 0.2 to 7 parts by mass, per 100 parts by mass of component (A). By using an amount of 0.05 to 20 parts by mass, the properties of the resin composition can be maintained without affecting its reactivity or storage stability.

[0022] The mass ratio of the (B) component to the (C) component is, for example, (B) component:(C) component=15:1 to 1:15, preferably 9:1 to 1:9, more preferably 8:2 to 2:8, and most preferably 7:3 to 3:7.

[0023] [Optional ingredients] In addition to the above components (A) to (C), the resin composition of the present invention may contain optional components different from the above components (A) to (C), such as fillers, antioxidants, light stabilizers, storage stabilizers, antifoaming agents, coupling agents, leveling agents, dispersants, pH adjusters, rheology control agents, solvents, adhesion promoters, plasticizers, pigments, flame retardants, and surfactants, within the scope of the object of the present invention. The addition of these components provides a resin composition with excellent coatability, film-forming properties, storage stability, etc. In the present invention, a filler may be added to the resin composition to an extent that does not impair storage stability, with the aim of improving the elastic modulus, resin strength, fluidity, etc. of the cured product. Specific examples include organic powders, inorganic powders, metallic powders, etc. Examples of inorganic powder fillers include glass, alumina, mica, ceramics, silicone rubber powder, calcium carbonate, aluminum nitride, carbon powder, kaolin clay, dried clay minerals, and dried diatomaceous earth. The amount of inorganic powder added is preferably about 0.1 to 100 parts by mass per 100 parts by mass of component (A). If the amount is 100 parts by mass or less, sufficient fluidity and good workability can be obtained as a resin composition.

[0024] Examples of organic powder fillers include polyethylene, polypropylene, nylon, cross-linked acrylic, cross-linked polystyrene, polyester, polyvinyl alcohol, polyvinyl butyral, and polycarbonate. The amount of organic powder blended is preferably about 0.1 to 100 parts by mass per 100 parts by mass of component (A). If the amount is more than 0.1 part by mass, the effect is not diminished, and even if it is 100 parts by mass or less, sufficient fluidity as a resin composition is obtained, and good workability is achieved.

[0025] Examples of metallic powder fillers include gold, platinum, silver, copper, indium, palladium, nickel, alumina, tin, iron, aluminum, stainless steel, etc. The amount of metallic powder added is preferably about 0.1 to 100 parts by mass, and more preferably 1 to 50 parts by mass, per 100 parts by mass of component (A).

[0026] Examples of antioxidants include quinone compounds such as β-naphthoquinone, 2-methoxy-1,4-naphthoquinone, methylhydroquinone, hydroquinone, hydroquinone monomethyl ether, mono-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, and 2,5-di-tert-butyl-p-benzoquinone; phenothiazine, 2,2-methylene-bis(4-methyl-6-tert-butylphenol), catechol, tert-butylcatechol, and 2-butyl-4 -Hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 3,9-bis[2-[3-(3-tert- butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-hexane-1,6-diylbis[3-(3,5 -di-tert-butyl-4-hydroxyphenyl)propionamide], benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy, C7-C9 side chain alkyl ester, 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-tolyl)tri-p-cresol, calcium diethylbis[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)methyl)phosphonate, 4,6-bis(octylthiomethyl)-o-cresol, ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzoyl) 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-xylyl)methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-xylyl)methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, reaction products of N-phenylbenzenamine with 2,4,6-trimethylpentene, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)pheno Phenols such as ethanol, picric acid, and citric acid; tris(2,4-di-tert-butylphenyl)phosphite, tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphen-6-yl]oxy]ethyl]amine, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl ester Examples of suitable compounds include phosphorus compounds such as sterphosphorous acid, tetrakis(2,4-di-tert-butylphenyl)[1,1-bisphenyl]-4,4'-diylbisphosphonite, and 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosphene; amine compounds such as phenothiazine; lactone compounds; and vitamin E compounds. Among these, phenolic compounds are preferred.

[0027] Examples of the light stabilizer include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1-[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidine, Lysinyl methacrylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, decanedioic acid bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidinyl) ester, reaction products of 1,1-dimethylethyl hydroperoxide with octane, N,N',N'',N'''-tetrakis-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazine- 2-yl)-4,7-diazadecane-1,10-diamine, polycondensate of dibutylamine·1,3,5-triazine·N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino] ], polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetramethyl-20-(β-lauryloxycarbonyl)ethyl-7-oxa-3,20-diazadispiro[5,1,11,2]heneicosan-21-one, β-alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl)-dodecyl ester / tetradecyl ester, N-acetyl-3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, 2,2,4,4-Tetramethyl-7-oxa-3,20-diazadispiro[5,1,11,2]heneicosan-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo-[5,1,11,2]-heneicosane-20-propanoic acid dodecyl ester / tetradecyl ester, propanediol acid, [(4-methoxyphenyl)-methylene]-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 2, Hindered amine compounds such as higher fatty acid esters of 2,6,6-tetramethyl-4-piperidinol, 1,3-benzenedicarboxamide, and N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl); benzophenone compounds such as octabenzone; 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-[2-hydroxyphenyl]benzotriazole, benzotriazole-based compounds such as 2-(3,4,5,6-tetrahydrophthalimido-methyl)-5-methylphenyl)benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-pentylphenyl)benzotriazole, reaction products of methyl 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate with polyethylene glycol, and 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol; benzoate-based compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; and triazine-based compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]phenol. Particularly preferred are hindered amine compounds.

[0028] The amount of optional components contained in the resin composition of the present invention is, for example, 0.05 to 100 parts by mass, preferably 0.1 to 50 parts by mass, and more preferably 0.2 to 20 parts by mass, per 100 parts by mass of component (A).

[0029] In the present invention, a (meth)acrylic monomer other than component (A) may be contained within a range that allows the properties to be maintained. A (meth)acrylic monomer is a compound having one or more (meth)acryloyl groups in the molecule.

[0030] As the (meth)acrylic monomer, a conventionally known substance can be used, for example, a monofunctional (meth)acrylate or a polyfunctional (meth)acrylate. The polyfunctional (meth)acrylate includes a difunctional (meth)acrylate and a trifunctional or higher polyfunctional (meth)acrylate.Examples of the monofunctional (meth)acrylate include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, and n-octyl (meth)acrylate. ) acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth) Acrylate, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate, γ-(meth)acryloyloxypropyltrimethoxysilane, ethylene oxide adduct of (meth)acrylic acid, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, glycerol (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, epichlorohydrin (hereinafter abbreviated as ECH) modified acrylate Examples of the ethylene oxide (hereinafter abbreviated as EO)-modified phthalic acid (meth)acrylate include ethylene oxide (hereinafter abbreviated as EO)-modified succinic acid (meth)acrylate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, morpholino (meth)acrylate, and EO-modified phosphate (meth)acrylate.Examples of polyfunctional (meth)acrylates include 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, EO-modified neopentyl glycol di(meth)acrylate, and propylene oxide. Side (hereinafter abbreviated as PO) modified neopentyl glycol di(meth)acrylate, bisphenol A di(meth)acrylate, EO modified bisphenol A di(meth)acrylate, ECH modified bisphenol A di(meth)acrylate, EO modified bisphenol S di(meth)acrylate, hydroxypivalic acid ester neopentyl glycol di(meth)acrylate, caprolactone modified hydroxypivalic acid ester neopentyl glycol di(meth)acrylate, neopentyl glycol modified trimethylolpropane di(meth)acrylate Bifunctional (meth)acrylic group-containing compounds such as stearic acid-modified pentaerythritol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, EO-modified dicyclopentenyl di(meth)acrylate, and di(meth)acryloyl isocyanurate, as well as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, and ECH-modified trimethylolpropane tri(meth)acrylate Examples of the polyfunctional (meth)acrylic group-containing compound include ECH-modified glycerol tri(meth)acrylate, tris(acryloyloxyethyl)isocyanurate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, alkyl-modified dipentaerythritol pentaacrylate, dipentaerythritol hexa(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate.These (meth)acrylic monomers may be used alone or in combination of two or more kinds.

[0031] In the present invention, the content of the (meth)acrylic monomer is preferably 5 to 60 parts by mass, and more preferably 10 to 50 parts by mass, relative to 100 parts by mass of the component (A). When the content of the (meth)acrylic monomer is 5 to 60 parts by mass, the curability of the curable resin composition can be maintained.

[0032] <Curable resin composition> Furthermore, the resin composition of the present invention may be present as a curable resin composition by further adding a radical polymerization initiator as component (D). The curable resin composition can be further cured under any conditions to obtain a cured product of the curable resin composition. The curable resin composition of the present invention can be used not only as a one-component curable resin composition obtained by mixing all components, but also as a two-component curable resin composition kit in which some components are prepared and stored separately and mixed at the time of use. Here, examples of the radical polymerization initiator as component (D) include photoradical polymerization initiators and thermal radical polymerization initiators. The curing form of the curable resin composition of the present invention can be selected to be photocuring, heat curing, or redox curing depending on the radical polymerization initiator selected. For example, if it is desired to impart photocurability to the curable resin composition, a photoradical polymerization initiator can be selected, and if it is desired to impart heat curability or curability by a redox reaction, an organic peroxide or the like, which is a thermal radical polymerization initiator, can be selected.

[0033] The photoradical polymerization initiator is not particularly limited as long as it is a compound that generates radicals when irradiated with active energy rays. Specific examples of the photoradical polymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, methyl benzoyl formate, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, ... benzoins such as benzoin isobutyl ether; benzophenones such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, and (4-benzoylbenzyl)trimethylammonium chloride; and thioxanthones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one mesochloride.Among these, from the viewpoint of versatility, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, methyl benzoyl formate, and 2-hydroxy-2-methyl-1-phenylpropan-1-one are preferred, with 1-hydroxycyclohexyl phenyl ketone being particularly preferred. The above photoradical polymerization initiators may be used alone or in combination of two or more.

[0034] Furthermore, in the present invention, from the viewpoint of suppressing yellowing during curing of the resin composition, it is preferable to contain a visible light type photoradical polymerization initiator as component (D). Visible light type photoradical polymerization initiators are photopolymerization initiators that exhibit maximum light absorption in the visible light region, and examples thereof include acylphosphine oxide photopolymerization initiators having a phosphorus atom. Specific examples of visible light type photoradical polymerization initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and of these, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide is particularly preferred from the viewpoint of improving photocurability.

[0035] Examples of active energy rays include radiation with a wavelength of less than 100 nm, such as gamma rays and X-rays, ultraviolet rays with a wavelength of 100 nm to 400 nm, and visible light with a wavelength of 400 to 800 nm. Visible light with a wavelength of 400 to 800 nm is preferred in order to enable curing of materials that are sensitive to ultraviolet rays or that do not easily transmit ultraviolet rays.

[0036] Examples of the thermal radical polymerization initiator include organic peroxides. Examples include hydroperoxides such as cumene hydroperoxide, t-butyl hydroperoxide, p-methane hydroperoxide, methyl ethyl ketone peroxide, cyclohexane peroxide, dicumyl peroxide, and diisopropylbenzene hydroperoxide, as well as ketone peroxides, diallyl peroxides, and peroxyesters. These organic peroxides may be used alone or in combination of two or more.

[0037] In the present invention, the content of the component (D) is 1 to 20 parts by mass per 100 parts by mass of the component (A). D When the amount of the ) component is 1 to 20 parts by mass, both curability and storage stability can be achieved.

[0038] <Application> The resin composition of the present invention is used as part of a material for a curable resin composition for use in a sealant, adhesive, or coating agent. The curable resin composition of the present invention can be used as a sealant, adhesive, or coating agent. A cured product obtained by curing the curable resin composition of the present invention can be used as a sealing layer or sealing portion formed by curing the sealing material, an adhesive layer or adhesive portion formed by curing the adhesive, or a coating layer or coating portion formed by curing the coating agent. <Application method> The resin composition and curable resin composition of the present invention can be applied to an adherend using a known method such as a sealant or adhesive. For example, methods such as dispensing using an automatic coater, spraying, inkjet printing, screen printing, gravure printing, dipping, and spin coating can be used. From the viewpoint of coatability, the resin composition and curable resin composition of the present invention are preferably liquid at 25°C.

[0039] <Curing method and cured product> The curable resin composition of the present invention can be cured to obtain a cured product by a known method using photocuring, heat curing, redox curing, etc. More specifically, the method includes a step of mixing the above components (A) to (C) and, if necessary, the above optional components to produce a resin composition, a step of mixing a radical polymerization initiator as component (D) with the resin composition, and a step of curing the resin composition by light or heat to produce a cured product. Examples of the method for producing a cured product include the following. As described above, the component (D) may include, as a polymerization initiator, a photoradical polymerization initiator, a thermal radical polymerization initiator, etc. When a photoradical polymerization initiator is used to cure the resin composition according to the present invention, a cured product can be obtained by curing the composition by light irradiation. In this case, the light to be irradiated may be either ultraviolet light or visible light. There are no particular restrictions on the light source used, and examples that can be used include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a black light lamp, a microwave-excited mercury lamp, a metal halide lamp, a sodium lamp, a halogen lamp, a xenon lamp, an LED, a fluorescent lamp, sunlight, and an electron beam irradiation device. The cumulative light dose of the light irradiation is 30 kJ / m 2 From the viewpoint of curing efficiency, it is preferable that the curing efficiency is 5 kJ / cm or less. 2 It is preferable that this is equal to or greater than this.

[0040] When a thermal radical polymerization initiator is used as component (D), a cured product can be obtained by heat curing. The heating temperature is not particularly limited, but is preferably 30 to 300°C, more preferably 50 to 200°C, and most preferably 60 to 150°C. The curing time is not particularly limited, but when the temperature is 30 to 300°C, it is preferably 1 minute or more and less than 3 hours.

[0041] A cured product formed from the resin composition preferably does not yellow and has a colorless, transparent appearance. Specifically, the transmittance at a wavelength of 400 nm is preferably 10.0% or more, more preferably 20.0% or more. The transmittance is measured in accordance with JIS K 0115, using, for example, a UV-2450 ultraviolet-visible spectrophotometer manufactured by Shimadzu Corporation, as the transmittance of light passing through a 10 mm thick sample.

[0042] <Method of manufacturing resin composition> The resin composition of the present invention is produced by mixing the components. The order of mixing the components is not particularly limited, and the components may be added and mixed all at once or sequentially. A curable resin composition can be prepared by further adding a curable component such as a radical polymerization catalyst to the resin composition of the present invention. Specifically, the curable resin composition can be prepared by the following procedure: A step of mixing components (A) to (C) and any optional components with stirring; and (D) component is further added and mixed with stirring, optionally under reduced pressure; It is manufactured in [Example]

[0043] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0044] [Example 1, Comparative Examples 1 to 6] The following ingredients were prepared to prepare the desired resin composition:

[0045] (A) Component: XMAP RC100C (Kaneka): an acrylic copolymer with one acryloyl group at each end. (B) Component: AEROSIL R805 (manufactured by Evonik): fumed silica powder surface-treated with octylsilane, average primary particle size of 12 nm, BET specific surface area of ​​150 m 2 / g, apparent specific gravity 60g / l (B') Component: AEROSIL 200 (manufactured by Nippon Aerosil Co., Ltd.): untreated silica powder, average primary particle size of 12 nm, BET specific surface area of ​​200 m 2 / g, apparent specific gravity 50g / l (C) Component: Tributyl borate (reagent) (C'-1) Component: Phosphoric acid (reagent) Component (C'-2): methacrylic acid (manufactured by Mitsubishi Rayon Co., Ltd.) (C'-3) Component: Acetic acid (reagent)

[0046] The component (A) was weighed into a stirring vessel, the component (B) was weighed into a stirring vessel, and the mixture was stirred for 30 minutes. The component (C) was weighed and stirred for 10 minutes to obtain each resin composition. The detailed amounts prepared are shown in Table 1, and all values ​​are expressed in parts by mass. All tests were performed at 25°C.

[0047] [viscosity] The viscosity (Pa·s) of the curable resin composition was measured using a cone-plate viscometer under the following measurement conditions. The viscosity was evaluated according to the following criteria, and the results are shown in Table 1. Shear rate: 1.0 s -1 Measurement time: 3 min Temperature conditions: 25℃ Resin amount: 0.5mL By measuring the viscosity, it is possible to evaluate the thixotropy of the sample, such as whether the viscosity is low under high shear rate conditions when the sample is applied. [Sagging evaluation] Sagging is measured by measuring the vertical movement of the applied coating material after a specified period of time has elapsed since application to the surface. Sagging measurement can be used to evaluate the thixotropy of a sample, such as whether the sample exhibits high viscosity at low shear rates after application. Specifically, a marked line was drawn 10 mm from the short edge of a SUS304 test piece (1.0 mm thick, 25 mm short edge, 100 mm long edge), and a 2.5 mm diameter bead of each resin composition was applied to the marked line using a dispenser. The test piece was placed vertically at 25°C, and the distance traveled by the resin composition from the marked line after 60 minutes was measured. A displacement of less than 5 mm after 60 minutes was considered acceptable. When measuring sagging, the ease of application and workability were also evaluated.

[0048] Table 1 TIFF0007752303000001.tif49150

[0049] As shown in Table 1, it can be seen that Example 1 has a sufficiently low viscosity and is easy to apply. Furthermore, when actually measuring sagging, application was easy and the work was carried out smoothly. Furthermore, Example 1 had good sagging properties. On the other hand, Comparative Examples 1 to 6 did not have satisfactory results in terms of sagging properties. Furthermore, even Comparative Examples 2 and 4, which have higher viscosities than Example 1, also had poor results in terms of sagging properties.

[0050] [Light transmittance] The light transmittance at each wavelength was measured using the resin composition of Example 1 and component (A) alone using an ultraviolet-visible spectrophotometer UV-2450 manufactured by Shimadzu Corporation. The test was conducted in accordance with JIS K 0115, with the thickness of the sample (optical path length) through which light of each wavelength passed being 10 mm.

[0051] Table 2 TIFF0007752303000002.tif31146

[0052] As shown in Table 2, no increase in transmittance was observed when comparing the transmittance of component (A) alone with that of the resin composition of Example 1, and it can be seen that transparency is maintained despite the inclusion of a filler. [Industrial Applicability]

[0053] The resin composition of the present invention can effectively impart thixotropy without impairing transparency, and is therefore extremely useful because it can be widely deployed in fields where transparency is required.

Claims

1. (A) a polymer having two or more (meth)acryloyl groups in one molecule, provided that the (meth)acryloyl groups are not (meth)acryloyl groups substituted with a cyano group; (B) a silica powder whose surface has been treated with octylsilane and whose primary particles have an average particle size of 1 to 300 nm; and (C) boric acid or a boric acid ester, (D) a photoradical polymerization initiator, A resin composition comprising:

2. The component (C) is represented by the following general formula (1): B-(OR) 3 (1) (In formula (1), R may be the same or different and represent hydrogen or a functional group selected from an alkyl group having 1 to 6 carbon atoms, an aryl group, a carbonyl group, and an acetyl group, which may have a substituent.) The resin composition according to claim 1, wherein the compound is a compound represented by the formula:

3. The resin composition according to claim 1 or 2, wherein the silica powder of the component (B) is a fumed silica powder.

4. 4. The resin composition according to claim 1, wherein the component (A) is a polymer or copolymer of an acrylic acid ester monomer.

5. The resin composition according to any one of claims 1 to 4, wherein the number average molecular weight of the component (A) is 5,000 to 50,000.

6. The resin composition according to any one of claims 1 to 5, wherein the component (B) is contained in an amount of 0.5 to 30 parts by mass per 100 parts by mass of the component (A).

7. The resin composition according to any one of claims 1 to 6, wherein the mass ratio of the component (B) to the component (C) is 9:1 to 1:

9.

8. The resin composition according to any one of claims 1 to 7, wherein the component (C) is tributyl borate.

9. A cured product obtained by curing the resin composition according to any one of claims 1 to 8.

10. An adhesive comprising the resin composition according to any one of claims 1 to 8.

11. A sealing agent comprising the resin composition according to any one of claims 1 to 8.

12. (A) a polymer having two or more (meth)acryloyl groups in one molecule, provided that the (meth)acryloyl groups are not (meth)acryloyl groups substituted with a cyano group; (B) a silica powder whose surface has been treated with octylsilane and whose primary particles have an average particle size of 1 to 300 nm; and (C) boric acid or a boric acid ester, (D) a photoradical polymerization initiator, A method for producing a resin composition, comprising mixing the above components.

13. (A) a polymer having two or more (meth)acryloyl groups in one molecule, provided that the (meth)acryloyl groups are not (meth)acryloyl groups substituted with a cyano group; (B) a silica powder whose surface has been treated with octylsilane and whose primary particles have an average particle size of 1 to 300 nm; and (C) boric acid or a boric acid ester, to produce a resin composition; and (D) mixing a photoradical polymerization initiator with the resin composition; and a step of curing the resin composition with light to produce a cured product; A method for producing a cured product, comprising:

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