JP2011202070A - Curable resin composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition that has good curability and also has low hygroscopicity of a cured product and to provide its cured product.SOLUTION: An active energy ray-curable resin composition is characterized by containing urethane(meth)acrylate (A) having a diene structure and a thiol compound (B) such as pentaerythritol tetrakis(3-mercaptopropionate).

Description

  The present invention relates to a curable composition and a cured product thereof. More specifically, the present invention relates to a curable composition having good curability and low moisture absorption of the cured product and the cured product thereof.

  Since the photocurable composition has a characteristic that it is cured in a short time at room temperature by irradiation with an active energy ray typified by ultraviolet rays, the demand for electronic components is expanding.

  One of the materials used for electronic component applications is an adhesive or a sealing material. In addition to requiring adhesive strength, these materials are required to have a low cure shrinkage during curing of the curable composition and a low hygroscopic property of the cured product in order to reduce distortion of the cured product. The Therefore, the most general radical polymerization type photocurable composition is not suitable because of its high curing shrinkage.

  In order to solve this problem, a curing technique using an ene / thiol curing reaction has been proposed. The curable composition of the ene / thiol curing system has characteristics such as small curing shrinkage, no inhibition of curing by air, and high flexibility. However, there are problems such as a unique odor derived from thiol and poor moisture resistance of the cured product.

  As a curable composition having good curability and excellent moisture resistance of a cured product of the curable composition, for example, one diene compound selected from alkadienes such as polybutadiene glycol, polymers of alkadienes and cyclic dienes, and butane A curable composition containing a secondary or tertiary thiol group such as diol bis (3-mercaptobutyrate) has been disclosed (for example, see Patent Document 1). However, the curable composition is not well cured by irradiation with active energy rays and has insufficient wear resistance.

JP 2008-231409 A

  An object of the present invention is to provide a curable composition having good curability and a low hygroscopic property of the cured product, and a cured product thereof.

  As a result of intensive studies, the present inventors have used a thiol compound having a primary thiol group having a specific structure as a thiol compound, and a urethane (meth) acrylate having a diene structure as a diene compound. The present invention has been completed by finding that a curable composition having good properties and a low hygroscopicity of the cured product can be obtained.

  That is, the present invention comprises a urethane (meth) acrylate (A) having a diene structure and a thiol compound (B) represented by the following general formula (1) or general formula (2). An active energy ray-curable resin composition is provided.

（式中、Ｒ_１、Ｒ_２はそれぞれ独立に炭素原子数１〜２０の炭化水素基を表す。Ｒはそれぞれ独立にＣＯＲ_３ＣＨ_２ＳＨで表される基または水素原子を表す。Ｒ₃はそれぞれ独立に炭素原子数１〜２０の炭化水素基を表す。

(Wherein R ₁ and R ₂ each independently represents a hydrocarbon group having 1 to 20 carbon atoms. R independently represents a group represented by COR ₃ CH ₂ SH or a hydrogen atom. R ₃ represents Each independently represents a hydrocarbon group having 1 to 20 carbon atoms.

  The present invention also provides a cured product obtained by curing the active energy ray-curable resin composition.

  The active energy ray-curable resin composition of the present invention exhibits good curability. In addition, a cured product obtained by curing the composition has high hardness and low hygroscopicity.

  The urethane (meth) acrylate (A) used in the present invention has a urethane structure and a diene structure. As urethane (meth) acrylate (A), the urethane (meth) acrylate etc. which are obtained with a manufacturing method below can be mentioned preferably, for example.

(1): Urethane (meth) acrylate obtained by reacting a diisocyanate compound, a hydroxyl group-containing (meth) acrylate compound and a polybutadiene polyol [hereinafter sometimes abbreviated as urethane acrylate (A1). ]].
(2): Urethane (meth) acrylate obtained by reacting a compound having one isocyanate group and one (meth) acryloyl group with a polybutadiene polyol [hereinafter sometimes abbreviated as urethane acrylate (A2). ]].

As urethane (meth) acrylate obtained by said (1), the urethane (meth) acrylate obtained by the following manufacturing method etc. can be mentioned preferably further.
(1-1): Urethane (meth) acrylate obtained by reacting an isocyanate group-containing compound obtained by reacting a diisocyanate compound and a hydroxyl group-containing (meth) acrylate compound with a polybutadiene polyol [hereinafter referred to as urethane acrylate (A1) -1) may be abbreviated. ]].
(1-2): Urethane (meth) acrylate obtained by reacting an isocyanate group-containing compound obtained by reacting a diisocyanate compound with polybutadiene polyol and a hydroxyl group-containing (meth) acrylate compound [hereinafter referred to as urethane acrylate (A1) -2). ]].

  Examples of the diisocyanate compound include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetra Examples thereof include aliphatic or alicyclic diisocyanates such as methylxylylene isocyanate. Among them, alicyclic diisocyanate is preferable and isophorone diisocyanate is more preferable because of good storage stability and weather resistance.

  Examples of the hydroxyl group-containing (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone or alkylene oxide adduct of each acrylate, glycerin mono ( (Meth) acrylate, glycerin di (meth) acrylate, glycidyl methacrylate-acrylic acid adduct, trimethylolpropane mono (meth) acrylate, trimethylol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) ) Acrylate, ditrimethylolpropane tri (meth) acrylate, trimethylolpropane-alkylene oxide adduct-di (meth) acrylate, etc. That. Of these, hydroxyethyl (meth) acrylate is preferred.

  Examples of the compound having one isocyanate group and one (meth) acryloyl group include compounds represented by the following general formula (3).

（式中Ｒ_１は水素原子又はメチル基である。Ｒ_２は炭素原子数２から４のアルキレン基である。ｎは１〜５の整数である。）

(In the formula, R ₁ is a hydrogen atom or a methyl group. R ₂ is an alkylene group having 2 to 4 carbon atoms. N is an integer of 1 to 5.)

  Specific examples of the compound represented by the general formula (3) include, for example, Karenz AOI, Karenz MOI, Karenz BEI (trade name, manufactured by Showa Denko K.K.), and reaction addition of a diisocyanate compound and hydroxyacrylate. Things can be exemplified. Here, as a diisocyanate compound, a well-known thing can be used without being specifically limited, For example, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate etc. are mentioned. The hydroxy acrylate is not particularly limited as long as it is a compound having a hydroxyl group and a (meth) acryl group, and a known one can be used. For example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4- Examples thereof include hydroxybutyl acrylate, glycerin diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and the like.

  Among polybutadiene polyols, a polybutadiene polyol having a number average molecular weight of 200 to 100,000 is preferable because an active energy ray-curable resin composition having a cured product having good strength and low viscosity can be obtained, and more preferably 500 to 10,000. preferable.

  Examples of the polybutadiene polyol include a hydroxyl group at the terminal or main chain skeleton of a butadiene polymer. As the polybutadiene polyol, polybutadiene glycol is preferable because an active energy ray-curable resin composition having good curability and excellent storage stability can be obtained.

  The isocyanate group-containing compound may be, for example, a reaction ratio between a diisocyanate compound and a hydroxyl group-containing (meth) acrylate compound, for example, an isocyanate group (NCO) in the isocyanate group-containing compound and a hydroxyl group in the hydroxyl group-containing (meth) acrylate compound ( The ratio [OH] / (NCO)] may be set to 0.1 to 0.99. The temperature at the time of making it react is 70-100 degreeC, for example, and reaction time is 3 to 12 hours, for example.

  As a reaction ratio of the isocyanate group-containing compound and the polybutadiene polyol when the isocyanate group-containing compound and the polybutadiene polyol are reacted, for example, an isocyanate group (NCO) in the isocyanate group-containing compound and a hydroxyl group (OH) in the polybutadiene polyol are used. The ratio [(OH) / (NCO)] may be set to a ratio of 1.0 to 1.2. The temperature at the time of making it react is 70-100 degreeC, for example, and reaction time is 3 to 12 hours, for example.

  In the production method (1-1) or the production method (1-2), the reaction ratio when the diisocyanate compound, the hydroxyl group-containing (meth) acrylate compound and the polybutadiene polyol are reacted is an isocyanate group (NCO in the isocyanate group-containing compound). ), The hydroxyl group-containing (meth) acrylate compound and the hydroxyl group (OH) ratio [(OH) / (NCO)] in the polybutadiene polyol is preferably 1.0 to 1.2. The temperature at the time of making it react is 70-100 degreeC, for example, and reaction time is 3 to 12 hours, for example.

  Moreover, in the said manufacturing method (1-1) and manufacturing method (1-2), the usage-amount of a polybutadiene polyol has preferable 30-95 weight% with respect to the sum total of a diisocyanate compound, a hydroxyl-containing (meth) acrylate compound, and a polybutadiene polyol, 60 to 95% by weight is more preferable.

  In the production method (2), the reaction ratio when the compound having one isocyanate group and one (meth) acryloyl group and the polybutadiene polyol are reacted is one isocyanate group and one (meth) acryloyl group. The ratio [(OH) / (NCO)] of the hydroxyl group (OH) in the isocyanate group (NCO), the hydroxyl group-containing (meth) acrylate compound and the polybutadiene polyol in the compound having A is 1.0 to 1.2. A ratio is preferred. The temperature at the time of making it react is 70-100 degreeC, for example, and reaction time is 3 to 12 hours, for example.

  The thiol compound (B) used in the present invention is represented by the following general formula (1) or general formula (2).

（式中、Ｒ_１、Ｒ_２はそれぞれ独立に炭素原子数１〜２０の炭化水素基を表す。Ｒはそれぞれ独立にＣＯＲ_３ＣＨ_２ＳＨで表される基または水素原子を表す。Ｒ₃はそれぞれ独立に炭素原子数１〜２０の炭化水素基を表す。）

(Wherein R ₁ and R ₂ each independently represents a hydrocarbon group having 1 to 20 carbon atoms. R independently represents a group represented by COR ₃ CH ₂ SH or a hydrogen atom. R ₃ represents Each independently represents a hydrocarbon group having 1 to 20 carbon atoms.)

Examples of the compound represented by the general formula (1) include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tris [(3-mercaptopropionyloxy). ) -Ethyl] isocyanurate and the like.

  Examples of the compound represented by the general formula (2) include dipentaerythritol hexakis (3-mercaptopropionate).

  Among the thiol compounds (B) used in the present invention, the thiol compound represented by the general formula (1) is preferable, and among them, pentaerythritol tetrakis (3-mercaptopropionate) is more preferable.

  As content of urethane (meth) acrylate (A) and thiol compound (B) in the active energy ray hardening-type resin composition of this invention, urethane (meth) acrylate (A) and thiol compound (B) are weight. The ratio of [(A) / (B)] = 50/50 to 90/10 is preferable, and 60/40 to 80/20 is more preferable.

  The content ratio of the urethane (meth) acrylate (A) and the thiol compound (B) in the active energy ray-curable resin composition of the present invention is [total number of thiol groups contained in the thiol compound (B)] / The ratio in which [the total number of carbon-carbon double bonds contained in the diene compound (A)] is 0.01 to 1.0 is preferable, and 0.1 to 0.8 is more preferable.

  The active energy ray-curable resin composition of the present invention includes compounds other than the urethane (meth) acrylate (A) and unsaturated thiol compound (B) other than the urethane (meth) acrylate (A) within a range not impairing the effects of the present invention. Thiol compounds can be included.

  Examples of the compound having an unsaturated double bond other than the diene compound (A) include allyl alcohol derivatives, vinyl ethers, (meth) acrylates other than urethane (meth) acrylate (A), (meth) acrylamides, Examples include olefins, styrenes, and other vinyl monomers.

  Examples of the allyl alcohol derivatives include triallyl isocyanurate, triallyl cyanurate, diallyl maleate, diallyl adipate, diallyl phthalate, triallyl trimellitate, tetraallyl pyromellitate, glyceryl diallyl ether, trimethylolpropane diallyl ether. , Pentaerythritol, diallyl ether and the like.

  Furthermore, as allyl alcohol derivatives, for example, urethane (meth) allyl ethers obtained by reacting allyl alcohol with at least one organic diisocyanate compound, alkane diol, polyether diol, polybutadiene diol, polyester diol, polycarbonate diol, amide diol. Urethane (meth) allyl ethers in which allyl alcohol is reacted with an isocyanate group of a urethane prepolymer obtained by adding an organic diisocyanate compound to the hydroxyl group of at least one alcohol such as a spiroglycol compound may also be used. it can.

  Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxy vinyl ether, 2-ethylhexyl vinyl ether, methoxyethyl vinyl ether, cyclohexyl vinyl ether, and chloroethyl vinyl ether.

  Examples of (meth) acrylates other than the urethane (meth) acrylate (A) include, for example, monofunctional (meth) acrylate, bifunctional (meth) acrylate, trifunctional (meth) acrylate, and tetrafunctional or higher (meta) ) Acrylate and other (meth) acrylates.

  Examples of the monofunctional (meth) acrylate include hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, and isodecyl (meth). Acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate, cyanoethyl (Meth) acrylate, benzyl (meth) acrylate, butoxymethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, alkoxymethyl (meth) acrylate, alkoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl ( (Meth) acrylate, 2- (2-butoxyethoxy) ethyl (meth) acrylate, 2,2,2-tetrafluoroethyl (meth) acrylate, 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4- Butylphenyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate, 4-chlorophenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate Rate, glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, glycidyloxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3 -Hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, Dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethylsilyl Rupropyl (meth) acrylate, polyethylene oxide monomethyl ether (meth) acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, oligoethylene oxide (meth) acrylate, oligoethylene oxide monoalkyl ether (meth) acrylate, polyethylene oxide Monoalkyl ether (meth) acrylate, dipropylene glycol (meth) acrylate, polypropylene oxide monoalkyl ether (meth) acrylate, oligopropylene oxide monoalkyl ether (meth) acrylate, 2- (meth) acryloyloxysuccinic acid, 2- ( (Meth) acryloyloxyhexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, butoxydiethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, ethylene oxide modified phenol (meth) Examples include acrylate, ethylene oxide-modified cresol (meth) acrylate, ethylene oxide-modified nonylphenol (meth) acrylate, propylene oxide-modified nonylphenol (meth) acrylate, and ethylene oxide-modified-2-ethylhexyl (meth) acrylate.

  Examples of the bifunctional (meth) acrylate include 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 2,4- Dimethyl-1,5-pentanediol di (meth) acrylate, butylethylpropanediol (meth) acrylate, ethoxylated cyclohexanemethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoethylene glycol di (meth) acrylate , Ethylene glycol di (meth) acrylate, 2-ethyl-2-butyl-butanediol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A (Meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, polypropylene glycol di (meth) acrylate, oligopropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 2-ethyl-2-butylpropane Examples include diol di (meth) acrylate, 1,9-nonane di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, and tricyclodecane di (meth) acrylate.

  Examples of the trifunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide-modified tri (meth) acrylate, and pentaerythritol tri (meth). Acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide modified tri (meth) acrylate, dipentaerythritol tri (meth) acrylate propionate, tri (( (Meth) acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylolpropane tri (meth) acrylate, sorbitol tri (meta) Acrylate, propoxylated trimethylolpropane tri (meth) acrylate and ethoxylated glycerol triacrylate, and the like.

  Examples of the tetrafunctional or higher functional (meth) acrylate include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate propionate, and ethoxy. Pentaerythritol tetra (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide modified hexa (meth) Examples include acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

  Examples of the other (meth) acrylates include bisphenol-type epoxy resins obtained by condensation reaction of bisphenols such as bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, or hydrogenated products thereof with epichlorohydrin; A polyepoxy resin such as an alkanediol-based polyepoxy resin obtained by a condensation reaction of an alkanediol such as (repeating unit n = 2 to 15) or polybutylene glycol (repeating unit n = 2 to 15) and epichlorohydrin; Epoxy poly (meth) acrylates reacted with acrylic acid; and polybasic acids such as phthalic acid, succinic acid, hexahydrophthalic acid, tetrahydrophthalic acid, terephthalic acid, azelaic acid, adipic acid, and ethylene Call, hexanediol, polyethylene glycol, polytetramethylene glycol, trimethylolethane, polyhydric alcohol and (meth) polyester obtained by the reaction of acrylic acid or its derivative (meth) acrylates such as trimethylolpropane.

  Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N-t-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (Meth) acrylamide and (meth) acryloylmorpholine are mentioned.

  Examples of the olefins include ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, and vinylidene chloride.

  Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, and vinyl benzoic acid methyl ester. 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4-hexylstyrene , 3-octylstyrene, 4-octylstyrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allylstyrene, isopropenylstyrene, butenylstyrene, octenyl Styrene, 4-t-butoxycarbonyl styrene, and 4-methoxystyrene and 4-t-butoxystyrene.

  Examples of the other vinyl monomers include butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, and methyl vinyl. Ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, N-vinyl oxazolidone, N-vinyl pyrrolidone, vinyl formamide, vinylidene chloride, vinylidene cyanide, vinylidene, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl Phosphate, dibutyl-2-acryloyloxyethyl phosphate, dioctyl-2-methacryloyloxyethyl phosphate, vinyl acetate, vinyl benzoate and N- It includes nil carbazole.

  Examples of thiol compounds other than the thiol compound (B) include ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), and octanediol. Bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2- Mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol bis (2-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), Pentaerythritol tetrakis (2-mercaptopropionate), ethylene glycol bis (3-mercapto isobutyrate),

Propylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), octanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), penta Erythritol tetrakis (3-mercaptoisobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), propylene glycol bis (2-mercaptoisobutyrate), butanediol bis (2-mercaptoisobutyrate), octanediol bis (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), ethylene glycol bis (4-me Mercapto valerate), propylene glycol bis (4-mercapto iso valerate), butanediol bis (4-mercapto valerate), octanediol bis (4-mercapto valerate),

Trimethylolpropane tris (4-mercaptovalerate), pentaerythritol tetrakis (4-mercaptovalerate), ethylene glycol bis (3-mercaptovalerate), propylene glycol bis (3-mercaptovalerate), butanediol bis (3 -Mercaptovalerate), octanediol bis (3-mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate), pentaerythritol tetrakis (3-mercaptovalerate), 2,5-hexanedithiol, 2,9 -Decanedithiol, 1,4-bis (1-mercaptoethyl) benzene, phthalic acid di (1-mercaptoethyl ester), phthalic acid di (2-mercaptopropyl ester), phthalic acid di (3-mercaptobutyl ester) Le) and phthalate (3-mercapto isobutyl ester),

1,4-butanediol bisthioglycolate, ethylene glycol bismercaptoglycolate, propylene glycol bismercaptoglycolate, butanediol bismercaptoglycolate, octanediol bismercaptoglycolate, trimethylolpropane trismercaptoglycolate, pentaerythritol tetrakis Mercaptoglycolate, ethylene glycol bis (3-mercaptopropionate), propylene glycol bis (3-mercaptopropionate), butanediol bis (3-mercaptopropionate), octanediol bis (3-mercaptopropionate) ),

Trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), ethylene glycol bis (4-mercaptobutyrate), propylene glycol bis (4-mercaptobutyrate), butanediol bis (4-mercaptobutyrate), octanediol bis (4-mercaptobutyrate), trimethylolpropane tris (4-mercaptobutyrate), pentaerythritol tetrakis (4-mercaptobutyrate), ethylene glycol bis (6-mercaptobutyrate) Rate), propylene glycol bis (6-mercaptovalerate),

Butanediol bis (6-mercaptovalerate), octanediol bis (6-mercaptovalerate), trimethylolpropane tris (6-mercaptovalerate), pentaerythritol tetrakis (6-mercaptovalerate), 1,6-hexane Dithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 4,4′-bis (mercaptomethyl) phenyl sulfide, 2,4′-bis (mercaptomethyl) phenyl sulfide, 2,4,4′-tri (Mercaptomethyl) phenyl sulfide, 2,2 ′, 4,4′-tetra (mercaptomethyl) phenyl sulfide,

4,4′-bis (4-mercapto-2-thiabutyl) phenyl sulfide, 2,4′-bis (4-mercapto-2-thiabutyl) phenyl sulfide, 2,4,4′-tri (4-mercapto-2) -Thiabutyl) phenyl sulfide, 2,2 ', 4,4'-tetra (4-mercapto-2-thiabutyl) phenyl sulfide, 4,4'-bis (7-mercapto-2,5-dithiaheptyl) phenyl sulfide, 2 , 4′-bis (7-mercapto-2,5-dithiaheptyl) phenyl sulfide, 2,4,4′-tri (7-mercapto-2,5-dithiaheptyl) phenyl sulfide,

2,2 ′, 4,4′-tetra (7-mercapto-2,5-dithiaheptyl) phenyl sulfide, 4-mercaptomethyl-4 ′-(4-mercapto-2-thiabutyl) phenyl sulfide, 2-mercaptomethyl- 4 '-(4-mercapto-2-thiabutyl) phenyl sulfide, 4-mercaptomethyl-2'-(4-mercapto-2-thiabutyl) phenyl sulfide, 4- (4-mercapto-2-thiabutyl) -4'- (7-mercapto-2,5-dithiaheptyl) phenyl sulfide, 2- (4-mercapto-2-thiabutyl) -4 '-(7-mercapto-2,5-dithiaheptyl) phenyl sulfide, 4- (4-mercapto- 2-thiabutyl) -2 '-(7-mercapto-2,5-dithiaheptyl) phenyl sulfide,

4-mercaptomethyl-4 '-(7-mercapto-2,5-dithiaheptyl) phenyl sulfide, 2-mercaptomethyl-4'-(7-mercapto-2,5-dithiaheptyl) phenyl sulfide, 4-mercaptomethyl-2 '-(7-mercapto-2,5-dithiaheptyl) phenyl sulfide, bis (2-mercaptoethyl) sulfide, bis (3-mercaptopropyl) sulfide, bis (4-mercaptobutyl) sulfide, bis (8-mercaptooctyl) Sulfide, 1,2-benzenedithiol, 1,4-benzenedithiol, 4-methyl-1,2-benzenedithiol,

4-butyl-1,2-benzenedithiol, 4-chloro-1,2-benzenedithiol, tetrakis- (7-mercapto-2,5-dithiaheptyl) methane, 2,4,6-trimercapto-1, 3,5-triazine, 2,4-dimercapto-6- (2-mercaptoethylthio) -1,3,5-triazine, 2,6-dimercapto-4- (2-mercaptoethylthio) -1,3 5-triazine, 4,6-dimercapto-2- (2-mercaptoethylthio) -1,3,5-triazine, 2,4,6-tri (2-mercaptoethylthio) -1,3,5-triazine 2,4-di (2-mercaptoethylthio) -6-mercapto-1,3,5-triazine,

2,6-di (2-mercaptoethylthio) -4-mercapto-1,3,5-triazine, 4,6-di (2-mercaptoethylthio) -2-mercapto-1,3,5-triazine, 2,4,6-tri (5-mercapto-3-thiapentathio) -1,3,5-triazine, 2,4-di (5-mercapto-3-thiapentathio) -6-mercapto-1,3,5- Triazine, 2,6-di (5-mercapto-3-thiapentathio) -4-mercapto-1,3,5-triazine, 4,6-di (5-mercapto-3-thiapentathio) -2-mercapto-1, 3,5-triazine, 2,4-di (5-mercapto-3-thiapentathio) -6- (2-mercaptoethylthio) -1,3,5-triazine, 2,6-di (5-mercapto-3) -Thiapentathio) 4- (2-mercaptoethyl thio) -1,3,5-triazine,

4,6-di (5-mercapto-3-thiapentathio) -2- (2-mercaptoethylthio) -1,3,5-triazine, 4- (5-mercapto-3-thiapentathio) -2,6-dimercapto -1,3,5-triazine, 2-mercapto-4- (5-mercapto-3-thiapentathio) -6- (2-mercaptoethylthio) -1,3,5-triazine, 2,4,6-tri (8-mercapto-3,6-thiapentathio) -1,3,5-triazine, 2,4,6-tri (11-mercapto-3,6,9-trithiaundecathio) -1,3,5- Triazine, 2,4,6-tri (14-mercapto-3,6,9,12-tetrathiatetradecathio) -1,3,5-triazine,

2- (5-mercapto-3-thiapentathio) -4,6-di (8-mercapto-3,6-dithiaoctathio) -1,3,5-triazine, 2,4-di (5-mercapto-3-thiapentathio) ) -6- (8-mercapto-3,6-dithiaoctathio) -1,3,5-triazine, 2- (2-mercaptoethylthio) -4- (5-mercapto-3-thiapentathio) -6- (8 -Mercapto-3,6-dithiaoctathio) -1,3,5-triazine, 4,6-di (11-mercapto-3,6,9-trithiaundecathio) -2- (5-mercapto-3-thiapentathio ) -1,3,5-triazine,

2- (5-mercapto-3-thiapentathio) -4- (8-mercapto-3,6-dithiaoctathio) -6- (11-mercapto-3,6,9-trithiaundecathio) -1,3,5 Triazine, 2- (2-mercaptoethylthio) -4- (5-mercapto-3-thiapentathio) -6- (11-mercapto-3,6,9-trithiaundecathio) -1,3,5- Triazine, 2,4-di (5-mercapto-3-thiapentathio) -6- (11-mercapto-3,6,9-trithiaundecathio) -1,3,5-triazine, 2,4-di ( 5-mercapto-3-thiapentathio) -6- (14-mercapto-3,6,9,12-tetrathiatetradecathio) -1,3,5-triazine,

2- (5-mercapto-3-thiapentathio) -4- (8-mercapto-3,6-dithiaoctathio) -6- (14-mercapto-3,6,9,12-tetrathiatetradecathio) -1, 3,5-triazine, 2- (5-mercapto-3-thiapentathio) -4- (11-mercapto-3,6,9-trithiaundecathio) -6- (14-mercapto-3,6,9, 12-tetrathiatetradecathio) -1,3,5-triazine and 4,6-di (14-mercapto-3,6,9,12-tetrathiatetradecathio) -2- (5-mercapto-3) -Thiapentathio) -1,3,5-triazine.

  Furthermore, the condensate of the silane compound which has a mercapto group can also be used as thiol compounds other than a thiol compound (B). As the silane compound having a mercapto group, for example, a compound represented by the following structural formula can be preferably used.

(In the formula, R ₁ represents an alkylene group having 1 to 10 carbon atoms. R ₂ and R ₃ each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. A represents an integer of 0 to 2. .)

  Examples of the compound represented by the structural formula include 3-mercaptodimethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, (mercaptopropyl) methyldimethoxysilane, (mercaptopropyl) methyldiethoxysilane, and the like. These may be used alone or in combination of two or more.

  In the silane compound having a mercapto group, a mercapto group bonded to a silicon atom is hydrolyzed to form a silanol group, and condensed by a condensation reaction. The silane compound having a mercapto group may have a hydrolyzable group bonded to a silicon atom in addition to the mercapto group.

  Examples of the hydrolyzable group bonded to the silicon atom include, for example, a halogen atom, an alkoxy group, a substituted alkoxy group, an acyloxy group, a phenoxy group, an amino group, an amide group, an aminooxy group, and an iminooxy group bonded to the silicon atom, respectively. Or the group etc. which hydrolyze and produce | generate a silanol group, such as an alkenyloxy group, are mentioned.

  The condensate can be obtained, for example, by adding water to a silane compound having a mercapto group, partially or completely hydrolyzing, and simultaneously or later performing a condensation reaction (hydrolytic condensation).

  In preparing the condensate, the amount of water used for hydrolysis is 0.5 mol or more with respect to 1 mol of the hydrolyzable group of the silane compound having a mercapto group, preferably 0 The range is from 8 to 2 mol.

  Here, a catalyst may be used for the hydrolysis condensation. When the catalyst is used, any of various known and commonly used catalysts can be used. You may use together.

  Examples of the catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate, and acetic acid;

  Inorganic bases such as sodium hydroxide or potassium hydroxide; titanates such as tetraisopropyl titanate or tetrabutyl titanate; tin carboxylates such as dibutyltin dilaurate or tin octylate;

Metal carboxylates such as naphthenate or octylate of metals such as iron, cobalt, manganese or zinc; various aluminum compounds such as aluminum trisacetylacetonate;

1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1,4-diazabicyclo [2.2.2] Octane (DABCO), tri-n-butylamine, butylamine, octylamine, dimethylbenzylamine,

Amine compounds such as triethylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole or 1,4-diethylimidazole;

Tetramethylammonium salt, tetrabutylammonium salt, trimethyl (2-hydroxylpropyl) ammonium salt, cyclohexyltrimethylammonium salt, tetrakis (hydroxylmethyl) ammonium salt, dilauryldimethylammonium salt, trioctylmethylammonium salt or o-trifluoromethyl And quaternary ammonium salts such as phenyltrimethylammonium salt.

  The amount of the catalyst used is preferably in the range of 0.001 to 10% by weight, more preferably in the range of 0.005 to 5% by weight, based on the silane compound subjected to the hydrolysis condensation reaction. A range of 01 to 1% by weight is more preferable.

  The reaction temperature for hydrolysis condensation is usually about 0 ° C to 150 ° C, preferably 20 ° C to 100 ° C. As the pressure of the hydrolysis reaction, it can be carried out under any conditions of normal pressure and increased or reduced pressure.

  Alcohol and water are produced as by-products of the hydrolysis reaction, but can be removed out of the system by means such as distillation. If there is no problem, they may be left in the system as they are. .

  In addition, an organic solvent may or may not be used for the hydrolysis condensation reaction.

  In the case of using an organic solvent, any of publicly known organic solvents can be used. Examples of the organic solvent include water-insoluble organic solvents such as aromatic organic solvents such as toluene and xylene, and ester solvents such as ethyl acetate and butyl acetate;

Alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol; ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone ;

Ethylene glycol solvents such as ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-n-butyl ether, cellosolve acetate; methyl carbitol, ethyl carbitol, butyl carbitol, etc. Diethylene glycol solvent;

Propylene glycol solvents such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-tert-butyl ether; dipropylene glycol monomethyl ether, dipropylene Di- or tripropylene glycol-based solvents such as glycol mono-n-butyl ether and tripropylene glycol mono-n-butyl ether;

Examples thereof include water-soluble organic solvents having good solubility in water, such as tetrahydrofuran, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, and sulfolane.

  In obtaining the condensate, a silane compound other than a silane compound having a mercapto group may be used as long as the effects of the present invention are not impaired. Examples of such silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ- (2-aminoethyl) aminopropyl. Triethoxysilane, 3-anilinopropyltrimethoxysilane, 3-anilinopropyltriethoxysilane, 3-dimethylaminopropyltrimethoxysilane, 3-dimethylaminopropyltriethoxysilane, 3-diethylaminopropyltrimethoxysilane, 3- Diethylaminopropyltriethoxysilane, 3-dipropylaminopropyltrimethoxysilane, 3-dipropylaminopropyltriethoxysilane, 3-diisopropylaminopropyltrimethoxysilane, 3-diisopropylamino Amino group-containing monoorganotrialkoxysilanes such as propyltriethoxysilane, 3-dibutylaminopropyltrimethoxysilane, 3-dibutylaminopropyltriethoxysilane;

3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, 3-anilino Propylmethyldimethoxysilane, 3-anilinopropylmethyldiethoxysilane, 3-dimethylaminopropylmethyldimethoxysilane, 3-dimethylaminopropylmethyldiethoxysilane, 3-diethylaminopropylmethyldimethoxysilane, 3-diethylaminopropylmethyldiethoxysilane 3-dipropylaminopropylmethyldimethoxysilane, 3-dipropylaminopropylmethyldiethoxysilane, 3-diisopropylaminopropylmethyldimethoxysilane, 3-diisopropyl Amino group-containing diorganodialkoxysilanes such as propylaminopropylmethyldiethoxysilane, 3-dibutylaminopropylmethyldimethoxysilane, 3-dibutylaminopropylmethyldiethoxysilane;

  3-aminopropyldimethylmonomethoxysilane, 3-aminopropyldimethylmonoethoxysilane, γ- (2-aminoethyl) aminopropyldimethylmonomethoxysilane, γ- (2-aminoethyl) aminopropyldimethylmonoethoxysilane, 3- Anilinopropyldimethylmonomethoxysilane, 3-anilinopropyldimethylmonoethoxysilane, 3-dimethylaminopropyldimethylmonomethoxysilane, 3-dimethylaminopropyldimethylmonoethoxysilane, 3-diethylaminopropyldimethylmonomethoxysilane, 3-diethylamino Propyldimethylmonoethoxysilane, 3-dipropylaminopropyldimethylmonomethoxysilane, 3-dipropylaminopropyldimethylmonoethoxysilane, 3-diisopropyla Amino group-containing triorganomonoalkoxysilanes such as minopropyldimethylmonomethoxysilane, 3-diisopropylaminopropyldimethylmonoethoxysilane, 3-dibutylaminopropyldimethylmonomethoxysilane, 3-dibutylaminopropyldimethylmonoethoxysilane;

Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-butoxysilane;

  Methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n- Butyltrimethoxysilane, n-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-butoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-butoxysilane, vinyltris (2 -Methoxyethoxy) silane, allyltrimethoxysilane, 2-trimethoxysilylethyl vinyl ether, 2-triethoxysilylethyl vinyl ether, 3-trimethoxysilylpropyl vinyl ether , 3-triethoxysilylpropyl vinyl ether, 3- (meth) acryloyloxy propyl trimethoxy silane, 3- (meth) acryloyl mono organotrialkoxysilane such as trimethoxy silane;

Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-butyldimethoxysilane, Di-n-butyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-butoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, vinylmethyldimethoxysilane, 2- (methyldimethoxysilyl) ethyl Diorganodialkoxysilanes such as vinyl ether, 3- (methyldimethoxysilyl) propyl vinyl ether, 3- (meth) acryloyloxypropylmethyldimethoxysilane;

Tetrachlorosilane, methyltrichlorosilane, ethyltrichlorosilane, n-propyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, 3- (meth) acryloyloxypropyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, diphenyldichlorosilane, methylphenyl Chlorosilanes such as dichlorosilane, vinylmethyldichlorosilane, 3- (meth) acryloyloxypropylmethyldichlorosilane;

Acetoxysilanes such as tetraacetoxysilane, methyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane or diphenyldiacetoxysilane;

And monofunctional silicon compounds such as trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, trimethylchlorosilane, triethylchlorosilane, and triphenylchlorosilane.

  The condensate is preferably a condensate having a number average molecular weight of 200 to 2,000.

  Furthermore, a photopolymerization initiator, an inorganic filler, a polymerization inhibitor and the like can be added to the active energy ray-curable resin composition of the present invention as necessary.

  Examples of the photopolymerization initiator include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophene, methylorthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2- Ethyl anthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl Ether, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) - butanone -1, diethyl thioxanthone,

Isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine Oxide, methylbenzoylformate, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-benzyl-2-dimethyl Examples include amino-4-morpholinobutyrophenone and 2- (dimethylamino) -2- (4-methylbenzyl) -1- (4-morpholinophenyl) -butan-1-one.

  Among these, benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morphol At least one selected from linopropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and methylbenzoylformate has curability. It is preferable because it becomes better.

  The amount of the photopolymerization initiator is such that the curability of the active energy ray-curable resin composition of the present invention and the mechanical strength of the cured product obtained by curing the composition are improved, so that the diene compound (A) 0.01-30 mass parts is preferable with respect to 100 mass parts of total amount of thiol compound (B) component, and 0.1-15 mass parts is more preferable.

  Examples of the inorganic filler include metal oxides such as silica, alumina, and titanium oxide in terms of shape stability, heat resistance, flame retardancy, insulation, etc. of the cured product; and silane coupling of these metal oxides. Surface-treated metal oxides coated with an agent, etc .; hydroxides such as aluminum hydroxide, magnesium hydroxide and potassium hydroxide, and complex oxides thereof are preferred.

  In order to improve conductivity, the inorganic filler includes metal particles such as gold, silver, copper, nickel and alloys thereof, conductive particles such as carbon, carbon nanotube, carbon nanohorn, and fullerene, and glass, ceramic, and plastic. Particles obtained by coating the surface of the nucleus such as metal oxide with metal or ITO are preferable. The conductive particles preferably have an aspect ratio of 5 or more in terms of conductivity. The aspect ratio is determined by (major axis) / (minor axis).

  As the particle diameter of the inorganic filler, an area average particle diameter of 1 μm or less is optically preferable.

  The compounding quantity of an inorganic filler can be adjusted according to the use for which this composition is used, the required mechanical strength, fluidity, etc.

  Examples of the polymerization inhibitor include nitroso polymerization inhibitors such as nitrosophenylhydroxylamine ammonium salt, quinones such as hydroquinone, hydroquinone monomethyl ether and benzoquinone, N, N-diphenylpicrylhydrazyl (DPPH), and triphenyl. Examples thereof include radical scavengers such as methyl and benzotriazole antioxidants. These can be used alone or in combination of two or more.

  Further, the active energy ray-curable composition of the present invention includes addition of a plasticizer, a rheology modifier, a surface modifier, an ultraviolet absorber, a light stabilizer, an antioxidant, a flame retardant, a release agent, an organic filler, and the like. If necessary, the agent can be appropriately blended using a known means.

  The active energy ray-curable resin composition of the present invention can be used as a coating material for coating various films and molded products. Moreover, the film | membrane obtained by hardening | curing the active energy ray hardening-type resin composition of this invention can also be used as a film product.

  Furthermore, the active energy ray-curable resin composition of the present invention is suitable for lens molding and fine molding for optical members such as Fresnel lenses, lenticular lenses, light guide plates, light diffusion plates, and prism sheets.

  Moreover, the active energy ray-curable resin composition of the present invention can be used for various uses such as adhesives, electronic parts, semiconductor sealants, sealants, paste agents, potting agents, etc. in addition to the above uses.

  Examples of the base material when the active energy ray-curable resin composition of the present invention is used as a coating material for the base material include cellulose resin, polyester resin, methacrylic resin, polycarbonate resin, polystyrene resin, crystalline polyolefin resin, Examples thereof include plastic base materials such as crystalline polyolefin resin, polyether sulfone resin, acrylonitrile-styrene copolymer resin, polyamide resin, polyarylate resin, and polymethacrylimide resin, and glass plates. Moreover, what provided the handle | pattern and the easily bonding layer on the base-material surface can also be used.

  The coating method when using the active energy ray-curable resin composition of the present invention as a coating material includes a bar coater coating method, a Mayer bar coating method, an air knife coating method, a gravure coating method, a reverse gravure coating method, and a micro gravure coating. Examples thereof include known coating methods such as coating, brush coating, spray coating, shower flow coating, dip coating, curtain coating, offset printing, flexographic printing, screen printing, and potting.

  When the active energy ray-curable resin composition of the present invention is used as a coating material, the composition can be diluted with an organic solvent in order to adjust the viscosity of the composition according to the coating method.

  Examples of the organic solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, cyclohexyl rule, diacetone alcohol; methyl cellosolve, cellosolve, butyl cellosolve, methyl Ether solvents such as carbitol, carbitol, butyl carbitol, diethyl carbitol, propylene glycol monomethyl ether; SWAZOL 1000 (trade name, manufactured by Maruzen Petrochemical Co., Ltd.), SUPERSOL 100 (trade name, Shin Nippon Petrochemical) Co., Ltd.), Supersol 150 (trade name, manufactured by Nippon Petrochemical Co., Ltd.), aromatic solvents such as benzene, toluene and xylene; cyclic hydrocarbon solvents such as cyclohexane; acetone, Methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ketone solvents and ethyl acetate and cyclohexanone, n- butyl acetate, isobutyl acetate, n- amyl acetate, include acetate-based solvents such as propylene glycol acetate. These organic solvents can be used alone or in combination of two or more.

  The content of the organic solvent is preferably 30 to 100% by mass of the final composition when the hardened component in the composition is applied, from the viewpoint of coating workability. In addition, when spraying the composition, the Ford Cup No. is usually used. It is preferable to add an organic solvent using a 4 viscometer so that the viscosity is about 15 to 60 seconds at 20 ° C.

  The cured product of the present invention is obtained by curing the active energy ray-curable resin composition of the present invention.

  Examples of the active energy rays irradiated when obtaining the cured product of the present invention include α rays, β rays, γ rays, ultraviolet rays, and the like, and ultraviolet rays are preferable from the viewpoint of versatility.

  Examples of the ultraviolet ray generation source include commonly used ultraviolet lamps from the viewpoint of practicality and economy. For example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, and a magnetron There may be mentioned an electrodeless UV lamp using

  When obtaining the main cured product, when using active energy rays, the atmosphere for curing may be either air or an inert gas such as nitrogen or argon, but it is cured in an air atmosphere in terms of practicality and economy. It is preferable to make it.

  Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following, all parts and “%” are “% by mass” unless otherwise specified.

Synthesis Example 1 [Preparation of urethane (meth) acrylate compound (A)]
Dry air was blown into a flask having a stirring bar, a temperature sensor, a gas introduction tube and a condenser, and then 67.2 g of isophorone diisocyanate and 0.01 g of methoquinone were added to the flask, and the temperature was raised to 40 ° C. while stirring. Next, after 35.3 g of 2-hydroxyethyl acrylate was charged over 3 hours, the mixture was further maintained at 80 ° C. for 6 hours, and urethane acrylate having one acryloyl group and one isocyanate group in the molecule [Gardner viscosity (25 ° C. ): Z2-Z3, Gardner color: 1 or less, NCO% = 12.3%], 102.5 g was obtained. Furthermore, after cooling the temperature in the flask to 60 ° C., 0.01 g of octyl tin was added, and 325.1 g of polybutadiene glycol (number average molecular weight 2100, hydroxyl value 52.8) was added over 3 hours, and at 80 ° C. for 8 hours. Hold and add 106.9 g of butyl acetate to obtain a urethane acrylate resin solution having two acryloyl groups in one molecule [Gardner color: 1 or less, Gardner viscosity: Z4-Z5, nonvolatile content = 80.8%]. It was. Hereinafter, this is abbreviated as urethane acrylate (A1).

Synthesis example 2 (same as above)
After blowing dry air into a flask having a stir bar, temperature sensor, gas inlet tube and condenser, 144.8 g of 2-isocyanatoethyl acrylate, 0.37 g of methoquinone and 0.37 g of octyl tin were added to the flask while stirring. The temperature was raised to 40 ° C. Next, after charging 1085.7 g of polybutadiene glycol (number average molecular weight 2100, hydroxyl value 52.8) over 5 hours, the mixture was further maintained at 80 ° C. for 6 hours, and 307.2 g of butyl acetate was added. To obtain a urethane acrylate resin solution having two acryloyl groups [Gardner color: 1 or less, Gardner viscosity: Y-Z, nonvolatile content = 80.0%]. Hereinafter, this is abbreviated as urethane acrylate (A2).

Synthesis example 3 (same as above)
Dry air was blown into a flask having a stirring bar, a temperature sensor, a gas introduction tube and a condenser, and then 44.4 g of isophorone diisocyanate and 0.08 g of methoquinone were added to the flask, and the temperature was raised to 40 ° C. while stirring. Next, 0.08 g of octyl tin is added, 212.5 g of polybutadiene glycol (number average molecular weight 2100, hydroxyl value 52.8) is added over 3 hours, and the mixture is held at 80 ° C. for 6 hours to add 2 isocyanate groups in the molecule. 256.9 g of urethane resin [NCO% = 3.3%] was obtained. Next, after 23.3 g of 2-hydroxyethyl acrylate was charged over 3 hours, the mixture was further maintained at 80 ° C. for 3 hours, 120.1 g of butyl acetate was added, and urethane acrylate having two acryloyl groups in one molecule A resin solution (Gardner color: 1 or less, Gardner viscosity: Z1-Z2, nonvolatile content = 70.2%) was obtained. Hereinafter, this is abbreviated as urethane acrylate (A3).

Examples 1-4 and Comparative Examples 1-3
A compound containing a diene structure, a thiol compound and a photoinitiator are blended in the formulations shown in Tables 1 and 2, and the active energy ray-curable resin compositions 1 to 4 of the present invention and the comparative active energy beam are used. Curable resin compositions 1 ′ to 3 ′ were prepared. The storage stability of these compositions, the curability of these compositions, and the water absorption and gel fraction of the cured products of the compositions were evaluated. The evaluation method is shown below. Also. The evaluation results are shown in Tables 3 and 4.

<Method for evaluating storage stability of composition>
The viscosity immediately after the preparation of the active energy ray-curable resin compositions 1 to 8 of the present invention and the comparative active energy ray-curable resin compositions 1 ′ to 4 ′ and the viscosity after standing at 20 ° C. for 7 days are 25 It measured using the E-type viscosity meter (the Toki Sangyo Co., Ltd. make, RE-800) in the atmosphere of ° C, and the storage stability was evaluated by the following criteria.
○: Viscosity change rate is less than 5%.
X: Viscosity change rate is 5% or more.

<Method for preparing test piece used for evaluation of curability of composition and coating film refractive index of cured product of composition>
Active energy ray-curable resin compositions 1 and 2 and comparative control active energy ray-curable resin compositions 1 'to 3' of the present invention are dissolved in butyl acetate, and active energy ray-cured with a nonvolatile content (NV) of 40%. A solution of the mold composition was obtained. After applying this solution to a PET film (Toyobo Co., Ltd., A-4300 (125 μm)) using a bar coater, it was left in an oven at 70 ° C. for 3 minutes to evaporate the solvent in the composition. Was used to irradiate ultraviolet rays with an integrated light quantity of 500 mJ / cm 2 to obtain a coated film having a cured coating film with a thickness of 5 μm.

<Evaluation method of curability>
The curability was evaluated according to the following criteria.
○: There is no tackiness when the finger is pressed against the cured coating film.
(Triangle | delta): When a finger is pressed on a cured coating film, there exists a feeling of a little tack.
X: When a finger is pressed against the cured coating film, there is a feeling of tack.

<Evaluation method of coating film refractive index>
The refractive index of the coating film was measured using a refractive index measuring device (Model 2010, manufactured by METORICON). A wavelength of 594 nm was used as the light source.

<Method for creating test piece used for evaluation of gel fraction and water absorption of cured product>
Active energy ray curable resin compositions 1 to 8 of the present invention and comparative active energy ray curable resin compositions 1 'to 4' are dissolved in butyl acetate, and active energy ray curable with a nonvolatile content (NV) of 40%. A solution of the mold composition was obtained. After applying this solution to a mirror-finished aluminum plate (A1050P manufactured by Engineering Test Service Co., Ltd.) with an applicator, it is left in an oven at 70 ° C. for 5 minutes to volatilize the solvent in the composition, and integrated light quantity using an 80W high-pressure mercury lamp The coated film was cured by irradiating with 400 mJ / cm ² of ultraviolet rays. Then, the coating film was peeled from the mirror surface aluminum plate to obtain a cured coating film having a thickness of 50 μm.

<Evaluation method of gel fraction of cured product>
The cured coating film was immersed in acetone at 20 ° C. for 24 hours. The weight retention before and after immersion was expressed as a gel fraction (%).

<Evaluation method of water absorption of cured product>
The cured coating film was immersed in ion exchange water at 20 ° C. for 24 hours. The weight change rate before and after the immersion was expressed as a water absorption rate (%).

Footnotes in Tables 1 and 2 Diene compound (a1): polybutadiene glycol (number average molecular weight 2100)
Diene compound (a2): hydrogenated polybutadiene glycol (number average molecular weight 1500)
Thiol compound (B): pentaerythritol tetrakis (3-mercaptopropionate) (number average molecular weight 495)
Thiol compound (b): pentaerythritol tetrakis (3-mercaptobutyrate) (number average molecular weight 545)
Photoinitiator: Benzophenone

Footnotes in Table 4 In coating film refractive index-: Not evaluated because a cured coating film could not be obtained.
In terms of gel fraction-: Evaluation was not possible because a cured coating film could not be obtained.
In terms of water absorption rate: Not evaluated because a cured coating film could not be obtained.

Claims (10)

An active energy ray-curable resin comprising a urethane (meth) acrylate (A) having a diene structure and a thiol compound (B) represented by the following general formula (1) or general formula (2) Composition.

(Wherein R ₁ and R ₂ each independently represents a hydrocarbon group having 1 to 20 carbon atoms. R independently represents a group represented by COR ₃ CH ₂ SH or a hydrogen atom. R ₃ represents Each independently represents a hydrocarbon group having 1 to 20 carbon atoms.) The active energy ray curing according to claim 1, wherein the urethane (meth) acrylate (A) is a urethane (meth) acrylate (A1) obtained by reacting a diisocyanate compound, a hydroxyl group-containing (meth) acrylate compound and a polybutadiene polyol. Resin composition. The urethane (meth) acrylate is obtained by reacting an isocyanate group-containing (meth) acrylate compound obtained by reacting a diisocyanate compound and a hydroxyl group-containing (meth) acrylate compound with a polybutadiene polyol. Item 3. The active energy ray-curable resin composition according to Item 2. The active energy ray-curable resin composition according to claim 3, wherein the isocyanate group-containing (meth) acrylate compound is a compound obtained by reacting an alicyclic diisocyanate and a hydroxyl group-containing (meth) acrylate compound. The urethane (meth) acrylate reacts an isocyanate group-containing (meth) acrylate compound obtained by reacting isophorone diisocyanate with a hydroxyl group-containing (meth) acrylate compound and a polybutadiene polyol having a number average molecular weight of 200 to 100,000. The active energy ray-curable resin composition according to claim 3, which is obtained. 2. The active energy according to claim 1, wherein the urethane (meth) acrylate (A) is obtained by reacting a compound having one isocyanate group and one (meth) acryloyl group in one molecule with a polybutadiene polyol. A linear curable resin composition. The number average molecular weight of the said thiol compound (B) is 100-2000, The active energy ray-curable resin composition of any one of Claims 1-6. The urethane (meth) acrylate (A) and the thiol compound (B) are contained at a ratio of [(A) / (B)] = 60/40 to 80/20 by weight ratio. The active energy ray-curable resin composition according to claim 1. The active energy ray-curable resin composition according to claim 1, wherein the thiol compound (B) is pentaerythritol tetrakis (3-mercaptopropionate). A cured product obtained by curing the active energy ray-curable resin composition according to any one of claims 1 to 9.