TW201317315A - Curable resin composition - Google Patents

Abstract

Provided is a curable resin composition exhibiting high adhesion durability. The curable resin composition contains: a (meth)acrylate oligomer (A) selected from the group consisting of urethane-based (meth)acrylate oligomers, polyester-based (meth)acrylate oligomers, polyether-based (meth)acrylate oligomers, epoxy-based (meth)acrylate oligomers, diene polymer-based (meth)acrylate oligomers, and oligomers having a backbone of the hydrogenated product of a diene polymer-based (meth)acrylate; a (meth)acrylate (B) exhibiting a homopolymer glass transition temperature of -100 DEG C to 60 DEG C; one or more compounds (C) having one mercapto group per molecule, the compound(s) being selected from the group consisting of alkanethiols and carboxythiols; and a photopolymerization initiator (D).

Description

Curable resin composition

The present invention relates to a curable resin composition.

The touch panel mounted on a display body such as an LCD includes a resistive film type, an electrostatic capacity type, an electromagnetic induction type, an optical type, and the like. A decorative panel for making a good design or a label for specifying a touch position is sometimes adhered to the above touch panel. The electrostatic capacitance type touch panel has a structure in which a transparent electrode is formed on a transparent substrate and a transparent plate is bonded thereon.

In recent years, glass of display bodies such as LCDs has been continuously thinned. When the glass is thinned, the LCD is easily deformed by external stress. When an optical functional material such as an LCD such as an acrylic resin sheet or a polycarbonate sheet is bonded to the thin glass, the linear expansion of the glass and the acrylic resin, and the plastic such as an acrylic resin sheet or a polycarbonate. The strain at the time of molding of the molding material, the relaxation of the molding strain and the moisture absorption/drying occur in the heat resistance test or the moisture resistance test, causing variations in surface precision such as dimensional change or warpage. When it is intended to suppress deformation by a conventional adhesive (for example, Patent Document 1), there is a problem that the adhesive surface is peeled off, the LCD is broken, or the LCD display is uneven. As a countermeasure against the above problems, a UV curable resin disclosed in Patent Document 2 has been proposed.

Further, in the application of the attachment of the decorative panel and the touch panel, the attachment of the label to the touch panel, and the adhesion of the transparent substrate and the transparent plate forming the transparent electrode in the electrostatic capacitance type touch panel, it is preferable to have a followability It is assumed that the flexibility of the deformation of the adherend under the heating atmosphere of the use environment is high. As a composition for imparting flexibility, there is a curable resin composition containing a diene polymer and a compound having two mercapto groups as essential components as disclosed in Patent Document 3. In addition, as a composition containing a compound having a mercapto group, there are a curable resin composition as disclosed in Patent Document 4 and Patent Document 5. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2004-77887 [Patent Document 3] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. 2010/027041 [Patent Document 5] Japanese Patent Laid-Open No. 2011-26492

[Problems to be solved by the invention]

However, since the UV curable resin of the above Patent Document 2 is a highly elastic resin based on a rigid skeleton monomer of isobornyl (meth) acrylate, it can be considered that it cannot withstand the expansion of the adherend in the high temperature reliability test. Peeling and peeling.

Furthermore, the inventors of the present invention have confirmed that one or more kinds of molecules selected from the group consisting of alkylthiols and carboxythiols are used as the compound having a mercapto group as a component of the curable resin composition. When a compound having one fluorenyl group is used, a curable resin composition having high adhesive durability can be obtained (for example, refer to Examples described later). On the other hand, in the above-mentioned Patent Documents 3 to 5, it is considered that the flexibility, adhesiveness, and the like of the curable resin composition cannot be controlled because the above-described compound having a specific type of mercapto group is not used.

An object of the present invention is to provide a curable resin composition capable of solving the following problems, for example, when a decorative sheet and a label used in a display body such as a touch panel are attached, and a transparent electrode formed in a capacitance type touch panel is pasted. In the case of a transparent substrate, when a portion to be printed is pasted, it is difficult to impart sufficient adhesiveness to the prior art; or when the display body and the optical functional material are pasted, the adhesive surface is peeled off or the glass of the display body is broken. . [Technical means to solve the problem]

That is, according to the present invention, there is provided a curable resin composition comprising: (A) selected from the group consisting of a urethane (meth) acrylate oligomer, a polyester (meth) acrylate oligomer, and a polyether ( Methyl) acrylate oligomer, epoxy (meth) acrylate oligomer, diolefin polymer (meth) acrylate oligomer, and diene polymer (meth) acrylate One or more (meth) acrylate oligomers in the group consisting of oligomers of the skeleton of the additive; (B) (meth)acrylic acid having a glass transition temperature of -100 to 60 ° C (C) a compound having one thiol group in one or more molecules selected from the group consisting of alkylthiols and carboxy thiols; and (D) a photopolymerization initiator.

Furthermore, according to the present invention, a curable resin composition containing the (meth) acrylate other than the above (A) and (B) as the component (E) is further contained in the curable resin composition. Further, according to the present invention, there is provided a curable resin composition in which the component (E) is trimethylolpropane tri(meth)acrylate and/or tricyclodecane dimethanol (meth)acrylate. Furthermore, according to the present invention, the compound containing one mercapto group in the molecule of the above (C) is a curable resin composition of an alkyl mercaptan represented by the following formula (1). C _n H _2n+1 SH Formula (1), where n is an integer from 4 to 19. Furthermore, according to the present invention, the compound containing one fluorenyl group in the molecule of (C) is a curable resin composition of a carboxy thiol represented by the following formula (2). ROOC(CH ₂ ) _p SH Formula (2) wherein R is hydrogen or a hydrocarbon group having 1 to 19 carbon atoms, and p is an integer. Further, according to the invention, there is provided a curable resin composition having a weight average molecular weight of the component (A) of from 500 to 100,000. Further, according to the invention, there is provided a curable resin composition having a number average molecular weight of the component (A) of from 500 to 100,000. Further, according to the present invention, there is provided an adhesive composition comprising the above curable resin composition. Further, according to the present invention, a cured product of the above adhesive composition is provided. Further, according to the present invention, a composite body obtained by coating or bonding an adherend by the above-mentioned cured product is provided. Further, according to the invention, the above-mentioned adherend is provided as one or more composites selected from the group consisting of triacetyl cellulose, fluoropolymer, polyester, polycarbonate, polyolefin, glass, and metal. Further, according to the present invention, there is provided a touch panel laminate in which an adhesive body is adhered by the above-mentioned adhesive composition. Further, according to the present invention, there is provided a liquid crystal panel laminate in which an adherend is adhered by the above-mentioned adhesive composition. Further, according to the present invention, there is provided a display using the above touch panel laminate. Further, according to the present invention, there is provided a display using the above liquid crystal panel laminate. [effect of the invention]

The curable resin composition of the present invention exhibits high adhesive durability.

Hereinafter, embodiments of the present invention will be described in detail. The polyfunctional (meth) acrylate means a (meth) acrylate containing two or more (meth) acrylonitrile groups in one molecule. The monofunctional (meth) acrylate means a (meth) acrylate containing one (meth) acrylonitrile group in one molecule.

((A) component: urethane (meth) acrylate oligomer, polyester (meth) acrylate oligomer, polyether (meth) acrylate oligomer, epoxy (methyl) ) an acrylate oligomer, a diene polymer (meth) acrylate oligomer, or an oligomer having a skeleton of an additive of a diolefin polymer (meth) acrylate) as (A) The oligomer of the component is preferably a liquid oligomer having a (meth) acrylonitrile group. As the liquid oligomer, an oligomer having at least two (meth)acryl fluorenyl groups in the molecule can be preferably used from the viewpoint of curability. The number of (meth)acrylonyl groups in one molecule is preferably 2 to 6, more preferably 2 to 4, and most preferably 2. The (meth)acrylonyl group may be located at both ends or a single terminal of the oligomer of the component (A). The (meth) acrylonitrile group means an acryl fluorenyl group or a methacryl fluorenyl group.

The oligomer having a (meth) acrylonitrile group is not particularly limited, and examples thereof include those selected from the group consisting of urethane (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and polyethers. Methyl (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, diolefin polymer (meth) acrylate oligomers, and diene polymer (meth) acrylates One or more (meth) acrylate oligomers or the like in the group consisting of ester hydrogen additives.

The main chain skeleton of the oligomer having a (meth)acryl fluorenyl group is not particularly limited, and may be, for example, a hydrogen additive selected from polybutadiene, polybutadiene, polyisoprene, polyisoprene. One or more of hydrogen additive, polyester, dibutylene glycol, polycarbonate, and polyether.

The urethane (meth) acrylate oligomer is, for example, a (meth) acrylate oligomer having a urethane bond in the molecule. The urethane-based (meth) acrylate oligomer can be obtained, for example, by reacting a polybutadiene diol, a polyether polyol, a polyester polyol, a polycarbonate diol, or the like with a polyisocyanate to obtain a urethane oligomer. (Methyl) acrylated to obtain. A polybutadiene-modified urethane (meth) acrylate obtained by modifying (meth)acrylic acid to polybutadiene is also included in the urethane (meth) acrylate oligomer. The hydrogenated polybutadiene-modified urethane (meth) acrylate obtained by modifying (meth)acrylic acid to hydrogenated polybutadiene is also included in the urethane (meth) acrylate oligomer. Examples of the urethane (meth) acrylate oligomer include 1,2-polybutadiene modified urethane (meth) acrylate oligomer, and polyester urethane (meth) acrylate oligomerization. A dibutylene glycol urethane (meth) acrylate oligomer, a polycarbonate urethane (meth) acrylate oligomer, a polyether urethane (meth) acrylate oligomer, and the like.

The polyester (meth) acrylate oligomer can be obtained, for example, by esterifying a hydroxyl group of a polyester oligomer having a hydroxyl group at both terminals obtained by condensing a polyvalent carboxylic acid and a polyhydric alcohol with (meth)acrylic acid. Alternatively, an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid is obtained by esterifying a hydroxyl group at the terminal of the obtained oligomer with (meth)acrylic acid.

The polyether (meth) acrylate oligomer can be obtained, for example, by esterifying a hydroxyl group of a polyether polyol with (meth) acrylate.

The epoxy (meth) acrylate oligomer can be reacted, for example, with an oxirane ring of a lower molecular weight bisphenol type epoxy resin or a novolac type epoxy resin, and an ester Get it. Alternatively, a carboxy-modified epoxy (meth) acrylate oligomer in which the epoxy (meth) acrylate oligomer is partially modified with a dicarboxylic carboxylic anhydride may be used.

Examples of the diolefin polymer-based (meth) acrylate oligomer include SBR di(meth)acrylate obtained by modifying a liquid styrene-butadiene copolymer with (meth)acrylic acid, and A polyisoprene di(meth)acrylate obtained by modifying polyisoprene with (meth)acrylic acid or the like.

An oligomer having a skeleton of a hydrogen additive of a diolefin polymer (meth) acrylate, for example, can be obtained by hydrogenating a polybutadiene having a hydroxyl group at both terminals or a hydroxyl group of hydrogenated polyisoprene (A) Base) obtained by acrylated.

In the present embodiment, the liquid oligomer having a (meth)acryl fluorenyl group may be used singly or in combination of two or more. Among the liquid oligomers, a urethane (meth) acrylate oligomer is preferred from the viewpoint of curability and the like, and a difunctional urethane (meth) acrylate oligomer is more preferred. The difunctional urethane (meth) acrylate oligomer means that two molecules of the urethane (meth) acrylate oligomer contain two (meth) acrylonitrile groups.

The difunctional urethane (meth) acrylate oligomer can be obtained by esterifying a urethane oligomer with (meth) acrylate. The urethane oligomer can be obtained by reacting a polyether polyol, a polyester polyol, a polycarbonate diol or the like having two hydroxyl groups in the molecule with a polyisocyanate.

As the polyether polyol having two hydroxyl groups, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol (polybutylene glycol), polyhexylene glycol, 1,3-butylene glycol, 1,4-butanediol, neopentyl glycol, cyclohexanedimethanol, 2,2-bis(4-hydroxycyclohexyl)propane, bisphenol A, etc. are added to ethylene oxide or propylene oxide. The obtained compound and the like.

The polyester polyol having two hydroxyl groups can be obtained, for example, by reacting an alcohol component with an acid component. A polyester polyol having two hydroxyl groups, which can be used by reacting an alcohol component with an acid component, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol (polybutylene glycol) 1, 3 -butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 2,2-bis(4-hydroxycyclohexyl)propane, A compound obtained by adding ethylene oxide or propylene oxide or the like to a bisphenol A or the like, or a compound obtained by adding ε-caprolactone as an alcohol component, and adipic acid, sebacic acid, and sebacic acid. A dibasic acid such as dodecanedicarboxylic acid or an acid anhydride thereof is used as an acid component. A compound obtained by simultaneously reacting the above-mentioned alcohol component, acid component, and ε-caprolactone can also be used as a polyester polyol.

The weight average molecular weight and the number average molecular weight of the urethane (meth) acrylate oligomer are preferably from 500 to 100,000, and more preferably from 1,000 to 50,000, from the viewpoint of workability and the like. The value is not particularly limited and may be, for example, 500, 1000, 2000, 3000, 4000, 5000, 7000, 10000, 20000, 30000, 40,000, 50000 or 100000, and may be within the range of any of the above values. The average molecular weight is a standard polystyrene equivalent value measured by a gel permeation chromatography (GPC) method. Specifically, the average molecular weight was determined by using a GPC system (SC-8010, manufactured by Tosoh Corporation) using tetrahydrogen as a solvent under the following conditions, and using a commercially available standard polystyrene to prepare a standard curve. of. Flow rate: 1.0 ml/min; Set temperature: 40 ° C; Column composition: "TSK guardcolumn MP (×L)" manufactured by Tosoh Corporation 6.0 mm ID × 4.0 cm, and "TSK-GELMULTIPOREHXL-M" 7.8 manufactured by Tosoh Corporation mmID × 30.0cm (the number of theoretical segments 16000) two, a total of three (the total theoretical number of segments 32000); sample injection amount: 100μl (sample solution concentration 1mg / ml); liquid supply pressure: 39kg / cm ² ; Device: RI detector.

In the present embodiment, the urethane-based (meth) acrylate oligomer can be represented, for example, by the following general formula (1). 【化1】 (R' of the formula is H or CH ₃ ) Among them, the structure obtained by hydrogenating butadiene shown below can also be selected, [Chemical 2] Instead of the butadiene structure shown below. [化3] Incidentally, the above-mentioned general formula (1), R 'is CH ₃ compounds, R' is H the compound, or R 'is H and selected as shown above in place of the above structure after butadiene hydrogenation The compound of the butadiene structure shown, for example, can be purchased from Japan Soda Corporation (trade name is TE-2000, TEA-1000, TEAI-1000).

((B) component: (meth) acrylate having a homopolymer glass transition temperature of -100 ° C to 60 ° C) as a homopolymer glass transition temperature of -100 ° C to 60 ° C (methyl) The acrylate may, for example, be a dodecyl (meth) acrylate (homopolymer homopolymer glass transition temperature: acrylate -30 ° C, homopolymer glass transition temperature of methacrylate: -65 ° C , 2-ethylhexyl (meth) acrylate (homopolymer homopolymer glass transition temperature: -85 ° C, homopolymer glass transition temperature of methacrylate: -10 ° C), (methyl ) n-butyl acrylate (homopolymer glass transition temperature of methacrylate: 20 ° C), isobutyl (meth)acrylate (homopolymer glass transition temperature of methacrylate: 20 ° C), ( Tert-butyl methyl methacrylate (homopolymer glass transition temperature of methacrylate: 20 ° C), methoxyethyl (meth) acrylate (polymerization of acrylate glass transition temperature: -50 ° C ), ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate (homopolymerization) Glass transition temperature: 25 ° C), 2-hydroxyethyl (meth) acrylate (homopolymer glass transition temperature of methacrylate: 55 ° C), 2-hydroxypropyl (meth) acrylate ( Acrylate homopolymer glass transition temperature: -7 ° C, homopolymer glass transition temperature of methacrylate: 26 ° C), 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( Methyl) acrylate (polymer homopolymer glass transition temperature: -80 ° C), isooctyl (meth) acrylate (polymer acrylate glass transition temperature: -58 ° C, methacrylate Homopolymer glass transition temperature: -30 ° C), isostearyl 醯 (meth) acrylate (polymer acrylate glass transition temperature: -18 ° C, methacrylate homopolymer vitrification Transition temperature: 30 ° C), isodecyl (meth)acrylate (homopolymer glass transition temperature of acrylate: -58 ° C, homopolymer glass transition temperature of methacrylate: -30 ° C), 壬Phenoxy-polyethylene glycol (having -(CH ₂ CH ₂ O) _n - structure, n=1~17) (meth) acrylate (homopolymer glass transition temperature: -25 to 20 ° C), Phenoxy B Glycol acrylate (homopolymer glass transition temperature: -25 to 30 ° C) and the like. One type or two or more types of these (meth) acrylates can be used. The above -100 ° C ~ 60 ° C can be, for example, -100 ° C, -90 ° C, -80 ° C, -70 ° C, -60 ° C, -50 ° C, -40 ° C, -30 ° C, -20 ° C, -10 ° C, 0 ° C, 10 ° C, 20 ° C, 30 ° C, 40 ° C, 50 ° C or 60 ° C may also be within the range of any of the above values.

The glass transition refers to a change in the viscosity of a substance such as glass which is liquid at a high temperature due to a decrease in temperature due to a decrease in temperature, thereby causing an almost loss of fluidity. The method for measuring the glass transition temperature is not particularly limited, and generally means a glass transition temperature calculated by thermogravimetry, differential scanning calorimetry, differential calorimetry, and dynamic viscoelasticity measurement. Among them, dynamic viscoelasticity measurement is preferred.

The glass transition temperature of the (meth) acrylate homopolymer is in J. Brandrup, EH Immergut, Polymer Handbook, 2nd Ed., J. Wiley, New York 1975, Photocuring Technical Data Sheet (TECHNONETBooks Press), etc. There are records.

Among these ultraviolet curable compounds whose homopolymer glass transition temperature is -100 to 60 ° C, a compound conforming to the general formula (2) is preferred from the viewpoint of having a large adhesiveness. Formula (2) ZOR ₁ [wherein, Z represents a (meth) acrylonitrile group, and R ₁ represents a functional group having an aromatic ring or a hydrocarbon group having 9 to 20 carbon atoms. 〕

The compound of the formula (2) further improves the flexibility of the cured product, and further improves the adhesion to polyethylene terephthalate or the like. Examples of the compound of the formula (2) include (meth)acrylic acid having an aromatic ring such as a nonylphenyl group, a nonylphenoxy polyethylene glycol group, a phenoxy group or a phenoxyethylene group. Ester; having fluorenyl, isodecyl, fluorenyl, isodecyl, dodecyl, lauryl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl An ester of (meth)acrylic acid having a hydrocarbon group having 9 to 20 carbon atoms such as octadecyl group, nonadecyl group or eicosyl group. Among them, a linear or branched alkyl group having 9 to 20 carbon atoms is preferable, an alkyl group having 10 to 16 carbon atoms is more preferable, and an alkyl group having 11 to 14 carbon atoms is most preferable, and preferably selected. One or more of the group consisting of lauric acid and isostearyl groups. More than one of the above (meth) acrylates may be used. The number of aromatic rings is, for example, 1, 2 or 3, preferably 1.

(Component (C): Compound having one mercapto group) The mercapto group-containing compound in the present embodiment may be exemplified by the following materials.

((C1) component: alkyl mercaptan) The alkyl mercaptan is a mercaptan having an alkyl group. The alkyl group may be a linear structure or a branched structure. Among the alkyl mercaptans, an alkyl mercaptan represented by the following formula (1) is preferred. C _n H _2n+1 SH Formula (1) (wherein n is an integer), and n is preferably 4 to 19, and more preferably 6 to 12.

Among the alkyl mercaptans, decanethiol and/or dodecanethiol are preferred.

((C2) component: carboxy thiol) The carboxy thiol is a thiol having a carboxyl group. Among the carboxy thiols, a carboxy thiol represented by the following formula (2) is preferred. ROOC(CH ₂ ) _p SH Formula (2) (wherein R is hydrogen or a hydrocarbon group having 1 to 19 carbon atoms, and p is an integer), and the hydrocarbon group of the above R preferably has 2 to 16 carbon atoms, more preferably 5~12. The above p is preferably from 1 to 30, and more preferably from 1 to 2.

Examples of the carboxy thiol include thioglycolic acid, β-mercaptopropionic acid, thioglycolate (methyl thioglycolate, octyl thioglycolate, etc.), and β-mercaptopropionate (methyl 3-mercaptopropionate, 3) - methyl mercaptopropionate, n-octyl 3-mercaptopropionate, stearic acid 3-mercaptopropionate, and the like. Among the carboxy thiols, thioglycolic acid and/or β-mercaptopropionic acid are preferred.

(Component (D): Photopolymerization Initiator) The photopolymerization initiator of the present embodiment may, for example, be the following. The photopolymerization agent is not particularly limited as long as it is a material in which the (meth) acrylate having a homopolymer glass transition temperature of -100 ° C to 60 ° C starts to polymerize.

Examples of the photopolymerization initiator include an ultraviolet polymerization initiator and a visible light polymerization initiator, and the like can be used without any limitation. Examples of the ultraviolet polymerization initiator include benzoin, benzophenone, and acetophenone. Examples of the visible light polymerization initiator include fluorenylphosphine oxides, 噻 ketones, metallocenes, 醌 and α-aminoalkylphenones.

Examples of the photopolymerization initiator include benzophenone, 4-phenylbenzophenone, benzamidine benzoic acid, 2,2-diethoxyacetophenone, and bisdiethylaminobenzophenone. , 苄 base, benzoin, benzamidine isopropyl ether, 苄 dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 噻 ketone, 2-methyl 噻 tons of ketone, 2,4-dimethyl 噻 tons of ketone, isopropyl 噻 tons of ketone, 2,4-diethyl 噻 tons of ketone, 2,4-two Isopropyl 噻 ketone, 1-(4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 1-(4-(2-hydroxyethoxy)-benzene 2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, camphor 醌, 2,4,6 -trimethylbenzimidium diphenylphosphine oxide, bis(2,4,6-trimethylbenzhydrazide)-phenylphosphine oxide, 2-methyl-1-(4-(methylthio) Phenyl)-2-?啉 generation propane-1-one, 2-苄yl-2-dimethylamino-1-(4-?啉 phenyl)-1- Butanone-1,2-dimethylamino-2-(4-methyl-苄yl)-1-(4-?啉-4-yl-phenyl)-butane-1 -ketone, bis(2,6-dimethoxybenzamide)-2,4,4-trimethyl - pentyl phosphine oxide and the like.

(E) component: (meth) acrylate other than (A) and (B)) The curable resin composition of this embodiment is especially used in order to further improve the adhesiveness of each adhesive body as a (E) component. The component (E) may contain: (A) a urethane (meth) acrylate oligomer, a polyester (meth) acrylate oligomer, a polyether (meth) acrylate oligomer, and an epoxy a (meth) acrylate oligomer, a diene polymer (meth) acrylate oligomer, and an oligomer having a skeleton of a hydrogen additive of a diolefin polymer (meth) acrylate, Alternatively, the (B) homopolymer glass transition temperature is (meth) acrylate other than (meth) acrylate at -100 ° C to 60 ° C.

As the (E) component ((meth)acrylate other than (A) and (B)), various monofunctional (meth)acrylates or difunctional, trifunctional, tetrafunctional, pentafunctional, and hexafunctional groups can be used. A polyfunctional (meth) acrylate or the like. Among them, a monofunctional (meth) acrylate or a difunctional (meth) acrylate is preferable.

In the component (E) of the present embodiment, examples of the monofunctional (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (methyl). ) stearyl acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, bicyclo (meth) acrylate Pentene ester, isobornyl (meth)acrylate, (meth)acrylic acid 苄 ester, phenyl (meth)acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene Alcohol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy ethyl (meth) acrylate, Nonylphenoxytetraethylene glycol (meth) acrylate, methoxy diethylene glycol (meth) acrylate, ethoxy diethylene glycol (meth) acrylate, butoxyethyl ( Methyl) acrylate, butoxy triethylene glycol (meth) acrylate, 2-ethylhexyl polyethylene glycol (meth) acrylate, thiol ﾌ phenyl polypropylene glycol (methyl) Acrylate, methoxydipropylene glycol (methyl Acrylate, glycidyl (meth)acrylate, glyceryl (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, epichlorohydrin (hereinafter abbreviated as ECH) Modification of butyl (meth)acrylate, epichlorohydrin (hereinafter abbreviated as ECH) modified phenoxy (meth) acrylate, ethylene oxide (hereinafter abbreviated as EO) modified phthalic acid (methyl Acrylate, EO modified succinic acid (meth) acrylate, caprolactone modified 2-hydroxyethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N,N-diethylaminoethyl (meth) acrylate, &啉 generation (meth) acrylate, EO modified phosphoric acid (meth) acrylate, and the like. A (meth) acrylate having a quinone imine group such as quinone imine (meth) acrylate (product name: M-140, manufactured by Toagosei Co., Ltd.) may be mentioned.

In the above-mentioned component (E), as the monofunctional (meth) acrylate, in order to improve the adhesiveness to a polyolefin such as a cycloolefin polymer, dicyclopenteneoxyethyl group (A) may be mentioned. (meth) acrylate having a dicyclopentenyl group represented by acrylate, dicyclopentenyloxypropyl (meth) acrylate, dicyclopentenyl (meth) acrylate or the like.

Among the monofunctional (meth) acrylates in the component (E), from the viewpoint of improving the adhesion to the cycloolefin, a (meth) acrylate having a dicyclopentenyl group and/or an isobornyl group is more preferable. (Meth) acrylate.

In the component (E) of the present embodiment, examples of the polyfunctional (meth)acrylate include di(meth)acrylated isocyanide 脲 acid ester, tri(meth)acrylated isocyanide &# 33074; acid ester, 1,3-dibutanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylic acid Ester, 1,9-nonanediol di(meth)acrylate, EO (ethylene oxide) modified bisphenol A di(meth)acrylate, diethylene glycol di(meth)acrylate, ECH (epichlorohydrin) modified hexahydrophthalic acid di(meth) acrylate, neopentyl glycol di(meth) acrylate, EO modified neopentyl glycol di(meth) acrylate, Ester-modified hydroxypivalate neopentyl glycol di(meth)acrylate, stearic acid modified pentaerythritol di(meth)acrylate, ECH modified phthalic acid diacrylate, poly(ethylene glycol Tetramethylene glycol) di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ECH modified propylene glycol di(meth)acrylate, three Cyclodecane dimethanol (meth) acrylate, tripropylene glycol di(a) ) acrylate, triglycerin di(meth) acrylate, ECH modified glycerol tri(meth) acrylate, pentaerythritol tri (meth) acrylate, EO modified tris (meth) acrylate, trishydroxyl Propane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, EO modified trimethylolpropane tri(meth)acrylate, PO modified trishydroxyl Propane tri(meth) acrylate, tris((meth) propylene methoxyethyl) isocyanide 脲 acid ester, dipentaerythritol hexa(meth) acrylate, pentaerythritol tetra(meth) acrylate Pentaerythritol ethoxytetra(meth)acrylate.

In the above-mentioned component (E), examples of the polyfunctional (meth) acrylate include a (meth) acrylate having a dicyclopentenyl group represented by dicyclopentenyl bis(meth)acrylate or the like. . Among the polyfunctional (meth) acrylates in the above component (E), trimethylolpropane tri(meth) acrylate and/or tricyclodecane dimethanol are more preferable in view of oligomer solubility. (Meth) acrylate.

In the present embodiment, a decane coupling agent may be contained in order to increase the adhesion to the glass.

The curable resin composition of the present embodiment contains, as an essential component, (A) selected from the group consisting of urethane (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and polyethers (A). Acrylate oligomer, epoxy (meth) acrylate oligomer, diolefin polymer (meth) acrylate oligomer, and diolefin polymer (meth) acrylate One or more (meth) acrylate oligomers in the group consisting of oligomers of the skeleton of the hydrogen additive; (B) the glass transition temperature of the homopolymer is (100) at -100 ° C to 60 ° C Acrylate; (C) a compound having one mercapto group; and (D) a photopolymerization initiator. The curable resin composition of the present embodiment can achieve curing by ultraviolet light or visible light.

In the curable resin composition of the present embodiment, the mass ratio of the component (A) to the component (B) is considered to be high in adhesiveness and good in curability, and in the component (A) and (B) Among the total of 100 parts by mass of the components, component (A): component (B) = 10 to 95: 90 to 5, more preferably component (A): component (B) = 25 to 90: 75 to 10. The numerical value of the component (A) at the time of expressing the ratio is not particularly limited, and may be, for example, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 95, or may be within the range of any of the above values. . Further, the numerical value of the component (B) at the time of expressing the ratio is not particularly limited, and may be, for example, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 95, or may be any of the above values. Within the scope.

The amount of the component (C) to be used is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 100 parts by mass based on 100 parts by mass of the total of the component (A), the component (B) and the component (E) to be used. 8 parts by mass. The amount of use is not particularly limited and may be, for example, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 15, and may be in the range of any of the above values. .

The amount of the component (D) to be used is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 100 parts by mass based on 100 parts by mass of the total of the component (A), the component (B) and the component (E) to be used. 10 parts by mass. The amount of use is not particularly limited and may be, for example, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20 or 25, or may be any of the above Within the range of values.

The amount of the component (E) to be used is preferably 1 to 30 parts by mass, and more preferably 5 to 15 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). The amount of use is not particularly limited and may be, for example, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 30 or 35, or may be within the range of any of the above values. .

In addition, in order to accelerate the curing of the portion in contact with the air of the curable resin composition of the present embodiment, various paraffin waxes can be used.

Further, in order to maintain storage stability, a commercially available antioxidant or the like containing a polymerization inhibitor may be used.

Further, in addition to the above, a known substance such as an elastomer, a plasticizer, a filler, a colorant or a rust preventive agent may be used as needed.

The curable resin composition in the present embodiment can be used as an adhesive composition. In another embodiment, the cured body of the adhesive composition may be used to bond or coat the adherend to produce a composite. The cured product can be obtained, for example, by UV irradiation of the adhesive composition. The various materials of the adherend are preferably one or more selected from the group consisting of polyolefins such as triacetyl cellulose, fluoropolymer, polyester, polycarbonate, and cycloolefin polymer, glass, and metal. It is preferably one or more selected from the group consisting of polycarbonate, polyolefin, and glass.

The cured product which is adhered by the curable resin composition of the present embodiment can be reconstituted (recycled) after being completely cured. The method of the reconstitution is not particularly limited, and the adherends can be disintegrated by loading a load of 0.01 to 100 N between the adhered one or two kinds of adherends, and the disassembled adherend can be reused.

Although the embodiment of the present invention has been described above, all of the above are examples of the present invention, and various configurations other than the above may be employed. Further, the configuration described in the above embodiment may be used in combination. [Examples]

Hereinafter, the present invention will be described in more detail by way of Experimental Examples, but the present invention is not limited by these Examples. In the curable resin composition described in the examples, the following compounds were selected.

As a material selected from the group consisting of urethane (meth) acrylate oligomers, polyester (meth) acrylate oligomers, polyether (meth) acrylate oligomers, and epoxy (meth) acrylates One or more of the group consisting of oligomers, diene polymer (meth) acrylate oligomers, and oligomers having a skeleton of a hydrogen additive of a diolefin polymer (meth) acrylate (Meth) acrylate oligomer (A): (A-1) 1,2-polybutadiene modified urethane methacrylate oligomer ("TE-2000" manufactured by Nippon Soda Co., Ltd.) GPC polystyrene-equivalent number average molecular weight of 2000, difunctional methacrylate oligomer), (A-2) mixture of acrylate polymer and urethane acrylate oligomer (manufactured by Osaka Organic Chemical Industry Co., Ltd.) PM-654") (polystyrene-converted number average molecular weight 20,000 by GPC, difunctional acrylate oligomer), (A-3) polyester urethane acrylate oligomer (KHP-made by Kokusai Kogyo Co., Ltd.) 17") (weight-average molecular weight of 40,000 polystyrene-equivalent acrylate oligomer using GPC), (A-4) dibutene diol polyamine Ester acrylate oligomer ("UV-3000B" manufactured by Nippon Synthetic Chemical Co., Ltd. (weight average molecular weight 18,000 in terms of polystyrene by GPC, difunctional acrylate oligomer), (A-5) polycarbonate polyurethane Acrylate oligomer ("UN-9000PEP" manufactured by Kokusai Kogyo Co., Ltd.) (weight-average molecular weight 5000 using polystyrene equivalent of GPC, difunctional acrylate oligomer), (A-6) polyether urethane-based acrylic acid Ester oligomer ("UV-3700B" manufactured by Nippon Synthetic Chemical Co., Ltd.) (weight-average molecular weight of 38,000 in terms of polystyrene by GPC, difunctional acrylate oligomer); as a homopolymer glass transition temperature is shown as - (M) acrylate (B) at 100 to 60 ° C: (B-1) EO modified nonyl phenyl acrylate ("M-111" manufactured by Toagosei Co., Ltd.: homopolymer glass transition temperature: -25 °C), (B-2) isostearyl acrylate ("ISTA" manufactured by Osaka Organic Chemical Industry Co., Ltd.: homopolymer glass transition temperature: -18 ° C), (B-3) 4-hydroxybutyl acrylate ("4-HBA" manufactured by Nippon Kasei Co., Ltd.: homopolymer glass transition temperature: -80 ° C); as a mercapto group-containing compound (C): (C-1) n-decyl mercaptan ( Ardorich "decanethiol"), (C-2) n-dodecyl mercaptan ("dodecanethiol" by Ardorich), (C-3) β-mercaptopropionic acid (SC organic chemical industry) Company "BMPA"), (C-4) 3-mercaptopropionate n-octyl ester ("NOMP" manufactured by SC Organic Chemical Industry Co., Ltd.); as photopolymerization initiator (D): (D-1) 1-hydroxyl ring Hexyl phenyl ketone ("Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.), (D-2) phenyl bis(2,4,6-trimethylbenzhydrazide) phosphine oxide ((Ciba Specialty) (Irgacure 819) manufactured by Chemicals Inc.); (meth) acrylate (E) other than (A) and (B): (E-1) dicyclopentenylacrylate (manufactured by Hitachi Chemical Co., Ltd.) FA-511AS": homopolymer glass transition temperature: 120 ° C), (E-2) dicyclopentenyldiacrylate ("DCP" manufactured by Shin-Nakamura Chemical Co., Ltd.): homopolymer glass transition temperature: 100 ° C), (E-3) tricyclodecanedimethanol acrylate (KAYARADR-684, manufactured by Nippon Kayaku Co., Ltd.: homopolymer glass transition temperature: 150 ° C), (E-4) Trimethylolpropane III Trimethylolpropane triacrylate ("A-TMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.: homopolymer glass transition temperature: >250 ° C), (E-5) isobornylacrylate (Hitachi Chemical Co., Ltd.) Company-made "IBXA": homopolymer glass transition temperature: 180 ° C); as a comparative example: (C-5) DMDO: triglycoldimercaptan ("DMDO" manufactured by Maruzen Oil Chemical Co., Ltd.), (C -6) 3-mercaptopropyltrimethoxysilane ("KBM-803" manufactured by Shin-Etsu Chemical Co., Ltd.).

Various physical properties were determined as follows.

[Glass transition temperature] The measurement was carried out by dynamic viscoelasticity measurement.

[Photocurability] The measurement was carried out at a temperature of 23 °C. With respect to photocurability, a curable resin composition was applied to the surface of TEMPAX glass (25 × 25 × 2 mm) to have a thickness of 0.1 mm. Then, UV light having a wavelength of 365 nm was irradiated and cured by a curing device manufactured by Fusion Co., Ltd. using an electrodeless discharge lamp under conditions of a cumulative light amount of 2000 mJ/cm ² . It should be noted that the evaluation of photocurability was calculated by FT-IR. Based on the assignment of the non-reactive reaction, the attenuation of the C=C double bond-associated peak such as 1600 cm ^{-1 was} confirmed and calculated before and after the irradiation.

[Polyethylene terephthalate (PET) adhesive evaluation (peeling adhesive strength between polyethylene terephthalate test sheets)] Using a curable resin composition as an adhesive composition, The thickness of the adhesive layer was 30 μm so that the adhesive area was 40 mm in the longitudinal direction and 10 mm in the transverse direction, and the test pieces (50 mm × 10 mm × 0.19 mm) of the biaxially stretched PET film (lumirror T60, average thickness: 190 μm, manufactured by Toray Industries, Inc.) were adhered to each other. After curing by light irradiation, the portions of the film which were not adhered by the adhesive sheet which were adhered by the adhesive were stretched, and the portions where the films were in close contact with each other were peeled off, and the initial 180° peeling adhesive strength was measured. The light irradiation conditions are based on the method described in [Photocurability]. In addition, the peeling adhesive strength (unit: N/cm) was measured at a tensile speed of 10 mm/min in an environment of a temperature of 23 ° C and a humidity of 50% using a tensile tester.

[Glass Adhesive Evaluation (Tensile Adhesive Strength Between Heat-Resistant Glass Test Pieces)] A Teflon (registered trademark) tape having a thickness of 80 μm × a width of 12.5 mm × a length of 25 mm was used as a spacer, and a curable resin composition was used. The heat-resistant glass test pieces (25 mm × 25 mm × 2.0 mm) were adhered to each other (adhesive area: 3.125 cm ² ). The light irradiation conditions are in accordance with the method described in [Photocurability]. After the adhesive composition was cured under the above conditions, the adhesive composition "G-55" made of Electrochemical Industry Co., Ltd., and the galvanized steel sheet (100 mm × 25 mm × 2.0 mm, were further used on both surfaces of the test piece. EngineeringTest Service company). After curing, the test piece adhered with the adhesive composition was used, and the galvanized steel sheet was clamped, and the initial tensile shear adhesive strength was measured. For the tensile shearing adhesive strength (unit: MPa), the tensile tester was used, and the measurement was carried out at a tensile speed of 10 mm/min in an environment of a temperature of 23 ° C and a humidity of 50%.

[Evaluation of adhesiveness of cycloolefin polymer (COP) (peeling adhesive strength between test pieces of cycloolefin polymer)] Using a curable resin composition as an adhesive composition, the thickness of the adhesive layer was 10 μm, and the adhesive The adhesive area was 40 mm in the longitudinal direction and 10 mm in the lateral direction, and the test pieces (50 mm × 10 mm × 0.04 mm) of the COP film (ZEONOR, average thickness: 40 μm, manufactured by Nippon Seychelles Co., Ltd.) were adhered to each other. After curing by light irradiation, the portions of the film which were not adhered by the adhesive sheet which were adhered by the adhesive were stretched, and the portions where the films were in close contact with each other were peeled off, and the initial 180° peeling adhesive strength was measured. The light irradiation conditions are in accordance with the method described in [Photocurability]. In addition, the peeling adhesive strength (unit: N/cm) was measured at a tensile speed of 10 mm/min in an environment of a temperature of 23 ° C and a humidity of 50% using a tensile tester.

[Evaluation of adhesiveness of triacetyl cellulose (peeling adhesive strength between triacetonitrile cellulose test pieces)] Using a curable resin composition as an adhesive composition, with a thickness of 10 μm of adhesive layer, adhesive The area was 40 mm in the longitudinal direction and 10 mm in the lateral direction, and the test pieces (width 50 mm × length 10 mm × thickness 0.04 mm) of a triacetyl cellulose (TAC) film (average thickness 40 μm, manufactured by Fuji Film Co., Ltd.) were adhered to each other. After curing by light irradiation, the portions of the film which were not adhered by the adhesive sheet which were adhered by the adhesive were stretched, and the portions where the films were in close contact with each other were peeled off, and the initial 180° peeling adhesive strength was measured. The light irradiation conditions are in accordance with the method described in [Photocurability]. In addition, the peeling adhesive strength (unit: N/cm) was measured at a tensile speed of 50 mm/min in an environment of a temperature of 23 ° C and a humidity of 50% using a tensile tester.

[Evaluation of adhesiveness of fluoropolymer (peeling adhesive strength between test pieces of fluorine-containing film)] Using a curable resin composition as an adhesive composition, the thickness of the adhesive layer was 10 μm, and the adhesive area was longitudinal. 40 mm × 10 mm in the transverse direction, a test piece (width 50 mm × length 10 mm × thickness 0.04 mm) of a PVDF film (average thickness 40 μm, "DX film" manufactured by Denki Kagaku Kogyo Co., Ltd.) was adhered to each other. After curing by light irradiation, the portions of the film which were not adhered by the adhesive sheet were stretched, and the portions where the films were in close contact with each other were peeled off, and the initial 180° peeling adhesive strength was measured. The light irradiation conditions are in accordance with the method described in [Photocurability]. In addition, the peeling adhesive strength (unit: N/cm) was measured at a tensile speed of 50 mm/min in an environment of a temperature of 23 ° C and a humidity of 50% using a tensile tester.

[Polyurethane Adhesive Evaluation (Tensile Adhesive Strength Between Polycarbonate Test Pieces)] Teflon (registered trademark) tape having a thickness of 80 μm × 11.5 mm in width × 25 mm in length was used as a liner, and curability was used. The resin composition was made to have a polycarbonate (Panglite) test piece (width: 25 mm × length 25 mm × thickness: 2.0 mm) adhered to each other (adhesive area: 3.125 cm ² ). The light irradiation conditions are in accordance with the method described in [Photocurability]. After the adhesive composition was cured under the above conditions, the adhesive composition "G-55" made of Electrochemical Industry Co., Ltd., and the galvanized steel sheet (100 mm × 25 mm × 2.0 mm, were further used on both surfaces of the test piece. EngineeringTest Service company). After curing, the test piece adhered with the adhesive composition was used, and the galvanized steel sheet was clamped, and the initial tensile shear adhesive strength was measured. For the tensile shearing adhesive strength (unit: MPa), the tensile tester was used, and the measurement was carried out at a tensile speed of 10 mm/min in an environment of a temperature of 23 ° C and a humidity of 50%.

[Metal Adhesiveness Evaluation (Tensile Adhesive Strength Between SPCC Test Pieces)] A Teflon (registered trademark) tape having a thickness of 80 μm × 11.5 mm in width × 25 mm was used as a spacer, and a curable resin composition was used. The SPCC test piece (width 25 mm x length 25 mm x thickness 1.6 mm) was glued to TEMPAX glass (width 25 mm x length 25 mm x thickness 2 mm) (adhesive area 3.125 cm ² ). The light irradiation conditions are in accordance with the method described in [Photocurability]. After the adhesive composition was cured under the above conditions, an adhesive composition "G-55" adhesive galvanized steel sheet made of Electrochemical Industry Co., Ltd. was used on the TEMPAX test sheet side (width 100 mm × length 25 mm × thickness 2.0 mm, Engineering Test Service). After curing, the test piece adhered with the adhesive composition was used, and the galvanized steel sheet was clamped, and the initial tensile shear adhesive strength was measured. For the tensile shearing adhesive strength (unit: MPa), the tensile tester was used, and the measurement was carried out at a tensile speed of 10 mm/min in an environment of a temperature of 23 ° C and a humidity of 50%.

[Damp heat resistance evaluation (stretching adhesive strength between heat-resistant glass test pieces after high-temperature and high-humidity exposure)] Using a curable resin composition as an adhesive composition, the thickness of the adhesive layer is 100 μm, and the adhesive area is For 1.0 mm ² , TEMPAX glass (25 mm × 25 mm × 2 mm) was adhered to each other and cured. The light irradiation conditions are in accordance with the method described in [Photocurability]. After curing, the test piece adhered with the adhesive composition was exposed to an environment of a temperature of 85 ° C and a relative humidity of 85% for 1000 hours using a constant temperature and humidity chamber. The tensile shear strength was measured using the exposed test piece. The appearance of the adhesive portion was visually observed to examine whether yellowing occurred. After the exposure, a "G-55" adhesive galvanized steel sheet (width 100 mm × length 25 mm × thickness 2.0 mm, manufactured by Engineering Test Service Co., Ltd.) made of an electric chemical industry company was further used on the TEMPAX test piece side. After curing, the test piece adhered with the adhesive composition was used, and the galvanized steel sheet was clamped, and the initial tensile shear adhesive strength was measured. For the tensile shearing adhesive strength (unit: MPa), the tensile tester was used, and the measurement was carried out at a tensile speed of 10 mm/min in an environment of a temperature of 23 ° C and a humidity of 50%.

[Appearance observation (degree of yellowness)] Using a curable resin composition as an adhesive composition, the thickness of the adhesive layer was 100 μm, the adhesive area was 1.0 mm 2 , and the TEMPAX glass (25 mm × 25 mm × 2 mm) were glued to each other and allowed to cure. The light irradiation conditions are in accordance with the method described in [Photocurability]. After the curing, Δb of the test piece adhered with the adhesive composition was measured as a yellowing degree by a color measuring device ("UV-VISIBLE SPECTROPOHOTOMETER" manufactured by SHIMADZU Co., Ltd.).

(Experimental Example) A curable resin composition having the compositions shown in Tables 1 to 4 was prepared, and various physical properties were measured. The results are shown in Tables 1 to 4.

【Table 1】

【Table 2】

【table 3】

【Table 4】

According to this experimental example, the following is known. The material provided by the invention has high adhesiveness. The substance provided by the present invention has a high degree of moist heat resistance because it has flexibility to the extent that it can follow the deformation of the adherend in a heating atmosphere. When DMDO which is a compound having two or more mercapto groups is used, flexibility and adhesiveness are small. [Industrial use possibilities]

In the material provided by the present invention, since bubbles are less likely to be mixed, it is possible to impart sufficient adhesiveness, and it is possible to bond a transparent substrate and bond a portion to be printed. The substance provided by the present invention can be used in a heating atmosphere because of its high heat and humidity resistance. The present invention is industrially available.

Claims (16)

A curable resin composition comprising: (A) selected from the group consisting of polyurethane (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and polyether (meth) acrylate oligomers , an epoxy (meth) acrylate oligomer, a diene polymer (meth) acrylate oligomer, and a skeleton of a hydrogen additive having a diolefin polymer (meth) acrylate One or more (meth) acrylate oligomers in the group consisting of oligomers; (B) (meth) acrylate having a glass transition temperature of -100 ° C to 60 ° C; (C) One or more compounds having one fluorenyl group in the group selected from the group consisting of alkyl thiols and carboxy thiols; and (D) a photopolymerization initiator. The curable resin composition according to the first aspect of the invention, further comprising (E) a (meth) acrylate other than the above (A) and (B). The curable resin composition according to claim 2, wherein the component (E) is trimethylolpropane tri(meth)acrylate and/or tricyclodecane dimethanol (meth)acrylate. . The curable resin composition according to any one of claims 1 to 3, wherein the compound having one mercapto group in the molecule of (C) is an alkylsulfide represented by the following formula (1) Alcohol, C _n H _2n+1 SH In the formula (1), n is an integer of 4 to 19. The curable resin composition according to any one of claims 1 to 3, wherein the compound containing one thiol group in the molecule of (C) is a carboxy thiol represented by the following formula (2). ,ROOC(CH ₂ ) _p SH In the formula (2), R is hydrogen or a hydrocarbon group having 1 to 19 carbon atoms, and p is an integer. The curable resin composition according to any one of claims 1 to 3, wherein the component (A) has a weight average molecular weight of 500 to 100,000. The curable resin composition according to any one of claims 1 to 3, wherein the component (A) has a number average molecular weight of 500 to 100,000. The curable resin composition according to any one of claims 1 to 3, wherein the component (A) is a urethane (meth) acrylate oligomer. An adhesive composition comprising the curable resin composition according to any one of claims 1 to 3. A cured product which is a cured product of the adhesive composition according to claim 9 of the patent application. A composite obtained by coating or joining a cured product as described in claim 10 of the patent application. The composite according to claim 11, wherein the adherend is one selected from the group consisting of triacetyl cellulose, fluoropolymer, polyester, polycarbonate, polyolefin, glass, and metal. the above. A touch panel laminate obtained by bonding an adhesive composition as described in claim 9 of the patent application. A liquid crystal panel laminate obtained by adhering an adhesive body with an adhesive composition as described in claim 9 of the patent application. A display using the touch panel laminate as described in claim 13 of the patent application. A display using the liquid crystal panel laminate as described in claim 14.