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WO2012039051A1 - Composition de résine durcissable sous l'action d'un rayonnement énergétique, adhésif la comprenant et objet durci obtenu à partir de cette composition - Google Patents

Composition de résine durcissable sous l'action d'un rayonnement énergétique, adhésif la comprenant et objet durci obtenu à partir de cette composition Download PDF

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Publication number
WO2012039051A1
WO2012039051A1 PCT/JP2010/066506 JP2010066506W WO2012039051A1 WO 2012039051 A1 WO2012039051 A1 WO 2012039051A1 JP 2010066506 W JP2010066506 W JP 2010066506W WO 2012039051 A1 WO2012039051 A1 WO 2012039051A1
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WIPO (PCT)
Prior art keywords
resin composition
curable resin
energy
energy ray
derivatives
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
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PCT/JP2010/066506
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English (en)
Japanese (ja)
Inventor
貴子 星野
慶次 後藤
啓之 栗村
渡辺　淳
大島　和宏
公彦 依田
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Denka Co Ltd
Original Assignee
Denki Kagaku Kogyo KK
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Filing date
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Application filed by Denki Kagaku Kogyo KK filed Critical Denki Kagaku Kogyo KK
Priority to JP2012534867A priority Critical patent/JP5684275B2/ja
Priority to CN201080069246.4A priority patent/CN103119080B/zh
Priority to KR1020137009562A priority patent/KR101541184B1/ko
Priority to PCT/JP2010/066506 priority patent/WO2012039051A1/fr
Publication of WO2012039051A1 publication Critical patent/WO2012039051A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08G59/40—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 curing agents used
    • 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
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • 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
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/06—Crosslinking by radiation

Definitions

  • the present invention relates to an energy ray curable resin composition, an adhesive using the same, and a cured product.
  • optical pickup devices used for reproducing and recording optical recording media such as Blu-ray discs and HD-DVDs that support CDs, DVDs, and blue semiconductor lasers
  • display components such as liquid crystals and organic electroluminescence, CCDs
  • CCDs organic electroluminescence
  • Patent Document 1 discloses that the resin composition for optical modeling contains an energy ray-curable cationic polymerizable organic substance and an energy ray-sensitive cationic polymerization initiator, thereby improving adhesion and It has been proposed to improve cure shrinkage.
  • an energy ray curable resin composition uses a highly toxic element such as arsenic (As) or antimony (Sb) at the anion site of the cationic polymerization initiator, so there are concerns about the effects on handling and the environment. There was a problem.
  • fluoride ions are released by decomposition of the anion site and exhibit corrosiveness to metals (hereinafter referred to as “corrosive”).
  • Patent Document 2 uses an energy ray curable resin composition to which a photocationic polymerization initiator is added, without impairing fast curability. It has been proposed to improve corrosivity and safety. However, when stored for a long time in a state where a cationic polymerization initiator is added to the cationic polymerizable compound, cations may be spontaneously generated from the cationic polymerization initiator even in a state where ultraviolet rays are blocked. This cation initiates polymerization of the cationically polymerizable compound to cause thickening and gelation, resulting in a problem of poor storage stability.
  • Patent Document 3 discloses that an oxetane compound can be obtained by adding a basic compound such as an amine to the oxetane compound. It has been proposed to improve storage stability without compromising polymerizability. However, the addition of a basic organic compound such as an amine may still fail to provide a sufficient effect of inhibiting the polymerization of a cationic polymerizable compound, resulting in a problem that sufficient storage stability that can withstand practical use cannot be obtained. .
  • JP 2003-155413 A describes the polymerization performance of a cationic polymerization initiator by blending a phosphine oxide derivative with a compound having a cationic polymerizable group. It has been proposed to improve storage stability without lowering.
  • Japanese Patent Application Laid-Open No. 2009-215329 discloses a method for solving the storage stability problem of an energy ray curable resin composition using a photocationic polymerization initiator containing a filler of 1 ppb or less. It has been proposed to use a uranium-containing silica filler. Furthermore, Japanese Patent Application Laid-Open No.
  • Patent Document 6 proposes an adhesive having both high adhesiveness, applicability, and low moisture permeability necessary for bonding packages in the electronics field. However, there is no description that sufficient storage stability can be obtained by the present invention. JP-A-1-213304 Japanese National Patent Publication No. 11-501909 JP 2003-292606 A JP 2003-155413 A JP 2009-215329 A JP 2010-24364 A
  • the present invention relates to an energy ray-curable resin composition that exhibits rapid curability and has storage stability that can be stored for a long period of time, and an adhesive using the same.
  • the gist of the present invention is as follows. (1) (A) a cationically polymerizable compound, (B) a photocationic polymerization initiator represented by the formula (1), (C) one of the group consisting of a phenolic antioxidant and a quinone antioxidant Or the energy beam curable resin composition characterized by containing 2 or more types. (2) wherein (1) B in the formula (1) of the described energy ray-curable resin composition characterized by being represented by CF 3. (3) 100 parts by weight of component (A), 0.1 to 10 parts by weight of component (B), 0.01 to 20 parts by weight of component (C), (1) or (2) The energy ray-curable resin composition according to any one of the above.
  • the energy ray-curable resin composition having the above-described configuration can satisfy, for example, curability, adhesiveness, and storage stability.
  • 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.
  • storage stability means that neither thickening nor gelation occurs even after long-term storage.
  • the energy ray-curable resin composition according to the present embodiment includes (A) a cationic polymerizable compound, (B) a cationic photopolymerization initiator, (C) a phenolic antioxidant and a quinone antioxidant described below. It contains 1 type or 2 types of the group which consists of.
  • the energy ray-curable resin composition having the above configuration has excellent safety, corrosivity, curability, storage stability, and adhesiveness.
  • the energy beam curable resin composition according to the present embodiment includes (A) a cationic polymerizable compound as an essential component.
  • Examples of the cationically polymerizable compound include cyclic ethers and cationically polymerizable vinyl compounds.
  • Cyclic ethers include compounds such as epoxy and oxetane.
  • Examples of the cationically polymerizable vinyl compound include vinyl ether, vinylamine, and styrene. These compounds or derivatives may be used alone or in combination of two or more.
  • any of a monomer, an oligomer, or a polymer can be used as the cationic polymerization compound.
  • an epoxy compound for example, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a biphenyl type epoxy compound, a fluorene type epoxy compound, a novolak phenol type epoxy compound, a cresol novolak type epoxy Compounds, aromatics such as modified products thereof, or diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol or diglycidyl ether of 1,6-hexanediol, glycerin or the like Polyglycidyl ether of polyhydric alcohol such as di- or triglycidyl ether of alkylene oxide adduct, polyethylene glycol or its alcohol Diglycidyl ether of alkylene oxide adduct, polypropylene glycol or aliphatic such as diglycidyl ether of polyalkylene glycol diglycidyl ethers of alkylene oxide adducts
  • (a-1) an alicyclic epoxy compound and / or (a-2) an epoxy resin having an aromatic ring is preferable in that excellent adhesion, low moisture permeability, and adhesion durability can be obtained. More preferably, (a-1) an alicyclic epoxy compound and (a-2) an epoxy resin having an aromatic ring are used in combination.
  • (A-1) As the alicyclic epoxy compound, a compound having at least one cyclohexene or cycloalkane ring such as cyclopentene ring, pinene ring, etc. is epoxidized with an appropriate oxidizing agent such as hydrogen peroxide or peracid. And alicyclic epoxy compounds such as hydrogenated epoxy compounds obtained by hydrogenating aromatic epoxy compounds such as bisphenol A-type epoxy compounds. These compounds may be used alone or in combination of two or more.
  • an alicyclic epoxy compound containing one or more epoxy groups and one or more ester groups in one molecule is preferable.
  • Such an alicyclic epoxy compound is preferable because it is particularly excellent in adhesion and photocurability.
  • Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexenecarboxylate, 3,4-epoxycyclohexylmethyl methacrylate, and the like. Of these, 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexenecarboxylate is preferred.
  • A-2) As an epoxy resin having an aromatic ring, any of a monomer, an oligomer or a polymer can be used, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, Naphthalene type epoxy resin, fluorene type epoxy resin, novolak phenol type epoxy resin, cresol novolak type epoxy resin, modified products thereof and the like can be mentioned.
  • These epoxy resins may be used alone or in combination of two or more.
  • one or more members selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, and biphenyl type epoxy resins are preferable in terms of excellent adhesiveness and low moisture permeability.
  • bisphenol F type epoxy resin is preferable.
  • component (a-2) is contained in 100 parts by mass of (a-1) and (a-2) in total.
  • the range is preferably 20 to 80 parts by mass, and more preferably 40 to 60 parts by mass.
  • the oxetane compound is not particularly limited, but 3-ethyl-3-hydroxymethyloxetane (trade name OXT101 manufactured by Toa Gosei Co., Ltd.), 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] Benzene (same as OXT121), 3-ethyl-3- (phenoxymethyl) oxetane (same as OXT211), di (1-ethyl-3-oxetanyl) methyl ether (same as OXT221), 3-ethyl-3- (2 -Ethylhexyloxymethyl) oxetane (OXT212, etc.).
  • An oxetane compound refers to a compound having one or more oxetane rings in the molecule.
  • the vinyl ether compound 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, butanediol divinyl ether.
  • Di- or trivinyl ether compounds such as vinyl ether, hexanediol divinyl ether, cyclohexanedimethanol 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
  • the vinylamine compound is not particularly limited, and examples thereof include N-vinyldimethylamine, N-vinylethylbutylamine, N-vinyldiphenylamine, N-vinylformamide, and N-vinylacetamide compound.
  • an epoxy compound is preferable in that excellent adhesiveness, low moisture permeability, and adhesion durability can be obtained.
  • the cationic photopolymerization initiator is a compound described below that generates cationic species upon irradiation with energy rays.
  • the cation cation is preferably an onium cation.
  • the onium cation include arylsulfonium salt derivatives and aryliodonium salt derivatives.
  • a compound represented by the formula (1) is used in terms of safety such as carcinogenesis, corrosiveness, curability, adhesiveness, and storage stability.
  • B of the formula (1) is CF 3.
  • B in the formula (1) is CF 3
  • examples of the photocationic polymerization initiator in which B in the formula (1) is CF 3 include, but are not limited to, bis- (4-t-butyl-phenyl) -iodonium-tris (Ciba Japan) Trifluoromethanesulfonyl) methide (CGI * BBI C1), triphenylsulfonium-tris (trifluoromethanesulfonyl) methide (CGI * TPS C1), tris- ⁇ 4-acetyl-sulfanyl ⁇ -phenyl ⁇ -sulfonium-tris (trifluoromethanesulfonyl) ) Methide (GSID26-1) and the like.
  • bis- (4-tert-butyl-phenyl) -iodonium-tris (trifluoromethanesulfonyl) methide, triphenylsulfonium-tris (trifluoromethanesulfonyl) methide and tris- ⁇ 4-acetyl-sulfanyl ⁇ -phenyl ⁇ -Sulfonium-tris (trifluoromethanesulfonyl) methide is preferably one or more, more preferably bis- (4-tert-butyl-phenyl) -iodonium-tris (trifluoromethanesulfonyl) methide .
  • Examples of the cationic photopolymerization initiator include arylsulfonium salt derivatives (for example, CGI * TPS C1, GSID26-1 manufactured by Ciba Japan), aryliodonium salt derivatives (for example, CGI * manufactured by Ciba Japan) . BBI C1) and the like.
  • a photocationic polymerization initiator may be used alone or in combination of two or more.
  • the (B) photocationic polymerization initiator is preferably contained in a proportion of 0.1 to 10 parts by mass with respect to 100 parts by mass of the (A) photocationic polymerization compound. If it exists in this range, sclerosis
  • the energy beam curable resin composition according to the present embodiment must contain one or two of the group consisting of a phenolic antioxidant and a quinone antioxidant as an antioxidant.
  • phenolic antioxidants examples include phenothiazine, 2,2-methylene-bis (4-methyl-6-tert-butylphenol), catechol, tert-butylcatechol, 2-butyl-4-hydroxyanisole, and 2,6-dithiol.
  • quinone antioxidants examples include ⁇ -naphthoquinone, 2-methoxy-1,4-nophthoquinone, methylhydroquinone, hydroquinone, hydroquinone monomethyl ether, mono-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, p -Benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-di-tert-butyl-p-benzoquinone and the like.
  • pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]
  • octadecyl-3- 3,5-di-t-butyl-4-hydroxy
  • pentaerythrityl tetrakis [3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionate] is more preferred.
  • One or two of the group consisting of a phenolic antioxidant and a quinone antioxidant are in a ratio of 0.01 to 20 parts by mass with respect to 100 parts by mass of the (A) photocationic polymerization compound. It is preferable to contain. If it is 0.01 mass part or more, storage stability will improve, and if it is 20 mass parts or less, sclerosis
  • the energy beam curable resin composition according to the present embodiment may use a phosphine oxide derivative represented by formula (2) in terms of storage stability.
  • the salt represented by the formula (2) can be used alone or in combination of two or more.
  • Examples of the compound represented by the formula (2) include, but are not limited to, sodium tripolyphosphate, sodium tetrapolyphosphate, ammonium phosphate, tricalcium phosphate, silver phosphate, and the like. Of these, sodium tripolyphosphate is preferred.
  • the phosphine oxide derivative is preferably contained at a ratio of 0.01 to 10 parts by mass with respect to 100 parts by mass of the (A) photocationic polymerization compound. If it is 0.01 mass part or more, storage stability will improve, and if it is 10 mass parts or less, sclerosis
  • the energy beam curable resin composition according to the present embodiment may further contain a filler (inorganic filler).
  • the filler examples include silica particles, glass filler, spherical alumina, crushed alumina, oxides such as magnesium oxide, beryllium oxide, and titanium oxide, nitrides such as boron nitride, silicon nitride, and aluminum nitride, and carbides such as silicon carbide. , Hydroxides such as aluminum hydroxide and magnesium hydroxide, metals and alloys such as copper, silver, iron, aluminum, nickel and titanium, carbon-based fillers such as diamond and carbon, silica particles, etc. .
  • the 50% particle size of the filler is preferably in the range of 0.1 ⁇ m to 15 ⁇ m, and the 90% particle size is preferably in the range of 3 ⁇ m to 20 ⁇ m. By being in these ranges, the particle size is not too small to easily aggregate, and the particle size is not too large to easily settle. Of these, silica particles are preferred.
  • the 50% particle diameter and 90% particle diameter here refer to the particle diameters when the volume cumulative frequency is 50% and 90%.
  • the method for measuring the particle size is not particularly limited, and examples thereof include a laser diffraction particle size distribution meter, a laser Doppler particle size distribution meter, a dynamic light scattering particle size distribution meter, and an ultrasonic particle size distribution meter.
  • Silica particles are silica particles having a purity of 99% or more represented by SiO X (1 ⁇ X ⁇ 2) as a chemical composition, and refer to low uranium silica particles having a uranium content of 1 ppb or less.
  • the method of synthesizing the silica particles is not particularly limited, but is a method of neutralizing alkali silicate, gel drying, flame melting after pulverization, flame decomposition of alkoxysilane, and vapor phase of volatile silicon compounds such as silicon tetrachloride. Examples thereof include a method of hydrolyzing, a method of pulverizing and melting low uranium quartz, and the like. These methods are preferable because stable low uranium silica particles can be easily obtained.
  • the (E) filler is preferably contained in a proportion of 50 to 300 parts by mass with respect to 100 parts by mass of the (A) photocationic polymerization compound. If it is 50 parts by mass or more, low moisture permeability can be obtained, and if it is 300 parts by mass or less, it is possible to maintain a dispersed state without aggregation of fillers.
  • the amount of filler used is more preferably 100 to 200 parts by weight, and most preferably 120 to 180 parts by weight, because the effect is great.
  • the energy beam curable resin composition according to the present embodiment may use various photosensitizers in combination.
  • a photosensitizer means a compound that absorbs energy rays and efficiently generates cations from a photocationic polymerization initiator.
  • the photosensitizer is not particularly limited, but benzophenone derivatives, phenothiazine derivatives, phenyl ketone derivatives, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, naphthacene derivatives, chrysene derivatives, perylene derivatives, pentacene 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, indoline derivatives, azulene derivatives, trines Allylmethane derivatives, phthalocyanine
  • phenylketone derivatives such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one are preferred, and 2-hydroxy-2-methyl-1-phenyl-propan-1-one is more preferred. .
  • the photosensitizer is preferably contained at a ratio of 0.1 to 10 parts by mass with respect to 100 parts by mass of the (A) photocationic polymerization compound. If it exists in this range, sclerosis
  • 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.
  • silane coupling agent can be contained 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 is used for optical pickup devices used for reproducing and recording optical recording media such as Blu-ray discs and HD-DVDs that support CDs, DVDs, and blue semiconductor lasers, display components such as liquid crystals and organic electroluminescence,
  • it can be suitably used for bonding in the electronic field such as an electronic component such as an image sensor such as an image sensor such as a CCD or CMOS, or an element package used in a semiconductor component.
  • 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.
  • 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.
  • 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.
  • component (A) 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (“Celoxide 2021P” manufactured by Daicel Chemical Industries)
  • A-2) Bisphenol F type epoxy resin (“YL-938U” manufactured by Japan Epoxy Resin)
  • A-3) Novolac phenol type epoxy resin (Japan Epoxy Resin “EP-152”)
  • A-4) Polypropylene glycol type epoxy resin (“SR-PTMG” manufactured by Sakamoto Pharmaceutical Co., Ltd.)
  • A-5) Di (1-ethyl-3-oxetanyl) methyl ether Di (1-ethyl-3-oxetanyl) methyl ether (Toa Gosei Co., Ltd. “OXT221”)
  • component (B) Bis- (4-t-butyl-phenyl) -iodonium-tris (trifluoromethanesulfonyl) methide (“CGI * BBI C1” manufactured by Ciba Japan)
  • B-2) Triphenylsulfonium-tris (trifluoromethanesulfonyl) methide (“CGI * TPS C1” manufactured by Ciba Japan)
  • B-3) Tris- ⁇ 4-acetyl-sulfanyl ⁇ -phenyl ⁇ -sulfonium-tris (trifluoromethanesulfonyl) methide (“GSID26-1” manufactured by Ciba Japan)
  • GSID26-1 Trifluoromethanesulfonyl
  • C The following were used as a phenolic antioxidant or a quinone antioxidant.
  • C-1 Pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (“Irganox-1010” manufactured by Ciba Japan)
  • C-2) Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (“Irganox-1076” manufactured by Ciba Japan)
  • C-4) 4,4′-thiobis (6-tetra-butyl 1-3-methylphenol) (SUMIZER WX-R manufactured by Sumitomo Chemical Co., Ltd.)
  • (D) The following was used as the phosphine oxide derivative represented by the formula (2).
  • D-1 Sodium polyphosphate (manufactured by Kanto Chemical Co., Inc.)
  • D-2 diethyl phosphite
  • D-2 Diethyl phosphite (manufactured by Wako Pure Chemical Industries, Ltd.)
  • Examples 1 to 9 The raw materials of the types shown in Table 1 were mixed at the composition ratios shown in Table 1 to prepare resin compositions of Examples 1 to 9. The photocurability, tensile shear bond strength and storage storage stability were evaluated as described below, and the results are shown in Table 1.
  • Examples 10 to 13 The raw materials of the types shown in Table 3 were mixed at the composition ratios shown in Table 3 to prepare resin compositions of Examples 10 to 13. The evaluation results are shown in Table 3.
  • 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 (illuminance at 365 nm: 150 mW / cm 2 ) at 25 ° C. ( ⁇ 0.5 ° C.), The frequency was 10 Hz. A case where the storage rigidity G ′ increased to 1.00E + 4 (1.00 ⁇ 10 4 ) or more by 200 seconds after the start of UV irradiation was judged as good, and a symbol “ ⁇ ” was given. On the other hand, when the storage rigidity G ′ was less than 1.00E + 4 by 200 seconds after the start of UV irradiation, it was judged as defective and marked with “x”.
  • 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.
  • a heat-resistant glass trade name “heat-resistant Pyrex (registered trademark) glass”
  • Two pieces of heat-resistant glass were laminated together, using a UV irradiator, integrated light quantity 52000 mJ / cm 2 (365 nm illuminance: 400 mW / cm 2 , “US-7 SP-7 (UV curing with mercury xenon lamp)
  • the test piece was cured under the conditions of the apparatus)) to produce a tensile strength test piece.
  • the prepared test piece was measured for tensile shear adhesive strength using a universal testing machine in an environment of 23 ° C. and 50% humidity.
  • the viscosity of the composition was measured using an E-type viscometer under the conditions of a temperature of 25 ° C. and a rotation speed of 10 rpm.
  • an energy ray-curable resin composition containing two types is provided.
  • the energy ray-curable resin composition having the above-described structure not only has high adhesiveness and low curing shrinkage, but can satisfy corrosiveness, safety, curability, and storage stability.
  • the energy ray curable resin composition can be used as an adhesive.
  • This adhesive is used for optical pickup devices used for reproducing and recording optical recording media such as Blu-ray discs and HD-DVDs that support CDs, DVDs, and blue semiconductor lasers, display components such as liquid crystals and organic electroluminescence, Used in electronics fields such as electronic components such as image sensors such as image sensors such as CCD and CMOS, as well as device packages used in semiconductor components, and for craft glass pedestals, plate fixing applications, lenses, prisms, cameras, binoculars and microscopes, etc.
  • it is a suitable adhesive that can satisfy safety, corrosiveness, curability, adhesiveness, and storage stability.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Epoxy Resins (AREA)

Abstract

L'invention concerne une composition de résine durcissable sous l'action d'un rayonnement énergétique qui satisfait une aptitude au durcissement, des propriétés adhésives et une stabilité au stockage, caractérisée en ce qu'elle comprend (A) un composé polymérisable par voie cationique, (B) un initiateur de photopolymérisation cationique spécifique, et (C) un ou plusieurs anti-oxydants choisis dans le groupe consistant en les anti-oxydants phénoliques et les anti-oxydants à base de composés quinones. L'invention concerne également un objet durci obtenu par durcissement de la composition de résine durcissable sous l'action d'un rayonnement énergétique et un adhésif comprenant la composition de résine durcissable sous l'action d'un rayonnement énergétique.
PCT/JP2010/066506 2010-09-24 2010-09-24 Composition de résine durcissable sous l'action d'un rayonnement énergétique, adhésif la comprenant et objet durci obtenu à partir de cette composition Ceased WO2012039051A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2012534867A JP5684275B2 (ja) 2010-09-24 2010-09-24 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
CN201080069246.4A CN103119080B (zh) 2010-09-24 2010-09-24 能量射线固化性树脂组合物与使用该组合物的粘合剂及固化体
KR1020137009562A KR101541184B1 (ko) 2010-09-24 2010-09-24 에너지선 경화성 수지 조성물과 그것을 이용한 접착제 및 경화체
PCT/JP2010/066506 WO2012039051A1 (fr) 2010-09-24 2010-09-24 Composition de résine durcissable sous l'action d'un rayonnement énergétique, adhésif la comprenant et objet durci obtenu à partir de cette composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2010/066506 WO2012039051A1 (fr) 2010-09-24 2010-09-24 Composition de résine durcissable sous l'action d'un rayonnement énergétique, adhésif la comprenant et objet durci obtenu à partir de cette composition

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WO2012039051A1 true WO2012039051A1 (fr) 2012-03-29

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JP (1) JP5684275B2 (fr)
KR (1) KR101541184B1 (fr)
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WO2015005211A1 (fr) * 2013-07-09 2015-01-15 株式会社Adeka Composition polymérisable par voie cationique
KR20160030068A (ko) * 2013-07-09 2016-03-16 가부시키가이샤 아데카 양이온 중합성 조성물
JP2019070120A (ja) * 2012-07-26 2019-05-09 デンカ株式会社 樹脂組成物
JP2023092544A (ja) * 2021-12-22 2023-07-04 東洋インキＳｃホールディングス株式会社 活性エネルギー線重合性樹脂組成物及び積層体

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Publication number Priority date Publication date Assignee Title
US11111417B2 (en) 2016-05-19 2021-09-07 Sicpa Holding Sa Adhesives for assembling components of inert material

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JP2000044923A (ja) * 1998-05-27 2000-02-15 Sekisui Chem Co Ltd 硬化型粘接着剤組成物及び硬化型粘接着シ―ト
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JP2019070120A (ja) * 2012-07-26 2019-05-09 デンカ株式会社 樹脂組成物
WO2015005211A1 (fr) * 2013-07-09 2015-01-15 株式会社Adeka Composition polymérisable par voie cationique
KR20160030069A (ko) * 2013-07-09 2016-03-16 가부시키가이샤 아데카 양이온 중합성 조성물
KR20160030068A (ko) * 2013-07-09 2016-03-16 가부시키가이샤 아데카 양이온 중합성 조성물
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KR102248332B1 (ko) * 2013-07-09 2021-05-06 가부시키가이샤 아데카 양이온 중합성 조성물
JP2023092544A (ja) * 2021-12-22 2023-07-04 東洋インキＳｃホールディングス株式会社 活性エネルギー線重合性樹脂組成物及び積層体

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CN103119080B (zh) 2015-07-29
JP5684275B2 (ja) 2015-03-11
KR101541184B1 (ko) 2015-07-31
JPWO2012039051A1 (ja) 2014-02-03
KR20130108355A (ko) 2013-10-02
CN103119080A (zh) 2013-05-22

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