TW201708485A - Composition - Google Patents

Abstract

Provided is a composition that maintains adhesiveness at the surface thereof even after curing. The composition comprises (P) and (C) to (E). (P) is a polymerizable vinyl compound; (C) is a photopolymerization initiator; (D) is a dicarboxylic acid diester; and (E) is a tackifier. Also provided is an adhesive composition comprising the composition. The composition may further comprise (F), a thiol, and (G), an antioxidant. The polymerizable vinyl compound (P) preferably comprises: (A), a polyfunctional (meth)acrylate; and (B), a monofunctional (meth)acrylate.

Description

Composition

The present invention is directed to a composition.

Among the touch panels mounted on a display body such as an LCD (Liquid Crystal Display), there are a resistive film type, a capacitive type, an electromagnetic induction type, an optical type, and the like. A decorative panel that makes the design better or a graphic table that specifies the touch position is sometimes attached to the surface of the touch panel. The capacitive touch panel has a structure in which a transparent electrode is formed on a transparent substrate and a transparent plate is bonded thereon.

Conventionally, an adhesive is used in the bonding of a decorative panel and a touch panel, the bonding of a pictorial panel and a touch panel, and the bonding of a transparent substrate and a transparent panel.

In particular, when a photocurable adhesive composition is bonded between the members, a representative method is to irradiate the front side of the display after the adhesive is adhered to the two adhesives. Visible light or ultraviolet light, which hardens the adhesive, in this way followed by two methods of adhering the body.

Patent Document 1 describes (A) a (meth) acrylate oligomer having a polyisoprene, a polybutadiene or a polyurethane in a skeleton, (B) a softening component, and (C1) Selected from phenoxyethyl (meth)acrylate, phenoxy polyethylene glycol (meth) acrylate, (meth) acrylate 2-hydroxy-3-phenoxypropyl acrylate, cyclohexyl (meth) acrylate, phenol EO adduct (meth) acrylate, methoxy triethylene glycol (meth) acrylate, and (methyl A photocurable resin composition of a (meth) acrylate monomer of tetrahydrofuran methyl acrylate. However, the composition of the present invention is not particularly described in Patent Document 1 regarding the composition containing the (D) dicarboxylic acid diester.

In recent years, the glass of a display body such as an LCD has been thinned. When the glass is thinned, it becomes easy to deform the LCD with external stress. When a display body such as an LCD using a thin glass is bonded to an optical functional material such as an acrylic plate or a polycarbonate plate, a plastic molding material such as an acrylic plate or a polycarbonate is used because of a difference in linear expansion between glass and acrylic. The strain at the time of molding causes relaxation or moisture absorption/drying of the molding strain in the heat resistance test or the moisture resistance test, and causes dimensional change such as dimensional change or warpage.

Patent Document 2 describes a cured resin containing urethane-based (meth) acrylate, polybutadiene-based (meth) acrylate, and isoprene-based (meth) acrylate as components. However, in the method of Patent Document 2, when the deformation is to be suppressed, there is a problem that the surface is peeled off, the LCD is broken, and the LCD becomes uneven.

The UV-curable resin of Patent Document 3 is described as a solution to the problem of Patent Document 2. Patent Document 3, because it is a highly elastic resin based on a rigid skeleton monomer such as isodecyl (meth)acrylate, it cannot withstand the expansion and contraction of the adherend in the high-temperature reliability test, and there is a possibility of peeling. Sex. The present invention has a design that withstands the expansion and contraction of the adherend in the high-temperature reliability test even if a rigid skeleton monomer such as isodecyl (meth)acrylate is not used.

In the use of a decorative panel and a touch panel, a combination of a pictogram panel and a touch panel, and a bonding between a transparent substrate and a transparent panel, it is desirable to have an adherent body that can follow a heating environment in a hypothetical use environment. The degree of flexibility of the deformation.

On the other hand, since it has flexibility to follow the degree of deformation of the adherend in a heating environment under the assumed use environment, there is a problem that the color after the heat resistance test, the discoloration, and the strength after the moisture resistance test are lowered. As a solution to the above problem, Patent Document 4 describes that the content contains a polyisoprene (meth) acrylate oligomer, a polybutadiene (meth) acrylate oligomer, and a polyurethane urethane. One or more oligomers of the group of the ester (meth) acrylate oligomers and the photocurable type of the hindered amine. However, the composition of the present invention is not particularly described in Patent Document 4 regarding the composition containing the (D) dicarboxylic acid diester.

Patent Document 5 describes a photocurable composition characterized by comprising a specific sulfur-containing (meth) acrylate compound or a radical-reactive composition containing the same, an ultraviolet absorber, a photopolymerization initiator, and Antioxidants. However, the composition of the present invention is not particularly described in Patent Document 4 regarding the composition containing the (D) dicarboxylic acid diester.

Patent Document 6 describes a photocurable transparent adhesive composition comprising two or more ethyl urethane (meth) acrylates (A) having a functional group containing an unsaturated double bond, and having an unsaturated group. A monomer (B) having a functional group of a double bond, a photopolymerization initiator (C), and a composition of two or more polythiol compounds (D) having a thiol group, the composition The weight ratio of the ethyl urethane (meth) acrylate (A) is from 2% by weight to 30% by weight. However, the composition of the present invention is not particularly described in Patent Document 6 regarding the composition containing the (D) dicarboxylic acid diester.

As a method of maintaining the adhesion of the surface after the curing of the adhesive composition, there is a method of adding an adhesion-imparting agent. Patent Document 7 describes a hydrogenated rosin resin adhesion-imparting agent, an aliphatic fully saturated hydrocarbon resin adhesion-imparting agent, or an acrylic-based pressure-sensitive adhesive containing a hydrogenated terpene resin adhesion-imparting agent as an adhesion-imparting agent. However, the composition of the present invention is not particularly described in Patent Document 7 with respect to the composition containing the (D) dicarboxylic acid diester.

Prior technical literature Patent literature

Patent Document 1 International Publication No. 2010/027041

Patent Document 2 Japanese Patent Laid-Open Publication No. 2004-77887

Patent Document 3 Japanese Patent Laid-Open No. 64-85209

Patent Document 4 Japanese Patent Laid-Open Publication No. 2012-46658

Patent Document 5 Japanese Patent Laid-Open Publication No. 2002-097224

Patent Document 6 Japanese Patent Laid-Open Publication No. 2009-001655

Patent Document 7 Japanese Patent Laid-Open Publication No. 2006-225531

The present invention provides a curable resin composition, for example, when a decorative sheet or a graphic sheet for use in a display body such as a touch panel is bonded, and when a transparent substrate and a transparent substrate are bonded, a display body and an optical machine are bonded together. In the case of a material, there is a problem in the prior art that the surface is peeled off, the glass of the display body is broken, the heat resistance, the discoloration after the moisture resistance test, and the strength are lowered.

That is, the present invention is a composition containing the following (P), (C) to (E); (P) a polymerizable vinyl compound; (C) a photopolymerization initiator; (D) a dicarboxylic acid diester (E) Adhesive-imparting agent.

Such a composition, wherein (D) is a dicarboxylic acid diester represented by the formula (1).

(wherein R ₁ and R ₂ are an alkyl group having 1 to 18 carbon atoms; R ₃ is an alkylene group having 1 to 10 carbon atoms; and R ₁ and R ₂ may be the same or different.) Wherein (D) is a sebacic acid diester; and the composition further comprises (F) a mercaptan; as in the composition, the (F) mercaptan is a polythiol; and the composition is further Containing (G) an antioxidant; such as the composition, wherein the (P) polymerizable vinyl compound contains (A) a polyfunctional (meth) acrylate and (B) a monofunctional (meth) acrylate; And (A) the polyfunctional (meth) acrylate is ethyl urethane (meth) acrylate; and the composition, wherein (B) the monofunctional (meth) acrylate is selected from the group consisting of phenolic One or more groups of alkylene oxide-modified (meth) acrylate, alkyl (meth) acrylate, and hydroxyalkyl (meth) acrylate; if the composition, (D) is used, 5 to 50 parts by mass in 100 parts by mass of the total of (P) and (D); wherein the (E) adhesion-imparting agent comprises a fully hydrogenated rosin resin, an aromatic modified terpene resin, and ruthenium One or more of the group of enephenol-based resins; A curable resin composition comprising the composition; an adhesive composition comprising the composition; a cured product which is a cured product of an adhesive composition; and a composite which is utilized The cured product is coated or bonded to the adherend; such as the composite, wherein the adhesion system is selected from the group consisting of triacetyl cellulose, fluorine polymer, polyester, polycarbonate, polyolefin, glass, and metal. One or more types; a touch panel laminate, wherein the adhesive composition is adhered by the adhesive composition; a liquid crystal panel laminate using the adhesive composition to adhere the adhesive; and a display using the same a touch panel laminate; a display using the liquid crystal panel laminate; such as the adhesive composition, the (P) polymerizable vinyl compound contains (A) a polyfunctional (meth) acrylate and (B) Monofunctional (meth) acrylate, (A) polyfunctional (meth) acrylate is ethyl urethane (meth) acrylate, (B) monofunctional (meth) acrylate is selected from phenolic ring Oxyalkane modified (meth) acrylate, (meth) propyl One or more groups of the acid alkyl ester and the hydroxyalkyl (meth) acrylate, and the amount of the (A) polyfunctional (meth) acrylate used in total of (A), (B), and (D) 10 to 90 parts by mass in 100 parts by mass, and the amount of (B) monofunctional (meth) acrylate used is 3 to 80 parts by mass in 100 parts by mass of the total of (A), (B) and (D). (D) The amount of the dicarboxylic acid diester used is 1 to 50 parts by mass based on 100 parts by mass of the total of (P) and (D), and (E) the adhesion-imparting agent contains a completely hydrogenated rosin resin and an aromatic modification. The amount of the (E) adhesion-imparting agent used is 1 to 40 parts by mass based on 100 parts by mass of the total of (P) and (D). Further, it is further contained in an amount of 0.1 to 10 parts by mass of the (F) polythiol, and further contains (G) an antioxidant, in an amount of 100 parts by mass based on the total of (P) and (D).

The present invention can provide a composition which, for example, retains adhesion to the surface after hardening.

Form of implementing the invention

As the (P) polymerizable vinyl compound, a (meth) acrylate is preferable, and (A) a polyfunctional (meth) acrylate and (B) a monofunctional (meth) acrylate are more preferable. (A) A polyfunctional (meth)acrylate means a (meth)acrylate which has two or more (meth) propylene groups. Examples of the polyfunctional (meth) acrylate include oligomers having two or more polyfunctional (meth) acrylates which have been (meth) acrylated at the oligomer/polymer terminal or side chain. /polymer, etc.

Examples of the polyfunctional (meth) acrylate oligomer/polymer include 1,2-polybutadiene terminal urethane (meth) acrylate and 1,2-hydrogenated polybutadiene terminal. Ethyl urethane (meth) acrylate (for example, "TEAI-1000" manufactured by Nippon Soda Co., Ltd.), 1,4-polybutadiene urethane (meth) acrylate, polyisoprene terminal (Meth) acrylate, polyester urethane (meth) acrylate, polyether urethane (meth) acrylate, bisphenol A epoxy (meth) acrylate, and the like. Polybutadiene terminal (methyl) urethane acrylate or hydrogenation Polybutadiene terminal urethane (meth) acrylate having a molecular structure at the end of the (meth) acrylate. Among these, ethyl urethane (meth) acrylate is preferable from the viewpoint of a large effect. The ethyl urethane (meth) acrylate comprises polybutadiene urethane (meth) acrylate, hydrogenated polybutadiene urethane (meth) acrylate, polyester amine One or more selected from the group consisting of ethyl formate (meth) acrylate and polyether urethane (meth) acrylate, and hydrogenated polybutadiene urethane (meth) acrylate One or more of the group of ester and polyester urethane (meth) acrylate is more preferable. Among the hydrogenated polybutadiene urethane (meth) acrylates, 1,2-hydrogenated polybutadiene terminal urethane (meth) acrylate is preferred.

Here, the urethane (meth) acrylate means, for example, by making a polyol compound (hereinafter referred to as X) with an organic polyisocyanate compound (hereinafter referred to as Y) and hydroxy (meth) acrylate ( Ethyl urethane (meth) acrylate having an urethane linkage in the molecule obtained by a reaction (for example, a polycondensation reaction) is obtained by Z (hereinafter).

Examples of the polyol compound (X) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, and 1,4. -butanediol, polytetramethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5 - pentanediol, 2,4-diethyl-1,5-pentanediol, 2,2-butylethyl-1,3-propanediol, neopentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone, trimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, glycerol, polyglycerol, polytetra a polyol such as methylene glycol or a polyepoxy a block of ethane, polypropylene oxide, ethylene oxide/propylene oxide, or a polyether polyol having at least one structure of a random copolymerization, a caprolactone-modified polytetramethylene polyol, or the like. Caprolactone modified polyol, polyolefin polyol, polycarbonate polyol, polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol, hydrogenated polyisoprene A polydiene polyol such as a polyhydric alcohol or an fluorenone polyol such as a polydimethyl siloxane polyol. The polyhydric alcohol or a condensate of the polyhydric acid of the polyhydric alcohol with maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid or the like may also be mentioned. Ester polyols and the like.

Among these, the polyol compound (X) is selected from one or more selected from the group consisting of polybutadiene polyols, hydrogenated polybutadiene polyols, polyether polyols, and polyester polyols. Preferably, it is more preferably one or more selected from the group consisting of hydrogenated polybutadiene polyols and polyester polyols. Among the hydrogenated polybutadiene polyols, the compound of the formula (2) (n is a positive number) is preferred.

(where n is a positive number.)

Here, the polybutadiene-based urethane (meth) acrylate, for example, the polyol compound (X) is a polybutadiene polyol. Polyester The urethane (meth) acrylate, for example, the polyol compound (X) is a polyester polyol. The polyether urethane (meth) acrylate, for example, the polyol compound (X) is a polyether polyol.

The organic polyisocyanate compound (Y) is not particularly limited, and examples thereof include polyisocyanates such as aromatic, aliphatic, cyclic aliphatic, and alicyclic. Among them, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H-MDI), polyphenylmethane polyisocyanate (crude MDI), modified diphenylmethane diisocyanate can be suitably used. (Modified MDI), hydrogenated dimethyl diisocyanate (H-XDI), benzodimethyl diisocyanate (XDI), hexamethylene diisocyanate (HMDI), trimethylhexamethylene diisocyanate (TMXDI) ), tetramethyl dimethyl diisocyanate (m-TMXDI), isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), 1,3-bis(isocyanatomethyl)cyclohexane A polyisocyanate such as an alkane (H6XDI), a trimer compound of the polyisocyanate, a reaction product of the polyisocyanate and a polyhydric alcohol, and the like. Among these, hydrogenated dimethyl diisocyanate (H-XDI) and/or isophorone diisocyanate (IPDI) are preferred.

Examples of the hydroxy (meth)acrylate (Z) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and the like. Hydroxyalkyl (meth) acrylate, 2-hydroxyethyl (meth) propylene decyl phosphate, 4-hydroxybutyl (meth) acrylate, 2-(methyl) propylene oxirane ethyl-2- Hydroxypropyl phthalate, glycerol di(meth) acrylate, 2-hydroxy-3-(methyl) propylene oxypropyl acrylate, caprolactone modified 2-hydroxy (meth) acrylate Ethyl ester, pentaerythritol tri(meth) acrylate, two Pentaerythritol penta (meth) acrylate, caprolactone modified 2-hydroxyethyl (meth) acrylate, and the like. Among these, a hydroxyalkyl (meth) acrylate is preferred.

Among the hydroxyalkyl (meth)acrylates, the hydroxyalkyl (meth)acrylate represented by the formula (3) is preferred.

Formula (3) ZO-(R ₄ -O-) _p -H

(wherein Z represents a (meth)acrylinyl group, R ₄ represents an alkylene group, and p represents an integer of 1 to 10.)

The carbon number of the alkyl group of R ₄ of the formula (3) is preferably from 1 to 8, more preferably from 2 to 6.

The hydroxyalkyl (meth) acrylate is selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. One or more of them are preferred. The method of producing a urethane (meth) acrylate is described in, for example, Japanese Laid-Open Patent Publication No. Hei. 7-25957, JP-A-2002-173515, JP-A-7-292048, and JP-A-2000-351819. Bulletin, etc.

The weight average molecular weight of the polyfunctional (meth) acrylate is preferably from 1,000 to 60,000, more preferably from 1,500 to 40,000. The weight average molecular weight was determined by using a GPC system (SC-8010 manufactured by Tosoh Co., Ltd.) or the like under the following conditions, using a commercially available standard polystyrene as a calibration curve.

Flow rate: 1.0ml/min

Set temperature: 40 ° C

Pipe column structure: "TSK guardcolumn MP (×L)" manufactured by Tosoh Co., Ltd. 6.0 mmID × 4.0 cml, and "TSK-GELMULTIPOREHXL-M" manufactured by Tosoh Co., Ltd. 7.8 mmID × 30.0 cm (16,000 layers of theoretical layers) 3 (all, theoretical layer 32,000 layers)

Sample injection amount: 100 μl (sample solution concentration 1 mg/ml)

Liquid supply pressure: 39kg/cm ²

Detector: RI detector

(P) When the polymerizable vinyl compound contains (A) a polyfunctional (meth) acrylate and (B) a monofunctional (meth) acrylate, the amount of the (A) polyfunctional (meth) acrylate is used. The total amount of (A), (B), and (D) is preferably 10 to 90 parts by mass, more preferably 30 to 90 parts by mass, more preferably 40 to 85 parts by mass, and further preferably 30 to 80 parts by mass. More preferably, 40 to 75 parts by mass is the best. When it is 10 parts by mass or more, the adhesiveness does not decrease, and when it is 90 parts by mass or less, good curability is obtained.

(B) Monofunctional (meth) acrylate means a (meth) acrylate having one (meth) acrylonitrile group. (B) Among the monofunctional (meth) acrylates, one of the group consisting of a phenolic alkylene oxide-modified (meth) acrylate, an alkyl (meth) acrylate, and a hydroxyalkyl (meth) acrylate More preferably the above.

Among the phenolic alkylene oxide-modified (meth) acrylates, the phenol-based alkylene oxide-modified (meth) acrylate represented by the formula (4) is preferred.

(wherein R ¹ is hydrogen or an alkyl group having 1 to 16 carbon atoms. R ² is an alkylene group. R ³ is hydrogen or a methyl group. m is 1 to 6.)

R ¹ is preferably an alkyl group. The carbon number of the alkyl group is preferably from 5 to 13, more preferably 9. R ² is preferably an extended ethyl group. m is preferably 4. Examples of the indophenol alkylene oxide-modified (meth)acrylate in which R ¹ is an alkyl group having 9 carbon atoms include indophenol ethylene oxide-modified (meth)acrylate and indophenol (ethylene oxide). 4 Moer modified) (meth) acrylate, indophenol (ethylene oxide 8 molar modified) (meth) acrylate, indophenol (propylene oxide 2.5 mole modified) (meth) acrylic acid Ester and the like.

Among the alkyl (meth)acrylates, an alkyl (meth)acrylate having an alkyl group having 2 to 16 carbon atoms is preferred. The alkyl group is preferably a saturated aliphatic hydrocarbon group. The alkyl group is preferably unsubstituted.

Examples of the (meth)acrylic acid alkyl ester having an alkyl group having 2 to 16 carbon atoms include ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and (methyl). 2-ethylhexyl acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate , (stearyl methacrylate), isostearyl (meth) acrylate, and the like. Among these, octyl (meth)acrylate is preferred from the viewpoint of adhesion or moisture resistance, and n-octyl (meth)acrylate is more preferable.

Among the hydroxyalkyl (meth)acrylates, the hydroxyalkyl (meth)acrylate represented by the above formula (3) is preferred.

Formula (3) ZO-(R ₄ -O-) _p -H

(Z represents a (meth) acrylonitrile group, R ₄ represents an alkylene group, and p represents an integer of 1 to 10.)

The carbon number of the alkyl group of R ₄ of the formula (3) is preferably from 1 to 8, more preferably from 2 to 6.

Examples of the hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and (methyl). 4-hydroxybutyl acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol (meth) acrylate, and the like. Among these, 4-hydroxybutyl (meth)acrylate is preferred from the viewpoint of adhesion or moisture resistance.

(P) When the polymerizable vinyl compound contains (A) a polyfunctional (meth) acrylate and (B) a monofunctional (meth) acrylate, the amount of the (B) monofunctional (meth) acrylate is used. The total amount of (A), (B), and (D) is preferably 3 to 80 parts by mass, more preferably 5 to 80 parts by mass, more preferably 15 to 65 parts by mass, and most preferably 20 to 60 parts by mass. . When the amount is 3 parts by mass or more, good curability is obtained, and when it is 80 parts by mass or less, the adhesion does not decrease.

(C) A photopolymerization initiator which is used for sensitization using active light rays of visible light or ultraviolet rays and promoting photohardening of a resin composition. Examples of the photopolymerization initiator include benzophenone and its derivatives, benzhydryl and its derivatives, hydrazine and its derivatives, benzoin, benzoin methyl ether, and benzoin ethyl ether. a benzoin derivative such as benzoin propyl ether, benzoin isobutyl ether or benzyl dimethyl ketal, diethoxyacetophenone, 4-tert-butyltrichloroacetophenone or the like Acetophenone derivative, 2-dimethylaminoethyl benzoate, p-dimethylaminoethyl benzoate, diphenyl disulfide, 9-oxosulfur And its derivatives, camphorquinone, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxylic acid, 7,7-dimethyl-2,3-di Oxobicyclo[2.2.1]heptane-1-carboxy-2-bromoethyl ester, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxy-2 - cerebral quinone derivative such as methyl ester, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxyindole chloride, 2-methyl-1-[4- (methylthio)phenyl]-2-N- Orolinyl propan-1-one, 2-benzyl-2-yldimethylamino-1-(4-N- An a-aminoalkyl ketone derivative such as phenylphenyl)-butanone-1, benzamidine diphenylphosphine oxide, 2,4,6-trimethylbenzhydryldiphenylphosphine oxide, Benzopyridyldiethoxyphosphine oxide, 2,4,6-trimethylbenzimidyldimethoxyphenylphosphine oxide, 2,4,6-trimethylbenzhydryldiethoxy A fluorenylphosphine derivative such as phenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide or the like, oxy-phenyl-acetic acid 2-[2-oxo- 2-phenyl-ethoxycarbonyl-ethoxy]-ethyl ester and oxo-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester, 1-hydroxy-cyclohexyl-phenyl- Ketones, etc. The photopolymerization initiator may be used alone or in combination of two or more. Among these, one or more selected from the group consisting of a benzoin derivative, a 1-hydroxy-cyclohexyl-phenyl-ketone, and a decylphosphine oxide derivative are preferred from the viewpoint of the effect. Among the benzoin derivatives, benzyldimethylketal is preferred. The fluorenylphosphine oxide derivative comprises 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide One or more of the groups are preferred.

(C) The amount of the photopolymerization initiator to be used is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 1 part by mass, per 100 parts by mass of the total of (A), (B) and (D). When the amount is 0.01 parts by mass or more, good curability is obtained, and when it is 10 parts by mass or less, good deep hardenability can be obtained.

As the (D) dicarboxylic acid diester, an aliphatic dibasic acid diester is preferred. As the aliphatic dibasic acid diester, a compound represented by the formula (1) is preferred.

(wherein, R ₁ , R ₂ , and R _{3 are} as defined above.)

R ₁ and R ₂ of the compound represented by the formula (1) are preferably a saturated aliphatic hydrocarbon group. Further, it is preferred that R ₁ and R _{2 are} unsubstituted. The above R ₁ and R ₂ are preferably an alkyl group having 2 to 12 carbon atoms, more preferably an alkyl group having 4 to 10 carbon atoms, and most preferably an alkyl group having 8 carbon atoms. R ₃ of the compound represented by the formula (1) is preferably a saturated aliphatic hydrocarbon group. Further, it is preferable that the above R _{3 is} unsubstituted. The above R ₃ is preferably an alkylene group having 4 to 10 carbon atoms, more preferably an alkylene group having 7 to 8 carbon atoms, and the most preferred alkyl group having 8 carbon atoms.

(D) The dicarboxylic acid diester is, for example, a compound used to adjust the viscosity in order to improve the deep hardenability.

Examples of the dicarboxylic acid diester represented by the formula (1) (1) include dimethyl oxalate, diethyl oxalate, dipropyl oxalate, diisopropyl oxalate, dibutyl oxalate, and dihexyl oxalate. , dioctyl oxalate, diisopropyl malonate, dibutyl malonate, diethyl succinate, dipropyl succinate, diisopropyl succinate, dibutyl succinate, succinic acid Tributyl ester, bis(2-ethylhexyl) succinate, bis(2-ethoxyethyl) succinate, diethyl glutarate, dibutyl glutarate, dimethyl adipate, Diethyl adipate, dipropyl adipate, diisopropyl adipate, butyl adipate, di-tert-butyl adipate, bis(2-ethylhexyl) adipate, Dioctyl adipate, g Dimethyl dicarboxylate, diethyl pimelate, diisopropyl pimelate, dibutyl pimelate, dimethyl suberate, diethyl suberate, dipropyl suberate, xin Diisopropyl diacrylate, dimethyl sebacate, diethyl sebacate, dipropyl sebacate, diisopropyl sebacate, dibutyl sebacate, dimethyl sebacate, Diethyl sebacate, dipropyl sebacate, dipropyl sebacate, diisopropyl sebacate, dibutyl sebacate, bis(2-ethylhexyl) sebacate, and the like. These dicarboxylic acid diesters may be used alone or in combination of two or more. Among the dicarboxylic acid diesters (D), sebacic acid diesters are preferred. Among the sebacic acid diesters, bis(2-ethylhexyl) sebacate is preferred.

(D) The amount of the dicarboxylic acid diester used is preferably 1 to 50 parts by mass, more preferably 5 to 45 parts by mass, and most preferably 8 to 20 parts by mass, based on 100 parts by mass of the total of (P) and (D). . When the amount is 1 part by mass or more, a good viscosity can be obtained, and if it is 50 parts by mass or less, good deep-curing property can be obtained.

(E) The adhesion-imparting agent is, for example, a compound generally referred to as a tackifier or an adhesive-imparting resin, and is a compound used to maintain adhesion to the surface of the cured product after hardening. Among the adhesion-imparting agents, an adhesion-imparting agent which is less likely to be deteriorated by ultraviolet rays and has high weather resistance is preferable. Examples of the adhesion-imparting agent include hydrogenated rosin resin (fully hydrogenated rosin resin), aliphatic fully saturated hydrocarbon resin, hydrogenated terpene resin (completely hydrogenated terpene resin), aromatic modified hydrogenated terpene resin, and aromatic modification. Terpene resin, styrene resin, terpene phenol resin, hydrogenated terpene phenol resin, and the like. Among these, one or more selected from the group consisting of a fully hydrogenated rosin resin, an aromatic modified terpene resin, and a terpene phenol resin are preferable.

(E) The amount of the adhesion-imparting agent to be used is preferably 1 to 40 parts by mass, more preferably 3 to 30 parts by mass, based on 100 parts by mass of the total of (P) and (D). 5 to 25 parts by mass is best, and 10 to 20 parts by mass will be even better. When the amount is 1 part by mass or more, a good adhesion can be obtained on the surface after hardening, and when it is 40 parts by mass or less, good transparency can be obtained.

As the composition of the present invention, (F) a mercaptan can be used. (F) Thiol refers to a compound having one or more thiol groups. Among the mercaptans, polythiol is preferred from the viewpoint of deep hardenability. (F) Polythiol means a compound having two or more thiol groups. Examples of the polythiol include trimethylolpropane thiopropionate, pentaerythritol thiopropionate, dipentaerythritol (3-thiol propionate), and ginseng [(3-thiolpropionate). Oxy)-ethyl]isocyanate, 2-ethylhexyl-3-thiol propionate, 3-thiol butyrate derivative, and the like. These polythiols may be used alone or in combination of two or more.

(F) The polythiol is preferably one or more selected from the group consisting of a 3-thiol butyrate derivative and a thiol propionate derivative. For example, 1,4-bis(3-thiolbutoxy)butane, 1,3,5-gin(3-thiolbutoxyethyl)-1,3,5-three -2,4,6-(1H,3H,5H)-trione, pentaerythritol bismuth (3-thiol butyrate), pentaerythritol bismuth (3-thiol butyrate), trimethylolpropane ginseng (3 - thiol propionate), 2-ethylhexyl-3-thiol propionate, and the like. Among the (F) polythiols, the polythiol of the first or second stage is preferred.

(F) The amount of the polythiol used is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the total of (P) and (D). When the amount is 0.1 part by mass or more, good deep-lubricity is obtained, and when it is 10 parts by mass or less, coloring or discoloration due to heat of the curable resin composition is small.

In order to enhance the storage stability of the composition of the present invention, (G) an antioxidant can be used. Examples of the antioxidant include methylhydroquinone, hydroquinone, 2,2-methylene-bis(4-methyl-6-tert-butylphenol), and 6-t-butyl-4-[3- [(2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphospholene-6-yl)oxy]propyl ]-2-methylphenol (6-tert-butyl-4-[3-[(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl Oxy]propyl]-2-methylpheno 1), catechol, hydroquinone monomethyl ether, mono-tert-butylhydroquinone, 2,5-di-t-butylhydroquinone, p-benzoquinone, 2,5 -diphenyl-p-benzoquinone, 2,5-di-t-butyl-p-benzoquinone, picric acid, citric acid, phenolic thiophene , tert-butylcatechol, 2-butyl-4-hydroxyanisole, and 2,6-di-t-butyl-p-cresol. Among these, 6-t-butyl-4-[3-[(2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxo Heterophosphazene-6-yl)oxy]propyl]-2-cresol is preferred.

(G) The amount of the antioxidant to be used is preferably 0.001 to 0.5 parts by mass, more preferably 0.005 to 0.1 parts by mass, per 100 parts by mass of the total of (P) and (D). When the amount of the curable resin composition is less than 0.001 parts by mass, the coloring or discoloration is small, and when it is 0.5 parts by mass or less, good deep-curing property can be obtained.

The composition of the present invention can also be used in various elastomers such as acrylic rubber, urethane rubber, acrylonitrile-butadiene-styrene rubber, and the like, which are generally used, without departing from the object of the present invention. Additives such as solvents, extenders, reinforcing materials, plasticizers, tackifiers, dyes, pigments, flame retardants, decane coupling agents, and surfactants.

The cured product which is followed by the composition of the present invention can be reworked (recycled) after being completely cured. As a method of reprocessing, there is no In particular, it is possible to disassemble the adherends by using a load of 0.01 to 100 N between the adhered one or two types of adherends, and to reuse the disassembled adherends.

The composition of the present invention is, for example, a curable resin composition, and can be used as an adhesive composition. The composition of the present invention is a composition in which a cured material having a curing rate of 90% or more and a sufficient adhesion/adhesion property can be maintained by bonding to various adherends. The composition of the present invention is, for example, by irradiating visible light rays or ultraviolet rays on an adhesive composition applied to a one-side adhesive body, and then adhering to the other side of the adhesive body, even if visible light or ultraviolet light is not transmitted. An adhesive composition that is still hardenable and that can be bonded to the adherend.

The adhesive composition of the present invention can obtain a cured product of the adhesive composition by, for example, irradiation with visible light or ultraviolet rays.

By the cured product of the present invention, a composite covering or bonding the adherend can be obtained. The adhesive is not particularly limited, but is preferably one or more selected from the group consisting of triacetyl cellulose, a fluorine polymer, polyester, polycarbonate, polyolefin, glass, and metal.

By using the adhesive composition of the present invention, a touch panel laminate in which an adherend is attached can be obtained.

By using the adhesive composition of the present invention, a touch panel laminate in which an adherend is attached can be obtained. The display can be obtained by using the touch panel laminate described above.

By using the adhesive composition of the present invention, a liquid crystal panel laminate in which a bonded body is bonded can be obtained. A display can be obtained by using the liquid crystal panel laminate described above.

[Examples]

Hereinafter, the present invention will be described in more detail by way of Experimental Examples, but the present invention is not limited thereto. The experiment was carried out at 23 ° C unless otherwise specified.

(Experimental Example 1)

The curable resin composition of the composition shown in Table 1 was prepared and evaluated. The results are shown in Table 1.

The following compounds were selected as the respective components in the curable resin composition described in the experimental examples.

As the polyfunctional (meth) acrylate of the component (A), the following compounds were selected.

(A-2) a polyester urethane acrylate oligomer ("oligomer 2", the structure is as follows, the polyol compound has a condensate as 1,4-butanediol and adipic acid Polyester polyol, and a polyester polyol as a condensate of ethylene glycol and adipic acid (polyester polyol as a condensate of 1,4-butanediol and adipic acid: as ethylene glycol) Polyester polyol of condensate of alcohol and adipic acid = 2:3 (mole ratio), organic polyisocyanate compound is isophorone diisocyanate, and hydroxyethyl (meth)acrylate is 2-hydroxyethyl acrylate , using GPC polystyrene-converted weight average molecular weight of 18,000)

(A-1) a polyester urethane acrylate oligomer ("oligomer 1", the structure is as follows, the polyol compound has a condensate as a hydrogenated polybutadiene polyol and adipic acid Polyester polyol, organic polyisocyanate compound is isophorone diisocyanate, hydroxy (meth) acrylate is 4-hydroxybutyl acrylate, weight converted by polystyrene using GPC The average molecular weight is 25,000, and the hydrogenated polybutadiene polyol is a compound represented by the formula (3) (n is a positive number))

(A-3) hydrogenated polybutadiene urethane acrylate ("oligomer 3", which is an urethane acrylate having a hydrogenated polybutadiene skeleton. Further, the structure is as follows, plural The alcohol compound is a hydrogenated polybutadiene polyol, the organic polyisocyanate compound is isophorone diisocyanate, the hydroxyethyl (meth)acrylate is 2-hydroxyethyl acrylate, the weight average molecular weight is 19,000, and the hydrogenated polybutadiene polyol Is a compound represented by formula (2) (n is a positive number))

(A-4) hydrogenated polybutadiene urethane acrylate ("oligomer 4", but containing 20% by mass of n-octyl acrylate as a dilute monomer, and a carboxylic acid having a hydrogenated polybutadiene skeleton Ethyl ester acrylate. Further, the structure is as follows, the polyol compound is a hydrogenated polybutadiene polyol, the organic polyisocyanate compound is isophorone diisocyanate, and the hydroxy (meth) acrylate is 2-hydroxyethyl acrylate. Ester, weight average molecular weight 35000, hydrogenated polybutadiene polyol is a compound represented by formula (2) (n is a positive number)

As the monofunctional (meth) acrylate of the component (B), the following compounds were selected.

(B-1) Polyethylene glycol decyl phenoxy acrylate (m=4 in the formula (4)) ("M-113" manufactured by Toagosei Co., Ltd.)

(B-2) Lauryl Acrylate ("LA" by Osaka Organic Co., Ltd.)

(B-3) 4-hydroxybutyl (meth)acrylate ("HH 4" in Japan)

(B-4) n-octyl acrylate (hereinafter referred to as "NOAA")

As the photopolymerization initiator of the component (C), the following compounds were selected.

(C-1) 1-hydroxycyclohexyl benzophenone ("Irgacure 184" manufactured by BASF Corporation)

(C-2) 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide ("LucirinTPO" manufactured by BASF Corporation)

(C-3) bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide ("Irgacure 819" manufactured by BASF Corporation)

As the dicarboxylic acid diester of the component (D), the following compounds were selected.

(D-1) bis(2-ethylhexyl) sebacate ("SANSO CIZER DOS" manufactured by Nippon Chemical and Chemical Co., Ltd.) (hereinafter referred to as "DOS")

(D-2) bis(2-ethylhexyl) adipate (hereinafter referred to as "DOA")

As the adhesion-imparting agent of the component (E), the following compounds were selected.

(E-1) HARAMIACK F85 (fully hydrogenated rosin resin)

(E-2) YS Resin TR105 (aromatic modified terpene resin) manufactured by YASUHARA CHEMICAL

(E-3) YS Polyster TH130 (terpene phenol resin) manufactured by YASUHARA CHEMICAL

As the thiol compound as the component (F), the following compounds were selected.

(F-1) Pentaerythritol bismuth (3-thiol butyrate) ("Karenz MT PE1" manufactured by Showa Denko Co., Ltd.) (hereinafter referred to as "MT-PE1")

(F-2) 2-ethylhexyl-3-thiol propionate ("EHMP" manufactured by SC Organic Chemicals)

As the antioxidant of the component (G), the following compounds were selected.

(G-1)6-Tertibutyl-4-[3-[(2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxo Heterophosphoroprene- 6-yl)oxy]propyl]-2-cresol ("Sumitiol GP" manufactured by Sumitomo Chemical Industries, Ltd.) (hereinafter referred to as "GP")

Various physical properties were measured as follows.

[Photohardenability]

The measurement was carried out at a temperature of 23 °C. With respect to photocurability, the curable resin composition was applied to a surface of TEMPAX glass (width: 25 mm × length: 25 mm × thickness: 2 mm) to a thickness of 0.1 mm. Thereafter, UV light having a wavelength of 365 nm was irradiated with a cumulative light amount of 1500 mJ/cm ² by a curing device manufactured by Fusion Co., Ltd. using an electrodeless discharge lamp to be cured.

The hardening rate was calculated by the following formula using FT-IR. The absorption spectrum of the double bond of carbon and carbon is a peak near 1600 cm ^-1 .

(hardening rate) = 100 - (the intensity of the absorption spectrum of the double bond of carbon and carbon after hardening) / (the intensity of the absorption spectrum of the double bond of carbon and carbon before hardening) × 100 (%)

[Glass adhesion evaluation (glass tensile evaluation)]

In the center portion of a slide test piece (commercial product, width 20 mm × length 76 mm × thickness 1.1 mm), a Teflon (registered trademark) tape having a thickness of 200 μm × a width of 20 mm × a length of 20 mm was used as a spacer, and The curable resin composition was applied to a circular shape having a radius of 4 mm, and then cured by irradiation with light. Light irradiation system according to the method described in [photocurable] of the item, the hardened resin composition after curing, and slide the test piece of the same size are bonded together to become a cross shape, and applying 1kgf / cm ² of The pressure is then carried out (following an area of 50 mm ² ). After the slide test pieces were placed on each other under the above conditions, pressure was applied to only one of the slide test pieces next to the cross shape using a universal testing machine, and the tensile strength (unit: kPa) was measured. The tensile strength was measured at a speed of 10 mm/min in an environment of a temperature of 23 ° C and a humidity of 50%.

[Polycarbonate adhesion evaluation (polycarbonate tensile evaluation)]

In a central portion of a polycarbonate test piece (Panlite, manufactured by Teijin Co., Ltd., width 25 mm × length 25 mm × thickness 2.0 mm), a Teflon (registered trademark) tape having a thickness of 200 μm × a width of 20 mm × a length of 20 mm was used as a spacer. After the curable resin composition was applied into a circular shape having a radius of 4 mm, it was cured by irradiation with light. The light-irradiation conditions are obtained by curing the curable resin composition according to the method described in the item [Photo-curing property], and then bonding them to a polycarbonate test piece of the same size in a cross shape and applying 1 kgf/cm ² . The pressure is then carried out (following an area of 50 mm ² ). After the polycarbonate test pieces were placed on each other under the above conditions, pressure was applied to only one of the polycarbonate test pieces which were then cross-shaped, and the tensile strength (unit: kPa) was measured using a universal testing machine. The tensile strength was measured at a speed of 10 mm/min in an environment of a temperature of 23 ° C and a humidity of 50%.

[Damp heat resistance evaluation (appearance observation (yellowness)]]

EAGLE XG (registered trademark) glass (width 50 mm × length 70 mm × thickness 0.7 mm) is made of a curable resin The thickness of the curable resin composition layer was set to 200 μm, and then hardened. The light irradiation conditions are based on the method described in the above item [Photocurability]. After hardening, the test piece was exposed to a constant temperature and humidity chamber at a temperature of 85 ° C and a relative humidity of 95% for 1,000 hours. After the exposure, the Δb value of the test piece was measured by a color measuring device ("UV-VISIBLE SPECTROPHOTOMETER" manufactured by SHIMADZU Co., Ltd.) and used as a yellowing degree.

The following is confirmed according to Table 1. The present invention has an excellent effect. When the adhesion-imparting agent was not used (Comparative Example 1), the adhesion was small and the effects of the present invention were not obtained. When the amount of the adhesion-imparting agent is large, the transparency is small and the hardenability is small (Example 6).

(Experimental Example 2)

The deep curability was evaluated using the curable resin composition of the composition shown in Table 2. The results are shown in Table 2.

[deep sclerosing]

The black tube was filled with a curable resin composition having a length of 5 mmφ and an opening diameter of 5 mmφ, and light of 1 mW/cm ² (365 nm) was irradiated with invisible light for 100 seconds from the upper portion (accumulated light amount was 100 mJ/cm ² ). Thereafter, the cured product was taken out from the black tube to remove the unhardened portion, and the thickness of the hardened portion was measured by a micrometer.

The following is confirmed according to Table 2. When thiol is used, it has deep hardenability.

(Experimental Example 3)

The curable resin composition having the composition shown in Table 3 was used, and the viscosity was evaluated. The results are shown in Table 3.

[viscosity]

The viscosity of the composition was measured using an E-type viscometer at a temperature of 25 ° C and a number of revolutions of 20 rpm.

The following is confirmed according to Table 3. The present invention has an excellent effect. When the dicarboxylic acid diester was not used (Comparative Example 2), the viscosity was large. When the viscosity is small, it becomes easy to apply to the adherend, and the coating workability is good.

The present invention can provide a composition which, for example, retains adhesion to the surface after hardening. It also has the following effects.

As the illustration table or the touch panel of the adhesive body, the driving IC or the wiring of the display body or the frame sealing agent of the LCD is hidden so that only the display area is seen, and in order to improve the design, the light shielding portion is sometimes Printing and other coatings. The past photohardenable adhesive composition, the harder it is, the adhesion of the surface (also known as adhesion, adhesion in this paper) Uniform) has a tendency to fall. Therefore, when the adhesive is to be adhered to each other, it is often used to apply the adhesive to the one-side adhesive to maintain the uncured liquid or to harden the adhesive to an extent that is not completely cured (also referred to as " In a state of semi-hardening or "temporary hardening", it adheres to the other side of the adherend, and is irradiated with ultraviolet light to be hardened. In this case, when the light-shielding portion is present, the photocurable adhesive composition under the light-shielding portion is not cured because it is not irradiated with light, and thus may not be sufficient.

The present invention is an invention that solves the above problems, and has the following effects, for example. In the present invention, the adhesive composition is applied to the adhesive body applied to one side of the adhesive body in advance, and then the adhesive bodies are bonded to each other, and the light-shielding portion is not affected by the adhesive body, and the curable resin composition can be cured. According to the present invention, the rate of hardening shrinkage is small, and variations in surface precision such as dimensional change or warpage are not caused. According to the present invention, in the high temperature reliability test, the expansion and contraction of the adherend can be withstood. The present invention does not cause the problem of color reduction, discoloration, and strength reduction after the moisture resistance test after the heat resistance test.

The present invention can provide a curable resin composition, for example, when a decorative board or a display sheet used for a display body such as a touch panel is bonded, when a transparent substrate and a transparent substrate are bonded, and a portion to be printed is bonded Even in the case where the visible light or the ultraviolet ray is not irradiated from the front surface of the adhesive body according to the light-shielding portion such as printing, the adhesive applied to the one-side adhesive body is irradiated with visible light or before the adhesive body is bonded. Ultraviolet rays are hardened in advance, and the adhesive of the surface to be bonded is cured in the same manner regardless of the presence or absence of the light-shielding portion. The curable adhesive resin under the light-shielding portion of the present invention has an effect of suppressing hardening failure of the adhesive.

Claims (21)

A composition comprising the following (P), (C) to (E); (P) a polymerizable vinyl compound; (C) a photopolymerization initiator; (D) a dicarboxylic acid diester; Adhesive imparting agent. The composition of claim 1, wherein (D) is a dicarboxylic acid diester represented by formula (1); (wherein R ₁ and R ₂ are an alkyl group having 1 to 18 carbon atoms; R ₃ is an alkylene group having 1 to 10 carbon atoms; and R ₁ and R ₂ may be the same or different). The composition of claim 1 or 2, wherein (D) is a sebacic acid diester. The composition of any one of claims 1 to 3 which further contains (F) a mercaptan. The composition of claim 4, wherein the (F) thiol is a polythiol. The composition of any one of claims 1 to 5, which further contains (G) an antioxidant. The composition according to any one of claims 1 to 6, wherein the (P) polymerizable vinyl compound contains (A) a polyfunctional (meth) acrylate and (B) a monofunctional (meth) acrylate. The composition of claim 7, wherein the (A) polyfunctional (meth) acrylate is urethane (meth) acrylate. The composition of claim 7, wherein the (B) monofunctional (meth) acrylate is selected from the group consisting of phenolic alkylene oxide-modified (meth) acrylate, (methyl) One or more groups of the alkyl acrylate and the hydroxyalkyl (meth) acrylate. The composition of any one of the items 1 to 9, wherein the amount of (D) used is 5 to 50 parts by mass in 100 parts by mass of the total of (P) and (D). The composition according to any one of claims 1 to 10, wherein the (E) adhesion-imparting agent is one or more selected from the group consisting of a fully hydrogenated rosin resin, an aromatic modified terpene resin, and a terpene phenol resin. . A curable resin composition comprising the composition according to any one of claims 1 to 11. An adhesive composition comprising the composition of any one of claims 1 to 11. A cured product which is a cured product of the adhesive composition of claim 13. A composite which is coated or bonded with an adherent as claimed in claim 14. The composite according to claim 15, wherein the adhesion system is one or more selected from the group consisting of triacetyl cellulose, fluorine polymer, polyester, polycarbonate, polyolefin, glass, and metal. A touch panel laminate which adheres to an adherend using an adhesive composition as claimed in claim 13. A liquid crystal panel laminate which is bonded to an adherend by using an adhesive composition as claimed in claim 13. A display using the touch panel laminate of claim 17. A display using the liquid crystal panel laminate of claim 18. An adhesive composition comprising the composition according to any one of claims 1 to 11, the (P) polymerizable vinyl compound comprising (A) a polyfunctional (meth) acrylate and (B) a monofunctional group (meth) acrylate, (A) polyfunctional (meth) acrylate is urethane (meth) acrylate, (B) monofunctional (meth) acrylate is selected from phenolic epoxy One or more groups of alkane-modified (meth) acrylate, alkyl (meth) acrylate, and hydroxyalkyl (meth) acrylate, and (A) a polyfunctional (meth) acrylate, 10 to 90 parts by mass of the total of 100 parts by mass of (A), (B) and (D), and (B) the amount of monofunctional (meth) acrylate used in (A), (B) and The total amount of D) is 3 to 80 parts by mass based on 100 parts by mass, and the amount of (D) dicarboxylic acid diester used is 1 to 50 parts by mass based on 100 parts by mass of (P) and (D), (E) The adhesion-imparting agent is one or more selected from the group consisting of a fully hydrogenated rosin resin, an aromatic modified terpene resin, and a terpene phenol resin, and (E) an amount of the adhesion-imparting agent used, relative to (P) and (D) The total amount of 100 parts by mass is 1 to 40 parts by mass, relative to the total of (P) and (D) 1 The 00 parts by mass further contains 0.1 to 10 parts by mass of the (F) polythiol, and may further contain (G) an antioxidant.