JP2013253117A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition exhibiting excellent adhesion durability.SOLUTION: A curable resin composition includes: an oligomer (A) having a diene-based or a hydrogenated diene-based skeleton; a (meth)acrylate (B) exhibiting a homopolymer glass transition temperature of from -100°C to 60°C; a photopolymerization initiator (C); a thermal polymerization initiator (D); and a reducing agent (E). A lauryl methacrylate and a 2-hydroxyethyl methacrylate are usable as the component (B). Preferably, the component (D) is an organic peroxide, and the reducing agent (E) is a thiourea derivative, β-diketone chelate, or β-ketoester. The curable resin composition may include a (meth)acrylate (F) except the components (A) and (B), and a silane coupling agent (G). Preferably, the skeleton of the component (A) is polybutadiene, polyisoprene, hydrogenated polybutadiene, or hydrogenated polyisoprene. The curable resin composition can be used as an adhesive composition and can be used in touch panel laminates and liquid crystal panel laminates.

Description

The present invention relates to a curable resin composition.

There are a resistive film type, a capacitance type, an electromagnetic induction type, an optical type and the like as a touch panel mounted on a display body such as an LCD (liquid crystal display). There is a case where a decorative board for improving the appearance design and an icon sheet for designating a touch position are attached to the surface of these touch panels. The capacitive touch panel has a structure in which a transparent electrode is formed on a transparent substrate and a transparent plate is bonded thereon.

Conventionally, the bonding of the decorative plate and the touch panel, the bonding of the icon sheet and the touch panel, and the bonding of the transparent substrate and the transparent plate have used an adhesive. The technique using such an adhesive has a problem of insufficient adhesion (Patent Document 1).

In recent years, the glass of a display body such as an LCD has become thinner. When the glass becomes thinner, the LCD is easily deformed by external stress. When this thin glass LCD or other optical display material is bonded to an optical functional material such as an acrylic plate or a polycarbonate plate, the difference in linear expansion between the glass and acrylic or the molding of a plastic molding material such as an acrylic plate or polycarbonate Due to this distortion, mold distortion is relaxed and moisture absorption / drying occurs in the heat resistance test and moisture resistance test, and surface accuracy changes such as dimensional changes and warpage occur. When trying to suppress this deformation with a conventional adhesive (for example, Patent Document 2), there are problems that the adhesive surface is peeled off, the LCD is cracked, or the LCD becomes uneven in display.

As a solution to the above problem, there is a UV curable resin as in Patent Document 3. Since Patent Document 3 is a highly elastic resin based on a rigid skeletal monomer such as isobornyl (meth) acrylate, it cannot withstand the expansion and contraction of the adherend in a high temperature reliability test, causing peeling. There was a possibility.

When the bonded surface is printed, there is a problem that the printed portion is difficult to bond with light energy rays and the adhesiveness is lowered due to the influence of the uncured portion.

For applications such as bonding of decorative plates and touch panels, bonding of icon sheets and touch panels, bonding of transparent substrates and transparent plates, etc. It is considered desirable to have sex.

International Publication No. 2010/027041 Japanese Patent Laid-Open No. 2004-77887 JP-A 64-85209

The present invention provides, for example, sufficient adhesion when a decorative plate or icon sheet used for a display body such as a touch panel is bonded, when a transparent substrate and a transparent substrate are bonded, or when a printed part is bonded. Resolves the problems of the prior art that it is difficult to impart properties, or the problems of the prior art that the adhesive surface peels off or the glass of the display breaks when the display and optical functional material are bonded together A curable resin composition is provided.

That is, this invention is curable resin composition containing the following (A)-(C) component,
(A) Oligomer having a diene-based or hydrogenated diene-based skeleton (B) Homopolymer (meth) acrylate (C) photopolymerization initiator (D) thermal polymerization initiation having a glass transition temperature of −100 to 60 ° C. The curable resin composition in which the agent (E) reducing agent (B) component is a compound of the general formula (1) and / or a compound of the general formula (2),
General formula (1) Z—O—R ₁
[Wherein, Z represents a (meth) acryloyl group, and R ₁ represents an alkyl group having 9 to 20 carbon atoms. ]
General formula (2) Z—O—R ₂ —OH
[In formula, Z shows a (meth) acryloyl group and R2 represents a C2-C20 alkylene group. ]
Furthermore, it is this curable resin composition containing (meth) acrylate other than (A) component and (B) component as (F) component, and also contains a silane coupling agent as (G) component. The curable resin composition, wherein the (A) component diene-based or hydrogenated diene-based skeleton is selected from the group consisting of polybutadiene, polyisoprene, a polybutadiene hydrogenated product, and a polyisoprene hydrogenated product. The curable resin composition having one or more skeletons, wherein the molecular weight of the oligomer (A) having a diene-based or hydrogenated diene-based skeleton is 500 to 70000 (C) the curable resin composition in which the thermal polymerization initiator is an organic peroxide, and (D) the reducing agent is a thiourea derivative, β-diketone chelate and β-ketoester 1 type or 2 types or more of these curable resin compositions, wherein the first agent contains at least (C) a thermal polymerization initiator, and the second agent contains at least (D) a reducing agent. The curable resin composition, wherein the first agent comprises at least (C) a thermal polymerization initiator, and the second agent comprises at least (D) a primer comprising a reducing agent and a solvent. A curable resin composition, an adhesive composition comprising the curable resin composition, a cured product of the adhesive composition, and a composite in which an adherend is coated or bonded by the cured product. And the adherend is a composite which is at least one selected from the group consisting of triacetylcellulose, fluoropolymer, polyester, polycarbonate, polyolefin, glass, and metal, and the adherend is formed by the adhesive composition. Bonded touch panel A layer material, by adhesive composition is a liquid crystal panel laminate bonded to the adherend, a display using the touch panel laminate is a display using the liquid crystal panel laminate.

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

The component (A) in the present invention is an oligomer having a diene-based or hydrogenated diene-based skeleton.

The main chain skeleton of the oligomer in the present invention is a diene-based or hydrogenated diene-based skeleton. The diene-based or hydrogenated diene-based skeleton is preferably at least one skeleton selected from the group consisting of polybutadiene, polyisoprene, a hydrogenated polybutadiene, and a hydrogenated polyisoprene. Among these, at least one selected from the group consisting of polybutadiene and polyisoprene is preferable, and polybutadiene is more preferable in terms of high adhesion durability.

The oligomer preferably has one or more (meth) acryloyl groups at the terminal or side chain of the main chain skeleton. Among these, those having (meth) acryloyl groups at both ends of the main chain skeleton are preferable.

The molecular weight of the oligomer is preferably 500 to 70000, more preferably 1000 to 60000, and most preferably 1000 to 55000. If the molecular weight is 500 or more, the hardness of the cured product obtained by curing the curable resin composition of the present invention is high, so that it is easy to form an adhesive layer. When the molecular weight is 70,000 or less, the viscosity of the resulting curable resin composition is small, so that the workability in mixing during the production process and the workability in practical applications are improved.

The molecular weight of the oligomer refers to the number average molecular weight calculated as the average molecular weight per molecule. In the Example of this invention, the number average molecular weight of polystyrene conversion measured by GPC (gel permeation chromatography) was used.

As the oligomer of the component (A), “UC-203” manufactured by Kuraray (esterified oligomer of maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl methacrylate), “LIR-50” (isoprene manufactured by Kuraray) Oligomer), Kuraray "LBR-50" (butadiene oligomer), Nippon Soda "TEAI-1000" (terminally acrylic-modified hydrogenated 1,2-polybutadiene oligomer), Nippon Soda "TE-2000" ( 1,2-polybutadiene oligomer modified with terminal acrylic), “Byron” (amorphous polyester resin) manufactured by Toyobo Co., Ltd., and the like. Among these, isoprene oligomers and / or 1,2-polybutadiene oligomers are preferable, and 1,2-polybutadiene oligomers are more preferable.

The component (B) in the present invention is (meth) acrylate having a homopolymer glass transition temperature of −100 ° C. to 60 ° C. A (meth) acrylate having a homopolymer glass transition temperature of −80 ° C. to −40 ° C. is more preferable. (Meth) acrylate having a homopolymer glass transition temperature of −100 ° C. to 60 ° C. includes lauryl (meth) acrylate (acrylate homopolymer glass transition temperature: acrylate-30 ° C., methacrylate homopolymer glass transition temperature: −65 ° C), 2-ethylhexyl (meth) acrylate (homopolymer glass transition temperature of acrylate: -85 ° C, homopolymer glass transition temperature of methacrylate: -10 ° C), n-butyl (meth) acrylate (homopolymer glass transition of methacrylate) Temperature: 20 ° C., i-butyl (meth) acrylate (methacrylate homopolymer glass transition temperature: 20 ° C.), t-butyl (meth) acrylate (methacrylate homopolymer glass transition temperature: 20 ° C.), methoxyethyl (meth) Acry (Homopolymer glass transition temperature of acrylate: -50 ° C), ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate (homopolymer glass transition Temperature: 25 ° C., 2-hydroxyethyl (meth) acrylate (methacrylate homopolymer glass transition temperature: 55 ° C.), 2-hydroxypropyl (meth) acrylate (acrylate homopolymer glass transition temperature: −7 ° C., methacrylate Homopolymer glass transition temperature: 26 ° C.), 2-hydroxybutyl (meth) acrylate and the like. These (meth) acrylates can be used alone or in combination of two or more.

The glass transition refers to, for example, a change in which a substance such as glass that is liquid at a high temperature suddenly increases its viscosity in a certain temperature range due to a temperature drop, almost loses fluidity and becomes an amorphous solid. Examples of the method for measuring the glass transition temperature include thermogravimetry, differential scanning calorimetry, differential heat measurement, and dynamic viscoelasticity measurement.

The glass transition temperature of the (meth) acrylate homopolymer is described in J. Org. Brandrup, E .; H. Immergut, Polymer Handbook, 2nd Ed. , J .; Wiley, New York 1975, photocuring technology data book (Technonet Books, Inc.) and the like.

In these (B) components, the compound of General formula (1) and / or the compound of General formula (2) are preferable at a point with big adhesiveness.
General formula (1) Z—O—R ₁
[Wherein, Z represents a (meth) acryloyl group, and R ₁ represents an alkyl group having 6 to 20 carbon atoms. ]
General formula (2) Z—O—R ₂ —OH
Wherein, Z is shown a (meth) acryloyl group, _{R 2} represents 2-20 alkylene group having a carbon. ]

The compound of the general formula (1) further improves the flexibility of the cured product and further improves the adhesion to polyethylene terephthalate and the like. As the compound of the general formula (1), nonyl group, isononyl group, decyl group, isodecyl group, dodecyl group, lauryl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicodecyl group And (meth) acrylic acid ester having a linear or branched alkyl group having 9 to 20 carbon atoms such as a group. R ₁ is preferably an alkyl group having 10 to 16 carbon atoms, more preferably an alkyl group having 11 to 14 carbon atoms, and most preferably a lauryl group. These (meth) acrylates can be used alone or in combination of two or more.

(C) A component is a photoinitiator (henceforth a photoinitiator). The photopolymerization agent is not particularly limited as long as it initiates polymerization of (meth) acrylate such as component (A), component (B), and component (F).

(C) As a photoinitiator, although an ultraviolet polymerization initiator, a visible light polymerization initiator, etc. are mentioned, both are used without a restriction | limiting. Examples of the ultraviolet polymerization initiator include benzoin, benzophenone, and acetophenone. Examples of visible light polymerization initiators include acylphosphine oxides, thioxanthones, metallocenes, quinones, and α-aminoalkylphenones.

(C) Photoinitiators include benzophenone, 4-phenylbenzophenone, benzoylbenzoic acid, 2,2-diethoxyacetophenone, bisdiethylaminobenzophenone, benzyl, benzoin, benzoylisopropyl ether, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone Thioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropane-1 -One, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-fur Nylpropan-1-one, camphorquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-1- (4- (methylthio) phenyl ) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone-1,2-dimethylamino-2- (4-methyl-benzyl) ) -1- (4-Morifolin-4-yl-phenyl) -butan-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, and the like.

Component (D) is a thermal polymerization initiator. As the thermal polymerization initiator, an organic peroxide is preferable. Examples of organic peroxides include cumene hydroperoxide, paramentane hydroperoxide, tertiary butyl hydroperoxide, diisopropylbenzene dihydroperoxide, methyl ethyl ketone peroxide, benzoyl peroxide, and tertiary butyl peroxybenzoate. . Among these, cumene hydroperoxide is preferable in terms of reactivity.

The component (E) is a reducing agent. The reducing agent accelerates the decomposition of the thermal polymerization initiator and accelerates the curing of the curable resin composition.

(E) As a reducing agent, it is preferable that it is 1 type (s) or 2 or more types which consist of a thiourea derivative, (beta) -diketone chelate, and (beta) -ketoester. Examples of thiourea derivatives include acetyl-2-thiourea, benzoylthiourea, N, N-diphenylthiourea, N, N-diethylthiourea, N, N-dibutylthiourea, tetramethylthiourea and the like. Can be mentioned. Among these, the group consisting of acetyl-2-thiourea, benzoylthiourea, N, N-diphenylthiourea, N, N-diethylthiourea, N, N-dibutylthiourea, and tetramethylthiourea is effective. 1 type or 2 types or more consisting of is preferable, and acetyl-2-thiourea is more preferable. Examples of the β-diketone chelate include vanadyl acetylacetonate, cobalt acetylacetonate, and copper acetylacetonate. Examples of the β-ketoester include vanadyl naphthenate, vanadyl stearate, copper naphthenate, cobalt octylate and the like. These 1 type (s) or 2 or more types can be used. Among these, β-diketone chelates are preferable in terms of reactivity, and vanadyl acetylacetonate is more preferable.

 Component (E) can also be used as a primer. That is, the action as a curing accelerator can be improved by dissolving or dispersing the component (E) in a solvent to serve as a primer and using the primer as a second agent described later.

As the solvent, a volatile organic solvent is preferable. The volatile organic solvent preferably has a boiling point of 35 to 110 ° C. Examples of the volatile solvent having a boiling point of 35 to 110 ° C. include acetone, methanol, ethanol, butanol, isopropyl alcohol, ethyl acetate, toluene, methylene chloride, trichloroethane, tetrahydrofuran, hexane, diethyl ether, benzene, chloroform and the like. As the solvent, (meth) acrylate can also be used.

When used as a primer, the concentration of the component (F) in the primer is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass.

The curable resin composition of the present invention contains a (meth) acrylate other than the component (A) or the component (B) as the component (F), particularly for the purpose of further improving the adhesion to each adherend. can do. Examples of (meth) acrylates other than component (A) and component (B) include monofunctional (meth) acrylates, polyfunctional (meth) acrylates such as bifunctional, trifunctional, tetrafunctional, pentafunctional, and hexafunctional. Can be mentioned. Among these, monofunctional (meth) acrylate is preferable.

Among the (meth) acrylates used as the component (F) in the present invention, as the monofunctional (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, stearyl (meth) acrylate , Tetrahydrofurfuryl (meth) acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxypolyethylene Recall (meth) acrylate, nonylphenoxyethyl (meth) acrylate, nonylphenoxytetraethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, butoxyethyl (meth) acrylate, butoxytriethylene glycol ( (Meth) acrylate, 2-ethylhexyl polyethylene glycol (meth) acrylate, nonylphenyl polypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, glycidyl (meth) acrylate, glycerol (meth) acrylate, polyethylene glycol (meth) acrylate , Polypropylene glycol (meth) acrylate, epichloro Dorin (hereinafter abbreviated as ECH) modified butyl (meth) acrylate, epichlorohydrin (hereinafter abbreviated as ECH) modified phenoxy (meth) acrylate, ethylene oxide (hereinafter abbreviated as EO) modified phthalic acid (meth) acrylate, EO modified succinate Acid (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, morpholino (meth) acrylate, EO-modified phosphoric acid (Meth) acrylate etc. are mentioned. Examples thereof include (meth) acrylate having an imide group such as imide (meth) acrylate (product name: M-140, manufactured by Toagosei Co., Ltd.).

As monofunctional (meth) acrylates, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxypropyl (meth) acrylate, for the purpose of improving adhesion to polyolefins including cycloolefin polymers, Examples include (meth) acrylates having a dicyclopentenyl group such as dicyclopentenyl (meth) acrylate.

Among monofunctional (meth) acrylates, a (meth) acrylate having a dicyclopentenyl group is preferable, and dicyclopentenyl (meth) acrylate is more preferable in terms of improving adhesion to cycloolefin.

In the present invention, a silane coupling agent can be contained as the component (G) for the purpose of improving the adhesion to glass. As silane coupling agents, γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ- (meth) acryloxypropyltrimethoxy Silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) ) -Γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, and the like. Among these, γ-glycidoxypropyltrimethoxysilane and / or γ- (meth) acryloxypropyltrimethoxysilane are preferable from the viewpoint of adhesion to glass or the like, and γ-glycidoxypropyltrimethoxysilane is preferable. Is more preferable.

The curable resin composition in the present invention can be used as a two-part curable resin composition divided into a first agent and a second agent. In the case of a two-component curable resin composition, the first agent contains at least (C) a thermal polymerization initiator, and the second agent contains at least (D) a reducing agent.

The use ratio of the first agent and the second agent is, by volume ratio, first agent: second agent = 1 to 5: 5-1 is preferable, 1-3: 3 to 1 is more preferable, and 1: 1 is the most. preferable.

In the present invention, the second agent may be used as a primer. When using the second agent as a primer, a method in which the primer composition is applied to the surface of the adherend and coated via the first agent or joined to another adherend is preferable.

The present invention contains the components (A) to (E) as essential components. The components (A) to (E) can be cured at room temperature and cured with light or ultraviolet rays.

The curable resin composition in the present invention contains 30 to 98 parts by mass of the (A) component and 2 to 70 parts by mass of the (B) component in a total of 100 parts by mass of the (A) component and the (B) component. More preferably, the component (A) contains 40 to 95 parts by mass, the component (B) contains 5 to 60 parts by mass, the component (A) 80 to 90 parts by mass, and the component (B) 10 Most preferably, it contains ~ 20 parts by mass.

(C) The usage-amount of a component may contain 0.01-10 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and the (F) component used as needed. The adhesive property of the curable resin composition to the adherend is particularly high, and the curability is favorable, and the content of 0.1 to 5 parts by mass is more preferable.

(D) The usage-amount of a component may contain 0.1-7 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and the (F) component used as needed, The adhesiveness of the curable resin composition to the adherend is particularly high and the curability is favorable, and the case of containing 0.5 to 5 parts by mass is more preferable.

(E) The usage-amount of a component may contain 0.01-10 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and the (F) component used as needed, The adhesiveness with respect to the adherend of the curable resin composition is particularly high, and is preferable in that the curability is good, and the case of containing 0.1 to 5 parts by mass is more preferable.

The amount of component (F) used is preferably 1 to 10 parts by mass, and 3 to 7 parts by mass in 100 parts by mass of component (A), component (B) and component (F) used as necessary. More preferred.

The amount of the component (G) used is preferably 0.01 to 10 parts by mass with respect to a total of 100 parts by mass of the component (A), the component (B) and the component (F) used as necessary. 5 parts by mass is more preferable.

It is also possible to divide the curable resin composition of the present invention into (D) a first agent containing a thermal polymerization initiator and (E) a second agent containing a reducing agent. Other components are appropriately contained in the two components. It is also possible to cure at normal temperature by bringing the first agent and the second agent into contact immediately before use and curing. In the case of a two-component type curable resin composition, the amounts of (D) thermal polymerization initiator and (E) reducing agent used are double the above-mentioned parts by mass.

The curable resin composition of the present invention can use various paraffins in order to quickly cure the portion in contact with air.

Furthermore, for the purpose of maintaining storage stability, a commercially available antioxidant containing a polymerization inhibitor can be used.

In addition to these, elastomers, various paraffins, plasticizers, fillers, colorants, rust inhibitors and the like can be used as desired.

The curable resin composition of the present invention can be used as an adhesive composition. In the present invention, a composite can be produced by bonding or coating an adherend with a cured body of the adhesive composition. The various materials of the adherend are preferably at least one selected from the group consisting of polyolefins such as cycloolefin polymers, triacetyl cellulose, fluoropolymers, polyesters such as polyethylene terephthalate, polycarbonates, glasses, metals, polyesters, polyolefins, One or more selected from the group consisting of glass is more preferable.

The cured product bonded with the curable resin composition of the present invention can be reworked (reused) after being completely cured. The rework method is not particularly limited, but the adherends are disassembled by applying a load of 0.01 to 100 N between the bonded one or two adherends, and the adherend after disassembly is performed. The body can be reused.

Hereinafter, the present invention will be described in more detail with reference to experimental examples, but the present invention is not limited thereto.

(Experimental example)
Unless otherwise stated, experiments were conducted at 23 ° C. Curable resin compositions having the compositions shown in Tables 1 to 3 were prepared and evaluated. The results are shown in Tables 1-3.

The following compounds were selected as each component in the curable resin composition described in the experimental examples.

The following compounds were selected as oligomers having a diene-based or hydrogenated diene-based skeleton as the component (A).
(A-1) 1,2-polybutadiene oligomer (“TE-2000” manufactured by Nippon Soda Co., Ltd.) (number average molecular weight 2000 in terms of polystyrene by GPC)
(A-2) Isoprene oligomer (“LIR-50” manufactured by Kuraray Co., Ltd.) (number average molecular weight in terms of polystyrene by GPC 54000)
As the (meth) acrylate having a homopolymer glass transition temperature of -100 to 60 ° C. as the component (B), the following compounds were selected.
(B-1) Lauryl methacrylate (“Kyoeisha Chemical Co., Ltd.“ Light Ester L ”: homopolymer glass transition temperature: −65 ° C.)
(B-2) 2-hydroxyethyl methacrylate (“Kyoeisha Chemical Co., Ltd.“ Light Ester HO ”: homopolymer glass transition temperature: 55 ° C.)
The following compounds were selected as the photoinitiator for component (C).
(C-1) 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Specialty Chemicals)
(C-2) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (“Darocur TPO” manufactured by Ciba Specialty Chemicals)
The following compounds were selected as the thermal polymerization initiator of component (D).
(D-1) The following compounds were selected as reducing agents for the cumene hydroperoxide (E) component.
(E-1) Trimethylthiourea (E-2) Vanadyl acetylacetonate (F) The following compounds were selected as (meth) acrylates other than the (A) component and (B) component.
(F-1) The following compounds were selected as the silane coupling agent of the dicyclopentenyl acrylate (G) component.
(G-1) γ-Glycidoxypropyltrimethoxysilane

Various physical properties were measured as follows.

[Photocurability] Measured at a temperature of 23 ° C. Regarding photocurability, a curable resin composition was applied to a surface of Tempax glass (width 25 mm × length 25 mm × thickness 2 mm) to a thickness of 0.1 mm. Thereafter, using a curing device manufactured by Fusion Corporation using an electrodeless discharge lamp, UV light having a wavelength of 365 nm was irradiated and cured under the condition of an integrated light quantity of 2000 mJ / cm ² . Thereafter, the tensile shear bond strength was measured. The curable resin composition was prepared by mixing the first agent (A agent) and the second agent (B agent) at a volume ratio of 1: 1 using a static mixer. When the second agent was used as a primer (Experimental Example 9), the second agent primer was applied to the surface of Tempax glass, and then the first agent was further applied.

[Normal temperature curability (tensile bond strength)] The temperature was measured at 23 ° C. Regarding room temperature curability, a curable resin composition was applied to the surface of an SPCC test piece (width 100 mm × length 25 mm × thickness 1.6 mm) to a thickness of 0.05 mm. Then, it hardened | cured for 24 hours in 23 degreeC x 50% RH environment, and measured the tensile shear bond strength. When the bond strength was 5 MPa or more, it was considered that the curability at room temperature was good in a light-shielding environment. The curable resin composition was prepared by mixing the first agent (A agent) and the second agent (B agent) at a volume ratio of 1: 1 using a static mixer. When the second agent was used as a primer (Experimental Example 9), the second agent primer was applied to the surface of the SPCC test piece, and then the first agent was further applied.

[Polyethylene terephthalate (PET) adhesion evaluation (peel adhesion strength between polyethylene terephthalate test pieces)] Test pieces (width 50 mm × length 10 mm) of biaxially stretched PET film (Lumirror T60, average thickness 190 μm, manufactured by Toray Industries, Inc.) × 0.05 mm thickness) were bonded to each other using a curable resin composition as an adhesive composition with an adhesive layer thickness of 30 μm and an adhesive area of 40 mm long × 10 mm wide. After curing by room temperature curing, by pulling the two film end portions of the test piece adhered with the adhesive composition that are not in close contact with each other, the portions where the films are in close contact with each other are peeled off, and the initial 180 ° The peel adhesion strength was measured. The room temperature curing conditions followed the method described in [Room Temperature Curability (Tensile Adhesive Strength)]. When the second agent is used as a primer (Experimental Example 9), the primer of the second agent is applied to the surface of one test piece, the first agent is applied to the surface of the other test piece, Glued. The peel adhesion strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.

[Glass Adhesion Evaluation (Tensile Adhesive Strength Between Heat-Resistant Glass Test Pieces)] Heat-resistant glass test pieces (width 25 mm × length 25 mm × thickness 2.0 mm) are 80 μm thick × 11.5 mm wide × 25 mm long. The Teflon (registered trademark) tape was used as a spacer and the curable resin composition was used as an adhesive composition for adhesion (adhesion area: 3.125 cm ² ). The room temperature curing conditions followed the method described in [Room Temperature Curability (Tensile Adhesive Strength)]. When the second agent is used as a primer (Experimental Example 9), the primer of the second agent is applied to the surface of one test piece, the first agent is applied to the surface of the other test piece, Glued. After the adhesive composition was cured under the above conditions, an adhesive composition “G-55” manufactured by Denki Kagaku Kogyo Co., Ltd. was used on both sides of the test piece, and a galvanized steel sheet (width 100 mm × length 25 mm × A thickness of 2.0 mm, manufactured by Engineering Test Service Co., Ltd.) was adhered. After the curing, using the test piece bonded with the adhesive composition, the galvanized steel sheet was chucked, and the initial tensile shear bond strength was measured. The tensile shear bond strength (unit: MPa) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.

[Cycloolefin polymer (COP) adhesion evaluation (peel adhesion strength between cycloolefin polymer test pieces)] COP film (ZEONOR, average thickness 40 μm, manufactured by Nippon Zeon Co., Ltd.) test piece (width 50 mm × length 10 mm × 0.05 mm thick) were bonded to each other with the adhesive layer having a thickness of 10 μm and a bonding area of 40 mm in length and 10 mm in width by using the curable resin composition as an adhesive composition. After curing by room temperature curing, by pulling the two end portions of the film that are not in close contact with the test piece bonded with the adhesive composition, the portions where the films are in close contact with each other are peeled off, and the initial 180 ° peeling is performed. The bond strength was measured. The room temperature curing conditions followed the method described in [Room Temperature Curability (Tensile Adhesive Strength)]. When the second agent is used as a primer (Experimental Example 9), the primer of the second agent is applied to the surface of one test piece, the first agent is applied to the surface of the other test piece, Glued. The peel adhesion strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.

[Heat and heat resistance evaluation (tensile bond strength between heat-resistant glass test pieces after exposure to high temperature and high humidity)] Tempax glass (width 25 mm x length 25 mm x thickness 2 mm) and curable resin composition as adhesive composition It was used as a product, and was bonded and cured with an adhesive layer thickness of 100 μm and an adhesive area of 1.0 mm ² . The room temperature curing conditions followed the method described in [Room Temperature Curability (Tensile Adhesive Strength)]. When the second agent is used as a primer (Experimental Example 9), the primer of the second agent is applied to the surface of one test piece, the first agent is applied to the surface of the other test piece, Glued. After curing, the test piece bonded with the adhesive composition was exposed to an environment of 85 ° C. and 85% relative humidity for 1000 hours using a constant temperature and humidity chamber. The tensile shear bond strength was measured using the test piece after exposure. The appearance of the bonded part was visually observed to determine whether it was yellowed. The peel adhesion strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.

[Observation of appearance (degree of yellowing)] Tempax glass (width 25 mm x length 25 mm x thickness 2 mm), using a curable resin composition as an adhesive composition, the adhesive area with an adhesive layer thickness of 100 μm It was made to adhere and harden as 1.0 mm ² . The room temperature curing conditions followed the method described in [Room Temperature Curability (Tensile Adhesive Strength)]. When the second agent is used as a primer (Experimental Example 9), the primer of the second agent is applied to the surface of one test piece, the first agent is applied to the surface of the other test piece, Glued. After curing, the test piece bonded with the adhesive composition was subjected to a color measuring device (“UV-VISABLE SPECTROPOHOTOMETER” manufactured by SHIMADZU Co., Ltd.), and the Δb value was determined as the degree of yellowing.

The following can be seen from the experimental example. The curable resin composition of the present invention exhibits high adhesiveness. The curable resin composition of the present invention exhibits high adhesiveness. In particular, it exhibits high adhesion to polycarbonate, polyolefin, and glass. Since the curable resin composition of the present invention exhibits high adhesiveness, when a display body such as a thin glass LCD is bonded to an optical functional material such as an acrylic plate or a polycarbonate plate, the adhesive surface may be peeled off, or the LCD Will not break or the LCD will not display unevenly. The curable resin composition of the present invention has a high resistance to moist heat and can follow the deformation of the adherend in a heated atmosphere, so that the adherend is not peeled off. The curable resin composition of the present invention can provide sufficient adhesion both when a printed part is bonded and when a non-printed part is bonded.

In the case of a comparative example, it does not have the effect of this invention.

The curable resin composition of the present invention can be used for an adhesive composition for a touch panel laminate or a liquid crystal panel laminate. The touch panel laminate and the liquid crystal panel laminate of the present invention can be used as a display. The curable resin composition of the present invention can improve curability even when a transparent part or a translucent part is bonded.

Claims (18)

Curable resin composition containing the following (A)-(C) component.
(A) Oligomer having a diene-based or hydrogenated diene-based skeleton (B) Homopolymer (meth) acrylate (C) photopolymerization initiator (D) thermal polymerization initiation having a glass transition temperature of −100 to 60 ° C. Agent (E) Reducing Agent The curable resin composition according to claim 1, wherein the component (B) is a compound of the general formula (1) and / or a compound of the general formula (2).
General formula (1) Z—O—R ₁
[Wherein, Z represents a (meth) acryloyl group, and R ₁ represents an alkyl group having 9 to 20 carbon atoms. ]
General formula (2) Z—O—R ₂ —OH
[In formula, Z shows a (meth) acryloyl group and R2 represents a C2-C20 alkylene group. ] Furthermore, curable resin composition of Claim 1 or 2 containing (meth) acrylates other than (A) component and (B) component as (F) component. Furthermore, the curable resin composition of any one of Claims 1-3 which contains a silane coupling agent as (G) component. The diene-based or hydrogenated diene-based skeleton of the component (A) is at least one skeleton selected from the group consisting of polybutadiene, polyisoprene, a hydrogenated polybutadiene, and a hydrogenated polyisoprene. Item 5. The curable resin composition according to any one of Items 1 to 4. The molecular weight of the oligomer having a diene-based or hydrogenated diene-based skeleton of the component (A) is 500 to 70000. The curable resin composition according to any one of claims 1 to 5. (C) A thermal-polymerization initiator is an organic peroxide, The curable resin composition of any one of Claims 1-6. (D) The curable resin composition according to any one of claims 1 to 7, wherein the reducing agent is one or more of a thiourea derivative, a β-diketone chelate, and a β-ketoester. The two-component curable product according to claim 1, wherein the first agent contains at least (C) a thermal polymerization initiator, and the second agent contains at least (D) a reducing agent. Resin composition. The first agent comprises at least (C) a thermal polymerization initiator, and the second agent is a primer comprising at least (D) a reducing agent and a solvent. Two-part curable resin composition. The adhesive composition which consists of a curable resin composition of any one of Claims 1-10. A cured product of the adhesive composition according to claim 11. A composite in which an adherend is coated or bonded with the cured body according to claim 12. The composite_body | complex which the to-be-adhered body of Claim 13 is 1 or more types chosen from the group which consists of a triacetyl cellulose, a fluorine-type polymer, polyester, a polycarbonate, polyolefin, glass, and a metal. The touch-panel laminated body which bonded together the to-be-adhered body with the adhesive composition of Claim 11. The liquid crystal panel laminated body which bonded together the to-be-adhered body with the adhesive composition of Claim 11. A display using the touch panel laminate according to claim 15. A display using the liquid crystal panel laminate according to claim 16.