TWI582121B - A curable resin composition - Google Patents

Description

Curable resin composition

The present invention relates to a curable resin composition.

The touch panel mounted on a display device such as an LCD (Liquid Crystal Display) includes a resistive film type, an electrostatic capacitance type, an electromagnetic induction type, an optical type, and the like. A decorative board for designing goodness or a label for specifying a touch position may be adhered to the surface of these touch panels. 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 the past, the decorative board and the touch panel, the label and the touch panel, and the transparent substrate and the transparent plate were bonded together using an adhesive. Patent Document 1 describes a photocurable resin composition containing (A) a poly(methyl) polybutoprene (polybutadiene) or a polyurethane (poly) in a skeleton. Acrylate oligomer (meth) acrylate oligomer, (B) softening component, and (C1) selected from Phenoxy ethyl (meth) acrylate, phenoxy poly Ethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, nonyl phenol EO adduct (meth) acrylate A (meth) acrylate monomer in an ester, methoxy triethylene glycol (meth) acrylate or tetrahydroindenyl (meth) acrylate (Patent Document 1).

In recent years, glass of display devices such as LCDs has been continuously thinned. When the glass is thinned, the LCD is easily deformed by external stress. When a display device such as an LCD such as an LCD is bonded to an optical functional material such as an acrylic resin plate or a polycarbonate plate, the linear expansion of the glass and the acrylic resin, and the plastic such as an acrylic resin plate or a polycarbonate are used. The strain at the time of molding of the molding material is moderated or moisture absorbing/drying in the heat resistance test or the moisture resistance test, and causes surface dimensional changes such as dimensional change or warpage. When the conventional adhesive (for example, Patent Document 1) is used to suppress the deformation, there are problems such as peeling of the adhesive surface, cracking of the LCD, or unevenness of the LCD display.

As a countermeasure against the above problems, a UV curable resin as disclosed in Patent Document 3 has been proposed. Patent Document 3 is a highly elastic resin based on a rigid skeleton monomer such as isobornyl (meth) acrylate.

In the application of the adhesion of the decorative board to the touch panel, the bonding of the label to the touch panel, and the adhesion of the transparent substrate to the transparent plate, it is preferable to be adapted to be adapted to be stuck in the use environment (ie, the heating state). The degree of softness of the body deformation.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2010/027041

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

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

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

For example, the photocurable resin composition described in Patent Document 1 has insufficient adhesive durability or adhesive strength when printing the adhesive surface.

Further, the UV-curable resin of Patent Document 3 cannot undergo expansion and contraction of the adherend in the high-temperature reliability test, and peeling may occur.

Further, in the technique of any of the documents, when the printing surface is subjected to printing processing, the portion to be printed is less likely to be adhered by the light energy ray, and is affected by the uncured portion to lower the adhesiveness.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a curable resin composition capable of solving the following problems: for example, when bonding a decorative sheet and a label used in a display device such as a touch panel, bonding a transparent substrate and being transparent In the case of a substrate, when a portion to be printed is bonded, it is difficult to provide a sufficient adhesive durability, or a conventional technique in which the adhesive surface is peeled off or the glass of the display device is broken when the display device and the optical functional material are bonded together. Question.

That is, according to the present invention, there is provided a curable resin composition containing the following components (A) to (D): (A) having a (meth)acryloyl group and having a diene 100 parts of oligomers of a hydrogenated or diene skeleton, (B) an oligomer having more than 400 parts by mass and having no (meth)acryl fluorenyl group and having a diene or hydrogenated diene skeleton, and (C) having an aromatic ring of more than 100 parts by mass ( Methyl) acrylate, (D) photopolymerization initiator.

Moreover, according to the present invention, the curable resin composition further containing a silane coupling agent as the component (E) in the curable resin composition is provided. Moreover, according to the present invention, the curable resin composition further containing a polymerization stopper as the component (F) in the curable resin composition is provided. Further, according to the present invention, there is provided the above curable resin composition, wherein the diene or hydrogenated diene skeleton of the component (A) and/or the component (B) is selected from the group consisting of polybutadiene and polyisoprene. One or more skeletons in the group consisting of a hydride of polybutadiene and a hydride of polyisoprene. Moreover, according to the present invention, the curable resin composition is provided, and the oligomer having a diene or hydrogenated diene skeleton of the component (A) and/or the component (B) has a molecular weight of 500 to 70,000. Further, according to the present invention, there is provided an adhesive composition comprising the above curable resin composition. Further, according to the present invention, there is provided a cured product of the above adhesive composition. Further, according to the present invention, there is provided a composite in which the cured product is coated or bonded to the adherend. Further, according to the present invention, the above-mentioned adherend is provided to be selected from the group consisting of triacetyl cellulose, fluoropolymer, polyester, polycarbonate, polyolefine. One or more composites of the group consisting of glass and metal. Further, the present invention provides a touch panel laminate obtained by bonding an adherend using the above adhesive composition. Further, the present invention provides a liquid crystal panel laminate obtained by bonding an adherend using the above adhesive composition. In addition, the present invention also provides a display using the above touch panel laminate. Further, the present invention also provides a display using the above liquid crystal panel laminate.

The curable resin composition of the present invention is excellent in adhesive durability or adhesive strength in printing processing on an adhesive 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.

About (A) ingredients

In the present embodiment, as the component (A), an oligomer having a (meth) acrylonitrile group and having a diene or a hydrogenated die skeleton can be used.

The main chain skeleton of the oligomer in the present embodiment is a diene or a hydrogenated diene skeleton. The diene or hydrogenated diene skeleton is preferably one or more selected from the group consisting of hydrogenated products of polybutadiene, polyisoprene, polybutadiene, and polyisoprene. skeleton. Among these, in terms of having a large adhesive durability, it is preferably one or more selected from the group consisting of polybutadiene and polyisoprene, and more preferably polyisoprene.

The oligomer preferably has one or more (meth)acryl fluorenyl groups at the terminal or side chain of the main chain skeleton. Among these, it is preferred to have a (meth)acryl fluorenyl group at both ends of the main chain skeleton.

The molecular weight of the oligomer is preferably from 500 to 70,000, more preferably from 1,000 to 60,000, and most preferably from 1,000 to 55,000. When the molecular weight is within this range, the cured product obtained by curing the curable resin composition of the present embodiment has a high hardness, and therefore, the adhesive layer is easily formed, and the obtained curable resin composition is formed. Since the viscosity is small, the workability in the workability and the practical use such as mixing in the manufacturing process is improved. It should be noted that the molecular weight may be, for example, 500, 1000, 2000, 3000, 4000, 5000, 7000, 10000, 15000, 20000, 25000, 30000, 35000, 4000, 45000, 50000, 55000, 60000, 65000, 70000. Within the range of any two values.

The molecular weight of the oligomer means the number average molecular weight calculated as the average molecular weight per molecule. In the examples described later, 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 esterified oligomer of a maleic anhydride adduct of an isoprene polymer and 2-hydroxyethyl (meth) acrylate (the structure is as follows) (1), "UC-203" by Kuraray Co., Ltd., etc., "TEAI-1000" manufactured by Japan Soda Co., Ltd. (hydrogenated 1,2-polybutadiene oligomerization after terminal acrylic acid modification) "TE-2000" (1,2-polybutadiene oligomer modified with terminal acrylic acid) manufactured by Japan Soda Co., Ltd., and the like. Among these, an esterified oligomer of a maleic anhydride adduct of an isoprene polymer and 2-hydroxyethyl (meth) acrylate is preferable.

【化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 above formula is set so as to satisfy the number of functional groups: 1 to 10 and a molecular weight of 3,000 to 50,000. ]

About (B) ingredients

In the present embodiment, as the component (B), an oligomer having no (meth) acrylonitrile group and having a diene or a hydrogenated die skeleton can be used.

The main chain skeleton of the oligomer in the present embodiment is a diene or a hydrogenated diene skeleton. The diene or hydrogenated diene skeleton is preferably one or more selected from the group consisting of hydrogenated products of polybutadiene, polyisoprene, polybutadiene, and polyisoprene. skeleton. Among these, in terms of having a large adhesive durability, it is preferably one or more selected from the group consisting of polybutadiene and polyisoprene, and more preferably polybutadiene.

The oligomer preferably has one or more (meth)acryl fluorenyl groups at the terminal or side chain of the main chain skeleton. Among these, it is preferred to have a (meth)acryl fluorenyl group at both ends of the main chain skeleton.

The molecular weight of the oligomer is preferably from 500 to 70,000, more preferably from 1,000 to 60,000, and most preferably from 1,000 to 55,000. When the molecular weight is within this range, the cured product obtained by curing the curable resin composition of the present embodiment has a high hardness, and therefore, the adhesive layer is easily formed, and the obtained curable resin composition is formed. Since the viscosity is small, workability and workability in mixing and the like in the manufacturing process are improved. It should be noted that the molecular weight may be, for example, 500, 1000, 2000, 3000, 4000, 5000, 7000, 10000, 15000, 20000, 25000, 30000, 35000, 4000, 45000, 50000, 55000, 60000, 65000, 70000. Within the range of any two values.

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

Examples of the oligomer of the component (B) include "LIR-50" (isoprene oligomer) manufactured by Kuraray Co., Ltd., and "LBR-50" (LBR-50) (butadiene manufactured by Kuraray Co., Ltd.). "Opide", "Byron" (amorphous polyester resin) manufactured by Toyobo Co., Ltd., and the like. Among these, it is preferably one or more selected from the group consisting of an isoprene oligomer, a 1,2-polybutadiene oligomer, and a 1,4-polybutadiene oligomer, and more preferably The 1,2-polybutadiene oligomer and the 1,4-polybutadiene oligomer are most preferably a 1,4-polybutadiene oligomer.

About (C) ingredients

In the present embodiment, a (meth) acrylate having an aromatic ring can be used as the component (C). Examples of the (meth) acrylate having an aromatic ring include nonylphenoxy polyethylene glycol (meth) acrylate, benzyl (meth) acrylate, and ethoxylated phenyl (methyl). Acrylate, neopentyl glycol benzoate (meth) acrylate, ECH (ECH is abbreviated as epichlorohydrin) modified phenoxy (meth) acrylate, phenoxy diethylene glycol ( Methyl) acrylate, phenoxy hexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate Ester and the like. These (meth)acrylates may be used alone or in combination of two or more. Among these, a (meth) acrylate having a phenoxy group is preferable. The phenoxy group preferably has a structure represented by the following formula (2). R represents an arbitrary substituent. R may be exemplified by hydrogen, an alkyl group, a hydroxyl group or the like. R is preferably an alkyl group. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 6 to 12 carbon atoms. Among the (meth) acrylate having a phenoxy group, a (meth) acrylate having a mercaptophenoxy group and/or a phenoxyethyl (meth) acrylate is preferable, and a mercapto benzene is more preferable. A (meth) acrylate of an oxy group. Among the (meth) acrylates having a mercaptophenoxy group, a mercaptophenoxy polyalkylene glycol (meth) acrylate is preferred, preferably a nonylphenoxy polyethylene glycol (meth) acrylate. Nonylphenoxy polyethylene glycol (metha) acrylate and/or nonylphenoxy polypropylene glycol (meth) acrylate. The ethylene glycol chain of the nonylphenoxy polyethylene glycol (meth) acrylate - (CH ₂ CH ₂ O) n - is preferably n = 1 to 30. The propylene glycol chain -(CH ₂ CH ₂ O)n- of nonylphenoxypolypropylene glycol (meth) acrylate is preferably n = 1 to 30. The number of aromatic rings is, for example, 1, 2 or 3, and preferably one.

[Chemical 2]

R represents an arbitrary substituent.

About (D) ingredients

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

Examples of the (D) photoinitiator include an ultraviolet polymerization initiator and a visible light polymerization initiator, and the like can be used without limitation. Examples of the ultraviolet polymerization initiator include benzoin, benzophenone, and acetophenone. Examples of the visible light polymerization initiator include acyl phosphine oxides, thioxanthones, metallocenes, quinones, and α-aminoalkylphenones (α). -aminoalkylphenone) class and so on.

Examples of the (D) photoinitiator include benzophenone, 4-phenylbenzophenone, benzamidine benzoic acid, 2,2-diethoxyacetophenone, and bisdiethylaminodiphenyl. Methyl ketone, benzil, benzoin, benzamidine isopropyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl ketone, thioxanthone , 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthene Ketone, 2,4-diisopropylthioxanthone, 1-(4-isopropylphenyl)2-hydroxy-2-methylpropan-1-one, 1-(4-(2-hydroxyethoxy) -Phenyl)-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, camphorquinone, 2,4, 6-trimethylbenzimidium diphenylphosphine oxide, bis(2,4,6-trimethylbenzhydrazide)-phenylphosphine oxide, 2-methyl-1-(4-(methylthio) Phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone-1, 2-di Methylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, bis(2,6-dimethoxybenzene Formamidine)-2,4,4-trimethyl-pentylphosphine oxide, and the like.

In particular, in order to further improve the adhesiveness to each adherend, the curable resin composition of the present embodiment may contain (meth) acrylate other than the component (A) or (methyl) acrylate (C). )Acrylate.

About (E) ingredients

In the present embodiment, in order to increase the adhesion to the glass, a decane coupling agent may be contained as the component (E). As the decane coupling agent, γ-chloropropyltrimethoxydecane, vinyltrimethoxydecane, vinyltrichlorodecane, vinyltriethoxydecane, vinyl-tris(β-methoxyl) may be mentioned. Ethoxy)decane, γ-(meth)acrylomethoxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyl Trimethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β-(aminoethyl)-γ-aminopropyltrimethoxydecane, N-β- (aminoethyl)-γ-aminopropylmethyldimethoxydecane, γ-ureidopropyltriethoxydecane, and the like. Among these, from the viewpoint of adhesion to glass or the like, γ-glycidoxypropyltrimethoxydecane and/or γ-(meth)acryloxypropyltrimethoxydecane are preferred, and more preferred. It is γ-(meth)acrylomethoxypropyltrimethoxydecane.

About (F) ingredients

In the present embodiment, a polymerization inhibitor may be contained as the component (F) from the viewpoint of storage stability. Examples of the polymerization inhibitor include hindered phenols, bisphenols, and phosphoric acids. Among these, hindered phenols are preferable. Among the hindered phenolic antioxidants, butylhydroxytoluene (BHT), butylated hydroxyanisole (BHA), 2,4-dimethyl-6-tert-butylphenol, n-octadecyl-β- (4'-hydroxy-3',5'-di-tert-butylphenyl)propionate, styrenated phenol, styrenated cresol, tocopherol, 2,2'-methylene double (4-B -6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-butylene-bis(4-methyl-6-tert Butylphenol), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-trimethyl-2,4 ,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetrakis[methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propanoic acid Ester] methane, propyl gallate, octyl gallate, dodecyl gallate, 2,4,6-tri-tert-butylphenol, 2,5-di-tert-butylhydroquinone, 2 ,5-di-tert-amylhydroquinone, 4,4'-methylene-bis-(2,6-di-tert-butylphenol) 1,3,5-trimethyl-2,4,6-tri ( 3,5-di-tert-butyl-4-hydroxybenzyl)benzene, phenylpropionic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain alkyl ester (C is the number of carbon) and the like.

About the content of each component

In the present embodiment, the components (A) to (D) described above are contained as an essential component, whereby they can be cured by light or ultraviolet rays.

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 curable resin composition has a particularly high adhesiveness to the adherend, and the curability is improved, and the bonding surface is made from the bonding surface. It is preferable from the viewpoint of excellent adhesiveness at the time of printing, and more preferably contains 401 to 600 parts by mass, and most preferably contains 410 to 450 parts by mass. Here, the amount of the component (B) may be 400 or 4 with respect to 100 parts by mass of the component (A). 01, 402, 403, 404, 405, 410, 420, 430, 440, 450, 500, 550, 600 are within the range of any two values (may or may not include values at both ends).

The amount of the component (C) used is more than 100 parts by mass, preferably more than 100 parts by mass and 450 parts by mass or less, more preferably from 101 to 400 parts by mass, and most preferably from 150 to 350 masses, per 100 parts by mass of the component (A). unit. When the curable resin composition is more than 100 parts by mass, the adhesiveness of the curable resin composition is particularly high, and the curability is improved, and the adhesive strength at the time of printing the adhesive surface is excellent. Here, the amount of the component (C) used may be 100, 101, 102, 103, 104, 105, 110, 120, 130, 140, 150, 200, 250, 300 with respect to 100 parts by mass of the component (A). Within the range of any two of 350, 400, 450 (may or may not include values at both ends).

When the amount of the component (D) is 0.01 to 20 parts by mass based on the total of 100 parts by mass of the component (A), the component (B), and the component (C), the adhesiveness of the curable resin composition to the adherend It is particularly high and has good curability, and is preferably from the viewpoint of excellent adhesion at the time of printing the adhesive surface, and more preferably contains 0.5 to 5 parts by mass. Here, the amount of the component (D) to be used may be 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 15, for a total of 100 parts by mass of the component (A), the component (B), and the component (C). Within any range of 20 values (may or may not include values at both ends).

The amount of the component (E) to be used is preferably 0.01 to 20 parts by mass, and more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the total of the component (A), the component (B), and the component (C). Here, the amount of the component (E) used may be 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 15, for a total of 100 parts by mass of the component (A), the component (B), and the component (C). Within any range of 20 values (may or may not include values at both ends).

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, and most preferably 0.05, based on 100 parts by mass of the total of the component (A), the component (B), and the component (C). ~1 quality department. Here, the amount of the component (F) used may be 0.00001, 0.0001, 0.001, 0.01, 0.1, 1, 2, 3 with respect to 100 parts by mass of the total of the component (A), the component (B), and the component (C). Any range of 2 values (may or may not include values at both ends).

In addition to these components, elastomers, various paraffin waxes, plasticizers, fillers, colorants, rust inhibitors, and the like can be used as needed.

The curable resin composition of the present embodiment can be used as an adhesive composition. In the present embodiment, a composite can be produced by joining or coating an adherend with a cured product of the adhesive composition. The various materials of the adherend are preferably selected from the group consisting of polyolefins such as cycloolefin polymers, triethylene phthalocyanine, fluoropolymers, polyethylene terephthalate and the like, polycarbonate, glass, and metal. One or more of the above-described groups is more preferably one or more selected from the group consisting of polyester, polyolefin, and glass.

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

In the case where the curable resin composition of the present embodiment is bonded to a portion after being processed by printing, Can impart sufficient adhesive durability. As a printing processing method, a method of printing a printing ink in which a pigment and a binder are mixed on an adherend is exemplified. The thickness of the printing surface is not particularly limited as long as light such as ultraviolet rays and visible light passes through the printing surface to irradiate the curable resin composition, and the curable resin composition can be cured. From the viewpoint that light can pass through the printing surface, the thickness of the printing surface can be reduced to several μm.

The embodiments of the present invention have been described above with reference to the drawings, but these are examples of the invention, and various configurations other than the above may be employed.

[Examples]

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)

As long as there is no special description, it is equivalent to conducting an experiment at 23 °C. The curable resin composition of the composition shown in Tables 1-2 was prepared and evaluated. The results are shown in Tables 1 and 2.

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

As the oligomer having a (meth) acrylonitrile group and having a diene or a hydrogenated diene skeleton as the component (A), the following compounds were selected.

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

(A-2): Isoprene oligomer ("UC-203" manufactured by Kuraray Co., Ltd.) (a number average molecular weight of 36,000 in terms of polystyrene by GPC, maleic anhydride additive of isoprene polymer) Esterified oligomer with 2-hydroxyethyl ((meth) acrylate, Y in the formula (1) is ethylene, R is methyl)

As the (B) component, an oligomer having no (meth) acrylonitrile group and having a diene or a hydrogenated diene skeleton, the following compounds were selected.

(B-1): Isoprene oligomer ("LIR-30" manufactured by Kuraray Co., Ltd.) (number average molecular weight of 28,000 in terms of polystyrene by GPC)

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

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

(C-1): nonylphenoxy polyethylene glycol acrylate (n=1) ("M-111" manufactured by Toagosei Co., Ltd.)

(C-2): 2-hydroxy-3-phenoxypropyl acrylate ("ARONIX M-5700" manufactured by Toagosei Co., Ltd.)

(C-3): nonylphenoxy polypropylene glycol acrylate (n=2.5) ("M-117" manufactured by Toagosei Co., Ltd.)

(C-4): a mixture of nonylphenoxy polyethylene glycol (n=7) and polypropylene glycol (n=2) acrylate (referred to as "nonylphenoxy polyethylene glycol (n=7) /polypropylene glycol (n=2) acrylate", "BLEMMER 75ANEP-600" manufactured by Nippon Oil Co., Ltd.)

As the photoinitiator of the component (D), the following compounds were selected.

(D-1): 1-hydroxycyclohexyl phenyl ketone ("Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.)

(D-2): 2,4,6-trimethylbenzhydrazide-diphenyl-phosphine oxide ("DarocurTPO" manufactured by Ciba Specialty Chemicals Co., Ltd.)

As the decane coupling agent of the component (E), the following compounds were selected.

(E-1): γ-methacryloxypropyltrimethoxydecane ("SILQUEST A-174" manufactured by Momentive Co., Ltd.)

As a polymerization inhibitor of the component (F), the following compounds were selected.

(F-1): phenylpropionic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxyl, C7-9 side chain alkyl ester ("Irganox 1135" manufactured by BASF Corporation)

Various physical properties were determined as follows.

[Photocuring]

Measured at a temperature of 23 °C. With respect to photocurability, a curable resin composition was applied to the surface of TEMPAX glass (width 25 mm × length 25 mm × thickness 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 . Then, the tensile shear adhesive strength was measured. A curable resin composition was prepared and applied. When the test piece is subjected to printing processing, the printing process is performed by the following method. A test piece having a printing surface having a thickness of several μm was produced by spray coating a black paint composed of carbon powder and a solvent on the entire surface of the test piece.

[Polyethylene terephthalate (PET) adhesive evaluation (peeling adhesive strength between polyethylene terephthalate test pieces)]

The curable resin composition was used as an adhesive composition, and the biaxially stretched PET film (lumirror T60) was made to have a thickness of 30 μm of the adhesive layer and a thickness of 30 μm in the longitudinal direction and 10 mm in the transverse direction in a state where the adhesive surface was subjected to printing processing. Test piece after printing processing with an average thickness of 190 μm and manufactured by Toray Industries Co., Ltd. (width 50 mm × Adhesive between 10 mm long and 0.19 mm thick. After curing by photocuring, the film-end portions of the two portions of the test piece which were adhered by the adhesive composition were not stretched, and the portions which were in close contact with each other were peeled off, and the initial 180 was measured. ° Peel off the adhesive strength. The light irradiation conditions in photocuring are in accordance with the method described in [Photocurability]. The peeling adhesive strength (unit: N/cm) was measured at a tensile speed of 50 mm/min in 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 11.5 mm, and a length of 25 mm is used as a spacer, and a curable resin composition is used as an adhesive composition, and printing processing is performed in a state where printing is performed on the bonding surface. The heat-resistant glass test piece (width 25 mm × length 25 mm × thickness 2.0 mm) was adhered (adhesive area 3.125 cm ² ). The light irradiation conditions in photocuring are in accordance with the method described in [Photocurability]. After the adhesive composition was cured under the above conditions, an adhesive composition "G-55" made by Electric Chemical Industry Co., Ltd. was used, and a galvanized steel sheet was adhered to both sides of the test piece (width 100 mm × length 25 mm). × thickness 2.0 mm, manufactured by Engineering Test Service Co., Ltd.). After curing, the test piece bonded by the adhesive composition was used, and the galvanized steel sheet was clamped, and the initial tensile shear adhesive strength was measured. Tensile shear adhesive strength (unit: MPa) was measured at a tensile speed of 10 mm/min in a temperature of 23 ° C and a humidity of 50% using a tensile tester.

[Evaluation of adhesiveness of cycloolefin polymer (COP) (peeling adhesive strength between test pieces of cycloolefin polymer)]

The curable resin composition is used as an adhesive composition, and in the state where the adhesive surface is subjected to printing processing, the adhesive surface is made of a thickness of 10 μm, and the adhesive area is 40 mm in the longitudinal direction and 10 mm in the lateral direction to make the COP film. The test piece (width: 50 mm × length: 10 mm × thickness: 0.04 mm) after printing (ZEONOR, average thickness: 40 μm, manufactured by Zeon Corporation) was adhered. After curing by photocuring, the film-end portions of the two portions of the test piece which were adhered by the adhesive composition were not stretched, and the portions which were in close contact with each other were peeled off, and the initial 180 was measured. ° Peel off the adhesive strength. The light irradiation conditions in photocuring are in accordance with the method described in [Photocurability]. The peeling adhesive strength (unit: N/cm) was measured at a tensile speed of 50 mm/min in a temperature of 23 ° C and a humidity of 50% using a tensile tester.

[Evaluation of Adhesiveness of Triethylene Cellulose (Removal Adhesive Strength Between Triethylene Cellulose Test Pieces)]

The curable resin composition was used as an adhesive composition, and in the state where the adhesive surface was subjected to printing processing, the adhesive area was 10 μm in thickness and the adhesive area was 40 mm in the longitudinal direction and 10 mm in the transverse direction to make triethylcellulose (TAC). The test piece (width 50 mm × length 10 mm × thickness 0.04 mm) after the printing process of the film (average thickness: 40 μm, manufactured by Fujifilm Co., Ltd.) was adhered. The film end portions of the two portions of the test piece which were adhered by the adhesive composition were not stretched, and the portions which were in close contact with each other were peeled off, and the initial 180° peeling adhesive strength was measured. The light irradiation conditions in photocuring are in accordance with the method described in [Photocurability]. The peeling adhesive strength (unit: N/cm) was measured at a tensile speed of 50 mm/min in a temperature of 23 ° C and a humidity of 50% using a tensile tester.

[Evaluation of adhesiveness of fluoropolymer (peeling adhesive strength between fluorine-containing film test pieces)]

The curable resin composition is used as an adhesive composition, and in the state where the adhesive surface is subjected to printing processing, the adhesive area is 10 μm in the longitudinal direction and the adhesive area is 40 mm in the longitudinal direction and 10 mm in the lateral direction to make PVDF (polyvinylidene fluoride, The test piece (width: 50 mm × length: 10 mm × thickness: 0.04 mm) after the printing process of the film (average thickness: 40 μm, "DX film" manufactured by Denki Kagaku Kogyo Co., Ltd.) was adhered. Pulling The film end portions of the two portions of the test piece which were adhered by the adhesive composition were not peeled, and the portions which were in close contact with each other were peeled off, and the initial 180° peeling adhesive strength was measured. The light irradiation conditions in photocuring are in accordance with the method described in [Photocurability]. The peeling adhesive strength (unit: N/cm) was measured at a tensile speed of 50 mm/min in a temperature of 23 ° C and a humidity of 50% using a tensile tester.

[Polycarbon adhesion evaluation (stretching adhesive strength between polycarbonate test pieces)]

A Teflon (registered trademark) tape having a thickness of 80 μm, a width of 12.5 mm, and a length of 25 mm is used as a spacer, and a curable resin composition is used as an adhesive composition, and printing processing is performed in a state where printing is performed on the bonding surface. The polycarbonate (Panlite) test piece (width: 25 mm × length 25 mm × thickness 2.0 mm) was adhered (adhesive area: 3.125 cm ² ). The light irradiation conditions in photocuring are in accordance with the method described in [Photocurability]. Tensile shear adhesive strength (unit: MPa) was measured at a tensile speed of 10 mm/min in a temperature of 23 ° C and a humidity of 50% using a tensile tester.

[Metal Adhesive Evaluation (Tensile Adhesive Strength Between SPCC Test Pieces and Glass Test Pieces)]

A Teflon (registered trademark) tape having a thickness of 80 μm, a width of 12.5 mm, and a length of 25 mm is used as a spacer, and a curable resin composition is used as an adhesive composition, and printing processing is performed in a state where printing is performed on the bonding surface. The latter SPCC test piece (width 25 mm × length 25 mm × thickness 1.6 mm) was adhered to TEMPAX glass (width 25 mm × length 25 mm × thickness 2 mm) (adhesive area 3.125 cm ² ). The light irradiation conditions in photocuring 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 by Electrochemical Industry Co., Ltd. was further used, and the galvanized steel sheet was glued on the side of the TEMPAX test piece (width 100 mm × length 25 mm × thickness). 2.0mm, manufactured by Engineering Test Service). After curing, the test piece bonded by the adhesive composition was used, and the galvanized steel sheet was clamped, and the initial tensile shear adhesive strength was measured. Tensile shear adhesive strength (unit: MPa) was measured at a tensile speed of 10 mm/min in a temperature of 23 ° C and a humidity of 50% using a tensile tester.

[Damp heat resistance evaluation (stretching adhesive strength between heat-resistant glass test pieces after high-temperature and high-humidity exposure)]

The curable resin composition was used as an adhesive composition, and in the state where the adhesive surface was subjected to printing processing, the adhesive area was 1.0 mm ² with a thickness of the adhesive layer of 100 μm, and the TEMPAX glass (width 25 mm) after printing was processed. × Length 25mm × thickness 2mm) is glued and solidified. The light irradiation conditions in photocuring are in accordance with the method described in [Photocurability]. After curing, the test piece adhered by 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 adhesive strength was measured using the exposed test piece. The appearance of the adhesive portion was visually observed to examine whether it was yellow. Tensile shear adhesive strength (unit: MPa) was measured at a tensile speed of 10 mm/min in a temperature of 23 ° C and a humidity of 50% using a tensile tester.

[Appearance observation (yellowness)]

The curable resin composition was used as an adhesive composition, and the adhesive area was 1.0 mm ² with a thickness of the adhesive layer of 100 μm, and the TEMPAX glass (width 25 mm × length 25 mm × thickness 2 mm) was adhered and cured. The light irradiation conditions in photocuring are in accordance with the method described in [Photocurability]. After the curing, the test piece which was adhered with the adhesive composition was subjected to a color measuring device (UV-VISIBLE SPECTROPOHOTOMETER, manufactured by SHIMADZU Co., Ltd.), and the Δb value was regarded as yellowing degree.

The following facts are known from experimental examples. The curable resin composition relating to the embodiment of the present invention exhibits high adhesiveness and exhibits good curing characteristics as well as moist heat resistance. Further, the curable resin composition according to the examples of the present invention can impart sufficient adhesive durability in the case of bonding the portion after the printing process. In particular, it exhibits high adhesiveness to triacetyl cellulose, fluoropolymer, polyester, polycarbonate, polyolefin, glass, and metal. The curable resin composition according to the embodiment of the present invention exhibits high adhesiveness, and therefore, when a display device such as a thin glass LCD is bonded to an optical functional material such as an acrylic resin plate or a polycarbonate plate, Peeling of the adhesive surface, LCD cracking or uneven LCD display. The curable resin composition according to the embodiment of the present invention has a large heat and humidity resistance and can follow the deformation of the adherend in a heating atmosphere, so that the adherend does not peel off. In the case where the curable resin composition according to the above embodiment was bonded to the portion after the printing process, the experiment was carried out. However, when the portion where the printing process was not performed was bonded, it was confirmed by experiments that sufficient glue could be imparted. Sticky.

The curable resin composition according to the comparative example does not have the effects of the present invention.

[Industrial availability]

The curable resin composition of the present invention can be used as an adhesive composition for a touch panel laminate and 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. When the curable resin composition of the present invention is bonded to a transparent portion and a translucent portion, the curability can be improved.

Claims (13)

A curable resin composition containing the following components (A), (B), (C), and (D), (A) having 100 parts by mass, having (meth)acryl fluorenyl group, and having a diene An oligomer of a hydrogenated or diene skeleton; (B) an oligomer having more than 400 parts by mass and having no (meth) acrylonitrile group and having a diene or hydrogenated die skeleton; More than 100 parts by mass of nonylphenoxypolyalkylene glycol (meth) acrylate; and (D) photopolymerization initiator. The curable resin composition according to claim 1, further comprising a decane coupling agent as the component (E). The curable resin composition according to claim 1, further comprising a polymerization inhibitor as the component (F). The curable resin composition according to claim 1, wherein the (A) component and/or the diene or hydrogenated diene skeleton of the component (B) is selected from the group consisting of polybutadiene. One or more skeletons of the group consisting of polyisoprene, a hydride of polybutadiene, and a hydride of polyisoprene. The curable resin composition according to claim 1, wherein the molecular weight of the oligomer having the diene or hydrogenated diene skeleton of the component (A) and/or the component (B) It is 500~70000. An adhesive composition comprising the curable resin composition according to any one of the first to fifth aspects of the invention. A cured product which is a cured product of the adhesive composition as described in claim 6 of the patent application. A composite body obtained by coating or joining an adherend as disclosed in claim 7 of the patent application. The composite according to claim 8, wherein the adherend is selected from the group consisting of triacetyl cellulose, fluoropolymer, polyester, polycarbonate, polyolefin, glass, and metal. More than one of them. A touch panel laminate obtained by bonding an adherend with an adhesive composition as described in claim 6 of the patent application. A liquid crystal panel laminate obtained by bonding an adherend with an adhesive composition as described in claim 6 of the patent application. A display using the touch panel laminate as described in claim 10 of the patent application. A display using the liquid crystal panel laminate as described in claim 11.