WO2016158522A1 - Composition - Google Patents
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- WO2016158522A1 WO2016158522A1 PCT/JP2016/058815 JP2016058815W WO2016158522A1 WO 2016158522 A1 WO2016158522 A1 WO 2016158522A1 JP 2016058815 W JP2016058815 W JP 2016058815W WO 2016158522 A1 WO2016158522 A1 WO 2016158522A1
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- 0 *c(cc1)ccc1S(c(cc1)ccc1OCCO)c(cc1)ccc1Sc(cc1)ccc1S(c1ccc(*)cc1)(c1ccc(*)cc1)=C Chemical compound *c(cc1)ccc1S(c(cc1)ccc1OCCO)c(cc1)ccc1Sc(cc1)ccc1S(c1ccc(*)cc1)(c1ccc(*)cc1)=C 0.000 description 3
Classifications
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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
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- 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 a composition and a cured product obtained by irradiating the composition with active energy rays.
- the 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 Documents 1 to 3 disclose various cationic polymerizable compositions.
- the cured product of the cationically polymerizable composition described in these documents is not sufficient in adhesiveness or heat resistance.
- An object of the present invention is to provide a composition excellent in adhesiveness, heat resistance and liquid storage stability.
- the present invention has been made on the basis of the above knowledge, and comprises a mixture (1) of cationically polymerizable compounds, and the mixture (1) is an aromatic ring-containing epoxy compound represented by the following general formula (I):
- a composition comprising (1A) as a main component and further comprising at least one selected from an aliphatic epoxy compound (1B), an alicyclic epoxy compound (1C), and an oxetane compound (1D) is provided.
- R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 5 carbon atoms. Represents an alkenyl group or a halogen atom, and m is an integer of 0 to 10.
- the present invention also provides an adhesive comprising the above composition.
- composition of the present invention is particularly useful as an adhesive because it has excellent adhesion and heat resistance.
- composition of the present invention and the adhesive comprising the composition will be described in detail based on preferred embodiments.
- the cationic polymerizable compound constituting the mixture is a compound that undergoes a polymerization or a crosslinking reaction by a cationic polymerization initiator activated by light irradiation.
- a cationic polymerizable compound an epoxy compound, an oxetane compound, a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiroorthoester compound, a vinyl ether, or the like can be used, and the fragrance represented by the above general formula (I) It is essential to contain the ring-containing epoxy compound (1A) as a main component.
- a main component means what mixes several kinds of cationically polymerizable compounds, and has the largest total mass of the same kind of cationically polymerizable compounds.
- R 1 , R 2 , R 3 and R 4 having 1 to 5 carbon atoms are represented.
- alkyl group include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl, tert-amyl and the like.
- Examples of the alkoxy group having 1 to 8 carbon atoms represented by R 1 , R 2 , R 3 and R 4 include methoxy, ethoxy, propyloxy, iso-propyloxy, butoxy, pentyloxy, iso-pentyloxy, Xyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and the like,
- Examples of the alkenyl group having 2 to 5 carbon atoms represented by R 1 , R 2 , R 3 and R 4 include vinyl, allyl, butenyl, propenyl
- Examples of the halogen atom represented by R 1 , R 2 , R 3 and R 4 include fluorine, chlorine, bromine and iodine. In addition, all the halogen atoms in this specification are the same as this.
- aromatic ring-containing epoxy compound (1A) represented by the general formula (I) those in which R 1 , R 2 , R 3 and R 4 are hydrogen or a methyl group are preferable from the viewpoint that the epoxy equivalent becomes small Particularly preferred is hydrogen.
- Examples of the aliphatic epoxy compound (1B) include monofunctional epoxy compounds such as glycidyl ethers of aliphatic alcohols and glycidyl esters of alkyl carboxylic acids, polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, Examples include polyfunctional epoxy compounds such as polyglycidyl esters of aliphatic long-chain polybasic acids.
- Representative compounds include allyl glycidyl ether, butyl glycidyl ether, sec-butylphenyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexane Diol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, neopentyl glycol diglycidyl ether, diglycidyl ether of polyethylene glycol, polypropylene glycol Polyglycol glycidyl ether such as diglycidyl ether, propylene glycol, Examples include poly
- the aliphatic epoxy compound (1B) is preferably a diglycidyl ether of an aliphatic diol having 1 to 6 carbon atoms from the viewpoint of the viscosity of the adhesive and the heat resistance of the cured product.
- aliphatic epoxy compound (1B) commercially available products can be used.
- the alicyclic epoxy compound (1C) is a cyclohexene oxide obtained by epoxidizing a polyglycidyl etherified product of a polyhydric alcohol having at least one alicyclic ring or a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. And cyclopentene oxide-containing compounds.
- the alicyclic epoxy compound (1C) is preferably 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate from the viewpoint of the viscosity of the adhesive and the heat resistance of the cured product.
- alicyclic epoxy compound (1C) Commercially available products can be used as the alicyclic epoxy compound (1C), and examples thereof include Celoxide 2021P, Celoxide 2081, Celoxide 2000, and Celoxide 3000 (manufactured by Daicel Corporation).
- Examples of the oxetane compound (1D) include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1, 2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ) Ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) Bifunctional such as butane and 1,6-bis (3-ethyl-3-oxe
- the oxetane compound (1D) is particularly preferably 3-ethyl- ⁇ [(3-ethyloxetane-3-yl) methoxy] methyl ⁇ oxetane from the viewpoints of the viscosity of the adhesive and the heat resistance of the cured product.
- oxetane compound (1D) such as Aron Oxetane EXOH, POX, OXA, OXT-101, OXT-211, OXT-212, OXT-221 (manufactured by Toagosei Co., Ltd.), and the like. Can be mentioned.
- the aromatic epoxy compound (1A), the aliphatic epoxy compound (1B), the alicyclic epoxy compound (1C), and the oxetane compound represented by the general formula (I) is 20 to 80 parts by mass, preferably 30 to 70 parts by mass, more preferably 30 to 70 parts by mass of the aromatic polyfunctional epoxy compound (1A) in 100 parts by mass of the mixture (1) of the cationic polymerizable compound.
- Is 30 to 60 parts by mass, and the aliphatic epoxy compound (1B) is 0 to 70 parts by mass, preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass.
- (1C) is 0 to 20 parts by mass, preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, and the oxetane compound (1D) is 0 to 70 parts by mass
- Mashiku is preferably 5 to 60 parts by mass, and more preferably 10 to 50 parts by weight.
- the aromatic epoxy compound (1A) represented by the general formula (I) is a main component, the content thereof is the highest as compared with other compounds.
- Examples of the cationic polymerizable compound include aromatic ring-containing epoxy compounds other than the aromatic ring-containing epoxy compound (1A) represented by the general formula (I), and aromatic ring-containing epoxy compounds represented by the general formula (I). (1A) can be used in combination.
- aromatic ring-containing epoxy compound examples include monovalent phenols having at least one aromatic ring such as phenol, cresol, and butylphenol, or glycidyl etherified products of alkylene oxide adducts thereof such as bisphenol A, bisphenol F, or Glycidyl etherified compounds and epoxy novolac resins of compounds further added with alkylene oxide; glycidyl ethers of aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone and catechol; benzenedimethanol, benzenediethanol and benzenedi Mono / polyglycidyl etherified products of aromatic compounds having two or more alcoholic hydroxyl groups such as butanol; two or more carboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid Glycidyl esters of polybasic acid aromatic compound having, benzoic acid and toluic acid, glycidyl esters of benzoic acids such as naphtho
- the content of the aromatic ring-containing epoxy compound other than the aromatic ring-containing epoxy compound (1A) represented by the general formula (I) is the aromatic ring-containing epoxy compound (1A) represented by the general formula (I).
- the composition of the present invention may further contain a cationic polymerization initiator (2).
- the cationic polymerization initiator (2) used in the present invention may be any compound that can generate an acid upon irradiation with energy rays. It is a double salt that is an onium salt that releases an acid, or a derivative thereof. Representative examples of such compounds include the following general formula: p [A] q + ⁇ s [B] t ⁇ (A represents a cationic species, B represents an anionic species, q and t each independently represents 1 or 2, and p and s represent charges. And a salt of a cation and an anion.
- the cation [A] q + is preferably onium, and the structure thereof is, for example, the following general formula: [(R 10 ) a Q] q + Can be expressed as
- R 10 is an organic group having 1 to 60 carbon atoms and may contain any number of atoms other than carbon atoms.
- a is an integer of 1 to 5.
- the a R 10 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.
- the anion [B] t- is preferably a halide complex, and the structure thereof is, for example, the following general formula: [LX b ] t- 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 ] t- of 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] t ⁇ is represented by the following general formula: [LX b-1 (OH)] t-
- 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.
- Trinitrobenzenesulfonic acid 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 can be mixed and used.
- Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate
- Diaryls such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, and tricumyliodonium tetrakis (pentafluorophenyl) borate Iodonium salt
- (C) sulfonium salts such as sulfonium cations represented by the following group I or group II, hexafluoroantimony ions, tetrakis (pentafluorophenyl) borate ions, etc.
- 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 cationic polymerization initiator (2) to the mixture (1) of the cationic polymerizable compound 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.
- the cationic polymerization initiator (2) can be preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the mixture (1) of the cationic polymerizable compound. . If the amount is too small, curing tends to be insufficient, and if the amount is too large, various physical properties such as the water absorption rate and the strength of the cured product may be adversely affected.
- composition of the present invention preferably contains 0.05 to 3 parts by mass of water with respect to 100 parts by mass of the total composition (excluding the solvent).
- a silane coupling agent can be used as necessary.
- the silane coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane.
- Alkyl-functional alkoxysilanes vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and other alkenyl-functional alkoxysilanes, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, ⁇ Epoxy-functional alkoxysilanes such as glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N- ⁇ (aminoethyl) - ⁇ Aminofunctional alkoxysilanes such as amino
- 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 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 glycidyl ether, bisphenol
- 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, do Candiic 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 diacids, hydrogenated dimer acids and dimer acids; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; trimellitic acid , Tricar
- 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 solids in the composition.
- the composition of the present invention is preferably heated at 130 to 180 ° C. for 20 minutes to 1 hour when it is cured.
- 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 composition of the present invention is not particularly limited, and a solvent that can dissolve or disperse the components (1) to (4) that are usually used can be used.
- a solvent that can dissolve or disperse the components (1) to (4) that are usually used can be used.
- methyl ethyl ketone, methyl amyl ketone, diethyl ketone, Ketones such as acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether, dipropylene glycol Ether solvents such as dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, n-butyl
- composition of the present invention preferably has a viscosity of 1 to 200 mPa ⁇ s because it is excellent in curability and coatability.
- 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 alcohol (PVA), polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; Acrylic resins such as polymethyl methacrylate and polyacrylate; Polycarbonate; Polysulfone; Polyethersulfone; Polyetherketone Polyetherimide; polymer materials such as polyoxyethylene, norbornene resin, and cycloolefin polymer (COP).
- 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.
- Polymerization initiators radical polymerization initiators, inorganic fillers, organic fillers, colorants such as pigments, dyes, photosensitizers, antifoaming agents, thickeners, surfactants, leveling agents, flame retardants, thixotropic agents, dilution
- resin additives such as an agent, a plasticizer, a stabilizer, a polymerization inhibitor, an ultraviolet absorber, an antioxidant, an antistatic agent, a flow regulator, and an adhesion promoter can be added.
- the composition of the present invention is cured by irradiation with active energy rays
- the active energy rays include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies, and ultraviolet rays are most preferable economically.
- the ultraviolet light source include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp.
- 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, insulating varnishes, insulating materials. Sheets, laminates, printed circuit boards, semiconductor devices, LED packages, liquid crystal injection ports, organic ELs, optical elements, electrical insulation, electronic components, separation membranes, sealing materials, molding materials, putty Glass fiber impregnating agent, sealing agent, passivation film for semiconductors and solar cells, interlayer insulating film, protective film, prism lens sheet used for backlight of liquid crystal display device, screen for projection TV etc.
- My lens parts of lens sheets such as Fresnel lens sheets and lenticular lens sheets, or backlights using such sheets, etc.
- Examples include optical lenses such as Lolens, optical elements, optical connectors, optical waveguides, casting agents for optical modeling, etc.
- Examples of substrates that can be used as coating agents include metals, wood, rubber, plastics, glass, ceramics Product etc. can be mentioned.
- composition of the present invention and the cured product obtained by curing the composition will be specifically described with reference to examples, evaluation examples, and comparative examples, but the present invention is not limited to the examples.
- “part” means “part by mass”.
- Examples 1 to 16 and Comparative Examples 1 to 4 The components shown in [Table 1] to [Table 4] below were mixed thoroughly to obtain Example Compositions 1 to 16 and Comparative Compositions 1 to 4, respectively.
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Abstract
Description
しかしながら、これらの文献に記載のカチオン重合性組成物の硬化物は、接着性又は耐熱性において十分ではなかった。 For example, the following Patent Documents 1 to 3 disclose various cationic polymerizable compositions.
However, the cured product of the cationically polymerizable composition described in these documents is not sufficient in adhesiveness or heat resistance.
R1、R2、R3及びR4で表される炭素原子数1~8のアルコキシ基としては、メトキシ、エトキシ、プロピルオキシ、iso-プロピルオキシ、ブトキシ、ペンチルオキシ、iso-ペンチルオキシ、へキシルオキシ、へプチルオキシ、オクチルオキシ、2-エチルへキシルオキシ等が挙げられ、
R1、R2、R3及びR4で表される炭素原子数2~5のアルケニル基としては、ビニル、アリル、ブテニル、プロペニル等が挙げられ、
R1、R2、R3及びR4で表されるハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられる。尚、本明細書中におけるハロゲン原子はすべてこれと同様である。 In the aromatic ring-containing epoxy compound (1A) represented by the above general formula (I), in the above general formula (I), R 1 , R 2 , R 3 and R 4 having 1 to 5 carbon atoms are represented. Examples of the alkyl group include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl, tert-amyl and the like.
Examples of the alkoxy group having 1 to 8 carbon atoms represented by R 1 , R 2 , R 3 and R 4 include methoxy, ethoxy, propyloxy, iso-propyloxy, butoxy, pentyloxy, iso-pentyloxy, Xyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and the like,
Examples of the alkenyl group having 2 to 5 carbon atoms represented by R 1 , R 2 , R 3 and R 4 include vinyl, allyl, butenyl, propenyl,
Examples of the halogen atom represented by R 1 , R 2 , R 3 and R 4 include fluorine, chlorine, bromine and iodine. In addition, all the halogen atoms in this specification are the same as this.
本発明に使用する上記カチオン重合開始剤(2)とは、エネルギー線照射により酸を発生することが可能な化合物であればどのようなものでも差し支えないが、好ましくは、エネルギー線の照射によってルイス酸を放出するオニウム塩である複塩、又はその誘導体である。かかる化合物の代表的なものとしては、下記一般式、
p[A]q+・s[B]t-(Aは陽イオン種を表し、Bは陰イオン種を表し、q及びtは、それぞれ独立に1又は2を表し、p及びsは、電荷を中性に保つ係数を表す。)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。 The composition of the present invention may further contain a cationic polymerization initiator (2).
The cationic polymerization initiator (2) used in the present invention may be any compound that can generate an acid upon irradiation with energy rays. It is a double salt that is an onium salt that releases an acid, or a derivative thereof. Representative examples of such compounds include the following general formula:
p [A] q + · s [B] t− (A represents a cationic species, B represents an anionic species, q and t each independently represents 1 or 2, and p and s represent charges. And a salt of a cation and an anion.
[(R10)aQ]q+
で表すことができる。 Here, the cation [A] q + is preferably onium, and the structure thereof is, for example, the following general formula:
[(R 10 ) a Q] q +
Can be expressed as
[LXb]t-
で表すことができる。 The anion [B] t- is preferably a halide complex, and the structure thereof is, for example, the following general formula:
[LX b ] t-
Can be expressed as
[LXb-1(OH)]t-
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、ノナフルオロブタンスルフォネート、ヘキサデカフルオ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。 Further, the anion [B] t− is represented by the following general formula:
[LX b-1 (OH)] t-
The thing of the structure represented by can also be used preferably. 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. , Trinitrobenzenesulfonic acid anion, camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate and the like.
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等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等のアルケニル官能性アルコキシシラン、3-メタクリロキシプロピルトリエトキシシラン、3-メタクリロキシプ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等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)等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等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等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等のイソシアネートシラン類等を用いることができる。 In the composition of the present invention, a silane coupling agent can be used as necessary.
Examples of the silane coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Alkyl-functional alkoxysilanes, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and other alkenyl-functional alkoxysilanes, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, γ Epoxy-functional alkoxysilanes such as glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β (aminoethyl) -γ Aminofunctional alkoxysilanes such as aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, mercaptofunctional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, titanium Titanium alkoxides such as tetraisopropoxide and titanium tetranormal butoxide, titanium chelates such as titanium dioctyloxybis (octylene glycolate), titanium diisopropoxybis (ethyl acetoacetate), zirconi Arm tetraacetyl acetonate, zirconium chelates such as zirconium tributoxy monoacetylacetonate, zirconium acylates such as zirconium tributoxy monostearate, an isocyanate silane such as methyl triisocyanate silane.
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、ダイマー酸等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;トリメリット酸、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。 In the composition of the present invention, a thermal polymerization initiator can be used as necessary.
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 glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, etc. Polyepoxy addition-modified products produced by reacting various types of epoxy resins such as glycidyl ethers or glycidyl esters of carboxylic acids in a conventional manner; the organic polyamines, phthalic acid, isophthalic acid, dimer acid, etc. An amidation modified product produced by reacting carboxylic acids with a conventional method; at least one aldehyde reaction in the nucleus of polyamines and aldehydes such as formaldehyde and phenol, cresol, xylenol, tert-butylphenol, resorcin, etc. 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, do Candiic 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 diacids, hydrogenated dimer acids and dimer acids; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; trimellitic acid , Tricarboxylic acids such as trimesic acid and trimer of castor oil fatty acid; tetracarboxylic acids such as pyromellitic acid) acid anhydrides; dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters, amine imides, etc. .
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。 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. 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 alcohol (PVA), polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; Acrylic resins such as polymethyl methacrylate and polyacrylate; Polycarbonate; Polysulfone; Polyethersulfone; Polyetherketone Polyetherimide; polymer materials such as polyoxyethylene, norbornene resin, and cycloolefin polymer (COP).
Note that 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.
下記の[表1]~[表4]に示す配合で各成分を十分に混合して、各々実施組成物1~16、比較組成物1~4を得た。 [Examples 1 to 16 and Comparative Examples 1 to 4]
The components shown in [Table 1] to [Table 4] below were mixed thoroughly to obtain Example Compositions 1 to 16 and Comparative Compositions 1 to 4, respectively.
化合物1A-1:EPOX-MK R1710(プリンテック社製ビスフェノールE型エポキシ樹脂)
化合物1A’-1:EP-4901L(ADEKA社製ビスフェノールF型エポキシ樹脂)
化合物1A’-2:EP-4100L(ADEKA社製ビスフェノールA型エポキシ樹脂)
化合物1B-1:1,4-ブタンジオールジグリシジルエーテル
化合物1B-2:ネオペンチルグリコールジグリシジルエーテル
化合物1C-1: セロキサイド2021P(ダイセル社製脂環式エポキシ化合物)
化合物1C-2:(4R)-1,2-エポキシ-4-(2-メチルオキシラニル)-1-メチルシクロヘキサン
化合物1D-1:アロンオキセタンOXT-221(東亞合成社製)
化合物1D-2:アロンオキセタンOXT-101(東亞合成社製) As cationically polymerizable compounds, the following compounds (1A-1), (1A′-1) to (1A′-2), (1B-1) to (1B-3), (1C-1) to (1C— 2), (1D-1) to (1D-2) were used.
Compound 1A-1: EPOX-MK R1710 (Bisphenol E type epoxy resin manufactured by Printec)
Compound 1A′-1: EP-4901L (bisphenol F type epoxy resin manufactured by ADEKA)
Compound 1A′-2: EP-4100L (bisphenol A type epoxy resin manufactured by ADEKA)
Compound 1B-1: 1,4-butanediol diglycidyl ether compound 1B-2: Neopentyl glycol diglycidyl ether compound 1C-1: Celoxide 2021P (alicyclic epoxy compound manufactured by Daicel)
Compound 1C-2: (4R) -1,2-epoxy-4- (2-methyloxiranyl) -1-methylcyclohexane Compound 1D-1: Aron oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)
Compound 1D-2: Aron Oxetane OXT-101 (manufactured by Toagosei Co., Ltd.)
化合物2-1:[化4]で表される化合物及び[化5]で表される化合物の混合物のプロピレンカーボネート50%溶液 The following compound (2-1) was used as the cationic polymerization initiator (2).
Compound 2-1: 50% solution of propylene carbonate in a mixture of the compound represented by [Chemical Formula 4] and the compound represented by [Chemical Formula 5]
上記実施例1~16で得られた実施組成物及び比較例1~4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4]に示す。
(密着性)
得られた実施組成物1~16、比較組成物の1~4のそれぞれを、一枚のTACフィルム又はPMMAフィルムに塗布した後、ラミネーターを用いてコロナ放電処理を施したCOP(シクロオレフィンポリマー)フィルムと貼り合わせ、コールドミラー型高圧Hg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度ピール試験を行った。
(Tg)
得られた実施組成物1~16、比較組成物の1~4のそれぞれをPETフィルム上にバーコーターで3μmの厚さに塗布し、コールドミラー型高圧Hgランプを用いて2000mJ/cm2のエネルギーを照射した。24時間後にフィルムから接着剤硬化物を取り出し、(株)日立ハイテクサイエンス製の粘弾性測定装置(DMA7100)を用いTgを測定した。結果を[表1]~[表4]に示す。
(粘度)
得られた実施組成物の1~16、比較組成物の1~4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4]に示す。 [Evaluation Examples 1 to 16 and Comparative Evaluation Examples 1 to 4]
The following evaluations were performed on the working compositions obtained in Examples 1 to 16 and the comparative compositions obtained in Comparative Examples 1 to 4. The results are shown in the above [Table 1] to [Table 4].
(Adhesion)
COP (cycloolefin polymer) obtained by applying each of the obtained working compositions 1 to 16 and comparative compositions 1 to 4 to a single TAC film or PMMA film and then applying a corona discharge treatment using a laminator A test piece was obtained by laminating the film and bonding it by applying energy of 1000 mJ / cm 2 using a cold mirror type high-pressure Hg lamp. The obtained test piece was subjected to a 90 degree peel test.
(Tg)
Each of the obtained working compositions 1 to 16 and comparative compositions 1 to 4 was applied to a PET film with a bar coater to a thickness of 3 μm, and an energy of 2000 mJ / cm 2 using a cold mirror type high pressure Hg lamp. Was irradiated. After 24 hours, the cured adhesive was taken out from the film, and Tg was measured using a viscoelasticity measuring device (DMA7100) manufactured by Hitachi High-Tech Science Co., Ltd. The results are shown in [Table 1] to [Table 4].
(viscosity)
The viscosity of each of the obtained practical compositions 1 to 16 and the comparative compositions 1 to 4 was measured with an E-type viscometer at 25 ° C. The results are shown in [Table 1] to [Table 4].
Claims (6)
- カチオン重合性化合物の混合物(1)を含んでなり、該混合物(1)が、下記一般式(I)で表される芳香環含有エポキシ化合物(1A)を主成分として含有し、さらに脂肪族エポキシ化合物(1B)、脂環式エポキシ化合物(1C)及びオキセタン化合物(1D)から選ばれる少なくとも一種を含むことを特徴とする組成物。
- 上記脂肪族エポキシ化合物(1B)が、炭素原子数1~6の脂肪族ジオールのジグリシジルエーテルであることを特徴とする請求項1記載の組成物。 The composition according to claim 1, wherein the aliphatic epoxy compound (1B) is a diglycidyl ether of an aliphatic diol having 1 to 6 carbon atoms.
- 上記カチオン重合性化合物の混合物(1)100質量部に対し、カチオン重合開始剤(2)を0.1~20質量部含むことを特徴とする請求項1又は2に記載の組成物。 The composition according to claim 1 or 2, which comprises 0.1 to 20 parts by mass of the cationic polymerization initiator (2) with respect to 100 parts by mass of the mixture (1) of the cationic polymerizable compound.
- 上記カチオン重合開始剤が、p[A]q+・s[B]t-(Aは陽イオン種を表し、Bは陰イオン種を表し、q及びtは、それぞれ独立に1又は2を表し、p及びsは、電荷を中性に保つ係数を表す。)で表される陽イオンと陰イオンの塩である請求項1~3の何れか一項に記載の組成物。 The cationic polymerization initiator is p [A] q + · s [B] t− (A represents a cationic species, B represents an anionic species, q and t each independently represent 1 or 2, The composition according to any one of claims 1 to 3, which is a salt of a cation and an anion represented by p and s each representing a coefficient for maintaining a neutral charge).
- 組成物全量(但し、溶媒は除く)の100質量部に対し、水分を0.05~3質量部含むことを特徴とする請求項1~4の何れか一項に記載の組成物。 The composition according to any one of claims 1 to 4, wherein the composition contains 0.05 to 3 parts by mass of water with respect to 100 parts by mass of the total amount of the composition (excluding the solvent).
- 請求項1~5の何れか一項に記載の組成物からなることを特徴とする接着剤。 An adhesive comprising the composition according to any one of claims 1 to 5.
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Also Published As
Publication number | Publication date |
---|---|
TW201700524A (en) | 2017-01-01 |
JP6879903B2 (en) | 2021-06-02 |
TWI764862B (en) | 2022-05-21 |
CN107075082B (en) | 2020-10-30 |
KR20170133311A (en) | 2017-12-05 |
JPWO2016158522A1 (en) | 2018-01-18 |
CN107075082A (en) | 2017-08-18 |
KR102563226B1 (en) | 2023-08-03 |
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