WO2015005210A1 - カチオン重合性組成物 - Google Patents
カチオン重合性組成物 Download PDFInfo
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- WO2015005210A1 WO2015005210A1 PCT/JP2014/067778 JP2014067778W WO2015005210A1 WO 2015005210 A1 WO2015005210 A1 WO 2015005210A1 JP 2014067778 W JP2014067778 W JP 2014067778W WO 2015005210 A1 WO2015005210 A1 WO 2015005210A1
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- epoxy compound
- cationically polymerizable
- polymerizable composition
- compound
- organic substance
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- 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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/36—Epoxy compounds containing three or more epoxy groups together with mono-epoxy compounds
-
- 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
Definitions
- the present invention relates to a cationic polymerizable composition and a cured product obtained by irradiating the cationic polymerizable composition with active energy rays.
- the cationically polymerizable composition is particularly useful for adhesives.
- Cationic polymerizable compositions are used in the fields of inks, paints, various coating agents, adhesives, optical members and the like.
- Patent Document 1 discloses various photocurable adhesives.
- An object of the present invention is to provide a curable composition having high curability and adhesiveness, low viscosity, excellent coatability, and high water resistance after curing.
- the present invention has been made on the basis of the above findings, and (1) contains at least one of an aliphatic epoxy compound (1A) or an alicyclic epoxy compound (1B) as a cationically polymerizable organic substance, As the epoxy compound (1A) or the alicyclic epoxy compound (1B), it contains a cationically polymerizable organic substance mixture containing at least one monofunctional epoxy compound, and (2) an energy ray-sensitive cationic polymerization initiator.
- the above object is achieved by providing a cationically polymerizable composition.
- this invention contains at least 1 type of an aliphatic epoxy compound (1A) or an alicyclic epoxy compound (1B) as a cationically polymerizable organic substance, and contains an aromatic epoxy compound (1C).
- a cationically polymerizable organic substance mixture containing at least one monofunctional epoxy compound as the aliphatic epoxy compound (1A), alicyclic epoxy compound (1B) or aromatic epoxy compound (1C), and (2) energy rays
- the object is achieved by providing a cationically polymerizable composition characterized by containing a sensitive cationic polymerization initiator.
- the present invention also provides an adhesive comprising the above cationic polymerizable composition.
- the cationically polymerizable composition of the present invention is particularly useful as an adhesive because it is excellent in curability, adhesiveness, coating property, water resistance after curing, and has a high elastic modulus.
- the cationic polymerizable organic substance constituting the mixture is polymerized or crosslinked by an energy ray sensitive cationic polymerization initiator activated by light irradiation.
- An epoxy compound is preferable.
- the epoxy compound an aliphatic epoxy compound (1A) or an alicyclic epoxy compound (1B) is used, an aromatic epoxy compound (1C), and a high molecular weight polymer having an epoxy group and having a weight average molecular weight of 1,000 to 1,000,000 ( 1D) can be used.
- a vinyl ether compound or an oxetane compound (1E) can be used as the cationically polymerizable organic substance.
- alicyclic epoxy compound (1B) is obtained by epoxidizing a polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring or a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent.
- examples include cyclohexene oxide and cyclopentene oxide-containing compounds.
- cyclohexene oxide hydrogenated bisphenol A diglycidyl ether
- ethylene bis 3,4-epoxycyclohexanecarboxylate
- 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxy Rate 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate
- bis (3,4-epoxycyclohexylmethyl) adipate 3,4-epoxy-6-methylcyclohexyl Carboxylate
- methylenebis 3,4-epoxycyclohexane) propane-2,2-
- alicyclic epoxy compound (1B) those having an epoxy equivalent of 80 to 500 or a viscosity of 2000 mPa ⁇ s or less are preferable from the viewpoint of curability and lowering the viscosity of the composition.
- the viscosity is a viscosity at 25 ° C., and is measured by the method described in Examples described later.
- alicyclic epoxy compound (1B) Commercially available products can be used as the alicyclic epoxy compound (1B), and examples thereof include Celoxide 2021P, Celoxide 2081, Celoxide 2000, and Celoxide 3000 (manufactured by Daicel Corporation).
- aliphatic epoxy compound (1A) examples include monofunctional epoxy compounds such as glycidyl ethers of aliphatic alcohols and glycidyl esters of alkylcarboxylic acids, polyglycidyls of aliphatic polyhydric alcohols or alkylene oxide adducts thereof.
- monofunctional epoxy compounds such as glycidyl ethers of aliphatic alcohols and glycidyl esters of alkylcarboxylic acids, polyglycidyls of aliphatic polyhydric alcohols or alkylene oxide adducts thereof.
- polyfunctional epoxy compounds such as etherified products and polyglycidyl esters of aliphatic long-chain polybasic acids.
- Representative compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin Triglycidyl ether, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, glycidyl ether of polyhydric alcohol such as diglycidyl ether of polypropylene glycol, and propylene One or more alkyles in aliphatic polyhydric alcohols such as glycol, trimethylolpropane and glycerin And polygly
- aliphatic epoxy compound (1A) those having an epoxy equivalent of 80 to 500 or a viscosity of 2000 mPa ⁇ s or less are preferable from the viewpoints of curability and low viscosity of the composition. This viscosity is a viscosity at 25 ° C., and is measured by the method described in Examples described later.
- aliphatic epoxy compound (1A) commercially available products can be used.
- the aromatic epoxy compound (1C) refers to an epoxy compound containing an aromatic ring, and specific examples of the aromatic epoxy compound include monovalent phenols having at least one aromatic ring such as phenol, cresol, and butylphenol.
- mono / polyglycidyl etherified products of the alkylene oxide adducts such as bisphenol A, bisphenol F, or glycidyl etherified products of compounds obtained by further adding alkylene oxide to these and epoxy novolac resins; two such as resorcinol, hydroquinone and catechol Mono / polyglycidyl etherified products of aromatic compounds having the above phenolic hydroxyl groups; aromatic compounds having two or more alcoholic hydroxyl groups such as benzenedimethanol, benzenediethanol, and benzenedibutanol Glycidyl ester of polybasic acid aromatic compound having two or more carboxylic acids such as phthalic acid, terephthalic acid, trimellitic acid; benzoic acid such as glycidyl
- the aromatic epoxy compound (1C) contains at least one selected from the group of glycidyl ethers of phenols, glycidyl esters of benzoic acid or styrene oxides from the viewpoint of reducing the viscosity of the composition. preferable.
- the aromatic epoxy compound those having an epoxy equivalent of 80 to 500 or a viscosity of 2000 mPa ⁇ s or less are preferable because they are excellent in curability and low viscosity of the composition. This viscosity is a viscosity at 25 ° C., and is measured by the method described in Examples described later.
- the aromatic epoxy compound (1C) commercially available products can be used.
- the cationically polymerizable composition of the present invention contains at least one monofunctional epoxy compound as the above-mentioned aliphatic epoxy compound (1A), alicyclic epoxy compound (1B) or aromatic epoxy compound (1C). Furthermore, the cationically polymerizable composition of the present invention contains at least one monofunctional epoxy compound as the aliphatic epoxy compound (1A) or the alicyclic epoxy compound (1B), or contains the aromatic epoxy compound (1C). It is essential to contain. When the cationically polymerizable composition of the present invention contains a monofunctional epoxy compound as the aliphatic epoxy compound (1A) or the alicyclic epoxy compound (1B), the content of this monofunctional epoxy compound is determined based on the epoxy compound used.
- the total amount of the monofunctional aliphatic epoxy compound (1A) and the monofunctional alicyclic epoxy compound (1B) is (1) a cation polymerizable organic substance mixture 100, although it varies depending on the type and use of the composition.
- the amount is preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass with respect to parts by mass.
- the content of the monofunctional aliphatic epoxy compound (1A) is preferably 0 to 30 parts by mass with respect to 100 parts by mass of the cation polymerizable organic substance mixture (1), and the monofunctional alicyclic epoxy compound
- the content of (1B) is preferably 0 to 40 parts by mass.
- the content of the monofunctional aliphatic epoxy compound (1A) is preferably 25 to 100 parts by mass with respect to 100 parts by mass of the aliphatic epoxy compound (1A), and 100 parts by mass of the alicyclic epoxy compound (1B).
- the content of the monofunctional alicyclic epoxy compound (1B) is preferably 5 to 100 parts by mass.
- the amounts of (1A) and (1B) are amounts including those corresponding to (1D).
- the aromatic epoxy compound (1C) contains at least one monofunctional epoxy compound for water resistance and adhesiveness. It is preferable from the viewpoint.
- the monofunctional epoxy compound is contained as the aromatic epoxy compound (1C)
- the content of the monofunctional aromatic epoxy compound is, for example, 0 to 70 with respect to 100 parts by mass of (1) the cationic polymerizable organic substance mixture. It is preferable that the amount is 10 parts by mass, particularly 10 to 60 parts by mass.
- the content of the monofunctional aromatic epoxy compound (1C) is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the aromatic epoxy compound (1C).
- the content of the monofunctional aromatic epoxy compound (1C) is preferably larger than the content of the polyfunctional aromatic epoxy compound (1C) from the viewpoint of reducing the viscosity of the composition.
- the amount of (1C) includes the amount corresponding to (1D).
- Examples of the high molecular weight polymer (1D) having a weight average molecular weight of 1,000 to 1,000,000 having an epoxy group include a polymer obtained by radical polymerization, and homopolymerizing one kind of ethylenically unsaturated monomer having a cationic polymerizable substituent. Preferred is a polymer copolymerized with an ethylenically unsaturated monomer that does not have a polymer or a cationically polymerizable substituent.
- the ethylenically unsaturated monomer constituting the high molecular weight product (1D) having a weight average molecular weight of 1,000 to 1,000,000 having the epoxy group is not particularly limited, and known ones can be used.
- an example of an ethylenically unsaturated monomer having no cationically polymerizable substituent includes a group represented by the following general formula (1), and an ethylenically unsaturated group having a cationically polymerizable substituent.
- the monomer one or more hydrogen atoms in the alkyl group, aryl group or alicyclic hydrocarbon group in the following general formula (1) are substituted with an epoxy group, an oxetane group or a vinyl ether group. Groups.
- R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or 6 to 12 carbon atoms.
- An aryl group or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, and a methylene group in these groups may be substituted with —CO—, —O— or —COO—)
- the high molecular weight body (1D) contains 10 to 10 ethylenically unsaturated monomers having a structure substituted with a cationic polymerizable substituent such as an epoxy group, an oxetane group or a vinyl ether group.
- methyl group, ethyl group or branched alkyl group having 3 to 7 carbon atoms, aryl group having 6 to 12 carbon atoms, 6 to 10 carbon atoms, which is not substituted with a cationic polymerizable substituent The content of the ethylenically unsaturated monomer substituted with an alicyclic hydrocarbon group is preferably 20 to 90% by mass, and the total together with other ethylenically unsaturated monomers is preferably 100% by mass.
- the high molecular weight product (1D) having a weight average molecular weight of 1,000 to 1,000,000 having an epoxy group preferably has a weight average molecular weight of 5,000 to 100,000, more preferably 7,000 to 70,000.
- Examples of the vinyl ether compound or oxetane compound (1E) include ethylene glycol divinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloroethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, triethylene.
- the vinyl ether compound preferably has a molecular weight of 58 to 500, more preferably 70 to 300.
- the oxetane compound preferably has a molecular weight of 100 to 1000, more preferably 110 to 500.
- the vinyl ether compound or oxetane compound (1E) may be monofunctional or polyfunctional, but has one or two vinyl ether groups or oxetane groups having one or two vinyl ether groups. It is preferable to use an oxetane compound.
- vinyl ether compound or oxetane compound (1E) commercially available products mainly composed of a cationic polymerizable monomer can be used.
- the use ratio of the alicyclic epoxy compound (1B), aliphatic epoxy compound (1A), aromatic epoxy compound (1C), etc. is as follows: (1) cation polymerizable organic
- the alicyclic epoxy compound (1B) is preferably 1 to 60 parts by mass and the aliphatic epoxy compound (1A) is preferably 0 to 70 parts by mass with respect to 100 parts by mass of the substance mixture.
- Cationic polymerization 1 to 50 parts by weight, especially 5 to 50 parts by weight of the alicyclic epoxy compound (1B), 0 to 50 parts by weight of the aliphatic epoxy compound (1A), and 100 parts by weight of the aromatic organic compound mixture, aromatic epoxy compound (1C) 20 to 80 parts by mass, particularly 30 to 70 parts by mass, high molecular weight polymer having an epoxy group and a weight average molecular weight of 1,000 to 1,000,000 (1D) 0 to 50 parts by mass, particularly 0 to 2 Parts by weight, a vinyl ether compound or oxetane compound (1E) 0 ⁇ 30 parts by weight, especially 0-20 parts by weight, the aromatic epoxy compound (1C) is that the main component further preferable.
- the amounts of (1A) and (1B) above are amounts excluding those corresponding to (1D) above, and the amount of (1C) is an amount including those corresponding to (1D).
- the main component means the one having the largest total amount of the same kind of epoxy compound when several kinds of epoxy compounds are mixed, and the cationic polymerizable organic substance mixture is a cationic polymerizable organic other than the epoxy compound.
- the total amount of the type having the largest total amount among several types of epoxy compounds is assumed to be larger than the total amount of cationically polymerizable organic materials other than the epoxy compound.
- the total amount of each type of epoxy compound includes those corresponding to (1D).
- the ratio of the monofunctional epoxy compound is 20 to 80 parts by mass with respect to 100 parts by mass of (1) cation polymerizable organic substance mixture. It is preferable from the viewpoint of lowering the viscosity.
- the (2) energy ray-sensitive cationic polymerization initiator used in the present invention may be any compound that can release a substance that initiates cationic polymerization by irradiation with energy rays, but is preferably Is a double salt that is an onium salt that releases a Lewis acid upon irradiation with energy rays, or a derivative thereof.
- Representative examples of such compounds include the following general formula: [A] r + [B] r- (In the formula, A represents a cationic species, B represents an anionic species, and r represents a valence.) And cation and anion salts represented by the formula:
- the cation [A] r + is preferably onium, and the structure thereof is, for example, the following general formula: [(R 1 ) a Q] r + It can be expressed as
- R 1 is an organic group having 1 to 60 carbon atoms and any number of atoms other than carbon atoms.
- a is an integer of 1 to 5.
- the a R 1 s are independent and may be the same or different.
- at least one is preferably an organic group as described above having an aromatic ring.
- anion [B] r- is preferably a halide complex, and the structure thereof is, for example, the following general formula: [LX b ] r- It can be expressed as
- L is a metal or metalloid which is a central atom of a halide complex
- B P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co and the like.
- X is a halogen atom.
- b is an integer of 3 to 7.
- anion [LX b ] r- in the above general formula examples include tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate (BF 4 ) ⁇ , Examples include hexafluorophosphate (PF 6 ) ⁇ , hexafluoroantimonate (SbF 6 ) ⁇ , hexafluoroarsenate (AsF 6 ) ⁇ , hexachloroantimonate (SbCl 6 ) ⁇ and the like.
- the anion [B] r ⁇ is represented by the following general formula: [LX b-1 (OH)] r-
- L, X, and b are the same as described above.
- Other anions that can be used include perchlorate ion (ClO 4 ) ⁇ , trifluoromethyl sulfite ion (CF 3 SO 3 ) ⁇ , fluorosulfonate ion (FSO 3 ) ⁇ , and toluenesulfonate anion.
- Trinitrobenzenesulfonate anion camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate and the like.
- onium salts it is particularly effective to use the following aromatic onium salts (a) to (c).
- aromatic onium salts (a) to (c) one of them can be used alone, or two or more of them can be mixed and used.
- Aryl diazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate, etc.
- Diaryls such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, and tricumyliodonium tetrakis (pentafluorophenyl) borate Iodonium salt
- preferable examples include ( ⁇ 5 -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6- ⁇ )-(1-methylethyl) benzene] -iron.
- -Iron-arene complexes such as hexafluorophosphate
- aluminum complexes such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum, and silanols such as triphenylsilanol
- silanols such as triphenylsilanol
- aromatic iodonium salts aromatic sulfonium salts, and iron-arene complexes are preferably used from the viewpoints of practical use and photosensitivity.
- the use ratio of the (2) energy ray sensitive cationic polymerization initiator to the above (1) cationic polymerizable organic substance mixture is not particularly limited, and may be used at a generally normal use ratio within a range not impairing the object of the present invention.
- a silane coupling agent can be used as necessary.
- the silane coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane.
- the amount of the silane coupling agent used is not particularly limited, but is usually in the range of 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of solids in the cationic polymerizable composition.
- thermal polymerization initiator is a compound that generates a cationic species or Lewis acid by heating, such as a salt of sulfonium salt, thiophenium salt, thiolanium salt, benzylammonium, pyridinium salt, hydrazinium salt; diethylenetriamine, triethylenetriamine, tetraethylenepenta Polyalkylpolyamines such as min; alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophoronediamine; m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone Aromatic polyamines such as; such polyamines; phenyl glycidyl ether, butyl glycid
- Mannich-modified products produced by reacting phenols having sex sites by a conventional method polyvalent carboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelain Acid, sebacic acid, Decanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecane Aliphatic dicarboxylic acids such as diacid, hydrogenated dimer acid and dimer acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; trimellitic acid, Tri
- thermal polymerization initiator Commercially available products may be used as the thermal polymerization initiator.
- Adeka Opton® CP77 Adeka Opton CP66 (manufactured by ADEKA), CI-2539, CI-2624 (manufactured by Nippon Soda Co., Ltd.), Sun-Aid® SI-60L, Sun-Aid SI -80L, Sun Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) and the like.
- the amount of the thermal polymerization initiator used is not particularly limited, but is usually in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the total amount of solids in the cationic polymerizable composition.
- an initiator it is preferable to heat the cationically polymerizable composition of the present invention at 130 to 180 ° C. for 20 minutes to 1 hour.
- a cured product can be obtained by using a thermoplastic organic polymer (excluding a high molecular weight polymer (1D) having a weight average molecular weight of 1,000 to 1,000,000 having an epoxy group) as necessary. It is possible to improve the characteristics.
- a thermoplastic organic polymer excluding a high molecular weight polymer (1D) having a weight average molecular weight of 1,000 to 1,000,000 having an epoxy group
- thermoplastic organic polymer examples include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- Examples include methyl methacrylate copolymer, glycidyl (meth) acrylate-polymethyl (meth) acrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester.
- the cationically polymerizable composition of the present invention is not particularly limited, and a solvent that can dissolve or disperse the components (1) and (2) that are usually used can be used.
- a solvent that can dissolve or disperse the components (1) and (2) that are usually used can be used.
- methyl ethyl ketone, methyl amyl ketone, Ketones such as diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether, Ether solvents such as dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate,
- BTX solvents aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclohexane; terpenes such as turpentine oil, D-limonene, and pinene Hydrocarbon oils; paraffinic solvents such as mineral spirits, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2- Halogenated aliphatic hydrocarbon solvents such as dichloroethane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Propylene carbonate, carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N- Examples thereof include dimethylformamide, N, N-dimethylacetamide, N-methylpyrrol
- the total amount of optional components other than (1) the cationic polymerizable organic substance mixture and (2) the energy ray sensitive cationic polymerization initiator depends on the use of the present invention, etc. From the viewpoint of further enhancing the effects of the present invention, (1) it is preferably 20 parts by mass or less, particularly 10 parts by mass or less with respect to 100 parts by mass of the cationically polymerizable organic substance mixture.
- the water content is preferably 5% by mass or less, more preferably 3% by mass or less from the viewpoints of curability, adhesiveness, and liquid storage stability. Too much moisture is not preferable because it may cause cloudiness or components may precipitate. The amount of water is measured by the method described in the examples described later.
- the cationically polymerizable composition of the present invention preferably has a viscosity of 200 mPa ⁇ s or less, and more preferably 1 to 100 mPa ⁇ s from the viewpoint of coatability.
- This viscosity is a viscosity at 25 ° C., and is measured by the method described in Examples described later.
- the cationically polymerizable composition of the present invention is applied onto a supporting substrate by a known means such as a roll coater, a curtain coater, various types of printing, and immersion. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base
- the material for the support substrate is not particularly limited and may be any commonly used material, such as inorganic materials such as glass; diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetylpropionyl.
- inorganic materials such as glass
- Cellulose esters such as cellulose and nitrocellulose; polyamide; polyimide; polyurethane; epoxy resin; polycarbonate; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxy Polyester such as ethane-4,4′-dicarboxylate, polybutylene terephthalate, etc .; polystyrene; polyethylene, polypropylene, polymethylpentene, etc.
- Polyolefins Vinyl compounds such as polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; Acrylic resins such as polymethyl methacrylate and polyacrylate; Polycarbonate; Polysulfone; Polyethersulfone; Polyetherketone; Polyetherimide; Polymer materials such as oxyethylene, norbornene resin, and cycloolefin polymer (COP) can be used.
- the support substrate may be subjected to surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment and the like.
- the cationic polymerizable composition of the present invention is cured by irradiation with active energy rays.
- active energy rays include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies, and ultraviolet rays are the most economical.
- ultraviolet light source include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp.
- cationically polymerizable composition of the present invention include glasses, optical materials represented by imaging lenses, paints, coating agents, lining agents, inks, resists, liquid resists, adhesives, printing plates, and insulation. Varnish, insulating sheet, laminate, printed circuit board, sealing agent for molding of semiconductor devices, LED packages, liquid crystal inlets, organic EL, optical elements, electrical insulation, electronic components, separation membranes, etc. Materials, putty, glass fiber impregnating agent, sealant, semiconductor / solar cell passivation film, interlayer insulating film, protective film, prism lens sheet used for backlight of liquid crystal display, screen for projection TV, etc.
- the lens portion of a lens sheet such as a Fresnel lens sheet or a lenticular lens sheet, or a bag using such a sheet.
- a lens sheet such as a Fresnel lens sheet or a lenticular lens sheet, or a bag using such a sheet.
- Examples include light, optical lenses such as microlenses, optical elements, optical connectors, optical waveguides, optical molding casting agents, etc.
- substrates that can be used as coating agents include metals, wood, rubber, and plastics. , Glass, ceramic products and the like.
- cationic polymerizable composition of the present invention and the cured product obtained by curing the cationic polymerizable composition will be described in detail with reference to examples, evaluation examples, and comparative examples.
- “part” means “part by mass”
- “%” means “% by mass”.
- Example Compositions 1 to 20 and Comparative Compositions 1 to 2 were applied to a single COP (cycloolefin polymer) film subjected to corona discharge treatment, and then the film was laminated using a laminator.
- COP cycloolefin polymer
- a test piece was obtained by bonding to another COP (cycloolefin polymer) film that had been subjected to corona discharge treatment, and using an electrodeless ultraviolet lamp to irradiate with 1000 mJ / cm 2 of energy.
- a 90 degree peel test is performed on the obtained test piece.
- a specimen having a strength of 2.0 N / cm or more is indicated by ⁇
- a specimen having a strength of 1.0 to 2.0 N / cm is ⁇
- a specimen having a strength of 1.0 N / cm or less. was evaluated as x.
- the results are shown in the above [Table 1] to [Table 3].
- (amount of water) The water content of each of the obtained practical compositions 1 to 20 and the comparative compositions 1 to 2 was measured according to the Karl Fischer method. The results are shown in the above [Table 1] to [Table 3].
- the cationically polymerizable composition of the present invention is low in viscosity and excellent in coating property and curability, and is excellent in adhesion and hot water resistance after curing.
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Abstract
Description
上記脂環式エポキシ化合物(1B)としては、エポキシ当量が80~500又は粘度が2000mPa・s以下であるものが硬化性及び組成物の低粘度化の観点から好ましい。前記の粘度は、25℃における粘度であり、後述する実施例に記載の方法によって測定される。
上記脂肪族エポキシ化合物(1A)としては、エポキシ当量が80~500又は粘度が2000mPa・s以下であるものが硬化性及び組成物の低粘度化の観点から好ましい。この粘度は、25℃における粘度であり、後述する実施例に記載の方法によって測定される。
中でも、上記芳香族エポキシ化合物(1C)として、フェノール類のグリシジルエーテル、安息香酸のグリシジルエステル類又はスチレンオキサイド類の群から選ばれる少なくとも一種を含有することが、組成物の低粘度化の観点から好ましい。
上記芳香族エポキシ化合物としては、エポキシ当量が80~500又は粘度が2000mPa・s以下であるものが、硬化性及び組成物の低粘度化に優れるため好ましい。この粘度は、25℃における粘度であり、後述する実施例に記載の方法によって測定される。
ここで上記(1A)及び(1B)の量は(1D)に該当するものを含む量である。
芳香族エポキシ化合物(1C)において、単官能芳香族エポキシ化合物(1C)の含有量が多官能芳香族エポキシ化合物(1C)の含有量より多い方が、組成物の低粘度化の点から好ましい。
ここで上記(1C)の量は(1D)に該当するものを含む量である。
ただし、ここで上記(1A)及び(1B)の量は上記(1D)に該当するものを除く量であり、(1C)の量は(1D)に該当するものを含む量である。
また、ここで、主成分とは、エポキシ化合物を数種類混ぜたときに、同じ種類のエポキシ化合物の合計量が一番多いものを言い、カチオン重合性有機物質混合物がエポキシ化合物以外のカチオン重合性有機物質を含む場合、数種類のエポキシ化合物のうち合計量が一番多い種類の該合計量は、エポキシ化合物以外のカチオン重合性有機物質の合計量よりも多いものとする。ここでいう各種類のエポキシ化合物の合計量は、(1D)に該当するものを含む。
[A]r+[B]r-
(式中、Aは陽イオン種を表し、Bは陰イオン種を表し、rは価数を表す。)
で表される陽イオンと陰イオンの塩を挙げることができる。
[(R1)aQ]r+
で表すことができる。
[LXb]r-
で表すことができる。
[LXb-1(OH)]r-
で表される構造のものも好ましく用いることができる。L,X,bは上記と同様である。また、その他用いることのできる陰イオンとしては、過塩素酸イオン(ClO4)-、トリフルオロメチル亜硫酸イオン(CF3SO3)-、フルオロスルホン酸イオン(FSO3)-、トルエンスルホン酸陰イオン、トリニトロベンゼンスルホン酸陰イオン、カンファースルフォネート、ノナフロロブタンスルフォネート、ヘキサデカフロロオクタンスルフォネート、テトラアリールボレート、テトラキス(ペンタフルオロフェニル)ボレート等を挙げることができる。
シランカップリング剤としては、例えば、ジメチルジメトキシシラン、ジメチルジエトキシシラン、メチルエチルジメトキシシラン、メチルエチルジエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリメトキシシランなどのアルキル官能性アルコキシシラン、ビニルトリクロロシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、アリルトリメトキシシランなどのアルケニル官能性アルコキシシラン、3-メタクリロキシブロピルトリエトキシシラン、3-メタクリロキシブロピルトリメトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン、3-メタクリロキシプロピルメチルジメトキシシラン、2-メタクリロキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルメチルジエトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン等のエポキシ官能性アルコキシシラン、N-β(アミノエチル)-γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、N-フェニル-γ-アミノプロピルトリメトキシシラン等のアミノ官能性アルコキシシラン、γ-メルカプトプロピルトリメトキシシラン等のメルカプト官能性アルコキシシラン、チタンテトライソプロポキシド、チタンテトラノルマルブトキシドなどのチタンアルコキシド類、チタンジオクチロキシビス(オクチレングリコレート)、チタンジイソプロポキシビス(エチルアセトアセテート)などのチタンキレート類、ジルコウニウムテトラアセチルアセトネート、ジルコニウムトリブトキシモノアセチルアセトネートなどのジルコニウムキレート類、ジルコニウムトリブトキシモノステアレートなどのジルコニウムアシレート類、メチルトリイソシアネートシランなどのイソシアネートシラン類等を用いることができる。
熱重合開始剤とは、加熱によりカチオン種又はルイス酸を発生する化合物として、スルホニウム塩、チオフェニウム塩、チオラニウム塩、ベンジルアンモニウム、ピリジニウム塩、ヒドラジニウム塩等の塩;ジエチレントリアミン、トリエチレントリアミン、テトラエチレンペンタミン等のポリアルキルポリアミン類;1,2-ジアミノシクロヘキサン、1,4-ジアミノ-3,6-ジエチルシクロヘキサン、イソホロンジアミン等の脂環式ポリアミン類;m-キシリレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン等の芳香族ポリアミン類;前記ポリアミン類と、フェニルグリシジルエーテル、ブチルグリシジルエーテル、ビスフェノールA-ジグリシジルエーテル、ビスフェノールF-ジグリシジルエーテル等のグリシジルエーテル類又はカルボン酸のグリシジルエステル類等の各種エポキシ樹脂とを常法によって反応させることによって製造されるポリエポキシ付加変性物;前記有機ポリアミン類と、フタル酸、イソフタル酸、ダイマー酸などのカルボン酸類とを常法によって反応させることによって製造されるアミド化変性物;前記ポリアミン類とホルムアルデヒド等のアルデヒド類及びフェノール、クレゾール、キシレノール、第三ブチルフェノール、レゾルシン等の核に少なくとも一個のアルデヒド化反応性場所を有するフェノール類とを常法によって反応させることによって製造されるマンニッヒ化変性物;多価カルボン酸(シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカン二酸、2-メチルコハク酸、2-メチルアジピン酸、3-メチルアジピン酸、3-メチルペンタン二酸、2-メチルオクタン二酸、3,8-ジメチルデカン二酸、3,7-ジメチルデカン二酸、水添ダイマー酸、ダイマー酸等の脂肪族ジカルボン酸類;フタル酸、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸類;シクロヘキサンジカルボン酸等の脂環式ジカルボン酸類;トリメリト酸、トリメシン酸、ひまし油脂肪酸の三量体等のトリカルボン酸類;ピロメリット酸等のテトラカルボン酸類等)の酸無水物;ジシアンジアミド、イミダゾール類、カルボン酸エステル、スルホン酸エステル、アミンイミド等を挙げることができる。
尚、上記支持基体に、コロナ放電処理、火炎処理、紫外線処理、高周波処理、グロー放電処理、活性プラズマ処理、レーザー処理等の表面活性化処理を行ってもよい。
下記の[表1]~[表3]に示す配合で各成分を十分に混合して、各々実施組成物1~20及び比較組成物1~2を得た。
化合物1A-1:2-エチルヘキシルグリシジルエーテル
化合物1A-2:アリルグリシジルエーテル
化合物1A-3:ネオペンチルグリコールジグリシジルエーテル
化合物1A-4:トリグリシジルトリス(2-ヒドロキシエチル)イソシアヌレート
化合物1B-1:セロキサイド2021P(脂環式エポキシ;ダイセル社製)
化合物1B-2:メチル 3,4-エポキシシクロヘキサンカルボキシレート
化合物1B-3:セロキサイド3000(脂環式エポキシ:ダイセル社製)
化合物1C-1:フェニルグリシジルエーテル
化合物1C-2:スチレンオキサイド
化合物1C-3:グリシジルフタルイミド(EX-731:ナガセケムテックス社製)
化合物1C-4:レゾルシノールジグリシジルエーテル
化合物1C-5:アデカグリシロールED-509S(ADEKA社製)
化合物1C-6:アデカグリシロールED-501(ADEKA社製)
化合物1C-7:アデカレジンEP-4100L(ADEKA社製)
化合物1D-1:GMA/MMA=3/7の共重合体(Mw:8000)
化合物1D-2:GMA/MMA=3/7の共重合体(Mw:15000)
化合物1E-1:アロンオキセタンOXT-101(東亞合成社製)
化合物1E-2:アロンオキセタンOXT-221(東亞合成社製)
化合物1E-3:ヒドロキシブチルビニルエーテル
化合物1E-4:1,4-ブタンジオールジビニルエーテル
化合物2-1:CPI-100P(サンアプロ社製)
上記実施例1~20で得られた実施組成物及び比較例1~2で得られた比較組成物について、下記評価を行った。結果を上記[表1]~[表3]に示す。
(粘度)
得られた実施組成物の1~20、比較組成物の1~2のそれぞれを25℃においてE型粘度計で粘度を測定した。結果を[表1]~[表3]に示す。
(硬化性)
得られた実施組成物の1~20、比較組成物の1~2のそれぞれをPETフィルム上にバーコーターで3~6μmの厚さに塗布し、無電極紫外光ランプを用いて1000mJ/cm2のエネルギーを照射した。照射5分後に塗布面がタックフリーになっているものを◎、15分後にタックフリーになっているものを○、15分後でもタックが残っているものを×として評価した。結果を上記[表1]~[表3]に示す。
(耐温水試験)
得られた実施組成物1~20、比較組成物の1~2のそれぞれをTAC(トリアセチルセルロース)フィルムに塗布した後、ラミネーターを用いてCOP(シクロオレフィンポリマー)フィルムと貼り合わせ、COPフィルム側から無電極紫外光ランプを用いて1000mJ/cm2のエネルギーを照射して接着して試験片を得た。48時間後、2cm×4cmに試験片を切り出し、60℃の温水につけて経過を観察した。12、24時間後に試験片の状態を観察し、開始前と変化が見られないものを〇、端面にハガレが見られるものを△、フィルムの貼り合わせが剥がれて完全に脱落したものを×として評価した。結果を上記[表1]~[表3]に示す。
(接着性)
得られた実施組成物1~20、比較組成物の1~2のそれぞれを、一枚のコロナ放電処理を施したCOP(シクロオレフィンポリマー)フィルムに塗布した後、該フィルムを、ラミネーターを用いてコロナ放電処理を施したもう一枚のCOP(シクロオレフィンポリマー)フィルムと貼り合わせ、無電極紫外光ランプを用いて1000mJ/cm2のエネルギーを照射して接着して試験片を得た。得られた試験片の90度ピール試験を行い、強度が2.0N/cm以上あるものを◎、1.0~2.0N/cmであるものを〇、1.0N/cm以下であるものを×として評価した。結果を上記[表1]~[表3]に示す。
(水分量)
得られた実施組成物の1~20、比較組成物の1~2のそれぞれについて、カールフィッシャー法に従い水分量を測定した。結果を上記[表1]~[表3]に示す。
Claims (10)
- (1)カチオン重合性有機物質として、脂肪族エポキシ化合物(1A)又は脂環式エポキシ化合物(1B)の少なくとも一方を含有し、該脂肪族エポキシ化合物(1A)又は脂環式エポキシ化合物(1B)として、単官能エポキシ化合物を少なくとも一種含有するカチオン重合性有機物質混合物、及び(2)エネルギー線感受性カチオン重合開始剤を含有することを特徴とするカチオン重合性組成物。
- (1)カチオン重合性有機物質として、脂肪族エポキシ化合物(1A)又は脂環式エポキシ化合物(1B)の少なくとも一種を含有し、及び芳香族エポキシ化合物(1C)を含有し、該脂肪族エポキシ化合物(1A)、脂環式エポキシ化合物(1B)又は芳香族エポキシ化合物(1C)として、単官能エポキシ化合物を少なくとも一種含有するカチオン重合性有機物質混合物、及び(2)エネルギー線感受性カチオン重合開始剤を含有することを特徴とするカチオン重合性組成物。
- 上記カチオン重合性有機物質混合物が上記芳香族エポキシ化合物(1C)を主成分とする請求項2に記載のカチオン重合性組成物。
- 上記芳香族エポキシ化合物(1C)のエポキシ当量が80~500又は粘度が2000mPa・s以下であることを特徴とする請求項2又は3に記載のカチオン重合性組成物。
- 上記芳香族エポキシ化合物(1C)として、フェノール類のグリシジルエーテル、安息香酸のグリシジルエステル類又はスチレンオキサイド類の群から選ばれる少なくとも一種を含有することを特徴とする請求項2~4のいずれか一項に記載のカチオン重合性組成物。
- (1)カチオン重合性有機物質として、さらにエポキシ基を有する重量平均分子量1000~1000000の高分子量体(1D)、ビニルエーテル化合物又はオキセタン化合物(1E)の少なくとも一方を含む請求項1~5のいずれか一項に記載のカチオン重合性組成物。
- (2)エネルギー線感受性カチオン重合開始剤が、[A]r+[B]r-(式中、Aは陽イオン種を表し、Bは陰イオン種を表し、rは価数を表す。)で表される陽イオンと陰イオンの塩である請求項1~6のいずれか一項に記載のカチオン重合性組成物。
- 水分量が5質量%以下であることを特徴とする請求項1~7のいずれか一項に記載のカチオン重合性組成物。
- 粘度が200mPa・s以下であることを特徴とする請求項1~8のいずれか一項に記載のカチオン重合性組成物。
- 請求項1~9のいずれか一項に記載のカチオン重合性組成物からなることを特徴とする接着剤。
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JP2022501461A (ja) * | 2018-09-28 | 2022-01-06 | エルジー・ケム・リミテッド | 密封材組成物 |
JP7180837B2 (ja) | 2018-09-28 | 2022-11-30 | エルジー・ケム・リミテッド | 密封材組成物 |
WO2020153259A1 (ja) * | 2019-01-25 | 2020-07-30 | 株式会社ダイセル | カバー部材 |
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JPWO2015005210A1 (ja) | 2017-03-02 |
TWI638849B (zh) | 2018-10-21 |
JP6400005B2 (ja) | 2018-10-03 |
KR102248332B1 (ko) | 2021-05-06 |
TW201502195A (zh) | 2015-01-16 |
KR20160030068A (ko) | 2016-03-16 |
CN104937005A (zh) | 2015-09-23 |
CN104937005B (zh) | 2017-09-05 |
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