KR102006993B1 - Energy-beam-curable resin composition - Google Patents

Abstract

This invention provides the compound which has a (meth) acryloyl group and an alicyclic epoxy group in the molecule | numerator represented by following formula (1) for the purpose of providing the energy-beam curable resin composition which can satisfy | fasten a fast curing property (A) Energy beam containing 65 mass parts or more and 100 mass parts or less, (B) photocationic polymerization initiator, and (C) radical photopolymerization initiator among 100 mass parts of total amounts of the polymerization component which consists of a component, (D) component, and (E) component. It is curable resin composition: R in a formula represents hydrogen or a methyl group, X represents a C1-C6 alkylene chain or a C1-C6 oxyalkylene chain.

Description

Energy-beam curable resin composition {Energy-beam-curable resin composition}

The present invention relates to an energy ray curable resin composition, an adhesive and a cured product using the same.

BACKGROUND ART In recent years, energy ray-curable adhesives that can be cured in a short time by energy rays such as ultraviolet rays have been applied to assembly of components and packaging of semiconductor devices and the like. Examples of the component include electronic products such as liquid crystal panels, organic electroluminescent panels, touch panels, projectors, smartphones, mobile phones, digital cameras, digital movies, LEDs, and solar cells. As a semiconductor element, CCD, CMOS, a flash memory, DRAM etc. are mentioned.

Energy ray-curable adhesives used in these fields are required to have high adhesion to various materials and high reliability that can withstand heat, humidity, heat cycles, and the like. Moreover, since the adhesive agent is exposed to chemicals, such as alcohol, an acid, and alkali, in the washing | cleaning process, an etching process, etc., the energy-beam hardening-type adhesive agent used in these fields is calculated | required the adhesive agent which has what is called chemical resistance to these various chemical | medical agents.

When bonding optical elements, such as a lens, a prism, and a filter used for a digital camera, a binocular, a microscope, etc., an energy ray hardening-type adhesive agent requires high transparency in visible range of 400 nm-800 nm.

As an energy ray hardening-type adhesive agent, adhesives, such as an acryl type, an epoxy type, and an n-thiol type, are marketed. Acrylic and N-thiol adhesives are excellent in fast curing and adhesiveness, but have a problem of poor chemical resistance. Epoxy adhesives are excellent in chemical resistance and adhesiveness, but have a problem of poor fast curing.

As a means of making both the acryl-type object and the epoxy-type object mentioned above, the resin composition (patent document 1-3) which has an acrylic compound and an epoxy compound, the compound which has an acryl group and an epoxy group in the same molecule, and a resin composition (patent document 4- 8) is disclosed. However, these well-known resin compositions did not satisfy | fasten the fast hardening property, adhesiveness, and chemical-resistance calculated | required by the adhesive mentioned above. In the case of this invention, the quantity of (A) component differs from patent document 7.

Patent Document 1: Japanese Patent Application Laid-Open No. 11-35846 Patent Document 2: Japanese Patent Application Laid-Open No. 2006-233009 Patent Document 3: Japanese Patent Application Laid-Open No. 2008-260879 Patent Document 4: Japanese Patent Application Laid-Open No. 2003-55362 Patent Document 5: Japanese Patent Application Laid-Open No. 2008-88167 Patent Document 6: Japanese Patent No. 4095380 Patent Document 7: Japanese Patent Application Laid-Open No. 2008-260879 Patent Document 8: Japanese Patent Application Laid-Open No. 2010-248500

The present invention relates to an energy ray curable resin composition having rapid curability.

This invention includes the following aspects (1)-(7).

(1) (A) Compound which has a (meth) acryloyl group and an alicyclic epoxy group in the molecule represented by following formula [1]

(Wherein R represents hydrogen or a methyl group, X represents an alkylene chain having 1 to 6 carbon atoms or an oxyalkylene chain having 1 to 6 carbon atoms); and a polymerization comprising (A) component, (D) component and (E) component 65 mass parts or more and 100 mass parts or less in 100 mass parts of total amounts of a component

(B) photocationic polymerization initiator

(C) An energy ray curable resin composition containing an optical radical polymerization initiator.

(2) The energy ray curable resin composition as described in (1) containing the oligomer which has two or more epoxy groups in (D) molecule.

(3) The energy-beam curable resin composition as described in (2) whose molecular weight of the oligomer which has two or more epoxy groups in (D) molecule is 350-100,000.

(4) The energy ray curable resin composition as described in (1) containing cationically polymerizable monomers other than (E) (A) and (D).

(5) Adhesive which consists of energy-beam curable resin composition in any one of (1)-(4).

Hardened | cured material formed by hardening | curing the energy-beam curable resin composition in any one of (6) (1)-(4).

(7) A bonded body using the energy ray curable resin composition according to any one of (1) to (4).

The energy ray curable resin composition which consists of the said structure can satisfy | fill fast curing property, for example.

<Explanation of Terms>

In this specification, an energy ray curable resin composition means the resin composition which can be hardened by irradiating an energy ray. Here, the energy rays mean energy rays represented by ultraviolet rays, visible rays and the like.

In this specification, molecular weight means the weight average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC).

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

The component of the energy-beam curable resin composition which concerns on this embodiment is demonstrated.

The energy-beam curable resin composition which concerns on this embodiment makes the compound which has a (meth) acryloyl group and an alicyclic epoxy group in an molecule | numerator represented by following formula [1] as (A) component an essential component.

(R in formula represents a hydrogen or a methyl group, X represents a C1-C6 alkyl chain or a C1-C6 oxyalkylene chain.)

-R'-O- is mentioned as an oxyalkylene chain. Here, R 'means C1-C6 alkylene. When the oxyalkylene chain is -R'-0-, formula [1] is represented by the following formula [1 '].

As (A) component used for this invention, 3, 4- epoxy cyclohexyl methyl (meth) acrylate, 3, 4- epoxy cyclohexyl ethyl (meth) acrylate, 3, 4- epoxy cyclohexyl propyl (meth) acryl Elate, 3,4-epoxycyclohexylbutyl (meth) acrylate, ethylene oxide modified 3,4-epoxycyclohexylmethyl (meth) acrylate, propylene oxide modified 3,4-epoxycyclohexylmethyl (meth) acrylate, etc. Can be mentioned. In these, 3, 4- epoxycyclohexyl methyl (meth) acrylate is preferable at the point which is excellent in chemical resistance.

It is preferable to contain (A) component in the ratio of 65 mass parts or more and 100 mass parts or less in 100 mass parts of total amounts of the polymerization component which consists of (A) component, (D) component, and (E) component. If it exists in this range, sclerosis | hardenability will not worsen and adhesiveness and chemical-resistance will not fall, either. In particular, 70 mass parts or more and 95 mass parts or less are more preferable at the point of curability, adhesiveness, and chemical-resistance.

The energy ray curable resin composition which concerns on this embodiment makes a photocationic polymerization initiator an essential component as (B) component. The photocationic polymerization initiator of (B) component will not be restrict | limited especially if it is a compound in which cationic species generate | occur | produce by irradiating an energy ray.

As a photocationic polymerization initiator of (B) component used for this invention, an aryl sulfonium salt derivative (for example, Cyracure UVI-6990, Cyracure UVI-6974 by Dow Chemical Co., Ltd., and Adeka of Asahi telephone company make) Optomer SP-150, Adeka Optomer SP-152, Adeka Optomer SP-170, Adeca Optomer SP-172, CPI-100P, CPI-101A, CPI-20OK, CPI-210S from San Aprosa , Chiba Cure 1190 from Double Bond, CGI * TPS C1 from Chiba Japan, GSID26-1, etc., aryl iodonium salt derivatives (e.g., Irugacure 250 from Chiba Specialty Chemicals, Chiba Japan) And acid generators such as CGI * BBI C1, RP-2074 manufactured by Rhodia Japan Co., Ltd., allene-ion complex derivatives, diazonium salt derivatives, triazine initiators and other halides. You may select 1 type (s) or 2 or more types, and you may use a photocationic polymerization initiator in arbitrary ratios. Onium cation is preferable as the cationic species of the photocationic polymerization initiator. As an onium cation, an arylsulfonium salt derivative, an aryl iodonium salt derivative, etc. are mentioned. Examples of the anionic species of the photocationic polymerization initiator include halides such as boron compounds, phosphorus compounds, antimony compounds, arsenic compounds, and alkyl sulfonic acid compounds. Among these, an arylsulfonium salt derivative is preferable at the point which is excellent in sclerosis | hardenability.

It is preferable to contain the photocationic polymerization initiator of (B) component in the ratio of 0.1-10 mass parts with respect to 100 mass parts of total amounts of the polymerization component which consists of (A) component, (D) component, and (E) component. If it exists in this range, sclerosis | hardenability will not worsen and adhesiveness and chemical-resistance will not fall, either. In particular, the amount of the photocationic polymerization initiator of (B) component is more preferably 0.3 to 5 parts by mass, and most preferably 0.5 to 3 parts by mass from the viewpoint of curability, adhesiveness, and chemical resistance.

The energy ray curable resin composition which concerns on this embodiment makes an optical radical polymerization initiator an essential component as (C) component. The radical photopolymerization initiator of the component (C) is not particularly limited as long as it is a compound in which radicals are generated by irradiation with energy rays.

As an optical radical polymerization initiator of (C) component used for this invention, benzophenone, 4-phenylbenzophenone, benzoyl benzoic acid, 2, 2- diethoxy acetophenone, bisdiethylamino benzophenone, benzyl, benzoin, benzoyl iso Propyl ether, benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, thioxanthone, 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, 2-hydroxy- 1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, camphorquinone, 2,4,6-trimethylbenzoyl diphenyl Phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone-1, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine The side etc. are mentioned. Among these, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylpropan-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2- Methyl-1-propane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl 1 or more types which consist of alpha-hydroxyacetophenones, such as -propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, are preferable at the point which is excellent in sclerosis | hardenability. These can be used 1 type or in combination or 2 or more types.

It is preferable to contain the optical radical polymerization initiator of (C) component in 0.1-10 mass parts with respect to 100 mass parts of total amounts of the polymerization component which consists of (A) component, (D) component, and (E) component. If it exists in this range, sclerosis | hardenability will not worsen and adhesiveness and chemical-resistance will not fall, either. In particular, 0.5-5 mass parts is more preferable, and 1-3 mass parts of the usage-amount of the radical photopolymerization initiator of (C) component from a sclerosis | hardenability, adhesiveness, and chemical-resistance point is most preferable.

You may use together various photosensitizers for the resin composition of this invention. The photosensitizer refers to a compound that absorbs energy rays and efficiently generates cations and radicals from photocationic polymerization initiators or photoradical polymerization initiators.

Although it does not specifically limit as a photosensitizer used for this invention, A benzophenone derivative, a phenothiazine derivative, a phenyl ketone derivative, a naphthalene derivative, an anthracene derivative, a phenanthrene derivative, a naphthacene derivative, a chrysene derivative, a perylene derivative, penta Sen derivatives, acridine derivatives, benzothiazole derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, xanthone derivatives, thioxanthene derivatives, thioxanthone derivatives, coumarin derivatives , Ketocoumarin derivatives, cyanine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolin derivatives, azulene derivatives, triallymethane derivatives, phthalocyanine derivatives, spiropyrane derivatives, spirooxazine derivatives, thiospyropyran derivatives, Organic ruthenium complexes; and the like.

It is preferable to contain a photosensitizer in the ratio of 0.1-5 mass parts with respect to 100 mass parts of total amounts of a polymerization component, and if it exists in this range, adhesiveness and chemical-resistance will not fall, either. 0.3-3 mass parts is more preferable, and, as for the usage-amount of the photosensitizer from a point of sclerosis | hardenability, adhesiveness, and chemical resistance especially, 0.5-2 mass parts is the most preferable.

It is preferable that the energy-beam curable resin composition which concerns on this embodiment contains the oligomer which has one or more epoxy groups in a molecule | numerator as (D) component.

As an oligomer which has one or more epoxy groups in the molecule | numerator of (D) component used for this invention, aromatic, aliphatic, alicyclic oligomer is mentioned. As an aromatic system, bisphenol-A epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, novolak phenol type epoxy resin, cresol novolak-type epoxy resin, these modification | modified these Water and the like. As an aliphatic type, polyalkylene glycol, such as epoxidation modified polyolefin, such as epoxidation modified polybutadiene and epoxidation modified polyisoprene, diglycidyl ether of a polyethyleneglycol adduct, and diglycidyl ether of a polypropylene glycol adduct, Diglycidyl ether and the like. Examples of the alicyclic system include 1,2-epoxy-4- (2-oxyranyl) cyclohexane adducts of 2,2-bis (hydroxymethyl) -1-butanol and hydrogenated products of the aromatic epoxy resins described above. . Among these, an epoxidized modified polybutadiene, an epoxidized modified polyisoprene and a 1,2-epoxy-4- (2-oxyranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol 1 or more types are preferable at the point which is excellent in chemical resistance, and epoxidation modified polybutadiene is more preferable.

There is no restriction | limiting in particular about the microstructure of polybutadiene, The low-cis polybutadiene frame | skeleton with a small 1, 4-cis body unit ratio, The high-cis polybutadiene skeleton with a large 1, 4-cis body unit ratio, 1,2- It may be any of a 1,2-cis body and the like showing a polybutadiene skeleton. You may mix these 1 or more types.

350-100,000 are preferable, as for the molecular weight of the oligomer which has one or more epoxy groups in the molecule | numerator of (D) component, 500-50,000 are more preferable, 2,000-20,000 are the most preferable. If molecular weight is 350 or more, chemical resistance will not fall, and if it is 100,000 or less, sclerosis | hardenability will not fall.

In addition, molecular weight here means the number average molecular weight, and means the number average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC).

The oligomer which has one or more epoxy groups in the molecule | numerator of (D) component is 100 mass of the total amount of the polymerization component which consists of (A) component, (D) component, and (E) component, when the balance of fast curing, adhesiveness, and chemical-resistance is considered 5-35 mass parts is preferable in a part, and 10-30 mass parts is more preferable.

The energy-beam curable resin composition which concerns on this embodiment can contain cationically polymerizable monomers other than (A) and (D) component as (E) component in the range which does not impair the target physical property.

As cationic polymerizable monomers other than (A) and (D) component which are (E) component used for this invention, a cyclic ether monomer, a cyclic thioether monomer, a cationically polymerizable vinyl monomer, etc. are mentioned. As a cyclic ether monomer, monomers, such as an epoxy and an oxetane, are mentioned. Isobutyrene sulfide etc. are mentioned as a thioether monomer.

Vinyl ether, vinyl amine, styrene, etc. are mentioned as a cationically polymerizable vinyl monomer. These monomers or derivatives may be used alone or in combination of two or more.

Although it does not specifically limit as cyclic ether monomer, 1,2-epoxycyclohexane, 1- (epoxyethyl) -3,4-epoxycyclohexane, 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclo Hexene carboxylate, di (1-ethyl-3-oxetanyl) methyl ether, 4-hydroxybutyl methacrylate glycidyl ether, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) Acrylate glycidyl ether, (meth) acrylic acid = (3-ethyloxetan-3-yl) methyl, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3- Oxetanyl) methoxymethyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, di (1-ethyl-3-oxetanyl) methylether, 3-ethyl-3- (2-ethylhex And siloxymethyl) oxetane. Oxetane refers to a monomer having at least one oxetanyl group in the molecule.

Although it does not specifically limit as a vinyl ether monomer, Ethylene glycol divinyl ether, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene Di or tri, such as glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexane dimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, and trimetholpropane trivinyl ether Vinyl ether compound, 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, iso Monovinyl ether compounds, such as propenyl ether-o-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether, etc. are mentioned.

Although it does not specifically limit as a vinylamine monomer, N-vinyl dimethylamine, N-vinyl ethyl butylamine, N-vinyl diphenylamine, N-vinylformamide, an N-vinylacetoamide compound, etc. are mentioned.

In cationic polymerizable monomers other than (A) and (D) component which are (E) component, a cyclic ether monomer is preferable and 3, 4- epoxycyclohexenylmethyl-3 ', 4'- epoxycyclohexene carboxylate And 1 or more types which consist of di (1-ethyl-3- oxetanyl) methyl ether are preferable.

When cationic polymerizable monomers other than (A) and (D) component which are (E) component are considered, the balance which consists of (A) component, (D) component, and (E) component is considered 5-35 mass parts is preferable in 100 mass parts of total amounts of a polymerization component, and 10-30 mass parts is more preferable.

In this invention, 1 type (s) or 2 or more types of group which consists of a phenolic antioxidant and quinone type antioxidant can be contained as antioxidant.

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

In this invention, you may contain the filler (inorganic filler) further.

Graft copolymers, such as various elastomers, such as an acrylic rubber and a urethane rubber, a methyl methacrylate butadiene-styrene graft copolymer, an acrylonitrile butadiene-styrene graft copolymer, in the range which does not impair the objective of this embodiment. And additives such as solvents, extenders, reinforcing agents, plasticizers, thickeners, dyes, pigments, flame retardants and surfactants.

In this invention, a silane coupling agent can contain 1 type (s) or 2 or more types in arbitrary ratios.

The energy ray curable resin composition which consists of the said structure may be hardened | cured by irradiation of an energy ray, and may be set as a hardened | cured material.

You may use the energy-beam curable resin composition which consists of the said structure as an adhesive agent. This adhesive is used to assemble parts of electronic products such as liquid crystal panels, organic electroluminescent panels, touch panels, projectors, smartphones, mobile phones, digital cameras, digital movies, LEDs, solar cells, lithium ion batteries, CCD, CMOS, It can be used suitably for packaging of semiconductor elements, such as a flash memory and DRAM. Moreover, it is suitable adhesive for the bonding of optical elements used for the base of craft glass, the fixing of dishes, and two or more lenses or prisms, cameras, binoculars and microscopes.

There is no restriction | limiting in particular about the manufacturing method of the energy-beam curable resin composition which concerns on this embodiment as long as the said material can fully be mixed. Although it does not specifically limit as a mixing method of a material, The stirring method using the stirring force according to the rotation of a propeller, the method of using normal dispersers, such as a planetary stirrer by rotating revolution, etc. are mentioned. These mixing methods are preferable because they can perform stable mixing at low cost.

After performing the said mixing, you may harden an energy-beam curable resin composition by irradiation of an energy beam using the following light sources.

In this embodiment, although it does not specifically limit as a light source used for hardening and adhesion | attachment of an energy-beam curable resin composition, A halogen lamp, a metal halide lamp, a high power metal halide lamp (containing indium etc.), a low pressure mercury lamp, a high pressure Mercury lamps, ultrahigh pressure mercury lamps, xenon lamps, xenon excimer lamps, xenon flash lamps, light emitting diodes (hereinafter referred to as LEDs), and the like. These light sources are preferable at the point which can irradiate an energy beam corresponding to the reaction wavelength of each photoinitiator efficiently.

The light source differs in emission wavelength and energy distribution, respectively. Therefore, the said light source is suitably selected by the reaction wavelength of a photoinitiator, etc. In addition, natural light (sunlight) can also be a reaction start light source.

The said light source may perform condensing irradiation by direct irradiation, condensing irradiation by a reflector, etc., a fiber, etc. A low wavelength cut filter, a hot wire cut filter, a cold mirror, etc. can also be used.

The energy ray curable resin composition which consists of the said structure can provide the energy ray curable resin composition excellent in curability, adhesiveness, and chemical-resistance, and the adhesive agent using the same.

Example

Although an Example and a comparative example are given to the following and this invention is demonstrated in more detail, this invention is not limited to these.

In the examples, the following compounds were used.

The following was used as (A) component.

(A-1) 3,4-epoxycyclohexylmethyl methacrylate ("Cyclomer M-100" of Daicel Chemical Co., Ltd.)

(A-2) 3,4-epoxycyclohexylmethyl acrylate ("Cyclemer A-200" from Daicel Chemical Co., Ltd.)

The following was used as photocationic polymerization initiator of (B) component.

(B-1) Aromatic Sulfonium SbF ₆ Salt (ADECA Co., Ltd. `` ADECA OPTOMER SP-170 '')

(B-2) Aromatic Sulfonium PF ₆ Salt (ADECA Co., Ltd. `` ADECA OPTOMER SP-150 '')

The following was used as optical radical polymerization initiator of (C) component.

(C-1) 2-hydroxy-2-methyl-1-phenyl-propan-1-one ("Tarocure 1173" by Chiba Japan)

(C-2) 1-hydroxycyclohexylphenyl ketone (`` Irugacure 184 '' from Chiba Japan)

(C-3) 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one (Chiba Japan Co., Ltd.) Product `` Irugacure 127 '')

The following was used as an oligomer which has an epoxy group of (D) component.

(D-1) Bisphenol A type epoxy resin (Adeka Optomer KRM-2410, Molecular Weight: 400)

(D-2) Bisphenol F type epoxy resin (Adeka Optomer KRM-2490, made by Adeka Co., Ltd., molecular weight: 380)

(D-3) Hydrogenated Bisphenol A epoxy resin (YX-8000, manufactured by Mitsubishi Chemical Corporation, Molecular Weight: 410)

(D-4) 1,2-epoxy-4- (2-oxyranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol ("EHPE-3150" made by Daicel Chemical Industries, Ltd.) 2,400

(D-5) Epoxylated Polybutadiene (1) (`` BF-1000 '' made by Adeka Co., Ltd. Molecular Weight: 4,300 microstructure: 1,2-polybutadiene)

(D-6) Epoxylated Polybutadiene (2) (JP-200, Nippon Soda Co., Ltd. Molecular Weight: 6,400 Microstructure: 1,2-Polybutadiene)

(D-7) Epoxylated polybutadiene (3) ("BP-3600" by Daicel Chemical Co., Ltd. molecular weight: 19,300 microstructure: 1,2-body / 1,4-cis body / 1,4-trans body = 40 mol) % / 40 mol% / 20 mol% copolymer)

(D-8) Copolymer of epoxidized polybutadiene and styrene (molecular weight: exceeding 20,000 of "Eepopren series" made by Daicel Chemical Co., Ltd.)

The following was used as cationically polymerizable monomers other than (A) and (D) component which are (E) component.

(E-1) 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate ("Celoxide 2021P" manufactured by Daicel Chemical Co., Ltd.)

(E-2) di (1-ethyl-3-oxetanyl) methyl ether (Toa synthesis company "OXT221")

(E-3) 4-hydroxybutyl methacrylate glycidyl ether (Nippon Chemical Co., Ltd. "Heatite G")

(Examples 1-16, Comparative Examples 1-6)

The raw materials of the kind shown in Table 1-Table 4 were mixed by the composition ratio (unit is a mass part) shown in Table 1-Table 4, the resin composition was prepared, and the evaluation mentioned later was performed. Various evaluation results are shown in Tables 1-4. Unless it mentions specially, it implemented in the environment of 23 degreeC, and 50% of humidity.

[Photocurability Evaluation]

Rheometers (MCR-301, manufactured by Atonpar) can measure the stiffness under UV irradiation. The measurement was carried out at 25 ° C. (± 0.5 ° C.) and frequency 10 Hz while the prepared resin composition was sandwiched from both sides in a circular plate having a diameter of 8 mm and irradiated with UV (365 nm roughness: 150 mW / cm 2) of the resin composition. It was judged that the thing whose storage rigidity (G ') increased to 1.00x10 <^4> or more until 200 second after the start of UV irradiation was made "good", and sclerosis | hardenability was favorable.

[Evaluation of fixation time]

After apply | coating resin composition so that it might become diameter 8mm, thickness 80μm on glass test piece (brand name "heat-resistant Pyrex (trademark) glass", 25mm * 25mm * 2.0mm), the second glass test piece was stuck together, and it was UV irradiator (365nm of Roughness: 150mW / cm <2>, UV light was irradiated by Ushio Electric Co., Ltd. "SP-7 (UV curing apparatus with mercury xenon lamp)"), and the time which two glass test pieces do not move was measured and set as fixing time. . In addition, the measurement time was made into 120 second at the maximum.

[Evaluation of Tensile Shear Adhesion Strength]

Tensile Shear Adhesion Strength: Measured according to JIS K 6850. Specifically, two pieces of heat-resistant glass in the resin composition produced by using a heat-resistant glass (trade name "Heat-resistant Pyrex (trade name) glass", 25mm x 25mm x 2.0mm) made into a to-be-adhered material by making the adhesive site circular 8 mm in diameter. And the test piece was made by curing under the conditions of accumulated light quantity 3,000mJ / ㎠ (365nm illuminance: 150mW / ㎠, Ushio Electric Co., Ltd. "SP-7 (UV curing apparatus with mercury xenon lamp)") using a UV irradiator. It was. The produced test piece measured the tensile shear adhesive strength using the tensile tester in the environment of 23 degreeC, 50% of humidity.

[Evaluation of Spectral Transmittance]

After apply | coating resin composition so that it may become diameter 20mm and thickness 80micrometer on glass test piece (brand name "heat-resistant Pyrex (trademark) glass", 25mm * 25mm * 2.0mm), the second glass test piece is stuck together and UV irradiator (365nm of Roughness: 150 mW / cm <2>, UV light was irradiated by Ushio Electric Co., Ltd. "SP-7 (UV curing apparatus with mercury xenon lamp)", and the test piece was created. Spectral transmittances of wavelength 405 nm and 500 nm of the prepared test piece were measured using the ultraviolet-visible spectrometer ("UV-2550" by Shimadzu Corporation). In addition, pure water was used as a reference.

[Evaluation of Chemical Resistance]

25mm × 25mm × 2.0mm under conditions of 4,000mJ / cm2 (365nm roughness: 150mW / cm2, Fusion Conveyor Beltless Electrodeless Discharge Lamp (D-Valve: Metal Halide Lamp)) Shaped hardened | cured material was produced, and the produced hardened | cured material was immersed in acetone for 4 hours in 23 degreeC environment, and the change rate (%) of the mass before and behind immersion was measured. The lower the rate of change of mass, the better the chemical resistance.

The following things are understood from the result shown to Tables 1-4. The present invention has rapid curability. The present invention also has high adhesiveness and chemical resistance. If the component (A) is 65 parts by mass or less, the effect of the present invention cannot be obtained (vs. Example 11 and Comparative Example 6). When (D) component is used, adhesive strength etc. improve (contrast of Example 12 and Examples 1-3). When (D) component is used, adhesive strength etc. improve compared with the case where (E) component is used (contrast of Examples 4-11 and Examples 14-15).

In addition, it can be seen that the present invention exhibits excellent transparency in the visible region in that it exhibits a transmittance of 90% or more at 405 nm and 98% or more at 550 nm.

According to the present invention as described above, since it is possible to provide an energy ray-curable resin composition having a fast curing property and high adhesiveness and chemical resistance and an adhesive using the same, a liquid crystal panel, an organic electroluminescent panel, a touch panel, a projector Suitable for assembly of electronic components such as smart phones, mobile phones, digital cameras, digital movies, LEDs, solar cells, lithium ion batteries, and packaging of semiconductor devices such as CCD, CMOS, flash memory, DRAM, etc. Can be. Moreover, it is suitable adhesive for the bonding of optical elements used for the base of craft glass, the fixing of dishes, and two or more lenses or prisms, cameras, binoculars and microscopes.

Claims (6)

delete As an adhesive used to bond two or more adherends,
(A) Compound which has a (meth) acryloyl group and an alicyclic epoxy group in the molecule represented by following formula [1]
[Chemical Formula 1]

(Wherein R represents hydrogen or a methyl group, X represents an alkylene chain having 1 to 6 carbon atoms or an oxyalkylene chain having 1 to 6 carbon atoms); and a polymerization comprising (A) component, (D) component and (E) 70 mass parts or more and 95 mass parts or less in 100 mass parts of total amounts of a component,
(B) photocationic polymerization initiator,
(C) radical photopolymerization initiator,
(D) an oligomer having two or more epoxy groups in the molecule,
(E) 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate, and 4-hydroxybutyl methacrylate glyco as cationically polymerizable monomers other than (A) and (D) The adhesive agent which consists of an energy-beam curable resin composition containing the 1 or more types of monomers chosen from the group which consists of cyl ether. The method according to claim 2,
(D) The adhesive whose molecular weight of the oligomer which has two or more epoxy groups in a molecule | numerator is 350-100,000. The method according to claim 2,
The adhesive whose (E) component is 5-35 mass parts in 100 mass parts of total amounts of the polymerization component which consists of (A) component, (D) component, and (E) component. Hardened | cured material formed by hardening | curing the adhesive agent of Claim 2. The joined body using the adhesive agent of Claim 2.