KR102004534B1

KR102004534B1 - Curable resin composition

Info

Publication number: KR102004534B1
Application number: KR1020147023752A
Authority: KR
Inventors: 유키 히샤; 요시츠구 고토; 기미히코 요다
Original assignee: 덴카 주식회사
Priority date: 2012-03-14
Filing date: 2013-02-22
Publication date: 2019-07-26
Also published as: KR20140134656A; WO2013136945A1; JP6088486B2; CN104159939B; TWI582121B; JPWO2013136945A1; CN104159939A; TW201336876A

Abstract

Thereby solving the problem that it is difficult to impart sufficient adhesiveness. A curable resin composition comprising the following components (A) to (D): (A) 100 parts by mass of an oligomer having a (meth) acryloyl group and having a diene-based or hydrogenated diene skeleton, (B) a diene-based or diene- An oligomer having a hydrogenated diene skeleton, (C) a (meth) acrylate having an aromatic ring exceeding 100 parts by mass, (D) a photopolymerization initiator. A silane coupling agent may be further contained or used as an adhesive composition.

Description

CURABLE RESIN COMPOSITION [0001]

The present invention relates to a curable resin composition.

A touch panel mounted on a display body such as an LCD (liquid crystal display) includes a resistive film, a capacitance type, an electromagnetic induction type, and an optical type. There is a case where an icon sheet for designating a touch position is attached to the surface of such a touch panel in order to improve the appearance of the touch panel. The capacitive touch panel has a structure in which a transparent electrode is formed on a transparent substrate and a transparent plate is attached on the transparent electrode.

Conventionally, when attaching the icon sheet and the touch panel to each other, an adhesive is used to attach the transparent plate and the transparent plate. Patent Document 1 discloses a thermosetting resin composition comprising (A) a (meth) acrylate oligomer having a polyisoprene, polybutadiene or polyurethane skeleton, (B) a softening component, and (C1) phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol Acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, nonylphenol EO adduct (meth) acrylate, methoxy triethylene glycol (Meth) acrylate monomer selected from tetrahydrofurfuryl (meth) acrylate (Patent Document 1).

In recent years, the glass of a display body such as an LCD has been thinned. When the glass is thin, the LCD is easily deformed by external stress. When a thin display glass such as an LCD or the like and an optical functional material such as an acrylic plate or a polycarbonate plate are laminated, a difference in linear expansion between glass and acrylic or a warpage during molding of an acrylic plate or polycarbonate, The mold warping is alleviated or the moisture absorption / drying occurs at the time of the humidity resistance test, and the surface precision such as dimensional change and warpage changes. In the case of attempting to suppress this deformation by a conventional adhesive (for example, Patent Document 2), there has been a problem that the adhesive surface is peeled off, the LCD is broken, and display unevenness occurs on the LCD.

As a solution to the above problem, UV curable resins such as the patent document 3 can be mentioned. Patent Document 3 is a high-elasticity resin based on rigid skeletal monomers such as isobonyl (meth) acrylate.

For example, when attaching a color plate and a touch panel, attaching an icon sheet and a touch panel, and attaching a transparent substrate and a transparent plate, It is believed that it is desirable to have a degree of flexibility.

Patent Document 1: International Publication No. 2010/027041 Patent Document 2: JP-A-2004-77887 Patent Document 3: Japanese Patent Application Laid-Open No. 64-85209

However, the prior art described in the above document has room for improvement in the following points.

For example, the photo-curable resin composition disclosed in Patent Document 1 has insufficient adhesive strength in the case of adhesion durability or in the case where printing is applied to the attachment surface.

In addition, the UV curable resin of Patent Document 3 has a possibility of being peeled off without being able to withstand the expansion and contraction of the adherend in the high temperature reliability test.

In addition, if any technique is applied to the attachment surface, there is a problem in that the adhesion of the printing processing portion due to the light energy ray is difficult due to the influence of the uncured portion.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a method of attaching a transparent plate or a transparent substrate, It is a further object of the present invention to provide a curable resin composition that solves the problems of the prior art, such as the problem of the prior art that it is difficult to impart adhesion durability, or that the adhesive surface is peeled off or the glass of the display body is broken when the display body and the optical functional material are bonded together .

That is, according to the present invention, there is provided a curable resin composition containing the following components (A) to (D).

(A) 100 parts by mass of an oligomer having a (meth) acryloyl group and having a diene-based skeleton of a diene or hydrogenation

(B) an oligomer having a skeleton of dienic system or hydrogenated diene skeleton having no (meth) acryloyl group and exceeding 400 parts by mass

(C), more than 100 parts by mass of (meth) acrylate having an aromatic ring

(D) a photopolymerization initiator

According to the present invention, there is also provided the curable resin composition further containing a silane coupling agent as the component (E) in the curable resin composition. According to the present invention, there is also provided the curable resin composition further containing a polymerization inhibitor as the component (F) in the curable resin composition. Further, according to the present invention, the diene-based or hydrogenated diene skeleton of the component (A) and / or the component (B) is selected from the group consisting of polybutadiene, polyisoprene, hydrogenated products of polybutadiene, and hydrogenated products of polyisoprene There is provided the above curable resin composition which is at least one skeleton to be selected. According to the present invention, there is also provided the above curable resin composition, wherein the molecular weight of the oligomer having a diene-based or hydrogenated diene-based skeleton of the component (A) and / or the component (B) is 500 to 7000. According to the present invention, there is also provided an adhesive composition comprising the curable resin composition. According to the present invention, there is also provided a cured product of the adhesive composition. According to the present invention, there is also provided a composite in which an adherend is covered or bonded by the cured body. According to the present invention, there is also provided a composite body in which the adherend is selected from the group consisting of triacetylcellulose, a fluoropolymer, a polyester, a polycarbonate, a polyolefin, a glass, and a metal. According to the present invention, there is provided a touch panel laminate to which an adherend is adhered by the adhesive composition. According to the present invention, there is also provided a laminate of a liquid crystal panel to which an adherend is adhered by the adhesive composition. According to the present invention, a display using the touch panel laminate is provided. According to the present invention, a display using the liquid crystal panel laminate is provided.

The curable resin composition of the present invention is excellent in adhesion durability or adhesive strength in the case where printing is performed on the attachment surface.

Hereinafter, embodiments of the present invention will be described in detail. In the present specification, A to B mean A or more and B or less.

&Lt; About the component (A) >

Component (A) that can be used in the present embodiment is an oligomer having a diene-based skeleton having a (meth) acryloyl group and also being a dienic or hydrogenated.

In the present embodiment, the main chain skeleton of the oligomer is a diene-based or hydrogenated diene-based skeleton. As the skeleton of the diene type or hydrogenated diene type, at least one skeleton selected from the group consisting of hydrogenated products of polybutadiene, polyisoprene, polybutadiene and hydrogenated polyisoprene is preferable. Among them, at least one selected from the group consisting of polybutadiene and polyisoprene is preferable, and polyisoprene is more preferable in view of high adhesion durability.

The oligomer preferably has at least one (meth) acryloyl group in the terminal or side chain of the main chain skeleton. Among them, those having a (meth) acryloyl group at both ends of the main chain skeleton are preferable.

The molecular weight of the oligomer is preferably 500 to 7000, more preferably 1000 to 60000, and most preferably 1000 to 55000. When the molecular weight is within this range, the hardness of the cured product obtained by curing the curable resin composition of the present embodiment is high, so that the adhesive layer can be easily formed. On the other hand, since the viscosity of the curable resin composition that can be obtained is small, The workability is improved with respect to workability and practical use such as when it is used. The molecular weight may be any one of 500, 1000, 2000, 3000, 4000, 5000, 7000, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000, 50000, 55000, 60000, 65000, It may be in the range of two values.

The molecular weight of the oligomer indicates the number average molecular weight calculated as the average molecular weight per molecule. In the examples described below, the number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) was used.

Examples of the oligomer of the component (A) include an anhydride maleic anhydride adduct of an isoprene polymer and an esterified oligomer of 2-hydroxyethyl (meth) acrylate (the structure is represented by the following formula (1), "UC-203" "TE-2000" (terminal acrylic-modified 1,2-polybutadiene oligomer) manufactured by Japan Soda, "TEAI-1000" (hydrogenated 1,2-polybutadiene oligomer with terminal acryl) . Among them, an esterified oligomer of an isoprene polymeric maleic anhydride adduct and 2-hydroxyethyl (meth) acrylate is preferable.

[Chemical Formula 1]

Wherein R represents a hydrogen atom or a methyl group, and Y represents an alkylene group. m and n are arbitrary positive integers, and the formula is set so as to satisfy the number of functional groups: 1 to 10 and the molecular weight of 3000 to 50000.

&Lt; (B) >

The component (B) usable in the present embodiment is an oligomer having a diene-based or a hydrogenated diene-based skeleton without a (meth) acryloyl group.

In the present embodiment, the main chain skeleton of the oligomer is a diene-based or hydrogenated diene-based skeleton. As the skeleton of the diene type or hydrogenated diene type, at least one skeleton selected from the group consisting of hydrogenated products of polybutadiene, polyisoprene, polybutadiene and hydrogenated polyisoprene is preferable. Of these, at least one selected from the group consisting of polybutadiene and polyisoprene is preferable in view of high adhesion durability, and polybutadiene is more preferable.

The molecular weight of the oligomer is preferably 500 to 7000, more preferably 1000 to 60000, and most preferably 1000 to 55000. When the molecular weight is within this range, an adhesive layer can be easily formed because the hardness of the cured product obtained by curing the curable resin composition of the present embodiment is high, while the viscosity of the curable resin composition that can be obtained is small. The workability is improved with respect to workability and practical use such as when it is used. The molecular weight may be any one of 500, 1000, 2000, 3000, 4000, 5000, 7000, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000, 50000, 55000, 60000, 65000, It may be in the range of two values.

LBR-307 "," LBR-50 "(butadiene oligomer) manufactured by Kuraray Co., Ltd., and" Viron "(amorphous polyester resin) such as Toyobo Co., Ltd. are used as the oligomer of the component (B) . Among them, at least one selected from the group consisting of isoprene oligomer, 1,2-polybutadiene oligomer and 1,4-polybutadiene oligomer is preferable, and 1,2-polybutadiene oligomer and 1,4-polybutadiene oligomer are preferable More preferred are 1,4-polybutadiene oligomers.

&Lt; (C) >

Component (C) usable in the present embodiment is (meth) acrylate having an aromatic ring. Examples of the (meth) acrylate having an aromatic ring include nonylphenoxypolyethylene glycol (meth) acrylate, benzyl (meth) acrylate, ethoxylated phenyl (meth) acrylate, neopentyl glycol benzoate (meth) (Meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like. These (meth) acrylates may be used alone or in combination of two or more. Of these, (meth) acrylates having a phenoxy group are preferred. The phenoxy group preferably has a structure represented by the following formula (2). R represents an arbitrary substituent. R is hydrogen, an alkyl group, or a hydroxyl group. R is preferably an alkyl group. The alkyl group is preferably an alkyl group having from 1 to 20 carbon atoms, more preferably an alkyl group having from 6 to 12 carbon atoms. Among (meth) acrylates having a phenoxy group, (meth) acrylate and / or phenoxyethyl (meth) acrylate having a nonylphenoxy group are preferable, and (meth) acrylate having a nonylphenoxy group is more preferable . Among the (meth) acrylates having a nonylphenoxy group, nonylphenoxypolyalkylene glycol (meth) acrylate is preferable, and nonylphenoxypolyethylene glycol (meth) acrylate and / or nonylphenoxypolypropylene glycol (meth) Acrylate is preferable. The ethylene glycol chain- (CH ₂ CH ₂ O) n- of nonylphenoxy polyethylene glycol (meth) acrylate is preferably n = 1 to 30. The propylene glycol chain- (CH ₂ CH ₂ O) n- of nonylphenoxy polypropylene glycol (meth) acrylate is preferably n = 1 to 30. The number of aromatic rings is, for example, 1, 2 or 3, preferably 1.

(2)

R represents an arbitrary substituent.

&Lt; (D) >

(D) is a photopolymerization initiator (hereinafter referred to as a photoinitiator). The photoinitiator is not particularly limited as long as it is capable of initiating polymerization of (meth) acrylate such as the component (A), the component (B), and the component (C).

Examples of the photoinitiator (D) include an ultraviolet polymerization initiator and a visible light polymerization initiator. Any of them may be used without limitation. Examples of the ultraviolet polymerization initiator include benzoin, benzophenone, and acetophenone. Examples of the visible light polymerization initiator include acylphosphine oxide-based, thioxanthone-based, metallocene-based, quinone-based, and -aminoalkylphenone based.

(D) photoinitiators include benzophenone, 4-phenylbenzophenone, benzoylbenzoic acid, 2,2-diethoxyacetophenone, bisdiethylaminobenzophenone, benzyl, benzoin, benzoylisopropylether, benzyldimethylketal, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthio 2-methylpropan-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy- 2-methyl-1-phenylpropan-1-one, camphorquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one, 2-benzyl- - (4-morpholin-4-yl-phenyl) -butane-l- - on, rain And the like pentyl phosphine oxide (2,6-dimethoxybenzoyl) -2,4,4- trimethyl.

The curable resin composition of the present embodiment may contain (meth) acrylate other than the component (A) and (meth) acrylate other than the component (C) for the purpose of further improving the adhesion to each adherend have.

&Lt; Component (E) >

In the present embodiment, a silane coupling agent may be contained as the component (E) for the purpose of improving adhesion to glass. Examples of the silane coupling agent include? -Chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (? -Methoxyethoxy) silane,? - (meth) (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Mercaptopropyltrimethoxysilane,? -Aminopropyl (Aminoethyl) -? - aminopropyltrimethoxysilane, N -? - (aminoethyl) -? - aminopropylmethyldimethoxysilane,? - ureidopropyltriethoxysilane And the like. Of these, γ-glycidoxypropyltrimethoxysilane and / or γ- (meth) acryloyloxypropyltrimethoxysilane are preferable in terms of adhesiveness to glass and the like, and γ- (meth) acryloyloxy Propyl trimethoxysilane is more preferable.

&Lt; (F) >

In the present embodiment, a polymerization inhibitor may be contained as the component (F) in terms of storage stability. Examples of the polymerization inhibitor include hindered phenol, bisphenol, and phosphoric acid. Of these, the incompatible phenol type is preferable. As the antioxidant for a handwheel phenolic antioxidant, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), 2,4-dimethyl-6-t-butylphenol, n-octadecyl-? - (4'- Butylphenyl) propionate, styrenated phenol, styrenated cresol, tocopherol, 2,2'-methylenebis (4-ethyl-6-t- (4-methyl-6-cyclohexylphenol), 2,2'-butylidene-bis (4-methyl- Butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di- Benzyl) benzene, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate] methane, propyl gallate, octylgalate, lauryl gallate, 2 Di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 4,4'-methylenebis (2,6- Butylphenol) 1,3,5-Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) , Benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-9 branched alkyl ester (C is the number of carbon atoms).

&Lt; Contents of each component >

The present embodiment can cure with light or ultraviolet rays by containing the components (A) to (D) as essential components.

When the amount of the component (B) is more than 400 parts by mass based on 100 parts by mass of the component (A), the adhesiveness of the curable resin composition to an adherend becomes particularly high and the curability becomes good, , More preferably from 401 to 600 parts by mass, and most preferably from 410 to 450 parts by mass. The amount of component (B) to be used may be any two values of 400, 401, 402, 403, 404, 405, 410, 420, 430, 440, 450, 500, (The values at both ends may be included or may not be included).

(C) is used in an amount of more than 100 parts by mass based on 100 parts by mass of the component (A), more preferably more than 100 parts by mass, more preferably from 101 to 400 parts by mass, most preferably from 150 to 350 parts by mass Do. When the amount is more than 100 parts by mass, the adhesion of the curable resin composition to the adherend becomes particularly high, and the curability becomes good, and the adhesive strength when the adhesive surface is printed is excellent. The amount of component (C) to be used is preferably in the range of 100, 101, 102, 103, 104, 105, 110, 120, 130, 140, 150, 200, 250, 300, 350, 400, 450 (The values at both ends may be included or may not be included).

(D) is contained in an amount of 0.01 to 20 parts by mass based on 100 parts by mass of the total of the component (A), the component (B) and the component (C), the adhesiveness of the curable resin composition to an adherend becomes particularly high The curing property is good and the adhesive strength is excellent in the case where the adhesive surface is subjected to printing, more preferably 0.5 to 5 parts by mass. The amount of the component (D) to be used is in the range of 0.01 to 0.05, 0.1, 0.5, 1, 5, 10, 15, and 20 to 100 parts by mass of the total of the components (A) (The numerical values at both ends may or may not be included).

The amount of the component (E) to be used is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the total of the components (A), (B) and (C). Further, the amount of the component (E) to be used is preferably 2 to 10 parts by weight per 100 parts by weight of the total of the components (A), (B) and (C) (The numerical values at both ends may or may not be included).

The amount of the component (F) to be used is preferably 0.00001 to 3 parts by mass, more preferably 0.001 to 2 parts by mass, still more preferably 0.05 to 1 part by mass relative to 100 parts by mass of the total of the components (A), (B) Most preferred. The amount of the component (F) to be used may be any two values of 0.00001, 0.0001, 0.001, 0.01, 0.1, 1, 2, and 3 per 100 parts by mass of the total of the components (A), (B) (The values at both ends may or may not be included).

In addition to these, elastomers, various paraffins, plasticizers, fillers, coloring agents, waterproofing agents and the like may be used as desired.

The curable resin composition of this embodiment can be used as an adhesive composition. In the present embodiment, the adherend may be bonded or coated with a cured product of the adhesive composition to prepare a composite. The various materials of the adherend are preferably at least one selected from the group consisting of polyolefins such as cycloolefin polymer, polyesters such as triacetylcellulose, fluoropolymer and polyethylene terephthalate, polycarbonate, glass and metal, Polyolefin, and glass are more preferable.

The cured product adhered with the curable resin composition of the present embodiment can be reworked (reused) after fully cured. The rework method is not particularly limited, but it is possible to disassociate the adherend bodies by applying a load of 0.01 to 100 N between the adherends of one kind or two kinds of the adhered bodies to reuse the adherend after disassembly.

The curable resin composition of the present embodiment can give sufficient adhesion durability when a printed part is pasted. As a printing processing method, there can be mentioned a method of printing a printing ink in which a pigment and a binder are mixed on an adherend. The thickness of the printed surface is not particularly limited as long as light such as ultraviolet rays or visible light is transmitted through the printed surface to the curable resin composition and the curable resin composition can be cured. The thickness of the printed surface may be reduced to a few 탆 in that light can transmit the printed surface.

The embodiments of the present invention have been described above with reference to the drawings. However, the present invention is not limited to these embodiments.

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)

Experiments were carried out at 23 ° C unless otherwise stated. Curable resin compositions having the compositions shown in Tables 1 and 2 were prepared and evaluated. The results are shown in Tables 1 and 2.

As the respective components in the curable resin composition described in the Experimental Example, the following compounds were selected.

The following compounds were selected as oligomers having a (meth) acryloyl group as the component (A) and also having a diene-based or hydrogenated diene-based skeleton.

(A-1) 1,2-polybutadiene oligomer ("TE-2000" manufactured by Japan Soda Co., Ltd.) (number average molecular weight 2000 in terms of polystyrene by GPC)

(A-2) isoprene oligomer ("UC-203" manufactured by Kuraray Co., Ltd. (number-average molecular weight in terms of polystyrene as determined by GPC: 36000), a maleic anhydride adduct of an isoprene polymer and 2-hydroxyethyl Oligomer, Y in formula (1) is an ethylene group, and R is a methyl group)

The following compounds were selected as oligomers of the component (A) having a diene-based or hydrogenated diene skeleton without a (meth) acryloyl group.

(B-1) isoprene oligomer ("LIR-30" manufactured by Kuraray Co., Ltd. (number average molecular weight in terms of polystyrene by GPC: 28000)

(B-2) butadiene oligomer ("LBR-307" manufactured by Kuraray Co., Ltd., 1,4-polybutadiene oligomer) (number average molecular weight 8000 in terms of polystyrene by GPC)

(Meth) acrylate having a phenoxy group or a nonylphenoxy group as the component (C), the following compounds were selected.

(C-1) nonylphenoxypolyethylene glycol acrylate (n = 1) ("M-111" manufactured by DOA Corporation)

(C-2) 2-hydroxy-3-phenoxypropyl acrylate (ARONIX M-5700, manufactured by TOA Corporation)

(C-3) nonylphenoxy polypropylene glycol acrylate (n = 2.5) ("M-117"

(N = 7) / polypropylene glycol (n = 2) acrylate (C-4) nonylphenoxypolyethylene glycol (n = 7) and polypropylene glycol Quot; Brenma 75ANEP-600 ", manufactured by Nikkei Corporation)

The following compounds were selected as photoinitiators of component (D).

(D-1) 1-hydroxycyclohexyl phenyl ketone ("Irgacure 184" manufactured by Ciba Specialty Chemicals)

(D-2) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide ("Darocur TPO" manufactured by Ciba Specialty Chemicals)

The following compounds were selected as the silane coupling agent of component (E).

(E-1) γ-methacryloyloxypropyltrimethoxysilane ("Silquest A-174" manufactured by Momentive)

The following compounds were selected as polymerization inhibitors of component (F).

(F-1) benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-9 branched alkyl ester ("Irganox 1135"

Various physical properties were measured as follows.

[Photocurable property]

And the temperature was measured at 23 캜. Regarding the photo-curability, the curable resin composition was applied to the surface of a tenpax glass (25 mm wide × 25 mm long × 2 mm thick) so as to have a thickness of 0.1 mm. Thereafter, UV light having a wavelength of 365 nm was irradiated under the condition of an accumulated light quantity of 2000 mJ / cm ² by using a Fusion-type curing apparatus using a non-electrode discharge lamp and cured. Thereafter, tensile shear bond strength was measured. A curable resin composition was prepared and applied. In the case of printing the test piece, the test piece was subjected to a printing process by the following method. A black paint made of carbon powder and a solvent was sprayed on the entire surface of the test piece to prepare a test piece having a printed surface with a thickness of several micrometers.

[Evaluation of adhesion of polyethylene terephthalate (PET) (peel adhesion strength between polyethylene terephthalate test pieces)]

(50 mm in width x 10 mm in length x 0.19 mm in thickness) of a biaxially stretched PET film (Lo Mirror T60, average thickness 190 占 퐉, manufactured by Toray Industries, Inc.) was printed with a curable resin composition as an adhesive composition In the state of being processed, the adhesive layer was bonded with a thickness of 30 mu m so that the bonding area was 40 mm long x 10 mm wide. After curing by photo-curing, the two unfilled film ends of the test specimens bonded with the adhesive composition were pulled out to peel off the portions where the films adhered to each other to measure the initial 180 ° peel adhesion strength. Light irradiation conditions at the time of photo-curing were in accordance with the method described in [Photocuring property]. The peel adhesion strength (unit: N / cm) was measured at a tensile speed of 50 mm / min under an environment of a temperature of 23 캜 and a humidity of 50% using a tensile tester.

[Evaluation of glass adhesion property (Tensile adhesion strength between heat resistant glass test pieces)]

A thermally-resistant glass test piece (25 mm in width x 25 mm in length x 2.0 mm in thickness), which had been subjected to the printing process, was made by using a Teflon (registered trademark) tape having a thickness of 80 m, a width of 11.5 mm and a length of 25 mm as a spacer, (Adhesive area: 3.125 cm < ² >). Light irradiation conditions at the time of photo-curing were in accordance with the method described in [Photocuring property]. After curing the adhesive composition under the above conditions, a galvanized steel sheet (100 mm wide × 25 mm long × 2.0 mm thick, manufactured by Engineering Test Service) was adhered to both surfaces of the test piece using an adhesive composition "G-55" manufactured by Denki Kagaku Kogyo Co., . The initial tensile shear bond strength was measured by chucking the galvanized steel sheet using the test specimen bonded with the adhesive composition after curing. The tensile shear bond strength (unit: MPa) was measured at a tensile speed of 10 mm / min under an environment of a temperature of 23 DEG C and a humidity of 50% using a tensile tester.

[Evaluation of Cycloolefin Polymer (COP) Adhesion (Peel Adhesion Strength Between Cycloolefin Polymer Test Specimens)]

(50 mm in width x 10 mm in length x 0.04 mm in thickness) of a COP film (ZEONOR, average thickness of 40 mu m, manufactured by Nippon Zeon Co., Ltd.) was used as an adhesive composition, The adhesive layer was adhered with a thickness of 10 mu m so that the adhesive area was 40 mm long x 10 mm wide. After curing by photo-curing, the two unfilled film ends of the test specimens bonded with the adhesive composition were pulled out to peel off the portions where the films adhered to each other to measure the initial 180 ° peel adhesion strength. Light irradiation conditions at the time of photo-curing were in accordance with the method described in [Photocuring property]. The peel adhesion strength (unit: N / cm) was measured at a tensile speed of 50 mm / min under an environment of a temperature of 23 캜 and a humidity of 50% using a tensile tester.

[Evaluation of Triacetyl Cellulose Adhesion (Peel Adhesion Strength Between Triacetyl Cellulose Test Specimens)]

(50 mm in width × 10 mm in length × 0.04 mm in thickness) of triacetyl cellulose (TAC) film (average thickness: 40 μm, manufactured by Fuji Photo Film Co., Ltd.) was printed and laminated by using the curable resin composition as an adhesive composition The adhesive layer was adhered with a thickness of 10 mu m so that the adhesive area was 40 mm long x 10 mm wide. The two adhered film ends of the test piece adhered with the adhesive composition were pulled out to peel off the adhered portions between the films to measure the initial 180 ° peel adhesion strength. Light irradiation conditions at the time of photo-curing were in accordance with the method described in [Photocuring property]. The peel adhesion strength (unit: N / cm) was measured at a tensile speed of 50 mm / min under an environment of a temperature of 23 캜 and a humidity of 50% using a tensile tester.

[Evaluation of fluoropolymer adhesiveness (peel adhesion strength between fluorine film test pieces)]

(50 mm in width x 10 mm in length x 0.04 mm in thickness) of a PVDF (polyvinylidene fluoride) film (average thickness 40 占 퐉, manufactured by Denki Kagaku Kogyo K.K.) was laminated to each other using a curable resin composition as an adhesive composition The adhesive layer was adhered with a thickness of 10 mu m and a bonding area of 40 mm long x 10 mm wide with printing on the attachment surface. The two adhered film ends of the test piece adhered with the adhesive composition were pulled out to peel off the adhered portions between the films to measure the initial 180 ° peel adhesion strength. Light irradiation conditions at the time of photo-curing were in accordance with the method described in [Photocuring property]. The peel adhesion strength (unit: N / cm) was measured at a tensile speed of 50 mm / min under an environment of a temperature of 23 캜 and a humidity of 50% using a tensile tester.

[Evaluation of Polycarbonate Adhesion (Tensile Adhesion Strength Between Polycarbonate Test Specimens)]

A Teflon (registered trademark) tape having a thickness of 80 占 퐉, a width of 12.5 mm, and a length of 25 mm was used as a spacer between the printed polycarbonate (25 mm in width x 25 mm in thickness and 2.0 mm in thickness) , And the curable resin composition was used as an adhesive composition, and adhered (adhesive area: 3.125 cm ² ) in the state of printing on the attachment face. Light irradiation conditions at the time of photo-curing were in accordance with the method described in [Photocuring property]. The tensile shear bond strength (unit: MPa) was measured at a tensile speed of 10 mm / min under an environment of a temperature of 23 DEG C and a humidity of 50% using a tensile tester.

[Evaluation of metal adhesion (tensile bond strength between SPCC test piece and glass test piece)]

(25 mm wide × 25 mm long × 2 mm thick) and a Teflon (registered trademark) tape having a thickness of 80 μm, a width of 12.5 mm and a length of 25 mm were laminated on a printed SPCC test piece (25 mm wide × 25 mm long × 1.6 mm thick) The curable resin composition was used as an adhesive composition, and adhered (adhesive area: 3.125 cm ² ) in a state of printing on the adhesive surface. Light irradiation conditions at the time of photo-curing were in accordance with the method described in [Photocuring property]. After curing the adhesive composition under the above conditions, a zinc-plated steel sheet (100 mm wide × 25 mm long × 2.0 mm thick, manufactured by Engineering Test Service) was applied to the tenpak specimen side using an adhesive composition "G-55" manufactured by Denki Kagaku Kogyo Co., . The initial tensile shear bond strength was measured by chucking the galvanized steel sheet using the test specimen bonded with the adhesive composition after curing. The tensile shear bond strength (unit: MPa) was measured at a tensile speed of 10 mm / min under an environment of a temperature of 23 DEG C and a humidity of 50% using a tensile tester.

[Evaluation of Humidity Durability (Tensile Adhesive Strength Between Heat-Resistant Glass Test Piece after High-Temperature and High-humidity Exposure)]

(25 mm in width x 25 mm in length x 2 mm in thickness) printed with the cured resin composition was used as an adhesive composition, and the adhesive layer had a thickness of 100 m and a bonding area of 1.0 mm < ^{2 &gt}; Followed by curing. Light irradiation conditions at the time of photo-curing were in accordance with the method described in [Photocuring property]. After curing, the test specimens adhered with the adhesive composition were exposed to the environment at 85 ° C and 85% RH for 1000 hours using a constant temperature and humidity bath. The tensile shear bond strength was measured using the test piece after exposure. The appearance of the adhesive area was visually observed to determine whether the yellowing occurred. The tensile shear bond strength (unit: MPa) was measured at a tensile speed of 10 mm / min under an environment of a temperature of 23 DEG C and a humidity of 50% using a tensile tester.

[Appearance observation (yellowing degree)]

Tensile glass (width 25 mm x length 25 mm x thickness 2 mm) was cured by bonding the curable resin composition as an adhesive composition at an adhesive layer thickness of 100 m and an adhesive area of 1.0 mm < ^{2 &} gt ;. Light irradiation conditions at the time of photo-curing were in accordance with the method described in [Photocuring property]. After curing, the test piece adhered with the adhesive composition was subjected to yellowing in the? B value in a color measuring device ("UV-Visible Spectrophotometer" manufactured by SHIMADZU).

From the experimental examples, the following can be known. The curable resin compositions corresponding to the examples of the present invention exhibit high adhesiveness and exhibit good curing properties and heat and humidity resistance. Further, the curable resin composition corresponding to the embodiment of the present invention can give sufficient adhesion durability when a printed part is pasted. Particularly, triacetylcellulose, fluoropolymer, polyester, polycarbonate, polyolefin, glass, and metal. The curable resin composition corresponding to the examples exhibits high adhesiveness. Therefore, when an optical functional material such as a thin glass LCD or the like and an acrylic plate or a polycarbonate plate is adhered, the adhesive surface is peeled off, the LCD is broken, There is no stain. The curable resin composition corresponding to the examples has a high resistance to humidity and humidity, and can follow the deformation of the adherend in the warmed atmosphere, so that the adherend does not peel off. In addition, the curable resin composition according to the above examples was tested for pasting a printed portion, but it was experimentally confirmed that sufficient adhesion can be imparted even when a non-printed portion is pasted.

In the case of the curable resin composition corresponding to the comparative example, the effect of the present invention is not obtained.

&Lt; Industrial applicability >

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

Claims

A curable resin composition comprising the following components (A) to (D):
(A) 100 parts by mass of an oligomer having a (meth) acryloyl group and having a diene-based skeleton of a dienic or hydrogenated group,
(B) an oligomer having a skeleton of a dienic or hydrogenated diene skeleton having no (meth) acryloyl group and exceeding 400 parts by mass,
(Meth) acrylate having an aromatic ring, which exceeds 100 parts by mass of (C)
(D) a photopolymerization initiator,
The (meth) acrylate having an aromatic ring is nonylphenoxypolypropylene glycol acrylate, or a mixture of nonylphenoxypolyethylene glycol and polypropylene glycol acrylate.

The curable resin composition according to claim 1, further comprising a silane coupling agent as the component (E).

The curable resin composition according to claim 1, further comprising a polymerization inhibitor as the component (F).

The fuel cell according to claim 1, wherein the diene-based or hydrogenated diene skeleton of the component (A) and / or the component (B) is composed of a hydrogenation product of polybutadiene, polyisoprene, polybutadiene and polyisoprene Lt; RTI ID = 0.0 > 1, < / RTI >

The curable resin composition according to claim 1, wherein the oligomer having a skeleton of a diene or hydrogenated diene of the component (A) and / or the component (B) has a molecular weight of 500 to 70000.

An adhesive composition comprising the curable resin composition according to any one of claims 1 to 5.

A cured product of the adhesive composition according to claim 6.

A composite in which an adherend is covered or bonded by the cured product of claim 7.

The composite according to claim 8, wherein the adherend is selected from the group consisting of triacetylcellulose, fluoropolymer, polyester, polycarbonate, polyolefin, glass, and metal.

A touch panel laminate having an adherend attached thereto according to claim 6.

A liquid crystal panel laminate obtained by adhering an adherend with the adhesive composition according to claim 6.

A display using the touch panel laminate according to claim 10.

A display using the liquid crystal panel laminate according to claim 11.