JP2016102200A - (meth)acrylic acid ester copolymer, resin composition and cured article - Google Patents
(meth)acrylic acid ester copolymer, resin composition and cured article Download PDFInfo
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- JP2016102200A JP2016102200A JP2015215868A JP2015215868A JP2016102200A JP 2016102200 A JP2016102200 A JP 2016102200A JP 2015215868 A JP2015215868 A JP 2015215868A JP 2015215868 A JP2015215868 A JP 2015215868A JP 2016102200 A JP2016102200 A JP 2016102200A
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- Prior art keywords
- meth
- epoxy resin
- acrylic acid
- ester copolymer
- acid ester
- Prior art date
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- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 title claims abstract description 64
- 239000011342 resin composition Substances 0.000 title claims description 31
- 239000003822 epoxy resin Substances 0.000 claims abstract description 81
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 81
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 47
- 239000000178 monomer Substances 0.000 claims abstract description 24
- -1 aromatic vinyl compound Chemical class 0.000 claims abstract description 23
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 12
- 239000004593 Epoxy Substances 0.000 claims abstract description 11
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 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 claims description 12
- 229920003986 novolac Polymers 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 5
- 229930003836 cresol Natural products 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 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 claims description 2
- 229920001577 copolymer Polymers 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 30
- 239000000203 mixture Substances 0.000 abstract description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 4
- 229920002126 Acrylic acid copolymer Polymers 0.000 abstract 1
- 239000000047 product Substances 0.000 description 25
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 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 4
- 238000007654 immersion Methods 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920000800 acrylic rubber Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- JMYZLRSSLFFUQN-UHFFFAOYSA-N (2-chlorobenzoyl) 2-chlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC=C1C(=O)OOC(=O)C1=CC=CC=C1Cl JMYZLRSSLFFUQN-UHFFFAOYSA-N 0.000 description 1
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- POTYORUTRLSAGZ-UHFFFAOYSA-N (3-chloro-2-hydroxypropyl) prop-2-enoate Chemical compound ClCC(O)COC(=O)C=C POTYORUTRLSAGZ-UHFFFAOYSA-N 0.000 description 1
- XBDOGXHLESIJJK-UHFFFAOYSA-N (3-chlorobenzoyl) 3-chlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC(C(=O)OOC(=O)C=2C=C(Cl)C=CC=2)=C1 XBDOGXHLESIJJK-UHFFFAOYSA-N 0.000 description 1
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-UHFFFAOYSA-N 0.000 description 1
- ZRSLOTOZLGLTSX-UHFFFAOYSA-N (4-nitrophenyl)-trityldiazene Chemical compound C1=CC([N+](=O)[O-])=CC=C1N=NC(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 ZRSLOTOZLGLTSX-UHFFFAOYSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- ZRKMQKLGEQPLNS-UHFFFAOYSA-N 1-Pentanethiol Chemical compound CCCCCS ZRKMQKLGEQPLNS-UHFFFAOYSA-N 0.000 description 1
- ZFJPOCMNOMSHAW-UHFFFAOYSA-N 1-[(1-cyanocycloheptyl)diazenyl]cycloheptane-1-carbonitrile Chemical compound C1CCCCCC1(C#N)N=NC1(C#N)CCCCCC1 ZFJPOCMNOMSHAW-UHFFFAOYSA-N 0.000 description 1
- CDDDRVNOHLVEED-UHFFFAOYSA-N 1-cyclohexyl-3-[1-[[1-(cyclohexylcarbamoylamino)cyclohexyl]diazenyl]cyclohexyl]urea Chemical compound C1CCCCC1(N=NC1(CCCCC1)NC(=O)NC1CCCCC1)NC(=O)NC1CCCCC1 CDDDRVNOHLVEED-UHFFFAOYSA-N 0.000 description 1
- OUSXYCTXXLYBGJ-UHFFFAOYSA-N 1-ethenyl-2,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C=C)C(C(C)C)=C1 OUSXYCTXXLYBGJ-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- YWBMNCRJFZGXJY-UHFFFAOYSA-N 1-hydroperoxy-1,2,3,4-tetrahydronaphthalene Chemical compound C1=CC=C2C(OO)CCCC2=C1 YWBMNCRJFZGXJY-UHFFFAOYSA-N 0.000 description 1
- HKNNAYPWWDWHFR-UHFFFAOYSA-N 1-sulfanylbutan-1-ol Chemical compound CCCC(O)S HKNNAYPWWDWHFR-UHFFFAOYSA-N 0.000 description 1
- LZDQRFAKPMTETN-UHFFFAOYSA-N 1-sulfanylbutane-1,1-diol Chemical compound CCCC(O)(O)S LZDQRFAKPMTETN-UHFFFAOYSA-N 0.000 description 1
- AEUVIXACNOXTBX-UHFFFAOYSA-N 1-sulfanylpropan-1-ol Chemical compound CCC(O)S AEUVIXACNOXTBX-UHFFFAOYSA-N 0.000 description 1
- VWNAITWBRLKIIS-UHFFFAOYSA-N 1-sulfanylpropane-1,1-diol Chemical compound CCC(O)(O)S VWNAITWBRLKIIS-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- IPYGDTHQCFDVGF-UHFFFAOYSA-N 2-(2-aminopropan-2-yldiazenyl)propan-2-amine nitric acid Chemical compound O[N+]([O-])=O.CC(C)(N)N=NC(C)(C)N IPYGDTHQCFDVGF-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QMYCJCOPYOPWTI-UHFFFAOYSA-N 2-[(1-amino-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidamide;hydron;chloride Chemical compound Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N QMYCJCOPYOPWTI-UHFFFAOYSA-N 0.000 description 1
- OALMZWNBNXQUAL-UHFFFAOYSA-N 2-[(1-amino-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanamide Chemical compound NC(=O)C(C)(C)N=NC(C)(C)C(N)=O OALMZWNBNXQUAL-UHFFFAOYSA-N 0.000 description 1
- HCZMHWVFVZAHCR-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol Chemical compound SCCOCCOCCS HCZMHWVFVZAHCR-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- VMKYTRPNOVFCGZ-UHFFFAOYSA-N 2-sulfanylphenol Chemical compound OC1=CC=CC=C1S VMKYTRPNOVFCGZ-UHFFFAOYSA-N 0.000 description 1
- OJHQXSRIBZMCSR-UHFFFAOYSA-N 3,3-dimethylbut-1-en-2-ylbenzene Chemical compound CC(C)(C)C(=C)C1=CC=CC=C1 OJHQXSRIBZMCSR-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- POZWNWYYFQVPGC-UHFFFAOYSA-N 3-methoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[SiH2]CCCOC(=O)C(C)=C POZWNWYYFQVPGC-UHFFFAOYSA-N 0.000 description 1
- POZGETMIPGBFGQ-UHFFFAOYSA-N 3-methylbut-1-en-2-ylbenzene Chemical compound CC(C)C(=C)C1=CC=CC=C1 POZGETMIPGBFGQ-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- WLHCBQAPPJAULW-UHFFFAOYSA-N 4-methylbenzenethiol Chemical compound CC1=CC=C(S)C=C1 WLHCBQAPPJAULW-UHFFFAOYSA-N 0.000 description 1
- UTKZHEXXFWCYCH-UHFFFAOYSA-N 4-tert-butyl-2-ethenyl-1-methylbenzene Chemical compound CC1=CC=C(C(C)(C)C)C=C1C=C UTKZHEXXFWCYCH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JLLMOYPIVVKFHY-UHFFFAOYSA-N Benzenethiol, 4,4'-thiobis- Chemical compound C1=CC(S)=CC=C1SC1=CC=C(S)C=C1 JLLMOYPIVVKFHY-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- JZNDEUVAGZPPOA-UHFFFAOYSA-N C(C)(=O)O.[Br-].[NH4+].[NH4+].[NH4+].[NH4+].[Br-].[Br-].[Br-] Chemical compound C(C)(=O)O.[Br-].[NH4+].[NH4+].[NH4+].[NH4+].[Br-].[Br-].[Br-] JZNDEUVAGZPPOA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、（メタ）アクリル酸エステル共重合体、樹脂組成物及び硬化物に関する。 The present invention relates to a (meth) acrylic acid ester copolymer, a resin composition, and a cured product.
エポキシ樹脂組成物は、その優れた接着性や電気・機械特性から、電気・電子部品の封止材や、各種構造部材のマトリックス材料、接着材等の各分野で広く使用されているが、通常、様々な添加剤を加えるなどして用途に応じた好ましい特性の付与が行われている。例えば、エポキシ樹脂組成物を封止材といった電気・電子部品関連の用途で使用する場合、外部環境による電気絶縁性や機械強度の劣化を防ぐため、エポキシ樹脂組成物には高い耐水性が求められてきた。例えば、特許文献１には、ノボラック型エポキシ樹脂に少量の環状ジメチルシロキサンを配合することで耐水性を改善したエポキシ樹脂組成物が開示されている。 Epoxy resin compositions are widely used in various fields such as sealing materials for electrical and electronic parts, matrix materials for various structural members, adhesives, etc. due to their excellent adhesion and electrical / mechanical properties. Further, by adding various additives, preferred properties are imparted according to the application. For example, when an epoxy resin composition is used for an electrical / electronic component-related application such as a sealing material, the epoxy resin composition is required to have high water resistance in order to prevent deterioration of electrical insulation and mechanical strength due to the external environment. I came. For example, Patent Document 1 discloses an epoxy resin composition in which water resistance is improved by adding a small amount of cyclic dimethylsiloxane to a novolac type epoxy resin.
一方で、エポキシ樹脂組成物を硬化物とした場合、弾性率の高さから剛直となり、熱膨張や硬化収縮により周辺部材に応力が加わりやすいことが知られていた。そのため、用途によっては、エポキシ樹脂組成物にシリコーンやアクリルゴム（（メタ）アクリル酸エステル共重合体等）といったゴム成分を配合することで、弾性率を下げる試みがなされてきた。例えば、特許文献２には、ビスフェノールＡ型エポキシ樹脂に末端カルボキシル変性アクリロニトリルブタジエンゴム（ＣＴＢＮ）を配合することが開示されている。 On the other hand, it has been known that when the epoxy resin composition is a cured product, it becomes rigid due to its high elastic modulus, and stress is easily applied to the peripheral members due to thermal expansion and curing shrinkage. Therefore, an attempt has been made to lower the elastic modulus by blending an epoxy resin composition with a rubber component such as silicone or acrylic rubber ((meth) acrylic acid ester copolymer or the like) depending on the application. For example, Patent Document 2 discloses that terminal carboxyl-modified acrylonitrile butadiene rubber (CTBN) is blended with a bisphenol A type epoxy resin.
しかしながら、弾性率を下げる目的でアクリルゴムをエポキシ樹脂組成物に配合した場合、アクリルゴムの高い吸水性が原因で硬化物の耐水性が低下するとの新たな問題が生じる。 However, when acrylic rubber is blended in the epoxy resin composition for the purpose of lowering the elastic modulus, a new problem arises that the water resistance of the cured product is lowered due to the high water absorption of the acrylic rubber.
本発明は、吸水性が低くエポキシ樹脂との相溶性に優れた（メタ）アクリル酸エステル共重合体であって、エポキシ樹脂組成物に配合し硬化させた場合に、弾性率が低く耐水性に優れた硬化物となる（メタ）アクリル酸エステル共重合体を提供することを目的とする。 The present invention is a (meth) acrylic acid ester copolymer having low water absorption and excellent compatibility with an epoxy resin, and when blended and cured in an epoxy resin composition, has a low elastic modulus and water resistance. It aims at providing the (meth) acrylic acid ester copolymer used as the outstanding hardened | cured material.
本発明者らは、上記課題を解決するために鋭意検討した結果、特定のモノマー成分を共重合させて得られる（メタ）アクリル酸エステル共重合体が、吸水性が低くエポキシ樹脂との相溶性に優れること、さらに、エポキシ樹脂組成物にこの（メタ）アクリル酸エステル共重合体を配合し硬化させることで、（メタ）アクリル酸エステル共重合体のその低い吸水性に起因して、弾性率が低く耐水性に優れた硬化物となることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors have found that a (meth) acrylic acid ester copolymer obtained by copolymerizing a specific monomer component has low water absorption and compatibility with an epoxy resin. In addition, the (meth) acrylic acid ester copolymer is blended in the epoxy resin composition and cured, resulting in the low water absorption of the (meth) acrylic acid ester copolymer. Was found to be a cured product having low water resistance and excellent water resistance, and the present invention was completed.
すなわち、本発明の（メタ）アクリル酸エステル共重合体は、
モノマー成分として、グリシジル（メタ）アクリレート、アルキル（メタ）アクリレート及び芳香族ビニル化合物を共重合させて得られる（メタ）アクリル酸エステル共重合体であって、
エポキシ価が０．０６〜１．２ｅｑ／ｋｇであり、
重量平均分子量が１００，０００〜１，０００，０００であることを特徴とする。
That is, the (meth) acrylic acid ester copolymer of the present invention is
As a monomer component, a (meth) acrylic acid ester copolymer obtained by copolymerizing glycidyl (meth) acrylate, alkyl (meth) acrylate and an aromatic vinyl compound,
The epoxy value is 0.06 to 1.2 eq / kg,
The weight average molecular weight is 100,000 to 1,000,000.
本発明の（メタ）アクリル酸エステル共重合体において、モノマー成分の重量割合が、グリシジル（メタ）アクリレート：アルキル（メタ）アクリレート：芳香族ビニル化合物＝１〜１５％：４５〜９８％：１〜４０％であることが好ましい。 In the (meth) acrylic acid ester copolymer of the present invention, the weight ratio of the monomer component is glycidyl (meth) acrylate: alkyl (meth) acrylate: aromatic vinyl compound = 1-15%: 45-98%: 1. It is preferably 40%.
本発明の（メタ）アクリル酸エステル共重合体は、重量平均分子量と数平均分子量との比が４以下であることが好ましい。 The (meth) acrylic acid ester copolymer of the present invention preferably has a ratio of the weight average molecular weight to the number average molecular weight of 4 or less.
本発明の硬化物は、（Ａ）エポキシ樹脂と、（Ｂ）本発明の（メタ）アクリル酸エステル共重合体とを含む樹脂組成物を硬化させて得られる硬化物であって、
（Ａ）エポキシ樹脂を含む海部と、（Ｂ）（メタ）アクリル酸エステル共重合体を含む島部とからなる海島構造を有し、
（Ｂ）（メタ）アクリル酸エステル共重合体を含む島部の長径は０．１〜１０μｍであることを特徴とする。
The cured product of the present invention is a cured product obtained by curing a resin composition containing (A) an epoxy resin and (B) the (meth) acrylic acid ester copolymer of the present invention,
(A) It has a sea-island structure consisting of a sea part containing an epoxy resin and an island part containing (B) a (meth) acrylic acid ester copolymer,
(B) The major axis of the island part containing the (meth) acrylic acid ester copolymer is 0.1 to 10 μm.
本発明の硬化物において、（Ａ）エポキシ樹脂と（Ｂ）（メタ）アクリル酸エステル共重合体との重量割合が９９〜５０％：１〜５０％であることが好ましい。 In the cured product of the present invention, the weight ratio of (A) epoxy resin and (B) (meth) acrylic acid ester copolymer is preferably 99 to 50%: 1 to 50%.
本発明の硬化物において、（Ａ）エポキシ樹脂が、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾ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、ナフタレン型エポキシ樹脂及びジシクロペンタジエン型エポキシ樹脂からなる群より選択される少なくとも１つであることが好ましい。 In the cured product of the present invention, (A) the epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, and dicyclohexane. It is preferably at least one selected from the group consisting of pentadiene type epoxy resins.
本発明の硬化物は、樹脂組成物が（Ｃ）硬化剤をさらに含むことが好ましい。 In the cured product of the present invention, the resin composition preferably further contains (C) a curing agent.
本発明の樹脂組成物は、本発明の硬化物を得るために用いられることを特徴とする。 The resin composition of the present invention is used for obtaining the cured product of the present invention.
本発明の（メタ）アクリル酸エステル共重合体は、特定のモノマー成分を共重合させて得られるため、吸水性が低く、エポキシ樹脂との相溶性に優れる。本発明の硬化物は、エポキシ樹脂及び本発明の（メタ）アクリル酸エステル共重合体を含む樹脂組成物を硬化させて得られるため、弾性率が低く耐水性に優れる。 Since the (meth) acrylic acid ester copolymer of the present invention is obtained by copolymerizing a specific monomer component, it has low water absorption and excellent compatibility with an epoxy resin. Since the hardened | cured material of this invention is obtained by hardening the resin composition containing an epoxy resin and the (meth) acrylic acid ester copolymer of this invention, its elasticity modulus is low and it is excellent in water resistance.
＜＜（メタ）アクリル酸エステル共重合体＞＞
本発明の（メタ）アクリル酸エステル共重合体は、モノマー成分として、グリシジル（メタ）アクリレート、アルキル（メタ）アクリレート及び芳香族ビニル化合物を共重合させて得られる（メタ）アクリル酸エステル共重合体であって、
エポキシ価が０．０６〜１．２ｅｑ／ｋｇであり、
重量平均分子量が１００，０００〜１，０００，０００であることを特徴とする。
なお、本明細書では、アクリル酸及びメタクリル酸を合わせて（メタ）アクリル酸と記載したり、アクリレート及びメタクリレートを合わせて（メタ）アクリレートと記載したりすることがある。
<< (Meth) acrylic acid ester copolymer >>
The (meth) acrylic acid ester copolymer of the present invention is a (meth) acrylic acid ester copolymer obtained by copolymerizing glycidyl (meth) acrylate, alkyl (meth) acrylate and an aromatic vinyl compound as monomer components. Because
The epoxy value is 0.06 to 1.2 eq / kg,
The weight average molecular weight is 100,000 to 1,000,000.
In this specification, acrylic acid and methacrylic acid may be combined and described as (meth) acrylic acid, or acrylate and methacrylate may be combined and described as (meth) acrylate.
まず、モノマー成分について説明する。
グリシジル（メタ）アクリレートとしては、グリシジルアクリレート又はグリシジルメタクリレートを使用することができる。これらは単独で用いても良いし、２種以上を併用しても良い。
First, the monomer component will be described.
As glycidyl (meth) acrylate, glycidyl acrylate or glycidyl methacrylate can be used. These may be used alone or in combination of two or more.
アルキル（メタ）アクリレートのアルキル基は、直鎖状であっても分岐していても良い。アルキル（メタ）アクリレートとしては、特に限定されないが、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、イソプロピル（メタ）アクリレート、イソブチル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート等が挙げられる。アルキル基の炭素数は、特に限定されないが、１〜１８であることが好ましく、１〜８であることがより好ましい。これらのアルキル（メタ）アクリレートは、単独で用いても良いし、２種以上を併用しても良い。 The alkyl group of the alkyl (meth) acrylate may be linear or branched. Although it does not specifically limit as alkyl (meth) acrylate, For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) ) Acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like. . Although carbon number of an alkyl group is not specifically limited, It is preferable that it is 1-18, and it is more preferable that it is 1-8. These alkyl (meth) acrylates may be used alone or in combination of two or more.
本発明の（メタ）アクリル酸エステル共重合体は、モノマー成分として芳香族ビニル化合物を共重合させて得られたものであるため、吸水性が低く、耐熱性に優れるとともに、エポキシ樹脂との相溶性にも優れる。芳香族ビニル化合物としては、特に限定されないが、例えば、スチレン、α−メチルスチレン、α−エチルスチレン、α−プロピルスチレン、α−イソプロピルスチレン、α−ｔ−ブチルスチレン、２−メチルスチレン、３−メチルスチレン、４−メチルスチレン、２，４−ジメチルスチレン、２，４−ジイソプロピルスチレン、４−ｔ−ブチルスチレン、５−ｔ−ブチル−２−メチルスチレン、ビニルトルエン等が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。 Since the (meth) acrylic acid ester copolymer of the present invention is obtained by copolymerizing an aromatic vinyl compound as a monomer component, it has low water absorption, excellent heat resistance, and phase compatibility with an epoxy resin. Excellent solubility. The aromatic vinyl compound is not particularly limited. For example, styrene, α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-isopropylstyrene, α-t-butylstyrene, 2-methylstyrene, 3-methylstyrene, Examples include methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, vinyltoluene and the like. These may be used alone or in combination of two or more.
（メタ）アクリル酸エステル共重合体は、グリシジル（メタ）アクリレート、アルキル（メタ）アクリレート及び芳香族ビニル化合物の他に、任意に他のモノマー成分を共重合させたものであっても良い。他のモノマー成分としては、特に限定されないが、例えば、（メタ）アクリル酸、β−カルボキシエチルアクリレート、イタコン酸、クロトン酸、マレイン酸、フマル酸、無水マレイン酸等のカルボキシル基含有モノマー；シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート等のアルキル基以外の脂肪族エステル基含有モノマー；フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート等の芳香族エステル基含有モノマー；２−ヒドロキシエチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、クロロ−２−ヒドロキシプロピルアクリレート、ジエチレングリコールモノ（メタ）アクリレート、アリルアルコール等のヒドロキシル基含有モノマー；アミノメチル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート等のアミノ基含有モノマー；アクリルアミド、メチロール（メタ）アクリルアミド、メトキシエチル（メタ）アクリルアミド等のアミド基含有モノマー；メタクリロキシプロピルメトキシシラン等のアルコキシ基含有モノマー；アセトアセトキシエチル（メタ）アクリレート等のアセトアセチル基含有モノマー；酢酸ビニル、塩化ビニル等のスチレン以外のビニル系モノマー；（メタ）アクリロニトリル等が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。 The (meth) acrylic acid ester copolymer may be obtained by arbitrarily copolymerizing other monomer components in addition to glycidyl (meth) acrylate, alkyl (meth) acrylate and aromatic vinyl compound. Although it does not specifically limit as another monomer component, For example, carboxyl group containing monomers, such as (meth) acrylic acid, (beta) -carboxyethyl acrylate, itaconic acid, crotonic acid, maleic acid, fumaric acid, maleic anhydride; cyclohexyl ( Aliphatic ester group-containing monomers other than alkyl groups such as meth) acrylate and isobornyl (meth) acrylate; Aromatic ester group-containing monomers such as phenyl (meth) acrylate and benzyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate Hydroxyl group-containing monomers such as 4-hydroxybutyl (meth) acrylate, chloro-2-hydroxypropyl acrylate, diethylene glycol mono (meth) acrylate, and allyl alcohol; aminomethyl (meth) acrylate, Amino group-containing monomers such as methylaminoethyl (meth) acrylate; amide group-containing monomers such as acrylamide, methylol (meth) acrylamide, methoxyethyl (meth) acrylamide; alkoxy group-containing monomers such as methacryloxypropylmethoxysilane; acetoacetoxyethyl Examples include acetoacetyl group-containing monomers such as (meth) acrylate; vinyl monomers other than styrene such as vinyl acetate and vinyl chloride; (meth) acrylonitrile and the like. These may be used alone or in combination of two or more.
（メタ）アクリル酸エステル共重合体において、モノマー成分の重量割合は特に限定されないが、グリシジル（メタ）アクリレート：アルキル（メタ）アクリレート：芳香族ビニル化合物＝１〜１５％：４５〜９８％：１〜４０％であることが好ましく、３〜１０％：６５〜９０％：５〜２５％であることがより好ましい。
グリシジル（メタ）アクリレートの重量割合が１％未満であると、十分に密着性を改善できない場合があり、１５％を超えると、可撓性が失われる結果、密着性が低下することがある。アルキル（メタ）アクリレートの重量割合が４５％未満であると、可撓性が失われることがあり、９８％を超えると、密着性が低下することがある。芳香族ビニル化合物の重量割合が１％未満であると、耐水性が低下することがあり、４０％を超えると、可撓性が失われることがある。
In the (meth) acrylic acid ester copolymer, the weight ratio of the monomer component is not particularly limited, but glycidyl (meth) acrylate: alkyl (meth) acrylate: aromatic vinyl compound = 1-15%: 45-98%: 1 It is preferably -40%, more preferably 3-10%: 65-90%: 5-25%.
If the weight ratio of glycidyl (meth) acrylate is less than 1%, the adhesion may not be sufficiently improved, and if it exceeds 15%, the flexibility may be lost, resulting in a decrease in adhesion. When the weight ratio of the alkyl (meth) acrylate is less than 45%, flexibility may be lost, and when it exceeds 98%, adhesion may be lowered. When the weight ratio of the aromatic vinyl compound is less than 1%, the water resistance may be lowered, and when it exceeds 40%, flexibility may be lost.
（メタ）アクリル酸エステル共重合体のエポキシ価は、０．０６〜１．２ｅｑ／ｋｇである限り特に限定されないが、０．１〜０．８ｅｑ／ｋｇであることが好ましく、０．２〜０．７ｅｑ／ｋｇであることがより好ましい。エポキシ価が０．０６ｅｑ／ｋｇ未満であると、十分に密着性を改善できないことがあり、１．２ｅｑ／ｋｇを超えると、可撓性が失われる結果、密着性が低下することがある。 The epoxy value of the (meth) acrylic acid ester copolymer is not particularly limited as long as it is 0.06 to 1.2 eq / kg, but is preferably 0.1 to 0.8 eq / kg, More preferably, it is 0.7 eq / kg. If the epoxy value is less than 0.06 eq / kg, the adhesion may not be sufficiently improved, and if it exceeds 1.2 eq / kg, the flexibility may be lost, resulting in a decrease in adhesion.
（メタ）アクリル酸エステル共重合体の重量平均分子量（Ｍｗ）は、１００，０００〜１，０００，０００である限り特に限定されないが、１００，０００〜８００，０００であることが好ましく、２００，０００〜６００，０００であることがより好ましい。重量平均分子量が１００，０００未満であると、耐熱密着特性が低下することがあり、１，０００，０００を超えると、溶媒に不溶となり、取り扱いが困難となることがある。本発明において、重量平均分子量とは、ゲル浸透クロマトグラフィー（ＧＰＣ）により測定されたスチレン換算の重量平均分子量をいう。 The weight average molecular weight (Mw) of the (meth) acrylic acid ester copolymer is not particularly limited as long as it is 100,000 to 1,000,000, but is preferably 100,000 to 800,000, More preferably, it is 000-600,000. When the weight average molecular weight is less than 100,000, the heat-resistant adhesion property may be deteriorated, and when it exceeds 1,000,000, it may become insoluble in a solvent and may be difficult to handle. In this invention, a weight average molecular weight means the weight average molecular weight of styrene conversion measured by gel permeation chromatography (GPC).
（メタ）アクリル酸エステル共重合体について、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）は、特に限定されないが、４以下であることが好ましく、３以下であることがより好ましい。重量平均分子量と数平均分子量との比が４を超えると、耐熱密着力が低下することがある。 About (meth) acrylic acid ester copolymer, ratio (Mw / Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn) is not specifically limited, However, It is preferable that it is 4 or less. More preferably. When the ratio of the weight average molecular weight to the number average molecular weight exceeds 4, the heat resistant adhesion may be lowered.
（メタ）アクリル酸エステル共重合体のガラス転移温度（Ｔｇ）は、特に限定されないが、−４０〜４０℃であることが好ましく、−２０〜２０℃であることがより好ましい。ガラス転移温度が−４０℃未満であると、タックが発現したり、ハンドリング性が著しく低下することがあり、４０℃を超えると、可撓性が失われる結果、密着性が低下することがある。 Although the glass transition temperature (Tg) of a (meth) acrylic acid ester copolymer is not specifically limited, It is preferable that it is -40-40 degreeC, and it is more preferable that it is -20-20 degreeC. If the glass transition temperature is less than −40 ° C., tack may appear or handling properties may be significantly reduced, and if it exceeds 40 ° C., flexibility may be lost, resulting in lower adhesion. .
（メタ）アクリル酸エステル共重合体の重合方法としては、特に限定されず、従来公知の重合方法を採用することができるが、重量平均分子量と数平均分子量との比を下げる点からは、懸濁重合が好ましい。 The polymerization method of the (meth) acrylic acid ester copolymer is not particularly limited, and a conventionally known polymerization method can be adopted. However, from the viewpoint of reducing the ratio of the weight average molecular weight to the number average molecular weight, Turbid polymerization is preferred.
モノマー成分を分散媒に分散させる際、必要に応じて、分散剤を添加しても良い。分散剤としては、特に限定されず、ポリビニルピロリドン、ポリビニルアルコール、(メタ)アクリル酸塩、ポリアクリルアミド、部分ケン化ポリアクリルアミド、カルボキシメチルセルロース、メチルセルロース、エチルセルロース等の水溶性高分子、リン酸カルシウム類、炭酸カルシウム等の無機塩粉体等が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。 When dispersing the monomer component in the dispersion medium, a dispersant may be added as necessary. The dispersant is not particularly limited, but water-soluble polymers such as polyvinylpyrrolidone, polyvinyl alcohol, (meth) acrylate, polyacrylamide, partially saponified polyacrylamide, carboxymethylcellulose, methylcellulose, ethylcellulose, calcium phosphates, calcium carbonate And inorganic salt powders. These may be used alone or in combination of two or more.
ラジカル重合開始剤としては、分解後の重合開始ラジカル種が油溶性であることが好ましい。このようなラジカル重合開始剤としては、例えば、２，２’−アゾビスプロパン、２，２’−ジクロロ−２，２’−アゾビスプロパン、１，１’−アゾ（メチルエチル）ジアセテート、２，２’−アゾビス（２−アミジノプロパン）塩酸塩、２，２’−アゾビス（２−アミノプロパン）硝酸塩、２，２’−アゾビスイソブタン、２，２’−アゾビスイソブチルアミド、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス−２−メチルプロピオン酸メチル、２，２’−ジクロロ−２，２’−アゾビスブタン、２，２’−アゾビス−２−メチルブチロニトリル、２，２’−アゾビスイソ酪酸ジメチル、１，１’−アゾビス（１−メチルブチロニトリル−３−スルホン酸ナトリウム）、２−（４−メチルフェニルアゾ）−２−メチルマロノジニトリル４，４’−アゾビス−４−シアノ吉草酸、３，５−ジヒドロキシメチルフェニルアゾ−２−アリルマロノジニトリル、２，２’−アゾビス−２−メチルバレロニトリル、４，４’−アゾビス−４−シアノ吉草酸ジメチル、２，２’−アゾビス−２，４−ジメチルバレロニトリル、１，１’−アゾビスシクロヘキサンニトリル、２，２’−アゾビス−２−プロピルブチロニトリル、１，１’−アゾビス−１−クロロフェニルエタン、１，１’−アゾビス−１−シクロヘキサンカルボニトリル、１，１’−アゾビス−１−シクロヘプタンニトリル、１，１’−アゾビス−１−フェニルエタン、１，１’−アゾビスクメン、４−ニトロフェニルアゾベンジルシアノ酢酸エチル、フェニルアゾジフェニルメタン、フェニルアゾトリフェニルメタン、４−ニトロフェニルアゾトリフェニルメタン、１，１’−アゾビス−１，２−ジフェニルエタン、ポリ（ビスフェノールＡ−４，４’−アゾビス−４−シアノペンタノエート）、ポリ（テトラエチレングリコール−２，２’−アゾビスイソブチレート）等のアゾ系ラジカル重合開始剤、過酸化アセチル、過酸化クミル、過酸化ｔｅｒｔ−ブチル、過酸化プロピオニル、過酸化ベンゾイル、過酸化２−クロロベンゾイル、過酸化３−クロロベンゾイル、過酸化４−クロロベンゾイル、過酸化２，４−ジクロロベンゾイル、過酸化４−ブロモメチルベンゾイル、過酸化ラウロイル、過硫酸カリウム、ペルオキシ炭酸ジイソプロピル、テトラリンヒドロペルオキシド、１−フェニル−２−メチルプロピル−１−ヒドロペルオキシド、過トリフェニル酢酸−ｔｅｒｔ−ブチル、ｔｅｒｔ−ブチルヒドロペルオキシド、過ギ酸ｔｅｒｔ−ブチル、過酢酸ｔｅｒｔ−ブチル、安息香酸ｔｅｒｔ−ブチル、過フェニル酢酸ｔｅｒｔ−ブチル、過４−メトキシ酢酸ｔｅｒｔ−ブチル、過Ｎ−（３−トルイル）カルバミン酸ｔｅｒｔ−ブチル等が挙げられる。重合開始剤を例示すると、過酸化ベンゾイル、過酸化ラウロイル、キュメンヒドロペルオキシド、ｔ−ブチルヒドロペルオキシド、ジ−ｔ−ブチルペルオキシド、メチルエチルケトンペルオキシド等の過酸化物系ラジカル重合開始剤等が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。 As the radical polymerization initiator, it is preferable that the polymerization initiation radical species after decomposition is oil-soluble. Examples of such radical polymerization initiators include 2,2′-azobispropane, 2,2′-dichloro-2,2′-azobispropane, 1,1′-azo (methylethyl) diacetate, 2,2′-azobis (2-amidinopropane) hydrochloride, 2,2′-azobis (2-aminopropane) nitrate, 2,2′-azobisisobutane, 2,2′-azobisisobutyramide, 2, 2′-azobisisobutyronitrile, methyl 2,2′-azobis-2-methylpropionate, 2,2′-dichloro-2,2′-azobisbutane, 2,2′-azobis-2-methylbutyro Nitrile, dimethyl 2,2′-azobisisobutyrate, 1,1′-azobis (sodium 1-methylbutyronitrile-3-sulfonate), 2- (4-methylphenylazo) -2-methylmalo Dinitrile 4,4′-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-allylmalonodinitrile, 2,2′-azobis-2-methylvaleronitrile, 4,4′-azobis- Dimethyl 4-cyanovalerate, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobiscyclohexanenitrile, 2,2′-azobis-2-propylbutyronitrile, 1,1 ′ -Azobis-1-chlorophenylethane, 1,1'-azobis-1-cyclohexanecarbonitrile, 1,1'-azobis-1-cycloheptanenitrile, 1,1'-azobis-1-phenylethane, 1,1 ' -Azobiscumene, 4-nitrophenylazobenzylethyl cyanoacetate, phenylazodiphenylmethane, phenylazotripheny Methane, 4-nitrophenylazotriphenylmethane, 1,1′-azobis-1,2-diphenylethane, poly (bisphenol A-4,4′-azobis-4-cyanopentanoate), poly (tetraethylene glycol) Azo radical polymerization initiators such as -2,2'-azobisisobutyrate), acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, 2-chlorobenzoyl peroxide, 3-chlorobenzoyl peroxide, 4-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 4-bromomethylbenzoyl peroxide, lauroyl peroxide, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl -2-methylpropyl-1-hydroperoxide, pertri Tert-butyl phenylacetate, tert-butyl hydroperoxide, tert-butyl performate, tert-butyl peracetate, tert-butyl benzoate, tert-butyl perphenylacetate, tert-butyl permethoxyacetate, per-N- And tert-butyl (3-toluyl) carbamate. Examples of the polymerization initiator include peroxide radical polymerization initiators such as benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, and methyl ethyl ketone peroxide. These may be used alone or in combination of two or more.
また、連鎖移動剤として、メルカプト化合物を加えることができる。例えば、メルカプトエタノール、メルカプトプロパノール、メルカプトブタノール、メルカプトプロパンジオール、メルカプトブタンジオール、ヒドロキシベンゼンチオール及びその誘導体等の水酸基を有する連鎖移動剤；１−ブタンチオール、ブチル−３−メルカプトプロピオネート、メチル−３−メルカプトプロピオネート、２，２−（エチレンジオキシ）ジエタンチオール、エタンチオール、４−メチルベンゼンチオール、ドデシルメルカプタン、プロパンチオール、ブタンチオール、ペンタンチオール、１−オクタンチオール、シクロペンタンチオール、シクロヘキサンチオール、チオグリセロール、４，４−チオビスベンゼンチオール等が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。 Moreover, a mercapto compound can be added as a chain transfer agent. For example, chain transfer agents having hydroxyl groups such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl- 3-mercaptopropionate, 2,2- (ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclopentanethiol, Examples include cyclohexanethiol, thioglycerol, and 4,4-thiobisbenzenethiol. These may be used alone or in combination of two or more.
以上に説明した本発明の（メタ）アクリル酸エステル共重合体は、後述する本発明の樹脂組成物において、（Ｂ）成分として含まれる。 The (meth) acrylic acid ester copolymer of the present invention described above is included as the component (B) in the resin composition of the present invention described later.
＜＜樹脂組成物＞＞
本発明の樹脂組成物は、（Ａ）エポキシ樹脂と、（Ｂ）本発明の（メタ）アクリル酸エステル共重合体とを含むことを特徴とし、本発明の硬化物を得るために用いられる。（Ｂ）（メタ）アクリル酸エステル共重合体については上述した通りである。
<< Resin composition >>
The resin composition of the present invention comprises (A) an epoxy resin and (B) the (meth) acrylic acid ester copolymer of the present invention, and is used for obtaining the cured product of the present invention. (B) The (meth) acrylic acid ester copolymer is as described above.
＜（Ａ）エポキシ樹脂＞
（Ａ）エポキシ樹脂としては、特に限定されず、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、アルキルフェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、脂環式エポキシ樹脂、脂肪族鎖状エポキシ樹脂、ビフェニル型エポキシ樹脂、ビフェノール型エポキシ樹脂、アラルキル型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、トリスヒドロキシフェニルメタン型エポキシ化合物、ビスフェノールのジグリシジルエーテル化物、ナフタレンジオールのジグリシジルエーテル化物、フェノール類のジグリシジルエーテル化物、アルコール類のジグリシジルエーテル化物、トリグリシジルイソシアヌレート、各種グリシジルエーテル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、酸化型エポキシ樹脂、リン変性エポキシ樹脂等が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。これらのエポキシ樹脂の中では、耐熱性の観点から、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾ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、ナフタレン型エポキシ樹脂及びジシクロペンタジエン型エポキシ樹脂からなる群より選択される少なくとも１つを用いることが好ましい。
<(A) Epoxy resin>
(A) The epoxy resin is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, alkylphenol novolac type epoxy resin, cresol novolak type epoxy resin. , Alicyclic epoxy resin, aliphatic chain epoxy resin, biphenyl type epoxy resin, biphenol type epoxy resin, aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, trishydroxyphenylmethane type epoxy compound, bisphenol Diglycidyl etherified product, naphthalenediol diglycidyl etherified product, phenolic diglycidyl etherified product, alcohol diglycidyl etherified product, Li triglycidyl isocyanurate, various glycidyl ether type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, oxidized epoxy resins, such as phosphorus-modified epoxy resin. These may be used alone or in combination of two or more. Among these epoxy resins, from the viewpoint of heat resistance, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, and dicyclo It is preferable to use at least one selected from the group consisting of pentadiene type epoxy resins.
本発明の樹脂組成物において、（Ａ）エポキシ樹脂と（Ｂ）（メタ）アクリル酸エステル共重合体との重量割合は、特に限定されないが、９９〜５０％：１〜５０％であることが好ましく、９０〜７０％：１０〜３０％であることがより好ましい。（Ａ）エポキシ樹脂の重量割合が５０％未満であると、（Ａ）エポキシ樹脂を含む海部と（Ｂ）（メタ）アクリル酸エステル共重合体を含む島部とが逆転する結果、耐水性が低下することがあり、９９％を超えると、海島構造を形成しなくなることがある。（Ｂ）（メタ）アクリル酸エステル共重合体の重量割合が１％未満であると、海島構造を形成しなくなることがあり、５０％を超えると、（Ａ）エポキシ樹脂を含む海部と（Ｂ）（メタ）アクリル酸エステル共重合体を含む島部とが逆転する結果、耐水性が低下することがある。 In the resin composition of the present invention, the weight ratio between the (A) epoxy resin and the (B) (meth) acrylic acid ester copolymer is not particularly limited, but may be 99 to 50%: 1 to 50%. Preferably, 90 to 70%: 10 to 30% is more preferable. When the weight ratio of the (A) epoxy resin is less than 50%, the sea part containing the (A) epoxy resin and the island part containing the (B) (meth) acrylic acid ester copolymer are reversed. When it exceeds 99%, the sea-island structure may not be formed. (B) When the weight ratio of the (meth) acrylic acid ester copolymer is less than 1%, a sea-island structure may not be formed. When it exceeds 50%, (A) a sea part containing an epoxy resin and (B ) As a result of reversing the island part containing the (meth) acrylic acid ester copolymer, the water resistance may be lowered.
本発明の樹脂組成物は、（Ａ）エポキシ樹脂及び（Ｂ）（メタ）アクリル酸エステル共重合体に加えて、任意に他の成分を含有していても良い。他の成分としては、特に限定されないが、例えば、（Ｃ）硬化剤、（Ｄ）無機充填材、（Ｅ）硬化促進剤、（Ｆ）有機溶剤、酸化防止剤、光安定剤、難燃剤、消泡剤、カップリング剤、イオントラップ剤、顔料、レベリング剤等が挙げられる。 The resin composition of the present invention may optionally contain other components in addition to (A) the epoxy resin and (B) (meth) acrylic acid ester copolymer. Examples of other components include, but are not limited to, (C) curing agent, (D) inorganic filler, (E) curing accelerator, (F) organic solvent, antioxidant, light stabilizer, flame retardant, Examples include an antifoaming agent, a coupling agent, an ion trapping agent, a pigment, and a leveling agent.
＜（Ｃ）硬化剤＞
（Ｃ）硬化剤としては、（Ａ）エポキシ樹脂の硬化剤として一般的に用いられているものを使用することができ、例えば、ジアミン系硬化剤、ポリアミド系硬化剤、酸無水物系硬化剤、フェノール系水酸基を１分子中に２個以上有する化合物、各種フェノール樹脂、ポリフェニレンエーテル化合物（ＰＰＥ）等が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。
<(C) Curing agent>
(C) As the curing agent, those generally used as the curing agent for (A) epoxy resin can be used. For example, diamine-based curing agent, polyamide-based curing agent, acid anhydride-based curing agent And compounds having two or more phenolic hydroxyl groups in one molecule, various phenol resins, polyphenylene ether compounds (PPE), and the like. These may be used alone or in combination of two or more.
本発明の樹脂組成物が（Ｃ）硬化剤を含有する場合、その含有量は特に限定されないが、（Ａ）エポキシ樹脂１００重量部に対し、１０〜１００重量部であることが好ましく、２０〜８０重量部であることがより好ましい。含有量が１０重量部未満であると、ガラス転移温度が低下する結果、耐熱性が低下することがあり、１００重量部を超えると、ガラス転移温度が低下する結果、耐熱性が低下することがある。 When the resin composition of this invention contains (C) hardening | curing agent, the content is not specifically limited, It is preferable that it is 10-100 weight part with respect to 100 weight part of (A) epoxy resin, and 20-20. More preferably, it is 80 parts by weight. If the content is less than 10 parts by weight, the glass transition temperature may decrease, resulting in a decrease in heat resistance. If the content exceeds 100 parts by weight, the glass transition temperature may decrease, resulting in a decrease in heat resistance. is there.
＜（Ｄ）無機充填材＞
本発明の樹脂組成物に（Ｄ）無機充填材を配合することにより、硬化物の熱膨張係数（ＣＴＥ）を低減させることができる。（Ｄ）無機充填材としては、特に限定されないが、例えば、シリカ、アルミナ等の金属酸化物や、金属水和物等が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。
<(D) Inorganic filler>
The thermal expansion coefficient (CTE) of hardened | cured material can be reduced by mix | blending (D) inorganic filler with the resin composition of this invention. (D) Although it does not specifically limit as an inorganic filler, For example, metal oxides, such as a silica and an alumina, a metal hydrate etc. are mentioned. These may be used alone or in combination of two or more.
＜（Ｅ）硬化促進剤＞
（Ｅ）硬化促進剤としては、特に限定されないが、例えば、イミダゾール類及びその誘導体、有機リン酸系化合物、第二級アミン類、第三級アミン類、第四級アンモニウム塩等が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。
<(E) Curing accelerator>
(E) Although it does not specifically limit as a hardening accelerator, For example, imidazoles and its derivative (s), an organic phosphate type compound, secondary amines, tertiary amines, a quaternary ammonium salt etc. are mentioned. These may be used alone or in combination of two or more.
本発明の樹脂組成物が（Ｅ）硬化促進剤を含有する場合、その含有量は特に限定されないが、（Ａ）エポキシ樹脂１００重量部に対し、１〜１０重量部であることが好ましく、３〜８重量部であることがより好ましい。含有量が１重量部未満であると、硬化不良を起こすことがあり、１０重量部を超えると、耐水性が低下することがある。 When the resin composition of this invention contains (E) hardening accelerator, the content is not specifically limited, However, It is preferable that it is 1-10 weight part with respect to 100 weight part of (A) epoxy resin, 3 More preferably, it is -8 weight part. If the content is less than 1 part by weight, curing failure may occur, and if it exceeds 10 parts by weight, the water resistance may decrease.
＜（Ｆ）有機溶剤＞
本発明の樹脂組成物に（Ｆ）有機溶剤を配合することにより、ワニスを調整することができる。（Ｆ）有機溶剤としては、特に限定されず、例えば、アセトン、メチルエチルケトン（ＭＥＫ）、メチルイソブチルケトン、シクロヘキサン等のケトン系溶剤、酢酸エチル、酢酸ブチル等のエステル系溶剤、トルエン、キシレン等の芳香族系溶剤、ジメチルホルムアミド等の窒素含有溶剤等が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。
<(F) Organic solvent>
A varnish can be adjusted by mix | blending (F) organic solvent with the resin composition of this invention. (F) The organic solvent is not particularly limited, and examples thereof include ketone solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone and cyclohexane, ester solvents such as ethyl acetate and butyl acetate, and aromatics such as toluene and xylene. And nitrogen-containing solvents such as dimethylformamide and dimethylformamide. These may be used alone or in combination of two or more.
本発明の樹脂組成物が（Ｆ）有機溶剤を含有する場合、その含有量は特に限定されないが、樹脂組成物中２０〜８０重量％であることが好ましく、３０〜６０重量％であることがより好ましい。含有量が２０重量％未満であると、粘度が上昇し、取り扱いが困難となることがあり、８０重量％を超えると、粘度が低下し、取り扱いが困難となることがある。 When the resin composition of this invention contains the (F) organic solvent, the content is not specifically limited, However, It is preferable that it is 20 to 80 weight% in a resin composition, and it is 30 to 60 weight%. More preferred. When the content is less than 20% by weight, the viscosity may increase and handling may be difficult. When the content exceeds 80% by weight, the viscosity may decrease and handling may be difficult.
＜＜硬化物＞＞
本発明の硬化物は、本発明の樹脂組成物を硬化させて得られる硬化物であって、
（Ａ）エポキシ樹脂を含む海部と、（Ｂ）（メタ）アクリル酸エステル共重合体を含む島部とからなる海島構造を有し、
（Ｂ）（メタ）アクリル酸エステル共重合体を含む島部の長径は０．１〜１０μｍであることを特徴とする。
<< cured product >>
The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention,
(A) It has a sea-island structure consisting of a sea part containing an epoxy resin and an island part containing (B) a (meth) acrylic acid ester copolymer,
(B) The major axis of the island part containing the (meth) acrylic acid ester copolymer is 0.1 to 10 μm.
本発明の硬化物は、例えば、本発明の樹脂組成物をロールコート法、バーコート法、ディップコーティング法、ブレードコート法、カーテンコート法、スプレーコート法、ドクターコート法等により塗布した後、６０〜２００℃で１０〜２００分間加熱処理することで製造することができる。 The cured product of the present invention can be obtained by, for example, applying the resin composition of the present invention by roll coating, bar coating, dip coating, blade coating, curtain coating, spray coating, doctor coating, etc. It can manufacture by heat-processing at -200 degreeC for 10 to 200 minutes.
本発明の硬化物はまた、本発明の樹脂組成物を半硬化状態（Ｂステージ）となるまで加熱乾燥したものを積層し、これを１４０〜２００℃で１０〜２００分間加熱硬化しＣステージに移行させることによっても製造することができる。 The cured product of the present invention is also laminated by heating and drying the resin composition of the present invention until it is in a semi-cured state (B stage), and this is heat cured at 140 to 200 ° C. for 10 to 200 minutes to form a C stage. It can also be manufactured by shifting.
本発明の硬化物を製造する際には、本発明の樹脂組成物を繊維基材に含浸させた後、上述の方法により半硬化状態（Ｂステージ）を経てＣステージに移行させても良い。繊維基材としては、特に限定されないが、例えば、ガラスクロス、アラミドクロス、ポリエステルクロス等を使用することができる。これらは単独で用いても良いし、２種以上を併用しても良い。 When producing the cured product of the present invention, the fiber base material may be impregnated with the resin composition of the present invention, and then transferred to the C stage through the semi-cured state (B stage) by the above-described method. Although it does not specifically limit as a fiber base material, For example, a glass cloth, an aramid cloth, a polyester cloth etc. can be used. These may be used alone or in combination of two or more.
本発明の硬化物は、（Ａ）エポキシ樹脂を含む海部と、（Ｂ）（メタ）アクリル酸エステル共重合体を含む島部とからなる海島構造を有する。（Ｂ）（メタ）アクリル酸エステル共重合体を含む島部の長径は、０．１〜１０μｍである。（Ｂ）（メタ）アクリル酸エステル共重合体を含む島部の長径が０．１μｍ未満であると応力緩和特性が低下することがあり、１０μｍを超えると耐水性が低下することがある。 The cured product of the present invention has a sea-island structure composed of (A) a sea part containing an epoxy resin and (B) an island part containing a (meth) acrylic acid ester copolymer. (B) The long diameter of the island part containing a (meth) acrylic acid ester copolymer is 0.1-10 micrometers. (B) When the major axis of the island part containing the (meth) acrylic acid ester copolymer is less than 0.1 μm, the stress relaxation property may be lowered, and when it exceeds 10 μm, the water resistance may be lowered.
以下、実施例を挙げて本発明を説明するが、本発明は以下の実施例に限定されない。以下、「部」又は「％」は特記ない限り、それぞれ「重量部」又は「重量％」を意味する。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to a following example. Hereinafter, “part” or “%” means “part by weight” or “% by weight”, respectively, unless otherwise specified.
（合成例１〜１３）（Ｂ）（メタ）アクリル酸エステル共重合体の作製
撹拌機を備えた四つ口フラスコに水１３００重量部を入れ、分散安定剤としてポリビニルアルコール３重量部を溶解し、撹拌しつつ、表１に示す重量比で各モノマー成分を混合した混合物４３０重量部と重合開始剤として２，２’−アゾビスイソブチロニトリル４重量部を一括投入し、懸濁液を作製した。この懸濁液を、撹拌継続下に６８℃まで昇温させ、４時間一定に保って反応させた。その後、室温（約２５℃）まで冷却した。次いで、反応物を固液分離し、水で十分に洗浄した後、乾燥機を用いて乾燥させることにより（Ｂ）（メタ）アクリル酸エステル共重合体を得た。
(Synthesis Examples 1 to 13) (B) Preparation of (meth) acrylic acid ester copolymer 1300 parts by weight of water was placed in a four-necked flask equipped with a stirrer, and 3 parts by weight of polyvinyl alcohol was dissolved as a dispersion stabilizer. While stirring, 430 parts by weight of a mixture in which the monomer components were mixed at a weight ratio shown in Table 1 and 4 parts by weight of 2,2′-azobisisobutyronitrile as a polymerization initiator were added all at once. Produced. The suspension was heated to 68 ° C. with continued stirring and reacted for 4 hours. Then, it cooled to room temperature (about 25 degreeC). Next, the reaction product was separated into solid and liquid, sufficiently washed with water, and then dried using a dryer to obtain a (B) (meth) acrylic acid ester copolymer.
合成例１〜１３で得られた（Ｂ）（メタ）アクリル酸エステル共重合体、及び、カルボキシ末端ブチルニトリルゴム（ＣＴＢＮ）（日本ゼオン株式会社製、１０７２Ｊ）について、下記の方法によりエポキシ価、重量平均分子量及び数平均分子量、溶剤溶解性、並びに、吸水性を評価した。結果を表１に示す。なお、合成例４で作製した（Ｂ）（メタ）アクリル酸エステル共重合体は、溶剤に難溶であったため、吸水性を評価することができなかった。 About the (B) (meth) acrylic acid ester copolymer and the carboxy terminal butyl nitrile rubber (CTBN) (manufactured by Nippon Zeon Co., Ltd., 1072J) obtained in Synthesis Examples 1 to 13, the epoxy value was determined by the following method. The weight average molecular weight and number average molecular weight, solvent solubility, and water absorption were evaluated. The results are shown in Table 1. In addition, since the (B) (meth) acrylic acid ester copolymer produced in Synthesis Example 4 was hardly soluble in a solvent, water absorption could not be evaluated.
（エポキシ価）
（Ｂ）（メタ）アクリル酸エステル共重合体を１．０ｇ秤量し、クロロホルム１０ｍＬと酢酸３０ｍＬに溶解させて溶液を得た。この溶液と２０％テトラアンモニウムブロマイド酢酸溶液５ｍＬとを混合して試料を得た。また、（Ｂ）（メタ）アクリル酸エステル共重合体を使用しないこと以外は同様にして、ブランク溶液を用意した。クリスタルバイオレット指示薬を用いて、０．１ｍｏｌ／Ｌ過塩素酢酸規定液で滴定した。エポキシ価は、以下の計算式で算出した。
エポキシ価（ｅｑ／ｋｇ）＝［（試料に要した規定液滴定量−ブランクに要した規定液滴定量）×グリシジル（メタ）アクリレートの分子量×規定液のファクター］／［試料量（ｇ）×１００］
(Epoxy value)
(B) 1.0 g of (meth) acrylic acid ester copolymer was weighed and dissolved in 10 mL of chloroform and 30 mL of acetic acid to obtain a solution. This solution was mixed with 5 mL of 20% tetraammonium bromide acetic acid solution to obtain a sample. A blank solution was prepared in the same manner except that (B) (meth) acrylic acid ester copolymer was not used. Using crystal violet indicator, the solution was titrated with 0.1 mol / L perchloric acid normal solution. The epoxy value was calculated by the following formula.
Epoxy value (eq / kg) = [(regular droplet quantification required for sample−regular droplet quantification required for blank) × molecular weight of glycidyl (meth) acrylate × factor of defined liquid] / [sample amount (g) × 100]
（重量平均分子量及び数平均分子量）
ゲル浸透クロマトグラフィー（ＧＰＣ）法により標準ポリスチレン換算で求めた。
(Weight average molecular weight and number average molecular weight)
It calculated | required in standard polystyrene conversion by the gel permeation chromatography (GPC) method.
（溶剤溶解性）
（Ｂ）（メタ）アクリル酸エステル共重合体又はＣＴＢＮ５重量部を、メチルエチルケトン（ＭＥＫ）９５重量部と混合した後６０℃に保ち、（Ｂ）（メタ）アクリル酸エステル共重合体又はＣＴＢＮが完全に溶解するまでに要した時間を計測し、下記の基準で評価した。
○：２４時間未満で完全に溶解した。
△：２４時間以上７２時間未満で完全に溶解した。
×：７２時間経過時点で不溶であった（完全には溶解していなかった）。
(Solvent solubility)
(B) 5 parts by weight of (meth) acrylic acid ester copolymer or CTBN is mixed with 95 parts by weight of methyl ethyl ketone (MEK) and kept at 60 ° C., and (B) (meth) acrylic acid ester copolymer or CTBN is completely The time required for dissolution was measured and evaluated according to the following criteria.
○: Completely dissolved in less than 24 hours.
(Triangle | delta): It melt | dissolved completely in 24 hours or more and less than 72 hours.
X: Insoluble at 72 hours (not completely dissolved).
（吸水性）
（Ｂ）（メタ）アクリル酸エステル共重合体又はＣＴＢＮを３０ｍｍ×４０ｍｍ×１ｍｍの大きさに成型して試料を作製した。この試料を、１００℃の沸騰水に３０分間浸漬し、その後の重量増加率を下記式により算出し、下記の基準で評価した。
重量増加率（％）＝（浸漬後の重量−浸漬前の重量）／浸漬前の重量×１００
◎：重量増加率が１％未満である。
○：重量増加率が１％以上２％未満である。
×：重量増加率が２％以上である。
(Water absorption)
(B) A sample was prepared by molding (meth) acrylic acid ester copolymer or CTBN into a size of 30 mm × 40 mm × 1 mm. This sample was immersed in boiling water at 100 ° C. for 30 minutes, and the weight increase rate thereafter was calculated by the following formula and evaluated according to the following criteria.
Weight increase rate (%) = (weight after immersion−weight before immersion) / weight before immersion × 100
A: Weight increase rate is less than 1%.
○: The weight increase rate is 1% or more and less than 2%.
X: The weight increase rate is 2% or more.
表１より、本発明の（メタ）アクリル酸エステル共重合体は、溶剤溶解性に優れ、吸水性が低いことが分かる。 From Table 1, it can be seen that the (meth) acrylic acid ester copolymer of the present invention has excellent solvent solubility and low water absorption.
（比較例１〜５、実施例１〜１７）樹脂組成物の作製
（Ａ）エポキシ樹脂としてクレゾールノボラック型エポキシ樹脂（ＤＩＣ株式会社製、Ｎ−６８０）１００重量部、（Ｃ）硬化剤としてフェノールノボラック（ＤＩＣ株式会社製、ＴＤ−２０９３）５０重量部、（Ｅ）硬化促進剤として２−メチルイミダゾール（四国化成株式会社製、２ＭＺ）１重量部、（Ｂ）（メタ）アクリル酸エステル共重合体としてＣＴＢＮ又は合成例１〜１３で作製した（Ｂ）（メタ）アクリル酸エステル共重合体、及び、（Ｆ）有機溶剤としてメチルエチルケトン（ＭＥＫ）（ナカライテスク株式会社製）を表２に示す重量比で混合し、樹脂組成物を得た。
(Comparative Examples 1-5, Examples 1-17) Production of Resin Composition (A) 100 parts by weight of cresol novolac type epoxy resin (manufactured by DIC Corporation, N-680) as an epoxy resin, (C) phenol as a curing agent 50 parts by weight of novolak (manufactured by DIC Corporation, TD-2093), (E) 1 part by weight of 2-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., 2MZ) as a curing accelerator, (B) (meth) acrylic acid ester copolymer The weight shown in Table 2 is CTBN as a coalescence or (B) (meth) acrylic acid ester copolymer produced in Synthesis Examples 1 to 13, and (F) methyl ethyl ketone (MEK) (manufactured by Nacalai Tesque Co., Ltd.) as an organic solvent. The resin composition was obtained by mixing at a ratio.
比較例１〜５、実施例１〜１７で得られた樹脂組成物を用いて、下記の方法により相分離状態（海島構造）及び吸水性を評価した。結果を表２に示す。なお、比較例５の樹脂組成物は、合成例４で作製した（Ｂ）（メタ）アクリル酸エステル共重合体が溶剤に難溶であったため、相分離状態（海島構造）及び吸水性のいずれも評価することができなかった。 Using the resin compositions obtained in Comparative Examples 1 to 5 and Examples 1 to 17, the phase separation state (sea-island structure) and water absorption were evaluated by the following methods. The results are shown in Table 2. In addition, since the (B) (meth) acrylic acid ester copolymer produced in Synthesis Example 4 was hardly soluble in the solvent, the resin composition of Comparative Example 5 was either a phase-separated state (sea-island structure) or water-absorbing. Also could not be evaluated.
（相分離状態（海島構造））
樹脂組成物を膜厚５０μｍ以下のフィルム状に成型し、１８０℃で１２０分間加熱硬化することにより硬化させて硬化物を得た。得られた硬化物表面の外観を電子顕微鏡にて観察し、島部の長径を測定し、下記の基準で評価した。
○：島部の長径が０．１〜１０μｍである。
×：島部の長径が０．１μｍ未満、又は、１０μｍを超えている。
(Phase separation state (sea island structure))
The resin composition was molded into a film having a film thickness of 50 μm or less and cured by heating and curing at 180 ° C. for 120 minutes to obtain a cured product. The appearance of the surface of the obtained cured product was observed with an electron microscope, the major axis of the island was measured, and evaluated according to the following criteria.
○: The major axis of the island is 0.1 to 10 μm.
X: The long diameter of an island part is less than 0.1 micrometer or exceeds 10 micrometers.
（吸水性）
樹脂組成物を３０ｍｍ×４０ｍｍ×４ｍｍの大きさに成型し、１８０℃で１２０分間加熱硬化することにより硬化物試料を作製した。この硬化物試料を、１００℃の沸騰水に２４時間浸漬し、その後の重量増加率を下記式により算出し、下記の基準で評価した。
重量増加率（％）＝（浸漬後の重量−浸漬前の重量）／浸漬前の重量×１００
◎：重量増加率が１．８％未満である。
○：重量増加率が１．８％以上３．０％未満である。
×：重量増加率が３．０％以上である。
(Water absorption)
The resin composition was molded into a size of 30 mm × 40 mm × 4 mm and cured by heating at 180 ° C. for 120 minutes to prepare a cured product sample. This hardened | cured material sample was immersed in boiling water of 100 degreeC for 24 hours, the weight increase rate after that was computed by the following formula, and the following reference | standard evaluated.
Weight increase rate (%) = (weight after immersion−weight before immersion) / weight before immersion × 100
A: Weight increase rate is less than 1.8%.
○: The weight increase rate is 1.8% or more and less than 3.0%.
X: The weight increase rate is 3.0% or more.
表２より、本発明の（メタ）アクリル酸エステル共重合体を（Ｂ）成分として含む樹脂組成物を硬化させて得られた硬化物は、良好な相分離状態（海島構造）を示し、吸水性が低い（耐水性に優れる）ことが分かる。 From Table 2, the hardened | cured material obtained by hardening the resin composition which contains the (meth) acrylic acid ester copolymer of this invention as a (B) component shows a favorable phase-separation state (sea-island structure), and water absorption It is understood that the property is low (excellent in water resistance).
Claims (8)
エポキシ価が０．０６〜１．２ｅｑ／ｋｇであり、
重量平均分子量が１００，０００〜１，０００，０００であることを特徴とする（メタ）アクリル酸エステル共重合体。 As a monomer component, a (meth) acrylic acid ester copolymer obtained by copolymerizing glycidyl (meth) acrylate, alkyl (meth) acrylate and an aromatic vinyl compound,
The epoxy value is 0.06 to 1.2 eq / kg,
A (meth) acrylic acid ester copolymer having a weight average molecular weight of 100,000 to 1,000,000.
（Ａ）エポキシ樹脂を含む海部と、（Ｂ）（メタ）アクリル酸エステル共重合体を含む島部とからなる海島構造を有し、
（Ｂ）（メタ）アクリル酸エステル共重合体を含む島部の長径は０．１〜１０μｍであることを特徴とする硬化物。 (A) A cured product obtained by curing a resin composition containing an epoxy resin and (B) the (meth) acrylic acid ester copolymer according to any one of claims 1 to 3,
(A) It has a sea-island structure consisting of a sea part containing an epoxy resin and an island part containing (B) a (meth) acrylic acid ester copolymer,
(B) Hardened | cured material characterized by the long diameter of the island part containing a (meth) acrylic acid ester copolymer being 0.1-10 micrometers.
The resin composition used in order to obtain the hardened | cured material of any one of Claims 4-7.
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