JP7477597B2 - Adhesive Composition - Google Patents
Adhesive Composition Download PDFInfo
- Publication number
- JP7477597B2 JP7477597B2 JP2022514084A JP2022514084A JP7477597B2 JP 7477597 B2 JP7477597 B2 JP 7477597B2 JP 2022514084 A JP2022514084 A JP 2022514084A JP 2022514084 A JP2022514084 A JP 2022514084A JP 7477597 B2 JP7477597 B2 JP 7477597B2
- Authority
- JP
- Japan
- Prior art keywords
- adhesive composition
- adhesive
- mass
- parts
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 230000001070 adhesive effect Effects 0.000 title claims description 189
- 239000000853 adhesive Substances 0.000 title claims description 184
- 239000000203 mixture Substances 0.000 title claims description 128
- 229920000058 polyacrylate Polymers 0.000 claims description 51
- 229920000800 acrylic rubber Polymers 0.000 claims description 50
- 239000007788 liquid Substances 0.000 claims description 38
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 229920001577 copolymer Polymers 0.000 claims description 22
- 239000005011 phenolic resin Substances 0.000 claims description 22
- 125000000524 functional group Chemical group 0.000 claims description 20
- 229920001568 phenolic resin Polymers 0.000 claims description 18
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 16
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 15
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 15
- 230000000977 initiatory effect Effects 0.000 claims description 15
- 238000009835 boiling Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 7
- 238000001723 curing Methods 0.000 description 58
- 229920005989 resin Polymers 0.000 description 56
- 239000011347 resin Substances 0.000 description 56
- 229910052751 metal Inorganic materials 0.000 description 36
- 239000002184 metal Substances 0.000 description 36
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 30
- 238000000576 coating method Methods 0.000 description 28
- 238000000465 moulding Methods 0.000 description 27
- 239000000463 material Substances 0.000 description 26
- 239000011248 coating agent Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 24
- 230000009477 glass transition Effects 0.000 description 19
- 230000035882 stress Effects 0.000 description 19
- 239000012790 adhesive layer Substances 0.000 description 17
- 229910052782 aluminium Inorganic materials 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 239000000178 monomer Substances 0.000 description 16
- 229920002799 BoPET Polymers 0.000 description 14
- 239000003973 paint Substances 0.000 description 13
- 229920001187 thermosetting polymer Polymers 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 239000004014 plasticizer Substances 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 10
- 125000003700 epoxy group Chemical group 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 239000000523 sample Substances 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- -1 acrylic ester Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 238000005304 joining Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000013618 particulate matter Substances 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical compound N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 125000002560 nitrile group Chemical group 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 238000001595 flow curve Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000728 polyester Chemical class 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000001029 thermal curing 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
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- DDKMFQGAZVMXQV-UHFFFAOYSA-N (3-chloro-2-hydroxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CCl DDKMFQGAZVMXQV-UHFFFAOYSA-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
- ZMAMKNPVAMKIIC-UHFFFAOYSA-N (5-benzyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC=1N=C(C=2C=CC=CC=2)NC=1CC1=CC=CC=C1 ZMAMKNPVAMKIIC-UHFFFAOYSA-N 0.000 description 1
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- WUAFLNUJIPFKHQ-UHFFFAOYSA-N 1,3-bis[2-(2-methyl-1h-imidazol-5-yl)ethyl]urea Chemical compound N1C(C)=NC=C1CCNC(=O)NCCC1=CN=C(C)N1 WUAFLNUJIPFKHQ-UHFFFAOYSA-N 0.000 description 1
- VOJAMWORWOLUKL-UHFFFAOYSA-N 1-benzyl-2-ethyl-5-methylimidazole Chemical compound CCC1=NC=C(C)N1CC1=CC=CC=C1 VOJAMWORWOLUKL-UHFFFAOYSA-N 0.000 description 1
- OQZDJLFNMXRJHZ-UHFFFAOYSA-N 1-benzyl-2-ethylimidazole Chemical compound CCC1=NC=CN1CC1=CC=CC=C1 OQZDJLFNMXRJHZ-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- XZKLXPPYISZJCV-UHFFFAOYSA-N 1-benzyl-2-phenylimidazole Chemical compound C1=CN=C(C=2C=CC=CC=2)N1CC1=CC=CC=C1 XZKLXPPYISZJCV-UHFFFAOYSA-N 0.000 description 1
- LIOJOGAWBPJICS-UHFFFAOYSA-N 1-benzyl-2-phenylimidazole;hydrochloride Chemical compound Cl.C1=CN=C(C=2C=CC=CC=2)N1CC1=CC=CC=C1 LIOJOGAWBPJICS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- BOANVMYDGKUJAC-UHFFFAOYSA-N 2-(2-ethylimidazol-1-yl)ethanamine Chemical compound CCC1=NC=CN1CCN BOANVMYDGKUJAC-UHFFFAOYSA-N 0.000 description 1
- QKVROWZQJVDFSO-UHFFFAOYSA-N 2-(2-methylimidazol-1-yl)ethanamine Chemical compound CC1=NC=CN1CCN QKVROWZQJVDFSO-UHFFFAOYSA-N 0.000 description 1
- VDAIJDKQXDCJSI-UHFFFAOYSA-N 2-(2-methylimidazol-1-yl)ethylurea Chemical compound CC1=NC=CN1CCNC(N)=O VDAIJDKQXDCJSI-UHFFFAOYSA-N 0.000 description 1
- MLPBASQNOQYIGL-UHFFFAOYSA-N 2-(2-propan-2-yl-1h-imidazol-5-yl)propanenitrile Chemical compound CC(C)C1=NC=C(C(C)C#N)N1 MLPBASQNOQYIGL-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
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- HQCSZRIVJVOYSU-UHFFFAOYSA-N 2-(ethoxymethyl)oxirane Chemical compound CCOCC1CO1 HQCSZRIVJVOYSU-UHFFFAOYSA-N 0.000 description 1
- SFPKYQLUNZBNQA-UHFFFAOYSA-N 2-[4,5-bis(2-cyanoethoxymethyl)-2-phenylimidazol-1-yl]propanenitrile Chemical compound N#CC(C)N1C(COCCC#N)=C(COCCC#N)N=C1C1=CC=CC=C1 SFPKYQLUNZBNQA-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- UINDRJHZBAGQFD-UHFFFAOYSA-N 2-ethyl-1-methylimidazole Chemical compound CCC1=NC=CN1C UINDRJHZBAGQFD-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- QFZKVFCEJRXRBD-UHFFFAOYSA-N 2-ethyl-4-[(2-ethyl-5-methyl-1h-imidazol-4-yl)methyl]-5-methyl-1h-imidazole Chemical compound N1C(CC)=NC(CC2=C(NC(CC)=N2)C)=C1C QFZKVFCEJRXRBD-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QXSNXUCNBZLVFM-UHFFFAOYSA-N 2-methyl-1h-imidazole;1,3,5-triazinane-2,4,6-trione Chemical compound CC1=NC=CN1.O=C1NC(=O)NC(=O)N1 QXSNXUCNBZLVFM-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- RJIQELZAIWFNTQ-UHFFFAOYSA-N 2-phenyl-1h-imidazole;1,3,5-triazinane-2,4,6-trione Chemical compound O=C1NC(=O)NC(=O)N1.C1=CNC(C=2C=CC=CC=2)=N1 RJIQELZAIWFNTQ-UHFFFAOYSA-N 0.000 description 1
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- SQTBDJHGOABYOB-UHFFFAOYSA-N 2h-benzotriazole;2-methyl-1h-imidazole Chemical compound CC1=NC=CN1.C1=CC=CC2=NNN=C21 SQTBDJHGOABYOB-UHFFFAOYSA-N 0.000 description 1
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 1
- SESYNEDUKZDRJL-UHFFFAOYSA-N 3-(2-methylimidazol-1-yl)propanenitrile Chemical compound CC1=NC=CN1CCC#N SESYNEDUKZDRJL-UHFFFAOYSA-N 0.000 description 1
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 1
- SZUPZARBRLCVCB-UHFFFAOYSA-N 3-(2-undecylimidazol-1-yl)propanenitrile Chemical compound CCCCCCCCCCCC1=NC=CN1CCC#N SZUPZARBRLCVCB-UHFFFAOYSA-N 0.000 description 1
- MLLXXNHPVFZVTB-UHFFFAOYSA-N 3-[2-(2-methylimidazol-1-yl)ethylamino]propanenitrile Chemical compound CC1=NC=CN1CCNCCC#N MLLXXNHPVFZVTB-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- YATKABCHSRLDGQ-UHFFFAOYSA-N 5-benzyl-2-phenyl-1h-imidazole Chemical compound C=1C=CC=CC=1CC(N=1)=CNC=1C1=CC=CC=C1 YATKABCHSRLDGQ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000005102 attenuated total reflection Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- LZLOFGMGFADIKQ-UHFFFAOYSA-N benzene;1,4-dioxane Chemical compound C1COCCO1.C1=CC=CC=C1 LZLOFGMGFADIKQ-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 238000007759 kiss coating Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- ZZSKMNCIAKKVRB-UHFFFAOYSA-N morpholin-4-yl-(2-nitrophenyl)methanone Chemical compound [O-][N+](=O)C1=CC=CC=C1C(=O)N1CCOCC1 ZZSKMNCIAKKVRB-UHFFFAOYSA-N 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 125000005591 trimellitate group Chemical class 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/18—Homopolymers or copolymers of nitriles
- C09J133/20—Homopolymers or copolymers of acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、接着剤組成物に関する。
本願は、２０２０年４月１０日に、日本に出願された特願２０２０－０７０８８６号に基づき優先権を主張し、その内容をここに援用する。
The present invention relates to an adhesive composition.
This application claims priority based on Japanese Patent Application No. 2020-070886, filed on April 10, 2020, the contents of which are incorporated herein by reference.
金属と樹脂の複合部品の製造方法としては、例えば、インサート成形や熱プレス成形等が挙げられる。複合部品を製造する際に、金属と樹脂の間を接合する方法としては、例えば、特許文献１～特許文献３に記載されているような方法が挙げられる。 Examples of methods for manufacturing composite parts of metal and resin include insert molding and hot press molding. Methods for joining metal and resin when manufacturing composite parts include the methods described in Patent Documents 1 to 3.
特許文献１には、物理的または化学的処理により、金属部材を表面処理して、その表面を粗くし、その粗くした表面に、溶融した樹脂を接触させて、その樹脂を固化させることにより、金属と樹脂の間でアンカー効果を発現させて、金属と樹脂を接合する方法が開示されている。
特許文献２には、金属部材の表面に接着剤を塗布し、その接着剤を介して、金属部材の表面に樹脂を接触させて、金属と樹脂を接合する方法が開示されている。
特許文献３には、射出成形に用いられる樹脂自体に金属接着性を付与し、その樹脂を金属に接触させて、金属と樹脂を接合する方法が開示されている。
Patent Document 1 discloses a method for joining metal and resin by performing surface treatment on a metal component using a physical or chemical treatment to roughen the surface, bringing molten resin into contact with the roughened surface and solidifying the resin, thereby creating an anchor effect between the metal and resin.
Patent Document 2 discloses a method of joining metal and resin by applying an adhesive to the surface of a metal member and bringing a resin into contact with the surface of the metal member via the adhesive.
Patent Document 3 discloses a method of imparting metal adhesiveness to a resin used in injection molding and bringing the resin into contact with a metal to bond the metal and the resin.
特許文献１に記載の発明では、金属と樹脂が直接接合されるため、複合部品は応力緩和性に劣っていた。また、金属部材の表面処理自体、可使時間が短いため、金属部材の表面処理から樹脂の成形までの管理が大変であった。さらに、成形条件に適合する樹脂が限定されていた。
特許文献２に記載の発明では、金属と樹脂の接着性が不十分であるため、複合部品の成形後に、金属から樹脂が剥離し易かった。また、樹脂の使用温度域において、金属と樹脂の接着性を確保することが難しかった。
特許文献３に記載の発明では、複合部品の形状や成形条件が制限されることがあった。
In the invention described in Patent Document 1, the metal and the resin are directly bonded, so the composite parts have poor stress relaxation properties. In addition, the surface treatment of the metal parts itself has a short pot life, so it is difficult to manage the process from the surface treatment of the metal parts to the molding of the resin. Furthermore, the resins that are suitable for the molding conditions are limited.
In the invention described in Patent Document 2, the adhesion between the metal and the resin is insufficient, so that the resin is easily peeled off from the metal after molding of the composite part. Also, it is difficult to ensure the adhesion between the metal and the resin in the operating temperature range of the resin.
In the invention described in Patent Document 3, the shape and molding conditions of the composite part were sometimes limited.
本発明は、上記事情に鑑みてなされたものであって、金属および樹脂との接着性に優れるとともに、応力緩和性、耐熱性に優れる接着剤組成物を提供することを目的とする。The present invention has been made in consideration of the above circumstances, and aims to provide an adhesive composition that has excellent adhesion to metals and resins, as well as excellent stress relaxation properties and heat resistance.
本発明は、以下の態様を有する。
［１］カルボキシル基の官能基を有するアクリルゴムと、前記官能基と反応するシランカップリング剤と、フェノール樹脂と、硬化促進剤と、液状媒体と、を含有する接着剤組成物であって、前記アクリルゴムが、アクリル酸エステルおよびその誘導体の少なくとも一方とアクリロニトリルおよびその誘導体の少なくとも一方の共重合体を含み、前記硬化促進剤が前記液状媒体に不溶であり、かつ前記硬化促進剤の反応開始温度が前記液状媒体の沸点より高い温度であり、前記硬化促進剤の粒子が分散されていることを特徴とする接着剤組成物。
The present invention has the following aspects.
[1] An adhesive composition comprising an acrylic rubber having a carboxyl functional group, a silane coupling agent that reacts with the functional group, a phenolic resin, a curing accelerator, and a liquid medium, wherein the acrylic rubber comprises a copolymer of at least one of an acrylic acid ester and its derivatives, and at least one of acrylonitrile and its derivatives, the curing accelerator is insoluble in the liquid medium, the reaction initiation temperature of the curing accelerator is higher than the boiling point of the liquid medium, and particles of the curing accelerator are dispersed in the adhesive composition.
本発明によれば、金属および樹脂との接着性に優れるとともに、応力緩和性、耐熱性に優れる接着剤組成物を提供することができる。 According to the present invention, it is possible to provide an adhesive composition that has excellent adhesion to metals and resins, as well as excellent stress relaxation properties and heat resistance.
本発明の接着剤組成物の実施の形態について説明する。
なお、本実施の形態は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明を限定するものではない。
An embodiment of the adhesive composition of the present invention will be described.
It should be noted that the present embodiment is specifically described to allow a better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.
［接着剤組成物］
本実施形態に係る接着剤組成物は、カルボキシル基、水酸基およびエポキシ基からなる群から選択される少なくとも１種の官能基を有するアクリルゴムと、前記官能基と反応するシランカップリング剤と、フェノール樹脂と、硬化促進剤と、を含む。
前記アクリルゴムは、アクリル酸エステルおよびその誘導体の少なくとも一方とアクリロニトリルおよびその誘導体の少なくとも一方の共重合体を含むことが好ましい。
[Adhesive composition]
The adhesive composition according to this embodiment contains an acrylic rubber having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, and an epoxy group, a silane coupling agent that reacts with the functional group, a phenolic resin, and a curing accelerator.
The acrylic rubber preferably contains a copolymer of at least one of an acrylic acid ester and its derivatives and at least one of acrylonitrile and its derivatives.
該共重合体全体を１００質量％とした場合、共重合体におけるアクリル酸エステルに由来する構造単位の含有量は、５０質量％以上であることが好ましく、６０質量％以上であることがより好ましい。
アクリル酸エステルに由来する構造単位の含有量が５０質量％未満では、接着剤組成物の硬化物の柔軟性も低下し、応力緩和性が悪くなる傾向がある。
When the entire copolymer is taken as 100% by mass, the content of structural units derived from an acrylic acid ester in the copolymer is preferably 50% by mass or more, and more preferably 60% by mass or more.
If the content of structural units derived from an acrylic acid ester is less than 50 mass %, the flexibility of the cured product of the adhesive composition also decreases, and the stress relaxation properties tend to be poor.
上記共重合体全体を１００質量％とした場合、共重合体におけるアクリロニトリルに由来する構造単位の含有量は、５０質量％以下であることが好ましく、４０質量％以下であることがより好ましい。
アクリロニトリルに由来する構造単位の含有量が５０質量％を超えると、接着剤組成物の溶剤への溶解性が低くなる、塗料化した際に塗料の粘度が高くなる、塗料の流動性がなくなる（ゲル化する）、接着剤用塗料の取り扱いが難しくなるといった不具合が生じる傾向がある。また、接着剤組成物の硬化物の柔軟性も低下し、応力緩和性が悪くなる傾向がある。
When the entire copolymer is taken as 100% by mass, the content of structural units derived from acrylonitrile in the copolymer is preferably 50% by mass or less, and more preferably 40% by mass or less.
If the content of structural units derived from acrylonitrile exceeds 50% by mass, problems such as reduced solubility of the adhesive composition in a solvent, increased viscosity of the paint when made into a paint, loss of fluidity of the paint (gelation), and difficulty in handling the adhesive paint tend to occur. In addition, the flexibility of the cured product of the adhesive composition also tends to decrease, and the stress relaxation property tends to deteriorate.
アクリル酸エステルとしては、アクリロニトリルと共重合可能なものであれば、特に限定されないが、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸２－エチルヘキシル、アクリル酸２－ジメチルアミノエチル、アクリル酸２－ヒドロシキエチル等、および、これらの誘導体が挙げられる。
アクリロニトリルの代わりに、アクリロニトリルの誘導体を用いてもよい。
The acrylic acid ester is not particularly limited as long as it is copolymerizable with acrylonitrile, and examples thereof include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-dimethylaminoethyl acrylate, 2-hydroxyethyl acrylate, and derivatives thereof.
Instead of acrylonitrile, derivatives of acrylonitrile may be used.
アクリルゴムは、カルボキシル基、水酸基およびエポキシ基からなる群から選択される少なくとも１種の官能基を有し、応力緩和性（低温特性）の観点から、カルボキシル基を好ましく有する。
アクリルゴムが有するカルボキシル基、水酸基およびエポキシ基からなる群から選択される少なくとも１種の官能基は、カルボキシル基含有モノマー、水酸基含有モノマーおよびエポキシ基含有モノマーからなる群から選択される少なくとも１種と、前記アクリル酸エステルおよびアクリロニトリルとを重合させて得られる化合物に起因することが好適である。
The acrylic rubber has at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, and an epoxy group, and preferably has a carboxyl group from the viewpoint of stress relaxation properties (low-temperature characteristics).
It is preferable that the at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, and an epoxy group, which the acrylic rubber has, is derived from a compound obtained by polymerizing at least one monomer selected from the group consisting of a carboxyl group-containing monomer, a hydroxyl group-containing monomer, and an epoxy group-containing monomer with the acrylic acid ester and acrylonitrile.
カルボキシル基含有モノマーとしては、特に限定されないが、例えば、（メタ）アクリル酸、イタコン酸、マレイン酸、フマル酸、クロトン酸等が挙げられる。また、これらのカルボキシル基含有モノマーの無水物も、カルボキシル基含有モノマーとして用いることができる。The carboxyl group-containing monomer is not particularly limited, but examples thereof include (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, etc. In addition, anhydrides of these carboxyl group-containing monomers can also be used as the carboxyl group-containing monomer.
水酸基含有モノマーとしては、例えば、アクリル酸２－ヒドロキシエチル、メタクリル酸２－ヒドロキシエチル、アクリル酸２－ヒドロキシプロピル、メタクリル酸２－ヒドロキシプロピル、アクリル酸３－ヒドロキシプロピル、メタクリル酸３－ヒドロキシプロピル、アクリル酸４－ヒドロキシブチル、メタクリル酸４－ヒドロキシブチル、アクリル酸２－ヒドロキシ－３－クロロプロピル、メタクリル酸２－ヒドロキシ－３－クロロプロピル、アクリル酸２－ヒドロキシ－３－フェノキシプロピル、メタクリル酸２－ヒドロキシ－３－フェノキシプロピル等が挙げられる。Examples of hydroxyl group-containing monomers include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-hydroxy-3-phenoxypropyl methacrylate.
エポキシ基含有モノマーとしては、例えば、アクリル酸グリシジルエーテル、メタクリル酸グリシジルエーテル、アクリル酸－２－エチルグリシジルエーテル、メタクリル酸－２－グリシジルエーテル等が挙げられる。 Examples of epoxy group-containing monomers include glycidyl ether of acrylic acid, glycidyl ether of methacrylic acid, 2-ethyl glycidyl ether of acrylic acid, and 2-glycidyl ether of methacrylic acid.
前記共重合体の重量平均分子量（Ｍｗ）は、特に限定されないが、１０００以上３００万以下であることが好ましく、１万以上１５０万以下であることがより好ましい。共重合体の重量平均分子量（Ｍｗ）が３００万を超えると、塗料化した際の塗料の著しい増粘により、塗料の流動性がなくなる（ゲル化する）、接着剤用塗料の取り扱いが難しくなるといった不具合が生じる傾向がある。一方、共重合体の重量平均分子量（Ｍｗ）が１０００未満では、接着剤組成物の硬化物の架橋密度が高くなり、硬化物の柔軟性が悪くなる傾向がある。アクリル系重合体のＭｗは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により、標準ポリスチレン換算で測定される。The weight average molecular weight (Mw) of the copolymer is not particularly limited, but is preferably 1,000 to 3,000,000, and more preferably 10,000 to 1,500,000. If the weight average molecular weight (Mw) of the copolymer exceeds 3,000,000, the paint tends to become significantly thickened when made into a paint, causing problems such as loss of fluidity (gelation) of the paint and difficulty in handling the adhesive paint. On the other hand, if the weight average molecular weight (Mw) of the copolymer is less than 1,000, the crosslink density of the cured product of the adhesive composition tends to be high, and the flexibility of the cured product tends to be poor. The Mw of the acrylic polymer is measured by gel permeation chromatography (GPC) in terms of standard polystyrene.
前記共重合体のガラス転移点（Ｔｇ）は、特に限定されないが、－６０℃以上０℃以下であることが好ましく、－４０℃以上－１５℃以下であることがより好ましく、－４０℃以上－２０℃以下であることがよりさらに好ましい。共重合体のガラス転移点（Ｔｇ）が０℃を超えると、接着剤組成物の硬化物の低温時における柔軟性が悪くなり、金属樹脂一体成形品が低温時に衝撃や、冷熱ストレスを受けた際、各部材間で生じる応力を緩和できず、各部材間での剥離が起こり易くなる傾向がある。一方、共重合体のガラス転移点（Ｔｇ）が－６０℃未満では、接着剤組成物の硬化物の高温時における凝集力が弱くなるため、金属樹脂一体成形品が、熱時に応力または荷重を受けた際、接着剤層の破壊または各部材間で剥離が起こりやすくなる傾向がある。ガラス転移点（Ｔｇ）は、示差走査熱量測定（ＤＳＣ：ｄｉｆｆｅｒｅｎｔｉａｌ ｓｃａｎｎｉｎｇ ｃａｌｏｒｉｍｅｔｒｙ）にて、窒素雰囲気で－８０℃～＋３００℃の範囲を１０℃／分の昇温速度の条件で行い、その熱流曲線の変曲点から決定される。The glass transition point (Tg) of the copolymer is not particularly limited, but is preferably -60°C or higher and 0°C or lower, more preferably -40°C or higher and -15°C or lower, and even more preferably -40°C or higher and -20°C or lower. If the glass transition point (Tg) of the copolymer exceeds 0°C, the flexibility of the cured product of the adhesive composition at low temperatures is deteriorated, and when the metal-resin integrally molded product is subjected to impact or thermal stress at low temperatures, the stress generated between each component cannot be alleviated, and peeling between each component tends to occur easily. On the other hand, if the glass transition point (Tg) of the copolymer is less than -60°C, the cohesive force of the cured product of the adhesive composition at high temperatures is weakened, and when the metal-resin integrally molded product is subjected to stress or load at high temperatures, the adhesive layer tends to be destroyed or peeling between each component tends to occur easily. The glass transition point (Tg) is determined from the inflection point of the heat flow curve by differential scanning calorimetry (DSC) performed in a nitrogen atmosphere at a temperature rise rate of 10° C./min in the range of −80° C. to +300° C.
接着剤組成物中におけるアクリルゴムの含有量は、特に限定されず、適宜製造条件に応じて選択可能であるが、例えば、接着剤組成物の総質量に対して、２０質量％以上９５質量％以下であることが好ましく、４０質量％以上９０質量％以下であることがより好ましく、６０質量％以上８０質量％以下であることがよりさらに好ましい。The content of acrylic rubber in the adhesive composition is not particularly limited and can be selected appropriately depending on the manufacturing conditions, but for example, it is preferably from 20% by mass to 95% by mass, more preferably from 40% by mass to 90% by mass, and even more preferably from 60% by mass to 80% by mass, relative to the total mass of the adhesive composition.
アクリルゴムは、共重合体の特性に影響を及ぼさない範囲で、上記の共重合体以外の他の成分を含んでいてもよい。
アクリルゴムに含まれる他の成分としては、例えば、アクリル酸ジメチルアミノエチル、メタクリル酸ジメチルアミノエチル、アクリル酸ジエチルアミノエチル、メタクリル酸ジエチルアミノエチル等のアミノ基含有モノマー、アクリルアミド、メタクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ－メチロールメタクリルアミド等のアミド基含有モノマー等が挙げられる。
The acrylic rubber may contain components other than the above copolymer, as long as the components do not affect the properties of the copolymer.
Examples of other components contained in the acrylic rubber include amino group-containing monomers such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, and diethylaminoethyl methacrylate, and amide group-containing monomers such as acrylamide, methacrylamide, N-methylol acrylamide, and N-methylol methacrylamide.
アクリル酸エステルとアクリロニトリルの共重合体を作製する方法としては、一般的な共重合法が用いられるが、例えば、懸濁重合、乳化重合等が用いられる。 A typical copolymerization method is used to prepare a copolymer of acrylic ester and acrylonitrile, such as suspension polymerization or emulsion polymerization.
前記アクリルゴムの官能基と反応するシランカップリング剤としては、１分子内に有機官能基と加水分解性シリル基とを有する化合物であり、例えば、Ｎ－（２－アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルメチルジエトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリエトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン等のアミノシラン類、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン等のエポキシシラン類、３－メルカプトプロピルトリメトキシシラン、３－メルカプトプロピルトリエトキシシラン等のメルカプトシラン類、３－メタクリロキシプロピルトリエトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２－メトキシエトキシ）シラン等のビニルシラン類等が挙げられる。特に、これらの中でも、アクリルゴムとの相溶性がよく、また熱によりアクリルゴムと容易に反応して、その硬化物が優れた耐熱性や接着性を示すことから、３－グリシドキシプロピルトリエトキシシラン等のエポキシシラン類、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン等のアミノシラン類が好ましい。該シランカップリング剤は、いずれか１種を単独で用いてもよく、２種以上混合して用いてもよい。The silane coupling agent that reacts with the functional group of the acrylic rubber is a compound having an organic functional group and a hydrolyzable silyl group in one molecule, such as aminosilanes such as N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane, 3-glycidoxypropyl. Examples of the epoxy silanes include propyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, etc., mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, etc., and vinyl silanes such as 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, etc. Among these, epoxy silanes such as 3-glycidoxypropyltriethoxysilane, and amino silanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, etc. are preferred because they have good compatibility with acrylic rubber, react easily with acrylic rubber by heat, and the cured product exhibits excellent heat resistance and adhesiveness. The silane coupling agents may be used alone or in combination of two or more.
インサート成形や熱プレス成形において、金属部材の表面に接着剤を塗布し、その接着剤を介して、金属部材の表面に樹脂を接触させて、金属と樹脂の接合をする際、樹脂成形時の熱や圧力によって接着剤が流動しないように、使用する接着剤を架橋型のものとし、それを樹脂成形前に架橋することで、接着剤の凝集力を高めることが効果的である。例えば、熱によって架橋する熱硬化性接着剤を用いて、金属部材の表面に接着剤を塗布した後、成形前に加熱することで、上記接着剤の凝集力を高めることが挙げられる。熱硬化以外の接着剤の架橋方法としては、紫外線硬化、湿気硬化などが挙げられる。しかし、接着剤が架橋することで、凝集力が上がる一方で、相対的に被着体界面への接着性は低下する。したがって、金属と成形樹脂間の接合状態を良好なものにするには、接着剤の凝集力と被着体界面への接着性とのバランスが重要になる。ここで、上記接着剤組成物において、カルボキシル基、水酸基およびエポキシ基からなる群から選択される少なくとも１種の官能基を有するアクリルゴムと、前記官能基と反応するシランカップリング剤を用いると、アクリルゴムがシランカップリング剤の官能基と反応し、接着剤組成物の凝集力を上げることができる。In insert molding and hot press molding, when an adhesive is applied to the surface of a metal member and a resin is brought into contact with the surface of the metal member through the adhesive to bond the metal and resin, it is effective to use a cross-linking adhesive and cross-link it before resin molding to increase the cohesive strength of the adhesive so that the adhesive does not flow due to the heat and pressure during resin molding. For example, a thermosetting adhesive that cross-links with heat can be used to apply the adhesive to the surface of a metal member, and then heat the adhesive before molding to increase the cohesive strength of the adhesive. Examples of cross-linking methods for adhesives other than heat curing include ultraviolet curing and moisture curing. However, while the cohesive strength increases when the adhesive is cross-linked, the adhesive's adhesiveness to the interface of the adherend decreases relatively. Therefore, in order to improve the bonding state between the metal and the molded resin, it is important to balance the adhesive's cohesive strength and its adhesiveness to the interface of the adherend. Here, when the above adhesive composition contains an acrylic rubber having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, and an epoxy group, and a silane coupling agent that reacts with the functional group, the acrylic rubber reacts with the functional group of the silane coupling agent, and the cohesive strength of the adhesive composition can be increased.
また、シランカップリング剤は、上記アクリルゴムと反応する官能基を分子内に１つしかもたないため、接着剤組成物の架橋反応を抑えることができる。つまり、接着剤組成物の凝集力上昇が緩やかとなるため、接着剤組成物の凝集力の調整が容易となる。加えて、シランカップリング剤のもう一方の官能基、加水分解性シリル基が、被着体表面と水素結合することで、接着剤組成物の被着体界面への接着性も向上することができる。したがって、金属と成形樹脂間の接合状態を良好にするために必要な、硬化条件の範囲を広くすることができるため、接合部材の品質は安定し易くなる。一方で、上記アクリルゴムと反応する官能基を分子内に２つ以上含有する樹脂を用いると、接着剤組成物の架橋反応が強まりやすい。つまり、接着剤組成物の凝集力上昇が著しくなるため、接着剤組成物の凝集力の調整が難しくなる。したがって、金属と成形樹脂間の接合状態を良好にするために必要な、硬化条件の範囲が狭くなるため、接合部材の品質は安定しにくくなる。In addition, since the silane coupling agent has only one functional group in the molecule that reacts with the acrylic rubber, the crosslinking reaction of the adhesive composition can be suppressed. In other words, the increase in the cohesive force of the adhesive composition is gradual, making it easy to adjust the cohesive force of the adhesive composition. In addition, the other functional group of the silane coupling agent, the hydrolyzable silyl group, forms a hydrogen bond with the surface of the adherend, thereby improving the adhesion of the adhesive composition to the interface of the adherend. Therefore, the range of curing conditions required to improve the bonding state between the metal and the molded resin can be widened, making it easier to stabilize the quality of the bonding member. On the other hand, if a resin containing two or more functional groups in the molecule that react with the acrylic rubber is used, the crosslinking reaction of the adhesive composition is likely to be strengthened. In other words, the increase in the cohesive force of the adhesive composition becomes significant, making it difficult to adjust the cohesive force of the adhesive composition. Therefore, the range of curing conditions required to improve the bonding state between the metal and the molded resin becomes narrower, making it difficult to stabilize the quality of the bonding member.
接着剤組成物中におけるシランカップリング剤の含有量は、特に限定されず、適宜製造条件に応じて選択可能であるが、例えば、アクリルゴム含有量１００質量部に対して、１質量部以上１００質量部以下であることが好ましく、５質量部以上５０質量部以下であることがより好ましく、１０質量部以上４０質量部以下であることがより更に好ましい。接着剤組成物中におけるシランカップリング剤の含有量が１質量部未満では、アクリルゴムとシランカップリング剤との架橋反応が進まず、接着剤組成物の硬化物が優れた接着性、耐熱性を発現し難い傾向がある。接着剤組成物中におけるシランカップリング剤の含有量が１００質量部を超えると、接着剤組成物の硬化物のＴｇが高くなり、低温時における柔軟性、応力緩和性が悪くなり易くなる傾向がある。The content of the silane coupling agent in the adhesive composition is not particularly limited and can be appropriately selected according to the manufacturing conditions, but for example, it is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, and even more preferably 10 parts by mass or more and 40 parts by mass or less, relative to 100 parts by mass of the acrylic rubber content. If the content of the silane coupling agent in the adhesive composition is less than 1 part by mass, the crosslinking reaction between the acrylic rubber and the silane coupling agent does not proceed, and the cured product of the adhesive composition tends not to exhibit excellent adhesion and heat resistance. If the content of the silane coupling agent in the adhesive composition exceeds 100 parts by mass, the Tg of the cured product of the adhesive composition becomes high, and the flexibility and stress relaxation properties at low temperatures tend to be easily deteriorated.
本実施形態に係る接着剤組成物は、さらに、フェノール樹脂を含有する。
フェノール樹脂としては、例えば、原料のフェノール類としてフェノール、クレゾール、ｐ－ｔ－ブチルフェノール等のアルキル置換フェノール、テルペン、ロジン、キシレン、ジシクロペンタジエン等の環状アルキル変性フェノール、ニトロ基、ハロゲン基、アミノ基、シアノ基等のヘテロ原子を含む官能基を有するもの、ナフタレン、アントラセン等の骨格を有するものなどを用いたもの等が挙げられ、アルキル置換フェノールが好ましく挙げられる。これらのフェノール樹脂は、いずれか１種を単独で用いてもよく、２種以上混合して用いてもよい。接着剤組成物がフェノール樹脂を含むことにより、接着剤組成物の硬化物が、優れた耐熱性や、高温時における優れた接着性を示す。
The adhesive composition according to this embodiment further contains a phenol resin.
Examples of the phenolic resin include those using alkyl-substituted phenols such as phenol, cresol, and p-t-butylphenol as raw phenols, cyclic alkyl-modified phenols such as terpene, rosin, xylene, and dicyclopentadiene, those having functional groups containing heteroatoms such as nitro groups, halogen groups, amino groups, and cyano groups, and those having skeletons such as naphthalene and anthracene, and the like, with alkyl-substituted phenols being preferred. Any one of these phenolic resins may be used alone, or two or more may be mixed and used. By including a phenolic resin in the adhesive composition, the cured product of the adhesive composition exhibits excellent heat resistance and excellent adhesion at high temperatures.
接着剤組成物中におけるフェノール樹脂の含有量は、特に限定されず、適宜製造条件に応じて選択可能であるが、例えば、アクリルゴム含有量１００質量部に対して、１質量部以上１００質量部以下であることが好ましく、５質量部以上５０質量部以下であることがより好ましく、１０質量部以上４０質量部以下がよりさらに好ましい。接着剤組成物中におけるフェノール樹脂の含有量が１質量部未満では、接着剤組成物の硬化物において、フェノール樹脂を含むことによる効果、つまり、硬化物に優れた耐熱性や、高温時における優れた接着性が得られ難い傾向がある。接着剤組成物中におけるフェノール樹脂の含有量が１００質量部を超えると、硬化後のＴｇが高くなり、接着剤組成物の硬化物の低温時における柔軟性、応力緩和性が悪くなり易い傾向がある。The content of the phenolic resin in the adhesive composition is not particularly limited and can be appropriately selected according to the manufacturing conditions, but for example, it is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, and even more preferably 10 parts by mass or more and 40 parts by mass or less, relative to 100 parts by mass of the acrylic rubber content. If the content of the phenolic resin in the adhesive composition is less than 1 part by mass, the effect of containing the phenolic resin in the cured product of the adhesive composition, that is, excellent heat resistance of the cured product and excellent adhesion at high temperatures, tends to be difficult to obtain. If the content of the phenolic resin in the adhesive composition exceeds 100 parts by mass, the Tg after curing becomes high, and the flexibility and stress relaxation properties of the cured product of the adhesive composition at low temperatures tend to be easily deteriorated.
硬化促進剤としては、アクリルゴムとシランカップリング剤の反応を促進することができるものであれば、特に限定されないが、例えば、イミダゾール化合物、三級アミン、有機リン化合物、ジシアンジアミド等が挙げられる。 The curing accelerator is not particularly limited as long as it can accelerate the reaction between the acrylic rubber and the silane coupling agent, but examples include imidazole compounds, tertiary amines, organic phosphorus compounds, dicyandiamide, etc.
イミダゾール化合物としては、例えば、１，２－ジメチルイミダゾール、１－メチル－２－エチルイミダゾール、２－メチルイミダゾール、２－エチル－４－メチルイミダゾール、２－ウンデシルイミダゾール、２－ヘプタデシルイミダゾール、２－フェニルイミダゾール、１－ベンジル－２－メチルイミダゾール、１－ベンジル－２－フェニルイミダゾール、１－ベンジル－２－フェニルイミダゾール・トリメリット酸塩、１－ベンジル－２－エチルイミダゾール、１－ベンジル－２－エチル－５－メチルイミダゾール、２－エチルイミダゾール、２－イソプロピルイミダゾール、２－フェニル－４－ベンジルイミダゾール、１－シアノエチル－２－メチルイミダゾール、１－シアノエチル－２－エチル－４－メチルイミダゾール、１－シアノエチル－２－ウンデシルイミダゾール、１－シアノエチル－２－イソプロピルイミダゾール、１－シアノエチル－２－フェニルイミダゾール、１－シアノエチル－２－メチルイミダゾリウムトリメリテート、１－シアノエチル－２－フェニルイミダゾリウムトリメリテート、２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン、２，４－ジアミノ－６－［２’－エチル－４－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン、２，４－ジアミノ－６－［２’－ウンデシルイミダゾリル－（１’）］－エチル－ｓ－トリアジン、２－メチルイミダゾリウムイソシアヌール酸付加物、２－フェニルイミダゾリウムイソシアヌール酸付加物、２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン－イソシアヌール酸付加物、２－フェニル－４，５－ジヒドロキシメチルイミダゾール、２－フェニル－４－ベンジル－５－ヒドロキシメチルイミダゾール、４，４’－メチレン－ビス－（２－エチル－５－メチルイミダゾール）、１－アミノエチル－２－メチルイミダゾール、１－シアノエチル－２－フェニル－４，５－ジ（シアノエトキシメチル）イミダゾール、１－ドデシル－２－メチル－３－ベンジルイミダゾリウムクロライド、２－メチルイミダゾール・ベンゾトリアゾール付加物、１－アミノエチル－２－エチルイミダゾール、１－（シアノエチルアミノエチル）－２－メチルイミダゾール、Ｎ，Ｎ’－［２－メチルイミダゾリル－（１）－エチル］－アジポイルジアミド、Ｎ，Ｎ’－ビス－（２－メチルイミダゾリル－１－エチル）尿素、Ｎ－（２－メチルイミダゾリル－１－エチル）尿素、Ｎ，Ｎ’－［２－メチルイミダゾリル－（１）－エチル］ドデカンジオイルジアミド、Ｎ，Ｎ’－［２－メチルイミダゾリル－（１）－エチル］エイコサンジオイルジアミド、１－ベンジル－２－フェニルイミダゾール・塩化水素酸塩等が挙げられる。 Examples of imidazole compounds include 1,2-dimethylimidazole, 1-methyl-2-ethylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-phenylimidazole trimellitate, 1-benzyl-2-ethylimidazole, 1-benzyl-2-ethyl-5-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-phenyl-4-benzylimidazole, and 1-cyanoethyl -2-Methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-isopropylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1') ]-ethyl-s-triazine, 2-methylimidazolium isocyanuric acid adduct, 2-phenylimidazolium isocyanuric acid adduct, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine-isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 4,4'-methylene-bis-(2-ethyl-5-methylimidazole), 1-aminoethyl-2-methylimidazole, 1-cyanoethyl-2-phenyl-4,5-di(cyanoethoxymethyl)imidazole, 1-dodecyl-2-methyl-3-benzyl midazolium chloride, 2-methylimidazole-benzotriazole adduct, 1-aminoethyl-2-ethylimidazole, 1-(cyanoethylaminoethyl)-2-methylimidazole, N,N'-[2-methylimidazolyl-(1)-ethyl]-adipoyldiamide, N,N'-bis-(2-methylimidazolyl-1-ethyl)urea, N-(2-methylimidazolyl-1-ethyl)urea, N,N'-[2-methylimidazolyl-(1)-ethyl]dodecane dioyldiamide, N,N'-[2-methylimidazolyl-(1)-ethyl]eicosane dioyldiamide, 1-benzyl-2-phenylimidazole hydrochloride, and the like.
三級アミンとしては、例えば、１，８－ジアザ－ビシクロ［５．４．０］ウンデセン－７、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス（ジメチルアミノメチル）フェノール等が挙げられる。Examples of tertiary amines include 1,8-diaza-bicyclo[5.4.0]undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol.
有機リン化合物としては、例えば、トリブチルホスフィン、メチルジフェニルホスフィン、トリフェニルホスフィン、ジフェニルホスフィン、フェニルホスフィン等が挙げられる。 Examples of organic phosphorus compounds include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, etc.
これらの硬化促進剤は、いずれか１種を単独で用いることができ、２種以上混合して用いることもでき、イミダゾール化合物またはそのアジン変性物が好ましく用いられる。
硬化促進剤を適宜選択することにより、アクリルゴムとシランカップリング剤の架橋反応（架橋密度）を調整することができる。
These curing accelerators may be used either alone or in combination of two or more. Imidazole compounds or azine-modified compounds thereof are preferably used.
By appropriately selecting the curing accelerator, the crosslinking reaction (crosslinking density) between the acrylic rubber and the silane coupling agent can be adjusted.
本発明の接着剤組成物は、下記で詳細に述べるように液状媒体に溶解して使用することが好ましい。このように本発明の接着剤組成物を液状媒体に溶解する場合、硬化促進剤は、液状媒体に不溶であり、かつ液状媒体の沸点より高い温度で、アクリルゴムとシランカップリング剤と反応する粒子であることが好ましい。液状媒体に不溶であり、かつ液状媒体の沸点より高い温度で反応する粒子状硬化促進剤は、粒子状態を維持しながら接着剤組成物中に分散することができる。
液状媒体に不溶とは、２５℃において、溶媒１００ｇ中１ｇ未満溶解のものを意味する。
本発明の接着剤組成物は、アクリルゴム、シランカップリング剤、硬化促進剤等の各成分を液状媒体に溶解または分散して得られる液状の接着剤組成物を、被着体に塗布し、乾燥して使用される。
硬化促進剤の反応開始温度が、液状媒体の沸点より高ければ、前記液状の接着剤組成物を被着体へ塗布、乾燥するときの温度（乾燥温度）を、液状媒体の沸点以上、硬化促進剤の反応開始温度未満にすることで、硬化促進剤を反応させずに液状媒体のみを揮発させることができる。このように、硬化促進剤を反応させずに液状媒体のみを揮発させることによって、粒子状硬化促進剤が粒子状態を維持しながら接着剤組成物中に分散された未硬化の状態の接着剤組成物ができる。この状態の接着剤組成物を硬化促進剤の反応開始温度以上の温度で加熱することで、粒子状硬化促進剤が熱により溶解してアクリルゴムとシランカップリング剤の反応を促進させ接着剤組成物は硬化し、耐熱性や被着体への充分な接合強度を有することができる。
硬化促進剤が液状媒体に溶解する場合、又は硬化促進剤の反応開始温度が液状媒体の沸点以下の場合は、液状媒体に溶解または分散された接着剤組成物を塗布、乾燥したときに、液状媒体を揮発させる際の乾燥熱により硬化促進剤が反応して、接着剤組成物の一部の硬化が生じる。このように一部硬化が生じた接着剤組成物は、被着体と接合した際の被着体への接合強度の低下、未硬化の状態の接着剤組成物の保存安定性の悪化などを招く懸念がある。
また、硬化促進剤が粒子であれば、液状媒体への分散性が良好である。分散性が良好であれば、接着剤層の面状悪化、硬化促進剤が偏在することによる硬化不良が起きにくい。加えて、硬化促進剤が、液状媒体に不溶であることから、保管安定性にも優れた接着剤組成物が作製できる。
このような液状媒体に不溶であり、かつ液状媒体の沸点より高い温度で反応する粒子状硬化促進剤は、反応開始温度が１２０℃以上であることが好ましい。
反応開始温度が１２０℃以上である粒子状硬化促進剤の具体例としては、四国化成社製２ＭＺ－Ａ（２，４－ジアミノ－６－（２’－メチルイミダゾリル－（１’））－エチル－ｓ－トリアジン、メチルエチルケトンに不溶、粒子状物、反応開始温度１２０℃））、四国化成社製２Ｅ４ＭＺ－Ａ（２，４－ジアミノ－６－（２’－エチル－４－メチルイミダゾリル－（１’））－エチル－ｓ－トリアジン、メチルエチルケトンに不溶、粒子状物、反応開始温度１３５℃）、四国化成社製２ＭＡ－ＯＫ（２，４－ジアミノ－６－（２’－メチルイミダゾリル－（１’））－エチル－ｓ－トリアジン イソシアヌル酸付加物、メチルエチルケトンに不溶、粒子状物、反応開始温度１２０℃）、四国化成社製２ＰＨＺ（２－フェニル－４，５－ジヒドロキシメチルイミダゾール、メチルエチルケトンに不溶、粒子状物、反応開始温度１４５℃）、四国化成社製２Ｐ４ＭＨＺ（２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール、メチルエチルケトンに不溶、粒子状物、反応開始温度１３０℃）などを挙げることができる。
The adhesive composition of the present invention is preferably used by dissolving it in a liquid medium as described in detail below. When the adhesive composition of the present invention is dissolved in a liquid medium in this way, the curing accelerator is preferably insoluble in the liquid medium and is a particle that reacts with the acrylic rubber and the silane coupling agent at a temperature higher than the boiling point of the liquid medium. A particulate curing accelerator that is insoluble in the liquid medium and reacts at a temperature higher than the boiling point of the liquid medium can be dispersed in the adhesive composition while maintaining a particulate state.
Insoluble in a liquid medium means that less than 1 g of the compound dissolves in 100 g of the solvent at 25°C.
The adhesive composition of the present invention is used by applying a liquid adhesive composition obtained by dissolving or dispersing each component, such as acrylic rubber, silane coupling agent, and curing accelerator, in a liquid medium to an adherend and drying it.
If the reaction initiation temperature of the curing accelerator is higher than the boiling point of the liquid medium, the temperature (drying temperature) when the liquid adhesive composition is applied to the adherend and dried can be set to be equal to or higher than the boiling point of the liquid medium and lower than the reaction initiation temperature of the curing accelerator, so that only the liquid medium can be volatilized without reacting the curing accelerator. In this way, by volatilizing only the liquid medium without reacting the curing accelerator, an uncured adhesive composition in which the particulate curing accelerator is dispersed in the adhesive composition while maintaining its particulate state can be obtained. By heating the adhesive composition in this state at a temperature equal to or higher than the reaction initiation temperature of the curing accelerator, the particulate curing accelerator is dissolved by heat to promote the reaction between the acrylic rubber and the silane coupling agent, and the adhesive composition is cured, and the adhesive composition can have sufficient heat resistance and bonding strength to the adherend.
When the curing accelerator is dissolved in the liquid medium, or when the reaction initiation temperature of the curing accelerator is equal to or lower than the boiling point of the liquid medium, when the adhesive composition dissolved or dispersed in the liquid medium is applied and dried, the curing accelerator reacts with the drying heat generated when the liquid medium is volatilized, causing a partial curing of the adhesive composition. There is a concern that such a partially cured adhesive composition may cause a decrease in the bonding strength to the adherend when bonded to the adherend, or a deterioration in the storage stability of the adhesive composition in an uncured state.
In addition, if the curing accelerator is a particle, it has good dispersibility in the liquid medium. If the dispersibility is good, the surface condition of the adhesive layer is deteriorated, and curing failure due to uneven distribution of the curing accelerator is unlikely to occur. In addition, since the curing accelerator is insoluble in the liquid medium, an adhesive composition with excellent storage stability can be produced.
Such a particulate hardening accelerator that is insoluble in the liquid medium and reacts at a temperature higher than the boiling point of the liquid medium preferably has a reaction initiation temperature of 120° C. or higher.
Specific examples of particulate hardening accelerators having a reaction initiation temperature of 120° C. or higher include 2MZ-A (2,4-diamino-6-(2'-methylimidazolyl-(1'))-ethyl-s-triazine, insoluble in methyl ethyl ketone, particulate, reaction initiation temperature 120° C.) manufactured by Shikoku Kasei Co., Ltd., 2E4MZ-A (2,4-diamino-6-(2'-ethyl-4-methylimidazolyl-(1'))-ethyl-s-triazine, insoluble in methyl ethyl ketone, particulate, reaction initiation temperature 135° C.) manufactured by Shikoku Kasei Co., Ltd., and 2MA-OK (2,4-diamino-6-(2'-methylimidazolyl-(1'))-ethyl-s-triazine, insoluble in methyl ethyl ketone, particulate, reaction initiation temperature 135° C.) manufactured by Shikoku Kasei Co., Ltd. Examples of such a copolymer include 2-phenyl-4,5-dihydroxymethylimidazole, insoluble in methyl ethyl ketone, particulate matter, reaction initiation temperature 120° C.), 2PHZ manufactured by Shikoku Kasei Corporation (2-phenyl-4,5-dihydroxymethylimidazole, insoluble in methyl ethyl ketone, particulate matter, reaction initiation temperature 145° C.), and 2P4MHZ manufactured by Shikoku Kasei Corporation (2-phenyl-4-methyl-5-hydroxymethylimidazole, insoluble in methyl ethyl ketone, particulate matter, reaction initiation temperature 130° C.).
接着剤組成物中における硬化促進剤の含有量は、特に限定されず、適宜製造条件に応じて選択可能であるが、アクリルゴムとシランカップリング剤の含有量の合計１００質量部に対して、例えば、０．１質量部以上１０質量部以下であることが好ましく、０．５質量部以上５質量部以下であることがより好ましく、０．５質量部以上１質量部以下であることがより好ましい。
接着剤組成物中における硬化促進剤の含有量が０．１質量部未満では、硬化促進剤を含むことによる効果、つまりアクリルゴムとシランカップリング剤の架橋反応を促進させる効果が得られ難く、接着剤組成物の熱硬化時間が長くなり、結果生産性が悪くなる傾向がある。また、接着剤硬化物の耐熱性も得られ難い傾向がある。接着剤組成物中における硬化促進剤の含有量が１０質量部を超えると、アクリルゴムとシランカップリング剤の架橋反応の促進が著しくなり、金属と樹脂を一体接合させる際の、製造条件の調整が難しくなる傾向がある。例えば、金属に接着剤組成物を付着させた部品を、成形金型にセットしてから成形樹脂を接触させるまでの間に、成形金型の熱により接着剤の反応が著しく進んでしまうことで、成形樹脂を接触させたときには接着剤が接着性を発現できず、成形樹脂を接着できなくなるといった不具合が起こる傾向がある。
The content of the curing accelerator in the adhesive composition is not particularly limited and can be appropriately selected depending on the production conditions; however, for example, it is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.5 parts by mass or more and 5 parts by mass or less, and even more preferably 0.5 parts by mass or more and 1 part by mass or less, relative to 100 parts by mass of the total content of the acrylic rubber and the silane coupling agent.
If the content of the curing accelerator in the adhesive composition is less than 0.1 parts by mass, the effect of containing the curing accelerator, that is, the effect of promoting the crosslinking reaction between the acrylic rubber and the silane coupling agent, is difficult to obtain, the heat curing time of the adhesive composition is long, and as a result, the productivity tends to deteriorate. In addition, the heat resistance of the adhesive cured product tends to be difficult to obtain. If the content of the curing accelerator in the adhesive composition exceeds 10 parts by mass, the crosslinking reaction between the acrylic rubber and the silane coupling agent is significantly promoted, and it tends to be difficult to adjust the manufacturing conditions when integrally joining the metal and the resin. For example, between the time when the part with the adhesive composition attached to the metal is set in the molding die and the time when the molding resin is contacted, the reaction of the adhesive progresses significantly due to the heat of the molding die, and the adhesive cannot exhibit adhesion when the molding resin is contacted, and there is a tendency for problems such as not being able to bond the molding resin.
本実施形態に係る接着剤組成物は、さらに、可塑剤を含むことが好ましい。
可塑剤としては、特に限定されないが、例えば、アクリル酸エステル系、フタル酸エステル系、アジピン酸エステル系、リン酸エステル系、トリメリット酸エステル系、クエン酸エステル系、エポキシ系およびポリエステル系等が挙げられる。これらの可塑剤は、いずれか１種を単独で用いることができ、２種以上混合して用いることもできる。また、上記の可塑剤は、水酸基、カルボキシル基、エポキシ基、アルコキシシリル基等の官能基を含んだものを用いてもよい。これらの中でも、アクリルゴムへの相溶性の観点から、アクリル酸エステル系が好ましい。接着剤組成物が可塑剤を含むことにより、接着剤組成物のガラス転移点（Ｔｇ）を下げることができる。接着剤組成物のガラス転移点（Ｔｇ）を下げることにより、接着剤組成物の低温時の柔軟性が向上し、応力緩和性、特に低温時における応力緩和性に優れた接着剤組成物を得ることができる。
The adhesive composition according to this embodiment preferably further contains a plasticizer.
The plasticizer is not particularly limited, but examples thereof include acrylic acid esters, phthalic acid esters, adipate esters, phosphate esters, trimellitate esters, citrate esters, epoxy esters, and polyester esters. Any one of these plasticizers can be used alone, or two or more can be mixed and used. The above plasticizers may also be used containing functional groups such as hydroxyl groups, carboxyl groups, epoxy groups, and alkoxysilyl groups. Among these, acrylic acid esters are preferred from the viewpoint of compatibility with acrylic rubber. By including a plasticizer in the adhesive composition, the glass transition point (Tg) of the adhesive composition can be lowered. By lowering the glass transition point (Tg) of the adhesive composition, the flexibility of the adhesive composition at low temperatures can be improved, and an adhesive composition having excellent stress relaxation properties, particularly at low temperatures, can be obtained.
前記アクリル酸エステルとしては、特に限定されないが、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸２－エチルヘキシル、アクリル酸２－ジメチルアミノエチル、アクリル酸２－ヒドロシキエチル等、および、これらの誘導体が挙げられる。 The acrylic acid esters are not particularly limited, but examples include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-dimethylaminoethyl acrylate, 2-hydroxyethyl acrylate, and derivatives thereof.
接着剤組成物中における可塑剤の含有量は、特に限定されず、適宜製造条件に応じて選択可能であるが、例えば、アクリルゴム含有量１００質量部に対して、１質量部以上１００質量部以下であることが好ましく、１０質量部以上１００質量部以下であることがより好ましい。接着剤組成物中における可塑剤の含有量が１質量部未満では、可塑剤を含むことによる効果、つまり、接着剤組成物のガラス転移点を下げる効果が得られ難い。接着剤組成物中における可塑剤の含有量が１００質量部を超えると、硬化時の接着剤組成物または接着剤組成物の硬化物から、可塑剤が接着剤組成物の表面にブリードアウトし易くなり、成形時における被着体への接着不良や、金属と樹脂を一体接合した後に、経時で被着体の界面から剥離するといった問題が生じる。The content of the plasticizer in the adhesive composition is not particularly limited and can be selected according to the manufacturing conditions. For example, it is preferably 1 part by mass or more and 100 parts by mass or less, and more preferably 10 parts by mass or more and 100 parts by mass or less, relative to 100 parts by mass of the acrylic rubber content. If the content of the plasticizer in the adhesive composition is less than 1 part by mass, it is difficult to obtain the effect of containing the plasticizer, that is, the effect of lowering the glass transition point of the adhesive composition. If the content of the plasticizer in the adhesive composition exceeds 100 parts by mass, the plasticizer is likely to bleed out from the adhesive composition or the cured product of the adhesive composition during curing to the surface of the adhesive composition, causing problems such as poor adhesion to the adherend during molding and peeling from the interface of the adherend over time after the metal and resin are integrally joined.
本実施形態に係る接着剤組成物は、さらに、液状媒体を含むことが好ましい。
液状媒体としては、例えば炭化水素類、アルコール類、ケトン類、エーテル類等の有機溶剤、水等が挙げられる。有機溶剤として具体的には、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、シクロペンタノン、トルエン、キシレン、酢酸エチル、酢酸ブチル、テトラヒドロフラン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、ジメチルスルホキサイド、エチレングリコールモノメチルエーテルアセテート、プロピレングリコールジメチルエーテル、ベンゼンジオキサン、シクロペンチルメチルエーテル、塩化メチレン、クロロホルム、１，２－ジクロロエタン、γ－ブチロラクトン、セロソルブ、ブチルセロソブル、カルビトール、ブチルカルビトール等が挙げられ、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類が好ましく挙げられる。上記の液状媒体は１種を単独で使用してもよく、２種以上を混合して使用してもよい。
The adhesive composition according to this embodiment preferably further contains a liquid medium.
Examples of the liquid medium include organic solvents such as hydrocarbons, alcohols, ketones, and ethers, and water. Specific examples of the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, toluene, xylene, ethyl acetate, butyl acetate, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, ethylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, benzenedioxane, cyclopentyl methyl ether, methylene chloride, chloroform, 1,2-dichloroethane, γ-butyrolactone, cellosolve, butyl cellosolve, carbitol, and butyl carbitol. Ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone are preferred. The above liquid mediums may be used alone or in combination of two or more.
接着剤組成物中の液状媒体の含有量は、特に限定されないが、アクリルゴム、シランカップリング剤、フェノール樹脂、硬化促進剤および可塑剤の総含有量１００質量部に対して、２００質量部以上５００質量部以下であることが好ましく、３００質量部以上４００質量部以下であることがより好ましい。The content of the liquid medium in the adhesive composition is not particularly limited, but is preferably 200 parts by mass or more and 500 parts by mass or less, and more preferably 300 parts by mass or more and 400 parts by mass or less, per 100 parts by mass of the total content of the acrylic rubber, silane coupling agent, phenolic resin, curing accelerator and plasticizer.
本実施形態に係る接着剤組成物は、接着剤組成物の特性に影響を及ぼさない範囲で他の成分を含んでいてもよい。
接着剤組成物に含まれる他の成分としては、例えば、酸アミド類、エステル類、パラフィン類等の離型剤、粘着付与剤、ニトリルゴム、ブタジエンゴム等の応力緩和剤、塩素化パラフィン、ブロムベンゼン、三酸化アンチモン等の難燃剤、チタネート系カップリング剤、溶融シリカ、ガラスフレーク、ガラスビーズ、ガラスバルーン、タルク、アルミナ、ケイ酸カルシウム、水酸化アルミニウム、炭酸カルシウム、硫酸バリウム、マグネシア、窒化ケイ素、窒化ホウ素、フェライト、希土コバルト、金、銀、ニッケル、銅、鉛、鉄粉、酸化鉄、砂鉄等の金属粉、黒鉛、カーボン、弁柄、黄鉛等の無機充填剤または導電性粒子等、染料や顔料等の着色剤、炭素繊維、ガラス繊維、ボロン繊維、シリコンカーバイト繊維、アルミナ繊維、シリカアルミナ繊維等の無機系繊維、ポリアミド繊維、ポリエステル繊維、セルロース繊維、炭素繊維等の有機系繊維、酸化防止剤、光安定剤、耐湿性向上剤、チキソトロピー付与剤、希釈剤、消泡剤、帯電防止剤、滑剤、紫外線吸収剤等を配合することができる。
The adhesive composition according to this embodiment may contain other components to the extent that they do not affect the properties of the adhesive composition.
Other components contained in the adhesive composition include, for example, release agents such as acid amides, esters, and paraffins, tackifiers, stress relaxation agents such as nitrile rubber and butadiene rubber, flame retardants such as chlorinated paraffin, bromobenzene, and antimony trioxide, titanate coupling agents, fused silica, glass flakes, glass beads, glass balloons, talc, alumina, calcium silicate, aluminum hydroxide, calcium carbonate, barium sulfate, magnesia, silicon nitride, boron nitride, ferrite, rare earth cobalt, Metal powders such as gold, silver, nickel, copper, lead, iron powder, iron oxide, and iron sand; inorganic fillers or conductive particles such as graphite, carbon, red oxide, and yellow lead; colorants such as dyes and pigments; inorganic fibers such as carbon fiber, glass fiber, boron fiber, silicon carbide fiber, alumina fiber, and silica alumina fiber; organic fibers such as polyamide fiber, polyester fiber, cellulose fiber, and carbon fiber; antioxidants, light stabilizers, moisture resistance improvers, thixotropy-imparting agents, diluents, antifoaming agents, antistatic agents, lubricants, and ultraviolet absorbers can be blended.
本実施形態に係る接着剤組成物は、ガラス転移点（Ｔｇ）が、－６０℃以上０℃以下であることが好ましく、－４０℃以上－２０℃以下であることがより好ましい。
接着剤組成物のガラス転移点（Ｔｇ）が０℃を超えると、接着剤組成物の硬化物の低温時における柔軟性が悪くなり、金属樹脂一体成形品が低温時に衝撃や、冷熱ストレスを受けた際、各部材間で生じる応力を緩和できず、各部材間での剥離が起こり易くなる傾向がある。一方、接着剤組成物のガラス転移点（Ｔｇ）が－６０℃未満では、接着剤組成物の硬化物の高温時における凝集力が弱くなるため、金属樹脂一体成形品が、熱時に応力または荷重を受けた際、接着剤層の破壊または各部材間で剥離が起こり易くなる傾向がある。
The adhesive composition according to this embodiment preferably has a glass transition point (Tg) of -60°C or more and 0°C or less, and more preferably -40°C or more and -20°C or less.
If the glass transition point (Tg) of the adhesive composition exceeds 0° C., the flexibility of the cured product of the adhesive composition at low temperatures will be poor, and when the metal-resin integrally molded product is subjected to impact or thermal stress at low temperatures, the stress generated between the respective members cannot be alleviated, and peeling between the respective members will tend to occur easily. On the other hand, if the glass transition point (Tg) of the adhesive composition is less than −60° C., the cohesive strength of the cured product of the adhesive composition at high temperatures will be weak, and when the metal-resin integrally molded product is subjected to stress or load at high temperatures, the adhesive layer will tend to be destroyed or peeling between the respective members will tend to occur easily.
本実施形態に係る接着剤組成物では、フーリエ変換赤外分光光度計（ＦＴ－ＩＲ）を用い、ＡＴＲ（Ａｔｔｅｎｕａｔｅｄ Ｔｏｔａｌ Ｒｅｆｌｅｃｔｉｏｎ）法により測定したアクリル酸エステルのカルボニル基（Ｃ＝Ｏ）に起因する波数（１７４０ｃｍ－１）における吸光度のピーク面積と、アクリロニトリルのニトリル基（Ｃ≡Ｎ）に起因する波数（２２４０ｃｍ－１）における吸光度のピーク面積の比（ニトリル基／カルボニル基）が、０．００１以上０．０２以下であり、０．００１５以上０．０１５以下であることが好ましく、０．００２以上０．０１以下であることがより好ましい。以下、このカルボニル基に対するニトリル基の比を、「Ｎ／Ｃ比」ということもある。 In the adhesive composition according to the present embodiment, the ratio (nitrile group/carbonyl group) of the absorbance peak area at a wave number (1740 cm -1 ) due to the carbonyl group (C═O) of the acrylic ester to the absorbance peak area at a wave number (2240 cm -1 ) due to the nitrile group (C≡N) of the acrylonitrile, measured by the ATR (Attenuated Total Reflection) method using a Fourier transform infrared spectrophotometer (FT-IR), is 0.001 or more and 0.02 or less, preferably 0.0015 or more and 0.015 or less, and more preferably 0.002 or more and 0.01 or less. Hereinafter, this ratio of nitrile groups to carbonyl groups may be referred to as the "N/C ratio".
「Ｎ／Ｃ比」が０．００１未満では、接着剤組成物の常温時および高温時の接着性が悪くなるため、金属樹脂一体成形時に部材同士を接合できない、または、接合できたとしても、金属樹脂一体成形品が、応力または荷重を受けた際、各部材間で容易に剥離してしまうといった不具合が生じやすくなる傾向がある。また、接着剤組成物の硬化物の高温時における凝集力が弱くなるため、金属樹脂一体成形品が、熱時に応力または荷重を受けた際、接着剤層の破壊または各部材間で剥離が起こりやすくなる傾向がある。一方、「Ｎ／Ｃ比」が０．０２を超えると、接着剤組成物の硬化物の低温時における柔軟性が悪くなり、金属樹脂一体成形品が低温時に衝撃や、冷熱ストレスを受けた際、各部材間で生じる応力を緩和できず、各部材間での剥離が起こり易くなる傾向がある。If the "N/C ratio" is less than 0.001, the adhesive composition has poor adhesion at room temperature and at high temperatures, so that the components cannot be joined during the metal-resin integral molding, or even if they can be joined, the metal-resin integral molding tends to easily peel off between the components when it is subjected to stress or load. In addition, the cohesive strength of the cured product of the adhesive composition is weak at high temperatures, so that the adhesive layer tends to break or peel off between the components when the metal-resin integral molding is subjected to stress or load during heating. On the other hand, if the "N/C ratio" exceeds 0.02, the flexibility of the cured product of the adhesive composition at low temperatures is poor, so that when the metal-resin integral molding is subjected to impact or thermal stress at low temperatures, the stress generated between the components cannot be alleviated, and peeling tends to occur easily between the components.
本実施形態に係る接着剤組成物の製造方法は、特に限定されないが、例えば、液状媒体を除く各成分（以下、「各成分」と略する場合がある）をロールミル等で混練したものを液状媒体に溶解する方法や、各成分を予め液状媒体に溶解または分散したものを混合または分散して得る方法が挙げられる。この各成分を液状媒体に溶解または分散したものを以下「接着剤用塗料」ともいう。更に該接着剤用塗料を使用して接着剤層を得るには、接着剤用塗料を被着体に塗布し、乾燥、脱溶剤して形成することにより作製できる。 The method for producing the adhesive composition according to this embodiment is not particularly limited, but examples include a method in which each component except the liquid medium (hereinafter sometimes abbreviated as "each component") is kneaded using a roll mill or the like and then dissolved in a liquid medium, or a method in which each component is dissolved or dispersed in a liquid medium in advance and then mixed or dispersed. Hereinafter, each component dissolved or dispersed in a liquid medium is also referred to as "adhesive paint". Furthermore, to obtain an adhesive layer using the adhesive paint, the adhesive paint can be applied to an adherend, dried, and the solvent removed to form the adhesive layer.
接着剤用塗料を塗布する方法としては、例えば、塗工方式、印刷方式、ディスペンス方式が挙げられ、寸法精度、塗布形状を制御できれば、何れの方法でもよい。
塗工方式としては、例えば、エアドクターコーティング、バーコーティング、ブレードコーティング、ナイフコーティング、リバースコーティング、トランスファロールコーティング、グラビアロールコーティング、キスコーティング、キャストコーティング、スプレーコーティング、スロットオリフィスコーティング、カレンダーコーティング、ダムコーティング、ディップコーティング、ダイコーティング等のコーティング方式が挙げられる。
Examples of methods for applying the adhesive coating material include a coating method, a printing method, and a dispensing method. Any method may be used as long as the dimensional accuracy and the coating shape can be controlled.
Examples of the coating method include air doctor coating, bar coating, blade coating, knife coating, reverse coating, transfer roll coating, gravure roll coating, kiss coating, cast coating, spray coating, slot orifice coating, calendar coating, dam coating, dip coating, and die coating.
塗工方式の場合、ロール状態に巻き取られた支持基材を巻き出し、その支持基材に接着剤用塗料を、公知のコーティング機等を用いて連続塗布し、接着剤用塗料が塗布された支持基材を乾燥炉に通し、５０℃～２００℃で１分～１０分間かけて乾燥させ、必要に応じて、乾燥炉から出た時点でロールラミネータを用いて保護フィルムを貼着し、形成された接着テープを巻き取ってロール状にする方法が用いられる。In the case of the coating method, the support substrate wound in a roll is unwound, and the adhesive coating is continuously applied to the support substrate using a known coating machine or the like. The support substrate coated with the adhesive coating is passed through a drying oven and dried at 50°C to 200°C for 1 to 10 minutes. If necessary, a protective film is attached using a roll laminator when the substrate leaves the drying oven, and the formed adhesive tape is then wound into a roll.
印刷方式としては、例えば、グラビア印刷等の凹版印刷、スクリーン印刷等の孔版印刷等が挙げられる。
塗布した接着剤用塗料を乾燥する際の乾燥温度は、特に制限はないが、室温～１５０℃の範囲が好ましい。乾燥時間についても特に制限は無いが、例えば、１分～２４時間の範囲が好ましい。乾燥温度、乾燥時間については、生産性に応じて適宜選択する。
Examples of printing methods include intaglio printing such as gravure printing, and stencil printing such as screen printing.
The drying temperature when drying the applied adhesive coating material is not particularly limited, but is preferably in the range of room temperature to 150° C. The drying time is also not particularly limited, but is preferably in the range of, for example, 1 minute to 24 hours. The drying temperature and drying time are appropriately selected depending on the productivity.
また、本実施形態における接着剤用塗料の粘度は、室温にて液状のものが好ましく、特に２５℃において０．００１Ｐａ・ｓ～１０００Ｐａ・ｓの範囲が好ましい。しかしながら、室温において固形であっても加熱して液状になるものであれば、本実施形態において使用可能である。
接着層の厚みは、接着剤用塗料の固形分濃度と塗布厚みによって調整できる。
The viscosity of the adhesive coating material in this embodiment is preferably liquid at room temperature, and is particularly preferably in the range of 0.001 Pa·s to 1000 Pa·s at 25° C. However, any material that is solid at room temperature but becomes liquid when heated can be used in this embodiment.
The thickness of the adhesive layer can be adjusted by the solids concentration of the adhesive coating material and the coating thickness.
以上説明した本実施形態の接着剤組成物においては、カルボキシル基、水酸基およびエポキシ基からなる群から選択される少なくとも１種の官能基を有するアクリルゴムと、前記官能基と反応するシランカップリング剤と、フェノール樹脂と、硬化促進剤とを含有する。したがって、本実施形態の接着剤組成物は、金属および樹脂との接着性に優れるとともに、応力緩和性、耐熱性にも優れる。そのため、本実施形態の接着剤組成物は、インサート成形や熱プレス成形において、金属と樹脂の一体成形に好適に用いることができる。The adhesive composition of the present embodiment described above contains an acrylic rubber having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, and an epoxy group, a silane coupling agent that reacts with the functional group, a phenolic resin, and a curing accelerator. Therefore, the adhesive composition of the present embodiment has excellent adhesion to metals and resins, as well as excellent stress relaxation and heat resistance. Therefore, the adhesive composition of the present embodiment can be suitably used for integral molding of metals and resins in insert molding and hot press molding.
以下、実施例および比較例により本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
［実施例１］
アクリルゴムＡ（カルボキシル基を有するモノマーと、アクリル酸エステルおよびアクリロニトリルとのゴム状共重合体（重量平均分子量（Ｍｗ）：９０万、ガラス転移点（Ｔｇ）：－１５℃、Ｎ／Ｃ比：０．００７０））１００質量部と、
シランカップリング剤Ａ（３－グリシドキシプロピルトリメトキシシラン）２５質量部と、
フェノール樹脂Ａ（商品名：ＴＤ－７７３、ＤＩＣ株式会社）２０質量部と
硬化促進剤A（２－エチル－４－メチルイミダゾール、四国化成社製２Ｅ４ＭＺ）１質量部とを、ロールミル（株式会社井上製作所社製）を用いて混合し、実施例１の接着剤組成物を得た。
[Example 1]
100 parts by mass of acrylic rubber A (a rubber-like copolymer of a monomer having a carboxyl group with an acrylic acid ester and acrylonitrile (weight average molecular weight (Mw): 900,000, glass transition point (Tg): -15°C, N/C ratio: 0.0070)),
25 parts by mass of silane coupling agent A (3-glycidoxypropyltrimethoxysilane);
20 parts by mass of phenolic resin A (product name: TD-773, DIC Corporation) and 1 part by mass of curing accelerator A (2-ethyl-4-methylimidazole, 2E4MZ manufactured by Shikoku Kasei Corporation) were mixed using a roll mill (manufactured by Inoue Seisakusho Co., Ltd.) to obtain an adhesive composition of Example 1.
［実施例２］
前記実施例１において、シランカップリング剤Ａの含有量を１０質量部にした以外は実施例１と同様にして、実施例２の接着剤組成物を得た。
[Example 2]
An adhesive composition of Example 2 was obtained in the same manner as in Example 1, except that the content of silane coupling agent A in Example 1 was changed to 10 parts by mass.
［実施例３］
前記実施例１において、シランカップリング剤Ａの含有量を４０質量部にした以外は実施例１と同様にして、実施例３の接着剤組成物を得た。
[Example 3]
An adhesive composition of Example 3 was obtained in the same manner as in Example 1, except that the content of silane coupling agent A in Example 1 was changed to 40 parts by mass.
［実施例４］
前記実施例１において、フェノール樹脂Ａの含有量を１０質量部にした以外は実施例１と同様にして、実施例４の接着剤組成物を得た。
[Example 4]
An adhesive composition of Example 4 was obtained in the same manner as in Example 1, except that the content of phenol resin A in Example 1 was changed to 10 parts by mass.
［実施例５］
前記実施例１において、フェノール樹脂Ａの含有量を４０質量部にした以外は実施例１と同様にして、実施例５の接着剤組成物を得た。
[Example 5]
An adhesive composition of Example 5 was obtained in the same manner as in Example 1, except that the content of phenol resin A in Example 1 was changed to 40 parts by mass.
［実施例６］
前記実施例４において、フェノール樹脂Ａをフェノール樹脂Ｂ（商品名：ＴＤ－１０９０、ＤＩＣ株式会社）１０質量部に変更した以外は実施例４と同様にして、実施例６の接着剤組成物を得た。
[Example 6]
An adhesive composition of Example 6 was obtained in the same manner as in Example 4, except that the phenolic resin A in Example 4 was changed to 10 parts by mass of phenolic resin B (product name: TD-1090, DIC Corporation).
［実施例７］
前記実施例５において、フェノール樹脂Ａをフェノール樹脂Ｂ４０質量部に変更した以外は実施例５と同様にして、実施例７の接着剤組成物を得た。
[Example 7]
An adhesive composition of Example 7 was obtained in the same manner as in Example 5, except that the phenolic resin A in Example 5 was changed to 40 parts by mass of phenolic resin B.
［実施例８］
前記実施例１において、アクリルゴムＡの代わりに、アクリルゴムＢ（エポキシ基を有するモノマーと、アクリル酸エステルおよびアクリロニトリルとのゴム状共重合体（重量平均分子量（Ｍｗ）：９０万、ガラス転移点（Ｔｇ）：－１５℃、Ｎ／Ｃ比：０．００７０））１００質量部にした以外は実施例１と同様にして、実施例８の接着剤組成物を得た。
[Example 8]
An adhesive composition of Example 8 was obtained in the same manner as in Example 1, except that in Example 1, acrylic rubber B (a rubber-like copolymer of a monomer having an epoxy group, an acrylic acid ester, and acrylonitrile (weight average molecular weight (Mw): 900,000, glass transition point (Tg): -15°C, N/C ratio: 0.0070)) was used in place of acrylic rubber A.
［実施例９］
前記実施例１において、アクリルゴムＡの代わりに、アクリルゴムＣ（水酸基を有するモノマーと、アクリル酸エステルおよびアクリロニトリルとのゴム状共重合体（重量平均分子量（Ｍｗ）：９０万、ガラス転移点（Ｔｇ）：－１５℃、Ｎ／Ｃ比：０．００７０））１００質量部にした以外は実施例１と同様にして、実施例９の接着剤組成物を得た。
[Example 9]
An adhesive composition of Example 9 was obtained in the same manner as in Example 1, except that in Example 1, acrylic rubber A was replaced with 100 parts by mass of acrylic rubber C (a rubber-like copolymer of a monomer having a hydroxyl group, an acrylic acid ester, and acrylonitrile (weight average molecular weight (Mw): 900,000, glass transition point (Tg): -15°C, N/C ratio: 0.0070)).
［実施例１０］
前記実施例１において、シランカップリング剤Ａの代わり、シランカップリング剤Ｂ（３－アミノプロピルトリメトキシシラン）２５質量部にした以外は実施例１と同様にして、実施例１０の接着剤組成物を得た。
[Example 10]
An adhesive composition of Example 10 was obtained in the same manner as in Example 1, except that 25 parts by mass of silane coupling agent B (3-aminopropyltrimethoxysilane) was used instead of silane coupling agent A.
［実施例１１］
前記実施例８において、シランカップリング剤Ａの代わり、シランカップリング剤Ｂ２５質量部にした以外は実施例８と同様にして、実施例１１の接着剤組成物を得た。
[Example 11]
An adhesive composition of Example 11 was obtained in the same manner as in Example 8, except that 25 parts by mass of silane coupling agent B was used instead of silane coupling agent A.
［実施例１２］
前記実施例２において、アクリルゴムＡの代わりに、アクリルゴムＤ（カルボキシル基を有するモノマーと、アクリル酸エステルおよびアクリロニトリルとのゴム状共重合体（重量平均分子量（Ｍｗ）：９０万、ガラス転移点（Ｔｇ）：－４０℃、Ｎ／Ｃ比：０．００２０）１００質量部にした以外は実施例２と同様にして、実施例１２の接着剤組成物を得た。
[Example 12]
An adhesive composition of Example 12 was obtained in the same manner as in Example 2, except that 100 parts by mass of acrylic rubber D (a rubber-like copolymer of a monomer having a carboxyl group, an acrylic acid ester, and acrylonitrile (weight average molecular weight (Mw): 900,000, glass transition point (Tg): -40°C, N/C ratio: 0.0020) was used instead of the acrylic rubber A in Example 2.
［実施例１３］
前記実施例３において、アクリルゴムＡの代わりに、アクリルゴムＤ１００質量部にした以外は実施例３と同様にして、実施例１３の接着剤組成物を得た。
[Example 13]
An adhesive composition of Example 13 was obtained in the same manner as in Example 3, except that 100 parts by mass of acrylic rubber D was used instead of acrylic rubber A.
［実施例１４］
前記実施例２において、アクリルゴムＡの代わりに、アクリルゴムＤ１００質量部にして、シランカップリング剤Ａの代わり、シランカップリング剤Ｂ１０質量部にした以外は実施例２と同様にして、実施例１４の接着剤組成物を得た。
[Example 14]
An adhesive composition of Example 14 was obtained in the same manner as in Example 2, except that in place of the acrylic rubber A, 100 parts by mass of acrylic rubber D was used, and in place of the silane coupling agent A, 10 parts by mass of silane coupling agent B was used.
［実施例１５］
前記実施例３において、アクリルゴムＡの代わりに、アクリルゴムＤ１００質量部にして、シランカップリング剤Ａの代わり、シランカップリング剤Ｂ４０質量部にした以外は実施例３と同様にして、実施例１５の接着剤組成物を得た。
[Example 15]
An adhesive composition of Example 15 was obtained in the same manner as in Example 3, except that in place of the acrylic rubber A, 100 parts by mass of acrylic rubber D was used, and in place of the silane coupling agent A, 40 parts by mass of silane coupling agent B was used.
［実施例１６］
前記実施例１２において、硬化促進剤Ａ（２－エチル－４－メチルイミダゾール）の代わりに、硬化促進剤Ｂ（２，４－ジアミノ－６－（２’－エチル－４－メチルイミダゾリル－（１’））－エチル－ｓ－トリアジン、四国化成社製２Ｅ４ＭＺ－Ａ、メチルエチルケトンに不溶、粒子状物、反応開始温度１３５℃）を１質量部にした以外は実施例１２と同様にして、実施例１６の接着剤組成物を得た。
[Example 16]
The adhesive composition of Example 16 was obtained in the same manner as in Example 12, except that in Example 12, the curing accelerator A (2-ethyl-4-methylimidazole) was replaced with 1 part by mass of curing accelerator B (2,4-diamino-6-(2'-ethyl-4-methylimidazolyl-(1'))-ethyl-s-triazine, Shikoku Chemical Industry Co., Ltd. 2E4MZ-A, insoluble in methyl ethyl ketone, particulate matter, reaction initiation temperature 135°C).
［実施例１７］
前記実施例１３において、硬化促進剤Ａの代わりに、硬化促進剤Ｂを１質量部にした以外は実施例１３と同様にして、実施例１７の接着剤組成物を得た。
[Example 17]
An adhesive composition of Example 17 was obtained in the same manner as in Example 13, except that the curing accelerator B was used in place of the curing accelerator A in an amount of 1 part by mass.
［実施例１８］
前記実施例１４において、硬化促進剤Ａの代わりに、硬化促進剤Ｂを１質量部にした以外は実施例１４と同様にして、実施例１８の接着剤組成物を得た。
[Example 18]
An adhesive composition of Example 18 was obtained in the same manner as in Example 14, except that the curing accelerator B was used in place of the curing accelerator A in the above-mentioned Example 14 in an amount of 1 part by mass.
［実施例１９］
前記実施例１５において、硬化促進剤Ａの代わりに、硬化促進剤Ｂを１質量部にした以外は実施例１５と同様にして、実施例１９の接着剤組成物を得た。
[Example 19]
An adhesive composition of Example 19 was obtained in the same manner as in Example 15, except that the curing accelerator B was used in place of the curing accelerator A in an amount of 1 part by mass.
［比較例１］
前記実施例１において、シランカップリング剤Ａの代わりに、エポキシ樹脂（商品名：ｊＥＲ８２８、三菱ケミカル株式会社）２５質量部にした以外は実施例１と同様にして、比較例１の接着剤組成物を得た。
[Comparative Example 1]
An adhesive composition of Comparative Example 1 was obtained in the same manner as in Example 1, except that in Example 1, 25 parts by mass of an epoxy resin (product name: jER828, Mitsubishi Chemical Corporation) was used instead of the silane coupling agent A.
［比較例２］
前記実施例１において、フェノール樹脂Ａを除いた以外は実施例１と同様にして、比較例２の接着剤組成物を得た。
[Comparative Example 2]
An adhesive composition of Comparative Example 2 was obtained in the same manner as in Example 1, except that the phenolic resin A was omitted.
［比較例３］
前記実施例１において、シランカップリング剤Ａを除いた以外は実施例１と同様にして、比較例３の接着剤組成物を得た。
[Comparative Example 3]
An adhesive composition of Comparative Example 3 was obtained in the same manner as in Example 1, except that silane coupling agent A was omitted.
［比較例４］
前記実施例１において、アクリルゴムＡの代わりに、アクリルゴムＥ（カルボキシル基、水酸基およびエポキシ基のいずれも有さないモノマーと、アクリル酸エステルおよびアクリロニトリルとのゴム状共重合体（重量平均分子量（Ｍｗ）：９０万、ガラス転移点（Ｔｇ）：－１５℃、Ｎ／Ｃ比：０．００７０））１００質量部にした以外は実施例１と同様にして、比較例４の接着剤組成物を得た。
[Comparative Example 4]
An adhesive composition of Comparative Example 4 was obtained in the same manner as in Example 1, except that in Example 1, 100 parts by mass of acrylic rubber E (a rubber-like copolymer of a monomer having no carboxyl group, no hydroxyl group, and no epoxy group, an acrylic acid ester, and acrylonitrile (weight average molecular weight (Mw): 900,000, glass transition point (Tg): -15°C, N/C ratio: 0.0070)) was used instead of acrylic rubber A.
［比較例５］
前記比較例１において、フェノール樹脂Ａの含有量を４０質量部にした以外は比較例１と同様にして、比較例５の接着剤組成物を得た。
[Comparative Example 5]
An adhesive composition of Comparative Example 5 was obtained in the same manner as in Comparative Example 1, except that the content of phenol resin A in Comparative Example 1 was changed to 40 parts by mass.
［比較例６］
前記実施例１において、硬化促進剤を除いた以外は実施例１と同様にして、比較例６の接着剤組成物を得た。
[Comparative Example 6]
An adhesive composition of Comparative Example 6 was obtained in the same manner as in Example 1, except that the curing accelerator was omitted.
［比較例７］
前記比較例６において、エポキシ樹脂（商品名：ｊＥＲ８２８、三菱ケミカル株式会社）２５質量部を加えた以外は比較例６と同様にして、比較例７の接着剤組成物を得た。
[Comparative Example 7]
An adhesive composition of Comparative Example 7 was obtained in the same manner as in Comparative Example 6, except that 25 parts by mass of an epoxy resin (product name: jER828, Mitsubishi Chemical Corporation) was added.
［比較例８］
前記比較例１において、アクリルゴムＡの代わりに、アクリルゴムＤ１００質量部にした以外は比較例１と同様にして、比較例８の接着剤組成物を得た。
[Comparative Example 8]
An adhesive composition of Comparative Example 8 was obtained in the same manner as in Comparative Example 1, except that 100 parts by mass of acrylic rubber D was used instead of acrylic rubber A.
前記実施例１～１９及び比較例１～８の接着剤組成物による配合をまとめて下記の表１～６に示した。表中の数値は質量部を示す。The formulations of the adhesive compositions of Examples 1 to 19 and Comparative Examples 1 to 8 are summarized in the following Tables 1 to 6. The values in the tables indicate parts by weight.
［評価］
「接着特性」
（１）ＰＥＴフィルム付き熱硬化性接着シートの作製
実施例１～１９および比較例１～８の接着剤組成物１００質量部を、各々メチルエチルケトン（沸点７９．６℃）４００質量部に分散または溶解して、各々接着剤用塗料を調製した。
実施例１６～１９の接着剤組成物を用いて調製した接着剤用塗料は、硬化促進剤Ｂからなる粒子の分散を確認した。
厚さ３８μｍの離型ＰＥＴフィルムの離型処理面上に、乾燥後の厚さが１００μｍになるように、接着剤用塗料を塗布した。
接着剤用塗料を塗布した離型ＰＥＴフィルムを、１００℃に設定した熱風循環型オーブン中で乾燥、脱溶剤させて、接着剤用塗料からなる塗膜（接着剤層）を形成し、直ちに、その塗膜（接着剤層）の離型ＰＥＴフィルムと接している面とは反対側の面に、他の離型ＰＥＴを貼り合わせて、ＰＥＴフィルム付き熱硬化性接着シートを作製した。
実施例１６～１９の接着剤組成物を用いて調製した接着剤用塗料から得られた熱硬化性接着シートは、熱硬化性接着シート中に硬化促進剤Ｂからなる粒子が分散されていることを確認した。
[evaluation]
"Adhesive properties"
(1) Preparation of Thermosetting Adhesive Sheet with PET Film Each of the adhesive compositions of Examples 1 to 19 and Comparative Examples 1 to 8 (100 parts by mass) was dispersed or dissolved in 400 parts by mass of methyl ethyl ketone (boiling point 79.6° C.) to prepare an adhesive coating material.
In the adhesive coating materials prepared using the adhesive compositions of Examples 16 to 19, it was confirmed that particles made of the curing accelerator B were dispersed.
The adhesive coating material was applied onto the release-treated surface of a 38 μm-thick release PET film so that the thickness after drying would be 100 μm.
The release PET film coated with the adhesive paint was dried and the solvent removed in a hot air circulating oven set at 100°C to form a coating film (adhesive layer) made of the adhesive paint. Immediately, another release PET was bonded to the side of the coating film (adhesive layer) opposite to the side in contact with the release PET film to produce a thermosetting adhesive sheet with a PET film.
It was confirmed that the thermosetting adhesive sheets obtained from the adhesive coating materials prepared using the adhesive compositions of Examples 16 to 19 contained particles of curing accelerator B dispersed in the thermosetting adhesive sheets.
（２）ＰＢＴ・アルミニウム接合サンプルの作製（１５０℃／１５ｍｉｎキュア）
上記のＰＥＴフィルム付き熱硬化性接着シートを、５ｍｍ×５ｍｍに裁断した。
ＰＥＴフィルム付き熱硬化性接着シートの一方の離型ＰＥＴフィルムを剥離し、接着剤層側を金属板へ貼りつけた。金属板としては、アルミニウムＡ５０５２材（２０ｍｍ×３０ｍｍ、厚さ１．５ｍｍ）を用いた。
ＰＥＴフィルム付き熱硬化性接着シートの他方の離型ＰＥＴフィルムを剥離し、金属・接着シート貼付品を得た。
上記の金属・接着シート貼付品を、熱循環型オーブンを用いて１５０℃にて１５ｍｉｎで熱処理し、接着剤層を熱硬化させた（このとき接着剤層は完全に硬化していない）。
２６０℃に加熱したホットプレート上に、接着剤層を熱硬化させた金属・接着シート貼付品を載せて、さらに、その接着剤層上にポリフェニレンサルファイド（ＰＢＴ）からなる樹脂材を載せて、そのＰＢＴ樹脂材側から５０ｋＰａにて２０ｓｅｃ加圧して、ＰＢＴ・アルミニウム接合サンプルを作製した。ＰＢＴ樹脂材としては、富山軽粗材株式会社製（１０ｍｍ×１０ｍｍ、厚さ１０ｍｍ）の板材を用いた。
なお、上記の加工時の熱によって、接着剤層自体も、アルミニウムとＰＢＴ樹脂材へ適度に濡れながら、架橋がさらに進むため、接着剤層と、アルミニウムおよびＰＢＴと強固に接合する。
(2) Preparation of PBT/aluminum bonded sample (150°C/15min cure)
The above thermosetting adhesive sheet with the PET film was cut into a size of 5 mm x 5 mm.
One of the release PET films of the thermosetting adhesive sheet with the PET film was peeled off, and the adhesive layer side was attached to a metal plate made of aluminum A5052 (20 mm x 30 mm, thickness 1.5 mm).
The release PET film on the other side of the thermosetting adhesive sheet with the PET film was peeled off to obtain a metal/adhesive sheet attached article.
The above metal/adhesive sheet attached article was heat treated at 150° C. for 15 minutes using a heat circulation type oven to thermally cure the adhesive layer (the adhesive layer was not completely cured at this stage).
A metal-adhesive sheet-attached product with a heat-cured adhesive layer was placed on a hot plate heated to 260° C., and a resin material made of polyphenylene sulfide (PBT) was placed on the adhesive layer, and pressure was applied from the PBT resin material side at 50 kPa for 20 sec to prepare a PBT-aluminum bonded sample. A plate material (10 mm x 10 mm, thickness 10 mm) manufactured by Toyama Light Sozai Co., Ltd. was used as the PBT resin material.
In addition, due to the heat generated during the above processing, the adhesive layer itself also becomes moderately wetted by the aluminum and the PBT resin material, and crosslinking proceeds further, so that the adhesive layer is firmly bonded to the aluminum and the PBT.
（３）常温における接着特性の評価（１５０℃／１５ｍｉｎキュアせん断強度（常温））
上記（２）におけるＰＢＴ・アルミニウム接合サンプルを、ＰＢＴ樹脂材に対して、せん断方向に押し付けた時の強度（せん断強度）を２５℃環境下で測定した。
せん断強度の測定には株式会社今田製作所製の剪断力試験機ＳＬ５０００を用いた。測定速度を５０ｍｍ／分とした。
ＰＢＴ樹脂材とアルミニウム材を接合できなかったものを「接合できず」、せん断強度が１００ｋＰａ未満を「×」、せん断強度が１００ｋＰａ以上のものを「○」とした。結果を表７～１２に示した。
(3) Evaluation of adhesive properties at room temperature (150°C/15 min cure shear strength (room temperature))
The strength (shear strength) of the PBT-aluminum bonded sample in (2) above when pressed against a PBT resin material in the shear direction was measured in a 25° C. environment.
The shear strength was measured using a shear strength tester SL5000 manufactured by Imada Seisakusho Co., Ltd. The measurement speed was 50 mm/min.
The case where the PBT resin material and the aluminum material could not be joined was marked "unjoined", the case where the shear strength was less than 100 kPa was marked "x", and the case where the shear strength was 100 kPa or more was marked "◯". The results are shown in Tables 7 to 12.
（４）熱時における接着特性の評価（１５０℃／１５ｍｉｎキュアせん断強度（熱時））
上記（２）におけるＰＢＴ・アルミニウム接合サンプルを、ＰＢＴ樹脂材に対して、せん断方向に押し付けた時の強度（せん断強度）を１３０℃環境下で測定した。
せん断強度の測定には 株式会社今田製作所製の剪断力試験機ＳＬ５０００を用いた。測定速度を５０ｍｍ／分とした。
ＰＢＴ樹脂材とアルミニウム材を接合できなかったものを「接合できず」、せん断強度が１００ｋＰａ未満を「×」、せん断強度が１００ｋＰａ以上のものを「○」とした。結果を表７～１２に示した。
(4) Evaluation of adhesive properties under heat (150°C/15 min cure shear strength (hot))
The PBT-aluminum bonded sample in (2) above was pressed against a PBT resin material in the shear direction, and the strength (shear strength) was measured in an environment of 130°C.
The shear strength was measured using a shear strength tester SL5000 manufactured by Imada Seisakusho Co., Ltd. The measurement speed was 50 mm/min.
The case where the PBT resin material and the aluminum material could not be joined was marked "unjoined", the case where the shear strength was less than 100 kPa was marked "x", and the case where the shear strength was 100 kPa or more was marked "◯". The results are shown in Tables 7 to 12.
（５）ＰＢＴ・アルミニウム接合サンプルの作製（１５０℃／６０ｍｉｎキュア）
前記（２）ＰＢＴ・アルミニウム接合サンプルの作製（１５０℃／１５ｍｉｎキュア）において、熱循環型オーブンを用いて接着剤層を熱硬化させる温度及び時間を、１５０℃にて６０ｍｉｎにした以外は同様にしてＰＢＴ・アルミニウム接合サンプルを作製した。
(5) Preparation of PBT/aluminum bonded sample (150°C/60min cure)
A PBT-aluminum bonded sample was prepared in the same manner as in (2) Preparation of a PBT-aluminum bonded sample (150°C/15 min cure) above, except that the temperature and time for thermally curing the adhesive layer using a heat circulation oven were changed to 150°C and 60 minutes.
（６）常温における接着性の評価（１５０℃／６０ｍｉｎキュアせん断強度（常温））
上記（５）におけるＰＢＴ・アルミニウム接合サンプルを、ＰＢＴ樹脂材に対して、せん断方向に押し付けた時の強度（せん断強度）を２５℃環境下で測定した。
せん断強度の測定には株式会社今田製作所製の剪断力試験機ＳＬ５０００を用いた。測定速度を５０ｍｍ／分とした。
ＰＢＴ樹脂材とアルミニウム材を接合できなかったものを「接合できず」、せん断強度が１００ｋＰａ未満を「×」、せん断強度が１００ｋＰａ以上のものを「○」とした。結果を表７～１２に示した。
(6) Evaluation of Adhesion at Room Temperature (150°C/60min Cure Shear Strength (Room Temperature))
The strength (shear strength) of the PBT-aluminum bonded sample in (5) above when pressed against a PBT resin material in the shear direction was measured in a 25° C. environment.
The shear strength was measured using a shear strength tester SL5000 manufactured by Imada Seisakusho Co., Ltd. The measurement speed was 50 mm/min.
The case where the PBT resin material and the aluminum material could not be joined was marked "unjoined", the case where the shear strength was less than 100 kPa was marked "x", and the case where the shear strength was 100 kPa or more was marked "◯". The results are shown in Tables 7 to 12.
（７）熱時における接着性の評価（１５０℃／６０ｍｉｎキュアせん断強度（熱時））
上記（５）におけるＰＢＴ・アルミニウム接合サンプルを、ＰＢＴ樹脂材に対して、せん断方向に押し付けた時の強度（せん断強度）を１３０℃環境下で測定した。
せん断強度の測定には 株式会社今田製作所製の剪断力試験機ＳＬ５０００を用いた。測定速度を５０ｍｍ／分とした。
ＰＢＴ樹脂材とアルミニウム材を接合できなかったものを「接合できず」、せん断強度が１００ｋＰａ未満を「×」、せん断強度が１００ｋＰａ以上のものを「○」とした。結果を表７～１２に示した。
(7) Evaluation of adhesiveness under heat (150°C/60min cure shear strength (hot))
The strength (shear strength) of the PBT-aluminum bonded sample in (5) above when pressed against a PBT resin material in the shear direction was measured in an environment of 130°C.
The shear strength was measured using a shear strength tester SL5000 manufactured by Imada Seisakusho Co., Ltd. The measurement speed was 50 mm/min.
The case where the PBT resin material and the aluminum material could not be joined was marked "unjoined", the case where the shear strength was less than 100 kPa was marked "x", and the case where the shear strength was 100 kPa or more was marked "◯". The results are shown in Tables 7 to 12.
「速硬化性」
前記「接着特性」（１）ＰＥＴフィルム付き熱硬化性接着シートの作製で得たＰＥＴフィルム付き熱硬化性接着シートを、接着剤が１ｍｍ厚となるように積層し、レオメーター（ＨＡＡＫＥ社製ＭＡＲＳＩ）を用いて、１５０℃経時における接着剤の硬化速度を確認するため、１５０℃経時におけるせん断貯蔵弾性率を測定した。評価プローブは、２０ｍｍΦパラレルプレートを使用した。測定荷重は１５Ｎとした。測定周波数は１Ｈｚとした。温度条件は、室温から１５０℃まで１０℃／ｍｉｎの速度で昇温させた後、１５０℃到達後、１５０℃で６０ｍｉｎ保持させた。ここで、１５０℃に達したときの１５０℃のせん断貯蔵弾性率をＧ１（初期の１５０℃粘度）、１５０℃で１５ｍｉｎ経過時における１５０℃せん断貯蔵弾性率をＧ２、１５０℃で６０ｍｉｎ経過時における１５０℃せん断貯蔵弾性率をＧ３とした。
次に、１５０℃で１５ｍｉｎ経過時における１５０℃の貯蔵弾性率の変化比率（Ｇ２／Ｇ１）をαと表した。αが１．５以上の場合は、速硬化性があるとして○とした。一方αが１．５未満の場合は、速硬化性がないとして×とした。結果を表７～１２に示した。
"Fast curing"
The thermosetting adhesive sheet with PET film obtained in the above "Adhesive properties" (1) Preparation of thermosetting adhesive sheet with PET film was laminated so that the adhesive was 1 mm thick, and a rheometer (MARSI manufactured by HAAKE) was used to measure the shear storage modulus at 150 ° C. in order to confirm the curing speed of the adhesive at 150 ° C. The evaluation probe used a 20 mm Φ parallel plate. The measurement load was 15 N. The measurement frequency was 1 Hz. The temperature conditions were that the temperature was raised from room temperature to 150 ° C. at a rate of 10 ° C. / min, and then after reaching 150 ° C., it was held at 150 ° C. for 60 min. Here, the shear storage modulus at 150 ° C. when it reached 150 ° C. was G1 (initial 150 ° C. viscosity), the 150 ° C. shear storage modulus after 15 min at 150 ° C. was G2, and the 150 ° C. shear storage modulus after 60 min at 150 ° C. was G3.
Next, the ratio of change in storage modulus at 150°C (G2/G1) after 15 minutes at 150°C was expressed as α. When α was 1.5 or more, it was judged to have fast curing properties and was marked as ○. On the other hand, when α was less than 1.5, it was judged not to have fast curing properties and was marked as ×. The results are shown in Tables 7 to 12.
「品質安定性」
前記「速硬化性」のせん断貯蔵弾性率測定結果から、１５０℃で１５ｍｉｎ経過時における１５０℃のせん断貯蔵弾性率の変化比率（Ｇ２／Ｇ１）をαと表した。また、１５０℃で６０ｍｉｎ経過時における１５０℃のせん断貯蔵弾性率の変化比率（Ｇ３／Ｇ１）をβと表した。
そして、β－α＝１．５以下の場合は、品質安定性は良好であり、○としして記した。また、β－α＝１．５を越えた場合は、品質不安定性は不良であり、×として記した。β－α＝１．５以下の場合は、熱硬化による接着剤の凝集力の変化率が低いことを示し、適切な接合状態が得るために必要な接着剤の硬化時間を広く設定できる（硬化条件のマージンを広くできる）。結果を表７～１２に示した。
"Quality stability"
From the results of the shear storage modulus measurement for "fast curing," the change ratio of the shear storage modulus at 150°C after 15 minutes at 150°C (G2/G1) was represented as α. Also, the change ratio of the shear storage modulus at 150°C after 60 minutes at 150°C (G3/G1) was represented as β.
When β-α=1.5 or less, the quality stability is good, and is marked with ○. When β-α=1.5 or more, the quality instability is poor, and is marked with ×. When β-α=1.5 or less, this indicates that the rate of change in the adhesive's cohesive strength due to thermal curing is low, and the adhesive curing time required to obtain an appropriate bonding state can be set widely (the margin of the curing conditions can be widened). The results are shown in Tables 7 to 12.
「低温特性」
応力緩和性を評価するため、接着剤を熱硬化した後の、接着剤のガラス転移点を示差走査熱量測定（ＤＳＣ：ｄｉｆｆｅｒｅｎｔｉａｌ ｓｃａｎｎｉｎｇ ｃａｌｏｒｉｍｅｔｒｙ）により測定した。
前記「接着特性」（１）ＰＥＴフィルム付き熱硬化性接着シートの作製で得たＰＥＴフィルム付き熱硬化性接着シートの接着剤部分を取り出し、それをアルミホイルシャーレに載せ、熱循環オーブンを用いて１５０℃で６０ｍｉｎ加熱し、次にホットプレートにて２６０℃で２０ｓｅｃの熱処理を行った。次に、熱処理した接着剤部分を１０ｍｇ取り出し、ＤＳＣ（日立ハイテクサイエンス社製 ＤＳＣ７０２０）を用いて接着剤のガラス転移点（Ｔｇ）を求めた。
ＤＳＣ測定は、窒素雰囲気で－８０℃～＋３００℃の範囲を１０℃／分の昇温速度の条件で行い、その熱流曲線の変曲点からガラス転移点を求めた。評価としては、ガラス転移点が－２０℃未満を○、－２０℃～０℃を△、０℃を越えた場合を×とした。結果を表７～１２に示した。
"Low temperature characteristics"
To evaluate the stress relaxation property, the glass transition point of the adhesive after thermal curing was measured by differential scanning calorimetry (DSC).
The adhesive portion of the thermosetting adhesive sheet with PET film obtained in the above "Adhesive properties" (1) Preparation of thermosetting adhesive sheet with PET film was removed, placed on an aluminum foil petri dish, heated at 150°C for 60 minutes using a heat circulation oven, and then heat-treated on a hot plate at 260°C for 20 seconds. Next, 10 mg of the heat-treated adhesive portion was removed, and the glass transition point (Tg) of the adhesive was determined using a DSC (DSC7020, manufactured by Hitachi High-Tech Science Corporation).
The DSC measurement was performed in a nitrogen atmosphere at a temperature range of -80°C to +300°C at a temperature rise rate of 10°C/min, and the glass transition temperature was determined from the inflection point of the heat flow curve. The glass transition temperature was evaluated as ◯ for less than -20°C, △ for -20°C to 0°C, and × for over 0°C. The results are shown in Tables 7 to 12.
上記表７～１２の結果から、実施例１～実施例１９の接着剤組成物は、比較例１～比較例８の接着剤組成物よりも、接着特性、速硬化性、品質安定性および低温特性に優れていることが確認された。From the results in Tables 7 to 12 above, it was confirmed that the adhesive compositions of Examples 1 to 19 have superior adhesive properties, rapid curing properties, quality stability and low temperature properties compared to the adhesive compositions of Comparative Examples 1 to 8.
本発明の接着剤組成物によれば、インサート成形や熱プレス成形において、金属と樹脂の一体成形に好適に用いることができる。The adhesive composition of the present invention can be suitably used for integral molding of metal and resin in insert molding and hot press molding.
Claims (1)
前記アクリルゴムが、アクリル酸エステルおよびその誘導体の少なくとも一方とアクリロニトリルおよびその誘導体の少なくとも一方の共重合体を含み、
前記硬化促進剤が前記液状媒体に不溶であり、かつ前記硬化促進剤の反応開始温度が前記液状媒体の沸点より高い温度であり、
前記硬化促進剤の粒子が分散されていることを特徴とする接着剤組成物。 An adhesive composition comprising an acrylic rubber having a carboxyl functional group, a silane coupling agent that reacts with the functional group, a phenolic resin, a curing accelerator, and a liquid medium,
the acrylic rubber contains a copolymer of at least one of an acrylic acid ester and a derivative thereof and at least one of acrylonitrile and a derivative thereof,
the curing accelerator is insoluble in the liquid medium, and the reaction initiation temperature of the curing accelerator is higher than the boiling point of the liquid medium;
An adhesive composition comprising dispersed particles of the curing accelerator.
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| PCT/JP2021/014621 WO2021206087A1 (en) | 2020-04-10 | 2021-04-06 | Adhesive composition |
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