TW201300484A - Energy-beam-curable resin composition - Google Patents

Abstract

The purpose of the invention is to provide an energy beam-curable resin composition that can achieve rapid curing. This energy beam-curable resin composition contains: (A) a compound represented by formula (1) having a (meth)acryloyl group and an alicyclic epoxy group in each molecule, the (A) compound content being greater than 65 mass parts and 100 mass parts or less per 100 weight parts in total of a polymer component comprising component (A), a component (D), and a component (E); (B) a photocationic polymerization initiator; and (C) a photoradical polymerization initiator. In the formula, R represents a hydrogen atom or a methyl group, and X represents a C1-6 alkylene chain or a C1-6 oxyalkylene chain.

Description

Energy ray hardening resin composition

The present application relates to an energy ray-curable resin composition, and an adhesive and a cured body using the same.

In recent years, an energy ray-curable adhesive which can be hardened by an energy ray such as ultraviolet rays for a short period of time is applied to assembly of components or packaging of a package of a semiconductor element or the like. The components include liquid crystal panels, organic electroluminescent panels, touch panels, projectors, smart phones, mobile phones, digital cameras, digital projectors, LEDs, solar cells, and the like. Examples of the semiconductor element include a CCD, a CMOS, a flash memory, a DRAM, and the like.

The energy ray-curable adhesive used in these fields needs to have high adhesion to various materials, and high reliability that can withstand heat, humidity, thermal cycling, and the like. Further, regarding the energy ray-curable adhesive used in these fields, in the cleaning step, the etching step, and the like, the adhesive is exposed to chemicals such as alcohols, acids, alkalis, etc., and therefore an adhesive is required for this. The resistance of various chemicals, the so-called chemical resistance.

When an optical element such as a lens, a cymbal, or a filter used in a digital camera, a binocular, or a microscope is attached, the energy ray-curable adhesive needs to have high transparency in a visible light region of 400 nm to 800 nm.

As the energy ray-curable adhesive, an adhesive such as an acrylic, epoxy or alkene thiol is commercially available. The acrylic or olefinic thiol-based adhesive is excellent in quick-curing property and adhesion, but has a problem that chemical resistance is not good. The epoxy-based adhesive is excellent in chemical resistance and adhesion, but has a problem that the quick-curing property is not good.

In the case of solving the problems of the acrylic type and the epoxy-based problem as described above, there are disclosed resin compositions having an acrylic compound and an epoxy compound (Patent Documents 1 to 3) or acrylic acid in the same molecule. A compound having a group and an epoxy group and a resin composition (Patent Documents 4 to 8). However, these well-known resin compositions do not satisfy the rapid hardenability, adhesiveness, and chemical resistance required for the above-mentioned adhesive. In the case of the present invention, the amount of the component (A) is different from that of Patent Document 7.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 11-35846

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2006-233009

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2008-260879

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2003-55362

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2008-88167

[Patent Document 6] Japanese Patent No. 4095380

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2008-260879

[Patent Document 8] Japanese Laid-Open Patent Publication No. 2010-248500

The present invention relates to an energy ray-curable resin composition which is fast-curable.

The present invention includes the following forms (1) to (7).

(1) An energy ray-curable resin composition comprising: (A) a component having a (meth)acryl fluorenyl group and an alicyclic epoxy group represented by the following formula [1] a compound of the base, and more than 65 parts by mass in 100 parts by mass of the total amount of the polymerization component and less than 100 parts by mass;

(wherein R represents hydrogen or a methyl group, X represents an alkylene chain having 1 to 6 carbon atoms or an alkyloxy chain having 1 to 6 carbon atoms), and a photocationic polymerization initiator of the component (B); A photoradical polymerization initiator of component C).

(2) The energy ray-curable resin composition according to (1), which comprises an oligomer having two or more epoxy groups in the molecule of the component (D).

(3) The energy ray-curable resin composition according to (2), wherein the oligomer of the component (D) having two or more epoxy groups in the molecule has a molecular weight of from 350 to 100,000.

(4) The energy ray-curable resin composition according to (1), which comprises a cationically polymerizable monomer other than (A) and (B) of the component (E).

(5) An adhesive comprising the energy ray-curable resin composition according to any one of (1) to (4).

(6) A hardened body obtained by curing the energy ray-curable resin composition according to any one of (1) to (4).

(7) A conjugate of the energy ray-curable resin composition according to any one of (1) to (4).

The energy ray-curable resin composition composed of the above configuration can satisfy, for example, rapid hardenability.

<Description of terms>

In the present specification, the energy ray-curable resin composition means a resin composition which can be hardened by irradiation with an energy ray. Here, the energy line means an energy line represented by ultraviolet rays, visible light, or the like.

In the present specification, the molecular weight means a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

In the present specification, the mass part means a part by mass in 100 parts by mass of the total amount of the polymerization component, unless otherwise noted. Here, the polymerization component means the component (A), the component (D) used as needed, and the component (E) used as needed.

The components of the energy ray-curable resin composition of the present embodiment will be described.

In the energy ray-curable resin composition of the present embodiment, the component (A) is a compound having a (meth)acrylonyl group and an alicyclic epoxy group in the molecule represented by the following formula [1]. .

(wherein R represents hydrogen or a methyl group, and X represents an alkyl chain having 1 to 6 carbon atoms or an oxygen alkyl group having 1 to 6 carbon atoms).

The oxygen chain alkyl chain can be exemplified by -R'-O-. Here, R' means an alkylene group having 1 to 6 carbon atoms. When the oxygen alkyl chain is -R'-O-, the formula [1] is as shown in the following formula [1']:

The component (A) used in the present invention may, for example, be 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, or 3,4-ring. Oxycyclohexyl propyl (meth) acrylate, 3,4-epoxycyclohexyl butyl (meth) acrylate, ethylene oxide modified 3,4-epoxycyclohexylmethyl (meth) acrylate The ester or propylene oxide is modified with 3,4-epoxycyclohexylmethyl (meth) acrylate. From the viewpoint of excellent chemical resistance, 3,4-epoxycyclohexylmethyl (meth) acrylate is preferred among these.

The content of the component (A) is more than 65 parts by mass based on 100 parts by mass of the total of the polymer components composed of the component (A), the component (D), and the component (E), and is 100 parts by mass or less. It is better. If it is this range, not only hardenability will not worsen, but adhesiveness or chemical resistance will not fall. In particular, from the viewpoint of curability, adhesion, and chemical resistance, it is preferably 70 parts by mass or more and 95 parts by mass or less.

The component (B) of the energy ray-curable resin composition of the present embodiment contains a photocationic polymerization initiator as an essential component. The photocationic polymerization initiator of the component (B) is not particularly limited as long as it is a compound which can generate a cationic species by irradiation with an energy ray.

The photocationic polymerization initiator of the component (B) used in the invention may, for example, be an arylsulfonium salt derivative (for example, CYRACURE UVI-6990, CYRACURE UVI-6974 manufactured by Dow Chemical Co., Ltd., Adeka optomer SP manufactured by Asahi Kasei Kogyo Co., Ltd.) -150, Adeka optomer SP-152, Adeka optomer SP-170, Adeka optomer SP-172, CPI-100P manufactured by San-Apro, CPI-101A, CPI-200K, CPI-210S, Chivacure-1190 manufactured by Double Bond Co., Ltd. (CGI*TPS C1, GSID26-1, etc., manufactured by Ciba Japan Co., Ltd.), and an aromatic sulfonium salt derivative (for example, Irgacure-250 manufactured by Chiba Specialty Chemicals Co., Ltd., CGI ^* BBI C1 manufactured by Ciba Japan Co., Ltd., manufactured by Rhodia Japan Co., Ltd.) An acid generator such as RP-2074), a propadiene ion complex derivative, a diazonium salt derivative, a triazine-based initiator, and other halides. The photocationic polymerization initiator may be used alone or in combination of two or more kinds in any ratio. The cationic species of the photocationic polymerization initiator is preferably a phosphonium cation. Examples of the phosphonium cation include an aryl sulfonium salt derivative, an aryl sulfonium salt derivative, and the like. Examples of the anion species of the photocationic polymerization initiator include halides such as a boron compound, a phosphorus compound, a ruthenium compound, an arsenic compound, and an alkylsulfonic acid compound. From the viewpoint of excellent hardenability, among these, an aromatic sulfonium salt derivative is preferred.

The content of the photocationic polymerization initiator of the component (B) is 0.1 to 10 parts by mass based on 100 parts by mass of the total of the polymerization components composed of the component (A), the component (D) and the component (E). The proportion of parts by mass is better. If it is this range, not only hardenability will not worsen, but adhesiveness or chemical resistance will not fall. In particular, the photocationic polymerization initiator of the component (B) is preferably used in an amount of 0.3 to 5 parts by mass, preferably 0.5 to 3 parts by mass, from the viewpoints of hardenability, adhesion, and chemical resistance. .

The component (C) of the energy ray-curable resin composition of the present embodiment contains a photoradical polymerization initiator as an essential component. The photoradical polymerization initiator of the component (C) is not particularly limited as long as it is a compound which generates a radical by irradiation with an energy ray.

The photoradical polymerization initiator of the component (C) used in the present invention can be enumerated Diphenyl ketone, 4-phenyldiphenyl ketone, benzamidine benzoic acid, 2,2-diethoxyacetophenone, bisdiethylaminodiphenyl ketone, benzyl, benzoin, benzene Methyl isopropyl isopropyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, thioxanthone, 1-(4-isopropylphenyl) 2-hydroxy-2-methyl propyl - 1-ketone, 1-(4-(2-hydroxyethoxy)-phenyl)-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methyl-propan-1 -ketone, camphorquinone, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, 2-methyl 1-(4-(methylthio)phenyl)-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylbenzene 1-butanone-1, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, and the like. From the viewpoint of excellent hardenability, among these, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropan-1-one, 1-(4-(2-hydroxyethyl) Oxy)-phenyl)-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1- 1 of α-hydroxyacetophenones such as {4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methyl-propan-1-one The above is better. These may be used alone or in combination of two or more.

The content of the photoradical polymerization initiator of the component (C) is 0.1% by mass based on 100 parts by mass of the total of the polymer components composed of the component (A), the component (D) and the component (E). A ratio of 10 parts by mass is preferred. If it is this range, not only hardenability will not worsen, but adhesiveness or chemical resistance will not fall. In particular, the photoradical polymerization initiator of the component (C) is preferably used in an amount of 0.5 to 5 parts by mass, and preferably 1 to 3 parts by mass, from the viewpoints of hardenability, adhesion, and chemical resistance. good.

Various photosensitizers can also be used in combination in the resin composition of the present invention. Photosensitizer refers to the absorption of energy rays, photocationic polymerization initiators or light freedom The base polymerization initiator effectively produces a cationic or free radical compound.

The photosensitizer to be used in the present invention is not particularly limited, and examples thereof include a diphenyl ketone derivative, a phenothiazine derivative, a phenyl ketone derivative, a naphthalene derivative, an anthracene derivative, a phenanthrene derivative, and a thick four. Benzene derivative, fused phthalene derivative, hydrazine derivative, condensed pentabenzene derivative, acridine derivative, benzothiazole derivative, benzoin derivative, anthracene derivative, naphthoquinone derivative, anthracene derivative, hydrazine Tons of derivatives, ketone derivatives, thioxanthene derivatives, thioxanthone derivatives, coumarin derivatives, coumarin derivatives, anthocyanin derivatives, pyridazine derivatives, thiazine derivatives, evil Azine derivative, porphyrin derivative, anthracene derivative, triallyl methane derivative, anthraquinone derivative, spiropyran derivative, spirooxazine derivative, thiospirone derivative, organic hydrazine Complex and so on.

The content of the photosensitizer is preferably from 0.1 to 5 parts by mass based on 100 parts by mass of the total of the polymerization components. If it is within this range, the adhesion or chemical resistance is not lowered. In particular, the use amount of the photosensitizer is preferably from 0.3 to 3 parts by mass, and most preferably from 0.5 to 2 parts by mass, from the viewpoints of hardenability, adhesion, and chemical resistance.

In the energy ray-curable resin composition of the present embodiment, the component (D) is preferably an oligomer containing one or more epoxy groups in the molecule.

The oligomer of the component (D) used in the present invention having one or more epoxy groups in the molecule may, for example, be an aromatic, aliphatic or alicyclic oligomer. Examples of the aromatic system include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, phenolic phenol type epoxy resin, and a phenol novolac type epoxy resin, the like, and the like.

Examples of the aliphatic group include an epoxidized modified polybutadiene, an epoxidized modified polyisoprene, an epoxidized modified polyolefin, and a polyethylene glycol adduct. A diglycidyl ether of a polyalkylene glycol such as a diglycidyl ether or a polypropylene glycol adduct. The alicyclic system may be a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol or the above aromatic A hydride of an epoxy resin. From the viewpoint of excellent chemical resistance, among these, epoxidized polybutadiene, epoxidized modified polyisoprene, 2,2-bis(hydroxymethyl)-1-butene One or more kinds of the 1,2-epoxy-4-(2-oxiranyl)cyclohexane adducts of the alcohol are preferred, and the epoxidized modified polybutadiene is preferred.

The microstructure of the polybutadiene is not particularly limited, and may be a low-cis polybutadiene skeleton having a low ratio of a 1,4-cis unit and a high-cis polymerization having a high ratio of a 1,4-cis unit. Any of a butadiene skeleton, a 1,2-cis body representing a 1,2-polybutadiene skeleton, and the like. One or more of these may be mixed.

The molecular weight of the oligomer of the component (D) having one or more epoxy groups in the molecule is preferably from 350 to 100,000, more preferably from 500 to 50,000, most preferably from 2,000 to 20,000. When the molecular weight is 350 or more, the chemical resistance does not decrease, and if it is 100,000 or less, the hardenability does not decrease.

Further, the molecular weight referred to herein means a number average molecular weight, and is a polystyrene-equivalent number average molecular weight measured by gel permeation chromatography (GPC).

When considering the balance of rapid hardenability, adhesion, and chemical resistance, the oligomer of the component (D) having one or more epoxy groups in the molecule is composed of the component (A), the component (D), and (E). The total amount of the polymerization components composed of the components is preferably 5 to 35 parts by mass, and preferably 10 to 30 parts by mass, based on 100 parts by mass of the total amount of the components.

The energy ray-curable resin composition of the present embodiment may contain a cationically polymerizable monomer other than the components (A) and (B) as the component (E), insofar as the target physical properties are not impaired.

The cationically polymerizable monomer other than the components (A) and (B) used as the component (E) used in the present invention may, for example, be a cyclic ether monomer, a cyclic thioether monomer or a cationically polymerizable vinyl monomer. . The cyclic ether monomer may, for example, be a monomer such as an epoxy group or an oxetane. Examples of the thioether monomer include isobutylene sulfide and the like.

Examples of the cationically polymerizable vinyl monomer include vinyl ether, vinylamine, and styrene. These monomers or derivatives may be used alone or in combination of two or more.

The cyclic ether monomer is not particularly limited, and examples thereof include 1,2-epoxycyclohexane, 1-(oxiranyl)-3,4-epoxycyclohexane, and 3,4-epoxycyclohexane. Alkenylmethyl-3',4'-epoxycyclohexenecarboxylate, bis(1-ethyl-3-oxetanyl)methyl ether, 4-hydroxybutyl methacrylate glycidyl ether, Glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, (meth) acrylate = (3-ethyl oxetan-3-yl) methyl, 3 -ethyl-3-hydroxymethyloxetane, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 3-ethyl-3 -(phenoxymethyl)oxetane, bis(1-ethyl-3-oxetanyl)methyl ether, 3-ethyl-3-(2-ethylhexyloxymethyl) Oxetane and the like. Oxetane refers to a monomer having one or more oxetanyl groups in the molecule.

The vinyl ether monomer is not particularly limited, and examples thereof include ethylene glycol divinyl ether, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, and triethylene glycol. Alcohol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexane dimethanol divinyl ether, hydroxyethyl monoethylene a di- or trivinyl ether compound such as an ether, hydroxydecyl monovinyl ether or trimethylolpropane trivinyl ether; ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, Octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexane dimethanol monovinyl Ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether-o-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl A monovinyl ether compound such as ether.

The vinylamine monomer is not particularly limited, and examples thereof include N-vinyldimethylamine, N-vinylethylbutylamine, N-vinyldiphenylamine, N-vinylformamide, and N-vinylethylamine. Amidoxime compounds and the like.

Among the cationically polymerizable monomers other than the components (A) and (B) as the component (E), a cyclic ether monomer is preferred, and 3,4-epoxycyclohexenylmethyl group is used. One or more of 3', 4'-epoxycyclohexene carboxylate and bis(1-ethyl-3-oxetanyl) methyl ether are preferred.

In consideration of the balance of the quick-curing property, the adhesion property, and the chemical resistance, the cationically polymerizable single system other than the components (A) and (B) of the component (E) is composed of the component (A) and the component (D). The total amount of the polymer component composed of the component (E) is preferably 5 to 35 parts by mass, and preferably 10 to 30 parts by mass, based on 100 parts by mass of the total amount of the polymer component.

In the present invention, one or two or more of the group consisting of a phenolic antioxidant and a lanthanoid antioxidant may be contained as an antioxidant.

In the present invention, a phosphine oxide derivative can also be used.

In the present invention, a filler (inorganic filler) may be further contained.

Various elastomers such as acrylic rubber or urethane rubber, methyl methacrylate-butadiene-styrene graft copolymer or acrylonitrile-butyl may be contained within a range not impairing the object of the present embodiment. An additive such as a graft copolymer such as a diene-styrene graft copolymer, a solvent, a bulking agent, a reinforcing material, a plasticizer, a tackifier, a dye, a pigment, a flame retardant, and a surfactant.

In the present invention, one or two or more kinds of decane coupling agents can be contained in an arbitrary ratio.

The energy ray-curable resin composition composed of the above composition can also be borrowed It is hardened by irradiation of an energy ray and becomes a hardened body.

The energy ray-curable resin composition composed of the above configuration can also be used as an adhesive. The adhesive can be suitably used for electronic parts of liquid crystal panels, organic electroluminescent panels, touch panels, projectors, smart phones, mobile phones, digital cameras, digital projectors, LEDs, solar cells, lithium ion batteries, and the like. Assembly, or packaging of a semiconductor device such as CCD, CMOS, flash memory, DRAM, or the like. It can be used as an adhesive suitable for the pedestal of the process glass, the fixed use of the vessel, two or more lenses or the optical elements used in the camera, binoculars, and microscope.

The method for producing the energy ray-curable resin composition of the present embodiment is not particularly limited as long as the above materials can be sufficiently mixed. The mixing method of the material is not particularly limited, and examples thereof include a stirring method in which a stirring force is generated by rotation of a propeller, a method using a conventional disperser such as a planetary mixer by autorotation and revolution, and the like. These mixing methods are suitable for low-cost and stable mixing.

After the above mixing, the energy ray-curable resin composition may be cured by irradiation with an energy ray using the following light source.

In the present embodiment, the light source used for curing the energy ray-curable resin composition is not particularly limited, and examples thereof include a halogen lamp, a metal halide lamp, a high-power metal halide lamp (including indium), a low-pressure mercury lamp, and a high voltage. Mercury lamps, ultra-high pressure mercury lamps, xenon lamps, xenon excimer lamps, xenon flash lamps, and light-emitting diodes (hereinafter referred to as LEDs). These light sources are suitable from the viewpoint of effectively illuminating the energy rays corresponding to the reaction wavelengths of the respective photopolymerization initiators.

The radiation wavelength and energy distribution of each of the above light sources are different. therefore, The above light source can be appropriately selected depending on the reaction wavelength of the photopolymerization initiator or the like. Or natural light (sunlight) can also be the starting source of the reaction.

The light source may be directly irradiated, or may be condensed by a mirror or the like, and concentrated by light irradiation. Low-wavelength filters, hot wire filters, cold mirrors, etc. can also be used.

The energy ray-curable resin composition having the above-described configuration can provide an energy ray-curable resin composition excellent in curability, adhesion, and chemical resistance, and an adhesive using the same.

[Examples]

The invention is further illustrated in the following examples and comparative examples, but the invention is not limited thereto.

The following compounds were used in the examples.

(A) ingredients are as follows:

(A-1) 3,4-epoxycyclohexylmethyl methacrylate ("CYCLOMER M-100", manufactured by DAICEL Chemical Industry Co., Ltd.)

(A-2) 3,4-epoxycyclohexyl methacrylate ("CYCLOMER A-200", manufactured by DAICEL Chemical Industry Co., Ltd.)

The photocationic polymerization initiator of the component (B) is the following:

(B-1) Aromatic antimony SbF ₆ salt ("Adeka optomer SP-170" manufactured by Adeka Co., Ltd.)

(B-2) Aromatic 鋶PF ₆ salt ("Adeka optomer SP-150" manufactured by Adeka Co., Ltd.)

The photoradical polymerization initiator of the component (C) is the following:

(C-1) 2-hydroxy-2-methyl-1-phenyl-propan-1-one ("Darocur 1173", manufactured by Ciba Japan Co., Ltd.)

(C-2) 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Japan Co., Ltd. "Irgacure-184")

(C-3) 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methyl-propan-1-one ( "Irgacure-127" by Ciba Japan)

The epoxy group-containing oligomer of the component (D) is the following:

(D-1) bisphenol A type epoxy resin (Adeka optomer KRM-2410 manufactured by Adeka Co., Ltd.): 400)

(D-2) bisphenol F type epoxy resin (Adeka optomer KRM-2490" manufactured by Adeka Co., Ltd.: 380)

(D-3) Hydrogenated bisphenol A type epoxy resin ("YX-8000" manufactured by Mitsubishi Chemical Corporation, molecular weight: 410)

(D-4) 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (DAICEL Chemical Industry Co., Ltd. "EHPE-3150" molecular weight: 2,400)

(D-5) Epoxidized polybutadiene (1) ("BF-1000" manufactured by Adeka Corporation: Molecular weight: 4,300 microstructure: 1,2-polybutadiene)

(D-6) Epoxidized polybutadiene (2) (JP-200, manufactured by Nippon Soda Co., Ltd.) Molecular weight: 6,400 microstructure: 1,2-polybutadiene

(D-7) Epoxidized polybutadiene (3) ("DB-3600" manufactured by DAICEL Chemical Industry Co., Ltd.) Molecular weight: 19,300 microstructure: 1,2-body/1,4-cis/1,4-trans = 40 mol% / 40 mol% / 20 mol% copolymer)

(D-8) Copolymer of epoxidized polybutadiene and styrene (Epofriend series manufactured by DAICEL Chemical Co., Ltd.) Molecular weight: more than 20,000)

The cationically polymerizable monomer other than the components (A) and (B) as the component (E) is the following:

(E-1) 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate ("Celloxide 2021P" manufactured by DAICEL Chemical Co., Ltd.)

(E-2) bis(1-ethyl-3-oxetanyl) methyl ether ("OXT221" manufactured by Toagosei Co., Ltd.)

(E-3) 4-Hydroxybutyl methacrylate glycidyl ether ("Hittait G" manufactured by Nippon Kasei Co., Ltd.)

(Examples 1 to 16 and Comparative Examples 1 to 6)

The raw materials of the types disclosed in Tables 1 to 4 were mixed at a composition ratio (unit: parts by mass) disclosed in Tables 1 to 4 to prepare a resin composition, and the evaluation described later was carried out. The various evaluation results are disclosed in Tables 1 to 4. Unless otherwise noted, it is carried out in an environment of 23 ° C and a humidity of 50%.

[Photohardenability assessment]

The modulus of rigidity under UV irradiation can be measured by a rheometer ("MCR-301" manufactured by Anton-Paar Co., Ltd.). The measurement was carried out by sandwiching the prepared resin composition on both sides with a disk having a diameter of 8 mm, and irradiating the resin composition with UV (illuminance at 365 nm: 150 mW/cm ² ) while at a frequency of 10 Hz at 25 ° C (± 0.5 ° C). get on. The case where the storage rigidity G′ was increased to 1.00×10 ⁴ or more after the start of the UV irradiation to 200 seconds was determined as “good”, and it was judged that the hardenability was good.

[Assessment of fixation time]

The resin composition was applied to a glass test piece (trade name "heat-resistant PYREX (registered trademark) glass", 25 mm × 25 mm × 2.0 mm) to have a diameter of 8 mm and a thickness of 80 μm, and then a second glass test piece was attached. UV light was irradiated by a UV irradiator (illuminance at 365 nm: 150 mW/cm ² , "SP-7 (UV curing device equipped with mercury xenon lamp) manufactured by Ushio Electric Co., Ltd.), and the time at which the two glass test pieces no longer moved was measured. And set the fixation time. In addition, the measurement time is set to a maximum of 120 seconds.

[Evaluation of tensile shear strength]

Tensile shear strength: measured according to JIS K 6850. Specifically, heat-resistant glass (trade name "heat-resistant PYREX (registered trademark) glass", 25 mm × 25 mm × 2.0 mm) was used as the material to be joined, and the subsequent portion was set to a circular shape having a diameter of 8 mm, and the resin composition was produced. Two pieces of heat-resistant glass were bonded to each other, and a UV illuminator was used to accumulate a light amount of 3,000 mJ/cm ² (illuminance at 365 nm: 150 mW/cm ² , manufactured by Ushio Electric Co., Ltd. "SP-7 (UV curing device equipped with a mercury xenon lamp) The condition of the resin was hardened to produce a test piece. The test piece prepared was measured for tensile shear strength at 23 ° C and a humidity of 50% using a tensile tester.

[Evaluation of spectral transmittance]

The resin composition was applied to a glass test piece (trade name "heat-resistant PYREX (registered trademark) glass", 25 mm × 25 mm × 2.0 mm) to have a diameter of 20 mm and a thickness of 80 μm, and then a second glass test piece was attached. A test piece was produced by irradiating UV light with a UV illuminator (illuminance at 365 nm: 150 mW/cm ² , "SP-7 (UV curing device equipped with a mercury xenon lamp) manufactured by Ushio Electric Co., Ltd.). The spectral transmittance at a wavelength of 405 nm and 500 nm was measured on the prepared test piece using an ultraviolet-visible spectrophotometer ("UV-2550" manufactured by Shimadzu Corporation). In addition, the standard uses pure water.

[Evaluation of chemical resistance]

Using a UV irradiator, the shape was made at 4,000 mJ/cm ² (illuminance at 365 nm: 150 mW/cm ² , "D-bulb (metal halide)" manufactured by Fusion Co., Ltd.). The cured product of 25 mm × 25 mm × 2.0 mm was immersed in acetone in an environment of 23 ° C for 4 hours, and the mass change rate (%) before and after immersion was measured. The lower the rate of change in mass, the better the chemical resistance.

The following phenomena were found from the results disclosed in Tables 1 to 4. The present invention has rapid hardenability. Further, the present invention also has high adhesion and chemical resistance. When the component (A) is 65 parts by mass or less, the effects of the present invention (comparison between Example 11 and Comparative Example 6) cannot be obtained. When the component (D) is used, the strength and the like are improved (comparison between Example 12 and Examples 1 to 3). When the component (D) was used, the strength and the like were further improved as compared with the case of using the component (E) (comparison of Examples 4 to 11 and Examples 14 to 15).

Further, the present invention exhibits a transmittance of 90% or more at 405 nm and a transmittance of 98% or more at 550 nm, and thus it is found that it has excellent transparency in the visible light region.

[Industrial Availability]

As described above, according to the present invention, it is possible to provide an energy ray-curable resin composition which is quick-curing, has high adhesion, chemical resistance, and an adhesive thereof, and thus can be suitably used for liquid crystal. Assembly of electronic parts such as panels, organic electroluminescent panels, touch panels, projectors, smart phones, mobile phones, digital cameras, digital projectors, LEDs, solar cells, lithium-ion batteries, etc., or CCD, CMOS, fast A package of a semiconductor device such as a flash memory or a DRAM. It can be used as an adhesive suitable for the pedestal of the process glass, the fixed use of the vessel, two or more lenses or the optical elements used in the camera, binoculars, and microscope.

Claims (7)

An energy ray-curable resin composition comprising: (A) a compound having a (meth)acryloyl group and an alicyclic epoxy group in the molecule represented by the following formula [1] And more than 65 parts by mass in 100 parts by mass of the total amount of the polymerization component and less than 100 parts by mass; (wherein R represents hydrogen or a methyl group, X represents an alkylene chain having 1 to 6 carbon atoms or an alkyloxy chain having 1 to 6 carbon atoms), and a photocationic polymerization initiator of the component (B); A photoradical polymerization initiator of component C). The energy ray-curable resin composition of claim 1, which comprises the oligomer of the component (D) having two or more epoxy groups in the molecule. An energy ray-curable resin composition according to claim 2, wherein the oligomer of the component (D) having two or more epoxy groups in the molecule has a molecular weight of from 350 to 100,000. The energy ray-curable resin composition of claim 1, which comprises a cationically polymerizable monomer other than (A) and (B) of the component (E). An adhesive comprising the energy ray-curable resin composition according to any one of claims 1 to 4. A hardened body obtained by hardening an energy ray-curable resin composition according to any one of claims 1 to 4. A bonded body using the energy ray-curable resin composition according to any one of claims 1 to 4.