Curable resin composition

Abstract

To provide a curable resin composition used to obtain a cured product with excellent release properties and adhesion to a substrate under high humidity and high temperature conditions. [Solution] A curable resin composition is used that contains an ethylenically unsaturated monomer (A) having a phosphate ester group, a monofunctional ethylenically unsaturated monomer (B) having an alicyclic hydrocarbon group and / or a polyfunctional ethylenically unsaturated monomer (C) having an alicyclic hydrocarbon group, a silane compound (D) represented by general formula (1), and a radical polymerization initiator (E), wherein the solution viscosity at 25°C is 2000 to 10000 mPa·s. [R 1 O represents an alkoxy group having 1 to 4 carbon atoms; X is an alkyl group, (meth)acryloyloxyalkyl group, aminoalkyl group, vinyl group, glycidoxyalkyl group, vinylphenyl group, iminoalkyl group, isocyanate alkyl group, isocyanurate group, ureidoalkyl group, or mercaptoalkyl group.

Description

Technical Field

[0001] The present invention relates to a curable resin composition.

Background Art

[0002] Conventionally, optical lenses such as prism sheets used in liquid crystal displays, Fresnel lenses and lenticular lenses used in projection TVs are manufactured by pouring a curable resin composition into a mold in which a resin substrate is set on the inner surface of the mold, irradiating active energy rays, and curing.

[0003] Since these prism sheets and optical lenses have a fine and minute uneven shape on their surfaces, they are easily damaged. As a method for preventing this, a method of introducing a rigid chemical structure such as a bisphenol skeleton is known (see, for example, Patent Document 1).

[0004] However, the method of introducing a rigid chemical structure such as a bisphenol skeleton to prevent damage to the uneven shape has a problem of poor mold release property. In general, mold release property and adhesion to a resin substrate are performance that are in conflict with each other, and there is a problem that the adhesion to the resin substrate decreases when trying to improve the mold release property.

[0005] In recent years, an active energy ray-curable composition containing urethane (meth) acrylate has been proposed for shaping applications from the viewpoint of yield (see, for example, Patent Document 2).

[0006] However, in the above composition, the adhesion to the substrate under high humidity and high temperature is not sufficient and there is room for improvement.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

[0008] The object of the present invention is to provide a curable resin composition that can be used to obtain a cured product with excellent release properties and adhesion to a substrate under high humidity and high temperature conditions. [Means for solving the problem]

[0009] The inventors of this invention arrived at this present invention after diligent research. The present invention relates to a curable resin composition comprising an ethylenically unsaturated monomer (A) having a phosphate ester group, a monofunctional ethylenically unsaturated monomer (B) having an alicyclic hydrocarbon group and / or a polyfunctional ethylenically unsaturated monomer (C) having an alicyclic hydrocarbon group, a silane compound (D) represented by the following general formula (1), and a radical polymerization initiator (E), wherein the curable resin composition has a solution viscosity of 2000 to 10000 mPa·s at 25°C; and a cured product obtained by curing the curable resin composition.

[0010] [ka] [In general formula (1), R 1 O represents an alkoxy group having 1 to 4 carbon atoms; X is an alkyl group, (meth)acryloyloxyalkyl group, aminoalkyl group, vinyl group, glycidoxyalkyl group, vinylphenyl group, iminoalkyl group, isocyanatealkyl group, isocyanurate group, ureidoalkyl group, or mercaptoalkyl group; R is used when there are multiple such groups. 1 O and X may be the same or different; n is an integer between 1 and 3. [Effects of the Invention]

[0011] The cured product obtained by curing the curable resin composition of the present invention exhibits excellent release properties and adhesion to substrates under high humidity and high temperature conditions. [Modes for carrying out the invention]

[0012] The curable resin composition of the present invention is a curable resin composition comprising an ethylenically unsaturated monomer (A) having a phosphate ester group, a monofunctional ethylenically unsaturated monomer (B) having an alicyclic hydrocarbon group and / or a polyfunctional ethylenically unsaturated monomer (C) having an alicyclic hydrocarbon group, a silane compound (D) represented by the above general formula (1), and a radical polymerization initiator (E), wherein the solution viscosity at 25°C is 2000 to 10000 mPa·s.

[0013] The ethylenically unsaturated monomer (A) having a phosphate ester group, which is an essential component of the curable resin composition of the present invention, is a monomer having at least one ethylenically unsaturated group and a phosphate ester group.

[0014] By including the ethylenically unsaturated monomer (A) in the curable resin composition, adhesion to the substrate can be imparted, and the adhesion of the cured product can be adjusted. Examples of ethylenically unsaturated groups include (meth)acryloyl groups, vinyl groups, allyl groups, and propenyl groups. In this invention, the notation "(meth)acryloyl" means acryloyl and / or methacryloyl, the notation "(meth)acrylate" means acrylate and / or methacrylate, the notation "(meth)acrylic" means acrylic and / or methacrylic, the notation "(meth)acryloyloxy" means acryloyloxy and / or methacryloyloxy, and the notation "(meth)allyl" means allyl and / or methallyl.

[0015] Examples of the ethylenically unsaturated monomer (A) having a phosphate group include phosphate ester compounds containing at least one (meth)acryloyl group. Specifically, 2-(meth)acryloyloxyethyl acid phosphate, bis[2-{(meth)acryloyloxy}ethyl] acid phosphate, diphenyl-2-methacryloyloxyethyl phosphate, caprolactone-modified [2-{(meth)acryloyloxy}ethyl] acid phosphate, caprolactone-modified bis[2-{(meth)acryloyloxy}ethyl] acid phosphate, caprolactone-modified bis[2-{(meth)acryloyloxy}methyl] acid phosphate, caprolactone-modified bis[2-{(meth)acryloyloxy}propyl] acid phosphate, and caprolactone-modified bis[2-{(meth)acryloyloxy}butyl] acid phosphate, etc. can be mentioned.

[0016] In the present invention, as the ethylenically unsaturated monomer (A) having a phosphate group, from the viewpoint of adhesion to a glass substrate, a phosphate ester compound containing at least one (meth)acryloyl group is preferable, and more preferably 2-(meth)acryloyloxyethyl acid phosphate, bis[2-{(meth)acryloyloxy}ethyl] acid phosphate, or diphenyl-2-methacryloyloxyethyl phosphate. Also, (A) may be used alone or in combination of two or more.

[0017] The content of the ethylenically unsaturated monomer (A) having a phosphate group is preferably 1 to 10% by weight, more preferably 1 to 5% by weight, based on the total weight of the curable resin composition.

[0018] The monofunctional ethylenically unsaturated monomer (B) having an alicyclic hydrocarbon group in the present invention is a monomer having one ethylenically unsaturated group and an alicyclic hydrocarbon group, and preferably a monomer having one (meth)acryloyl group.

[0019] By including the monofunctional ethylenically unsaturated monomer (B) in the curable resin composition, it is possible to impart mold release properties and adhesion to a substrate under high humidity and high temperature conditions, and it becomes possible to adjust the mold release properties and adhesion of the cured product.

[0020] Examples of the monofunctional ethylenically unsaturated monomer (B) having an alicyclic hydrocarbon group include cyclohexyl (meth)acrylate, t-butyl-cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and adamantyl (meth)acrylate.

[0021] As the monofunctional ethylenically unsaturated monomer (B) having an alicyclic hydrocarbon group in the present invention, from the viewpoint of adhesion to a glass substrate under high humidity and high temperature conditions, cyclohexyl (meth)acrylate, t-butyl-cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate are preferred. Also, (B) may be used alone or in combination of two or more.

[0022] The content of the monofunctional ethylenically unsaturated monomer (B) having an alicyclic hydrocarbon group is preferably 0 to 60% by weight, more preferably 10 to 50% by weight, based on the total weight of the curable resin composition.

[0023] The polyfunctional ethylenically unsaturated monomer (C) having an alicyclic hydrocarbon group of the present invention is a monomer having two or more ethylenically unsaturated groups and an alicyclic hydrocarbon group, preferably a monomer having two or more (meth)acryloyl groups, and more preferably a monomer having 2 to 6 (meth)acryloyl groups.

[0024] By including the polyfunctional ethylenically unsaturated monomer (C) in the curable resin composition, it is possible to impart mold release properties and adhesion to a substrate under high humidity and high temperature conditions, and it becomes possible to adjust the mold release properties and adhesion of the cured product. Also, it is preferable to use the above monofunctional ethylenically unsaturated monomer (B) and polyfunctional ethylenically unsaturated monomer (C) in combination, as the mold release properties and adhesion to the substrate become good.

[0025] Examples of polyfunctional ethylenically unsaturated monomers (C) having alicyclic hydrocarbon groups include di(meth)acrylates of polyhydric alcohols having an alicyclic skeleton and di(meth)acrylates of alkylene oxide adducts of polyhydric alcohols having an alicyclic skeleton.

[0026] Examples of polyhydric alcohol di(meth)acrylates having an alicyclic skeleton include tricyclodecanedimethanol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, and dicyclopentanedimethylol di(meth)acrylate. Examples of di(meth)acrylates of alkylene oxide adducts of polyhydric alcohols having an alicyclic skeleton include ethylene oxide-modified hydrogenated bisphenol A diacrylate.

[0027] In the present invention, the polyfunctional ethylenically unsaturated monomer (C) having an alicyclic hydrocarbon group is preferably a di(meth)acrylate of a polyhydric alcohol having an alicyclic skeleton, and more preferably tricyclodecanedimethanol di(meth)acrylate or cyclohexanedimethanol di(meth)acrylate, from the viewpoint of adhesion to a glass substrate under high humidity and high temperature. Furthermore, (C) may be used alone or in combination of two or more types.

[0028] The content of polyfunctional ethylenically unsaturated monomers (C) having alicyclic hydrocarbon groups is preferably 0 to 20% by weight, and more preferably 5 to 15% by weight, based on the total weight of the curable resin composition.

[0029] The silane compound (D), which is an essential component of the curable resin composition of the present invention, is represented by the following general formula (1).

[0030] [ka]

[0031] In general formula (1), R 1O represents an alkoxy group with 1 to 4 carbon atoms (such as a methoxy group, ethoxy group, propoxy group, and butoxy group). R is used when there are multiple such groups. 1 O can be the same or different. Also, n is an integer between 1 and 3.

[0032] In general formula (1), X is an alkyl group, (meth)acryloyloxyalkyl group, aminoalkyl group, vinyl group, glycidoxyalkyl group, vinylphenyl group, iminoalkyl group, isocyanate alkyl group, isocyanurate group, ureidoalkyl group, or mercaptoalkyl group. If there are multiple X's, they may be the same or different. Of these, (meth)acryloyloxyalkyl groups, aminoalkyl groups, and iminoalkyl groups are preferred. These silane compounds (D) are exemplified by their chemical names and structural formulas, categorized by functional group, in, for example, the product brochure for silane coupling agents from Shin-Etsu Chemical Co., Ltd.

[0033] Examples of silane compounds (D) represented by general formula (1) include silane compounds having a (meth)acryloyloxyalkyl group (D1), silane compounds having an aminoalkyl group (D2), silane compounds having a glycidoxyalkyl group (D3), silane compounds having an iminoalkyl group (D4), and silane compounds having a mercaptoalkyl group (D5). Note that (D) may be used alone or in combination of two or more types.

[0034] Examples of silane compounds (D1) having a (meth)acryloyloxyalkyl group as X in general formula (1) include (meth)acryloyloxyalkyltrialkoxysilane, bis[(meth)acryloyloxyalkyl]dialkoxysilane, and tris[(meth)acryloyloxyalkyl]alkoxysilane. Specifically, the following compounds are examples. Examples of silane compounds having n = 3, i.e., 3 alkoxy groups, include 3-(meth)acryloyloxypropyltrimethoxysilane and 3-(meth)acryloyloxypropyltriethoxysilane. Examples of silane compounds having n = 2, i.e., two alkoxy groups, include bis[3-(meth)acryloyloxypropyl]dimethoxysilane and bis[3-(meth)acryloyloxypropyl]diethoxysilane. Examples of silane compounds having n = 1, i.e., one alkoxy group, include tris[3-(meth)acryloyloxypropyl]methoxysilane and tris[3-(meth)acryloyloxypropyl]ethoxysilane.

[0035] Examples of silane compounds (D2) having an aminoalkyl group as X in general formula (1) include aminoalkyltrialkoxysilane, bis(aminoalkyl)dialkoxysilane, and tris(aminoalkyl)alkoxysilane. Specifically, the following compounds are examples. Examples of silane compounds having n = 3, i.e., 3 alkoxy groups, include 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane. Examples of silane compounds having n = 2, i.e., two alkoxy groups, include bis[N-(2-aminoethyl)-3-aminopropyl]dimethoxysilane, bis[N-(2-aminoethyl)-3-aminopropyl]diethoxysilane, bis(3-aminopropyl)dimethoxysilane, and bis(3-aminopropyl)diethoxysilane. Examples of silane compounds having n = 1, i.e., one alkoxy group, include tris[N-(2-aminoethyl)-3-aminopropyl]methoxysilane, tris[N-(2-aminoethyl)-3-aminopropyl]ethoxysilane, tris(3-aminopropyl)methoxysilane, and tris(3-aminopropyl)ethoxysilane.

[0036] Examples of silane compounds (D3) having a glycidoxyalkyl group as X in general formula (1) include the following compounds. Examples of silane compounds having n = 3, i.e., 3 alkoxy groups, include 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane. Examples of silane compounds having n = 2, i.e., two alkoxy groups, include 3-glycidoxypropylmethyldimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane. Examples of silane compounds having n = 1, i.e., one alkoxy group, include 3-glycidoxypropyldimethylmethoxysilane and 3-glycidoxypropyldimethylethoxysilane.

[0037] Examples of silane compounds (D4) having an iminoalkyl group as X in general formula (1) include the following compounds. Examples of silane compounds having n=3, i.e., three alkoxy groups, include 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine and 3-trimethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine.

[0038] Examples of silane compounds (D5) having a mercaptoalkyl group as X in general formula (1) include the following compounds. Examples of silane compounds having n = 3, i.e., 3 alkoxy groups, include 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane. Examples of silane compounds having n = 2, i.e., two alkoxy groups, include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropylmethyldiethoxysilane. Examples of silane compounds having n = 1, i.e., one alkoxy group, include 3-mercaptopropyldimethylmethoxysilane and 3-mercaptopropyldimethylethoxysilane.

[0039] Of the silane compounds (D) represented by the above general formula (1), those preferred from the viewpoint of adhesion to glass substrates under high humidity and high temperature are the silane compound (D1) in which X is (meth)acryloyloxyalkyl group in general formula (1), the silane compound (D2) in which X is an aminoalkyl group in general formula (1), and the silane compound (D4) in which X is an iminoalkyl group in general formula (1). Even more preferred are silane compounds having three alkoxy groups and one (meth)acryloyloxyalkyl group, silane compounds having three alkoxy groups and one aminoalkyl group, and silane compounds having three alkoxy groups and one iminoalkyl group. Particularly preferred are 3-(meth)acryloyloxypropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, with the most preferred being 3-(meth)acryloyloxypropyltrimethoxysilane.

[0040] The content of the silane compound (D) represented by the above general formula (1) is preferably 2 to 20% by weight, and more preferably 3 to 15% by weight, based on the total weight of the curable resin composition.

[0041] Examples of the radical polymerization initiator (E), which is an essential component of the curable resin composition of the present invention, include a photopolymerization initiator (E1) and a thermal polymerization initiator (E2). Examples of photopolymerization initiators (E1) include benzoin compounds (E1-1), alkylphenone compounds (E1-2), anthraquinone compounds (E1-3), thioxanthone compounds (E1-4), ketal compounds (E1-5), benzophenone compounds (E1-6), phosphine oxide compounds (E1-7), and oxime ester compounds (E1-8). (E) may be used alone or in combination of two or more types.

[0042] Examples of benzoin compounds (E1-1) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether.

[0043] Examples of alkylphenone compounds (E1-2) include acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methylphenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone.

[0044] Examples of anthraquinone compounds (E1-3) include 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone.

[0045] Examples of thioxanthone compounds (E1-4) include 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone.

[0046] Examples of ketal compounds (E1-5) include acetophenone dimethyl ketal and benzyl dimethyl ketal.

[0047] Examples of benzophenone compounds (E1-6) include benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 4,4'-bismethylaminobenzophenone.

[0048] Examples of phosphine oxide compounds (E1-7) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0049] Examples of oxime ester compounds (E1-8) include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime) and ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime).

[0050] Examples of thermal polymerization initiators (E2) include organic peroxides (E2-1) and azo-based initiators (E2-2).

[0051] Examples of organic peroxides (E2-1) include 1,1-bis(t-butylperoxy)2-methylcyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(4,4-di-butylperoxycyclohexyl)propane, and 1,1-bis(t-butylperoxy) -Oxy)cyclododecane, dilauroyl peroxide, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxymaleic acid, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxypivalate, t-hexyl peroxypivalate, 2,5-dimethyl-2,5-di(m-toluylperoxy)hexane, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl Monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl peroxyacetate, 2,2-bis(t-butylperoxy)butane, t-butyl peroxybenzoate, n-butyl-4,4-bis(t-butylperoxy)valerate, di-t-butyl peroxyisophthalate, α'α'-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butyl Examples include t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyn-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydroperoxide.

[0052] Examples of azo initiators (E2-2) include 1,1'-azobis(cyclohexane-1-carbonitride), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azodi-t-octane, and azodi-t-butane.

[0053] Furthermore, organic peroxides (E2-1) can also be used in combination with reducing agents [bisulfites (sodium bisulfite, potassium bisulfite, and ammonium bisulfite, etc.), reducing metal salts [iron(II) sulfate, etc.], amine complexes of transition metal salts [pentamethylenehexamine complex of cobalt(III) chloride and diethylenetriamine complex of copper(II) chloride, etc.], and organic reducing agents [ascorbic acid, tertiary amines (dimethylaminobenzoic acid (salt) and dimethylaminoethanol, etc.)], etc.] to cure curable resin compositions using redox reactions.

[0054] When using the thermal polymerization initiator (E2) alone, the process should be carried out according to the standard procedures for radical thermal polymerization. In some cases, it can be used in combination with the photopolymerization initiator (E1), and after photocuring, thermal curing can be performed to further improve the reaction rate.

[0055] Of these radical polymerization initiators (E), photopolymerization initiator (E1) is preferred from the viewpoint of shortening the process time for curing the curable resin composition. Among the photopolymerization initiators (E1), alkylphenone compounds (E1-2) and phosphine oxides (E1-7) are preferred from the viewpoint of light resistance, meaning that the cured product is less likely to yellow. More preferably are 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis-(2,6 The following are preferred: -dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, with 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0056] The content of the radical polymerization initiator (E) is preferably 0.1 to 10% by weight, and more preferably 1 to 5% by weight, based on the total weight of the curable resin composition.

[0057] The curable resin composition of the present invention may further contain an ethylenically unsaturated monomer (F) having a urethane group for the purpose of adjusting the viscosity of the composition. As the ethylenically unsaturated monomer (F) having a urethane group, urethane compounds containing a (meth)acryloyl group in the molecule are preferred, and examples include urethane (meth)acrylates obtained from polyols (a), polyisocyanates (b), and hydroxyl group-containing (meth)acrylates (c) or isocyanate group-containing (meth)acrylates (d). Furthermore, the ethylenically unsaturated monomer (F) having a urethane group may be used alone or in combination of two or more types.

[0058] The ethylenically unsaturated monomer (F) having a urethane group is a monomer having one or more ethylenically unsaturated groups, preferably a monomer having one or more (meth)acryloyl groups, and more preferably a monomer having one to two (meth)acryloyl groups.

[0059] The polyol (a) used as a raw material for the ethylenically unsaturated monomer (F) having a urethane group is not particularly limited as long as it is a compound having two or more hydroxyl groups. Specific examples of (a) include alkylenediol, polyether-type polyol, polyester-type polyol, and polycarbonate-type polyol. Polyol (a) may be used alone or in combination of two or more. Among these, polyether-type polyol and polycarbonate-type polyol are preferred, polyether-type diol and polycarbonate-type diol are more preferred from the viewpoint of adjusting molecular weight and preventing gelation, and polycarbonate-type diol is particularly preferred from the viewpoint of adhesion to the glass substrate.

[0060] Examples of polyisocyanates (b) include aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, and ω,ω'-diisocyanate dimethylcyclohexane; and aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tolidine diisocyanate, tetramethylene xylylene diisocyanate, and naphthalene-1,5-diisocyanate.

[0061] Examples of hydroxyl group-containing (meth)acrylates (c) include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerin di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and others. They are not particularly limited as long as they are compounds having a hydroxyl group and a (meth)acryloyl group in at least one molecule.

[0062] Examples of isocyanate group-containing (meth)acrylates (d) include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2-(isocyanatoethyloxy)ethyl acrylate, 2-(isocyanatoethyloxy)ethyl methacrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate, and are not particularly limited as long as they are compounds having an isocyanate group and a (meth)acryloyl group in at least one molecule.

[0063] The number-average molecular weight (hereinafter abbreviated as Mn; measured by gel permeation chromatography (GPC)) of the ethylenically unsaturated monomer (F) having a urethane group is preferably 1,000 to 10,000, and more preferably 1,200 to 8,000.

[0064] Furthermore, the Mn in this invention can be measured by gel permeation chromatography (GPC) under the following conditions. [1] Apparatus: Gel permeation chromatography "HLC-8120GPC", manufactured by Tosoh Corporation [2] Column: Two "TSKgel GMHXL" tubes + one "TSKgel Multipore HXL-M", manufactured by Tosoh Corporation [3] Eluent: Tetrahydrofuran [4] Reference material: Standard polystyrene (TSKstandard POLYSTYRENE), manufactured by Tosoh Corporation [5] Injection conditions: Sample concentration 0.25 wt%, column temperature 40°C

[0065] The ethylenically unsaturated monomer (F) having a urethane group in the present invention can be produced by reacting a polyol (a) and a polyisocyanate (b) with a hydroxyl group-containing (meth)acrylate (c) or an isocyanate group-containing (meth)acrylate (d) in a known manner. For example, one method involves reacting a terminal isocyanate urethane prepolymer obtained by reacting a polyol (a) with a polyisocyanate (b) with a hydroxyl group-containing (meth)acrylate (c), or reacting a terminal hydroxyl group urethane compound obtained by reacting a polyol (a) with a polyisocyanate (b) with an isocyanate group-containing (meth)acrylate (d). In particular, it is preferable to produce the product by reacting (a) and (b) to obtain a urethane prepolymer having an isocyanate group, and then reacting (c) with (a) in a urethane reaction. In the above reactions between (a) and (b) and between the urethane prepolymer and (c), a urethane catalyst may be used. Examples of urethane catalysts include metal compounds (organobismuth compounds, organotin compounds, organotitanium compounds, etc.) and quaternary ammonium salts.

[0066] The content of the ethylenically unsaturated monomer (F) having a urethane group is preferably 0 to 60% by weight, more preferably 0 to 50% by weight, and particularly preferably 10 to 45% by weight, based on the total weight of the curable resin composition of the present invention, from the viewpoint of adhesion to the substrate.

[0067] The curable resin composition of the present invention may further contain other ethylenically unsaturated monomers. Other ethylenically unsaturated monomers include difunctional polyoxyalkylene polyol (meth)acrylates (H1) and trifunctional or more lactone-modified (meth)acrylates (H2).

[0068] As a bifunctional polyoxyalkylene polyol (meth)acrylate (H1), compounds having two (meth)acryloyl groups in the molecule and 2 to 30 oxyalkylene groups (preferably with 2 to 4 carbon atoms) are preferred. Examples include di(meth)acrylates of alkylene oxide adducts to linear aliphatic polyhydric alcohols [e.g., di(meth)acrylates of ethylene oxide adducts of trimethylolpropane, di(meth)acrylates of ethylene oxide adducts of glycerin, di(meth)acrylates of polyethylene glycol, di(meth)acrylates of polypropylene glycol, and di(meth)acrylates of polytetramethylene glycol].

[0069] Preferred lactone-modified (meth)acrylates (H2) with three or more functionalities include compounds obtained by adding 1 to 15 moles of a lactone having 4 to 11 carbon atoms to a 3 to 8-valent alcohol, and then esterifying them with 3 to 6 moles of (meth)acrylic acid. Examples include tetra(meth)acrylate of a 4-mol δ-valerolactone adduct of pentaerythritol, penta(meth)acrylate of a 6-mol ε-caprolactone adduct of dipentaerythritol, hexa(meth)acrylate of a 6-mol ε-caprolactone adduct of dipentaerythritol, and hexa(meth)acrylate of a 12-mol ε-caprolactone adduct of dipentaerythritol.

[0070] The content of other ethylenically unsaturated monomers is preferably 0 to 30% by weight, and more preferably 0 to 5% by weight, based on the total weight of the curable resin composition.

[0071] The active energy ray curable composition of the present invention may contain other additives as needed, as long as they do not inhibit the effects of the present invention. Other additives include plasticizers, organic solvents, dispersants, defoamers, thixotropic agents (thickeners), slip agents, antioxidants, hindered amine light stabilizers, and ultraviolet absorbers.

[0072] The content of other additives is preferably 0 to 5% by weight, and more preferably 0 to 1% by weight, based on the total weight of the curable resin composition.

[0073] The solution viscosity of the active energy ray curable composition of the present invention at 25°C is 2000 to 10000 mPa·s. The solution viscosity can be adjusted by the content of an ethylenically unsaturated monomer having a phosphate ester group (A), a monofunctional ethylenically unsaturated monomer having an alicyclic hydrocarbon group (B), a polyfunctional ethylenically unsaturated monomer having an alicyclic hydrocarbon group (C), and a silane compound (D), the composition of an ethylenically unsaturated monomer having a urethane group (F), the number average molecular weight, and the like. The solution viscosity was measured using a viscometer under atmospheric pressure and at 25°C, under the following conditions. When the solution viscosity is less than 8000 mPa·s Viscometer: TVE-25L: Manufactured by Toki Sangyo Co., Ltd. Cone rotor: 1°34' × R24 Measurement range: 5 Rotation speed: 0.5 rpm When the solution viscosity is 8000 mPa·s or higher Viscometer: TVE-25H: Manufactured by Toki Sangyo Co., Ltd. Cone rotor: 3° × R9.7 Measurement range: R Rotation speed: 20 rpm

[0074] The cured product of the present invention is a cured product obtained by curing the above-mentioned curable composition. The cured product of the curable composition of the present invention exhibits excellent release properties from molds, making it useful as an optical component and an electrical / electronic component, for example, it can be used to manufacture molded articles that can be used as optical components.

[0075] The following describes a method for producing a molded article as a cured product by curing the curable composition of the present invention. The method for manufacturing a molded article as a cured product using the curable resin composition of the present invention is not particularly limited, but in the case of manufacturing a three-dimensional plastic lens having a fine uneven structure, for example, it can be obtained by photocuring the curable resin composition using a flat mold having a fine uneven structure and then releasing it from the mold. The resin composition of the present invention is preheated to 20-80°C, and then coated (or filled) into a mold (preferably at a mold temperature of 20-80°C, more preferably 25-40°C) that can produce a molded body shape (e.g., an optical lens shape) using a dispenser or the like, so that the cured thickness is 20-150 μm. A transparent substrate (including a transparent film) is then pressure-laminated onto the coating film, ensuring no air is trapped inside, and the coating film is cured by irradiating the transparent substrate with active energy rays. After that, the cured product is released from the mold to obtain a molded body.

[0076] Examples of the transparent substrates (including transparent films) mentioned above include those made using resins such as methyl methacrylate (co)polymer, polyethylene terephthalate, polycarbonate, polytriacetylcellulose, and polycycloolefin.

[0077] The active energy rays in this invention include ultraviolet rays, electron beams, X-rays, infrared rays, and visible light. Of these active energy rays, ultraviolet rays and electron beams are preferred from the viewpoint of curability and suppression of resin degradation.

[0078] When curing the curable composition of the present invention with ultraviolet light, various ultraviolet irradiation devices can be used (for example, an ultraviolet irradiation device [model number "VPS / I600", manufactured by Fusion UV Systems Co., Ltd.]). Examples of lamps that can be used include high-pressure mercury lamps and metal halide lamps. The amount of ultraviolet irradiation is preferably 10 to 10,000 mJ / cm² from the viewpoint of the curability of the composition and the flexibility of the cured product. 2 More preferably 100 to 5,000 mJ / cm² 2 That is the case.

[0079] From the viewpoint of adhesion, the storage modulus (E') of the cured product of the present invention at 25°C is preferably 100 MPa or more, and more preferably 500 MPa or more. From the viewpoint of adhesion, the storage modulus (E') of the cured product of the present invention at 65°C is preferably 10 MPa or more, and more preferably 50 MPa or more. Furthermore, from the viewpoint of adhesion, the ratio of E'(65) at 65°C to E'(25) at 25°C [E'(65) / E'(25)] is preferably 0.05 to 1.0, and more preferably 0.1 to 1.0.

[0080] The storage modulus (E') of the cured product of the present invention can be measured by the following method. The curable composition of the present invention is subjected to a total of 2000 mJ / cm² of ultraviolet irradiation using an ultraviolet irradiation device. 2 Test pieces measuring 40 mm in length, 5 mm in width, and 1 mm in thickness are prepared from the cured material that has been cured by irradiation with ultraviolet light. The viscoelastic behavior of the test pieces obtained above is measured under the following conditions using a dynamic viscoelasticity measurement (DMA) device [model number "Rheogel-E4000", manufactured by UBM Co., Ltd.]. • Frequency: 10Hz • Heating rate: 4°C / min [Examples]

[0081] The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, % refers to weight percent and parts refers to parts by weight.

[0082] <Manufacturing Example 1> In a reaction vessel equipped with a stirrer, condenser, and thermometer, 100 parts of polytetramethylene glycol [Mn 1,000, manufactured by Mitsubishi Chemical Corporation, trade name: PTMG-1000], 2.9 parts of ethylene glycol, 45.4 parts of isophorone diisocyanate, and 0.08 parts of bismuth tri(2-ethylhexanoate) (50% solution of 2-ethylhexanoic acid) as a catalyst were charged and reacted at 115°C for 8 hours. Then, 15.4 parts of 2-hydroxyethyl acrylate were added and reacted at 85°C for 2 hours to obtain urethane acrylate (F-2-1) with a Mn of 4,600.

[0083] <Examples 1-7, Comparative Examples 1-3> The ingredients were mixed together according to the formulations (parts by weight) listed in Table 1, and then mixed and stirred in a disperser until homogeneous to obtain the curable resin compositions of Examples 1-7 and Comparative Examples 1-3.

[0084] [Table 1]

[0085] The symbols in Table 1 indicate the following: (A-1): Caprolactone-modified [2-{(meth)acryloyloxy}ethyl] acid phosphate [product name "KAYAMER PM-21", manufactured by Nippon Kayaku Co., Ltd.] (A-2): Diphenyl-2-methacryloyloxyethyl phosphate [Product name "MR-260", manufactured by Daihachi Chemical Industry Co., Ltd.]

[0086] (B-1): Isobornyl acrylate [Product name "Light Acrylate IBXA", manufactured by Kyoeisha Chemical Co., Ltd., 1 functional group] (B-2): 4-tert-butylcyclohexyl acrylate [Trade name "TBCHA", manufactured by KJ Chemicals Co., Ltd., 1 functional group] (B-3): Cyclohexyl acrylate [Product name "Viscote #155", manufactured by Osaka Organic Chemical Industry Co., Ltd., 1 functional group]

[0087] (C-1): Dimethylol tricyclodecanediaacrylate [Product name "Light Acrylate DCP-A", manufactured by Kyoeisha Chemical Co., Ltd., 2 functional groups] (C-2): Cyclohexanedimethanol diacrylate [Trade name "CD406", manufactured by Arkema, Inc., 2 functional groups]

[0088] (D-1): 3-Acryloyloxypropyltrimethoxysilane [Product name "KBM-5103", manufactured by Shin-Etsu Chemical Co., Ltd.] (D-2): 3-Methacryloyloxypropyltrimethoxysilane [Product name "KBM-503", manufactured by Shin-Etsu Chemical Co., Ltd.] (D-3): N-(1,3-dimethyl-butylidene)-3-triethoxysilylpropylamine [Product name "KBE-9103", manufactured by Shin-Etsu Chemical Co., Ltd.]

[0089] (E1-2-1): 1-Hydroxycyclohexylphenyl ketone [Trade name "Irgacure 184", manufactured by BASF] (E1-7-1): 2,4,6-Trimethylbenzoyldiphenylphosphine oxide [Trade name "Irgacure TPO", manufactured by BASF] (E1-7-2): Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide [Trade name "Irgacure 819", manufactured by BASF] (E1-2-2):2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one [Trade name "Irgacure 907", manufactured by BASF]

[0090] (F-1-1): Urethane acrylate oligomer [Product name "CN8888NS", manufactured by Arkema Co., Ltd.]

[0091] (H-1): Polypropylene glycol diacrylate [Product name "NK Ester APG-700", manufactured by Shin Nakamura Chemical Industry Co., Ltd.] (H-2): Caprolactone-modified dipentaerythritol hexaacrylate [Product name "KAYARAD DPCA-120", manufactured by Nippon Kayaku Kogyo Co., Ltd.]

[0092] (I-1): Pentaerythritol tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate [product name "IRGANOX 1010", manufactured by BASF Japan Ltd.] (antioxidant) (I-2): Reaction product of 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-hydroxyphenyl and oxirane [(alkyloxymethyl with 10-16 carbon atoms)]oxirane / 1-methoxy-2-propanol = 85 / 15 (weight ratio) [Product name "TINUVIN 400", manufactured by BASF Japan Ltd.] (UV absorber)

[0093] For the curable resin compositions of Examples 1 to 7 and the comparative curable resin compositions of Comparative Examples 1 to 3, viscosity (25°C), release properties from resin molds, adhesion to glass substrates (initial), and adhesion to glass substrates (65°C, 95RH, 100h) were measured using the following methods.

[0094] <Viscosity> The viscosity of the curable resin composition obtained above at 25°C was measured using a viscometer [TVE-25L or TVE-25H, manufactured by Toki Sangyo Co., Ltd.].

[0095] <Release properties from resin molds> A 1g curable resin composition was applied to a 10cm square glass substrate [product name "Eagle XG", manufactured by Corning Inc.]. A lenticular resin mold with a maximum depth of 200μm and a pitch width of 1200μm was placed on top, and a roller was rolled over it to push out the air and bond the two surfaces together. Subsequently, an active energy ray irradiation device [model number "VPS / I600", manufactured by Fusion UV Systems Co., Ltd.] was used to irradiate the resin mold with an active energy ray at a rate of 1000mJ / cm². 2 After irradiation, the material was removed from the resin mold, and a laser microscope was used to determine whether the lenticular shape transfer was successfully reproduced. (Evaluation Criteria) ◎: There is no resin residue in the resin mold, the lenticular shape transfer is reproduced, and it detaches smoothly from the mold. ○: There is no resin residue in the resin mold, the lenticular shape transfer is reproduced, and it separates from the mold, although not smoothly. ×: Residue remains in the resin mold, preventing the lenticular shape from being properly transferred.

[0096] <Adhesion to glass substrate (initial stage)> In the mold release evaluation from the resin mold described above, the cured material peeled from the resin mold was cut with a utility knife at a 45-degree angle to the lenticular shape, with a width of 2 mm, in accordance with JIS K 5600-5-6, to create 25 squares (5 x 5). The adhesion was then measured. Based on the surface condition after peeling, the material was visually classified into categories 0 to 5. Samples for each category from 0 to 5 are shown in Table 2 below. (Evaluation Criteria) ◎: After testing, 25 grid squares remained on the glass substrate, the edges of the cuts were perfectly smooth, and there was no peeling at any of the grid squares (Classification 0). ○: After testing, 25 grid lines remain on the glass substrate and some of the cut intersections and / or edges are peeled off (Category 1 or Category 2). ×: The number of squares remaining on the glass substrate after the test is 24 or less (classification 3-5). - : Products whose release properties from resin molds were judged as "×" (could not be tested).

[0097] <Adhesion to glass substrate (65℃ 95RH, 100h)> In the above evaluation of release properties from resin molds, the cured material peeled from the resin mold was conditioned at a temperature of 65°C and a humidity of 95% for 100 hours. Then, in accordance with JIS K 5600-5-6, cuts were made with a utility knife at a 45-degree angle to the lenticular shape, with a width of 2 mm, to create 25 squares (5 x 5), and the adhesion was measured. Based on the surface condition after peeling, the materials were visually classified into categories 0 to 5. Samples for each category from 0 to 5 are shown in Table 2 below. (Evaluation Criteria) ◎: After testing, 25 grid squares remained on the glass substrate, the edges of the cuts were perfectly smooth, and there was no peeling at any of the grid squares (Classification 0). ○: After testing, 25 grid lines remain on the glass substrate and part of the cut intersections and / or edges are peeled off (Category 1 or Category 2). ×: The number of squares remaining on the glass substrate after the test is 24 or less (classification 3-5). - : Products whose release properties from resin molds were judged as "×" (could not be tested).

[0098] [Table 2] [Industrial applicability]

[0099] The cured product of the curable resin composition of the present invention is useful for shaping molded articles and optical components.

Claims

1. A curable resin composition comprising an ethylenically unsaturated monomer (A) having a phosphate ester group, a monofunctional ethylenically unsaturated monomer (B) having an alicyclic hydrocarbon group and / or a polyfunctional ethylenically unsaturated monomer (C) having an alicyclic hydrocarbon group, a silane compound (D) represented by the following general formula (1), and a radical polymerization initiator (E), wherein the solution viscosity at 25°C is 2000 to 10000 mPa·s. 【Chemistry 1】 [In general formula (1), R １ O represents an alkoxy group having 1 to 4 carbon atoms; X is an alkyl group, (meth)acryloyloxyalkyl group, aminoalkyl group, vinyl group, glycidoxyalkyl group, vinylphenyl group, iminoalkyl group, isocyanatealkyl group, isocyanurate group, ureidoalkyl group, or mercaptoalkyl group; R is used when there are multiple such groups. １ O and X may be the same or different; n is an integer between 1 and 3.

2. The curable resin composition according to claim 1, wherein the ethylenically unsaturated monomer (A) having a phosphate ester group has at least one (meth)acryloyl group.

3. The curable resin composition according to claim 1, wherein the monofunctional ethylenically unsaturated monomer (B) having an alicyclic hydrocarbon group has one (meth)acryloyl group.

4. The curable resin composition according to claim 1, wherein the polyfunctional ethylenically unsaturated monomer (C) having an alicyclic hydrocarbon group has 2 to 6 (meth)acryloyl groups.

5. Furthermore, the curable resin composition according to claim 1, further comprising an ethylenically unsaturated monomer (F) having a urethane group.

6. The curable resin composition according to claim 1, for use in optical components.

7. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 6.

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