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WO2012165259A1 - Energy-beam-curable resin composition - Google Patents

Energy-beam-curable resin composition Download PDF

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Publication number
WO2012165259A1
WO2012165259A1 PCT/JP2012/063192 JP2012063192W WO2012165259A1 WO 2012165259 A1 WO2012165259 A1 WO 2012165259A1 JP 2012063192 W JP2012063192 W JP 2012063192W WO 2012165259 A1 WO2012165259 A1 WO 2012165259A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
curable resin
component
energy ray
mass
Prior art date
Application number
PCT/JP2012/063192
Other languages
French (fr)
Japanese (ja)
Inventor
慶次 後藤
健司 深尾
貴子 星野
渡辺　淳
Original Assignee
電気化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 電気化学工業株式会社 filed Critical 電気化学工業株式会社
Priority to KR1020137033724A priority Critical patent/KR20140031948A/en
Priority to JP2013518000A priority patent/JP5973431B2/en
Priority to KR1020187033006A priority patent/KR102006993B1/en
Priority to CN201280025979.7A priority patent/CN103562267B/en
Publication of WO2012165259A1 publication Critical patent/WO2012165259A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/223—Di-epoxy compounds together with monoepoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Definitions

  • the present invention relates to an energy ray curable resin composition, an adhesive using the same, and a cured product.
  • energy ray curable adhesives that can be cured in a short time with energy rays such as ultraviolet rays have been applied to the assembly of components and the mounting of semiconductor device packages and the like.
  • the components include electronic products such as liquid crystal panels, organic electroluminescence panels, touch panels, projectors, smartphones, mobile phones, digital cameras, digital movies, LEDs, and solar cells.
  • the semiconductor element include a CCD, a CMOS, a flash memory, and a DRAM.
  • 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 cycle, and the like. Furthermore, the energy ray curable adhesives used in these fields are exposed to chemicals such as alcohol, acid, alkali, etc. in the cleaning process, etching process, etc., so that they are resistant to these various chemicals, so-called resistance. There is a need for adhesives having chemical properties.
  • the energy ray curable adhesive is required to have high transparency in the visible light range of 400 nm to 800 nm.
  • Acrylic, epoxy, and ene / thiol adhesives are on the market.
  • Acrylic and ene / thiol adhesives are excellent in fast curability and adhesiveness, but have a problem of poor chemical resistance.
  • Epoxy adhesives are excellent in chemical resistance and adhesiveness, but have a problem of inferior rapid curability.
  • Patent Documents 1 to 3 resin compositions having an acrylic compound and an epoxy compound
  • Patent Documents 4 to 8 resin compositions having an acrylic group and an epoxy group in the same molecule
  • these known resin compositions do not satisfy the fast curability, adhesiveness, and chemical resistance required for the above-mentioned adhesive.
  • the amount of component (A) is different from Patent Document 7.
  • the present invention relates to an energy beam curable resin composition having rapid curability.
  • the present invention includes the following aspects (1) to (7).
  • (1) Compound having (meth) acryloyl group and alicyclic epoxy group in the molecule represented by the following formula [1]
  • the energy ray-curable resin composition having the above-described configuration can satisfy, for example, quick curability.
  • the energy ray curable resin composition means a resin composition that can be cured by irradiation with energy rays.
  • the energy rays mean energy rays typified by ultraviolet rays and visible rays.
  • the molecular weight means a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).
  • a polymerization component means (A) component, (D) component used as needed, and (E) component used as needed.
  • the energy ray-curable resin composition according to the present embodiment includes, as an essential component, a compound having a (meth) acryloyl group and an alicyclic epoxy group in the molecule represented by the following formula [1] as the component (A). To do.
  • R represents hydrogen or a methyl group
  • X represents an alkyl chain having 1 to 6 carbon atoms or an oxyalkylene chain having 1 to 6 carbon atoms.
  • Examples of the oxyalkylene chain include —R′—O—.
  • R ′ refers to alkylene having 1 to 6 carbon atoms.
  • the formula [1] is represented by the following formula [1 ′].
  • 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate examples include 4-epoxycyclohexylbutyl (meth) acrylate, ethylene oxide-modified 3,4-epoxycyclohexylmethyl (meth) acrylate, and propylene oxide-modified 3,4-epoxycyclohexylmethyl (meth) acrylate.
  • 3,4-epoxycyclohexylmethyl (meth) acrylate is preferable in terms of excellent chemical resistance.
  • the component (A) is preferably contained in a proportion of more than 65 parts by mass and 100 parts by mass or less in a total amount of 100 parts by mass of the polymerization component composed of the components (A), (D) and (E). If it is in this range, the curability will not deteriorate, and the adhesiveness and chemical resistance will not deteriorate. In particular, 70 parts by mass or more and 95 parts by mass or less are more preferable in terms of curability, adhesiveness, and chemical resistance.
  • the energy ray-curable resin composition according to the present embodiment includes a cationic photopolymerization initiator as an essential component as the component (B).
  • the photocationic polymerization initiator as the component (B) is not particularly limited as long as it is a compound that generates a cationic species when irradiated with energy rays.
  • arylsulfonium salt derivatives for example, Cyracure UVI-6990, Cyracure UVI-6974, manufactured by Dow Chemical Co., Ltd., Adekaoptomer SP manufactured by Asahi Denka Kogyo Co., Ltd.
  • Adeka optomer SP-152 Adeka optomer SP-170
  • Adeka optomer SP-172 Adeka optomer SP-172, CPI-100P, CPI-101A, CPI-200K, CPI-210S made by San Apro, Ciba Cure 1190 made by Double Bond CGI * TPS C1, GSID26-1, etc.
  • aryliodonium salt derivatives for example, Irgacure 250 manufactured by Ciba Specialty Chemicals, CGI * BBI C1 manufactured by Ciba Japan, Rhodia Japan Co., Ltd.
  • RP- 074 aryliodonium salt derivatives
  • Allen - ion complex derivatives for example, Irgacure 250 manufactured by Ciba Specialty Chemicals, CGI * BBI C1 manufactured by Ciba Japan, Rhodia Japan Co., Ltd.
  • Allen - ion complex derivatives for example, Irgacure 250 manufactured by Ciba Specialty Chemicals, CGI * BBI C1 manufactured by Ciba Japan, Rhodia Japan Co., Ltd.
  • Allen - ion complex derivatives for example, Irgacure 250 manufactured by Ciba Specialty Chemicals, CGI * BBI C1 manufactured by Ciba Japan, Rhodia Japan Co., Ltd.
  • Allen - ion complex derivatives for example, Irgacure 250 manufactured
  • 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, arylsulfonium salt derivatives are preferable in terms of excellent curability.
  • the cationic photopolymerization initiator of component (B) is contained in a proportion of 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of polymerization components composed of component (A), component (D) and component (E). It is preferable to make it. If it is in this range, the curability will not deteriorate, and the adhesiveness and chemical resistance will not deteriorate. In particular, in terms of curability, adhesiveness, and chemical resistance, the amount of the photocationic polymerization initiator (B) used is more preferably 0.3 to 5 parts by mass, and most preferably 0.5 to 3 parts by mass. .
  • the energy beam curable resin composition according to the present embodiment includes a radical photopolymerization initiator as an essential component as the component (C).
  • the radical photopolymerization initiator of component (C) is not particularly limited as long as it is a compound that generates radicals when irradiated with energy rays.
  • radical photopolymerization initiator of the component (C) used in the present invention examples include benzophenone, 4-phenylbenzophenone, benzoylbenzoic acid, 2,2-diethoxyacetophenone, bisdiethylaminobenzophenone, benzyl, benzoin, benzoylisopropyl ether, benzyl Dimethyl ketal, 1-hydroxycyclohexyl phenyl 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] pheni ⁇ -2-Methyl-propan-1-one, camphorquinone, 2,4,6-
  • the (C) component radical photopolymerization initiator is contained in a proportion of 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the polymerization components composed of the (A), (D) and (E) components. It is preferable to make it. If it is in this range, the curability will not deteriorate, and the adhesiveness and chemical resistance will not deteriorate.
  • the amount of the radical photopolymerization initiator (C) used is more preferably 0.5 to 5 parts by mass, and most preferably 1 to 3 parts by mass.
  • a photosensitizer means a compound that absorbs energy rays and efficiently generates cations and radicals from a photocationic polymerization initiator or a photoradical polymerization initiator.
  • the photosensitizer is preferably contained in a proportion of 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the polymerization components. If it is within this range, the adhesiveness and chemical resistance will not be lowered.
  • the use amount of the photosensitizer is more preferably 0.3 to 3 parts by mass, and most preferably 0.5 to 2 parts by mass from the viewpoint of curability, adhesion, and chemical resistance.
  • the energy beam curable resin composition according to this embodiment preferably contains an oligomer having one or more epoxy groups in the molecule as the component (D).
  • oligomer having one or more epoxy groups in the molecule of the component (D) used in the present invention examples include aromatic, aliphatic and alicyclic oligomers.
  • Aromatic resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, novolac phenol type epoxy resin, cresol novolac type epoxy resin, and modified products thereof. Etc.
  • Aliphatics include epoxidized modified polyolefins such as epoxidized modified polybutadiene and epoxidized modified polyisoprene, diglycidyl ethers of polyethylene glycol adducts, diglycidyl ethers of polyalkylene glycols such as diglycidyl ethers of polypropylene glycol adducts, etc. Is mentioned.
  • Examples of the alicyclic system include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and hydrogenated products of the above-mentioned aromatic epoxy resins. Can be mentioned.
  • epoxidized modified polybutadiene epoxidized modified polyisoprene
  • epoxidized modified polybutadiene is more preferable.
  • the microstructure of polybutadiene is not particularly limited.
  • a low-cis polybutadiene skeleton with a small proportion of 1,4-cis isomer units, a high-cis polybutadiene skeleton with a large proportion of 1,4-cis isomer units, and a 1,2-polybutadiene skeleton are included. Any of the 1,2-cis bodies shown may be used. One or more of these may be mixed.
  • the molecular weight of the oligomer having one or more epoxy groups in the molecule of component (D) is preferably 350 to 100,000, more preferably 500 to 50,000, and most preferably 2,000 to 20,000. If the molecular weight is 350 or more, the chemical resistance is not lowered, and if it is 100,000 or less, the curability is not lowered.
  • the molecular weight said here means a number average molecular weight, and means the number average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC).
  • numerator of a component is (A) component, (D) component, and (E) component, when the balance of quick curability, adhesiveness, and chemical resistance is considered. 5 to 35 parts by mass is preferable, and 10 to 30 parts by mass is more preferable in a total amount of the polymerization component consisting of
  • the energy ray curable resin composition according to the present embodiment can contain a cationically polymerizable monomer other than the components (A) and (B) as the component (E) as long as the target physical properties are not impaired. .
  • Examples of the cationically polymerizable monomer other than the components (A) and (B) that are the component (E) used in the present invention include a cyclic ether monomer, a cyclic thioether monomer, and a cationic polymerizable vinyl monomer.
  • Examples of cyclic ether monomers include monomers such as epoxy and oxetane.
  • Examples of the thioether monomer include isobutylene sulfide.
  • Examples of the cationic polymerizable vinyl monomer include vinyl ether, vinyl amine, and styrene. These monomers or derivatives may be used alone or in combination of two or more.
  • the vinyl ether monomer is not particularly limited, but 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 glycol divinyl ether, butane Di- or trivinyl ether compounds such as diol divinyl ether, hexanediol divinyl ether, cyclohexane dimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, trimethylolpropane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl Monovinyl ethers such as nil ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-
  • the vinylamine monomer is not particularly limited, and examples thereof include N-vinyldimethylamine, N-vinylethylbutylamine, N-vinyldiphenylamine, N-vinylformamide, and N-vinylacetamide compound.
  • a cyclic ether monomer is preferable, and 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxy is preferable.
  • One or more of cyclohexenecarboxylate and di (1-ethyl-3-oxetanyl) methyl ether are preferred.
  • the cationic polymerizable monomers other than the components (A) and (B) which are the components (E) are components (A) and (D) when considering the balance between fast curability, adhesion and chemical resistance.
  • 5 to 35 parts by mass are preferable, and 10 to 30 parts by mass are more preferable, in 100 parts by mass of the total amount of the polymerization components composed of the component (E).
  • 1 type (s) or 2 or more types in the group which consists of a phenolic antioxidant and a quinone antioxidant can be contained as antioxidant.
  • a phosphine oxide derivative may be used.
  • a filler inorganic filler may further be contained.
  • various elastomers such as acrylic rubber and urethane rubber, and graft copolymers such as methyl methacrylate-butadiene-styrene graft copolymer and acrylonitrile-butadiene-styrene graft copolymer
  • Additives such as solvents, extenders, reinforcing materials, plasticizers, thickeners, dyes, pigments, flame retardants and surfactants may be contained.
  • a silane coupling agent can be contained 1 type or 2 types or more in arbitrary ratios.
  • the energy ray-curable resin composition having the above-described configuration may be cured by irradiation with energy rays to form a cured body.
  • This adhesive can be used to assemble parts of electronic products such as liquid crystal panels, organic electroluminescence panels, touch panels, projectors, smartphones, mobile phones, digital cameras, digital movies, LEDs, solar cells, lithium ion batteries, CCDs, CMOS, It can be suitably used for mounting a package of a semiconductor element such as a flash memory or a DRAM. Furthermore, it is a suitable adhesive for bonding optical elements used in craft glass pedestals, plate fixing applications, two or more lenses and prisms, cameras, binoculars, microscopes, and the like.
  • the mixing method of the material is not particularly limited, and examples thereof include a stirring method using a stirring force accompanying rotation of a propeller, a method using a normal disperser such as a planetary stirrer by rotation and revolution, and the like. These mixing methods are preferable because stable mixing can be performed at low cost.
  • the energy ray-curable resin composition may be cured by irradiation with energy rays using the following light source.
  • the light source used for curing and adhering the energy beam curable resin composition is not particularly limited, but is a halogen lamp, a metal halide lamp, a high power metal halide lamp (containing indium or the like), a low pressure mercury lamp, Examples thereof include a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a xenon excimer lamp, a xenon flash lamp, a light emitting diode (hereinafter referred to as LED), and the like.
  • LED light emitting diode
  • Each of the light sources has a different emission wavelength and energy distribution. Therefore, the light source is appropriately selected depending on the reaction wavelength of the photopolymerization initiator. Natural light (sunlight) can also be a reaction initiation light source.
  • the light source may perform direct irradiation, condensing irradiation using a reflecting mirror, or condensing irradiation using a fiber or the like.
  • a low wavelength cut filter, a heat ray cut filter, a cold mirror, or the like 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, adhesiveness, and chemical resistance and an adhesive using the energy ray curable resin composition.
  • component (B) Aromatic sulfonium SbF 6 salt (“Adekaoptomer SP-170” manufactured by Adeka)
  • B-2) Aromatic sulfonium PF 6 salt (“Adekaoptomer SP-150” manufactured by Adeka)
  • component (C) 2-Hydroxy-2-methyl-1-phenyl-propan-1-one (“Darocur 1173” manufactured by Ciba Japan)
  • C-2) 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Japan)
  • C-3) 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propan-1-one (“Irga” manufactured by Ciba Japan) Cure 127 ”)
  • D-1 Bisphenol A type epoxy resin (“ADEKA OPTOMER KRM-2410”, molecular weight: 400, manufactured by ADEKA)
  • D-2) Bisphenol F-type epoxy resin (“ADEKA OPTOMER KRM-2490” manufactured by ADEKA Corporation, molecular weight: 380)
  • D-3) Hydrogenated bisphenol A type epoxy resin (Mitsubishi Chemical Corporation “YX-8000” molecular weight: 410)
  • D-4) 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (“EHPE-3150” manufactured by Daicel Chemical Industries, Ltd., 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) (“J)
  • E-1 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate (“Celoxide 2021P” manufactured by Daicel Chemical Industries)
  • E-2) Di (1-ethyl-3-oxetanyl) methyl ether (Toa Gosei Co., Ltd. “OXT221”)
  • E-3) 4-hydroxybutyl methacrylate glycidyl ether (Nippon Kasei Co., Ltd. “Hite G”)
  • Examples 1 to 16 Comparative Examples 1 to 6
  • the raw materials of the types shown in Tables 1 to 4 were mixed at the composition ratios (units are parts by mass) shown in Tables 1 to 4 to prepare resin compositions, which were evaluated later.
  • Various evaluation results are shown in Tables 1 to 4. Unless otherwise specified, the test was carried out in an environment of 23 ° C. and 50% humidity.
  • a rheometer (“MCR-301” manufactured by Arton Pearl) can measure the rigidity under UV irradiation. The measurement is performed by sandwiching the prepared resin composition from both sides with a circular plate having a diameter of 8 mm, and irradiating the resin composition with UV (365 nm illuminance: 150 mW / cm 2 ) at 25 ° C. ( ⁇ 0.5 ° C.), The frequency was 10 Hz. A sample in which the storage rigidity G ′ increased to 1.00 ⁇ 10 4 or more by 200 seconds after the start of UV irradiation was regarded as “Good”, and the curability was judged to be good.
  • Tensile shear bond strength measured in accordance with JIS K 6850. Specifically, the resin composition produced by using a heat-resistant glass (trade name “heat-resistant Pyrex (registered trademark) glass”, 25 mm ⁇ 25 mm ⁇ 2.0 mm) as an adherend, and forming a bonded portion with a circle having a diameter of 8 mm. Two pieces of heat-resistant glass are laminated together, using a UV irradiator, integrated light intensity of 3,000 mJ / cm 2 (365 nm illuminance: 150 mW / cm 2 , “SP-7 (mercury xenon lamp installed) by USHIO ELECTRIC CO., LTD. A test piece was prepared by curing under the conditions of a UV curing apparatus))). The produced test piece was measured for tensile shear bond strength using a tensile tester in an environment of 23 ° C. and humidity of 50%.
  • a heat-resistant glass trade name “heat-resistant Pyrex (registered
  • the present invention has rapid curability. Furthermore, the present invention has high adhesion and chemical resistance.
  • the component (A) is 65 parts by mass or less, the effect of the present invention cannot be obtained (contrast of Example 11 and Comparative Example 6).
  • the component (D) is used, the adhesive strength and the like are improved (contrast of Example 12 and Examples 1 to 3).
  • the adhesive strength and the like are improved as compared with the case where the component (E) is used (contrast of Examples 4 to 11 and Examples 14 to 15).
  • the present invention exhibits a transmittance of 90% or more at 405 nm and 98% or more at 550 nm, it can be seen that the present invention has excellent transparency in the visible light region.
  • an energy beam curable resin composition having rapid curability and having high adhesiveness and chemical resistance, and an adhesive using the same.
  • Assembling parts of electronic products such as panels, organic electroluminescence panels, touch panels, projectors, smartphones, mobile phones, digital cameras, digital movies, LEDs, solar cells, lithium ion batteries, CCD, CMOS, flash memory, DRAM, etc. It can be suitably used for mounting a semiconductor element package or the like.
  • it is a suitable adhesive for bonding optical elements used in craft glass pedestals, plate fixing applications, two or more lenses and prisms, cameras, binoculars, microscopes, and the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polyethers (AREA)

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

エネルギー線硬化性樹脂組成物Energy ray curable resin composition
本願発明は、エネルギー線硬化性樹脂組成物とそれを用いた接着剤及び硬化体に関する。 The present invention relates to an energy ray curable resin composition, an adhesive using the same, and a cured product.
近年、部品の組み立てや、半導体素子のパッケージ等の実装には、紫外線等のエネルギー線により短時間で硬化可能なエネルギー線硬化型接着剤が適用されている。部品としては、液晶パネル、有機エレクトロルミネッセンスパネル、タッチパネル、プロジェクター、スマートフォン、携帯電話、デジタルカメラ、デジタルムービー、ＬＥＤ、太陽電池等のエレクトロニクス製品が挙げられる。半導体素子としては、ＣＣＤ、ＣＭＯＳ、フラッシュメモリー、ＤＲＡＭ等が挙げられる。 In recent years, energy ray curable adhesives that can be cured in a short time with energy rays such as ultraviolet rays have been applied to the assembly of components and the mounting of semiconductor device packages and the like. Examples of the components include electronic products such as liquid crystal panels, organic electroluminescence panels, touch panels, projectors, smartphones, mobile phones, digital cameras, digital movies, LEDs, and solar cells. Examples of the semiconductor element include a CCD, a CMOS, a flash memory, and a DRAM.
これらの分野で用いられるエネルギー線硬化型接着剤は、各種材料への高い接着性、及び熱、湿度、ヒートサイクル等に耐えうる高い信頼性が求められている。更に、これらの分野で用いられるエネルギー線硬化型接着剤は、洗浄工程やエッチング工程等で、接着剤がアルコール、酸、アルカリ等の薬品に曝されるため、これらの各種薬品に対する耐性、いわゆる耐薬品性を有する接着剤が求められている。 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 cycle, and the like. Furthermore, the energy ray curable adhesives used in these fields are exposed to chemicals such as alcohol, acid, alkali, etc. in the cleaning process, etching process, etc., so that they are resistant to these various chemicals, so-called resistance. There is a need for adhesives having chemical properties.
デジタルカメラ、双眼鏡及び顕微鏡等に用いられるレンズ、プリズム、フィルター等の光学素子を接着する場合、エネルギー線硬化型接着剤は、４００ｎｍ～８００ｎｍの可視光域での高い透明性が求められる。 When bonding optical elements such as lenses, prisms, and filters used in digital cameras, binoculars, and microscopes, the energy ray curable adhesive is required to have high transparency in the visible light range of 400 nm to 800 nm.
エネルギー線硬化型接着剤としては、アクリル系、エポキシ系、エン・チオール系等の接着剤が上市されている。アクリル系やエン・チオール系の接着剤は速硬化性、接着性に優れるが、耐薬品性が劣るという課題がある。エポキシ系の接着剤は耐薬品性、接着性に優れるが、速硬化性が劣るという課題がある。 As energy ray curable adhesives, acrylic, epoxy, and ene / thiol adhesives are on the market. Acrylic and ene / thiol adhesives are excellent in fast curability and adhesiveness, but have a problem of poor chemical resistance. Epoxy adhesives are excellent in chemical resistance and adhesiveness, but have a problem of inferior rapid curability.
上述のようなアクリル系の課題とエポキシ系の課題を両立する手段として、アクリル化合物とエポキシ化合物とを有する樹脂組成物（特許文献１～３）や、アクリル基とエポキシ基を同一分子内に有する化合物及び樹脂組成物（特許文献４～８）が開示されている。しかしながら、これらの公知の樹脂組成物は上述の接着剤に要求される速硬化性、接着性、耐薬品性を満足するものではなかった。本発明の場合、特許文献７とは、（Ａ）成分の量が異なる。 As means for satisfying both of the above-mentioned acrylic problems and epoxy problems, resin compositions having an acrylic compound and an epoxy compound (Patent Documents 1 to 3), and having an acrylic group and an epoxy group in the same molecule Compounds and resin compositions (Patent Documents 4 to 8) are disclosed. However, these known resin compositions do not satisfy the fast curability, adhesiveness, and chemical resistance required for the above-mentioned adhesive. In the case of the present invention, the amount of component (A) is different from Patent Document 7.
特開平１１－３５８４６号公報JP 11-35846 A 特開２００６－２３３００９号公報JP 2006-233009 A 特開２００８－２６０８７９号公報JP 2008-260879 A 特開２００３－５５３６２号公報JP 2003-55362 A 特開２００８－８８１６７号公報JP 2008-88167 A 特許第４０９５３８０号公報Japanese Patent No. 4095380 特開２００８－２６０８７９号公報JP 2008-260879 A 特開２０１０－２４８５００号公報JP 2010-248500 A
本発明は、速やかな硬化性を有するエネルギー線硬化性樹脂組成物に関する。 The present invention relates to an energy beam curable resin composition having rapid curability.
本発明は、以下の（１）～（７）の態様を包含する。
（１）（Ａ）下記式〔１〕で表される分子内に（メタ）アクリロイル基と、脂環式エポキシ基を有する化合物 The present invention includes the following aspects (1) to (7).
(1) (A) Compound having (meth) acryloyl group and alicyclic epoxy group in the molecule represented by the following formula [1]
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
（式中のＲは水素又はメチル基を表し、Ｘは炭素数１～６のアルキレン鎖又は炭素数１～６のオキシアルキレン鎖を表す。）を、（Ａ）成分、（Ｄ）成分及び（Ｅ）成分からなる重合成分の総量１００質量部中、６５質量部を超え１００質量部以下
（Ｂ）光カチオン重合開始剤
（Ｃ）光ラジカル重合開始剤
を含有するエネルギー線硬化型樹脂組成物。
（２）（Ｄ）分子内に２つ以上のエポキシ基を有するオリゴマーを含有する（１）に記載のエネルギー線硬化性樹脂組成物。
（３）（Ｄ）分子内に２つ以上のエポキシ基を有するオリゴマーの分子量が、３５０～１００，０００である（２）に記載のエネルギー線硬化性樹脂組成物。
（４）（Ｅ）（Ａ）および（Ｂ）以外のカチオン重合性単量体を含有する（１）に記載のエネルギー線硬化性樹脂組成物。
（５）（１）～（４）のいずれかに記載のエネルギー線硬化性樹脂組成物からなる接着剤。
（６）（１）～（４）のいずれかに記載のエネルギー線硬化性樹脂組成物が硬化してなる硬化体。
（７）（１）～（４）のいずれかに記載のエネルギー線硬化性樹脂組成物を用いる接合体。 (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), (A) component, (D) component and ( E) Energy beam curable resin composition containing 65 parts by mass and 100 parts by mass or less of (B) photocationic polymerization initiator (C) photoradical polymerization initiator in 100 parts by mass of the total amount of polymerization components comprising the component.
(2) The energy ray-curable resin composition according to (1), which contains (D) an oligomer having two or more epoxy groups in the molecule.
(3) The energy ray-curable resin composition according to (2), wherein (D) the molecular weight of the oligomer having two or more epoxy groups in the molecule is 350 to 100,000.
(4) (E) The energy ray-curable resin composition according to (1), which contains a cationically polymerizable monomer other than (A) and (B).
(5) An adhesive comprising the energy beam curable resin composition according to any one of (1) to (4).
(6) A cured product obtained by curing the energy beam curable resin composition according to any one of (1) to (4).
(7) A joined body using the energy ray-curable resin composition according to any one of (1) to (4).
上記構成からなるエネルギー線硬化性樹脂組成物は、例えば、速硬化性を満足することができる。 The energy ray-curable resin composition having the above-described configuration can satisfy, for example, quick curability.
＜用語の説明＞
本明細書において、エネルギー線硬化性樹脂組成物とは、エネルギー線を照射することによって硬化させることができる樹脂組成物を意味する。ここで、エネルギー線とは、紫外線、可視光線等に代表されるエネルギー線を意味する。 <Explanation of terms>
In this specification, the energy ray curable resin composition means a resin composition that can be cured by irradiation with energy rays. Here, the energy rays mean energy rays typified by ultraviolet rays and visible rays.
本明細書において、分子量とは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定されるポリスチレン換算の重量平均分子量を意味する。 In the present specification, the molecular weight means a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).
本明細書において、特記しない限り、質量部とは、重合成分の総量１００質量部中の質量部を意味する。ここで、重合成分とは、（Ａ）成分、必要に応じて使用する（Ｄ）成分、必要に応じて使用する（Ｅ）成分をいう。 In the present specification, unless otherwise specified, the part by mass means part by mass in 100 parts by mass of the total amount of polymerization components. Here, a polymerization component means (A) component, (D) component used as needed, and (E) component used as needed.
本実施形態に係るエネルギー線硬化性樹脂組成物の成分について説明する。 The components of the energy beam curable resin composition according to this embodiment will be described.
本実施形態に係るエネルギー線硬化性樹脂組成物は、（Ａ）成分として下記式〔１〕で表される分子内に（メタ）アクリロイル基と、脂環式エポキシ基を有する化合物を必須成分とする。 The energy ray-curable resin composition according to the present embodiment includes, as an essential component, a compound having a (meth) acryloyl group and an alicyclic epoxy group in the molecule represented by the following formula [1] as the component (A). To do.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
（式中のＲは水素又はメチル基を表し、Ｘは炭素数１～６のアルキル鎖又は炭素数１～６のオキシアルキレン鎖を表す。）
　オキシアルキレン鎖としては、－Ｒ’－Ｏ－が挙げられる。ここで、Ｒ’は炭素数１～６のアルキレンをいう。オキシアルキレン鎖が－Ｒ’－Ｏ－である場合、式〔１〕は下記式〔１’〕で表される。 (In the formula, R represents hydrogen or a methyl group, and X represents an alkyl chain having 1 to 6 carbon atoms or an oxyalkylene chain having 1 to 6 carbon atoms.)
Examples of the oxyalkylene chain include —R′—O—. Here, R ′ refers to alkylene having 1 to 6 carbon atoms. When the oxyalkylene chain is —R′—O—, the formula [1] is represented by the following formula [1 ′].
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
本発明に用いられる（Ａ）成分としては、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート、３，４－エポキシシクロヘキシルエチル（メタ）アクリレート、３，４－エポキシシクロヘキシルプロピル（メタ）アクリレート、３，４－エポキシシクロヘキシルブチル（メタ）アクリレート、エチレンオキサイド変性３，４－エポキシシクロヘキシルメチル（メタ）アクリレート、プロピレンオキサイド変性３，４－エポキシシクロヘキシルメチル（メタ）アクリレート等が挙げられる。これらの中では、３，４－エポキシシクロヘキシルメチル（メタ）アクリレートが、耐薬品性に優れている点で、好ましい。 As the component (A) used in the present invention, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, Examples include 4-epoxycyclohexylbutyl (meth) acrylate, ethylene oxide-modified 3,4-epoxycyclohexylmethyl (meth) acrylate, and propylene oxide-modified 3,4-epoxycyclohexylmethyl (meth) acrylate. Among these, 3,4-epoxycyclohexylmethyl (meth) acrylate is preferable in terms of excellent chemical resistance.
（Ａ）成分は、（Ａ）成分、（Ｄ）成分及び（Ｅ）成分からなる重合成分の総量１００質量部中、６５質量部を超え１００質量部以下の割合で含有させることが好ましい。この範囲にあれば硬化性が悪くなることもないし、接着性や耐薬品性も低下しない。特に硬化性と接着性、耐薬品性の点で、７０質量部以上９５質量部以下がより好ましい。 The component (A) is preferably contained in a proportion of more than 65 parts by mass and 100 parts by mass or less in a total amount of 100 parts by mass of the polymerization component composed of the components (A), (D) and (E). If it is in this range, the curability will not deteriorate, and the adhesiveness and chemical resistance will not deteriorate. In particular, 70 parts by mass or more and 95 parts by mass or less are more preferable in terms of curability, adhesiveness, and chemical resistance.
本実施形態に係るエネルギー線硬化性樹脂組成物は、（Ｂ）成分として光カチオン重合開始剤を必須成分とする。（Ｂ）成分の光カチオン重合開始剤は、エネルギー線を照射することによりカチオン種が発生する化合物であれば、特に制限されない。 The energy ray-curable resin composition according to the present embodiment includes a cationic photopolymerization initiator as an essential component as the component (B). The photocationic polymerization initiator as the component (B) is not particularly limited as long as it is a compound that generates a cationic species when irradiated with energy rays.
本発明に用いられる（Ｂ）成分の光カチオン重合開始剤としては、アリールスルホニウム塩誘導体（例えば、ダウケミカル社製のサイラキュアＵＶＩ－６９９０、サイラキュアＵＶＩ－６９７４、旭電化工業社製のアデカオプトマーＳＰ－１５０、アデカオプトマーＳＰ－１５２、アデカオプトマーＳＰ－１７０、アデカオプトマーＳＰ－１７２、サンアプロ社製のＣＰＩ－１００Ｐ、ＣＰＩ－１０１Ａ、ＣＰＩ－２００Ｋ、ＣＰＩ－２１０Ｓ、ダブルボンド社製チバキュアー１１９０、チバジャパン社製のＣＧＩ*ＴＰＳ　Ｃ１、ＧＳＩＤ２６－１等）、アリールヨードニウム塩誘導体（例えば、チバスペシャリティーケミカルズ社製のイルガキュアー２５０、チバジャパン社製のＣＧＩ*ＢＢＩ　Ｃ１、ローディア・ジャパン社製のＲＰ－２０７４）、アレン－イオン錯体誘導体、ジアゾニウム塩誘導体、トリアジン系開始剤及びその他のハロゲン化物等の酸発生剤が挙げられる。光カチオン重合開始剤は、１種又は２種以上を選択して任意の割合で使用してもよい。光カチオン重合開始剤のカチオン種としては、オニウムカチオンが好ましい。オニウムカチオンとしては、アリールスルホニウム塩誘導体、アリールヨードニウム塩誘導体等が挙げられる。光カチオン重合開始剤のアニオン種としては、ホウ素化合物、リン化合物、アンチモン化合物、ヒ素化合物、アルキルスルホン酸化合物等のハロゲン化物等が挙げられる。これらの中では、アリールスルホニウム塩誘導体が、硬化性に優れている点で、好ましい。 As the photocationic polymerization initiator of the component (B) used in the present invention, arylsulfonium salt derivatives (for example, Cyracure UVI-6990, Cyracure UVI-6974, manufactured by Dow Chemical Co., Ltd., Adekaoptomer SP manufactured by Asahi Denka Kogyo Co., Ltd.) -150, Adeka optomer SP-152, Adeka optomer SP-170, Adeka optomer SP-172, CPI-100P, CPI-101A, CPI-200K, CPI-210S made by San Apro, Ciba Cure 1190 made by Double Bond CGI * TPS C1, GSID26-1, etc. manufactured by Ciba Japan), aryliodonium salt derivatives (for example, Irgacure 250 manufactured by Ciba Specialty Chemicals, CGI * BBI C1 manufactured by Ciba Japan, Rhodia Japan Co., Ltd.) RP- 074), Allen - ion complex derivatives, diazonium salt derivatives, triazine type initiators and acid generator such as other halides. A photocationic polymerization initiator may be used alone or in combination of two or more. The cation cation is preferably an onium cation. Examples of the onium cation include arylsulfonium salt derivatives and aryliodonium salt derivatives. 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, arylsulfonium salt derivatives are preferable in terms of excellent curability.
（Ｂ）成分の光カチオン重合開始剤は、（Ａ）成分、（Ｄ）成分及び（Ｅ）成分からなる重合成分の総量１００質量部に対して、０．１～１０質量部の割合で含有させることが好ましい。この範囲にあれば硬化性が悪くなることもないし、接着性や耐薬品性も低下しない。特に硬化性と接着性、耐薬品性の点で、（Ｂ）成分の光カチオン重合開始剤の使用量は、０．３～５質量部がより好ましく、０．５～３質量部が最も好ましい。 The cationic photopolymerization initiator of component (B) is contained in a proportion of 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of polymerization components composed of component (A), component (D) and component (E). It is preferable to make it. If it is in this range, the curability will not deteriorate, and the adhesiveness and chemical resistance will not deteriorate. In particular, in terms of curability, adhesiveness, and chemical resistance, the amount of the photocationic polymerization initiator (B) used is more preferably 0.3 to 5 parts by mass, and most preferably 0.5 to 3 parts by mass. .
本実施形態に係るエネルギー線硬化性樹脂組成物は、（Ｃ）成分として光ラジカル重合開始剤を必須成分とする。（Ｃ）成分の光ラジカル重合開始剤は、エネルギー線を照射することによりラジカルが発生する化合物であれば、特に制限されない。 The energy beam curable resin composition according to the present embodiment includes a radical photopolymerization initiator as an essential component as the component (C). The radical photopolymerization initiator of component (C) is not particularly limited as long as it is a compound that generates radicals when irradiated with energy rays.
本発明に用いられる（Ｃ）成分の光ラジカル重合開始剤としては、ベンゾフェノン、４－フェニルベンゾフェノン、ベンゾイル安息香酸、２，２－ジエトキシアセトフェノン、ビスジエチルアミノベンゾフェノン、ベンジル、ベンゾイン、ベンゾイルイソプロピルエーテル、ベンジルジメチルケタール、１－ヒドロキシシクロヘキシルフェニルケトン、チオキサントン、１－（４－イソプロピルフェニル）２－ヒドロキシ－２－メチルプロパン－１－オン、１－（４－（２－ヒドロキシエトキシ）－フェニル）－２－ヒドロキシ－２－メチル－１―プロパン－１－オン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル｝－２－メチル－プロパン－１－オン、カンファーキノン、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）―フェニルホスフィンオキサイド、２－メチル―１―（４－（メチルチオ）フェニル）―２－モルフォリノプロパン－１－オン、２－ベンジル―２－ジメチルアミノ－１―（４－モルフォリノフェニル）―１－ブタノン－１、ビス（２，６－ジメトキシベンゾイル）―２，４，４―トリメチル－ペンチルホスフィンオキサイド等が挙げられる。これらの中では、１－ヒドロキシシクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチルプロパン－１－オン、１－（４－（２－ヒドロキシエトキシ）－フェニル）－２－ヒドロキシ－２－メチル－１―プロパン－１－オン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル｝－２－メチル－プロパン－１－オン等のα－ヒドロキシアセトフェノン類からなる１種以上が、硬化性に優れる点で、好ましい。これらは１種又は２種以上組み合わせて用いることができる。 Examples of the radical photopolymerization initiator of the component (C) used in the present invention include benzophenone, 4-phenylbenzophenone, benzoylbenzoic acid, 2,2-diethoxyacetophenone, bisdiethylaminobenzophenone, benzyl, benzoin, benzoylisopropyl ether, benzyl Dimethyl ketal, 1-hydroxycyclohexyl phenyl 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] pheni } -2-Methyl-propan-1-one, camphorquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-1- ( 4- (Methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone-1, bis (2,6-dimethoxy) And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Among these, 1-hydroxycyclohexyl phenyl ketone, 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 } One or more kinds of α-hydroxyacetophenones such as 2-methyl-propan-1-one are preferable in terms of excellent curability. These can be used alone or in combination of two or more.
（Ｃ）成分の光ラジカル重合開始剤は、（Ａ）成分、（Ｄ）成分及び（Ｅ）成分からなる重合成分の総量１００質量部に対して、０．１～１０質量部の割合で含有させることが好ましい。この範囲にあれば硬化性が悪くなることもないし、接着性や耐薬品性も低下しない。特に硬化性と接着性、耐薬品性の点で、（Ｃ）成分の光ラジカル重合開始剤の使用量は、０．５～５質量部がより好ましく、１～３質量部が最も好ましい。 The (C) component radical photopolymerization initiator is contained in a proportion of 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the polymerization components composed of the (A), (D) and (E) components. It is preferable to make it. If it is in this range, the curability will not deteriorate, and the adhesiveness and chemical resistance will not deteriorate. In particular, from the viewpoint of curability, adhesiveness, and chemical resistance, the amount of the radical photopolymerization initiator (C) used is more preferably 0.5 to 5 parts by mass, and most preferably 1 to 3 parts by mass.
本発明の樹脂組成物には、各種光増感剤を併用してもよい。光増感剤とは、エネルギー線を吸収して、光カチオン重合開始剤や光ラジカル重合開始剤からカチオンやラジカルを効率よく発生させる化合物をいう。 Various photosensitizers may be used in combination with the resin composition of the present invention. A photosensitizer means a compound that absorbs energy rays and efficiently generates cations and radicals from a photocationic polymerization initiator or a photoradical polymerization initiator.
本発明に用いられる光増感剤としては、特に限定されないが、ベンゾフェノン誘導体、フェノチアジン誘導体、フェニルケトン誘導体、ナフタレン誘導体、アントラセン誘導体、フェナントレン誘導体、ナフタセン誘導体、クリセン誘導体、ペリレン誘導体、ペンタセン誘導体、アクリジン誘導体、ベンゾチアゾール誘導体、ベンゾイン誘導体、フルオレン誘導体、ナフトキノン誘導体、アントラキノン誘導体、キサンテン誘導体、キサントン誘導体、チオキサンテン誘導体、チオキサントン誘導体、クマリン誘導体、ケトクマリン誘導体、シアニン誘導体、アジン誘導体、チアジン誘導体、オキサジン誘導体、インドリン誘導体、アズレン誘導体、トリアリルメタン誘導体、フタロシアニン誘導体、スピロピラン誘導体、スピロオキサジン誘導体、チオスピロピラン誘導体、有機ルテニウム錯体等が挙げられる。 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, a pentacene derivative, an acridine derivative , 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, indoline derivatives , Azulene derivatives, triallylmethane derivatives, phthalocyanine derivatives, spiropyran derivatives, spirooxazine Conductor, Chiosupiropiran derivatives, organic ruthenium complexes.
光増感剤は、重合成分の総量１００質量部に対して、０．１～５質量部の割合で含有させることが好ましく、この範囲にあれば接着性や耐薬品性も低下しない。特に硬化性と接着性、耐薬品性の点で、光増感剤の使用量は、０．３～３質量部がより好ましく、０．５～２質量部が最も好ましい。 The photosensitizer is preferably contained in a proportion of 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the polymerization components. If it is within this range, the adhesiveness and chemical resistance will not be lowered. In particular, the use amount of the photosensitizer is more preferably 0.3 to 3 parts by mass, and most preferably 0.5 to 2 parts by mass from the viewpoint of curability, adhesion, and chemical resistance.
本実施形態に係るエネルギー線硬化性樹脂組成物は、（Ｄ）成分として分子内に１つ以上のエポキシ基を有するオリゴマーを含有することが好ましい。 The energy beam curable resin composition according to this embodiment preferably contains an oligomer having one or more epoxy groups in the molecule as the component (D).
本発明に用いられる（Ｄ）成分の分子内に１つ以上のエポキシ基を有するオリゴマーとしては、芳香族系、脂肪族系、脂環系のオリゴマーが挙げられる。芳香族系としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビフェニル型エポキシ樹脂、フルオレン型エポキシ樹脂、ノボラックフェノール型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、これらの変性物等が挙げられる。
脂肪族系としては、エポキシ化変性ポリブタジエン、エポキシ化変性ポリイソプレン等のエポキシ化変性ポリオレフィン、ポリエチレングリコール付加体のジグリシジルエーテル、ポリプロピレングリコール付加体のジグリシジルエーテル等のポリアルキレングリコールのジグリシジルエーテル等が挙げられる。脂環系としては、２，２－ビス（ヒドロキシメチル）－１－ブタノールの１，２－エポキシ－４－（２－オキシラニル）シクロヘキサン付加物や、上述の芳香族系エポキシ樹脂の水素添加物が挙げられる。これらの中では、エポキシ化変性ポリブタジエン、エポキシ化変性ポリイソプレン、２，２－ビス（ヒドロキシメチル）－１－ブタノールの１，２－エポキシ－４－（２－オキシラニル）シクロヘキサン付加物からなる１種以上が、耐薬品性に優れる点で、好ましく、エポキシ化変性ポリブタジエンがより好ましい。 Examples of the oligomer having one or more epoxy groups in the molecule of the component (D) used in the present invention include aromatic, aliphatic and alicyclic oligomers. Aromatic resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, novolac phenol type epoxy resin, cresol novolac type epoxy resin, and modified products thereof. Etc.
Aliphatics include epoxidized modified polyolefins such as epoxidized modified polybutadiene and epoxidized modified polyisoprene, diglycidyl ethers of polyethylene glycol adducts, diglycidyl ethers of polyalkylene glycols such as diglycidyl ethers of polypropylene glycol adducts, etc. Is mentioned. Examples of the alicyclic system include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and hydrogenated products of the above-mentioned aromatic epoxy resins. Can be mentioned. Among these, epoxidized modified polybutadiene, epoxidized modified polyisoprene, and 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol The above is preferable in terms of excellent chemical resistance, and epoxidized modified polybutadiene is more preferable.
ポリブタジエンのミクロ構造については特に制限はなく、１，４－ｃｉｓ体ユニット割合の少ないｌｏｗ－ｃｉｓポリブタジエン骨格、１，４－ｃｉｓ体ユニット割合の多いｈｉｇｈ－ｃｉｓポリブタジエン骨格、１，２－ポリブタジエン骨格を示す１，２－ｃｉｓ体等いずれでも構わない。これらの１種以上を混合しても良い。 The microstructure of polybutadiene is not particularly limited. A low-cis polybutadiene skeleton with a small proportion of 1,4-cis isomer units, a high-cis polybutadiene skeleton with a large proportion of 1,4-cis isomer units, and a 1,2-polybutadiene skeleton are included. Any of the 1,2-cis bodies shown may be used. One or more of these may be mixed.
（Ｄ）成分の分子内に１つ以上のエポキシ基を有するオリゴマーの分子量は、３５０～１００，０００が好ましく、５００～５０，０００がより好ましく、２，０００～２０，０００が最も好ましい。分子量が３５０以上であれば耐薬品性が低下することもなく、１００，０００以下であれば硬化性が低下することもない。 The molecular weight of the oligomer having one or more epoxy groups in the molecule of component (D) is preferably 350 to 100,000, more preferably 500 to 50,000, and most preferably 2,000 to 20,000. If the molecular weight is 350 or more, the chemical resistance is not lowered, and if it is 100,000 or less, the curability is not lowered.
尚、ここで言う分子量とは、数平均分子量をいい、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定されるポリスチレン換算の数平均分子量をいう。 In addition, the molecular weight said here means a number average molecular weight, and means the number average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC).
（Ｄ）成分の分子内に１つ以上のエポキシ基を有するオリゴマーは、速硬化性、接着性、耐薬品性のバランスを考慮した場合、（Ａ）成分、（Ｄ）成分及び（Ｅ）成分からなる重合成分の総量１００質量部中、５～３５質量部が好ましく、１０～３０質量部がより好ましい。 (D) The oligomer which has one or more epoxy groups in the molecule | numerator of a component is (A) component, (D) component, and (E) component, when the balance of quick curability, adhesiveness, and chemical resistance is considered. 5 to 35 parts by mass is preferable, and 10 to 30 parts by mass is more preferable in a total amount of the polymerization component consisting of
本実施形態に係るエネルギー線硬化性樹脂組成物は、目的の物性を損なわない範囲で、（Ｅ）成分として（Ａ）および（Ｂ）成分以外のカチオン重合性単量体を含有することができる。 The energy ray curable resin composition according to the present embodiment can contain a cationically polymerizable monomer other than the components (A) and (B) as the component (E) as long as the target physical properties are not impaired. .
本発明に用いられる（Ｅ）成分である（Ａ）および（Ｂ）成分以外のカチオン重合性単量体としては、環状エーテル単量体、環状チオエーテル単量体、カチオン重合性ビニル単量体等が挙げられる。環状エーテル単量体としては、エポキシ、オキセタン等の単量体が挙げられる。チオエーテル単量体としては、イソブチレンスルフィド等が挙げられる。 Examples of the cationically polymerizable monomer other than the components (A) and (B) that are the component (E) used in the present invention include a cyclic ether monomer, a cyclic thioether monomer, and a cationic polymerizable vinyl monomer. Is mentioned. Examples of cyclic ether monomers include monomers such as epoxy and oxetane. Examples of the thioether monomer include isobutylene sulfide.
カチオン重合性ビニル単量体としては、ビニルエーテル、ビニルアミン、スチレン等が挙げられる。これらの単量体若しくは誘導体は、単独又は２種類以上を選択して使用してもよい。 Examples of the cationic polymerizable vinyl monomer include vinyl ether, vinyl amine, and styrene. These monomers or derivatives may be used alone or in combination of two or more.
環状エーテル単量体としては、特に限定されないが、１，２－エポキシシクロヘキサン、１－（エポキシエチル）－３，４－エポキシシクロヘキサン、３，４－エポキシシクロヘキセニルメチル－３’，４’－エポキシシクロヘキセンカルボキシレート、ジ（１－エチル－３－オキセタニル）メチルエーテル、４－ヒドロキシブチルメタクリレートグリシジルエーテル、グリシジル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレートグリシジルエーテル、（メタ）アクリル酸＝（３－エチルオキセタン－３－イル）メチル、３－エチル－３－ヒドロキシメチルオキセタン、１，４－ビス［（３－エチル－３－オキセタニル）メトキシメチル］ベンゼン、３－エチル－３－（フェノキシメチル）オキセタン、ジ（１－エチル－３－オキセタニル）メチルエーテル、３－エチル－３－（２－エチルヘキシロキシメチル）オキセタン等が挙げられる。オキセタンとは、分子内に１つ以上のオキセタニル基を有する単量体をいう。 The cyclic ether monomer is not particularly limited, but 1,2-epoxycyclohexane, 1- (epoxyethyl) -3,4-epoxycyclohexane, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxy Cyclohexene 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 -Ethyloxetane-3-yl) methyl, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3- (phenoxymethyl) Oxetane, di (1-ethyl- - 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.
ビニルエーテル単量体としては、特に限定されないが、エチレングリコールジビニルエーテル、エチレングリコールモノビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールモノビニルエーテル、トリエチレングリコールジビニルエーテル、プロピレングリコールジビニルエーテル、ジプロピレングリコールジビニルエーテル、ブタンジオールジビニルエーテル、ヘキサンジオールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、ヒドロキシエチルモノビニルエーテル、ヒドロキシノニルモノビニルエーテル、トリメチロールプロパントリビニルエーテル等のジ又はトリビニルエーテル化合物、エチルビニルエーテル、ｎ－ブチルビニルエーテル、イソブチルビニルエーテル、オクタデシルビニルエーテル、シクロヘキシルビニルエーテル、ヒドロキシブチルビニルエーテル、２－エチルヘキシルビニルエーテル、シクロヘキサンジメタノールモノビニルエーテル、ｎ－プロピルビニルエーテル、イソプロピルビニルエーテル、イソプロペニルエーテル－ｏ－プロピレンカーボネート、ドデシルビニルエーテル、ジエチレングリコールモノビニルエーテル、オクタデシルビニルエーテル等のモノビニルエーテル化合物等が挙げられる。 The vinyl ether monomer is not particularly limited, but 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 glycol divinyl ether, butane Di- or trivinyl ether compounds such as diol divinyl ether, hexanediol divinyl ether, cyclohexane dimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, trimethylolpropane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl Monovinyl ethers such as nil ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether-o-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether Compounds and the like.
ビニルアミン単量体としては、特に限定されないが、Ｎ－ビニルジメチルアミン、Ｎ－ビニルエチルブチルアミン、Ｎ－ビニルジフェニルアミン、Ｎ－ビニルホルムアミド、Ｎ－ビニルアセトアミド化合物等が挙げられる。 The vinylamine monomer is not particularly limited, and examples thereof include N-vinyldimethylamine, N-vinylethylbutylamine, N-vinyldiphenylamine, N-vinylformamide, and N-vinylacetamide compound.
（Ｅ）成分である（Ａ）および（Ｂ）成分以外のカチオン重合性単量体の中では、環状エーテル単量体が好ましく、３，４－エポキシシクロヘキセニルメチル－３’，４’－エポキシシクロヘキセンカルボキシレート、ジ（１－エチル－３－オキセタニル）メチルエーテルからなる１種以上が好ましい。 Among the cationically polymerizable monomers other than the components (A) and (B) as the component (E), a cyclic ether monomer is preferable, and 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxy is preferable. One or more of cyclohexenecarboxylate and di (1-ethyl-3-oxetanyl) methyl ether are preferred.
（Ｅ）成分である（Ａ）および（Ｂ）成分以外のカチオン重合性単量体は、速硬化性、接着性、耐薬品性のバランスを考慮した場合、（Ａ）成分、（Ｄ）成分及び（Ｅ）成分からなる重合成分の総量１００質量部中、５～３５質量部が好ましく、１０～３０質量部がより好ましい。 The cationic polymerizable monomers other than the components (A) and (B) which are the components (E) are components (A) and (D) when considering the balance between fast curability, adhesion and chemical resistance. In addition, 5 to 35 parts by mass are preferable, and 10 to 30 parts by mass are more preferable, in 100 parts by mass of the total amount of the polymerization components composed of the component (E).
本発明では、酸化防止剤として、フェノール系酸化防止剤とキノン系酸化防止剤からなる群のうちの１種又は２種以上を含有することができる。 In this invention, 1 type (s) or 2 or more types in the group which consists of a phenolic antioxidant and a quinone antioxidant can be contained as antioxidant.
本発明では、ホスフィンオキサイド誘導体を使用しても良い。 In the present invention, a phosphine oxide derivative may be used.
本発明では、フィラー（無機充填剤）を更に含有していてもよい。 In the present invention, a filler (inorganic filler) may further be contained.
本実施形態の目的を損なわない範囲で、アクリルゴム、ウレタンゴム等の各種エラストマー、メタクリル酸メチル－ブタジエン－スチレン系グラフト共重合体やアクリロニトリル－ブタジエン－スチレン系グラフト共重合体等のグラフト共重合体、溶剤、増量材、補強材、可塑剤、増粘剤、染料、顔料、難燃剤及び界面活性剤等の添加剤が含有しても良い。 As long as the purpose of the present embodiment is not impaired, various elastomers such as acrylic rubber and urethane rubber, and graft copolymers such as methyl methacrylate-butadiene-styrene graft copolymer and acrylonitrile-butadiene-styrene graft copolymer Additives such as solvents, extenders, reinforcing materials, plasticizers, thickeners, dyes, pigments, flame retardants and surfactants may be contained.
本発明では、シランカップリング剤を任意の割合で、１種又は２種以上を含有することができる。 In this invention, a silane coupling agent can be contained 1 type or 2 types or more in arbitrary ratios.
上記構成からなるエネルギー線硬化性樹脂組成物は、エネルギー線の照射により硬化させ、硬化体としてもよい。 The energy ray-curable resin composition having the above-described configuration may be cured by irradiation with energy rays to form a cured body.
上記構成からなるエネルギー線硬化性樹脂組成物は接着剤として用いてもよい。この接着剤は、液晶パネル、有機エレクトロルミネッセンスパネル、タッチパネル、プロジェクター、スマートフォン、携帯電話、デジタルカメラ、デジタルムービー、ＬＥＤ、太陽電池、リチウムイオン電池等のエレクトロニクス製品の部品の組み立てや、ＣＣＤ、ＣＭＯＳ、フラッシュメモリー、ＤＲＡＭ等の半導体素子のパッケージ等の実装に好適に用いることができる。更には工芸ガラスの台座、皿の固定用途、２個以上のレンズやプリズム、カメラ、双眼鏡及び顕微鏡等に用いられる光学素子の接着においても好適な接着剤となる。 You may use the energy-beam curable resin composition which consists of the said structure as an adhesive agent. This adhesive can be used to assemble parts of electronic products such as liquid crystal panels, organic electroluminescence panels, touch panels, projectors, smartphones, mobile phones, digital cameras, digital movies, LEDs, solar cells, lithium ion batteries, CCDs, CMOS, It can be suitably used for mounting a package of a semiconductor element such as a flash memory or a DRAM. Furthermore, it is a suitable adhesive for bonding optical elements used in craft glass pedestals, plate fixing applications, two or more lenses and prisms, cameras, binoculars, microscopes, and the like.
本実施形態に係るエネルギー線硬化性樹脂組成物の製造方法については、上記の材料を十分に混合できれば特に制限はない。材料の混合方法としては、特に限定されないが、プロペラの回転に伴う撹拌力を利用する撹拌法、自転公転による遊星式撹拌機等の通常の分散機を利用する方法等が挙げられる。これらの混合方法は、低コストで、安定した混合を行えるので好ましい。 About the manufacturing method of the energy beam curable resin composition which concerns on this embodiment, if said material can fully be mixed, there will be no restriction | limiting in particular. The mixing method of the material is not particularly limited, and examples thereof include a stirring method using a stirring force accompanying rotation of a propeller, a method using a normal disperser such as a planetary stirrer by rotation and revolution, and the like. These mixing methods are preferable because stable mixing can be performed at low cost.
上記の混合を行った後、下記の光源を用いたエネルギー線の照射により、エネルギー線硬化性樹脂組成物の硬化を行ってもよい。 After performing the above mixing, the energy ray-curable resin composition may be cured by irradiation with energy rays using the following light source.
本実施形態において、エネルギー線硬化性樹脂組成物の硬化、接着に用いられる光源としては、特に限定されないが、ハロゲンランプ、メタルハライドランプ、ハイパワーメタルハライドランプ（インジウム等を含有する）、低圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、キセノンランプ、キセノンエキシマランプ、キセノンフラッシュランプ、ライトエミッティングダイオード（以下、ＬＥＤという）等が挙げられる。これらの光源は、それぞれの光重合開始剤の反応波長に対応したエネルギー線の照射を効率よく行える点で、好ましい。 In the present embodiment, the light source used for curing and adhering the energy beam curable resin composition is not particularly limited, but is a halogen lamp, a metal halide lamp, a high power metal halide lamp (containing indium or the like), a low pressure mercury lamp, Examples thereof include a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a xenon excimer lamp, a xenon flash lamp, a light emitting diode (hereinafter referred to as LED), and the like. These light sources are preferable in that the irradiation of energy rays corresponding to the reaction wavelength of each photopolymerization initiator can be efficiently performed.
上記光源は、各々放射波長、エネルギー分布が異なる。そのため、上記光源は光重合開始剤の反応波長等により適宜選択される。又、自然光（太陽光）も反応開始光源になり得る。 Each of the light sources has a different emission wavelength and energy distribution. Therefore, the light source is appropriately selected depending on the reaction wavelength of the photopolymerization initiator. Natural light (sunlight) can also be a reaction initiation light source.
上記光源は、直接照射、反射鏡等による集光照射、ファイバー等による集光照射を行ってもよい。低波長カットフィルター、熱線カットフィルター、コールドミラー等も用いることもできる。 The light source may perform direct irradiation, condensing irradiation using a reflecting mirror, or condensing irradiation using a fiber or the like. A low wavelength cut filter, a heat ray cut filter, a cold mirror, or the like can also be used.
上記構成からなるエネルギー線硬化性樹脂組成物は、硬化性、接着性、耐薬品性に優れたエネルギー線硬化性樹脂組成物とそれを用いた接着剤を提供できる。 The energy ray curable resin composition having the above-described configuration can provide an energy ray curable resin composition excellent in curability, adhesiveness, and chemical resistance and an adhesive using the energy ray curable resin composition.
以下に、実施例及び比較例を挙げて、本発明を更に詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
実施例では、以下の化合物を使用した。
（Ａ）成分として下記を用いた。
（Ａ－１）３，４－エポキシシクロヘキシルメチルメタクリレート（ダイセル化学工業社「サイクロマーＭ－１００」）
（Ａ－２）３，４－エポキシシクロヘキシルメチルアクリレート（ダイセル化学工業社「サイクロマーＡ－２００」） In the examples, the following compounds were used.
The following was used as the component (A).
(A-1) 3,4-epoxycyclohexylmethyl methacrylate (Daicel Chemical Industries, Ltd. “Cyclomer M-100”)
(A-2) 3,4-epoxycyclohexylmethyl acrylate (Daicel Chemical Industries, Ltd. “Cyclomer A-200”)
（Ｂ）成分の光カチオン重合開始剤として下記を用いた。
（Ｂ－１）芳香族スルホニウムＳｂＦ6塩（アデカ社製「アデカオプトマーＳＰ－１７０」）
（Ｂ－２）芳香族スルホニウムＰＦ6塩（アデカ社製「アデカオプトマーＳＰ－１５０」） The following was used as the photocationic polymerization initiator of component (B).
(B-1) Aromatic sulfonium SbF 6 salt (“Adekaoptomer SP-170” manufactured by Adeka)
(B-2) Aromatic sulfonium PF 6 salt (“Adekaoptomer SP-150” manufactured by Adeka)
（Ｃ）成分の光ラジカル重合開始剤として下記を用いた。
（Ｃ－１）２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン（チバジャパン社製「ダロキュア１１７３」）
（Ｃ－２）１－ヒドロキシシクロヘキシルフェニルケトン（チバジャパン社製「イルガキュアー１８４」）
（Ｃ－３）２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル｝－２－メチル－プロパン－１－オン（チバジャパン社製「イルガキュアー１２７」） The following was used as the radical photopolymerization initiator of component (C).
(C-1) 2-Hydroxy-2-methyl-1-phenyl-propan-1-one (“Darocur 1173” manufactured by Ciba Japan)
(C-2) 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Japan)
(C-3) 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one (“Irga” manufactured by Ciba Japan) Cure 127 ")
（Ｄ）成分のエポキシ基を有するオリゴマーとして下記を用いた。
（Ｄ－１）ビスフェノールＡ型エポキシ樹脂（アデカ社製「アデカオプトマーＫＲＭ－２４１０」　分子量：４００）
（Ｄ－２）ビスフェノールＦ型エポキシ樹脂（アデカ社製「アデカオプトマーＫＲＭ－２４９０」　分子量：３８０）
（Ｄ－３）水添ビスフェノールＡ型エポキシ樹脂（三菱化学社製「ＹＸ－８０００」　分子量：４１０）
（Ｄ－４）２，２－ビス（ヒドロキシメチル）－１－ブタノールの１，２－エポキシ－４－（２－オキシラニル）シクロヘキサン付加物（ダイセル化学工業社製「ＥＨＰＥ－３１５０」　分子量：２，４００）
（Ｄ－５）エポキシ化ポリブタジエン（１）（アデカ社製「ＢＦ－１０００」　分子量：４，３００　ミクロ構造：１，２－ポリブタジエン）
（Ｄ－６）エポキシ化ポリブタジエン（２）（日本曹達社製「ＪＰ－２００」　分子量：６，４００　ミクロ構造：１，２－ポリブタジエン）
（Ｄ－７）エポキシ化ポリブタジエン（３）（ダイセル化学工業社製「ＢＰ－３６００」　分子量：１９，３００　ミクロ構造：１，２－体／１，４－ｃｉｓ体／１，４－ｔｒａｎｓ体＝４０ｍｏｌ％／４０ｍｏｌ％／２０ｍｏｌ％の共重合体）
（Ｄ－８）エポキシ化ポリブタジエンとスチレンの共重合体（ダイセル化学工業社製「エポフレンドシリーズ」　分子量：２０，０００を超える） The following was used as an oligomer having an epoxy group as component (D).
(D-1) Bisphenol A type epoxy resin (“ADEKA OPTOMER KRM-2410”, molecular weight: 400, manufactured by ADEKA)
(D-2) Bisphenol F-type epoxy resin (“ADEKA OPTOMER KRM-2490” manufactured by ADEKA Corporation, molecular weight: 380)
(D-3) Hydrogenated bisphenol A type epoxy resin (Mitsubishi Chemical Corporation “YX-8000” molecular weight: 410)
(D-4) 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (“EHPE-3150” manufactured by Daicel Chemical Industries, Ltd., 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) (“BP-3600” manufactured by Daicel Chemical Industries, Ltd.) Molecular weight: 19,300 Microstructure: 1,2-isomer / 1,4-cis isomer / 1,4-trans isomer = 40 mol% / 40 mol% / 20 mol% copolymer)
(D-8) Copolymer of epoxidized polybutadiene and styrene ("Epofriend series" manufactured by Daicel Chemical Industries, Ltd., molecular weight: over 20,000)
（Ｅ）成分である（Ａ）および（Ｂ）成分以外のカチオン重合性単量体として下記を使用した。
（Ｅ－１）３，４－エポキシシクロヘキセニルメチル－３’，４’－エポキシシクロヘキセンカルボキシレート（ダイセル化学社製「セロキサイド２０２１Ｐ」）
（Ｅ－２）ジ（１－エチル－３－オキセタニル）メチルエーテル（東亜合成社「ＯＸＴ２２１」）
（Ｅ－３）４－ヒドロキシブチルメタクリレートグリシジルエーテル（日本化成社「ヒッタイトＧ」） The following was used as a cationically polymerizable monomer other than the components (A) and (B) as the component (E).
(E-1) 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate (“Celoxide 2021P” manufactured by Daicel Chemical Industries)
(E-2) Di (1-ethyl-3-oxetanyl) methyl ether (Toa Gosei Co., Ltd. “OXT221”)
(E-3) 4-hydroxybutyl methacrylate glycidyl ether (Nippon Kasei Co., Ltd. “Hitite G”)
（実施例１～１６、比較例１～６）
表１～表４に示す種類の原材料を、表１～表４に示す組成割合（単位は質量部）で混合し、樹脂組成物を調製し、後述の評価を実施した。各種評価結果を表１～表４に示す。特記しない限り、２３℃、湿度５０％の環境下で実施した。 (Examples 1 to 16, Comparative Examples 1 to 6)
The raw materials of the types shown in Tables 1 to 4 were mixed at the composition ratios (units are parts by mass) shown in Tables 1 to 4 to prepare resin compositions, which were evaluated later. Various evaluation results are shown in Tables 1 to 4. Unless otherwise specified, the test was carried out in an environment of 23 ° C. and 50% humidity.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
〔光硬化性評価〕
レオメーター（アートンパール社製「ＭＣＲ－３０１」）ではＵＶ照射下の剛性率を測定することができる。測定は、調製した樹脂組成物を直径８ｍｍの円形のプレートで両面から挟み、該樹脂組成物にＵＶ（３６５ｎｍの照度：１５０ｍＷ／ｃｍ2）を照射しながら２５℃（±０．５℃）、周波数１０Ｈｚで行った。ＵＶ照射開始後２００秒までに、貯蔵剛性率Ｇ’が１．００×１０4以上に増加したものを「合格（Ｇｏｏｄ）」とし、硬化性が良好と判断した。 (Photocurability evaluation)
A rheometer (“MCR-301” manufactured by Arton Pearl) can measure the rigidity under UV irradiation. The measurement is performed by sandwiching the prepared resin composition from both sides with a circular plate having a diameter of 8 mm, and irradiating the resin composition with UV (365 nm illuminance: 150 mW / cm 2 ) at 25 ° C. (± 0.5 ° C.), The frequency was 10 Hz. A sample in which the storage rigidity G ′ increased to 1.00 × 10 4 or more by 200 seconds after the start of UV irradiation was regarded as “Good”, and the curability was judged to be good.
〔固着時間の評価〕
ガラス試験片（商品名「耐熱パイレックス（登録商標）ガラス」、２５ｍｍ×２５ｍｍ×２．０ｍｍ）上に、直径８ｍｍ、厚さ８０μｍになるように樹脂組成物を塗布した後、２枚目のガラス試験片を張り合わせ、ＵＶ照射器（３６５ｎｍの照度：１５０ｍＷ／ｃｍ2、ウシオ電機社製「ＳＰ－７（水銀キセノンランプ搭載ＵＶ硬化装置）」）によりＵＶ光を照射し、２枚のガラス試験片が動かなくなる時間を測定し、固着時間とした。尚、測定時間は最大で１２０秒までとした。 [Evaluation of fixing time]
On the glass test piece (trade name “Heat-resistant Pyrex (registered trademark) glass”, 25 mm × 25 mm × 2.0 mm), a resin composition was applied so as to have a diameter of 8 mm and a thickness of 80 μm. Two glass test pieces were irradiated by irradiating UV light with a UV irradiator (illuminance of 365 nm: 150 mW / cm 2 , “SP-7 (UV curing device equipped with mercury xenon lamp)” manufactured by USHIO INC.)). The time during which the film stopped moving was measured and used as the fixing time. The measurement time was up to 120 seconds.
〔引張剪断接着強さの評価〕
引張剪断接着強さ：ＪＩＳ　Ｋ　６８５０に従い測定した。具体的には被着材とした耐熱ガラス（商品名「耐熱パイレックス（登録商標）ガラス」、２５ｍｍ×２５ｍｍ×２．０ｍｍ）を用いて、接着部位を直径８ｍｍの円形として、作製した該樹脂組成物にて、２枚の耐熱ガラスを張り合わせ、ＵＶ照射器を使用し、積算光量３，０００ｍＪ／ｃｍ2（３６５ｎｍの照度：１５０ｍＷ／ｃｍ2、ウシオ電機社製「ＳＰ－７（水銀キセノンランプ搭載ＵＶ硬化装置）」）の条件にて硬化させ、試験片を作製した。作製した試験片は、２３℃、湿度５０％の環境で、引張試験機を使用して、引張剪断接着強さを測定した。 [Evaluation of tensile shear bond strength]
Tensile shear bond strength: measured in accordance with JIS K 6850. Specifically, the resin composition produced by using a heat-resistant glass (trade name “heat-resistant Pyrex (registered trademark) glass”, 25 mm × 25 mm × 2.0 mm) as an adherend, and forming a bonded portion with a circle having a diameter of 8 mm. Two pieces of heat-resistant glass are laminated together, using a UV irradiator, integrated light intensity of 3,000 mJ / cm 2 (365 nm illuminance: 150 mW / cm 2 , “SP-7 (mercury xenon lamp installed) by USHIO ELECTRIC CO., LTD. A test piece was prepared by curing under the conditions of a UV curing apparatus))). The produced test piece was measured for tensile shear bond strength using a tensile tester in an environment of 23 ° C. and humidity of 50%.
〔分光透過率の評価〕
ガラス試験片（商品名「耐熱パイレックス（登録商標）ガラス」、２５ｍｍ×２５ｍｍ×２．０ｍｍ）上に、直径２０ｍｍ、厚さ８０μｍになるように樹脂組成物を塗布した後、２枚目のガラス試験片を張り合わせ、ＵＶ照射器（３６５ｎｍの照度：１５０ｍＷ／ｃｍ2、ウシオ電機社製「ＳＰ－７（水銀キセノンランプ搭載ＵＶ硬化装置）」）によりＵＶ光を照射し、試験片を作成した。作成した試験片の波長４０５ｎｍと５００ｎｍの分光透過率を紫外－可視分光スペクトルメーター（島津製作所社製「ＵＶ－２５５０」）を用いて測定した。尚、リファレンスには純水を用いた。 [Evaluation of spectral transmittance]
On the glass test piece (trade name “Heat-resistant Pyrex (registered trademark) glass”, 25 mm × 25 mm × 2.0 mm), a resin composition is applied so as to have a diameter of 20 mm and a thickness of 80 μm. The test pieces were bonded together and irradiated with UV light using a UV irradiator (illuminance at 365 nm: 150 mW / cm 2 , “SP-7 (UV curing device equipped with a mercury xenon lamp)” manufactured by USHIO INC.) To prepare a test piece. Spectral transmittances at wavelengths of 405 nm and 500 nm of the prepared test pieces were measured using an ultraviolet-visible spectral spectrometer (“UV-2550” manufactured by Shimadzu Corporation). Note that pure water was used as a reference.
〔耐薬品性の評価〕
ＵＶ照射器を使用し、４，０００ｍＪ／ｃｍ2（３６５ｎｍの照度：１５０ｍＷ／ｃｍ2、フュージョン社製「ベルトコンベア式無電極放電ランプ（Ｄ－バルブ：メタルハライドランプ）」）の条件にて２５ｍｍ×２５ｍｍ×２．０ｍｍの形状の硬化物を作製し、作製した硬化物をアセトン中に２３℃の環境下で４時間浸漬し、浸漬前後での質量の変化率（％）を測定した。質量の変化率が低いもの程、耐薬品性に優れるものとして評価した。 [Evaluation of chemical resistance]
Using a UV irradiator, 4,000 mJ / cm 2 (365 nm illuminance: 150 mW / cm 2 , “Belt conveyor type electrodeless discharge lamp (D-bulb: metal halide lamp)” manufactured by Fusion) 25 mm × A cured product having a shape of 25 mm × 2.0 mm was produced, and the produced cured product was immersed in acetone at 23 ° C. for 4 hours, and a mass change rate (%) before and after immersion was measured. The lower the rate of change in mass, the better the chemical resistance.
表１～４に示した結果から以下のことが判る。本発明は、速やかな硬化性を有する。更に、本発明は、高接着性、耐薬品性も有する。（Ａ）成分が６５質量部以下だと、本発明の効果が得られない（実施例１１と比較例６の対比）。（Ｄ）成分を使用した場合、接着強さ等が向上する（実施例１２と実施例１～３の対比）。（Ｄ）成分を使用した場合、（Ｅ）成分を使用した場合よりも、接着強さ性等が向上する（実施例４～１１と実施例１４～１５の対比）。
さらに本発明は４０５ｎｍで９０％以上、５５０ｎｍで９８％以上の透過率を示すことから可視光域で優れた透明性を有することが判る。 From the results shown in Tables 1 to 4, the following can be understood. The present invention has rapid curability. Furthermore, the present invention has high adhesion and chemical resistance. When the component (A) is 65 parts by mass or less, the effect of the present invention cannot be obtained (contrast of Example 11 and Comparative Example 6). When the component (D) is used, the adhesive strength and the like are improved (contrast of Example 12 and Examples 1 to 3). When the component (D) is used, the adhesive strength and the like are improved as compared with the case where the component (E) is used (contrast of Examples 4 to 11 and Examples 14 to 15).
Furthermore, since the present invention exhibits a transmittance of 90% or more at 405 nm and 98% or more at 550 nm, it can be seen that the present invention has excellent transparency in the visible light region.
以上のように、本発明によれば、速やかな硬化性を有し、そして、高接着性、耐薬品性を有するエネルギー線硬化性樹脂組成物とそれを用いた接着剤を提供できるため、液晶パネル、有機エレクトロルミネッセンスパネル、タッチパネル、プロジェクター、スマートフォン、携帯電話、デジタルカメラ、デジタルムービー、ＬＥＤ、太陽電池、リチウムイオン電池等のエレクトロニクス製品の部品の組み立てや、ＣＣＤ、ＣＭＯＳ、フラッシュメモリー、ＤＲＡＭ等の半導体素子のパッケージ等の実装に好適に用いることができる。更には工芸ガラスの台座、皿の固定用途、２個以上のレンズやプリズム、カメラ、双眼鏡及び顕微鏡等に用いられる光学素子の接着においても好適な接着剤となる。 As described above, according to the present invention, it is possible to provide an energy beam curable resin composition having rapid curability and having high adhesiveness and chemical resistance, and an adhesive using the same. Assembling parts of electronic products such as panels, organic electroluminescence panels, touch panels, projectors, smartphones, mobile phones, digital cameras, digital movies, LEDs, solar cells, lithium ion batteries, CCD, CMOS, flash memory, DRAM, etc. It can be suitably used for mounting a semiconductor element package or the like. Furthermore, it is a suitable adhesive for bonding optical elements used in craft glass pedestals, plate fixing applications, two or more lenses and prisms, cameras, binoculars, microscopes, and the like.

Claims (7)

  1. （Ａ）下記式〔１〕で表される分子内に（メタ）アクリロイル基と、脂環式エポキシ基を有する化合物
    Figure JPOXMLDOC01-appb-C000001
     （式中のＲは水素又はメチル基を表し、Ｘは炭素数１～６のアルキレン鎖又は炭素数１～６のオキシアルキレン鎖を表す。）を、（Ａ）成分、（Ｄ）成分及び（Ｅ）成分からなる重合成分の総量１００質量部中、６５質量部を超え１００質量部以下
    （Ｂ）光カチオン重合開始剤
    （Ｃ）光ラジカル重合開始剤
    を含有するエネルギー線硬化型樹脂組成物。     (A) Compound having (meth) acryloyl group and alicyclic epoxy group in the molecule represented by the following formula [1]
    Figure JPOXMLDOC01-appb-C000001
     (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), (A) component, (D) component and ( E) Energy beam curable resin composition containing 65 parts by mass and 100 parts by mass or less of (B) photocationic polymerization initiator (C) photoradical polymerization initiator in 100 parts by mass of the total amount of polymerization components comprising the component.
  2. （Ｄ）分子内に２つ以上のエポキシ基を有するオリゴマーを含有する請求項１に記載のエネルギー線硬化性樹脂組成物。 (D) The energy ray-curable resin composition according to claim 1, comprising an oligomer having two or more epoxy groups in the molecule.
  3. （Ｄ）分子内に２つ以上のエポキシ基を有するオリゴマーの分子量が、３５０～１００，０００である請求項２に記載のエネルギー線硬化性樹脂組成物。 The energy ray-curable resin composition according to claim 2, wherein the molecular weight of the oligomer (D) having two or more epoxy groups in the molecule is 350 to 100,000.
  4. （Ｅ）（Ａ）および（Ｂ）以外のカチオン重合性単量体を含有する請求項１に記載のエネルギー線硬化性樹脂組成物。 (E) The energy ray-curable resin composition according to claim 1, comprising a cationically polymerizable monomer other than (A) and (B).
  5. 請求項１～４のいずれか１項に記載のエネルギー線硬化性樹脂組成物からなる接着剤。 An adhesive comprising the energy ray-curable resin composition according to any one of claims 1 to 4.
  6. 請求項１～４のいずれか１項に記載のエネルギー線硬化性樹脂組成物が硬化してなる硬化体。 A cured product obtained by curing the energy ray-curable resin composition according to any one of claims 1 to 4.
  7. 請求項１～４のいずれか１項に記載のエネルギー線硬化性樹脂組成物を用いる接合体。 A joined body using the energy ray-curable resin composition according to any one of claims 1 to 4.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017071708A (en) * 2015-10-08 2017-04-13 信越化学工業株式会社 Thermosetting epoxy resin composition and optical semiconductor device
DE102016207540A1 (en) 2016-05-02 2017-11-02 Tesa Se Water-vapor-blocking adhesive with highly functionalized poly (meth) acrylate
DE102016207550A1 (en) 2016-05-02 2017-11-02 Tesa Se Functionalized (co) polymers for adhesive systems and adhesive tapes
WO2018038221A1 (en) * 2016-08-24 2018-03-01 日立化成株式会社 Curable resin composition, image display device and manufacturing method of image display device
WO2019064385A1 (en) * 2017-09-27 2019-04-04 日立化成株式会社 Curable resin composition, image display device, and method for manufacturing image display device
JP2019077740A (en) * 2017-10-20 2019-05-23 日本化薬株式会社 Resin composition and adhesive for electronic component
US10808153B2 (en) 2016-05-02 2020-10-20 Tesa Se Curable adhesive compound and reactive adhesive tapes based thereon

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6608150B2 (en) * 2015-03-03 2019-11-20 三星エスディアイ株式会社 Polarizing plate and image display device including the same
JP7050411B2 (en) 2016-08-31 2022-04-08 東京応化工業株式会社 Negative type photosensitive resin composition, photosensitive resist film, pattern forming method, cured film, manufacturing method of cured film

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002332344A (en) * 2001-05-08 2002-11-22 Kansai Paint Co Ltd Thermosetting composition and film formation method using the same
JP2006233009A (en) * 2005-02-24 2006-09-07 Fujicopian Co Ltd Active energy ray-curable white ink composition
JP2008169327A (en) * 2007-01-12 2008-07-24 Toray Fine Chemicals Co Ltd Adhesive composition
JP2008174648A (en) * 2007-01-19 2008-07-31 Toray Fine Chemicals Co Ltd Adhesive composition
JP2008260879A (en) * 2007-04-13 2008-10-30 Okura Ind Co Ltd Active energy ray-curable adhesive composition, polarizing plate using the same, and method for producing the same
JP2010053233A (en) * 2008-08-27 2010-03-11 San Nopco Ltd Ultraviolet-curable composition

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1135846A (en) 1997-07-15 1999-02-09 Kansai Paint Co Ltd Active energy ray-curing resin composition and coating film formation using the same
JP4924783B2 (en) 2001-08-06 2012-04-25 昭和電工株式会社 Alicyclic compound
JP4095380B2 (en) 2001-09-03 2008-06-04 ダイセル化学工業株式会社 Method for producing (meth) acrylate compound and method for producing resin composition
CN101135850B (en) * 2002-08-07 2011-02-16 三菱化学株式会社 Image forming member having bluish purple laser photosensitive resist material layer and method for forming resist image
JP4292985B2 (en) * 2003-12-25 2009-07-08 Ｊｓｒ株式会社 Radiation-sensitive composition, microlens and method for forming the same, and liquid crystal display device
US20100184911A1 (en) * 2009-01-22 2010-07-22 Ppg Industries Ohio, Inc. Aqueous dispersions of polymer-enclosed particles, related coating compositions and coated substrates
TW200728379A (en) * 2005-09-06 2007-08-01 Taiyo Ink Mfg Co Ltd Resin composition, cured product of the same, and printed circuit board made of the same
JP2008088167A (en) 2006-09-07 2008-04-17 Mitsui Chemicals Inc Compound having (meth)acryloyl group and glycidyl group, polymerizable composition containing the compound and method for producing the compound
JP5101343B2 (en) * 2008-03-03 2012-12-19 株式会社ダイセル Manufacturing method of fine structure
JP5498832B2 (en) 2009-03-25 2014-05-21 電気化学工業株式会社 Energy ray curable resin composition, adhesive and cured product using the same
CN101592859B (en) * 2009-06-24 2011-12-28 广州机械科学研究院 Stereolithography rapid prototyping photosensitive resin, preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002332344A (en) * 2001-05-08 2002-11-22 Kansai Paint Co Ltd Thermosetting composition and film formation method using the same
JP2006233009A (en) * 2005-02-24 2006-09-07 Fujicopian Co Ltd Active energy ray-curable white ink composition
JP2008169327A (en) * 2007-01-12 2008-07-24 Toray Fine Chemicals Co Ltd Adhesive composition
JP2008174648A (en) * 2007-01-19 2008-07-31 Toray Fine Chemicals Co Ltd Adhesive composition
JP2008260879A (en) * 2007-04-13 2008-10-30 Okura Ind Co Ltd Active energy ray-curable adhesive composition, polarizing plate using the same, and method for producing the same
JP2010053233A (en) * 2008-08-27 2010-03-11 San Nopco Ltd Ultraviolet-curable composition

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017071708A (en) * 2015-10-08 2017-04-13 信越化学工業株式会社 Thermosetting epoxy resin composition and optical semiconductor device
DE102016207540A1 (en) 2016-05-02 2017-11-02 Tesa Se Water-vapor-blocking adhesive with highly functionalized poly (meth) acrylate
DE102016207550A1 (en) 2016-05-02 2017-11-02 Tesa Se Functionalized (co) polymers for adhesive systems and adhesive tapes
WO2017190878A1 (en) 2016-05-02 2017-11-09 Tesa Se Water vapor-blocking adhesive compound having highly functionalized poly(meth)acrylate
WO2017190911A1 (en) 2016-05-02 2017-11-09 Tesa Se Functionalized (co)polymers for adhesive systems
US10808153B2 (en) 2016-05-02 2020-10-20 Tesa Se Curable adhesive compound and reactive adhesive tapes based thereon
US11447669B2 (en) 2016-05-02 2022-09-20 Tesa Se Water vapor-blocking adhesive compound having highly functionalized poly(meth)acrylate
WO2018038221A1 (en) * 2016-08-24 2018-03-01 日立化成株式会社 Curable resin composition, image display device and manufacturing method of image display device
WO2018037517A1 (en) * 2016-08-24 2018-03-01 日立化成株式会社 Curable resin composition, image display device and manufacturing method of image display device
WO2019064385A1 (en) * 2017-09-27 2019-04-04 日立化成株式会社 Curable resin composition, image display device, and method for manufacturing image display device
JP2019077740A (en) * 2017-10-20 2019-05-23 日本化薬株式会社 Resin composition and adhesive for electronic component

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