TWI689569B - Composition - Google Patents

Abstract

The present invention provides a composition that maintains adhesion on the surface after hardening. A composition containing the following (P), (C) to (E); (P) polymerizable vinyl compound; (C) photopolymerization initiator; (D) dicarboxylic acid diester; and ( E) Adhesion-imparting agent. An adhesive composition comprising the composition. It may further contain (F) mercaptan or (G) antioxidant. (P) The polymerizable vinyl compound preferably contains (A) a polyfunctional (meth)acrylate and (B) a monofunctional (meth)acrylate.

Description

Composition

The present invention relates to a composition.

Touch panels mounted on displays such as LCDs (liquid crystal displays) include resistive film type, electrostatic capacitance type, electromagnetic induction type, and optical type. Sometimes, a decorative plate that improves the appearance design or an icon table that specifies the touch position is attached to the surface of the touch panel. The electrostatic capacitive touch panel has a structure in which a transparent electrode is formed on a transparent substrate, and a transparent plate is pasted thereon.

Conventionally, adhesives have been used in the bonding of decorative plates and touch panels, the bonding of icon tables and touch panels, and the bonding of transparent substrates and transparent plates.

Especially when the photohardenable adhesive composition is bonded to each of these components, as a representative method, there are two adhesive bodies (adherend) sandwiching the adhesive and bonding, and then irradiating from the front of the display Visible light or ultraviolet light to harden the adhesive, and in this way, the two adhesive bodies are attached.

Patent Document 1 describes that (A) a (meth)acrylate oligomer having polyisoprene, polybutadiene or polyurethane in its skeleton, (B) softening component, and (C1) Selected from phenoxyethyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, (meth)acrylic acid 2-hydroxy-3-phenoxypropyl ester, cyclohexyl (meth)acrylate, nonyl EO adduct (meth)acrylate, methoxytriethylene glycol (meth)acrylate and (meth ) A photo-curable resin composition of (meth)acrylate monomers of tetrahydrofuran acrylate. However, the composition of the present invention, particularly the composition containing (D) a dicarboxylic acid diester, is not described in Patent Document 1.

In recent years, the glass of displays such as LCDs has become thinner. If the glass becomes thinner, it becomes easier to deform the LCD with external stress. When a display such as an LCD using thin glass is bonded to an optical functional material such as an acrylic plate or a polycarbonate plate, the linear expansion of glass and acrylic is different, or a plastic molding material such as acrylic plate or polycarbonate The strain at the time of molding, so in the heat resistance test or moisture resistance test, it will cause the relaxation of the molding strain or moisture absorption/drying, and will cause changes in the surface accuracy such as dimensional changes or warpage.

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

As a solution decision of the problem of Patent Document 2, there is described a UV-curable resin as in Patent Document 3. Patent Document 3 is a highly elastic resin based on a rigid skeleton monomer such as isobornyl (meth)acrylate, so it cannot withstand the expansion and contraction of the adherend in the high-temperature reliability test, and there is a possibility of peeling. Sex. Even if the present invention does not use a rigid skeleton monomer such as isobornyl (meth)acrylate, it has a design to withstand the expansion and contraction of the adherend in the high-temperature reliability test.

For applications such as the bonding of decorative plates and touch panels, the bonding of icon tables and touch panels, and the bonding of transparent substrates and transparent plates, it is desirable to have an adherent that can follow the heating environment under the assumed use environment The degree of flexibility of the deformation.

On the other hand, since it has flexibility that can follow the deformation of the adherend under a heating environment that assumes the use environment, the problem of coloration, discoloration, and strength reduction after the heat resistance test after the heat resistance test becomes obvious. As a solution to the above problem, Patent Document 4 describes that it contains a material selected from the group consisting of polyisoprene (meth)acrylate oligomers, polybutadiene (meth)acrylate oligomers, and polyurethane A light-curable adhesive composition of one or more oligomers of the group of ester (meth)acrylate oligomers and hindered amines. However, the composition of the present invention, particularly the composition containing (D) a dicarboxylic acid diester, is not described in Patent Document 4.

Patent Document 5 describes a photocurable composition characterized by containing 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, particularly the composition containing (D) a dicarboxylic acid diester, is not described in Patent Document 4.

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

As a method of maintaining the adhesion of the surface even after the hardening 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 adhesive containing a hydrogenated terpene resin adhesion-imparting agent as an adhesion-imparting agent. However, the composition of the present invention, particularly the composition containing (D) a dicarboxylic acid diester, is not described in Patent Document 7.

Prior technical literature Patent Literature

Patent Literature 1 International Publication No. 2010/027041

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

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

Patent Document 4 Japanese Unexamined Patent Publication No. 2012-46658

Patent Document 5 Japanese Patent Application Publication No. 2002-097224

Patent Document 6 Japanese Patent Application Publication No. 2009-001655

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

The present invention provides a curable resin composition, for example, to solve the problem that when a display panel such as a touch panel is attached to a decorative board or an icon table, when a transparent substrate is attached to a transparent substrate, and between a display and an optical device When the material can be used, it is a problem of the prior art that the surface is peeled off and the glass of the display is broken, and the problem of discoloration and strength reduction after the heat resistance and humidity resistance tests.

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

In this composition, (D) is a dicarboxylic acid diester represented by formula (1).

(In the formula, R ₁ and R ₂ are alkyl groups 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.) Where (D) is a sebacic acid diester; if the composition, it further contains (F) thiol; if the composition, the (F) thiol is a polythiol; if the composition, it is further Contains (G) antioxidant; as in the composition, wherein the (P) polymerizable vinyl compound contains (A) polyfunctional (meth)acrylate and (B) monofunctional (meth)acrylate; as in the composition Substances, where (A) the multifunctional (meth)acrylate is urethane (meth)acrylate; as the composition, wherein (B) the monofunctional (meth)acrylate is selected from the group consisting of phenols Alkylene oxide modified (meth) acrylate, alkyl (meth) acrylate, and hydroxyalkyl (meth) acrylate, one or more of the group; if the composition, the use amount of (D), 5 to 50 parts by mass out of a total of 100 parts by mass of (P) and (D); as the composition, (E) the adhesion-imparting agent contains fully hydrogenated rosin resin, aromatic modified terpene resin, and terpene One or more of the phenolic resin group; a curable resin composition comprising the composition; an adhesive composition comprising the composition; a cured composition comprising the adhesive A hardened product; a composite which is coated or joined with an adherend by the hardened product; such as the composite, wherein the adhesive system is selected from the group consisting of triethyl cellulose, fluoropolymer, polyester, poly One or more of the group of carbonate, polyolefin, glass, metal; a touch panel laminate that uses the adhesive composition to adhere to the adherend; a liquid crystal panel laminate that uses the adhesive Bonded substrate; a display using the touch panel laminate; a display using the liquid crystal panel laminate; as the adhesive composition, the (P) polymerizable vinyl compound contains (A ) Multifunctional (meth)acrylate and (B) Monofunctional (meth)acrylate, (A) Multifunctional (meth)acrylate is urethane (meth)acrylate, (B) Monofunctional (Meth) acrylate is one or more selected from the group consisting of phenol-based alkylene oxide-modified (meth) acrylate, (meth) acrylate, and hydroxyalkyl (meth) acrylate, ( A) The amount of polyfunctional (meth)acrylate used is 10 to 90 parts by mass out of a total of 100 parts by mass of (A), (B) and (D). (B) Monofunctional (meth)acrylate The amount of use is 3 to 80 parts by mass in the total of 100 parts by mass of (A), (B) and (D). The amount of (D) dicarboxylic acid diester is relative to (P) and (D) The total 100 parts by mass is 1 to 50 parts by mass. (E) The adhesion-imparting agent is one or more of the group consisting of fully hydrogenated rosin resin, aromatic modified terpene resin, and terpene phenol resin. (E ) The amount of the adhesion-imparting agent is 1 to 40 parts relative to the total of 100 parts by mass of (P) and (D). The amount part further contains 0.1 to 10 parts by mass of (F) polythiol with respect to 100 parts by mass of (P) and (D) in total, and further contains (G) an antioxidant.

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

Forms for carrying out the invention

As the (P) polymerizable vinyl compound, (meth)acrylate is preferable, and it is more preferable to contain (A) polyfunctional (meth)acrylate and (B) monofunctional (meth)acrylate. (A) Multifunctional (meth)acrylate refers to a (meth)acrylate having two or more (meth)acryloyl groups. Examples of polyfunctional (meth)acrylates include oligomers in which at least two polyfunctional (meth)acrylates have been (meth)acrylic acid acylated on the end or side chain of the oligomer/polymer. /Polymer etc.

Examples of oligomers/polymers of polyfunctional (meth)acrylates include 1,2-polybutadiene-terminated urethane (meth)acrylate and 1,2-hydrogenated polybutadiene-terminated Urethane (meth)acrylate (for example, "TEAI-1000" manufactured by Soda Japan), 1,4-polybutadiene terminal urethane (meth)acrylate, polyisoprene terminal (Meth) acrylate, polyester urethane (meth) acrylate, polyether urethane (meth) acrylate, bisphenol A epoxy (meth) acrylate, etc. Polybutadiene terminal (meth)urethane acrylate or hydrogenated Polybutadiene terminal urethane (meth)acrylate, the molecular structure of the terminal is (meth)acrylate. Among these, urethane (meth)acrylate is preferable from the viewpoint of a large effect. The urethane (meth)acrylate contains polybutadiene urethane (meth)acrylate, hydrogenated polybutadiene terminal urethane (meth)acrylate, polyester amine One or more of the group of ethyl formate (meth)acrylate and polyether urethane (meth)acrylate are preferred, including hydrogenated polybutadiene urethane (meth)acrylic acid One or more of the group of ester and polyester urethane (meth)acrylate is more preferred. Among hydrogenated polybutadiene urethane (meth)acrylates, 1,2-hydrogenated polybutadiene terminal urethane (meth)acrylates are preferred.

Here, urethane (meth)acrylate refers to, for example, by combining a polyol compound (hereinafter denoted by X) with an organic polyisocyanate compound (hereinafter denoted by Y) and a hydroxy (meth)acrylate ( It is denoted by Z hereafter) reaction (for example, polycondensation reaction) to obtain urethane (meth)acrylate having a urethane bond in the molecule.

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, polybutanediol, 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, cyclohexane dimethanol, hydrogenated bisphenol A, Polycaprolactone, trimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, glycerol, polyglycerol, polytetramethylene Polyols such as methylene glycol, or polyepoxy Ethane, polypropylene oxide, ethylene oxide/propylene oxide block or random copolymerization of at least one structure of polyether polyol, caprolactone modified polytetramethylene polyol, etc. Caprolactone modified polyol, polyolefin polyol, polycarbonate polyol, polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol, hydrogenated polyisoprene Silicone polyols such as polydiene polyols such as polyols, polydimethylsiloxane polyols, etc. Mention may also be made of the polyhydric alcohol or a polycondensate of the polyhydric alcohol and polycondensate of maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid, etc. Ester polyols, etc.

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

(In the formula, n is a positive number.)

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

Although the organic polyisocyanate compound (Y) is not particularly limited, for example, polyisocyanates such as aromatic, aliphatic, cycloaliphatic, and alicyclic systems can be used. 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 xylylene diisocyanate (H-XDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), trimethyl hexamethylene diisocyanate (TMXDI ), tetramethyl xylylene diisocyanate (m-TMXDI), isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), 1,3-bis (methyl isocyanate) cyclohexane Polyisocyanates such as alkane (H6XDI), trimer compounds of these polyisocyanates, reaction products of such polyisocyanates and polyols, etc. Among these, hydrogenated xylylene diisocyanate (H-XDI) and/or isophorone diisocyanate (IPDI) are preferred.

Examples of hydroxy (meth)acrylate (Z) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. Of hydroxyalkyl (meth)acrylate, 2-hydroxyethyl (meth)acryloyl phosphate, 4-hydroxybutyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2- Hydroxypropylphthalate, glycerol di(meth)acrylate, 2-hydroxy-3-(meth)acryloxypropyl acrylate, caprolactone modified 2-hydroxy(meth)acrylate Ethyl ester, pentaerythritol tri(meth)acrylate, di Pentaerythritol penta (meth) acrylate, caprolactone modified 2-hydroxyethyl (meth) acrylate, etc. Among these, hydroxyalkyl (meth)acrylate is preferred.

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

Formula (3) ZO-(R ₄ -O-) _p -H

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

The carbon number of the alkylene group of R ₄ in formula (3) is preferably 1-8, more preferably 2-6.

The hydroxyalkyl (meth)acrylate is selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate One or more types are preferable. The production method of urethane (meth)acrylate is described in, for example, Japanese Patent Laid-Open No. 7-25957, Japanese Patent Laid-Open No. 2002-173515, Japanese Patent Laid-Open No. 7-292048, Japanese Patent Laid-Open No. 2000-351819 Bulletin, etc.

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

Flow rate: 1.0ml/min

Set temperature: 40℃

Column structure: "TSK guardcolumn MP (×L)" manufactured by Tosoh Corporation 6.0mmID×4.0cml support, and “TSK-GELMULTIPOREHXL-M” manufactured by Tosoh Corporation 7.8mmID×30.0cm (theoretical layer 16,000 layers) 2 total, total 3 (overall, 32,000 theoretical layers)

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

Liquid feeding pressure: 39kg/cm ²

Detector: RI detector

(P) When the polymerizable vinyl compound contains (A) polyfunctional (meth)acrylate and (B) monofunctional (meth)acrylate, the amount of (A) polyfunctional (meth)acrylate is Of the total 100 parts by mass of (A), (B) and (D), 10 to 90 parts by mass is preferred, 30 to 90 parts by mass is more preferred, 40 to 85 parts by mass is further preferred, and 30 to 80 parts by mass is further preferred Better, 40~75 parts by mass is the best. If it is 10 parts by mass or more, the adhesiveness will not be reduced, and if it is 90 parts by mass or less, good curability will be obtained.

(B) Monofunctional (meth)acrylate refers to a (meth)acrylate having one (meth)acryloyl group. (B) Among monofunctional (meth)acrylates, one of the group consisting of phenolic alkylene oxide-modified (meth)acrylates, (meth)acrylates, and hydroxyalkyl (meth)acrylates More than one species is preferred.

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

(In the formula, 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 methyl. m is 1 to 6.)

R ¹ is preferably an alkyl group. The carbon number of the alkyl group is preferably 5 to 13, and 9 is more preferable. R ² is preferably ethylidene. m is preferably 4. Nonylphenol alkylene oxide-modified (meth)acrylates where R ¹ is a C 9 alkyl group include nonylphenol ethylene oxide-modified (meth)acrylates and nonylphenol (ethylene oxide 4 molar modification) (meth)acrylate, nonylphenol (ethylene oxide 8 molar modification) (meth)acrylate, nonylphenol (propylene oxide 2.5 molar modification) (meth)acrylic acid Ester etc.

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

Examples of the alkyl (meth)acrylate having an alkyl group having 2 to 16 carbon atoms include ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and (meth) 2-ethylhexyl acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate , Stearyl (meth)acrylate, isostearyl (meth)acrylate, etc. Among these, from the viewpoint of adhesiveness or moisture resistance, octyl (meth)acrylate is preferred, and n-octyl (meth)acrylate is more preferred.

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 (meth)acryl acetyl group, R ₄ represents alkylene group, and p represents an integer from 1 to 10.)

The carbon number of the alkylene group of R ₄ in formula (3) is preferably 1-8, more preferably 2-6.

Examples of the hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth) 4-Hydroxybutyl acrylate, diethylene glycol mono(meth)acrylate, polypropylene glycol (meth)acrylate, etc. Among these, 4-hydroxybutyl (meth)acrylate is preferable from the viewpoint of adhesiveness or moisture resistance.

(P) When the polymerizable vinyl compound contains (A) polyfunctional (meth)acrylate and (B) monofunctional (meth)acrylate, the amount of (B) monofunctional (meth)acrylate is Of the total 100 parts by mass of (A), (B) and (D), 3 to 80 parts by mass is preferable, 5 to 80 parts by mass is better, 15 to 65 parts by mass is particularly good, and 20 to 60 parts by mass is the best . When it is 3 parts by mass or more, good hardenability can be obtained, and if it is 80 parts by mass or less, the adhesiveness does not decrease.

及其衍生物、樟腦醌、7,7-二甲基-2,3-二氧代 雙環[2.2.1]庚烷-1-羧酸、7,7-二甲基-2,3-二氧代雙環[2.2.1]庚烷-1-羧基-2-溴乙酯、7,7-二甲基-2,3-二氧代雙環[2.2.1]庚烷-1-羧基-2-甲酯、7,7-二甲基-2,3-二氧代雙環[2.2.1]庚烷-1-羧醯氯等之樟腦醌衍生物、2-甲基-1-[4-(甲硫基)苯基]-2-N-

啉基丙-1-酮、2-苯甲基-2-二甲胺基-1-(4-N-

啉基苯基)-丁酮-1等之α-胺烷基酮衍生物、苯甲醯基二苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦、苯甲醯基二乙氧基氧化膦、2,4,6-三甲基苯甲醯基二甲氧基苯基氧化膦、2,4,6-三甲基苯甲醯基二乙氧基苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦等之醯基氧化膦衍生物、氧基-苯基-乙酸2-[2-氧代-2-苯基-乙醯氧基-乙氧基]-乙酯及氧代-苯基-乙酸2-[2-羥基-乙氧基]-乙酯、1-羥基-環己基-苯基-酮等。光聚合起始劑，可使用1種或組合2種以上而使用。該等之中，從效果大之觀點來看，包含苯偶姻衍生物、1-羥基-環己基-苯基-酮、醯基氧化膦衍生物的群組中之1種以上較佳。苯偶姻衍生物中，苯甲基二甲基縮酮較佳。醯基氧化膦衍生物中，包含2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦的群組中之1種以上較佳。 (C) The photopolymerization initiator is used for sensitization by visible light or ultraviolet active light, and to promote photohardening of the resin composition. Examples of the photopolymerization initiator include benzophenone and its derivatives, benzhydryl and its derivatives, anthraquinone and its derivatives, benzoin, benzoin methyl ether, benzoin ethyl ether, Benzoin derivatives of benzoin propyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc., diethoxyacetophenone, 4-third butyl trichloroacetophenone, etc. Acetophenone derivatives, 2-dimethylaminoethyl benzoate, p-dimethylaminoethyl benzoate, diphenyl disulfide, 9-oxythio

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 -Camphorquinone derivatives such as methyl esters, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxamide chloride, 2-methyl-1-[4- (Methylthio)phenyl)-2-N-

Prolin-1-propanone, 2-benzyl-2-dimethylamino-1-(4-N-

(Phenylphenyl)-butanone-1 and other α-aminoalkyl ketone derivatives, benzoyl diphenyl phosphine oxide, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, Benzoyldiethoxyphosphine oxide, 2,4,6-trimethylbenzyldimethoxyphenylphosphine oxide, 2,4,6-trimethylbenzyldiethoxy Acylphosphine oxide derivatives such as phenylphosphine oxide, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, oxy-phenyl-acetic acid 2-[2-oxo- 2-phenyl-acetoxy-ethoxy]-ethyl ester and oxo-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester, 1-hydroxy-cyclohexyl-phenyl- Ketone etc. The photopolymerization initiator may be used alone or in combination of two or more. Among these, from the viewpoint of having a large effect, one or more of the group including benzoin derivatives, 1-hydroxy-cyclohexyl-phenyl-ketone, and acetylphosphine oxide derivatives are preferable. Among the benzoin derivatives, benzyl dimethyl ketal is preferred. Acyl phosphine oxide derivatives, including 2,4,6-trimethylbenzyl diphenyl phosphine oxide, bis (2,4,6-trimethyl benzoyl phenyl) phenyl phosphine oxide More than one of the groups is better.

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

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

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

In the compound represented by formula (1), R ₁ and R ₂ are preferably saturated aliphatic hydrocarbon groups. In addition, the above R ₁ and R _{2 are} preferably unsubstituted. R ₁ and R ₂ are preferably C 2-12 alkyl groups, C 4-10 alkyl groups are more preferred, and C 8 alkyl groups are most preferred. In the compound represented by formula (1), R ₃ is preferably a saturated aliphatic hydrocarbon group. Furthermore, the above R _{3 is} preferably 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 an alkylene group having 8 carbon atoms.

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

Examples of the dicarboxylic acid diester represented by (D) formula (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, dibutyl succinate 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, heptane Dimethyl diacid, diethyl pimelate, diisopropyl pimelate, dibutyl pimelate, dimethyl suberate, diethyl suberate, dipropyl suberate, octyl Diisopropyl diacid, dimethyl azelate, diethyl azelate, dipropyl azelate, diisopropyl azelate, dibutyl azelate, dimethyl sebacate, Diethyl sebacate, dipropyl sebacate, dipropyl sebacate, diisopropyl sebacate, dibutyl sebacate, bis(2-ethylhexyl) sebacate, etc. One or more of these dicarboxylic acid diesters can be used. Among (D) dicarboxylic acid diesters, sebacic acid diesters are preferred. Among sebacic diesters, bis(2-ethylhexyl sebacate) is preferred.

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

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

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

In the composition of the present invention, (F) mercaptan can be used. (F) Mercaptan means a compound having one or more thiol groups. Among thiols, polythiol is preferred from the viewpoint of deep curability. (F) Polythiol means a compound having two or more thiol groups. Examples of the polythiol include trimethylolpropane ginseng thiopropionate, pentaerythritol thiopropionate, dipentaerythritol (3-mercaptopropionate), ginseng [(3-mercaptopropionate) Oxy)-ethyl]isocyanurate, 2-ethylhexyl-3-thiol propionate, 3-thiol butyrate derivatives, etc. One or more of these polythiols can be used.

-2,4,6-(1H,3H,5H)-三酮、季戊四醇肆(3-硫醇丁酸酯)、季戊四醇肆(3-硫醇丁酸酯)、三羥甲基丙烷參(3-硫醇丙酸酯)、2-乙基己基-3-硫醇丙酸酯等。(F)聚硫醇中，1級或2級的聚硫醇較佳。 (F) In polythiol, one or more of the group consisting of 3-thiol butyrate derivatives and thiol propionate derivatives are preferred. For example, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-ginseng (3-mercaptobutoxyethyl)-1,3,5-tris

-2,4,6-(1H,3H,5H)-trione, pentaerythritol (3-mercaptobutyrate), pentaerythritol (3-mercaptobutyrate), trimethylolpropane ginseng (3 -Thiol propionate), 2-ethylhexyl-3-thiol propionate, etc. (F) Among the polythiols, polythiols of grade 1 or grade 2 are preferred.

(F) The amount of polythiol used is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of (P) and (D) in total, and more preferably 0.5 to 5 parts by mass. If it is 0.1 parts by mass or more, good deep-hardenability can be obtained, and if it is 10 parts by mass or less, coloring or discoloration due to heat of the curable resin composition becomes small.

、第三丁基兒茶酚、2-丁基-4-羥基苯甲醚及2,6-二第三丁基-p-甲酚等。該等之中，6-第三丁基-4-[3-[(2,4,8,10-四-第三丁基二苯并[d,f][1,3,2]二氧雜磷雜環庚三烯-6-基)氧基]丙基]-2-甲酚較佳。 In order to improve storage stability, the composition of the present invention may use (G) antioxidant. Examples of antioxidants include methylhydroquinone, hydroquinone, 2,2-methylene-bis(4-methyl-6-tert-butylphenol), and 6-tert-butyl-4-[3- [(2,4,8,10-Tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphorane-6-yl)oxy]propyl ]-2-cresol (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-third butyl hydroquinone, 2,5-di-third butyl hydroquinone, p-benzoquinone, 2,5 -Diphenyl-p-benzoquinone, 2,5-di-tert-butyl-p-benzoquinone, picric acid, citric acid, phenol thiophene

, Third-butyl catechol, 2-butyl-4-hydroxyanisole, 2,6-di-third-butyl-p-cresol, etc. Among these, 6-tert-butyl-4-[3-[(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]diox Heterophosphorane-6-yl)oxy]propyl]-2-cresol is preferred.

(G) The amount of antioxidant used is preferably 0.001 to 0.5 parts by mass relative to 100 parts by mass of (P) and (D) in total, and more preferably 0.005 to 0.1 parts by mass. If it is 0.001 part by mass or more, coloring or discoloration due to heat of the curable resin composition is small, and if it is 0.5 part by mass or less, good deep curability can be obtained.

The composition of the present invention can use various elastomers such as acrylic rubber, urethane rubber, acrylonitrile-butadiene-styrene rubber, etc., which are generally used, and polar organic compounds, without impairing the object of the present invention. Additives such as solvents, extenders, reinforcements, plasticizers, tackifiers, dyes, pigments, flame retardants, silane coupling agents and surfactants.

The cured product followed by the composition of the present invention can be reprocessed (reused) after being completely cured. As a method of reprocessing, no It is particularly limited to use a load of 0.01 to 100 N to disintegrate the adherends between the adhered one or two adherents, and the disassembled adherends can be reused.

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 in a state of a cured product with a curing rate of 90% or more, and can maintain sufficient adhesiveness/adhesion even when it is bonded to various adherends. The composition of the present invention is, for example, by irradiating visible light or ultraviolet light on the adhesive composition coated on one side of the adhesive body, and then bonding with the other side of the adhesive body, even if the visible light or ultraviolet light does not pass through All can be hardened, but can be adhered to the adhesive composition.

For the adhesive composition of the present invention, for example, by irradiating visible light or ultraviolet rays, a hardened product of the adhesive composition can be obtained.

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

Using the adhesive composition of the present invention, it is possible to obtain a touch panel laminate to which an adherend is attached.

Using the adhesive composition of the present invention, it is possible to obtain a touch panel laminate to which an adherend is attached. Using the above touch panel laminate, a display can be obtained.

Using the adhesive composition of the present invention, a liquid crystal panel laminate to which an adherend is bonded can be obtained. Using the above liquid crystal panel laminate, a display can be obtained.

[Example]

Experimental examples are given below to explain the present invention in more detail, but the present invention is not limited to these. Unless otherwise specified, experiments were conducted at 23°C.

(Experiment example 1)

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

As each component in the curable resin composition described in the experimental example, the following compounds were selected.

As the polyfunctional (meth)acrylate as the component (A), the following compounds are selected.

(A-2) Polyester urethane acrylate oligomer ("oligomer 2", the structure is as follows, the polyol compound is a condensate having 1,4-butanediol and adipic acid Of polyester polyols and polyester polyols as condensates of ethylene glycol and adipic acid (polyester polyols as condensates of 1,4-butanediol and adipic acid: as ethylene glycol Polyester polyol of the condensate of alcohol and adipic acid = 2:3 (molar ratio)), the organic polyisocyanate compound is isophorone diisocyanate, and the hydroxy (meth)acrylate is 2-hydroxyethyl acrylate , Using the weight average molecular weight of GPC polystyrene conversion 18000)

(A-1) Polyester urethane acrylate oligomer ("oligomer 1", structure is as follows, polyol compound is a condensate having hydrogenated polybutadiene polyol and adipic acid Polyester polyol, organic polyisocyanate compound is isophorone diisocyanate, hydroxy (meth) acrylate is 4-hydroxybutyl acrylate, using GPC polystyrene equivalent weight The average molecular weight is 25000, and the hydrogenated polybutadiene polyol is a compound represented by formula (3) (n is a positive number))

(A-3) Hydrogenated polybutadiene urethane acrylate ("oligomer 3", which is a urethane acrylate having a hydrogenated polybutadiene skeleton. The structure is as follows, multiple Alcohol compound is hydrogenated polybutadiene polyol, organic polyisocyanate compound is isophorone diisocyanate, hydroxy (meth) acrylate is 2-hydroxyethyl acrylate, weight average molecular weight 19000, 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 dilution monomer, and a urethane having a hydrogenated polybutadiene skeleton Ethyl acrylate. Furthermore, the structure is as follows, the polyol compound is 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 are selected.

(B-1) Polyethylene glycol nonylphenoxy acrylate (in formula (4), m=4) ("M-113" manufactured by East Asia Synthetic Corporation)

(B-2) Lauryl acrylate ("LA" manufactured by Osaka Organic Corporation)

(B-3) 4-Hydroxybutyl (meth)acrylate (Nippon Kasei "4HBA")

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

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

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

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

(C-3) Bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide ("Irgacure819" manufactured by BASF)

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

(D-1) bis(2-ethylhexyl sebacate) ("SANSO CIZER DOS" manufactured by New Japan Physical and Chemical Corporation) (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 are selected.

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

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

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

As the thiol compound of the component (F), the following compounds are selected.

(F-1) Pentaerythritol (3-mercaptobutyrate) ("KarenzMT PE1" manufactured by Showa Denko Corporation) (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 are selected.

(G-1)6-tert-butyl-4-[3-[(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]diox Heterophosphorane-6-yl)oxy]propyl]-2-cresol ("SUMILIZER GP" manufactured by Sumitomo Chemical Industries, Ltd.) (hereinafter referred to as "GP")

Various physical properties are measured as follows.

[Photohardenability]

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

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

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

[Evaluation of glass adhesion (evaluation of glass tensile strength)]

Teflon (registered trademark) tape with a thickness of 200 μm × width 20 mm × length 20 mm was used as a spacer at the center of a glass slide test piece (commercially available product, width 20 mm × length 76 mm × thickness 1.1 mm). After the curable resin composition was applied in a circular shape with a radius of 4 mm, it was irradiated with light to harden it. The light irradiation conditions are based on the method described in the above item [Photocurability]. After curing the curable resin composition, it is laminated with a glass slide test piece of the same size and applied with 1kgf/cm ² The pressure is followed (the area is then 50 mm ² ). After the slide glass test pieces were bonded to each other under the above conditions, using a universal testing machine, pressure was applied to only one of the cross-shaped slide glass test pieces to measure the tensile strength (unit: kPa). The tensile strength was measured at a speed of 10 mm/min in an environment with a temperature of 23° C. and a humidity of 50%.

[Evaluation of polycarbonate adhesion (evaluation of polycarbonate tensile strength)]

Teflon (registered trademark) tape with a thickness of 200 μm × width 20 mm × length 20 mm was used as a spacer at the center of a polycarbonate test piece (“Panlite” manufactured by Teijin Corporation, width 25 mm × length 25 mm × thickness 2.0 mm) After applying the curable resin composition into a circle with a radius of 4 mm, it is irradiated with light to harden it. The light irradiation conditions are in accordance with the method described in the above item [photocurability]. After curing the curable resin composition, it is laminated with a polycarbonate test piece of the same size in a cross shape and applied with 1 kgf/cm ² The pressure is followed (the area is then 50 mm ² ). After the polycarbonate test pieces were bonded to each other under the above conditions, using a universal testing machine, pressure was applied to only one of the polycarbonate test pieces followed by a cross shape, and the tensile strength (unit: kPa) was measured. The tensile strength was measured at a speed of 10 mm/min in an environment with a temperature of 23° C. and a humidity of 50%.

[Evaluation of Damp Heat Resistance (Observation of Appearance (Yellowness))]

EAGLE XG (registered trademark) glass (width 50mm × length 70mm × thickness 0.7mm) between each other, using a hardening resin composition The thickness of the curable resin composition layer was 200 μm, followed by curing. The light irradiation conditions are based on the method described in the above item [photocurability]. After curing, the subsequent test piece was exposed to an environment of a temperature of 85°C and a relative humidity of 95% for 1000 hours using a constant temperature and humidity bath. After exposure, the Δb value of the following test piece was measured with a color measuring device ("UV-VISIBLE SPECTROPHOTOMETER" manufactured by SHIMADZU Corporation), and regarded as the degree of yellowing.

Confirm the following according to Table 1. The present invention has excellent effects. When the adhesion-imparting agent is not used (Comparative Example 1), the adhesiveness is small, and the effect of the present invention is not obtained. When there are many adhesion-imparting agents, the transparency is reduced and the curability is reduced (Example 6).

(Experiment example 2)

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

[Deep sclerosis]

A 20 mm black tube with a hole diameter of 5 mmΦ and a length of 20 mm was filled with a curable resin composition, and 1 mW/cm ² (365 nm) of light was irradiated with invisible light from the top for 100 seconds (accumulated light amount is 100 mJ/cm ² ). After that, remove the hardened material from the black tube, remove the unhardened portion, and measure the thickness of the hardened portion with a micrometer.

Confirm the following according to Table 2. When mercaptan is used, it has deep hardening properties.

(Experimental example 3)

The curable resin composition with 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 under the conditions of a temperature of 25°C and a rotation number of 20 rpm.

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

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

As an icon table or a touch panel of an adherend, the driving IC or wiring of the display body or the frame sealant of the LCD is hidden so that only the display area can be seen, and in order to improve the design, the light shielding part is sometimes used Printing and other coatings. In the conventional photo-curable adhesive composition, as it hardens, the surface adhesion (also known as adhesion) is referred to as adhesion in this article. Unified) tends to decline. Therefore, when adhesives are to be adhered to each other, the adhesive is often applied to the unilateral adhesive to maintain the uncured liquid state, or to harden the adhesive to the extent of incomplete curing (also known as " "Semi-hardened", "temporary hardened", etc.), after being attached to the other side of the adherend, it is irradiated with ultraviolet light to cure. At this time, if the light-shielding portion is present, the photocurable adhesive composition under the light-shielding portion is not irradiated with light and is not cured, so the adhesion may not be sufficient.

The present invention is an invention that also solves the above-mentioned problems, and has the following effects, for example. In the present invention, after the adhesive composition coated on one side of the adherend is cured in advance, the adherends are adhered to each other, and even if there is a light-shielding portion in the adherend, it is not affected by it, and the curable resin composition can be cured. According to the present invention, the curing shrinkage rate is small, and there is no change in surface accuracy such as dimensional change or warpage. The invention can withstand the expansion and contraction of the adherend in the high-temperature reliability test. The present invention does not cause the problems of coloration, discoloration, and strength reduction after the humidity resistance test after the heat resistance test.

The present invention can provide a curable resin composition, for example, when attaching a decorative plate or an icon table used for a display body such as a touch panel, when attaching a transparent substrate to a transparent substrate, or when attaching a printed part , Even in areas where no visible light or ultraviolet light is exposed from the front of the adherend due to the shading part of printing, etc., before attaching each adherend, the adhesive applied on the single-sided adherend is pre-irradiated with visible light or Ultraviolet rays are hardened in advance, and whether or not there is a light-shielding portion, the adhesive on the bonded surface is also hardened in the same manner. The curable adhesive resin under the light-shielding portion of the present invention has an effect of suppressing poor curing of the adhesive.

Claims (21)

A composition containing the following (P), (C) to (E); (P) polymerizable vinyl compound; (C) photopolymerization initiator; (D) dicarboxylic acid diester; (E ) Adhesion-imparting agent. The composition of claim 1, wherein (D) is a dicarboxylic acid diester represented by formula (1);

(In the formula, R ₁ and R ₂ are alkyl groups 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 diester. The composition of claim 1 or 2 further contains (F) thiol. The composition of claim 4, wherein the (F) mercaptan is polythiol. The composition of claim 1 or 2 further contains (G) antioxidant. The composition according to claim 1 or 2, wherein the (P) polymerizable vinyl compound contains (A) a multifunctional (meth)acrylate and (B) a monofunctional (meth)acrylate. The composition of claim 7, wherein (A) the multifunctional (meth)acrylate is urethane (meth)acrylate. The composition of claim 7, wherein (B) the monofunctional (meth)acrylate is selected from the group consisting of phenolic alkylene oxide-modified (meth)acrylate, (meth)acrylate, and (A Group) one or more of the group of hydroxyalkyl acrylate. For the composition of claim 1 or 2, the amount of (D) used is 5 to 50 parts by mass in the total of 100 parts by mass of (P) and (D). The composition according to claim 1 or 2, wherein (E) the adhesion-imparting agent is one or more types 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 according to any one of claims 1 to 11. A hardened product which is a hardened product of the adhesive composition according to claim 13. A composite, which is to coat or join an adherent with a hardened material as in claim 14. The compound according to claim 15, wherein the adhesion system is selected from at least one group selected from the group consisting of triacetyl cellulose, fluoropolymer, polyester, polycarbonate, polyolefin, glass, and metal. A touch panel laminate that uses the adhesive composition according to claim 13 to adhere to an adherend. A laminate for a liquid crystal panel, which uses the adhesive composition according to claim 13 to adhere to an adherend. A display using the touch panel laminate as in claim 17. A display using the liquid crystal panel laminate as claimed in claim 18. An adhesive composition comprising the composition according to any one of claims 1 to 11, the (P) polymerizable vinyl compound containing (A) a multifunctional (meth)acrylate and (B) a monofunctional (Meth)acrylate, (A) multifunctional (meth)acrylate is urethane (meth)acrylate, (B) monofunctional (meth)acrylate is selected from the group consisting of phenolic epoxy One or more of the group of alkyl modified (meth)acrylate, alkyl (meth)acrylate, and hydroxyalkyl (meth)acrylate, (A) the amount of multifunctional (meth)acrylate used, 10 to 90 parts by mass out of a total of 100 parts by mass of (A), (B) and (D), the amount of (B) monofunctional (meth)acrylate used in (A), (B) and ( D) 3 to 80 parts by mass of the total 100 parts by mass, (D) the amount of the dicarboxylic acid diester used is 1 to 50 parts by mass relative to the total of 100 parts by mass of (P) and (D), (E ) The adhesion-imparting agent is one or more of the group consisting of a fully hydrogenated rosin resin, aromatic modified terpene resin, and terpene-phenol-based resin. The total 100 parts by mass of (D) is 1 to 40 parts by mass, and further contains 0.1 to 10 parts by mass of (F) polythiol relative to the total of 100 parts by mass of (P) and (D), and may further contain (G )Antioxidants.