KR20170115580A - Cationic polymerization initiator and epoxy resin composition - Google Patents
Cationic polymerization initiator and epoxy resin composition Download PDFInfo
- Publication number
- KR20170115580A KR20170115580A KR1020177024911A KR20177024911A KR20170115580A KR 20170115580 A KR20170115580 A KR 20170115580A KR 1020177024911 A KR1020177024911 A KR 1020177024911A KR 20177024911 A KR20177024911 A KR 20177024911A KR 20170115580 A KR20170115580 A KR 20170115580A
- Authority
- KR
- South Korea
- Prior art keywords
- group
- epoxy resin
- polymerization initiator
- cationic polymerization
- resin composition
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 56
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 56
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 238000010538 cationic polymerization reaction Methods 0.000 title claims abstract description 41
- 239000003505 polymerization initiator Substances 0.000 title claims abstract description 41
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 26
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 125000001424 substituent group Chemical group 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 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 19
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 14
- 239000003795 chemical substances by application Substances 0.000 description 35
- -1 benzyl cation Chemical class 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 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 14
- 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 14
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 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 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- 159000000000 sodium salts Chemical class 0.000 description 9
- 150000001450 anions Chemical class 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 7
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229910018286 SbF 6 Inorganic materials 0.000 description 5
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
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- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000000732 arylene group Chemical group 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 4
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- VKALYYFVKBXHTF-UHFFFAOYSA-N 4-(methylsulfanyl)-m-cresol Chemical compound CSC1=CC=C(O)C=C1C VKALYYFVKBXHTF-UHFFFAOYSA-N 0.000 description 3
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
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- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 2
- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical compound ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PSBPNWBGNOWCCU-UHFFFAOYSA-N OB(O)O.S.S.S Chemical compound OB(O)O.S.S.S PSBPNWBGNOWCCU-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000003963 antioxidant agent Substances 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
- 125000002091 cationic group Chemical group 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 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
- 238000006116 polymerization reaction Methods 0.000 description 2
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- 125000006017 1-propenyl group Chemical group 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
- RRMRAKTZIFIDNB-UHFFFAOYSA-N 2,3-dimethyl-4,4-bis(methylsulfanyl)cyclohexa-1,5-dien-1-ol Chemical compound CSC1(C(C(=C(C=C1)O)C)C)SC RRMRAKTZIFIDNB-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
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- 239000002184 metal Substances 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 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
- 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
- 238000002360 preparation method Methods 0.000 description 1
- 125000006410 propenylene group Chemical group 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 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
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
본 발명은, 에폭시 수지 조성물의 뛰어난 경화성과 저장 안정성을 양립할 수 있는 양이온 중합 개시제, 및, 그것을 함유하는 에폭시 수지 조성물을 제공하는 것을 과제로 한다. 본 발명의 양이온 중합 개시제는, 하기 일반식 (1)로 나타내지는 것을 특징으로 한다. (일반식 (1)에 있어서, R1은, 수산기, R5O기, R5COO기, R5NHCOO기 또는 R5OCOO기이고, R2, R3 및 R4는, 각각 독립하여, 수소 원자 또는 탄소수 1 ~ 6의 알킬기이다. R5는, 치환기를 가지고 있어도 무방한, 방향족 탄화수소기 또는 지방족 탄화수소기이다.)
Description
본 발명은, 양이온 중합 개시제 및 그것을 포함하는 에폭시 수지 조성물에 관한 것이다.The present invention relates to a cationic polymerization initiator and an epoxy resin composition containing the same.
에폭시 수지는, 뛰어난 기계 특성, 열 특성을 가지기 때문에 여러 분야에서 널리 이용되고 있고, 예를 들어, 수지 특유의 절연성이나 열 경화성으로부터, 전자 부품용의 접착제로서 이용되고 있다. 이와 같은 접착제로서 사용되는 에폭시 수지 조성물은, 통상, 에폭시 수지와 잠재성 경화제를 포함하며, 사용될 때까지는, 열 경화성의 에폭시 수지와 잠재성 경화제가 미반응 상태로 안정되게 존재하고, 사용될 때에는, 취급성에 뛰어나고 또한 단시간에 경화되는 것이 요구된다. BACKGROUND ART Epoxy resins are widely used in various fields because they have excellent mechanical properties and thermal properties. For example, they are used as adhesives for electronic parts because of their insulating properties and thermal curability specific to resins. The epoxy resin composition used as such an adhesive generally contains an epoxy resin and a latent curing agent. Until used, the thermosetting epoxy resin and the latent curing agent stably exist in an unreacted state, and when used, It is required to be cured in a short time.
그렇지만, 일반적으로, 저장 안정성에 뛰어난 에폭시 수지 조성물은, 경화성이 낮고, 경화에 고온 처리 또는 장시간 처리가 필요한 경향이 있다. 한편, 경화성이 높은 에폭시 수지 조성물은, 저장 안정성에 떨어지는 경향이 있다. 에폭시 수지 조성물의 경화성과 저장 안정성은, 조성물 중에 배합되는 잠재 경화제의 성질에 크게 영향을 받는 것이 밝혀져 있다.However, in general, an epoxy resin composition excellent in storage stability has a low curability and tends to require a high temperature treatment or a long time treatment for curing. On the other hand, an epoxy resin composition having high curability tends to be inferior in storage stability. It has been found that the curability and the storage stability of the epoxy resin composition are greatly affected by the properties of the latent curing agent incorporated in the composition.
이 에폭시 수지의 잠재성 경화제로서는, 예를 들어, p-하이드록시페닐-벤질-메틸술포늄 테트라키스(펜타플루오로페닐)보레이트 등의 술포늄 보레이트 착체가 알려져 있다(특허 문헌 1 참조).As a latent curing agent for this epoxy resin, for example, a sulfonium borate complex such as p-hydroxyphenyl-benzyl-methylsulfonium tetrakis (pentafluorophenyl) borate is known (see Patent Document 1).
그러나, 요즈음 전자 부품의 수요의 증가에 따라, 보다 뛰어난 경화성을 가지면서, 저장 안정성도 양립할 수 있는 신규 에폭시 수지 조성물, 및 그것을 가능하게 하는 신규 양이온 중합 개시제가 끊임없이 기대되고 있는 것이 현상(現狀)이다.However, with the recent increase in the demand for electronic components, new epoxy resin compositions capable of achieving both excellent curability and storage stability, and a novel cationic polymerization initiator capable of making such a composition, to be.
그래서, 본 발명은, 에폭시 수지 조성물의 뛰어난 경화성과 저장 안정성을 양립할 수 있는 양이온 중합 개시제, 및, 그것을 함유하는 에폭시 수지 조성물을 제공하는 것을 과제로 한다.Therefore, it is an object of the present invention to provide a cationic polymerization initiator and an epoxy resin composition containing the cationic polymerization initiator which can both achieve excellent curing property and storage stability of the epoxy resin composition.
본 발명자는, 술포늄 잔기에 특정의 치환기를 도입하고, 또한, 상대 음이온을 테트라키스(펜타플루오로페닐)보레이트로 하는 신규 술포늄 보레이트 착체에 의하면, 상기 과제를 해결할 수 있는 것을 찾아내어, 본 발명을 완성시키기에 이르렀다. The present inventors have found that a novel sulfonium borate complex having a specific substituent group introduced into a sulfonium moiety and having a counter anion as a tetrakis (pentafluorophenyl) borate can solve the above problems, Thereby completing the invention.
즉, 본 발명은 이하와 같다.That is, the present invention is as follows.
[1] 하기 일반식 (1)로 나타내지는 양이온 중합 개시제. [1] A cationic polymerization initiator represented by the following general formula (1).
(일반식 (1)에 있어서, R1은, 수산기, R5O기, R5COO기, R5NHCOO기 또는 R5OCOO기이고, R2, R3 및 R4는, 각각 독립하여, 수소 원자 또는 탄소수 1 ~ 6의 알킬기이다. R5는, 치환기를 가지고 있어도 무방한, 방향족 탄화수소기 또는 지방족 탄화수소기이다.)(In the formula (1), R 1 is hydroxy, R 5 O groups, R 5 COO group, R 5 NHCOO group or R 5 OCOO group and, R 2, R 3 and R 4 are, each independently, A hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 5 is an aromatic hydrocarbon group or aliphatic hydrocarbon group which may have a substituent.
[2] 상기 [1]에 기재된 양이온 중합 개시제와, 에폭시기를 가지는 화합물을 함유하는 에폭시 수지 조성물. [2] An epoxy resin composition comprising the cationic polymerization initiator according to [1] and a compound having an epoxy group.
[3] 상기 [2]에 있어서, 상기 양이온 중합 개시제의 함유량이, 상기 에폭시기를 가지는 화합물 100질량부에 대하여, 0.1 ~ 10질량부인, 에폭시 수지 조성물.[3] The epoxy resin composition according to [2], wherein the content of the cationic polymerization initiator is 0.1 to 10 parts by mass relative to 100 parts by mass of the compound having an epoxy group.
본 발명에 의하면, 에폭시 수지 조성물의 뛰어난 경화성과 저장 안정성을 양립할 수 있는 양이온 중합 개시제, 및, 그것을 함유하는 에폭시 수지 조성물을 제공할 수 있다.According to the present invention, it is possible to provide a cationic polymerization initiator and an epoxy resin composition containing the cationic polymerization initiator that can both achieve excellent curability and storage stability of the epoxy resin composition.
［양이온 중합 개시제］[Cation polymerization initiator]
본 발명의 양이온 중합 개시제는, 하기 일반식 (1)로 나타내지는 화합물이다.The cationic polymerization initiator of the present invention is a compound represented by the following general formula (1).
(일반식 (1)에 있어서, R1은, 수산기, R5O기, R5COO기, R5NHCOO기 또는 R5OCOO기이고, R2, R3 및 R4는, 각각 독립하여, 수소 원자 또는 탄소수 1 ~ 6의 알킬기이다. R5는, 치환기를 가지고 있어도 무방한, 방향족 탄화수소기 또는 지방족 탄화수소기이다.)(In the formula (1), R 1 is hydroxy, R 5 O groups, R 5 COO group, R 5 NHCOO group or R 5 OCOO group and, R 2, R 3 and R 4 are, each independently, A hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 5 is an aromatic hydrocarbon group or aliphatic hydrocarbon group which may have a substituent.
이와 같은 양이온 중합 개시제를 이용하는 것에 의하여, 에폭시 수지 조성물의 뛰어난 경화성과 저장 안정성을 양립할 수 있다. By using such a cationic polymerization initiator, excellent curability and storage stability of the epoxy resin composition can be achieved.
이것은, 상세하게는 분명하지 않지만, 본 발명자는 이하와 같이 추측하고 있다. This is not clear in detail, but the present inventors have assumed the following.
즉, 술포늄 잔기에 있어서, 유황 원자에 결합하는 벤질기의 벤젠 고리에 전자 공여기인 비닐을 도입한 것에 의하여, 중합 시에 발생하는 벤질 양이온을 공명 안정화시켜, 개시제 활성을 향상시킬 수 있고, 한편으로, 이 전자 공여기인 비닐기는 고리를 형성하고 있지 않기 때문에 입체 장해를 받기 힘들고, 상대 음이온인 테트라키스(펜타플루오로페닐)보레이트가 술포늄 이온 및 발생한 벤질 양이온에 접근하기 쉽게 하고 있기 때문에, 저장 시에는 S-C 간의 결합이 안정되어 있어, 열 등의 외부 환경에 의한 영향을 받기 어렵다고 생각된다. That is, by introducing vinyl which is an electron donor into a benzene ring of a benzyl group bonded to a sulfur atom in the sulfonium moiety, the benzyl cation generated at the time of polymerization can be resonated to stabilize the initiator activity, On the other hand, since this electron-excited vinyl group does not form a ring, it is difficult to obtain steric hindrance, and tetraquis (pentafluorophenyl) borate, which is a counter anion, is easily accessible to the sulfonium ion and the resulting benzyl cation , It is believed that the bond between the SCs is stable during storage and is less susceptible to external influences such as heat.
또한, 상기 양이온 개시제에 있어서는, 상대 음이온이 테트라키스(펜타플루오로페닐)보레이트이며, 전자 흡인기인 불소 원자의 영향에 의하여 붕소의 구핵성(求核性)이 현저하게 낮은 상태이고, 술포늄 양이온의 양이온성이 매우 높은 상태인 것으로부터, SbF6-나 BF4- 등과 비교하면 경화성에 뛰어나다.In the cationic initiator, the counter anion is tetrakis (pentafluorophenyl) borate, the nucleophilic property of boron is remarkably low due to the influence of fluorine atom which is an electron attracting group, and the sulfonium cation Is superior in curability as compared with SbF 6 -, BF 4 - and the like.
일반식 (1)에 있어서, R1은, 수산기, R5O기, R5COO기, R5NHCOO기 또는 R5OCOO기이고, R5는, 치환기를 가지고 있어도 무방한, 방향족 탄화수소기 또는 지방족 탄화수소기이다.In the formula (1), R 1 is hydroxy, R 5 O groups, R 5 COO group, R is a 5 NHCOO group or R 5 OCOO group, R 5 is a mubang may have a substituent, an aromatic hydrocarbon group, or Aliphatic hydrocarbon group.
방향족 탄화수소기로서는, 예를 들어, 아릴기, 아랄킬기, 아릴렌기를 들 수 있다. Examples of the aromatic hydrocarbon group include an aryl group, an aralkyl group and an arylene group.
아릴기로서는, 예를 들어, 탄소수 6 ~ 14(바람직하게는 탄소수 6 ~ 10)의 것을 들 수 있고, 구체적으로는, 페닐기, 나프틸기, 안트릴기, 페난트릴기, 비페닐기 등을 들 수 있다. 그 중에서도, 페닐기가 바람직하다. The aryl group includes, for example, those having 6 to 14 carbon atoms (preferably 6 to 10 carbon atoms), and specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, have. Among them, a phenyl group is preferable.
아랄킬기로서는, 예를 들어, 탄소수 7 ~ 13(바람직하게는 탄소수 7 ~ 11)의 것을 들 수 있고, 구체적으로는, 벤질기, 페네틸기, 페닐프로필기 등을 들 수 있다. 그 중에서도, 벤질기가 바람직하다. Examples of the aralkyl group include those having 7 to 13 carbon atoms (preferably 7 to 11 carbon atoms), and specific examples thereof include a benzyl group, a phenethyl group, and a phenylpropyl group. Among them, a benzyl group is preferable.
아릴렌기로서는, 예를 들어, 탄소수 6 ~ 14(바람직하게는 탄소수 6 ~ 10)의 것을 들 수 있고, 구체적으로는, 페닐렌기, 나프틸렌기, 안트릴렌기, 페난트릴렌기, 비페닐렌기를 들 수 있다. 그 중에서도, 페닐렌기가 바람직하다. 아릴렌기는, 아릴기, 아랄킬기 등의 1가의 기와 결합하는 것으로 R5를 구성한다.Examples of the arylene group include those having 6 to 14 carbon atoms (preferably 6 to 10 carbon atoms), and specific examples thereof include a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, . Among them, a phenylene group is preferable. The arylene group is bonded to a monovalent group such as an aryl group or an aralkyl group to constitute R 5 .
방향족 탄화수소기는, 한층 더 임의의 탄소 원자의 위치에, 예를 들어, 탄소수 1 ~ 4의 저급 알킬기, 하이드록실기, 아미노기, 니트로기, 할로겐 원자 등의 1 이상의 치환기를 가져도 무방하다. The aromatic hydrocarbon group may further have at least one substituent at a position of any carbon atom, for example, a lower alkyl group having 1 to 4 carbon atoms, a hydroxyl group, an amino group, a nitro group, a halogen atom and the like.
치환기를 가지는 방향족 탄화수소기로서는, 예를 들어, 톨릴기, 크실릴기, 페녹시기 등의, 치환기를 가지는 아릴기; 메틸벤질기, 에틸벤질기, 메틸페네틸기 등의, 치환기를 가지는 아랄킬기; 메틸페닐렌기, 디메틸페닐렌기, 메틸나프틸렌기 등의, 치환기를 가지는 아릴렌기를 들 수 있다. 그 중에서도, 페녹시기가 바람직하다.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; An aralkyl group having a substituent, such as a methylbenzyl group, an ethylbenzyl group or a methylphenethyl group; And an arylene group having a substituent, such as a methylphenylene group, a dimethylphenylene group and a methylnaphthylene group. Among them, a phenoxy group is preferable.
지방족 탄화수소기로서는, 예를 들어, 알킬기, 시클로알킬기, 알케닐기, 알케닐렌기, 알콕시기를 들 수 있다. The aliphatic hydrocarbon group includes, for example, an alkyl group, a cycloalkyl group, an alkenyl group, an alkenylene group, and an alkoxy group.
알킬기로서는, 예를 들어, 탄소수 1 ~ 18(바람직하게는 탄소수 1 ~ 6)의 직쇄(直鎖) 또는 분지상(分岐狀)의 것을 들 수 있고, 구체적으로는, 메틸기, 에틸기, n-프로필기, 이소프로필기, n-부틸기, 이소부틸기, sec-부틸기, tert-부틸기를 들 수 있다. 그 중에서도, 메틸기가 바람직하다. Examples of the alkyl group include straight chain (straight chain) or branched (branched) ones having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), and specific examples thereof include a methyl group, An isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among them, a methyl group is preferable.
시클로알킬기로서는, 예를 들어, 탄소수 3 ~ 10(바람직하게는 탄소수 3 ~ 6)의 것을 들 수 있고, 구체적으로는, 시클로프로필기, 시클로부틸기, 시클로펜틸기, 시클로헥실기를 들 수 있다. Examples of the cycloalkyl group include those having 3 to 10 carbon atoms (preferably 3 to 6 carbon atoms), and specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group .
알케닐기로서는, 예를 들어, 탄소수 2 ~ 18(바람직하게는 탄소수 2 ~ 6)의 직쇄 또는 분지상의 것을 들 수 있고, 구체적으로는, 비닐기, 1-프로페닐기, 알릴기, 이소프로페닐기, 1-부테닐기, 2-부테닐기, 아크릴로일기를 들 수 있다. Examples of the alkenyl group include straight chain or branched alkyl groups having 2 to 18 carbon atoms (preferably 2 to 6 carbon atoms), and specific examples thereof include a vinyl group, 1-propenyl group, allyl group, isopropenyl group , A 1-butenyl group, a 2-butenyl group, and an acryloyl group.
알케닐렌기로서는, 예를 들어, 탄소수 2 ~ 18(바람직하게는 탄소수 2 ~ 6)의 직쇄 또는 분지상의 것을 들 수 있고, 구체적으로는, 비닐렌기, 프로페닐렌기, 부타디에닐렌기를 들 수 있다. 알케닐렌기는, 알킬기, 시클로알킬기 등의 1가의 기와 결합하는 것으로 R5를 구성한다. The alkenylene group is, for example, a straight chain or branched chain having 2 to 18 carbon atoms (preferably 2 to 6 carbon atoms), and specific examples thereof include a vinylene group, a propenylene group and a butadienylene group. have. The alkenylene group is bonded to a monovalent group such as an alkyl group or a cycloalkyl group to constitute R 5 .
알콕시기로서는, 예를 들어, 탄소수 1 ~ 18(바람직하게는 탄소수 1 ~ 6)의 직쇄 또는 분지상의 것을 들 수 있고, 구체적으로는, 메톡시기, 에톡시기, n-프로폭시기, 이소프로폭시기, n-부톡시기, sec-부톡시기, tert-부톡시기를 들 수 있다. 그 중에서도, 메톡시기가 바람직하다.The alkoxy group is, for example, a straight chain or branched chain having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), and specific examples thereof include a methoxy group, ethoxy group, n-propoxy group, A n-butoxy group, a sec-butoxy group, and a tert-butoxy group. Among them, a methoxy group is preferable.
R5O기에 있어서는, 바람직한 R5로서, 메틸기, 메톡시기, 페닐기, 페녹시기를 들 수 있고, 그 중에서도, 메틸기가 보다 바람직하다. In the R 5 O group, preferable R 5 is a methyl group, a methoxy group, a phenyl group, or a phenoxy group, and among these, a methyl group is more preferable.
R5COO기에 있어서는, 바람직한 R5로서, 메틸기, 벤질기, 페닐기를 들 수 있고, 그 중에서도, 메틸기가 보다 바람직하다. In the R 5 COO group, preferable R 5 is a methyl group, a benzyl group or a phenyl group, and among these, a methyl group is more preferable.
R5NHCOO기에 있어서는, 바람직한 R5로서, 메틸기, 메톡시기, 페닐기, 페녹시기, 페닐렌기를 들 수 있고, 그 중에서도, 페닐기가 보다 바람직하다. In R 5 NHCOO group, preferable R 5 is a methyl group, a methoxy group, a phenyl group, a phenoxy group or a phenylene group, and more preferably a phenyl group.
R5OCOO기에 있어서는, 바람직한 R5로서, 메틸기, 페닐기, 페닐렌기를 들 수 있고, 그 중에서도, 페닐기가 보다 바람직하다.In the R 5 OCOO group, preferable R 5 is a methyl group, a phenyl group, or a phenylene group. Among them, a phenyl group is more preferable.
R5O기, R5COO기, R5NHCOO기 및 R5OCOO기 가운데, 그 중에서도, R5COO기, R5NHCOO기 및 R5OCOO기가 보다 바람직하다. 이러한 기는, 전자 흡인성기를 가지는 것으로부터 전자 흡인성이 높기 때문이다. 이것에 의하여, 술포늄 이온의 양이온성이 보다 향상하여, 경화성에 보다 뛰어나다. 특히, 전자 흡인성기의 전자 흡인성이 높은 것일수록 경화성에 보다 뛰어나다.R 5 O groups, R 5 COO group, R 5 and R 5 NHCOO group OCOO group of, inter alia, R 5 COO group, R 5 is more preferably a NHCOO group, and R 5 OCOO. This group is because it has an electron attractive group because it has an electron attractive group. As a result, the cationic property of the sulfonium ion is further improved, and the curing property is further improved. Particularly, the electron attracting property of the electron attractive group is more excellent in the curability.
R1로서는, 경화성에 보다 뛰어나다고 하는 관점으로부터, 수산기, R5COO기, R5NHCOO기, 또는, R5OCOO기가 바람직하고, 수산기가 보다 바람직하다. Examples of R 1, from the viewpoint of more excellent in high curability, a hydroxyl group, R 5 COO group, a NHCOO group R 5, or, R 5 OCOO groups are preferred, and more preferably a hydroxyl group.
R1의 배치는, 술포늄 이온에 대하여, 오르토 위치, 메타 위치, 파라 위치 중 어느 하나여도 무방하고, 경화성에 보다 뛰어나다고 하는 관점으로부터, 파라 위치인 것이 바람직하다.The arrangement of R < 1 > may be any one of ortho, meta, and para positions with respect to the sulfonium ion, and is preferably para-substituted from the viewpoint of better curability.
일반식 (1)에 있어서, R2 및 R3은, 각각 독립하여, 수소 원자 또는 탄소수 1 ~ 6의 알킬기이고, 바람직하게는 수소 원자 또는 탄소수 1 ~ 3의 알킬기이다. 알킬기로서는, 예를 들어, 메틸기, 에틸기, n-프로필기, 이소프로필기, n-부틸기, 이소부틸기, sec-부틸기, tert-부틸기를 들 수 있다. 그 중에서도, 수소 원자 또는 메틸기가 바람직하다.In the general formula (1), R 2 and R 3 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. Among them, a hydrogen atom or a methyl group is preferable.
일반식 (1)에 있어서, R4는, 수소 원자 또는 탄소수 1 ~ 6의 알킬기이고, 바람직하게는 수소 원자 또는 탄소수 1 ~ 3의 알킬기이다. 알킬기로서는, 예를 들어, 메틸기, 에틸기, n-프로필기, 이소프로필기, n-부틸기, 이소부틸기, sec-부틸기, tert-부틸기를 들 수 있다. 그 중에서도, 메틸기가 바람직하다.In the general formula (1), R 4 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. Among them, a methyl group is preferable.
일반식 (1)에 있어서, 술포늄 잔기의 벤질기에 결합하는 비닐기는, 벤질 위치에 대하여, 오르토 위치, 메타 위치, 파라 위치 중 어느 하나여도 무방하고, 경화성에 보다 뛰어나다고 하는 관점으로부터, 파라 위치인 것이 바람직하다.In the general formula (1), the vinyl group bonded to the benzyl group of the sulfonium moiety may be any one of ortho, meta, and para positions relative to the benzyl position, and from the standpoint of more excellent in curability, .
일반식 (1)로 나타내지는 양이온 중합 개시제는, 단독으로 또는 2종 이상을 조합하여 이용할 수 있다.The cationic polymerization initiators represented by the general formula (1) may be used alone or in combination of two or more.
일반식 (1)로 나타내지는 양이온 중합 개시제는, 그 제조 방법에 관하여 특별히 제한되지 않는다. 예를 들어, 하기 일반식 (2)로 나타내지는 화합물과 할로겐화 메틸스티렌을 반응시켜 할라이드 중간체를 얻은 후, 이 할라이드 중간체와 테트라키스(펜타플루오로페닐)보레이트의 나트륨염 수용액을 혼합하여, 반응시키는 것으로 얻을 수 있다.The cationic polymerization initiator represented by the general formula (1) is not particularly limited in terms of its production process. For example, a halide intermediate is obtained by reacting a compound represented by the following general formula (2) with halogenated methylstyrene, and then an aqueous sodium salt solution of the halide intermediate and tetrakis (pentafluorophenyl) borate is mixed and reacted .
(일반식 (2) 중의 R1, R2, R3 및 R4의 정의는, 일반식 (1) 중에 있어서의 R1, R2, R3 및 R4의 정의와 같다.)(Same as formula (2) in R 1, R 2, R 3 and R 4 are defined in the general formula (1) R 1, R 2, definition of the R 3 and R 4 in the.)
일반식 (2)로 나타내지는 화합물로서는, 예를 들어, 4-(메틸티오)페놀, 4-(메틸티오)-m-크레졸, 4-(메틸티오)-2-메틸페놀, 2,6-디메틸-4-(메틸티오)페놀, 3,5-디메틸-4-(메틸티오)페놀, 3-에틸-4-(메틸티오)페놀 등을 들 수 있다.Examples of the compound represented by the general formula (2) include 4- (methylthio) phenol, 4- (methylthio) -m-cresol, 4- (methylthio) Dimethyl-4- (methylthio) phenol, 3,5-dimethyl-4- (methylthio) phenol and 3-ethyl-4- (methylthio) phenol.
또한, 할로겐화 메틸스티렌으로서는, 예를 들어, 4-(클로로메틸)스티렌, 3-(클로로메틸)스티렌, 2-(클로로메틸)스티렌, 4-(브로모메틸)스티렌 등을 들 수 있다.Examples of halogenated methylstyrene include 4- (chloromethyl) styrene, 3- (chloromethyl) styrene, 2- (chloromethyl) styrene and 4- (bromomethyl) styrene.
［에폭시 수지 조성물］[Epoxy resin composition]
본 발명의 에폭시 수지 조성물은, 상술한 일반식 (1)로 나타내지는 양이온 중합 개시제와, 후술하는 에폭시기를 가지는 화합물을 함유하는 수지 조성물이다. The epoxy resin composition of the present invention is a resin composition containing a cationic polymerization initiator represented by the above-mentioned general formula (1) and a compound having an epoxy group described later.
＜에폭시기를 가지는 화합물＞≪ Compound having an epoxy group >
에폭시기를 가지는 화합물로서는, 에폭시기를 가지는 모노머 또는 폴리머 중 어느 하나여도 무방하다.As the compound having an epoxy group, any one of monomers or polymers having an epoxy group may be used.
(에폭시기를 가지는 모노머) (A monomer having an epoxy group)
에폭시기를 가지는 모노머로서는, 특별히 한정되지 않고, 예를 들어, 단관능 글리시딜에테르류, 다관능 지방족 글리시딜에테르류, 다관능 방향족 글리시딜에테르류, 글리시딜에스테르류, 지환식 에폭시 화합물 등을 들 수 있다.Examples of the monomer having an epoxy group include, but are not limited to, monofunctional glycidyl ethers, polyfunctional aliphatic glycidyl ethers, polyfunctional aromatic glycidyl ethers, glycidyl esters, alicyclic epoxy Compounds and the like.
단관능 글리시딜에테르류로서는, 예를 들어, 알릴글리시딜에테르, 부틸글리시딜에테르, 페닐글리시딜에테르, 2-에틸헥실글리시딜에테르, sec-부틸페닐글리시딜에테르, tert-부틸페닐글리시딜에테르, 2-메틸옥틸글리시딜에테르 등을 들 수 있다.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, 2-methyloctyl glycidyl ether, and the like.
다관능 지방족 글리시딜에테르류로서는, 예를 들어, 1,6-헥산디올 글리시딜에테르, 트리메틸올프로판 트리글리시딜에테르, 네오펜틸글리콜 디글리시딜에테르, 글리세롤 디글리시딜에테르, 글리세롤 트리글리시딜에테르, 에틸렌글리콜 디글리시딜에테르, 폴리에틸렌글리콜 디글리시딜에테르, 폴리프로필렌글리콜 디글리시딜에테르 등을 들 수 있다.Examples of polyfunctional aliphatic glycidyl ethers include 1,6-hexanediol glycidyl ether, trimethylol propane triglycidyl ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl ether, glycerol Triglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and the like.
다관능 방향족 글리시딜에테르류로서는, 예를 들어, 비스페놀 A 글리시딜에테르, 비스페놀 F 글리시딜에테르, 브롬화 비스페놀 A 글리시딜에테르, 비페놀 글리시딜에테르, 테트라메틸비페놀 글리시딜에테르, 레조르신 글리시딜에테르, 하이드로퀴논 글리시딜에테르, 디하이드록시나프탈렌 글리시딜에테르, 비스페놀 노볼락 수지 글리시딜에테르, 페놀 노볼락 수지 글리시딜에테르, 크레졸 노볼락 수지 글리시딜에테르, 디시클로펜타디엔 페놀 수지 글리시딜에테르, 테르펜 페놀 수지 글리시딜에테르, 나프톨 노볼락 수지 글리시딜에테르 등을 들 수 있다.Examples of the polyfunctional aromatic glycidyl ethers include bisphenol A glycidyl ether, bisphenol F glycidyl ether, brominated bisphenol A glycidyl ether, biphenol glycidyl ether, tetramethylbiphenol glycidyl Ether, resorcin glycidyl ether, hydroquinone glycidyl ether, dihydroxynaphthalene glycidyl ether, bisphenol novolak resin glycidyl ether, phenol novolak resin glycidyl ether, cresol novolak resin glycidyl Ether, dicyclopentadiene phenol resin glycidyl ether, terpene phenol resin glycidyl ether, naphthol novolak resin glycidyl ether, and the like.
글리시딜에스테르류로서는, 예를 들어, 글리시딜아크릴레이트, 글리시딜메타크릴레이트, 디글리시딜프탈레이트, 디글리시딜헥사하이드로프탈레이트, 디글리시딜테트라하이드로프탈레이트, 디메틸디글리시딜헥사하이드로프탈레이트 등을 들 수 있다.The glycidyl esters include, for example, glycidyl acrylate, glycidyl methacrylate, diglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, dimethyl diglycidyl Dicyclohexyl phthalate and dicyclohexyl phthalate.
지환식 에폭시 화합물로서는, 예를 들어, 3,4-에폭시시클로헥실메틸-3,4-에폭시시클로헥산 카르복실레이트, 3,4-에폭시시클로헥실에틸-3,4-에폭시시클로헥산 카르복실레이트, 비닐시클로헥센 디옥사이드, 알릴시클로헥센 디옥사이드, 3,4-에폭시-4-메틸시클로헥실-2-프로필렌 옥사이드, 2-(3,4-에폭시시클로헥실-5,5-스피로-3,4-에폭시)시클로헥산-m-디옥산, 비스(3,4-에폭시시클로헥실)아디페이트, 비스(3,4-에폭시시클로헥실메틸)아디페이트, 비스(3,4-에폭시시클로헥실)에테르, 비스(3,4-에폭시시클로헥실메틸)에테르, 비스(3,4-에폭시시클로헥실)디에틸실록산 등을 들 수 있다.Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, Vinylcyclohexene dioxide, allylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxycyclohexyl-5,5- spiro- Epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexyl) adipate, bis , 4-epoxycyclohexylmethyl) ether, and bis (3,4-epoxycyclohexyl) diethylsiloxane.
에폭시기를 가지는 모노머는, 단독으로 또는 2종 이상을 혼합하여 이용할 수 있다.The monomers having an epoxy group may be used alone or in combination of two or more.
(에폭시기를 가지는 폴리머) (A polymer having an epoxy group)
에폭시기를 가지는 폴리머로서는, 에폭시기를 2개 이상 가지는 것이면 특별히 제한되지 않는다. 예를 들어, 비스페놀 A형 에폭시 수지, 디시클로펜타디엔형 에폭시 수지, 디아미노디페닐메탄형 에폭시 수지, 아미노 페놀형 에폭시 수지, 나프탈렌형 에폭시 수지, 페놀 노볼락형 에폭시 수지, 비페닐형 에폭시 수지, 수첨(水添) 비페놀형 에폭시 수지, 지환식 에폭시 수지를 들 수 있다. The polymer having an epoxy group is not particularly limited as long as it has two or more epoxy groups. Examples of the epoxy resin include bisphenol A type epoxy resin, dicyclopentadiene type epoxy resin, diaminodiphenylmethane type epoxy resin, aminophenol type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, biphenyl type epoxy resin , Hydrogenated biphenol type epoxy resin, and alicyclic epoxy resin.
에폭시기를 가지는 폴리머는 각각 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.Each of the polymers having an epoxy group may be used alone or in combination of two or more.
＜양이온 중합 개시제의 함유량＞<Content of Cationic Polymerization Initiator>
에폭시 수지 조성물 중, 일반식 (1)로 나타내지는 양이온 중합 개시제의 함유량은, 경화성이 보다 양호하게 되는 관점으로부터, 에폭시기를 가지는 화합물 100질량부에 대하여, 0.1 ~ 10질량부인 것이 바람직하고, 0.1 ~ 5질량부인 것이 보다 바람직하다.The content of the cationic polymerization initiator represented by the general formula (1) in the epoxy resin composition is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the compound having an epoxy group from the viewpoint of better curability, More preferably 5 parts by mass.
본 발명의 에폭시 수지 조성물은, 경화제로서, 일반식 (1)로 나타내지는 양이온 중합 개시제 외에, 종래 공지의 다른 양이온 중합 개시제를 더 함유하여도 무방하다. 또한, 본 발명의 에폭시 수지 조성물은, 발명의 효과를 해치지 않는 범위에서, 루이스산 등의 종래 공지의 경화 촉진제를 더 함유하여도 무방하다.The epoxy resin composition of the present invention may further contain, as a curing agent, other cationic polymerization initiators known in the art, in addition to the cationic polymerization initiator represented by the general formula (1). The epoxy resin composition of the present invention may further contain conventionally known curing accelerators such as Lewis acid within the range not to impair the effects of the present invention.
＜임의 성분＞<Optional ingredients>
또한, 본 발명의 에폭시 수지 조성물은, 상술한 각 성분 이외에, 필요에 따라서, 한층 더 첨가제를 함유할 수 있다. 첨가제로서는, 예를 들어, 충전제(필러), 실란 커플링제, 반응성 희석제, 가소제, 틱소트로피성 부여제, 안료, 염료, 노화 방지제, 산화 방지제, 대전 방지제, 난연제, 접착성 부여제, 분산제, 용제를 들 수 있다. 충전제로서는, 실리카, 마이카 등을 들 수 있다. Further, the epoxy resin composition of the present invention may further contain additives in addition to the respective components described above, if necessary. Examples of the additive include additives such as fillers, silane coupling agents, reactive diluents, plasticizers, thixotropic agents, pigments, dyes, antioxidants, antioxidants, antistatic agents, flame retardants, . Examples of the filler include silica and mica.
또한, 본 발명의 에폭시 수지 조성물은 발명의 효과를 해치지 않는 범위에서 오늄염, 염기 등의 안정화제를 더 함유하여도 무방하다.The epoxy resin composition of the present invention may further contain a stabilizer such as an onium salt or a base, so long as the effect of the invention is not impaired.
＜에폭시 수지 조성물의 제조 방법＞≪ Process for producing epoxy resin composition >
본 발명의 에폭시 수지 조성물은, 그 제조에 관하여 특별히 제한되지 않는다. 본 발명의 에폭시 수지 조성물은, 예를 들어, 상술한 에폭시기를 가지는 화합물, 일반식 (1)로 나타내지는 양이온 중합 개시제, 및, 필요에 따라서 첨가되는 경화 촉진제 등의 첨가제를 혼합하고, 감압 하 또는 질소 분위기 하에 있어서 혼합 믹서 등의 교반 장치를 이용하여 혼련하여, 균일하게 분산시키는 것에 의하여, 1액형의 에폭시 수지 조성물로서 얻을 수 있다.The epoxy resin composition of the present invention is not particularly limited in terms of its production. The epoxy resin composition of the present invention is obtained by mixing, for example, the above-mentioned compound having an epoxy group, a cationic polymerization initiator represented by the general formula (1), and an additive such as a curing accelerator added as needed, The mixture is kneaded in a nitrogen atmosphere using a stirring device such as a mixing mixer and uniformly dispersed to obtain a one-pack type epoxy resin composition.
［용도］[Usage]
본 발명의 에폭시 수지 조성물은, 예를 들어, 접착제용, 도료용, 토목 건축용, 전기용, 수송기용, 의료용, 포장용, 섬유용, 스포츠·레저용으로서 사용할 수 있다. 특히, 에폭시 수지 조성물 중에 배합되는 일반식 (1)로 나타내지는 양이온 중합 개시제는, 상대 음이온이 테트라키스(펜타플루오로페닐)보레이트인 것으로부터, 상대 음이온이 SbF6-나 BF4- 등인 경우와 비교하여 중합 시에 불소 이온의 생성이 적다고 하는 이점을 가진다. 따라서, 전자 재료(예를 들어, 금속의 박막을 가공하여 형성된 회로 패턴을 기판 상에 가지는 각종 표시 디바이스)의 표면에 도포하여 이용하는 접착제 용도로 바람직하게 이용할 수 있다. 그 중에서도, ACF(이방 도전성 필름)의 조성물로서 보다 바람직하게 이용된다.The epoxy resin composition of the present invention can be used, for example, as an adhesive, a paint, a civil engineering construction, an electric appliance, a transporting machine, a medical appliance, a packaging, a fiber, a sports, or a leisure. Particularly, the cationic polymerization initiator represented by the general formula (1) to be incorporated in the epoxy resin composition is a cationic polymerization initiator in the case where the counter anion is SbF 6 - or BF 4 - or the like since the counter anion is tetrakis (pentafluorophenyl) There is an advantage that fluorine ion generation is small at the time of polymerization. Therefore, the present invention can be suitably used for an adhesive which is applied to the surface of an electronic material (for example, various display devices having a circuit pattern formed by processing a thin metal film) on the substrate. Among them, it is more preferably used as a composition of an ACF (anisotropic conductive film).
［경화 처리］[Curing Treatment]
본 발명의 에폭시 수지 조성물은, 가열에 의하여 경화시킬 수 있다. The epoxy resin composition of the present invention can be cured by heating.
본 발명의 에폭시 수지 조성물을 경화시킬 때의 온도는, 예를 들어, 에폭시기를 가지는 폴리머로서 아데카샤(ADEKA社)제 비스페놀 A형 에폭시 수지 EP4100E를 이용한 경우, 100 ~ 250℃인 것이 바람직하고, 120 ~ 200℃인 것이 보다 바람직하다. The temperature at which the epoxy resin composition of the present invention is cured is preferably 100 to 250 DEG C when the bisphenol A type epoxy resin EP4100E manufactured by Adeka Co., Ltd. is used as a polymer having an epoxy group, Deg.] C to 200 [deg.] C.
본 발명에 있어서, 「경화성」은, 에폭시 수지 조성물의 겔화 시간(겔 타임)으로 평가된다. 예를 들어, 후술하는 야스다식(安田式) 겔 타임 테스터를 사용하는 방법으로 측정할 수 있다. In the present invention, "curability" is evaluated by the gelation time (gel time) of the epoxy resin composition. For example, it can be measured by using a Yasuda gel time tester described later.
본 발명의 에폭시 수지 조성물의 겔화 시간은, 예를 들어, 에폭시기를 가지는 폴리머로서 아데카샤제 비스페놀 A형 에폭시 수지 EP4100E를 이용한 경우, 150℃에서 30초 미만인 것이 바람직하고, 20초 미만인 것이 보다 바람직하다.The gelation time of the epoxy resin composition of the present invention is preferably less than 30 seconds at 150 DEG C and less than 20 seconds when the adducted bisphenol A type epoxy resin EP4100E is used as the polymer having an epoxy group .
실시예Example
이하, 실시예를 나타내어, 본 발명을 구체적으로 설명한다. 단, 본 발명은 이것들로 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples. However, the present invention is not limited to these.
［에폭시 수지 조성물의 제조］[Preparation of epoxy resin composition]
실시예 1 ~ 4, 비교예 1 ~ 7로서, 하기 표 1에 나타내는 각 성분을, 각각 동표에 나타내는 배합비로 혼합하여, 에폭시 수지 조성물을 제조하였다. 표 중의 각 성분의 수치는 「질량부」를 나타낸다.As Examples 1 to 4 and Comparative Examples 1 to 7, the respective components shown in the following Table 1 were mixed at the compounding ratios shown in the same Tables to prepare an epoxy resin composition. The numerical values of each component in the table indicate " part by mass ".
표 1에 나타내는 각 성분의 상세는 이하대로이다. Details of each component shown in Table 1 are as follows.
·에폭시 수지 (A): 비스페놀 A형 에폭시 수지(상품명 EP4100E, 아데카샤제)Epoxy resin (A): Bisphenol A type epoxy resin (trade name: EP4100E, manufactured by ADPCASHA)
·경화제 (1): 하기 식으로 나타내지는 양이온 중합 개시제Curing agent (1): Cation polymerization initiator represented by the following formula
경화제 (1)은 다음과 같이 하여 조제하였다. The curing agent (1) was prepared as follows.
4-(클로로메틸)스티렌 152.62g과 4-(메틸티오)페놀 140.2g을, 메탄올 중에 있어서, 실온에서 24시간 반응시켰다. 반응 후, 여과 및 건조를 하여, 백색 결정을 얻었다. 그 다음에, 얻어진 백색 결정 100g에 초산 에틸 100g을 혼합하고, 한층 더 테트라키스(펜타플루오로페닐)보레이트의 나트륨염 수용액(고형분 10%) 2450g을 혼합하여, 실온에서 6시간 반응시켰다. 반응 후, 유기층을 수세(水洗)한 후에 유기층을 농축하여, 경화제 (1)을 얻었다.152.62 g of 4- (chloromethyl) styrene and 140.2 g of 4- (methylthio) phenol were reacted in methanol at room temperature for 24 hours. The reaction was followed by filtration and drying to obtain white crystals. Next, 100 g of the obtained white crystal was mixed with 100 g of ethyl acetate, and 2450 g of an aqueous solution of sodium salt of tetrakis (pentafluorophenyl) borate (solid content 10%) was further mixed and reacted at room temperature for 6 hours. After the reaction, the organic layer was washed with water and then the organic layer was concentrated to obtain a curing agent (1).
·경화제 (2): 하기 식으로 나타내지는 양이온 중합 개시제Curing agent (2): A cationic polymerization initiator represented by the following formula
경화제 (2)는 다음과 같이 하여 조제하였다. The curing agent (2) was prepared as follows.
4-(클로로메틸)스티렌 152.62g과 4-(메틸티오)-m-크레졸 154.23g을, 메탄올 중에 있어서, 실온에서 24시간 반응시켰다. 반응 후, 여과 및 건조를 하여, 백색 결정을 얻었다. 그 다음에, 얻어진 백색 결정 100g에 초산 에틸 100g을 혼합하고, 한층 더 테트라키스(펜타플루오로페닐)보레이트의 나트륨염 수용액(고형분 10%) 2350g을 혼합하여, 실온에서 6시간 반응시켰다. 반응 후, 유기층을 수세한 후에 유기층을 농축하여, 경화제 (2)를 얻었다.152.62 g of 4- (chloromethyl) styrene and 154.23 g of 4- (methylthio) -m-cresol were reacted in methanol at room temperature for 24 hours. The reaction was followed by filtration and drying to obtain white crystals. Subsequently, 100 g of the obtained white crystal was mixed with 100 g of ethyl acetate, and further 2350 g of an aqueous solution of sodium salt of tetrakis (pentafluorophenyl) borate (solid content 10%) was mixed and reacted at room temperature for 6 hours. After the reaction, the organic layer was washed with water and then the organic layer was concentrated to obtain a curing agent (2).
·경화제 (3): 하기 식으로 나타내지는 양이온 중합 개시제Curing agent (3): A cationic polymerization initiator represented by the following formula
경화제 (3)은 다음과 같이 하여 조제하였다. The curing agent (3) was prepared as follows.
3-(클로로메틸)스티렌 152.62g과 4-(메틸티오)-m-크레졸 154.23g을, 메탄올 중에 있어서, 실온에서 24시간 반응시켰다. 반응 후, 여과 및 건조를 하여, 백색 결정을 얻었다. 그 다음에, 얻어진 백색 결정 100g에 초산 에틸 100g을 혼합하고, 한층 더 테트라키스(펜타플루오로페닐)보레이트의 나트륨염 수용액(고형분 10%) 2350g을 혼합하여, 실온에서 6시간 반응시켰다. 반응 후에, 유기층을 수세한 후에 유기층을 농축하여, 경화제 (3)을 얻었다.152.62 g of 3- (chloromethyl) styrene and 154.23 g of 4- (methylthio) -m-cresol were reacted in methanol at room temperature for 24 hours. The reaction was followed by filtration and drying to obtain white crystals. Subsequently, 100 g of the obtained white crystal was mixed with 100 g of ethyl acetate, and further 2350 g of an aqueous solution of sodium salt of tetrakis (pentafluorophenyl) borate (solid content 10%) was mixed and reacted at room temperature for 6 hours. After the reaction, the organic layer was washed with water and then the organic layer was concentrated to obtain a curing agent (3).
·경화제 (4): 하기 식으로 나타내지는 양이온 중합 개시제Curing agent (4): Cation polymerization initiator represented by the following formula
경화제 (4)는 다음과 같이 하여 조제하였다. The curing agent (4) was prepared as follows.
상기 경화제 (1)의 합성예에 있어서, 테트라키스(펜타플루오로페닐)보레이트의 나트륨염 수용액(고형분 10%)을 헥사플루오로안티몬산나트륨 수용액(고형분 10%) 900g으로 변경한 것 이외에는, 경화제 (1)과 같이 합성을 행하여, 경화제 (4)를 얻었다.Except that the sodium salt aqueous solution (solid content: 10%) of tetrakis (pentafluorophenyl) borate was changed to 900 g of sodium hexafluoroantimonate aqueous solution (solid content 10%) in the synthesis example of the curing agent (1) (1), and a curing agent (4) was obtained.
·경화제 (5): 하기 식으로 나타내지는 양이온 중합 개시제Curing agent (5): Cation polymerization initiator represented by the following formula
경화제 (5)는 다음과 같이 하여 조제하였다. The curing agent (5) was prepared as follows.
상기 경화제 (1)의 합성예에 있어서, 테트라키스(펜타플루오로페닐)보레이트의 나트륨염 수용액(고형분 10%)을 사불화붕산나트륨 수용액(고형분 10%) 382g으로 변경한 것 이외에는, 경화제 (1)과 같이 합성을 행하여, 경화제 (5)를 얻었다.Except that 382 g of sodium tetrafluoroborate aqueous solution (solid content 10%) was used instead of the aqueous solution of sodium salt of tetrakis (pentafluorophenyl) borate (solid content 10%) in the synthesis example of the curing agent (1) ) To obtain a curing agent (5).
·경화제 (6): 하기 식으로 나타내지는 양이온 중합 개시제Curing agent (6): Cation polymerization initiator represented by the following formula
경화제 (6)은 다음과 같이 하여 조제하였다. The curing agent (6) was prepared as follows.
상기 경화제 (2)의 합성예에 있어서, 테트라키스(펜타플루오로페닐)보레이트의 나트륨염 수용액(고형분 10%)을 헥사플루오로안티몬산나트륨 수용액(고형분 10%) 905g으로 변경한 것 이외에는, 경화제 (2)와 같이 합성을 행하여, 경화제 (6)을 얻었다.In the synthesis example of the curing agent (2), except that 905 g of an aqueous solution of sodium salt of tetrakis (pentafluorophenyl) borate (solid content 10%) and sodium hexafluoroantimonate aqueous solution (solid content 10%) was changed, (2), to obtain a curing agent (6).
·경화제 (7): 하기 식으로 나타내지는 양이온 중합 개시제(SI-100L, 산신 카가쿠 코교샤(三新化學工業社)제)Curing agent (7): A cationic polymerization initiator (SI-100L, manufactured by SANSHIN KAGAKU KOGYO CO., LTD.) Represented by the following formula:
·경화제 (8): 하기 식으로 나타내지는 양이온 중합 개시제Curing agent (8): Cation polymerization initiator represented by the following formula
경화제 (8)은 다음과 같이 하여 조제하였다. The curing agent (8) was prepared as follows.
벤질클로라이드 10g과 4-(메틸티오)페놀 11.07g을 메탄올 중에 있어서 실온에서 24시간 반응시켜, 클로라이드 중간체를 얻었다. 한층 더 중간체 10g과 테트라키스(펜타플루오로페닐)보레이트의 나트륨염 수용액(고형분 10%) 263g을 혼합하여, 경화제 (8)을 얻었다.10 g of benzyl chloride and 11.07 g of 4- (methylthio) phenol were reacted at room temperature for 24 hours in methanol to obtain a chloride intermediate. Further, 10 g of the intermediate and 263 g of an aqueous sodium salt solution (solid content 10%) of tetrakis (pentafluorophenyl) borate were mixed to obtain a curing agent (8).
·경화제 (9): 하기 식으로 나타내지는 양이온 중합 개시제Curing agent (9): A cationic polymerization initiator represented by the following formula
경화제 (9)는 다음과 같이 하여 조제하였다. The curing agent (9) was prepared as follows.
1-(클로로메틸)나프탈렌 10g과 4-메틸티오페놀 7.9g을 메탄올 중에 있어서 실온에서 24시간 반응시켜, 클로라이드 중간체를 얻었다. 한층 더 중간체 10g과 테트라키스(펜타플루오로페닐)보레이트의 나트륨염 수용액(고형분 10%) 220.16g을 혼합하여, 경화제 (9)를 얻었다.10 g of 1- (chloromethyl) naphthalene and 7.9 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 220.16 g of an aqueous sodium salt solution (solid content 10%) of tetrakis (pentafluorophenyl) borate were mixed to obtain a curing agent (9).
［평가］[evaluation]
얻어진 각 에폭시 수지 조성물에 관하여, 각각, 하기의 방법으로 겔 타임(경화성), 저장 안정성 및 불소 이온 농도를 측정하였다. 결과를 표 1에 나타낸다. The gel time (curability), storage stability and fluorine ion concentration of each of the obtained epoxy resin compositions were measured by the following methods. The results are shown in Table 1.
(1) 겔 타임(경화성 평가) (1) Gel time (curability evaluation)
얻어진 각 조성물에 관하여, 야스다식 겔 타임 테스터(가부시키가이샤 야스다 세이키 세이사쿠쇼(株式會社安田精機製作所)제, No.153 겔 타임 테스터)를 이용하여 150℃에서의 겔 타임을 측정하였다. 야스다식 겔 타임 테스터는, 오일 배스 중, 시료를 넣은 시험관 안에서 로터를 회전시켜, 겔화가 진행되어 일정한 토크가 걸리면 자기 커플링 기구에 의하여 로터가 빠져 타이머가 멈추는 장치이다. With respect to each composition thus obtained, the gel time at 150 ° C was measured using a Yasuda gel time tester (No.153 gel time tester, manufactured by Yasuda Seiki Seisakusho Co., Ltd.). The Yasuda gel time tester is a device in which a rotor is rotated in a test tube containing a sample in an oil bath, and when the gelation proceeds and a constant torque is applied, the rotor is stopped by the magnetic coupling mechanism and the timer is stopped.
(2) 저장 안정성 (2) Storage stability
얻어진 각 조성물을 40℃의 오븐에 넣어, 초기 및 2시간 경과 후의 점도를 각각 측정하고, 그 증가율을 점도 상승률로 하였다. 점도는, 40℃에 있어서, E형 점도계 VISCONIC EHD형(토키 산교샤(東機産業社)제)을 이용하여 측정하였다. 그 다음에, 얻어진 초기 점도 및 2시간 후의 점도의 값을 하기 식에 적용시켜, 점도 상승률을 산출하였다. Each composition thus obtained was placed in an oven at 40 DEG C, and the viscosity after the initial and two hours had elapsed was measured, and the rate of increase was regarded as the viscosity increase rate. The viscosity was measured at 40 占 폚 using an E-type viscometer VISCONIC EHD (manufactured by Toki Sangyo Co., Ltd.). Then, the obtained initial viscosity and the value of the viscosity after 2 hours were applied to the following equation to calculate the viscosity increase rate.
(점도 상승률) = (2시간 후의 점도) / (초기 점도)(Viscosity increase rate) = (viscosity after 2 hours) / (initial viscosity)
(3) 불소 이온 농도 (3) Fluorine ion concentration
각 경화제의 불소 이온 농도: 경화제 0.5g을 순수(純水) 50mL 안에 투입하고, 100℃ 10시간 가열 추출을 행하여, 얻어진 추출액을 멤브레인 필터(OnGuardRP, 다이오넥스(Dionex)사제)로 여과를 행하였다. 얻어진 여액(濾液)에 대하여, 이온 크로마토그래프(ICS-1600, 다이오넥스사제)를 이용하여 불소 이온 농도의 분석을 행하였다.Fluoride ion concentration of each curing agent: 0.5 g of the curing agent was poured into 50 mL of pure water, followed by heating extraction at 100 DEG C for 10 hours. The resulting extract was filtered with a membrane filter (OnGuard RP, manufactured by Dionex) . The resulting filtrate (filtrate) was analyzed for fluorine ion concentration using an ion chromatograph (ICS-1600, manufactured by Dionex).
표 1에 나타내는 결과로부터 분명한 바와 같이, 실시예 1 ~ 4의 에폭시 수지 조성물은, 겔화 시간(150℃)이 모두 30초 미만이며, 또한 저장 안정성에도 뛰어났다. As is evident from the results shown in Table 1, the epoxy resin compositions of Examples 1 to 4 each had a gelation time (150 ° C) of less than 30 seconds and excellent storage stability.
실시예 1 ~ 4와 비교예 1 ~ 4를 비교하면, 일반식 (1)로 나타내지는 양이온 중합 개시제를 함유하는 실시예 1 ~ 4는, 경화성에 있어서, 상대 음이온이 SbF6-나 BF4-인 비교예 1 ~ 4보다도 현저하게 뛰어났다. Comparing Examples 1 to 4 and Comparative Examples 1 to 4, Examples 1 to 4 containing a cationic polymerization initiator represented by the general formula (1) show that the relative anions of SbF 6 - and BF 4 - Which is significantly superior to Comparative Examples 1 to 4,
또한, 실시예 1 ~ 4와 비교예 5를 비교하면, 일반식 (1)로 나타내지는 양이온 중합 개시제를 함유하는 실시예 1 ~ 4는, 경화성에 있어서, 술포늄 잔기에 비닐기를 가지지 않고, 또한, 상대 음이온이 SbF6-인 비교예 5보다도 현저하게 뛰어났다. Comparing Examples 1 to 4 with Comparative Example 5, Examples 1 to 4 containing a cationic polymerization initiator represented by the general formula (1) had no vinyl group in the sulfonium residue in curability, , And the counter anion was superior to Comparative Example 5 in which SbF 6 - was present.
나아가, 비교예 1 ~ 5의 양이온 중합 개시제는, 모두 상대 음이온이 테트라키스(펜타플루오로페닐)보레이트가 아니라 SbF6-나 BF4-이기 때문에, 중합 시에 생성하는 불소 이온 농도가 높은 결과가 되었다. Furthermore, since the cationic polymerization initiators of Comparative Examples 1 to 5 are all SbF 6 - or BF 4 - rather than tetrakis (pentafluorophenyl) borate as the counter anion, the result of high fluorine ion concentration .
한편, 실시예 1 ~ 4와 비교예 6을 비교하면, 비교예 6은, 저장 안정성에 관해서는 실시예 1 ~ 4와 같은 정도였지만, 경화성이 실시예 1 ~ 4보다도 떨어지는 결과가 되었다. On the other hand, in comparison between Examples 1 to 4 and Comparative Example 6, the storage stability of the Comparative Example 6 was about the same as that of Examples 1 to 4, but the curability was lower than that of Examples 1 to 4.
실시예 1 ~ 4와 비교예 7을 비교하면, 비교예 7은 경화성에 관해서는 실시예 1 ~ 4와 같은 정도였지만, 저장 안정성이 실시예 1 ~ 4보다도 떨어지는 결과가 되었다.Comparing the examples 1 to 4 and the comparative example 7, the curability of the comparative example 7 was about the same as those of the examples 1 to 4, but the storage stability was lower than those of the examples 1 to 4.
Claims (3)
[화학식 1]
(일반식 (1)에 있어서, R1은, 수산기, R5O기, R5COO기, R5NHCOO기 또는 R5OCOO기이고, R2, R3 및 R4는, 각각 독립하여, 수소 원자 또는 탄소수 1 ~ 6의 알킬기이다. R5는, 치환기를 가지고 있어도 무방한, 방향족 탄화수소기 또는 지방족 탄화수소기이다.)A cationic polymerization initiator represented by the following general formula (1).
[Chemical Formula 1]
(In the formula (1), R 1 is hydroxy, R 5 O groups, R 5 COO group, R 5 NHCOO group or R 5 OCOO group and, R 2, R 3 and R 4 are, each independently, A hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 5 is an aromatic hydrocarbon group or aliphatic hydrocarbon group which may have a substituent.
상기 양이온 중합 개시제의 함유량이, 상기 에폭시기를 가지는 화합물 100질량부에 대하여, 0.1 ~ 10질량부인, 에폭시 수지 조성물.3. The method of claim 2,
Wherein the content of the cationic polymerization initiator is 0.1 to 10 parts by mass relative to 100 parts by mass of the compound having the epoxy group.
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