JPWO2012042796A1 - Cationic polymerization initiator and thermosetting epoxy resin composition - Google Patents
Cationic polymerization initiator and thermosetting epoxy resin composition Download PDFInfo
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- JPWO2012042796A1 JPWO2012042796A1 JP2011552104A JP2011552104A JPWO2012042796A1 JP WO2012042796 A1 JPWO2012042796 A1 JP WO2012042796A1 JP 2011552104 A JP2011552104 A JP 2011552104A JP 2011552104 A JP2011552104 A JP 2011552104A JP WO2012042796 A1 JPWO2012042796 A1 JP WO2012042796A1
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- cationic polymerization
- polymerization initiator
- epoxy resin
- resin composition
- Prior art date
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- 238000010538 cationic polymerization reaction Methods 0.000 title claims abstract description 59
- 239000003505 polymerization initiator Substances 0.000 title claims abstract description 59
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 49
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 150000001875 compounds Chemical group 0.000 claims abstract description 12
- 125000001424 substituent group Chemical group 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000543 intermediate Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 13
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 11
- 230000009477 glass transition Effects 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- -1 ethylbenzyl group Chemical group 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 8
- WLHCBQAPPJAULW-UHFFFAOYSA-N 4-methylbenzenethiol Chemical compound CC1=CC=C(S)C=C1 WLHCBQAPPJAULW-UHFFFAOYSA-N 0.000 description 7
- 238000001879 gelation Methods 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000012776 electronic material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 5
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 5
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 5
- PSBPNWBGNOWCCU-UHFFFAOYSA-N OB(O)O.S.S.S Chemical compound OB(O)O.S.S.S PSBPNWBGNOWCCU-UHFFFAOYSA-N 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 125000000732 arylene group Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000004450 alkenylene group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
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- 125000003944 tolyl group Chemical group 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 208000034189 Sclerosis Diseases 0.000 description 2
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- 230000000996 additive effect Effects 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- SFSPUVKCNQHXPP-UHFFFAOYSA-N disodium dioxido-(2,3,4,5,6-pentafluorophenoxy)borane Chemical compound [Na+].B(OC1=C(C(=C(C(=C1F)F)F)F)F)([O-])[O-].[Na+] SFSPUVKCNQHXPP-UHFFFAOYSA-N 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- XMWGTKZEDLCVIG-UHFFFAOYSA-N 1-(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1 XMWGTKZEDLCVIG-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- SNGZGCFWZHOVOS-UHFFFAOYSA-N 2-(2-methyloctoxymethyl)oxirane Chemical compound CCCCCCC(C)COCC1CO1 SNGZGCFWZHOVOS-UHFFFAOYSA-N 0.000 description 1
- XKOWGGVJZHBDJA-UHFFFAOYSA-N 2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCCC1CC2OC2CC1 XKOWGGVJZHBDJA-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- WAPRZVXVTPSWEB-UHFFFAOYSA-N 2-[(2-butan-2-ylphenoxy)methyl]oxirane Chemical compound CCC(C)C1=CC=CC=C1OCC1OC1 WAPRZVXVTPSWEB-UHFFFAOYSA-N 0.000 description 1
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- DOQQIEJZBMOSKR-UHFFFAOYSA-N 2-[2,3,4,5-tetramethyl-6-(oxiran-2-ylmethoxy)phenyl]phenol Chemical compound CC=1C(C)=C(C)C(C)=C(C=2C(=CC=CC=2)O)C=1OCC1CO1 DOQQIEJZBMOSKR-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
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- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
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- OEIZUSDQPOLYGQ-UHFFFAOYSA-N 4-(7-oxabicyclo[4.1.0]heptan-4-yloxy)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2OC2CC1OC1CCC2OC2C1 OEIZUSDQPOLYGQ-UHFFFAOYSA-N 0.000 description 1
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- ORTNTAAZJSNACP-UHFFFAOYSA-N 6-(oxiran-2-ylmethoxy)hexan-1-ol Chemical compound OCCCCCCOCC1CO1 ORTNTAAZJSNACP-UHFFFAOYSA-N 0.000 description 1
- NHJIDZUQMHKGRE-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 2-(7-oxabicyclo[4.1.0]heptan-4-yl)acetate Chemical compound C1CC2OC2CC1OC(=O)CC1CC2OC2CC1 NHJIDZUQMHKGRE-UHFFFAOYSA-N 0.000 description 1
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- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000005562 phenanthrylene group Chemical group 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000006410 propenylene group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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
- C08G59/68—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 catalysts used
- C08G59/687—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 catalysts used containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing 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
- C08G59/68—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 catalysts used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/55—Boron-containing compounds
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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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
エポキシ樹脂組成物の硬化性に優れたカチオン重合開始剤および熱硬化性エポキシ樹脂組成物を提供する。下記一般式（Ｉ）で表されるカチオン重合開始剤。式（Ｉ）において、Ｒ１は、水酸基、Ｒ４Ｏ基、Ｒ４ＣＯＯ基、Ｒ４ＮＨＣＯＯ基又はＲ４ＯＣＯＯ基であり、Ｒ２は、炭素数１〜６のアルキル基であり、Ｒ３は、水素原子またはアルキル基である。Ｒ４は、置換基を有してもよい芳香族または脂肪族炭化水素基である。Ｘは、下記式（１）で表される化合物である。【化１】A cationic polymerization initiator and a thermosetting epoxy resin composition excellent in curability of an epoxy resin composition are provided. Cationic polymerization initiator represented by the following general formula (I). In the formula (I), R1 is a hydroxyl group, an R4O group, an R4COO group, an R4NHCOO group or an R4OCOO group, R2 is an alkyl group having 1 to 6 carbon atoms, and R3 is a hydrogen atom or an alkyl group. R4 is an aromatic or aliphatic hydrocarbon group which may have a substituent. X is a compound represented by the following formula (1). [Chemical 1]
Description
本発明は、カチオン重合開始剤および熱硬化性エポキシ樹脂組成物に関する。 The present invention relates to a cationic polymerization initiator and a thermosetting epoxy resin composition.
エポキシ樹脂のカチオン重合開始剤として、スルホニウムボレート錯体が知られている。スルホニウムボレート錯体としては、例えば、カウンターアニオンとして、下記式で表されるテトラキス（ペンタフルオロフェニル）ボレートアニオンを含むものが知られている（例えば、特許文献１参照）。 A sulfonium borate complex is known as a cationic polymerization initiator for epoxy resins. As a sulfonium borate complex, for example, a counter anion containing a tetrakis (pentafluorophenyl) borate anion represented by the following formula is known as a counter anion (see, for example, Patent Document 1).
上記スルホニウムボレート錯体をカチオン重合開始剤として含むエポキシ樹脂組成物は、硬化性に優れることが知られている。しかし、エポキシ樹脂組成物の硬化時間は、絶えず、より短いことが求められている。
本発明は、エポキシ樹脂組成物の硬化性に優れたカチオン重合開始剤および熱硬化性エポキシ樹脂組成物を提供することにある。It is known that an epoxy resin composition containing the sulfonium borate complex as a cationic polymerization initiator is excellent in curability. However, the curing time of the epoxy resin composition is constantly required to be shorter.
An object of the present invention is to provide a cationic polymerization initiator and a thermosetting epoxy resin composition excellent in curability of the epoxy resin composition.
本発明者は、上記課題を解決すべく鋭意研究した結果、下記一般式（Ｉ）で表されるスルホニウムボレート錯体をカチオン重合開始剤として使用することにより、硬化性に優れたエポキシ樹脂組成物が得られることを見出し、本発明を完成させた。 As a result of earnest research to solve the above problems, the present inventor has obtained an epoxy resin composition excellent in curability by using a sulfonium borate complex represented by the following general formula (I) as a cationic polymerization initiator. As a result, the present invention was completed.
すなわち、本発明は、式（Ｉ）で表されるカチオン重合開始剤を提供する。また、本発明は、式（Ｉ）で表されるカチオン重合開始剤と、エポキシ基を有するモノマー又はポリマーを含有する熱硬化性エポキシ樹脂組成物を提供する。 That is, the present invention provides a cationic polymerization initiator represented by the formula (I). Moreover, this invention provides the thermosetting epoxy resin composition containing the cationic polymerization initiator represented by Formula (I), and the monomer or polymer which has an epoxy group.
本発明によれば、硬化性に優れたエポキシ樹脂組成物が得られる。 According to the present invention, an epoxy resin composition excellent in curability can be obtained.
以下、本発明のカチオン重合開始剤および熱硬化性エポキシ樹脂組成物について詳細に説明する。
本発明のカチオン重合開始剤は、一般式（Ｉ）で表される。以下、このカチオン重合開始剤をカチオン重合開始剤１ともいう。Hereinafter, the cationic polymerization initiator and thermosetting epoxy resin composition of the present invention will be described in detail.
The cationic polymerization initiator of the present invention is represented by the general formula (I). Hereinafter, this cationic polymerization initiator is also referred to as cationic polymerization initiator 1.
（カチオン重合開始剤１）
式（Ｉ）において、Ｒ１は、水酸基、Ｒ４Ｏ基、Ｒ４ＣＯＯ基、Ｒ４ＮＨＣＯＯ基、Ｒ４ＳＯ２ＮＨＣＯＯ基又はＲ４ＯＣＯＯ基である。Ｒ４は、置換基を有してもよい芳香族または脂肪族炭化水素基である。(Cationic polymerization initiator 1)
In the formula (I), R 1 is a hydroxyl group, an R 4 O group, an R 4 COO group, an R 4 NHCOO group, an R 4 SO 2 NHCOO group or an R 4 OCOO group. R 4 is an aromatic or aliphatic hydrocarbon group which may have a substituent.
芳香族炭化水素基としては、例えば、アリール基、アラルキル基、アリーレン基が挙げられる。アリール基としては、例えば、炭素数６〜１４、好ましくは炭素数６〜１０のものが挙げられる。例えば、フェニル基、ナフチル基、アントリル基、フェナントリル基、ビフェニル基等が挙げられる。中でも、フェニル基が好ましく用いられる。
アラルキル基としては、例えば、炭素数７〜１３、好ましくは炭素数７〜１１のものが挙げられる。例えば、ベンジル基、フェネチル基、フェニルプロピル基等が挙げられる。中でも、ベンジル基が好ましく用いられる。
アリーレン基としては、例えば、炭素数６〜１４、好ましくは炭素数６〜１０のものが挙げられる。例えば、フェニレン基、ナフチレン基、アントリレン基、フェナントリレン基、ビフェニレン基が挙げられる。中でも、フェニレン基が好ましく用いられる。アリーレン基は、アリール基、アラルキル基等の１価の基と結合することでＲ４を構成する。Examples of the aromatic hydrocarbon group include an aryl group, an aralkyl group, and an arylene group. Examples of the aryl group include those having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms. Examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group. Of these, a phenyl group is preferably used.
Examples of the aralkyl group include those having 7 to 13 carbon atoms, preferably 7 to 11 carbon atoms. For example, benzyl group, phenethyl group, phenylpropyl group and the like can be mentioned. Of these, a benzyl group is preferably used.
Examples of the arylene group include those having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms. Examples thereof include a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, and a biphenylene group. Of these, a phenylene group is preferably used. The arylene group constitutes R 4 by bonding with a monovalent group such as an aryl group or an aralkyl group.
芳香族炭化水素基は、さらに任意の炭素原子の位置に、例えば、炭素数１〜４の低級アルキル基、ヒドロキシル基、アミノ基、ニトロ基、ハロゲン原子等の１以上の置換基を有してもよい。置換基を有する芳香族炭化水素基としては、例えば、トリル基、キシリル基、フェノキシ基等の置換基、を有するアリール基；メチルベンジル基、エチルベンジル基、メチルフェネチル基等の置換基、を有するアラルキル基；メチルフェニレン基、ジメチルフェニレン基、メチルナフチレン基等の置換基、を有するアリーレン基が挙げられる。中でも、フェノキシ基が好ましく用いられる。 The aromatic hydrocarbon group further has at least one substituent such as a lower alkyl group having 1 to 4 carbon atoms, a hydroxyl group, an amino group, a nitro group, and a halogen atom at an arbitrary carbon atom position. Also good. Examples of the aromatic hydrocarbon group having a substituent include an aryl group having a substituent such as a tolyl group, a xylyl group, and a phenoxy group; and a substituent such as a methylbenzyl group, an ethylbenzyl group, and a methylphenethyl group. An arylene group having an aralkyl group; a substituent such as a methylphenylene group, a dimethylphenylene group, or a methylnaphthylene group; Of these, a phenoxy group is preferably used.
脂肪族炭化水素基としては、例えば、アルキル基、シクロアルキル基、アルケニル基、アルケニレン基、アルコキシ基が挙げられる。アルキル基としては、例えば、炭素数１〜１８、好ましくは炭素数１〜６の直鎖又は分岐状のものが挙げられる。例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基が挙げられる。中でも、メチル基が好ましく用いられる。
シクロアルキル基としては、例えば、炭素数３〜１０、好ましくは３〜６のものが挙げられる。例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基が挙げられる。
アルケニル基としては、例えば、炭素数２〜１８、好ましくは炭素数２〜６の直鎖又は分岐状のものが挙げられる。例えば、ビニル基、１−プロペニル基、アリル基、イソプロペニル基、１−ブテニル基、２−ブテニル基が挙げられる。
アルケニレン基としては、例えば、炭素数２〜１８、好ましくは炭素数２〜６の直鎖または分岐状のものが挙げられる。例えば、ビニレン基、プロペニレン基、ブタジエニレン基が挙げられる。アルケニレン基は、アルキル基、シクロアルキル基等の１価の基と結合することでＲ４を構成する。
アルコキシ基としては、例えば、炭素数１〜１８、好ましくは炭素数１〜６の直鎖又は分岐状のものが挙げられる。例えば、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基が挙げられる。中でも、メトキシ基が好ましく用いられる。Examples of the aliphatic hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, an alkenylene group, and an alkoxy group. Examples of the alkyl group include linear or branched groups having 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms. Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Of these, a methyl group is preferably used.
Examples of the cycloalkyl group include those having 3 to 10 carbon atoms, preferably 3 to 6 carbon atoms. Examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
Examples of the alkenyl group include linear or branched groups having 2 to 18 carbon atoms, preferably 2 to 6 carbon atoms. For example, a vinyl group, 1-propenyl group, allyl group, isopropenyl group, 1-butenyl group, and 2-butenyl group can be mentioned.
As an alkenylene group, a C2-C18, Preferably a C2-C6 linear or branched thing is mentioned, for example. For example, vinylene group, propenylene group, butadienylene group can be mentioned. The alkenylene group constitutes R 4 by bonding with a monovalent group such as an alkyl group or a cycloalkyl group.
As an alkoxy group, C1-C18, Preferably a C1-C6 linear or branched thing is mentioned, for example. Examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, and tert-butoxy group. Of these, a methoxy group is preferably used.
Ｒ４Ｏ基においては、好ましいＲ４として、メチル基、メトキシ基、フェニル基、フェノキシ基が挙げられ、中でも、メチル基がより好ましく用いられる。
Ｒ４ＣＯＯ基においては、好ましいＲ４として、メチル基、ベンジル基、フェニル基が挙げられ、中でも、メトキシ基がより好ましく用いられる。
Ｒ４ＮＨＣＯＯ基においては、好ましいＲ４として、メチル基、メトキシ基、フェニル基、フェノキシ基、フェニレン基が挙げられ、中でも、フェニル基がより好ましく用いられる。
Ｒ４ＳＯ２ＮＨＣＯＯ基においては、好ましいＲ４として、メチル基、メトキシ基、フェニル基、フェノキシ基、フェニレン基、トリル基が挙げられ、中でも、トリル基がより好ましく、ｐ−トリル基がさらに好ましく用いられる。
Ｒ４ＯＣＯＯ基においては、好ましいＲ４として、メチル基、フェニル基、フェニレン基が挙げられ、中でも、フェニル基がより好ましく用いられる。In the R 4 O group, preferred R 4 includes a methyl group, a methoxy group, a phenyl group, and a phenoxy group, and among them, a methyl group is more preferably used.
In the R 4 COO group, preferred R 4 includes a methyl group, a benzyl group, and a phenyl group, and among them, a methoxy group is more preferably used.
In the R 4 NHCOO group, preferred R 4 includes a methyl group, a methoxy group, a phenyl group, a phenoxy group, and a phenylene group, and among them, a phenyl group is more preferably used.
In the R 4 SO 2 NHCOO group, preferred R 4 includes a methyl group, a methoxy group, a phenyl group, a phenoxy group, a phenylene group, and a tolyl group. Among them, a tolyl group is more preferred, and a p-tolyl group is more preferred. Used.
In the R 4 OCOO group, preferred R 4 includes a methyl group, a phenyl group, and a phenylene group, and among them, a phenyl group is more preferably used.
Ｒ４Ｏ基、Ｒ４ＣＯＯ基、Ｒ４ＮＨＣＯＯ基、Ｒ４ＳＯ２ＮＨＣＯＯ基及びＲ４ＯＣＯＯ基のうち、Ｒ４ＣＯＯ基、Ｒ４ＮＨＣＯＯ基、Ｒ４ＳＯ２ＮＨＣＯＯ基及びＲ４ＯＣＯＯ基は、電子吸引性基を有することでスルホニウムイオンのカチオン性が上がり、硬化性に優れるという点で、好ましく用いられる。特に、電子吸引性基の電子吸引性が高いものほど、硬化性により優れ、より好ましく用いられる。
Ｒ１としては、硬化性に優れるという観点から、水酸基、Ｒ４ＣＯＯ基、Ｒ４ＮＨＣＯＯ基、Ｒ４ＳＯ２ＮＨＣＯＯ基、Ｒ４ＯＣＯＯ基が好ましく用いられ、水酸基がより好ましく用いられる。
Ｒ１の配置は、スルホニウムイオンに対し、オルト位、メタ位、パラ位のいずれであってもよく、硬化性に優れるという観点から、パラ位であるのが好ましい。Among R 4 O group, R 4 COO group, R 4 NHCOO group, R 4 SO 2 NHCOO group and R 4 OCOO group, R 4 COO group, R 4 NHCOO group, R 4 SO 2 NHCOO group and R 4 OCOO group Is preferably used in that it has an electron-withdrawing group, so that the cationic property of the sulfonium ion is increased and the curability is excellent. In particular, the higher the electron-withdrawing property of the electron-withdrawing group, the better the curability and the more preferably used.
From the viewpoint of excellent curability, R 1 is preferably a hydroxyl group, an R 4 COO group, an R 4 NHCOO group, an R 4 SO 2 NHCOO group, or an R 4 OCOO group, and more preferably a hydroxyl group.
The arrangement of R 1 may be any of ortho-position, meta-position, and para-position with respect to the sulfonium ion, and is preferably para-position from the viewpoint of excellent curability.
Ｒ２は、炭素数１〜６、好ましくは炭素数１〜３のアルキル基である。例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基が挙げられる。中でも、メチル基が好ましく用いられる。R 2 is an alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Of these, a methyl group is preferably used.
Ｒ３は、水素原子またはアルキル基である。アルキル基は、Ｒ４の上述したアルキル基と同様である。Ｒ３としては、硬化性に優れるという観点から、水素原子が好ましく用いられる。Ｒ３の配置は、ビニレン基に対し、オルト位、メタ位、パラ位のいずれであってもよく、硬化性に優れるという観点から、オルト位又はパラ位であるのが好ましい。
Ｘは、式（１）で表される化合物である。R 3 is a hydrogen atom or an alkyl group. The alkyl group is the same as the alkyl group described above for R 4 . As R 3 , a hydrogen atom is preferably used from the viewpoint of excellent curability. The arrangement of R 3 may be any of the ortho, meta, and para positions relative to the vinylene group, and is preferably the ortho or para position from the viewpoint of excellent curability.
X is a compound represented by Formula (1).
式（Ｉ）で表されるカチオン重合開始剤１の具体例としては、例えば、下記式（Ｉａ）で表される化合物が挙げられる。 Specific examples of the cationic polymerization initiator 1 represented by the formula (I) include a compound represented by the following formula (Ia).
カチオン重合開始剤１は、その製造について特に制限されない。例えば、４−メチルチオフェノールとシンナミルクロリドを反応させ、クロライド中間体を得、さらに、クロライド中間体とテトラキス（ペンタフルオロフェニル）ボレートのナトリウム塩水溶液を混合し、反応させることで得ることができる。 The production of the cationic polymerization initiator 1 is not particularly limited. For example, 4-methylthiophenol and cinnamilk chloride are reacted to obtain a chloride intermediate, and further, the chloride intermediate and a sodium salt aqueous solution of tetrakis (pentafluorophenyl) borate are mixed and reacted.
本発明の熱硬化性エポキシ樹脂組成物は、カチオン重合開始剤１と、エポキシ基を有するモノマー又はポリマーを含有する。
（エポキシ基を有するモノマー）
エポキシ基を有するモノマーとしては、特に限定されず、例えば、単官能グリシジルエーテル類、多官能脂肪族グリシジルエーテル類、多官能芳香族グリシジルエーテル類、グリシジルエステル類、脂環式エポキシ化合物等が用いられる。The thermosetting epoxy resin composition of the present invention contains a cationic polymerization initiator 1 and a monomer or polymer having an epoxy group.
(Monomer having an epoxy group)
The monomer having an epoxy group is not particularly limited, and examples thereof include monofunctional glycidyl ethers, polyfunctional aliphatic glycidyl ethers, polyfunctional aromatic glycidyl ethers, glycidyl esters, and alicyclic epoxy compounds. .
単官能グリシジルエーテル類としては、例えば、アリルグリシジルエーテル、ブチルグリシジルエーテル、フェニルグリシジルエーテル、２−エチルヘキシルグリシジルエーテル、ｓｅｃ−ブチルフェニルグリシジルエーテル、ｔｅｒｔ−ブチルフェニルグリシジルエーテル、２−メチルオクチルグリシジルエーテル等が挙げられる。 Examples of monofunctional glycidyl ethers include allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, sec-butylphenyl glycidyl ether, tert-butylphenyl glycidyl ether, and 2-methyloctyl glycidyl ether. Can be mentioned.
多官能脂肪族グリシジルエーテル類としては、例えば、１，６−ヘキサンジオールグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、グリセロールジグリシジルエーテル、グリセロールトリグリシジルエーテル、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル等が挙げられる。 Examples of polyfunctional aliphatic glycidyl ethers include 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, and ethylene glycol diglycidyl ether. Polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and the like.
多官能芳香族グリシジルエーテル類としては、例えば、ビスフェノールＡグリシジルエーテル、ビスフェノールＦグリシジルエーテル、ブロモ化ビスフェノールＡグリシジルエーテル、ビフェノールグリシジルエーテル、テトラメチルビフェノールグリシジルエーテル、レゾルシングリシジルエーテル、ハイドロキノングリシジルエーテル、ジヒドロキシナフタレングリシジルエーテル、ビスフェノールノボラック樹脂グリシジルエーテル、フェノールノボラック樹脂グリシジルエーテル、クレゾールノボラック樹脂グリシジルエーテル、ジシクロペンタジエンフェノール樹脂グリシジルエーテル、テルペンフェノール樹脂グリシジルエーテル、ナフトールノボラック樹脂グリシジルエーテル等が挙げられる。 Examples of polyfunctional aromatic glycidyl ethers include bisphenol A glycidyl ether, bisphenol F glycidyl ether, brominated bisphenol A glycidyl ether, biphenol glycidyl ether, tetramethylbiphenol glycidyl ether, resorching glycidyl ether, hydroquinone glycidyl ether, dihydroxynaphthalene glycidyl ether Examples include ether, bisphenol novolac resin glycidyl ether, phenol novolac resin glycidyl ether, cresol novolac resin glycidyl ether, dicyclopentadiene phenol resin glycidyl ether, terpene phenol resin glycidyl ether, and naphthol novolac resin glycidyl ether.
グリシジルエステル類としては、例えば、グリシジルアクリレート、グリシジルメタクリレート、ジグリシジルフタレート、ジグリシジルヘキサヒドロフタレート、ジグリシジルテトラヒドロフタレート、ジメチルジグリシジルヘキサヒドロフタレート等が挙げられる。 Examples of the glycidyl esters include glycidyl acrylate, glycidyl methacrylate, diglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, dimethyldiglycidyl hexahydrophthalate, and the like.
脂環式エポキシ化合物としては、例えば、３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレート、３，４−エポキシシクロヘキシルエチル−３，４−エポキシシクロヘキサンカルボキシレート、ビニルシクロヘキセンジオキシド、アリルシクロヘキセンジオキシド、３，４−エポキシ−４−メチルシクロヘキシル−２−プロピレンオキシド、２−（３，４−エポキシシクロヘキシル−５，５−スピロ−３，４−エポキシ）シクロヘキサン−ｍ−ジオキサン、ビス（３，４−エポキシシクロヘキシル）アジペート、ビス（３，４−エポキシシクロヘキシルメチル）アジペート、ビス（３，４−エポキシシクロヘキシル）エーテル、ビス（３，４−エポキシシクロヘキシルメチル）エーテル、ビス（３，４−エポキシシクロヘキシル）ジエチルシロキサン等が挙げられる。
エポキシ基を有するモノマーは、単独でまたは２種以上を混合して用いることができる。Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, and allyl. Cyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis ( 3,4-epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4 Epoxycyclohexyl) diethyl siloxane, and the like.
The monomer which has an epoxy group can be used individually or in mixture of 2 or more types.
（エポキシ基を有するポリマー）
エポキシ基を有するポリマーは、エポキシ基を２個以上有するものであれば特に制限されず、例えば、ビスフェノールA型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ジアミノジフェニルメタン型エポキシ樹脂、アミノフェノール型エポキシ樹脂、ナフタレン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、水添ビフェノール型エポキシ樹脂、脂環式エポキシ樹脂が用いられる。
エポキシ基を有するポリマーはそれぞれ単独でまたは２種以上を組み合わせて使用することができる。(Polymer having epoxy group)
The polymer having an epoxy group is not particularly limited as long as it has two or more epoxy groups. For example, bisphenol A type epoxy resin, dicyclopentadiene type epoxy resin, diaminodiphenylmethane type epoxy resin, aminophenol type epoxy resin, Naphthalene type epoxy resins, phenol novolac type epoxy resins, biphenyl type epoxy resins, hydrogenated biphenol type epoxy resins, and alicyclic epoxy resins are used.
The polymer which has an epoxy group can be used individually or in combination of 2 or more types, respectively.
カチオン重合開始剤１の配合量は、速硬化性を十分に発揮させ、かつ、硬化物のガラス転移点が高いという観点から、全エポキシ基を有するモノマー又はポリマー１００重量部に対し、０．１〜１０重量部であるのが好ましく、０．１〜５重量部であるのがより好ましい。 The blending amount of the cationic polymerization initiator 1 is 0.1% with respect to 100 parts by weight of the monomer or polymer having all epoxy groups from the viewpoint of sufficiently exhibiting quick curability and having a high glass transition point of the cured product. It is preferably 10 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight.
（カチオン重合開始剤２）
本発明のエポキシ樹脂組成物は、下記一般式（ＩＩ）で表されるカチオン重合開始剤（以下、カチオン重合開始剤２ともいう）をさらに含有してもよい。カチオン重合開始剤２は、硬化性を損なうことなくガラス転移点の高い硬化物が得られるため、その用途に応じて、カチオン重合開始剤１との配合比を適宜定めて配合することができる。(Cationic polymerization initiator 2)
The epoxy resin composition of the present invention may further contain a cationic polymerization initiator represented by the following general formula (II) (hereinafter also referred to as cationic polymerization initiator 2). Since a cured product having a high glass transition point is obtained without impairing curability, the cationic polymerization initiator 2 can be appropriately blended with the cationic polymerization initiator 1 depending on its use.
式（ＩＩ）において、Ｒ５は、水酸基、Ｒ４Ｏ基、Ｒ４ＣＯＯ基、Ｒ４ＮＨＣＯＯ基、Ｒ４ＳＯ２ＮＨＣＯＯ基又はＲ４ＯＣＯＯ基であり、上述したカチオン重合開始剤１のＲ１と同様である。
Ｒ６は、水素原子またはアルキル基である。アルキル基は、上述したカチオン重合開始剤１のＲ４の上述したアルキル基と同様である。Ｒ６としては、硬化性に優れるという観点から、水素原子が好ましく用いられる。Ｒ６の配置は、メチレン基に対し、オルト位、メタ位、パラ位のいずれであってもよく、硬化性に優れるという観点から、オルト位又はパラ位であるのが好ましい。
Ｘは、下記式（２）で表される化合物である。In the formula (II), R 5 is a hydroxyl group, an R 4 O group, an R 4 COO group, an R 4 NHCOO group, an R 4 SO 2 NHCOO group or an R 4 OCOO group, and the R of the cationic polymerization initiator 1 described above Same as 1 .
R 6 is a hydrogen atom or an alkyl group. The alkyl group is the same as the alkyl group described above for R 4 of the cationic polymerization initiator 1 described above. As R 6 , a hydrogen atom is preferably used from the viewpoint of excellent curability. The arrangement of R 6 may be any of the ortho, meta, and para positions with respect to the methylene group, and is preferably the ortho or para position from the viewpoint of excellent curability.
X is a compound represented by the following formula (2).
式（ＩＩ）で表されるカチオン重合開始剤２の具体例としては、例えば、下記式（ＩＩａ）で表される化合物が挙げられる。 Specific examples of the cationic polymerization initiator 2 represented by the formula (II) include a compound represented by the following formula (IIa).
カチオン重合開始剤２は、その製造について特に制限されない。例えば、従来公知の方法（例えば、日本公開特許公報第２００８−３０８５９６号の参考例３参照）に従って得ることができる。また、一部のカチオン重合開始剤２は市販品として入手できる。
カチオン重合開始剤２の配合量は、電子材料の接着剤の用途で用いる場合は、硬化物のガラス転移点を十分に高める観点から、全エポキシ基を有するモノマー又はポリマー１００重量部に対し、０．１〜１０重量部であるのが好ましく、０．１〜５重量部であるのがより好ましい。
カチオン重合開始剤１のカチオン重合開始剤２に対する配合比は、電子材料の接着剤の用途で用いる場合は、硬化性が十分に優れ、ガラス転移点の十分に高い硬化物を得る観点から、重量比で、０．１〜１０の範囲内の値とすることが好ましく、０．２〜５の範囲内の値とすることがより好ましい。The production of the cationic polymerization initiator 2 is not particularly limited. For example, it can be obtained according to a conventionally known method (for example, see Reference Example 3 in Japanese Patent Publication No. 2008-308596). Some cationic polymerization initiators 2 can be obtained as commercial products.
The amount of the cationic polymerization initiator 2 is 0 for 100 parts by weight of the monomer or polymer having all the epoxy groups from the viewpoint of sufficiently increasing the glass transition point of the cured product when used in the application of an adhesive for electronic materials. 0.1 to 10 parts by weight is preferable, and 0.1 to 5 parts by weight is more preferable.
The blending ratio of the cationic polymerization initiator 1 to the cationic polymerization initiator 2 is, when used in the application of an adhesive for electronic materials, from the viewpoint of obtaining a cured product having sufficiently high curability and a sufficiently high glass transition point. The ratio is preferably a value in the range of 0.1 to 10, more preferably a value in the range of 0.2 to 5.
本発明のエポキシ樹脂組成物は、硬化剤として、カチオン重合開始剤１、又はカチオン重合開始剤１及びカチオン重合開始剤２のほか、従来公知の他のカチオン重合開始剤をさらに含有してもよい。また、本発明のエポキシ樹脂組成物は、エポキシ樹脂、カチオン重合開始剤に加えて、発明の効果を損なわない範囲で、ルイス酸等の従来公知の硬化促進剤をさらに含有してもよい。 The epoxy resin composition of the present invention may further contain other conventionally known cationic polymerization initiators in addition to the cationic polymerization initiator 1 or the cationic polymerization initiator 1 and the cationic polymerization initiator 2 as a curing agent. . In addition to the epoxy resin and the cationic polymerization initiator, the epoxy resin composition of the present invention may further contain a conventionally known curing accelerator such as a Lewis acid as long as the effects of the invention are not impaired.
また、本発明のエポキシ樹脂組成物は、上述した各成分以外に、必要に応じて、さらに添加剤を含有することができる。添加剤としては、例えば、充填剤（フィラー）、シランカップリング剤、反応性希釈剤、可塑剤、チクソトロピー性付与剤、顔料、染料、老化防止剤、酸化防止剤、帯電防止剤、難燃剤、接着性付与剤、分散剤、溶剤が挙げられる。充填剤としては、シリカ、マイカ等が挙げられる。 Moreover, the epoxy resin composition of this invention can contain an additive further as needed other than each component mentioned above. Examples of additives include fillers (fillers), silane coupling agents, reactive diluents, plasticizers, thixotropic agents, pigments, dyes, anti-aging agents, antioxidants, antistatic agents, flame retardants, Adhesiveness imparting agents, dispersants, and solvents can be mentioned. Examples of the filler include silica and mica.
本発明の組成物は、その製造について特に制限されない。例えば、上述したエポキシ基を有するモノマー又はポリマー、カチオン重合開始剤および必要に応じて添加される硬化促進剤、添加剤の各成分を減圧下または窒素雰囲気下において、混合ミキサー等の撹拌装置を用いて充分混練し、均一に分散させることによって、１液型のエポキシ樹脂組成物を得ることができる。 The composition of the present invention is not particularly limited for its production. For example, the above-described monomer or polymer having an epoxy group, a cationic polymerization initiator and a curing accelerator added as necessary, and each component of the additive are used under a reduced pressure or in a nitrogen atmosphere using a stirring device such as a mixing mixer. By sufficiently kneading and uniformly dispersing, a one-pack type epoxy resin composition can be obtained.
本発明の組成物は、例えば、接着剤用、塗料用、土木建築用、電気用、輸送機用、医療用、包装用、繊維用、スポーツ・レジャー用として使用することができる。本発明の組成物は、硬化性に優れ生産性が向上し、優れた物性を有する高品質のものが得られる観点から、電子材料（例えば、金属の薄膜を加工して形成された回路パターンを基板上に有する各種表示デバイス）の表面に塗布して用いる接着剤用途に好ましく用いられる。その中でも、ACF（異方導電性フィルム）の組成物としてより好ましく用いられる。 The composition of the present invention can be used, for example, for adhesives, paints, civil engineering and construction, electricity, transportation equipment, medical use, packaging use, textile use, and sports / leisure use. The composition of the present invention has excellent curability, improved productivity, and a circuit pattern formed by processing an electronic material (for example, a metal thin film) from the viewpoint of obtaining a high quality product having excellent physical properties. It is preferably used for adhesives used by applying to the surface of various display devices on the substrate. Among these, it is more preferably used as a composition of ACF (anisotropic conductive film).
本発明の組成物を硬化させる際の温度は、硬化性により優れ、硬化物のガラス転移点がより高いという観点から、例えば、エポキシ基を有するポリマーとしてADEKA社製ビスフェノールＡ型エポキシ樹脂EP4100Eを用いた場合、１００〜２５０℃であるのが好ましく、１２０〜２００℃であるのがより好ましい。
本発明において、硬化性は、エポキシ樹脂組成物のゲル化時間（ゲルタイム）で評価され、具体的には、後述する安田式ゲルタイムテスターを使用する方法で測定される。本発明の組成物のゲル化時間は、例えば、エポキシ基を有するポリマーとしてADEKA社製ビスフェノールＡ型エポキシ樹脂EP4100Eを用いた場合、１５０℃で３０秒未満であり、好ましくは２０秒未満である。
また、本発明において、ガラス転移点は、具体的には、後述するように硬化物について貯蔵弾性率を測定することにより評価される。本発明の組成物を硬化させて得られる硬化物のガラス転移点は、例えば、エポキシ基を有するポリマーとしてADEKA社製ビスフェノールＡ型エポキシ樹脂EP4100Eを用いた場合、好ましくは８０℃を超え、より好ましくは１００℃を超える。The temperature at which the composition of the present invention is cured is superior in curability and has a higher glass transition point of the cured product. For example, ADEKA's bisphenol A type epoxy resin EP4100E is used as a polymer having an epoxy group. When it is, it is preferable that it is 100-250 degreeC, and it is more preferable that it is 120-200 degreeC.
In this invention, sclerosis | hardenability is evaluated by the gelation time (gel time) of an epoxy resin composition, and is specifically measured by the method of using the Yasuda-type gel time tester mentioned later. The gelation time of the composition of the present invention is, for example, less than 30 seconds at 150 ° C., preferably less than 20 seconds when bisphenol A type epoxy resin EP4100E manufactured by ADEKA is used as the polymer having an epoxy group.
Moreover, in this invention, a glass transition point is specifically evaluated by measuring a storage elastic modulus about hardened | cured material so that it may mention later. The glass transition point of the cured product obtained by curing the composition of the present invention preferably exceeds 80 ° C., more preferably, when ADEKA bisphenol A type epoxy resin EP4100E is used as the polymer having an epoxy group. Exceeds 100 ° C.
以下に、実施例を示して本発明を具体的に説明する。
（エポキシ樹脂組成物の製造）
実施例１〜８、比較例１〜４、参考例として、下記表１及び表２に示す各成分を、それぞれ同表に示す配合比で混合し、エポキシ樹脂組成物を製造した。表中の各成分の数値は、重量部で表す。Hereinafter, the present invention will be specifically described with reference to examples.
(Manufacture of epoxy resin composition)
As Examples 1 to 8, Comparative Examples 1 to 4, and Reference Examples, the components shown in Table 1 and Table 2 below were mixed at the blending ratios shown in the same table to produce epoxy resin compositions. The numerical value of each component in the table is expressed in parts by weight.
表１、表２に示す各成分の詳細は以下のとおりである。
・ エポキシ樹脂：ビスフェノールA型エポキシ樹脂（商品名EP4100E、ADEKA社製）
・ 硬化剤（１）：式（Ｉａ）で表されるカチオン重合開始剤
硬化剤（１）は次のようにして調製した。４−メチルチオフェノール４．５９ｇとシンナミルクロリド５ｇをメタノールとメチルシクロヘキサンの１：１混合溶媒中で室温で２４時間反応させ、クロライド中間体を得た。さらに、中間体９ｇとテトラキス（ペンタフルオロフェニル）ボレートのナトリウム塩水溶液（固形分１０％）２１５．８ｇを混合し、室温で２４時間反応させることで化合物を得た。１Ｈ−ＮＭＲ分析の結果、この化合物は硬化剤（１）であることが確認された。
・ 硬化剤（２）：式（ＩＩａ）で表されるカチオン重合開始剤
硬化剤（２）は次のようにして調製した。ベンジルクロライド１０ｇと４−メチルチオフェノール１１．０７ｇをメタノール中で室温で２４時間反応させ、クロライド中間体を得た。さらに中間体１０ｇとテトラキス（ペンタフルオロフェニル）ボレートのナトリウム塩水溶液（固形分１０％）２６３ｇを混合し、硬化剤（２）を得た。
・ 硬化剤（３）：下記式で表されるカチオン重合開始剤Details of each component shown in Tables 1 and 2 are as follows.
・ Epoxy resin: Bisphenol A type epoxy resin (trade name EP4100E, manufactured by ADEKA)
Curing agent (1): cationic polymerization initiator represented by formula (Ia) Curing agent (1) was prepared as follows. A chloride intermediate was obtained by reacting 4.59 g of 4-methylthiophenol and 5 g of cinnamilk chloride in a 1: 1 mixed solvent of methanol and methylcyclohexane at room temperature for 24 hours. Furthermore, 9g of intermediates and 215.8 g of tetrakis (pentafluorophenyl) borate sodium salt aqueous solution (solid content 10%) were mixed and reacted at room temperature for 24 hours to obtain a compound. As a result of 1 H-NMR analysis, this compound was confirmed to be a curing agent (1).
Curing agent (2): cationic polymerization initiator represented by formula (IIa) Curing agent (2) was prepared as follows. 10 g of benzyl chloride and 11.07 g of 4-methylthiophenol were reacted in methanol at room temperature for 24 hours to obtain a chloride intermediate. Further, 10 g of the intermediate and 263 g of tetrakis (pentafluorophenyl) borate sodium salt aqueous solution (solid content 10%) were mixed to obtain a curing agent (2).
Curing agent (3): cationic polymerization initiator represented by the following formula
・ 硬化剤（４）：下記式で表されるカチオン重合開始剤
・ 硬化剤（５）：下記式で表されるカチオン重合開始剤Curing agent (4): cationic polymerization initiator represented by the following formula
Curing agent (5): cationic polymerization initiator represented by the following formula
・ 硬化剤（６）：下記式で表されるカチオン重合開始剤 Curing agent (6): cationic polymerization initiator represented by the following formula
・ 硬化剤（７）：下記式で表されるカチオン重合開始剤
Curing agent (7): cationic polymerization initiator represented by the following formula
（評価）
得られた各エポキシ樹脂組成物について、それぞれ、下記の方法でゲルタイムおよび貯蔵弾性率を測定し、硬化性およびガラス転移点を評価した。結果を表１及び表２に示す。
（１）ゲルタイム
得られた各組成物について、安田式ゲルタイムテスター（株式会社安田精機製作所製、Ｎｏ．１５３ゲルタイムテスター）を用いて１５０℃でのゲルタイムを測定した。安田式ゲルタイムテスターは、オイルバス中、試料を入れた試験管の中でローターを回転させ、ゲル化が進み一定のトルクが掛かると磁気カップリング機構によりローターが落ちタイマーが止まる装置である。
（２）貯蔵弾性率
得られた各組成物について、１５０℃のオーブンにてそれぞれ1時間硬化させた。各硬化物について、動的粘弾性測定(Dynamic Mechanical Analysis)を歪み０．０１％、周波数１０Ｈｚ、昇温速度５℃／分の条件で、室温から２００℃までの温度領域において、強制伸長加振を行って貯蔵弾性率を測定した。そして、tanδのピーク値を各組成物のガラス転移点Tｇとした。(Evaluation)
About each obtained epoxy resin composition, the gel time and the storage elastic modulus were measured with the following method, respectively, and sclerosis | hardenability and a glass transition point were evaluated. The results are shown in Tables 1 and 2.
(1) Gel time About each obtained composition, the gel time in 150 degreeC was measured using the Yasuda-type gel time tester (The Yasuda Seiki Seisakusho make, No.153 gel time tester). The Yasuda-type gel time tester is a device that rotates a rotor in a test tube containing a sample in an oil bath, and when the gelation proceeds and a certain torque is applied, the rotor is dropped by a magnetic coupling mechanism and the timer is stopped.
(2) Storage elastic modulus Each of the obtained compositions was cured in an oven at 150 ° C for 1 hour. For each cured product, dynamic viscoelasticity measurement (Dynamic Mechanical Analysis) was performed at a strain of 0.01%, a frequency of 10 Hz, and a heating rate of 5 ° C./min in a temperature range from room temperature to 200 ° C. And the storage modulus was measured. The peak value of tan δ was defined as the glass transition point Tg of each composition.
表１及び表２に示す結果から明らかなように、硬化剤として、カチオン重合開始剤１を含有しないエポキシ樹脂組成物（比較例１〜４）は、ゲル化時間は３０秒以上であり、硬化性が悪かった。
このうち、硬化剤として、カチオン重合開始剤１を含有せず、カチオン重合開始剤２を含有するエポキシ樹脂組成物（比較例４）は、硬化物のガラス転移点は１００℃を超えていたが、ゲル化時間は３０秒以上であり、硬化性が悪かった。
なお、硬化剤として、カチオン重合開始剤１を含有せず、硬化剤（７）を含有するエポキシ樹脂組成物（参考例）は、ゲル化時間は３０秒未満であったが、硬化物のガラス転移点は８０℃以下であった。このため、参考例のエポキシ樹脂組成物は、電子材料の接着剤としての使用には適さないと考えられる。As is clear from the results shown in Tables 1 and 2, the epoxy resin compositions (Comparative Examples 1 to 4) that do not contain the cationic polymerization initiator 1 as the curing agent have a gel time of 30 seconds or more and are cured. The nature was bad.
Among these, the epoxy resin composition (Comparative Example 4) containing no cationic polymerization initiator 1 and no cationic polymerization initiator 2 as a curing agent had a glass transition point of the cured product exceeding 100 ° C. The gelation time was 30 seconds or more and the curability was poor.
In addition, the epoxy resin composition (reference example) which does not contain the cationic polymerization initiator 1 as a curing agent and contains the curing agent (7) had a gelation time of less than 30 seconds, but it was a cured glass. The transition point was 80 ° C. or lower. For this reason, it is thought that the epoxy resin composition of a reference example is not suitable for use as an adhesive for electronic materials.
これに対し、硬化剤として、カチオン重合開始剤１を含有するエポキシ樹脂組成物（実施例１〜８）は、ゲル化時間が３０秒未満であり、硬化性に優れていることが確認された。
このうち、硬化剤として、カチオン重合開始剤１及びカチオン重合開始剤２の両方を含有するエポキシ樹脂組成物（実施例４〜７）は、ゲル化時間が３０秒未満であり、硬化性に優れるとともに、硬化物のガラス転移点は１００℃を超えていた。このため、実施例４〜７のエポキシ樹脂組成物は、電子材料の接着剤としての使用に特に適していると考えられる。On the other hand, the epoxy resin composition (Examples 1 to 8) containing the cationic polymerization initiator 1 as a curing agent has a gelation time of less than 30 seconds and is confirmed to be excellent in curability. .
Among these, the epoxy resin compositions (Examples 4 to 7) containing both the cationic polymerization initiator 1 and the cationic polymerization initiator 2 as curing agents have a gelation time of less than 30 seconds and are excellent in curability. At the same time, the glass transition point of the cured product exceeded 100 ° C. For this reason, it is thought that the epoxy resin composition of Examples 4-7 is especially suitable for the use as an adhesive agent of an electronic material.
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| JP2015108060A (en) * | 2013-12-04 | 2015-06-11 | 旭化成イーマテリアルズ株式会社 | Film-like connecting material, connected structure production method and connected structure |
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| JP6247875B2 (en) * | 2013-09-25 | 2017-12-13 | 旭化成株式会社 | Sulphonium salt cation generator and cation polymerizable composition containing the same |
| CN104558344B (en) * | 2013-10-18 | 2017-02-15 | 中国石油化工股份有限公司 | Cationic polymerization initiator system, application thereof and cationic polymerization method |
| KR101712703B1 (en) * | 2014-07-18 | 2017-03-06 | 삼성에스디아이 주식회사 | Adhesive composition, anisotropic conductive film and the semiconductor device using thereof |
| JP6434748B2 (en) * | 2014-08-29 | 2018-12-05 | 積水化学工業株式会社 | Sealant for organic electroluminescence display element |
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| KR102459581B1 (en) | 2017-01-10 | 2022-10-27 | 스미토모 세이카 가부시키가이샤 | epoxy resin composition |
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