WO2017221517A1 - Photocurable resin composition, and pressure-sensitive adhesive or adhesive each comprising same - Google Patents

Abstract

Provided are: a photocurable resin composition having excellent moist-heat resistance and high heat resistance; and a pressure-sensitive adhesive or an adhesive each comprising the photocurable resin composition. The photocurable resin composition comprises a polymeric crosslinking agent (A) and a hydroxylated acrylate (B) and may further contain a polymerizable compound (C) as an optional component. The polymeric crosslinking agent (A) is a (meth)acryl-group-terminated polyurethane acrylate which comprises repeating units represented by formula (1a), repeating units represented by formula (1b), and repeating units represented by formula (2). When the total amount of the polymeric crosslinking agent (A), hydroxylated acrylate (B), and polymerizable compound (C) is taken as 100 parts by mass, the photocurable resin composition includes at least 60 parts by mass of the polymeric crosslinking agent (A) and 15-40 parts by mass of the hydroxylated acrylate (B).

Description

Photo-curable resin composition and adhesive / adhesive using the same

The present invention relates to a photocurable resin composition and an adhesive / adhesive using the same.

Conventionally, a photocurable resin composition that is cured by irradiation with active energy rays such as ultraviolet rays and visible rays has been used as an adhesive / adhesive. For example, an example is described in Patent Document 1 and Patent Document 2 below.

For example, Patent Document 1 describes the use of polyurethane acrylate, polyisoprene acrylate, or the like as a touch panel adhesive / adhesive.

Patent Document 2 describes using urethane acrylate using polycarbonate diol as an adhesive material.

Japanese Patent No. 5310913 JP 2014-189723 A

Depending on the use of the adhesive / adhesive, it may be required to have excellent moisture and heat resistance.

The main object of the present invention is to provide a photocurable resin composition having excellent moisture and heat resistance and high heat resistance, and an adhesive / adhesive using the same.

The photocurable resin composition according to the present invention includes a polymer crosslinking agent (A) and a hydroxyl group-containing acrylate (B), and may further include a polymerizable compound (C) as an optional component. The polymer crosslinking agent (A) includes a repeating unit represented by the following formula (1a), a repeating unit represented by the formula (1b), and a repeating unit represented by the formula (2): It is a polyurethane acrylate having a meth) acrylic group at the end. When the total amount of the polymer crosslinking agent (A), the hydroxyl group-containing acrylate (B) and the polymerizable compound (C) is 100 parts by mass, the photocurable resin composition according to the present invention has a polymer crosslinking agent (A ) In an amount of 60 parts by mass or more and 15 to 40 parts by mass of the hydroxyl group-containing acrylate (B).

(In the formula (1a), Z ^a represents a divalent cycloaliphatic hydrocarbon group having 6 to 18 carbon atoms. In the formula (1a), one carbon atom contained in Z ^a is a sulfur atom. In the formula (1b), Z ^b is a divalent straight-chain aliphatic hydrocarbon group having 2 to 12 carbon atoms or a divalent branch having 3 to 12 carbon atoms. and n of one carbon atom contained in .Z ^b showing the Jo aliphatic hydrocarbon group may be substituted by a sulfur atom. formula (1a), and n in formula (1b), the same or different And each represents a natural number of 1 to 40. In the formula (2), R is a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms, and 3 to 12 carbon atoms. A divalent branched aliphatic hydrocarbon group, a divalent cyclic aliphatic hydrocarbon group having 6 to 18 carbon atoms, or a carbon atom number of Represents a divalent aromatic hydrocarbon group of 6 to 18.)

The adhesive / adhesive according to the present invention contains the photocurable resin composition.

In the present invention, the “viscous / adhesive” includes both an adhesive and an adhesive.

In the present invention, “polyurethane (meth) acrylate” is a general term for polyurethane acrylate having an acrylic group at the terminal and polyurethane methacrylate having a methacrylic group at the terminal.

In the present invention, “(meth) acryl group” refers to an atomic group having at least one (meth) acryloyl group. The “(meth) acryloyl group” refers to a functional group excluding the hydroxyl group of (meth) acrylic acid.

According to the present invention, it is possible to provide a photo-curable resin composition having excellent moisture and heat resistance and high heat resistance, and an adhesive / adhesive using the same.

The photo-curable resin composition according to the present invention can be used as, for example, an adhesive / adhesive material. The adhesive / adhesive may be composed only of the photocurable resin composition according to the present invention, or may further contain other components.

The photocurable resin composition according to the present invention includes a polymer crosslinking agent (A) and a hydroxyl group-containing acrylate (B). The photocurable resin composition according to the present invention may further contain a polymerizable compound (C) as an optional component.

(1) Polymer crosslinking agent (A)
In the present invention, the polymer crosslinking agent (A) includes a repeating unit represented by the following formula (1a), a repeating unit represented by the formula (1b), and a repeating unit represented by the formula (2): It is a polyurethane (meth) acrylate having a (meth) acrylic group at the end.

The repeating unit represented by the formula (1a) or the formula (1b) is a component derived from “polycarbonate polyol” used when synthesizing “polyurethane (meth) acrylate”.

In the formula (1a), Z ^a represents a divalent cycloaliphatic hydrocarbon group having 6 to 18 carbon atoms. One carbon atom contained in Z ^a may be replaced by a sulfur atom.
In the formula (1b), Z ^b represents a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms or a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms. Show. One carbon atom contained in ^Zb may be substituted with a sulfur atom.

The photocurable resin composition according to the present invention may contain a plurality of types of repeating units represented by formula (1a) or formula (1b).

The repeating unit represented by the formula (2) is a constituent derived from “polyisocyanate” when synthesizing “polyurethane (meth) acrylate”.

In the formula (2), R represents a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a carbon atom It represents a divalent cyclic aliphatic hydrocarbon group having 6 to 18 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.

The photocurable resin composition according to the present invention may include a plurality of types of repeating units represented by the formula (2).

In each of the formula (1a) and the formula (2), the “divalent cycloaliphatic hydrocarbon group having 6 to 18 carbon atoms” refers to “cycloaliphatic hydrocarbon having 6 to 18 carbon atoms”. A group without two hydrogens is shown. Specific examples of the divalent cycloaliphatic hydrocarbon group having 6 to 18 carbon atoms include, for example, 1,3-cyclohexylene group, 1,4-cyclohexylene group, 1,4-dimethylenecyclohexylene group ( Methylene-cyclohexylene-methylene group) and the like.

In each of the formula (1b) and the formula (2), “a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms” means “a linear fatty acid having 2 to 12 carbon atoms”. A group obtained by removing two hydrogens from "group hydrocarbon". Specific examples of the “divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms” include, for example, ethylene group, trimethylene group (propylene group), tetramethylene group (butylene group), pentamethylene group, hexamethylene group, Examples include a methylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, and a dodecamethylene group. Among these, preferred specific examples of the divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms include a tetramethylene group, a pentamethylene group, and a hexamethylene group.

In each of the formula (1b) and the formula (2), “a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms” means “a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms”. "Represents a group in which two hydrogen atoms are removed. Specific examples of the divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms include, for example, 2-methyl-1,3-trimethyl group, 2- or 3-methyl-1,5-pentyl group, Examples include 2,2,4- or 2,4,4-trimethylhexamethylene group, 1,5-hexylene group and the like.

In the formula (2), the “divalent aromatic hydrocarbon group having 6 to 18 carbon atoms” refers to a group obtained by removing two hydrogen atoms from the “aromatic hydrocarbon having 6 to 18 carbon atoms”. . Specific examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms include, for example, a phenylene group, a tolylene group, a xylylene group, a tetramethylxylylene group, and a 4,4′-diphenylenemethylene group. It is done.

N in the formula (1a) and n in the formula (1b) may be the same or different and each represents a natural number of 1 to 40. In the formula (1), n is preferably 2 to 30, and more preferably 3 to 25.

In the present invention, the polymer crosslinking agent (A) has a (meth) acryl group at the terminal. Examples of the (meth) acryl group include “polyfunctional (meth) acryl group” and “monofunctional (meth) acryl group”.

In the present invention, a polyfunctional (meth) acryl group or a monofunctional (meth) acryl group modified with an alkyleneoxy group such as an “ethyleneoxy group” or a “propyleneoxy group” is also a (meth) acryl group. Shall be included.

The polyfunctional (meth) acryl group is, for example, a group represented by the following formula (a-1), a group represented by the formula (a-2), a group represented by the formula (b-1) or a formula ( It is preferably a group represented by b-2).

The monofunctional (meth) acryl group is preferably a group represented by the following formula (c), for example.

In each of formula (a-1), formula (a-2), formula (b-1), formula (b-2) and formula (c), A represents a (meth) acryloyl group. In each of formula (a-1), formula (a-2), formula (b-1), formula (b-2), and formula (c), a plurality of A may be the same or different. It may be. In each of formula (a-1), formula (a-2), formula (b-1), formula (b-2), and formula (c), a part of A is replaced by hydrogen May be.

In the formula (c), m represents an integer of 2 to 8.

(Synthesis method of polymer cross-linking agent (A))
The polymer crosslinking agent (A) can be obtained, for example, in the following manner. That is, a “polycarbonate polyol” having a repeating unit represented by the formula (1a) or the formula (1b), a “polyisocyanate” having a repeating unit represented by the formula (2), a formula (a-1), Reaction with “hydroxyl group-containing (meth) acrylate compound” or isocyanate group-containing (meth) acrylate compound represented by formula (a-2), formula (b-1), formula (b-2) or formula (c) Can be obtained. The reaction for generating the polymer crosslinking agent (A) is not particularly limited, and can be performed by, for example, a one-shot method or a prepolymer method.

Specifically, the reaction for forming the polymer crosslinking agent (A) is preferably performed at a temperature of 0 ° C. to 150 ° C., more preferably 20 ° C. to 100 ° C. by mixing polycarbonate polyol, polyisocyanate, catalyst, and solvent. After the reaction, a polymerization inhibitor, an antioxidant, and a hydroxyl group-containing or isocyanate group-containing (meth) acrylate compound are added to the obtained reaction solution, and the reaction is preferably performed at the same temperature.

Since the obtained polyurethane (meth) acrylate is not necessarily stable to light and oxygen in the air, it is preferably used as a solution of polyurethane (meth) acrylate without being isolated or purified.

In order to improve the function and characteristics of the polymer cross-linking agent (A) of the present invention, the reaction for generating the polymer cross-linking agent (A) has a different molecular weight even if it is a plurality of types of polycarbonate polyols or the same type. Polycarbonate polyols may be used. Moreover, you may use multiple types of polyisocyanate for the same reason.

(Polycarbonate polyol)
The polycarbonate polyol used in the reaction for producing the polymer crosslinking agent (A) has a skeleton represented by the formula (1a) or the formula (1b). Such a polycarbonate polyol can be obtained, for example, by reacting a polyol with a carbonate ester in the presence of a catalyst.

The polyol preferably used includes a polyol having a divalent cycloaliphatic hydrocarbon group having 6 to 18 carbon atoms, and a polyol having a linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms. And a polyol having a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms. If it is the same kind of polyol, a plurality of different polyols among these polyols may be mixed and used.

Specific examples of the polyol having a divalent cycloaliphatic hydrocarbon group having 6 to 18 carbon atoms include 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. Is mentioned.

Specific examples of the polyol having a linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms include 1,2-ethanediol, 1,3-propanediol, 1,4-butane. Diol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-dodecanediol 1,12-undecanediol and the like. More preferable specific examples of the polyol having a linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms include 1,4-butanediol, 1,5-pentanediol, and 1,6-hexane. Diol etc. are mentioned.

Specific examples of the polyol having a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms include 2-methyl-1,3-propanediol and 2-methyl-1,5-pentanediol. Alternatively, 3-methyl-1,5-pentanediol, 2,2,4-trimethylhexanediol, 2,4,4-trimethylhexanediol, 1,5-hexanediol and the like can be mentioned.

Examples of the carbonic acid ester preferably used include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate; diaryl carbonates such as diphenyl carbonate; ethylene carbonate, propylene carbonate (4-methyl-1,3-dioxolan-2-one , Trimethylene carbonate), butylene carbonate (4-ethyl-1,3-dioxolan-2-one, tetramethylene carbonate), 5-methyl-1,3-dioxane-2-one and the like. Especially, as carbonate ester used more preferably, dimethyl carbonate, diethyl carbonate, ethylene carbonate etc. are mentioned, for example. Only one of these carbonate esters may be used alone, or a plurality of carbonate esters may be mixed and used.

The amount of carbonate ester to be used is preferably 0.8 mol to 2.0 mol, more preferably 0.9 mol to 1.5 mol, per 1 mol of polyol. By setting the amount of carbonate used within the above range, the desired polycarbonate polyol can be efficiently obtained at a sufficient reaction rate.

(Catalyst for producing polycarbonate polyol)
In carrying out the reaction for producing the polycarbonate polyol, a catalyst may be used. Examples of the catalyst preferably used for the reaction for producing the polycarbonate polyol include a transesterification catalyst. Specific examples of the transesterification catalyst include, for example, metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, zirconium, cobalt, germanium, tin, cerium, and the like. And hydroxides, alkoxides, carboxylates, carbonates, hydrogen carbonates, sulfates, phosphates, nitrates, and organic metals. Among them, sodium hydride, titanium tetraisopropoxide, titanium tetrabutoxide, zirconium tetrabutoxide, zirconium acetylacetonate, zirconium oxyacetate, dibutyltin dilaurate, dibutyltin dimethoxide, and dibutyltin oxide are used as catalysts for the reaction to produce polycarbonate polyol. Preferably used. In the reaction for producing the polycarbonate polyol, only one of these catalysts may be used alone, or a plurality of types may be mixed and used.

In the reaction for producing the polycarbonate polyol, the amount of the catalyst used is preferably 0.001 mmol to 0.1 mmol, more preferably 0.005 mmol to 0.05 mmol, more preferably 0, relative to 1 mol of the polyol. 0.01 mmol to 0.03 mmol. By setting the amount of the catalyst to be used within the above range, the desired polycarbonate polyol can be obtained efficiently without complicating the post-treatment.

In addition, the catalyst may be charged in the entire amount at the start of the reaction, or may be divided and added during the reaction.

The reaction temperature of the reaction for producing the polycarbonate polyol can be appropriately adjusted according to the type of carbonate, but is preferably 50 ° C. to 250 ° C., more preferably 70 ° C. to 230 ° C. The range of the preferable reaction temperature is the same when the reaction for producing the polycarbonate polyol is carried out by either the one-stage method or the two-stage method.

The reaction pressure of the reaction for producing the polycarbonate polyol is not particularly limited as long as it is within the pressure range in which the reaction can be performed while removing the low-boiling components, and is preferably 1 atm or 1 atm or less. By carrying out the reaction for producing the polycarbonate polyol within the above preferred reaction pressure range, the desired polycarbonate polyol can be suitably obtained efficiently with little occurrence of sequential reactions and side reactions.

(Polyisocyanate)
The polyisocyanate used in the reaction for producing the polymer crosslinking agent (A) has a skeleton represented by the formula (2).

The polyisocyanate preferably used in the reaction for forming the polymer crosslinking agent (A) includes a polyisocyanate having a linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms, and having 3 carbon atoms. A polyisocyanate having a divalent branched aliphatic hydrocarbon group of ˜12, a polyisocyanate having a divalent cyclic aliphatic hydrocarbon group of 6 to 18 carbon atoms, a divalent having 6 to 18 carbon atoms And polyisocyanates having an aromatic hydrocarbon group. Only one of these polyisocyanates may be used alone or a plurality of types may be mixed and used. Moreover, a part or all of the structure of the polyisocyanate may be derivatized such as isocyanurate, carbodiimidization or biuretization.

Examples of the polyisocyanate having a linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms include hexamethylene diisocyanate.

Examples of the polyisocyanate having a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms include 2- or 3-methyl-1,5-pentyl diisocyanate, 2,2,4- or 2, Examples include 4,4-trimethylhexamethylene diisocyanate.

Examples of polyisocyanates having a divalent cycloaliphatic hydrocarbon group having 6 to 18 carbon atoms include 1,4-cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, 4,4′-methylenebiscyclohexyl diisocyanate, and isophorone. Examples include diisocyanate, cyclohexane-1,2-diylbis (methylene) diisocyanate, and norbornyl diisocyanate.

Examples of the polyisocyanate having a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms include phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4 ′. -Diisocyanate, naphthalene-1,5-diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, tetramethylxylylene diisocyanate, xylylene diisocyanate (XDI) and the like.

(Hydroxyl-containing polyfunctional (meth) acrylate compound)
The hydroxyl group-containing polyfunctional (meth) acrylate compound used in the reaction for forming the polymer crosslinking agent (A) is represented by the formula (a-1), the formula (a-2), the formula (b-1) or the formula (b- It is not particularly limited as long as it has a group represented by 2) and has a hydroxyl group at the terminal, or an ethyleneoxy-modified product or a lactone-modified product.

As the hydroxyl group-containing polyfunctional (meth) acrylate compound preferably used, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane di (meta) ) Acrylates, ethyleneoxy-modified products, propyleneoxy-modified products, and lactone-modified products. Of these, pentaerythritol tri (meth) acrylate, dipetaerythritol penta (meth) acrylate, and dipentaerythritol tetra (meth) acrylate are more preferably used as the hydroxyl group-containing polyfunctional (meth) acrylate compound. In the reaction for generating the polymer crosslinking agent (A), only one of the hydroxyl group-containing polyfunctional (meth) acrylate compounds may be used alone, or a plurality of types may be used in combination. Good. In the reaction for generating the polymer crosslinking agent (A), a saturated polyfunctional (meth) acrylate compound that does not contain a hydroxyl group may be used.

(Hydroxyl-containing monofunctional (meth) acrylate compound)
The hydroxyl group-containing monofunctional (meth) acrylate compound used in the reaction for generating the polymer crosslinking agent (A) includes those having a group represented by the formula (c), ethyleneoxy-modified products and lactone-modified products, If it is an isomer, it will not specifically limit.

Examples of the hydroxyl group-containing monofunctional (meth) acrylate compound preferably used include, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, and hydroxyhexyl (meth). Examples thereof include acrylate, hydroxy (heptyl) methacrylate, hydroxyoctyl (meth) acrylate, and the like. Of these, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate are more preferably used as the hydroxyl group-containing monofunctional (meth) acrylate compound. In the reaction for generating the polymer crosslinking agent (A), only one of the hydroxyl group-containing monofunctional (meth) acrylate compounds may be used alone, or a plurality of types may be mixed and used. In the reaction for generating the polymer crosslinking agent (A), a saturated monofunctional (meth) acrylate compound not containing a hydroxyl group may be used.

(Isocyanate group-containing (meth) acrylate compound)
The isocyanate group-containing monofunctional (meth) acrylate compound used in the reaction for generating the polymer crosslinking agent (A) has a group represented by the formula (c), and these ethyleneoxy modified products and lactone modified products. If it is an isomer, it will not specifically limit.

Specific examples of the isocyanate group-containing monofunctional (meth) acrylate compound preferably used include, for example, 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethyloxy) ethyl isocyanate, 1,1 -Bis ((meth) acryloyloxymethyl) ethyl isocyanate and the like. Only one of these isocyanate group-containing (meth) acrylate compounds may be used alone, or a plurality of types may be mixed and used. Moreover, you may use the saturated monofunctional (meth) acrylate compound which does not contain an isocyanate group in reaction which produces | generates a polymeric crosslinking agent (A).

(Reaction catalyst that reacts polycarbonate polyol and polyisocyanate to produce urethane, and reacts polycarbonate polyol, polyisocyanate, and acrylate compound to produce a polymer crosslinking agent (urethane (meth) acrylate)) Catalyst)
Reaction rate in reaction to produce urethane by reacting polycarbonate polyol and polyisocyanate or reaction to produce polymer cross-linking agent (urethane (meth) acrylate) by reacting polycarbonate polyol, polyisocyanate and acrylate compound For example, a known polymerization catalyst can be used, for example, organic tin compounds such as dibutyltin diacetate and dibutyltin dilaurate, and organic titanium such as titanium tetraacetylacetonate and titanium diisopropoxybis (ethylacetoacetate). Compounds, organic zirconium compounds such as zirconium tetraacetylacetonate and zirconium dibutoxybis (ethylacetoacetate), and tertiary amines such as triethylamine are preferably used.

As for the catalyst, pages 23 to 32 of Keiji Yoshida “Polyurethane resin” (published by Nihon Kogyo Shimbun, 1969) can be referred to.

The amount of the catalyst used is preferably 0.0005 to 0.1% by mass, more preferably 0.001 based on the total amount of the polycarbonate polyol, polyisocyanate, and hydroxyl group-containing or isocyanate group-containing (meth) acrylate compound. It is -0.05 mass%.

In this range, a sufficient reaction rate can be obtained and the post-treatment is not complicated because the remaining amount of catalyst is small.

(solvent)
In the reaction for producing the polymer crosslinking agent (A), a solvent having low reactivity with an isocyanate group can be appropriately used. Specific examples of the solvent preferably used in the reaction for generating the polymer crosslinking agent (A) include, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, Esters such as propylene glycol monoethyl ether acetate and dipropylene glycol monomethyl ether acetate; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetrahydrofuran , Ethers such as dioxane; benzene, toluene, xylene Emissions, aromatic hydrocarbons such as tetramethyl benzene; dimethylformamide, diethylformamide, amides such as dimethylacetamide; sulfoxides such as dimethyl sulfoxide and the like. In the reaction for producing the polymer crosslinking agent (A), only one of these solvents may be used alone, or a plurality of kinds of solvents may be mixed and used. By using a solvent, a polyurethane acrylate solution can be obtained.

Although a solvent is not necessarily required for the reaction for producing the polymer crosslinking agent (A), the use of the solvent improves the uniformity and agitation of the reaction solution and prepares an adhesive with a high solid content concentration. Is possible.

(Chain extender)
In the reaction for producing the polymer crosslinking agent (A), in the reaction for producing urethane by reacting polycarbonate polyol and polyisocyanate, the chain extender is used for the purpose of increasing the molecular weight by extending the chain of urethanes. Can be used. The chain extender to be used can be appropriately selected depending on the purpose and application.

Specific examples of the chain extender preferably used include, for example, water; ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol 1,10-decanediol, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxyethoxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane Low molecular polyol such as polyester polyol, poly Polymer polyols such as stearamide polyol, polyether polyol, polyether ester polyol, polycarbonate polyol, polyolefin polyol; ethylenediamine, isophoronediamine, 2-methyl-1,5-pentanediamine, aminoethylethanolamine, diethylenetriamine, triethylenetetramine And polyamines such as tetraethylenepentamine and pentaethylenehexamine.

For the chain extender, for example, "Latest polyurethane application technology" (CMC Co., Ltd., issued in 1985) can be referred to. As for the polymer polyol, for example, “Polyurethane foam” (Polymer Publication, 1987) can be referred to.

(Polymerization inhibitor)
In the reaction to produce the polymer crosslinking agent (A), polymerization of the raw material hydroxyl group-containing polyfunctional (meth) acrylate compound, hydroxyl group-containing monofunctional (meth) acrylate compound, and poly (thio) urethane (meth) acrylate produced In order to suppress oxidation and oxidation, a polymerization inhibitor and an antioxidant are preferably present. Examples of polymerization inhibitors and antioxidants include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-t-butyl-p-cresol, p-benzoquinone, 2,5 -Dihydroxy-p-benzoquinone and the like are used. In addition, only 1 type in these polymerization inhibitors and antioxidants may be used independently, and multiple types may be mixed and used.

The addition amount of the polymerization inhibitor and the antioxidant is preferably 0.00005% by mass to 0.01% by mass with respect to the total amount of the polycarbonate polyol, polyisocyanate, hydroxyl group-containing or isocyanate group-containing (meth) acrylate compound. More preferably, it is 0.0001% by mass to 0.005% by mass, and more preferably 0.0003% by mass to 0.003% by mass. By setting the addition amount of the polymerization inhibitor and the antioxidant within the above ranges, polymerization and oxidation can be sufficiently suppressed, and post-treatment after the reaction is not complicated.

(Hydroxyl-containing acrylate (B))
Examples of the hydroxyl group-containing (meth) acrylate compound preferably used in the present invention include pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and dipentaerythritol penta (meth). ) Acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylol Propane di (meth) acrylate, or these polyfunctional (meth) acrylates such as ethyleneoxy modified products, propyleneoxy modified products, and lactone modified products Compounds, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxy (heptyl) methacrylate, hydroxyoctyl (meth) And monofunctional (meth) acrylate compounds such as acrylate. Of these, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate are more preferably used. Only one kind of these hydroxyl group-containing acrylates may be used alone, or a plurality of kinds may be mixed and used. Moreover, you may use together the saturated monofunctional (meth) acrylate compound which does not contain a hydroxyl group.

(Polymerizable compound (C))
The photocurable resin composition according to the present invention may further contain any polymerizable compound (C) other than the hydroxyl group-containing acrylate (B). The photocurable resin composition according to the present invention may not contain any polymerizable compound (C) other than the hydroxyl group-containing acrylate (B).

Specific examples of the polymerizable compound (C) preferably used include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and t-butyl (meth) acrylate. (Meth) acrylic acid alkyl esters such as isobutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) ) Monofunctional (meth) acrylate compounds such as acrylate; butanediol di (meth) acrylate, hexanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) a Relate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, trimethylolpropane tri ( Tri) such as meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, glycerin tri (meth) acrylate, etc. (Meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylol group Pantri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, Examples include polyfunctional (meth) acrylate compounds such as dipentaerythritol hexa (meth) acrylate and ditrimethylolpropane hexa (meth) acrylate, or ethyleneoxy-modified products, propyleneoxy-modified products, and lactone-modified products. Only 1 type in these polymeric compounds (C) may be used independently, and multiple types may be mixed and used.

(Photopolymerization initiator (D))
It is preferable that the photocurable resin composition according to the present invention further includes a photopolymerization initiator (D). Specific examples of the photopolymerization initiator (D) preferably used include, for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, Benzoin ethyl ether, benzoin-n-propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin n-butyl ether, benzoin dimethyl ketal, thioxanthone, p-isopropyl-α-hydroxyisobutylphenone, 2,2-dimethoxy-2-phenylacetophenone 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-hydroxy 2-methyl-1-phenylpropan-1-one, 2,4,6, -trimethylbenzophenone, 4-methylbenzophenone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,2-dimethoxy Examples include -1,2-diphenylethanone, and preferably 1-hydroxycyclohexyl phenyl ketone and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide. Only one of these photopolymerization initiators (D) may be used alone, or a plurality of them may be mixed and used.

The preferred amount of use of the photopolymerization initiator (D) is preferably 0.3% by mass to 10% by mass with respect to the mass of the polyurethane acrylate (A), the hydroxyl group-containing acrylate (B) and the polymerizable compound (D). is there. By making the usage-amount of a photoinitiator (D) into the said range, while being able to obtain sufficient reaction rate and remaining amount of a photoinitiator can be decreased, a refinement | purification process is simplified. be able to.

(Other ingredients)
The photocurable resin composition of the present invention may further include a photosensitizer, an antioxidant, a yellowing inhibitor, an ultraviolet absorber, a visible light absorber, a colorant, a plasticizer, a stabilizer, and a filler as necessary. An additive such as an agent may be added as long as the effects of the present invention are not impaired.

Specific examples of the photosensitizer preferably used include, for example, triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, Examples thereof include isoamyl 4-dimethylaminobenzoate.

The photocurable resin composition of the present invention may contain a thermoplastic organic polymer. By containing the thermoplastic organic polymer, the properties of the cured product of the photocurable resin composition can be improved.

Specific examples of the thermoplastic organic polymer preferably used include, for example, polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, ( And (meth) acrylic acid-methyl methacrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester. Only one of these thermoplastic organic polymers may be used alone, or a plurality of types may be mixed and used.

(Compounding ratio of each component in the photocurable resin composition according to the present invention)
When the total amount of the polymer crosslinking agent (A), the hydroxyl group-containing acrylate (B) and the polymerizable compound (C) is 100 parts by mass, the photocurable resin composition according to the present invention has a polymer crosslinking agent (A ) Is preferably included in an amount of 60 parts by mass or more, and more preferably 65 parts by mass or more. By setting the content of the polymer crosslinking agent (A) in the above range, a pressure-sensitive adhesive composition having high heat resistance and high heat and humidity resistance can be obtained. However, when there is too much content of a polymer crosslinking agent (A), heat-and-moisture resistance may fall. Therefore, when the total amount of the polymer crosslinking agent (A), the hydroxyl group-containing acrylate (B) and the polymerizable compound (C) is 100 parts by mass, the photocurable resin composition according to the present invention is a polymer crosslinking agent. It is preferable to contain 90 parts by mass or less of (A), and preferably 85 parts by mass or less.

When the total amount of the polymer crosslinking agent (A), the hydroxyl group-containing acrylate (B) and the polymerizable compound (C) is 100 parts by mass, the photocurable resin composition according to the present invention has a hydroxyl group-containing acrylate (B). 15 parts by mass or more is preferable, and 20 parts by mass or more is preferable. However, when there is too much content of a hydroxyl-containing acrylate (B), heat resistance and moist heat resistance may fall. Accordingly, when the total amount of the polymer crosslinking agent (A), the hydroxyl group-containing acrylate (B) and the polymerizable compound (C) is 100 parts by mass, the photocurable resin composition according to the present invention has a hydroxyl group-containing acrylate ( B) is preferably contained in an amount of 40 parts by mass or less, more preferably 35 parts by mass or less.

When the total amount of the polymer crosslinking agent (A), the hydroxyl group-containing acrylate (B) and the polymerizable compound (C) is 100 parts by mass, the photocurable resin composition according to the present invention has a polymerizable compound (C). Is not necessarily essential, but if the content of the polymerizable compound (C) is too large, the heat resistance may decrease. Therefore, when the total amount of the polymer crosslinking agent (A), the hydroxyl group-containing acrylate (B), and the polymerizable compound (C) is 100 parts by mass, the photocurable resin composition according to the present invention has a polymerizable compound ( It is preferable to contain 15 parts by mass or less of C).

(Photocurable resin composition)
The photocurable resin composition according to the present invention is cured by irradiating energy rays such as ultraviolet rays. Specifically, the photocurable resin composition of the present invention is, for example, a known ultraviolet light irradiation device such as a xenon lamp, a xenon-mercury lamp, a metal halide lamp, a high pressure mercury lamp, a low pressure mercury lamp, or a UV-LED lamp. It can be cured by irradiating with predetermined ultraviolet rays.

Cumulative radiation of the ultraviolet irradiating upon curing the photocurable resin composition according to the present invention is preferably ^{0.05J / cm 2 ~ 10J / cm} 2, more preferably 0.1J ^/ cm 2 ~ 5J ^/ cm ² .

(Sticky / adhesive)
As described above, the photocurable resin composition according to the present invention is cured by irradiation with energy rays. For this reason, an adhesive agent can be comprised by using the photocurable resin composition which concerns on this invention. Moreover, when the photocurable resin composition before irradiating energy has viscosity, the said photocurable resin composition can comprise an adhesive material.

The adhesive / adhesive according to the present invention may contain other components in addition to the photocurable resin composition according to the present invention.

The adhesive / adhesive according to the present invention is applied onto, for example, a plastic substrate, a flexible print substrate, a glass substrate, and a substrate on which a thin film such as indium tin oxide (ITO) is formed. By doing, the base material which has an adhesive layer can be comprised.

Examples of the plastic substrate preferably used as the substrate include acrylic resin, PC (polycarbonate), PBT (polybutylene terephthalate), PPS (polyphenylene sulfide), modified PPE (polyphenylene ether), PET (polyethylene terephthalate), and COP ( Examples thereof include base materials composed of cycloolefin polymer), TAC (triacetate cellulose) and the like.

The base material may be an antireflection film, an antifouling film, a transparent conductive film constituting a touch panel, or the like.

Hereinafter, the present invention will be described in more detail on the basis of specific examples. However, the present invention is not limited to the following examples, and may be appropriately modified and implemented without departing from the scope of the present invention. Is possible.

(Synthesis Example 1: Synthesis of polyurethane acrylate (UA-1))
A reactor equipped with a stirrer and a heater was charged with polycarbonate diol (trade name: UM-90 (1/3), manufactured by Ube Industries, Ltd., hydroxyl value 123.7 mgKOH / g, polyol component 1,6-hexane. 79.2 g (0.0873 mol) of diol and cyclohexanedimethanol), 0.02 g of methoquinone, 0.04 g of dibutylhydroxytoluene (BHT), and 0.02 g of dibutyltin dilaurate as a catalyst were charged while introducing nitrogen. . Then, it stirred at 70 degreeC. Next, 15.5 g (0.0699 mol) of isophorone diisocyanate (IPDI) was added and stirred at 80 ° C. for 2 hours. Next, air was introduced to create an air atmosphere. Thereafter, 4.71 g (0.0338 mol) of 2-acryloylethyloxyisocyanate (trade name: Karenz AOI, manufactured by Showa Denko KK) was added and reacted for 2 hours to obtain polyurethane acrylate (UA-1). It was.

(Synthesis Example 2: Synthesis of polyurethane acrylate (UA-2))
To a reaction apparatus equipped with a stirrer and a heater, polycarbonate diol (trade name: UM-90 (1/1), manufactured by Ube Industries, Ltd., hydroxyl value 129.1 mgKOH / g, polyol component 1,6-hexane 52.1 g (0.0575 mol) of polycarbonate diol (diol and cyclohexanedimethanol), 29.2 g of polycarbonate diol (trade name: UH-200, manufactured by Ube Industries, Ltd., seafood base value 56.1 mgKOH / g) 0.0146 mol), 0.03 g of methoquinone, 0.04 g of dibutylhydroxytoluene (BHT), and 0.03 g of dibutyltin dilaurate as a catalyst were charged while introducing nitrogen. Then, it stirred at 70 degreeC. Next, 12.4 g (0.0558 mol) of isophorone diisocyanate (IPDI) was added and stirred at 80 ° C. for 2 hours. Next, air was introduced to create an air atmosphere. Thereafter, 4.63 g (0.0327 mol) of 2-acryloylethyloxyisocyanate (trade name: Karenz AOI, Showa Denko KK) was added and reacted for 2 hours to obtain polyurethane acrylate (UA-2). .

(Synthesis Example 3: Synthesis of polyurethane acrylate (UA-3))
A reactor equipped with a stirrer and a heater was charged with polycarbonate diol (trade name: UM-90 (1/3), manufactured by Ube Industries, Ltd., hydroxyl value 123.7 mgKOH / g, polyol component 1,6-hexane. Diol and cyclohexanedimethanol polycarbonate diol) 70.3 g (0.0775 mol), methoquinone 0.02 g, dibutylhydroxytoluene (BHT) 0.03 g, and dibutyltin dilaurate 0.02 g as a catalyst were charged while introducing nitrogen. . Then, it stirred at 70 degreeC. Next, 20.6 g (0.0928 mol) of isophorone diisocyanate (IPDI) was added and stirred at 80 ° C. for 2 hours. Next, air was introduced to create an air atmosphere. Thereafter, 3.70 g (0.0319 mol) of 2-hydroxyethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and reacted for 2 hours to obtain polyurethane acrylate (UA-3).

(Synthesis Example 4 (Synthesis of polyurethane acrylate (UA-4))
To a reaction apparatus equipped with a stirrer and a heater, polycarbonate diol (trade name: UM-90 (1/1), manufactured by Ube Industries, Ltd., hydroxyl value 129.1 mgKOH / g, polyol component 1,6-hexane 74.1 g (0.0818 mol) of polycarbonate diol (diol and cyclohexanedimethanol), 37.0 g (0.0367) of polycarbonate diol (trade name UH-100, manufactured by Ube Industries, Ltd., marine product base price 111.1 mgKOH / g) Mol), 0.03 g of methoquinone, 0.03 g of dibutylhydroxytoluene (BHT), and 0.04 g of dibutyltin dilaurate as a catalyst were charged while introducing nitrogen. Then, it stirred at 70 degreeC. Next, 21.2 g (0.00952 mol) of isophorone diisocyanate (IPDI) was added to the reaction product, and the mixture was stirred at 80 ° C. for 2 hours. Next, air was introduced to create an air atmosphere. Thereafter, 6.24 g (0.0442 mol) of 2-acryloylethyloxyisocyanate (trade name: Karenz AOI, manufactured by Showa Denko KK) was added to the reaction product and reacted for 2 hours to react with polyurethane acrylate (UA-4 )

(Synthesis Example 5 (Synthesis of polyurethane acrylate (UA-5))
A reactor equipped with a stirrer and a heater was charged with polycarbonate diol (trade name: UM-90 (1/3), manufactured by Ube Industries, Ltd., hydroxyl value 123.7 mgKOH / g, polyol component 1,6-hexane. 60.3 g (0.0665 mol) of diol and polycarbonate diol which is cyclohexanedimethanol, 6.24 g (0.0124) of polycarbonate diol (trade name UH-50, manufactured by Ube Industries, Ltd., seafood base value 222.6 mgKOH / g) Mol), 0.02 g of methoquinone, 0.03 g of dibutylhydroxytoluene (BHT), and 0.03 g of dibutyltin dilaurate as a catalyst were charged while introducing nitrogen. Then, it stirred at 70 degreeC. Next, 14.3 g (0.0644 mol) of isophorone diisocyanate (IPDI) was added to the reaction product, and the mixture was stirred at 80 ° C. for 2 hours. Next, air was introduced to create an air atmosphere. Thereafter, 3.89 g (0.0276 mol) of 2-acryloylethyloxyisocyanate (trade name: Karenz AOI, manufactured by Showa Denko KK) was added to the reaction product and reacted for 2 hours to react with polyurethane acrylate (UA-5). )

(Examples 1 to 5)
Table 1 shows the polymer crosslinking agent (A) of the type shown in Table 1, the hydroxyl group-containing acrylate (B), the polymerizable compound (C) other than the hydroxyl group-containing acrylate (B), the photopolymerization initiator (D), and other components. And weighed and mixed until uniform. Then, it filtered with the syringe filter with a pore of 1.0 micrometer, and obtained the photocurable resin composition.

(Comparative Examples 1 to 5)
Table 2 shows the types and amounts of the polyurethane acrylate (A), the hydroxyl group-containing acrylate (B), the polymerizable compound (C) other than the hydroxyl group-containing acrylate (B), the photopolymerization initiator (D), and other components. A photocurable resin composition was prepared in the same manner as in Example 1 except that the above was changed. Comparative Example 5 was prepared according to the method described in Japanese Patent No. 4530913.

[Method for preparing samples for heat resistance test and wet heat resistance test]
A silicon sheet having a thickness of 0.3 mm was placed on the edge of the glass substrate to form a spacer. The photocurable resin composition obtained in each example and each comparative example was placed on this glass substrate, and the glass substrate was further placed thereon, and the photocurable resin composition layer was sandwiched between the two glass substrates. A laminated body was produced. This laminated body was irradiated with UV using a UV irradiation apparatus (UB-15201BY-A, manufactured by USHIO Electric Co., Ltd., light source UVL-1500M2-N1) so that the calculated light amount was 5 J / cm ^2. Samples for each comparative example were prepared.

[Moisture and heat resistance test]
The haze (%) of each sample prepared as described above was measured according to K 7361-1: 1997 using a turbidimeter (NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.). Thereafter, it was left for 500 hours in an atmosphere of 85 ° C. and humidity of 85%, and the haze (%) was again measured in the same manner and evaluated by the amount of change in haze.

As a result, when the haze change amount is 0.1% or less, “excellent”, and when the haze change amount is greater than 0.1% and less than 0.2%, “good”, the haze change amount. Was evaluated as “bad”. The results are shown in Tables 1 and 2.

[Heat resistance test]
The yellowing degree (b *) of each sample prepared above was measured in accordance with JISK7105-1981 using a light source C and a viewing angle of 2 ° with a variable angle spectroscopic colorimeter “Color Robo” (manufactured by Color Techno System). did. Moreover, after leaving each sample to stand in 100 degreeC atmosphere for 500 hours, yellowing degree (b *) was measured similarly, and the variation | change_quantity ((DELTA) b *) of b * was calculated | required using the following formula.

Δb * = b * (before test) −b * (after test)
As a result, the case where Δb * is less than 0.2 is “excellent”, the case where Δb * is 0.2 or more and less than 0.5 is “good”, and the case where Δb * is 0.5 or more is “bad”. ". The results are shown in Tables 1 and 2.

 
 

 
 

 
　なお、上記表１及び表２中の略号は、以下の通りである。

The abbreviations in Table 1 and Table 2 are as follows.

UV-3000B: Polyester polyurethane acrylate (manufactured by Nippon Synthetic Chemical Co., Ltd.)
UC-203: esterified product of polyisoprene polymer non-maleic anhydride and 2-hydroxyethyl methacrylate (manufactured by Kuraray Co., Ltd.)
4-HBA: 4-hydroxybutyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
2-HBMA: 2-hydroxybutyl methacrylate (trade name: light ester HOB (N)), manufactured by Kyoeisha Chemical Co., Ltd.
LA: Lauryl acrylate (Aldrich)
FA-512M: Dicyclopentenyloxyethyl methacrylate (trade name: FA-512M, manufactured by Hitachi Chemical Co., Ltd.)
IBXA: Isobornyl acrylate (trade name: IBXA, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
Clearon P-85: Terpene-based hydrogenated resin (manufactured by Yasuhara Chemical Co., Ltd.)
Polybest P110: Liquid polybutadiene polymer (Evonik)
IRGACURE 184: photopolymerization initiator, 1-hydroxy-cyclohexyl phenyl ketone, manufactured by BASF Lucirin TPO: photopolymerization initiator, diphenyl (2,4,6-trimethoxybenzoyl) phosphine oxide, manufactured by BASF)

Claims (2)

A polymer crosslinking agent (A);
A hydroxyl group-containing acrylate (B);
Including
It may further contain a polymerizable compound (C) as an optional component,
The polymer crosslinking agent (A) includes a repeating unit represented by the following formula (1a), a repeating unit represented by the formula (1b), and a repeating unit represented by the formula (2): It is a polyurethane acrylate having a meth) acrylic group at the end,
When the total amount of the polymer crosslinking agent (A), the hydroxyl group-containing acrylate (B) and the polymerizable compound (C) is 100 parts by mass, the polymer crosslinking agent (A) is contained in an amount of 60 parts by mass or more, and the hydroxyl group-containing acrylate ( A photocurable resin composition comprising 15 to 40 parts by mass of B).

(In the formula (1a), Za represents ^a divalent cycloaliphatic hydrocarbon group having 6 to 18 carbon atoms,
One carbon atom contained in Z ^a is may be substituted by a sulfur atom,
In the formula (1b), Z ^b represents a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms or a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms. Show
One carbon atom contained in ^Zb may be substituted with a sulfur atom. N in the formula (1a) and n in the formula (1b) may be the same or different and each represents a natural number of 1 to 40. In the formula (2), R represents a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a carbon atom It represents a divalent cyclic aliphatic hydrocarbon group having 6 to 18 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. ) A sticky / adhesive comprising the photocurable resin composition according to claim 1.