JP4539827B2 - Rubber article in which a perfluoropolyether-based fluorine-containing rubber molded article and a dissimilar material are bonded, and method for producing the same - Google Patents
Rubber article in which a perfluoropolyether-based fluorine-containing rubber molded article and a dissimilar material are bonded, and method for producing the same Download PDFInfo
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- JP4539827B2 JP4539827B2 JP2004235719A JP2004235719A JP4539827B2 JP 4539827 B2 JP4539827 B2 JP 4539827B2 JP 2004235719 A JP2004235719 A JP 2004235719A JP 2004235719 A JP2004235719 A JP 2004235719A JP 4539827 B2 JP4539827 B2 JP 4539827B2
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- 229920001971 elastomer Polymers 0.000 title claims description 108
- 239000005060 rubber Substances 0.000 title claims description 105
- 229910052731 fluorine Inorganic materials 0.000 title claims description 52
- 239000011737 fluorine Substances 0.000 title claims description 51
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 49
- 239000000463 material Substances 0.000 title claims description 47
- 239000010702 perfluoropolyether Substances 0.000 title claims description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000203 mixture Substances 0.000 claims description 109
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 82
- 239000007788 liquid Substances 0.000 claims description 52
- 239000000377 silicon dioxide Substances 0.000 claims description 38
- 239000003795 chemical substances by application Substances 0.000 claims description 37
- 238000004132 cross linking Methods 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 28
- 229920002379 silicone rubber Polymers 0.000 claims description 27
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 25
- 239000004944 Liquid Silicone Rubber Substances 0.000 claims description 20
- -1 perfluoro compound Chemical class 0.000 claims description 20
- 125000005372 silanol group Chemical group 0.000 claims description 16
- 125000003342 alkenyl group Chemical group 0.000 claims description 15
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 15
- 125000003277 amino group Chemical group 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 229920001973 fluoroelastomer Polymers 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 7
- 239000004945 silicone rubber Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 5
- 239000004971 Cross linker Substances 0.000 claims description 4
- 238000007259 addition reaction Methods 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
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- 239000004567 concrete Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 229920003051 synthetic elastomer Polymers 0.000 claims description 3
- 239000005061 synthetic rubber Substances 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 239000010408 film Substances 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 9
- 125000005843 halogen group Chemical group 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 125000000962 organic group Chemical group 0.000 description 8
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910008051 Si-OH Inorganic materials 0.000 description 6
- 229910006358 Si—OH Inorganic materials 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000000732 arylene group Chemical group 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 238000006482 condensation reaction Methods 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 229910021485 fumed silica Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000012756 surface treatment agent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000003944 tolyl group Chemical group 0.000 description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- 239000004642 Polyimide Substances 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 125000005998 bromoethyl group Chemical group 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000460 chlorine Chemical group 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 3
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004344 phenylpropyl group Chemical group 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000012744 reinforcing agent Substances 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 125000005023 xylyl group Chemical group 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
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- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
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- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000002993 cycloalkylene group Chemical group 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 229920000570 polyether Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
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- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
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- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 2
- QMTFKWDCWOTPGJ-KVVVOXFISA-N (z)-octadec-9-enoic acid;tin Chemical compound [Sn].CCCCCCCC\C=C/CCCCCCCC(O)=O QMTFKWDCWOTPGJ-KVVVOXFISA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- QYOLDSFFGZXYPC-UHFFFAOYSA-N 1-methyl-1,3,5,2,4,6-triazatrisilinane Chemical compound CN1[SiH2]N[SiH2]N[SiH2]1 QYOLDSFFGZXYPC-UHFFFAOYSA-N 0.000 description 1
- IHEDBVUTTQXGSJ-UHFFFAOYSA-M 2-[bis(2-oxidoethyl)amino]ethanolate;titanium(4+);hydroxide Chemical compound [OH-].[Ti+4].[O-]CCN(CC[O-])CC[O-] IHEDBVUTTQXGSJ-UHFFFAOYSA-M 0.000 description 1
- HNUKTDKISXPDPA-UHFFFAOYSA-N 2-oxopropyl Chemical group [CH2]C(C)=O HNUKTDKISXPDPA-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
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- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- YCNIBOIOWCTRCL-UHFFFAOYSA-N azane;2,2,2-trifluoroacetic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)F YCNIBOIOWCTRCL-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- WBQJELWEUDLTHA-UHFFFAOYSA-M benzyl(triethyl)azanium;acetate Chemical compound CC([O-])=O.CC[N+](CC)(CC)CC1=CC=CC=C1 WBQJELWEUDLTHA-UHFFFAOYSA-M 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 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
- QAEKNCDIHIGLFI-UHFFFAOYSA-L cobalt(2+);2-ethylhexanoate Chemical compound [Co+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O QAEKNCDIHIGLFI-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical compound [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- ZXDVQYBUEVYUCG-UHFFFAOYSA-N dibutyltin(2+);methanolate Chemical compound CCCC[Sn](OC)(OC)CCCC ZXDVQYBUEVYUCG-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- VEVVRTWXUIWDAW-UHFFFAOYSA-N dodecan-1-amine;phosphoric acid Chemical compound OP(O)(O)=O.CCCCCCCCCCCCN VEVVRTWXUIWDAW-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 208000023414 familial retinal arterial macroaneurysm Diseases 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 125000005816 fluoropropyl group Chemical group [H]C([H])(F)C([H])([H])C([H])([H])* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000004989 laser desorption mass spectroscopy Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- QFWAHMAYYWUGTI-UHFFFAOYSA-N methyl-tris(prop-1-enoxy)silane Chemical compound CC=CO[Si](C)(OC=CC)OC=CC QFWAHMAYYWUGTI-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- VMESOKCXSYNAKD-UHFFFAOYSA-N n,n-dimethylhydroxylamine Chemical compound CN(C)O VMESOKCXSYNAKD-UHFFFAOYSA-N 0.000 description 1
- LJZHQOFHXBAAAE-UHFFFAOYSA-N n-ethylethanamine;2,2,2-trifluoroacetic acid Chemical compound CC[NH2+]CC.[O-]C(=O)C(F)(F)F LJZHQOFHXBAAAE-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 1
- 125000005386 organosiloxy group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- LSZKGNJKKQYFLR-UHFFFAOYSA-J tri(butanoyloxy)stannyl butanoate Chemical compound [Sn+4].CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O LSZKGNJKKQYFLR-UHFFFAOYSA-J 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 description 1
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- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
本発明は、耐溶剤性、耐薬品性、耐熱性、低温特性が良好なパーフルオロポリエーテル系フッ素ゴムと異種材料とを接着させた複合物品及びその製造方法に関する。 The present invention relates to a composite article obtained by bonding a perfluoropolyether-based fluororubber having good solvent resistance, chemical resistance, heat resistance, and low-temperature characteristics and a dissimilar material, and a method for producing the same.
従来のフッ化ビニリデン系フッ素ゴムは、耐熱性、耐薬品性、機械的強度などに優れたエラストマーなので、自動車及び機械産業を中心に広い分野で工業的に使用されている。 Conventional vinylidene fluoride-based fluororubber is an elastomer excellent in heat resistance, chemical resistance, mechanical strength, and the like, and is therefore industrially used in a wide range of fields mainly in the automobile and machine industries.
しかしながら、その耐薬品性は不十分であり、ケトン系、低級アルコール系、カルボニル系、有機酸系などの極性溶剤には容易に膨潤してしまい、アミンを含む薬品には劣化してゴム強度や伸びが極端に低下してしまうという欠点を有している。また、低温特性においても、−２０℃以下ではゴム弾性を失ってしまい、シール材として使用できなくなってしまうため、寒冷地での使用には限界があるのが一般的である。 However, its chemical resistance is inadequate and easily swells in polar solvents such as ketones, lower alcohols, carbonyls, organic acids, etc. There is a disadvantage that the elongation is extremely lowered. Further, in terms of low temperature characteristics, rubber elasticity is lost at −20 ° C. or lower and the seal material cannot be used. Therefore, there is a general limit to use in cold regions.
そこで、それらの欠点を改善するために、パーフルオロ化合物と含フッ素オルガノ水素ポリシロキサンとを主成分とする液状もしくはミラブルタイプの含フッ素硬化性組成物が提案されている（特許文献１〜４：特許第２９９０６４６号（特開平８−１９９０７０号）公報、特開２０００−００７８３５号公報、特開２００１−１０６８９３号公報、特開２００３−２０１４０１号公報参照）。
Therefore, in order to improve these drawbacks, a liquid or millable type fluorinated curable composition mainly composed of a perfluoro compound and a fluorinated organohydrogenpolysiloxane has been proposed (
しかしながら、これらの含フッ素硬化性組成物は安定性に優れるために、金属、樹脂、セラミックなどの異種材料と接着させる場合に適当な接着剤が見出されていない。 However, since these fluorine-containing curable compositions are excellent in stability, no suitable adhesive has been found for bonding with dissimilar materials such as metals, resins, and ceramics.
そこで、異種材料との接着にはプライマーを用いた一体成形を行うのが一般的であるが、金型構造が複雑になったり、成形時に必要な圧力や熱に対して安定な材料に限定されてしまうという欠点を有している。 Therefore, it is common to perform integral molding using a primer for bonding to dissimilar materials, but the mold structure is complicated, and it is limited to materials that are stable against pressure and heat required during molding. Have the disadvantage of
本発明は、上記事情に鑑みなされたもので、含フッ素ゴム成形品と異種材料とを接着することができ、含フッ素ゴム成形品の耐溶剤性、耐薬品性、耐熱性、低温特性に優れた部分を持つ複合物品及びその製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and can bond a fluorine-containing rubber molded product and a different material, and is excellent in solvent resistance, chemical resistance, heat resistance, and low temperature characteristics of the fluorine-containing rubber molded product. It is an object of the present invention to provide a composite article having a portion and a method for manufacturing the same.
本発明者らは、上記目的を達成するために鋭意検討を行った結果、充填材としてシリカを含有するパーフルオロポリエーテル系含フッ素ゴム成形品と異種材料とを２液を混合することにより、水分を発生させる２液縮合架橋型液状シリコーンゴム組成物を介して接着可能であることを見出し、本発明をなすに至った。 As a result of intensive studies to achieve the above object, the present inventors have mixed two liquids of a perfluoropolyether-based fluorine-containing rubber molded product containing silica as a filler and a different material, It found that it is possible adhered via the 2 Ekichijimigo crosslinking liquid silicone rubber composition which generates moisture, leading to the completion of the present invention.
従って、本発明は、下記パーフルオロポリエーテル系含フッ素ゴム成形品と異種材料とを接着させたゴム物品及びその製造方法を提供する。
請求項１：
（ａ）充填材としてシリカを含有するパーフルオロポリエーテル系含フッ素ゴム成形品と、（ｂ）シリコーンゴム成形品以外の異種材料とを、
（ｃ）（Ｄ）下記一般式（９）：
で示される分子鎖両末端が加水分解性シリル基及び／又はシラノール基で封鎖されたジオルガノポリシロキサン、及び
（Ｅ）上記（Ｄ）成分を縮合架橋させる硬化剤及び／又は硬化触媒
を含む組成物を必須成分とし、（Ｄ）成分を含む液剤（ｉ）と（Ｅ）成分を含む液剤（ｉｉ）とが別包装されてなる２液縮合架橋型の液状シリコーンゴム組成物の硬化物を介して接着されてなることを特徴とするゴム物品。
請求項２：
（ａ）充填材としてシリカを含有するパーフルオロポリエーテル系含フッ素ゴム成形品と、（ｂ）シリコーンゴム成形品以外の異種材料とを、
（ｃ）（Ｄ）下記一般式（９）：
で示される分子鎖両末端が加水分解性シリル基及び／又はシラノール基で封鎖されたジオルガノポリシロキサン、
（Ｅ）上記（Ｄ）成分を縮合架橋させる硬化剤及び／又は硬化触媒、
（Ｆ）カルボニル基を有する化合物、及び
（Ｇ）アミノ基を有する化合物
を含む組成物を必須成分とし、（Ｆ）成分を含む液剤（ｉ）と（Ｇ）成分を含む液剤（ｉｉ）とが別包装されてなる２液縮合架橋型の液状シリコーンゴム組成物の硬化物を介して接着されてなることを特徴とするゴム物品。
請求項３：
上記（ａ）パーフルオロポリエーテル系含フッ素ゴム成形品が、
（Ａ）分子中に少なくとも２個のアルケニル基を有し、かつ主鎖中に二価のパーフルオロアルキレン構造又は二価のパーフルオロポリエーテル構造を有するパーフルオロ化合物の前記アルケニル基の一部に、分子中に少なくとも２個のヒドロシリル基を有するアルケニル基と付加反応可能な化合物が付加してなるポリマー、
（Ｂ）シリカ、及び
（Ｃ）分子中にヒドロシリル基を有する付加反応可能な架橋剤又はパーオキサイド架橋剤を前記（Ａ）成分を硬化させるのに十分な量
を含有してなる架橋性フッ素ゴム組成物を硬化させてなるものであることを特徴とする請求項１又は２記載のゴム物品。
請求項４：
上記（ａ）パーフルオロポリエーテル系含フッ素ゴム成形品中のシリカ含有率が１〜５０質量％であることを特徴とする請求項１〜３のいずれか１項記載のゴム物品。
請求項５：
上記（ｂ）異種材料が、少なくとも（ａ）の含フッ素ゴム成形品と接着される表面が金属、金属酸化物、セラミック、ガラス、コンクリート、石、プラスティック、塗膜、合成ゴム、木材から選ばれる材料にて形成された加工品である請求項１〜４のいずれか１項記載のゴム物品。
請求項６：
（ａ）充填材としてシリカを含有するパーフルオロポリエーテル系含フッ素ゴム成形品及び／又は（ｂ）シリコーンゴム成形品以外の異種材料に、
（Ｄ）下記一般式（９）：
で示される分子鎖両末端が加水分解性シリル基及び／又はシラノール基で封鎖されたジオルガノポリシロキサン、
（Ｅ）上記（Ｄ）成分を縮合架橋させる硬化剤及び／又は硬化触媒、
（Ｆ）カルボニル基を有する化合物、及び
（Ｇ）アミノ基を有する化合物
を含む組成物を必須成分とし、（Ｆ）成分を含む液剤（ｉ）と（Ｇ）成分を含む液剤（ｉｉ）とが別包装されてなる２液縮合架橋型の液状シリコーンゴム組成物又は液状パーフルオロポリエーテル系含フッ素ゴム組成物の上記両液剤（ｉ）及び（ｉｉ）の混合物を塗布し、該混合物を介在させた状態で上記（ａ）、（ｂ）を貼り合わせ、上記（Ｆ），（Ｇ）成分の混合により生成した水分で上記組成物を硬化すると共に、上記（ａ）、（ｂ）を接合することを特徴とするゴム物品の製造方法。
請求項７：
請求項１乃至５のいずれか１項記載のゴム物品を部分構造又は全体構造として有するゴム製品。
請求項８：
成形品がシール材、Ｏ−リング、ダイヤフラム、ホース、キャップ又はバルブ材である請求項７記載のゴム製品。
Accordingly, the present invention provides a rubber article obtained by bonding the following perfluoropolyether-based fluorine-containing rubber molded article and a different material, and a method for producing the same.
Claim 1:
(A) a perfluoropolyether-based fluorine-containing rubber molded product containing silica as a filler , and (b) a different material other than a silicone rubber molded product ,
(C) (D) The following general formula (9):
A diorganopolysiloxane in which both ends of the molecular chain represented by are blocked with hydrolyzable silyl groups and / or silanol groups, and
(E) Curing agent and / or curing catalyst for condensation crosslinking of component (D)
Curing of a two-component condensation-crosslinking type liquid silicone rubber composition in which a liquid composition (i) containing the component (D) and a liquid agent (ii) containing the component (E) are separately packaged. A rubber article which is bonded through an object.
Claim 2 :
(A) a perfluoropolyether-based fluorine-containing rubber molded product containing silica as a filler, and (b) a different material other than a silicone rubber molded product,
(C) (D) The following general formula (9):
A diorganopolysiloxane in which both ends of the molecular chain represented by are blocked with hydrolyzable silyl groups and / or silanol groups,
(E) a curing agent and / or a curing catalyst for condensation-crosslinking the component (D).
(F) a compound having a carbonyl group, and
(G) Compound having amino group
Curing of a two-component condensation-crosslinking type liquid silicone rubber composition in which a liquid composition (i) containing the component (F) and a liquid composition (ii) containing the component (G) are separately packaged. A rubber article which is bonded through an object.
Claim 3 :
The above (a) perfluoropolyether-based fluorine-containing rubber molded product is
(A) a part of the alkenyl group of the perfluoro compound having at least two alkenyl groups in the molecule and having a divalent perfluoroalkylene structure or a divalent perfluoropolyether structure in the main chain; A polymer formed by adding a compound capable of addition reaction with an alkenyl group having at least two hydrosilyl groups in the molecule,
Crosslinkable fluororubber comprising (B) silica, and (C) an addition-reactive crosslinker having a hydrosilyl group in the molecule or a peroxide crosslinker sufficient to cure the component (A) The rubber article according to claim 1 or 2 , wherein the rubber article is obtained by curing the composition.
Claim 4 :
The rubber article according to any one of
Claim 5 :
The (b) different material is selected from metal, metal oxide, ceramic, glass, concrete, stone, plastic, coating film, synthetic rubber, and wood, at least the surface to be bonded to the fluorine-containing rubber molded product of (a). The rubber article according to any one of
Claim 6 :
(A) Perfluoropolyether-based fluorine-containing rubber molded products containing silica as a filler and / or (b) different materials other than silicone rubber molded products,
(D) The following general formula (9):
In shown both molecular chain terminals are are blocked with a hydrolyzable silyl group and / or silanol groups di organopolysiloxane down,
(E) a curing agent and / or a curing catalyst for condensation-crosslinking the component (D).
A composition containing (F) a compound having a carbonyl group and (G) a compound having an amino group is an essential component, and a solution (i) containing the component (F) and a solution (ii) containing the component (G) Apply the mixture of the two liquid agents (i) and (ii) of the two-pack condensation-crosslinked liquid silicone rubber composition or liquid perfluoropolyether-based fluorine-containing rubber composition separately packaged, and interpose the mixture. The above (a) and (b) are bonded together, and the composition is cured with moisture generated by mixing the above (F) and (G) components, and the above (a) and (b) are joined. A method for producing a rubber article.
According to claim 7:
A rubber product comprising the rubber article according to any one of
Claim 8 :
The rubber product according to claim 7 , wherein the molded product is a seal material, an O-ring, a diaphragm, a hose, a cap, or a valve material.
本発明の物品は、パーフルオロポリエーテル系フッ素ゴムと異種材料とを２液縮合架橋タイプ液状シリコーンゴム接着剤で簡単に接着することができるので、工業的な利用価値が大きい。 The article of the present invention, since a perfluoropolyether fluororubber and different materials can be easily adhered with 2 Ekichijimigo crosslinking type liquid silicone rubber contact adhesives, a large industrial utility value.
本発明の（ａ）成分のパーフルオロポリエーテル系含フッ素ゴム成形品は、前記した特許第２９９０６４６号公報（特開平８−１９９０７０号公報）、特開２０００−００７８３５号公報、特開２００１−１０６８９３号公報、特開２００３−２０１４０１号公報等により詳しく記載されている、架橋サイトがＳｉ−ＣＨ＝ＣＨ2であるパーフルオロポリエーテル系含フッ素ゴム組成物を硬化成形したものであり、商品名ＳＩＦＥＬシリーズ（信越化学工業（株）製）として一般的に入手可能なものである。 The perfluoropolyether-based fluorine-containing rubber molded product of the component (a) of the present invention is disclosed in Japanese Patent No. 2990646 (Japanese Patent Laid-Open No. 8-199070), Japanese Patent Laid-Open No. 2000-007835, and Japanese Patent Laid-Open No. 2001-106893. The perfluoropolyether-based fluorine-containing rubber composition whose cross-linking site is Si—CH═CH 2, which is described in detail in JP-A No. 2003-201401 and the like, is obtained by curing and molding. Generally available as a series (manufactured by Shin-Etsu Chemical Co., Ltd.).
即ち、特開平８−１９９０７０号公報（特許文献１）では、（Ａ’）下記一般式（１）で示される含フッ素アミド化合物、
（Ｂ’）一分子中に一個以上の一価のパーフルオロオキシアルキル基、一価のパーフルオロアルキル基、二価のパーフルオロオキシアルキレン基又は二価のパーフルオロアルキレン基を有し、かつ二個以上のヒドロシリル基を有する含フッ素オルガノ水素シロキサン、（Ｃ’）触媒量の白金族化合物を含有する組成物であって、上記（Ｂ’）成分の量は該組成物中の脂肪族不飽和基１モルに対し、ヒドロシリル基（Ｓｉ−Ｈ基）が０．５〜５モルとなる量であることを特徴とする硬化性組成物が開示されている。 (B ′) one or more monovalent perfluorooxyalkyl groups, monovalent perfluoroalkyl groups, divalent perfluorooxyalkylene groups or divalent perfluoroalkylene groups in one molecule; A composition comprising a fluorine-containing organohydrogensiloxane having at least one hydrosilyl group and (C ′) a catalytic amount of a platinum group compound, wherein the amount of the component (B ′) is aliphatic unsaturation in the composition There is disclosed a curable composition characterized in that the amount of hydrosilyl group (Si-H group) is 0.5 to 5 mol per mol of group.
また、特開２０００−００７８３５号公報（特許文献２）において、（Ａ）分子中に少なくとも２個のアルケニル基を有し、かつ主鎖中に二価のパーフルオロアルキレン構造又は二価のパーフルオロポリエーテル構造を有するパーフルオロ化合物の前記アルケニル基の一部に、分子中に少なくとも２個のヒドロシリル基を有するアルケニル基と付加反応可能な化合物が付加してなるポリマー、（Ｂ）シリカ、（Ｃ）分子中にヒドロシリル基を有する付加反応可能な架橋剤又はパーオキサイド架橋剤を前記（Ａ）成分を硬化させるのに十分な量を含有してなることを特徴とする架橋性フッ素ゴム組成物が開示されている。 In addition, in Japanese Patent Application Laid-Open No. 2000-007835 (Patent Document 2), (A) a molecule having at least two alkenyl groups and a main chain having a divalent perfluoroalkylene structure or a divalent perfluoro group. A polymer in which a compound capable of addition reaction with an alkenyl group having at least two hydrosilyl groups in the molecule is added to a part of the alkenyl group of the perfluoro compound having a polyether structure, (B) silica, (C A crosslinkable fluororubber composition comprising a sufficient amount of an addition-reactive crosslinking agent or peroxide crosslinking agent having a hydrosilyl group in the molecule to cure the component (A). It is disclosed.
特開２００１−１０６８９３号公報（特許文献３）においては、前記した特許文献２と同じ（Ａ）成分、（Ｂ）成分、（Ｃ）成分に、（Ｄ’）成分として分子中に少なくとも１個のフルオロアルキル基又はフルオロポリアルキルエーテル基及び分子中に１個のシラノール基を有する表面処理剤を含有してなることを特徴とする架橋性フッ素ゴム組成物が開示されている。
In Japanese Patent Laid-Open No. 2001-106893 (Patent Document 3), the same component (A), component (B), component (C) as in
更に、特開２００３−２０１４０１号公報（特許文献４）では（Ａ”）２５℃における粘度が１，０００Ｐａ・ｓ以上である下記一般式（４）で表される高分子化合物
（Ｂ”）補強性フィラー、（Ｃ”）パーオキサイド架橋剤を含有してなることを特徴とする架橋性フッ素ゴム組成物が開示されている。
Furthermore, in Japanese Patent Application Laid-Open No. 2003-201401 (Patent Document 4), (A ″) a polymer compound represented by the following general formula (4) having a viscosity at 25 ° C. of 1,000 Pa · s or more.
A crosslinkable fluororubber composition comprising (B ″) a reinforcing filler and (C ″) a peroxide crosslinking agent is disclosed.
ここで、上記式（４）において、Ｒｆが、−ＣmＦ2m−（ｍ＝２〜１５）で示される二価のパーフルオロアルキレン基又は下記式（５），（６），（７）で示される基から選ばれる二価のパーフルオロオキシアルキレン基である。 Here, in the above formula (4), Rf is a divalent perfluoroalkylene group represented by —C m F 2m — (m = 2 to 15) or the following formulas (5), (6), (7) A divalent perfluorooxyalkylene group selected from the group represented by:
また、上記式（４）において、Ｑが、下記式（８）で表される基である。
更に、上記式（４）において、Ｚは酸素、窒素、硫黄及びケイ素から選ばれる原子を結合途中に有していてもよい炭素原子数１〜３０の一価の有機基である。 Furthermore, in the said Formula (4), Z is a C1-C30 monovalent organic group which may have the atom chosen from oxygen, nitrogen, sulfur, and silicon in the middle of a coupling | bonding.
この場合、上記含フッ素ゴム組成物は、その組成物形態が液状ゴム組成物とミラブルゴム組成物の２種類あるが、両者とも補強剤としてシリカ粉末が配合されているために本発明に適用する成形品としての接着特性は同じであり、従って、上記のいずれの組成物を用いてもよいが、特開２０００−００７８３５号公報（特許文献２）及び特開２００１−１０６８９３号公報（特許文献３）に記載された、
（Ａ）分子中に少なくとも２個のアルケニル基を有し、かつ主鎖中に二価のパーフルオロアルキレン構造又は二価のパーフルオロポリエーテル構造を有するパーフルオロ化合物の前記アルケニル基の一部に、分子中に少なくとも２個のヒドロシリル基を有するアルケニル基と付加反応可能な化合物が付加してなるポリマー、
（Ｂ）シリカ、及び
（Ｃ）パーオキサイド架橋剤を前記（Ａ）成分を硬化させるのに十分な量
を含有してなることを特徴とする架橋性フッ素ゴム組成物が好ましい。
In this case, the fluorine-containing rubber composition has two types of composition, a liquid rubber composition and a millable rubber composition, both of which are molded with silica powder as a reinforcing agent, and are therefore applied to the present invention. The adhesive properties as products are the same, and therefore any of the above compositions may be used, but JP 2000-007835 A (Patent Document 2) and JP 2001-106893 A (Patent Document 3). Described in
(A) a part of the alkenyl group of the perfluoro compound having at least two alkenyl groups in the molecule and having a divalent perfluoroalkylene structure or a divalent perfluoropolyether structure in the main chain; A polymer formed by adding a compound capable of addition reaction with an alkenyl group having at least two hydrosilyl groups in the molecule,
A crosslinkable fluororubber composition comprising (B) silica and (C) a peroxide crosslinking agent in an amount sufficient to cure the component (A) is preferred.
ここで、本発明において、上記含フッ素ゴム組成物中にシリカが配合されていることは重要であり、この含有シリカ表面のシラノール基及びシリカを疎水化表面処理剤で処理した場合、この疎水化表面処理剤が縮合架橋の液状シリコーンゴム組成物と反応して接着する。 Here, in the present invention, it is important that silica is blended in the fluorine-containing rubber composition. When silanol groups on the silica surface of the silica and silica are treated with a hydrophobizing surface treatment agent, this hydrophobization is performed. The surface treatment agent reacts with and adheres to the condensation-crosslinked liquid silicone rubber composition.
かかるシリカとしては、パーフルオロポリエーテル系含フッ素ゴム組成物において、機械的強度、熱安定性、耐候性、耐薬品性あるいは難燃性を向上させたり、硬化時における熱収縮の減少、硬化して得られる弾性体の熱膨張率を低下させたりする目的で、ヒュームドシリカ、湿式シリカ、粉砕シリカ等を挙げることができ、また、これらを各種表面処理剤で処理したものであってもよい。この中で、機械的強度の向上、各組成の分散安定性向上の点から、特にヒュームドシリカが好ましく、更に、分散性の向上の点から、ヒュームドシリカをシラン等のケイ素化合物系表面処理剤で処理したものが好ましい。 As such silica, in the perfluoropolyether-based fluorine-containing rubber composition, mechanical strength, thermal stability, weather resistance, chemical resistance or flame retardancy is improved, heat shrinkage during curing is reduced, and the composition is cured. Fumed silica, wet silica, pulverized silica and the like can be mentioned for the purpose of reducing the thermal expansion coefficient of the elastic body obtained in this manner, and these may be treated with various surface treatment agents. . Among these, fumed silica is particularly preferable from the viewpoint of improving mechanical strength and dispersion stability of each composition. Further, fumed silica is treated with a silicon compound-based surface treatment such as silane from the viewpoint of improving dispersibility. What was processed with the agent is preferable.
かかるヒュームドシリカと呼ばれている乾式法シリカの疎水化処理剤として、加水分解性基を有するケイ素化合物であるジメチルジクロロシラン、トリメチルクロロシラン等のオルガノクロロシラン、ヘキサメチルジシラザン等のシラザン化合物及びヘキサメチルシクロトリシラザン等の環状シラザン等が好ましい。 Hydrophobic treatment agents for dry silica called fumed silica include organohydrosilanes such as dimethyldichlorosilane and trimethylchlorosilane, which are silicon compounds having hydrolyzable groups, silazane compounds such as hexamethyldisilazane, hexa Cyclic silazanes such as methylcyclotrisilazane are preferred.
また、疎水化処理された又は未処理のシリカの比表面積は、機械的特性を向上させるため５０ｍ2／ｇ以上とすることが好ましい。更には組成物へのシリカ配合時の増粘が大きくなり、配合が困難となるため３００ｍ2／ｇ以下とすることが好ましい。 The specific surface area of the hydrophobized or untreated silica is preferably 50 m 2 / g or more in order to improve mechanical properties. Furthermore, since the thickening at the time of compounding silica into the composition becomes large and the compounding becomes difficult, it is preferably set to 300 m 2 / g or less.
この疎水化処理するため、表面処理剤を使用してシリカ表面を処理したシリカ微粉末は、予め粉体の状態で直接処理されたものがよく、通常処理方法としては一般周知の技術を採用することができ、例えば、常圧で密閉された機械混練り装置に、あるいは流動層に上記未処理のシリカ微粉末と処理剤を入れ、必要に応じて不活性ガス存在下において室温あるいは熱処理にて混合処理され、場合により触媒及び加水分解を促進するための水を使用してもよく、混練り後乾燥することにより調製することができる。処理剤の配合量は、その処理剤の被覆面積から計算される量以上であればよい。 In order to perform the hydrophobization treatment, the silica fine powder obtained by treating the silica surface with a surface treatment agent is preferably pretreated directly in a powder state, and a generally well-known technique is adopted as a normal treatment method. For example, the untreated silica fine powder and the treatment agent are placed in a mechanical kneading apparatus sealed at normal pressure or in a fluidized bed, and at room temperature or heat treatment in the presence of an inert gas as necessary. Mixing treatment may be used, and a catalyst and water for accelerating hydrolysis may be used in some cases, and it can be prepared by kneading and drying. The blending amount of the treatment agent may be equal to or more than the amount calculated from the coating area of the treatment agent.
更には、シリカは、その嵩密度が３０〜８０ｇ／ｌであることが好ましい。シリカの嵩密度が３０ｇ／ｌ未満では、組成物の粘度が増大するために配合が困難となるおそれがあり、８０ｇ／ｌを超えると、十分な補強効果が付与されないおそれがある。 Furthermore, the silica preferably has a bulk density of 30 to 80 g / l. If the bulk density of silica is less than 30 g / l, the viscosity of the composition increases, so that blending may be difficult. If it exceeds 80 g / l, a sufficient reinforcing effect may not be provided.
シリカの含有量は、パーフルオロポリエーテル系含フッ素ゴム組成物を硬化して得られるゴム成形品中１〜５０質量％であり、１質量％未満では接着に悪影響を与える上、ゴム物性が劣ったものになってしまうおそれがあり、また５０質量％を超えると、接着性は向上するものの、ゴム材料としての伸びや強度が不足する場合がある。更に好ましくは、５〜３０質量％のシリカ含有量である。 The content of silica is 1 to 50% by mass in a rubber molded product obtained by curing a perfluoropolyether-based fluorine-containing rubber composition, and if it is less than 1% by mass, it adversely affects adhesion and the rubber physical properties are inferior. If the amount exceeds 50% by mass, the adhesion may be improved, but the elongation and strength as a rubber material may be insufficient. More preferably, the silica content is 5 to 30% by mass.
一方、パーフルオロポリエーテル系含フッ素ゴム成形品と接着させる異種材料は、接着剤として作用する後述する２液縮合タイプの液状ゴム組成物が接着するものであれば良い。具体的には、少なくとも上記フッ素ゴム成形品と接着される面が、各種金属、金属酸化物、セラミック、ガラス、コンクリート、石材などの無機物、各種プラスチック、塗膜、シリコーンゴム以外の合成ゴム、木材などの有機物にて形成された加工品（フィルムを含む）などが挙げられ、接着性を向上させるためにプライマーを併用しても差し支えない。 On the other hand, the dissimilar material to be bonded to the perfluoropolyether-based fluorine-containing rubber molded article may be any one that adheres to a two-liquid condensation type liquid rubber composition described later that acts as an adhesive. Specifically, at least the surface to be bonded to the fluororubber-molded product is made of various metals, metal oxides, ceramics, glass, concrete, stones and other inorganic materials, various plastics, coating films, synthetic rubbers other than silicone rubber, wood For example, a processed product (including a film) formed of an organic substance such as a film may be used, and a primer may be used in combination to improve adhesion.
本発明においては、上記含フッ素ゴム組成物の成形品と異種材料とを接着させる接着剤として、２液縮合架橋型の液状シリコーンゴム組成物又は液状パーフルオロポリエーテル系含フッ素ゴム組成物を使用する。この接着剤として作用する２液タイプ縮合架橋の液状ゴム組成物は、１液タイプ縮合架橋のものと異なり、空気中の水分と反応しながら室温で硬化するものでなく、２液を混合することで縮合反応が開始されるものであり、シーリング剤をはじめとして幅広い用途で使用されており、容易に入手可能である。 In the present invention, a two-component condensation-crosslinking liquid silicone rubber composition or a liquid perfluoropolyether-based fluorine-containing rubber composition is used as an adhesive for bonding the molded product of the fluorine-containing rubber composition to a different material. To do. This two-component type condensation-crosslinked liquid rubber composition that acts as an adhesive is different from the one-component type condensation-crosslinked liquid rubber composition in that it does not cure at room temperature while reacting with moisture in the air, and the two components are mixed. The condensation reaction is started at, and it is used in a wide range of applications including sealing agents and is readily available.
かかる２液縮合架橋型の液状シリコーンゴム組成物の一つの形態としては、
（Ｄ）分子鎖両末端が加水分解性シリル基及び／又はシラノール基で封鎖された主鎖がジオルガノポリシロキサンもしくは主鎖がパーフルオロアルキレン構造及び／又はパーフルオロポリエーテル構造からなる直鎖状ポリマー、
（Ｅ）上記（Ｄ）成分を縮合架橋させる硬化剤及び／又は硬化触媒を含む組成物を必須成分とし、（Ｄ）成分を含む液剤（ｉ）と（Ｅ）成分を含む液剤（ｉｉ）とが別包装されてなるものを混合して硬化してなるものが挙げられる。
As one form of such a two-component condensation-crosslinking type liquid silicone rubber composition,
(D) A linear chain in which both ends of the molecular chain are blocked with hydrolyzable silyl groups and / or silanol groups, the main chain is a diorganopolysiloxane, or the main chain is a perfluoroalkylene structure and / or a perfluoropolyether structure. polymer,
(E) A liquid agent (i) containing the component (D) and a liquid agent (ii) containing the component (E), comprising a composition containing a curing agent and / or a curing catalyst for condensing and crosslinking the component (D). Can be obtained by mixing and curing what is separately packaged.
もう一つの形態としては、（ｃ）の２液縮合架橋型の液状シリコーンゴム組成物が、
（Ｄ）分子鎖両末端が加水分解性シリル基及び／又はシラノール基で封鎖された主鎖がジオルガノポリシロキサンもしくは主鎖がパーフルオロアルキレン構造及び／又はパーフルオロポリエーテル構造からなる直鎖状ポリマー、
（Ｅ）上記（Ｄ）成分を縮合架橋させる硬化剤及び／又は硬化触媒、
（Ｆ）カルボニル基を有する化合物、及び
（Ｇ）アミノ基を有する化合物を含む組成物
を必須成分とし、（Ｆ）成分を含む液剤（ｉ）と（Ｇ）成分を含む液剤（ｉｉ）とが別包装されてなるものを混合して硬化してなるものが挙げられる。
As another form, the two-component condensation crosslinking type liquid silicone rubber composition of (c),
(D) A linear chain in which both ends of the molecular chain are blocked with hydrolyzable silyl groups and / or silanol groups, the main chain is a diorganopolysiloxane, or the main chain is a perfluoroalkylene structure and / or a perfluoropolyether structure. polymer,
(E) a curing agent and / or a curing catalyst for condensation-crosslinking the component (D).
A composition containing (F) a compound having a carbonyl group and (G) a compound having an amino group is an essential component, and a solution (i) containing the component (F) and a solution (ii) containing the component (G) The thing formed by mixing and hardening what is packaged separately is mentioned.
ここで、（Ｄ）成分としては、分子鎖両末端が加水分解性シリル基及び／又はシラノール基で封鎖されていることが必要である。即ち、この加水分解性基の存在により、かかるポリマーは、水分の存在により加水分解及び重縮合し、又はシラノール基の存在により、硬化剤及び／又は硬化触媒により縮合架橋し、ゴム弾性体の硬化物を形成する。この加水分解性シリル基は、ケイ素原子に少なくとも１個の加水分解性基が結合したものであり、加水分解性基としては、カルボキシル基、ケトオキシム基、アルコキシ基、アルケノキシ基、アミノ基、アミノキシ基、アミド基等を例示することができる。ケイ素原子に結合しているこれらの加水分解性基は、１個に限定されず、２個あるいは３個の加水分解性基が同一のケイ素原子に結合していてもよい。また、これらの加水分解性基が結合しているケイ素原子には、当然、他の有機基が結合していてよいが、かかる有機基としては、例えばメチル基、エチル基、プロピル基等のアルキル基、シクロヘキシル基等のシクロアルキル基、ビニル基、アリル基等のアルケニル基、フェニル基、トリル基等のアリール基あるいはこれらの基の水素原子が部分的にハロゲン原子などで置換された基、例えばクロロメチル基、３，３，３−トリフルオロプロピル基等を例示することができる。 Here, as the component (D), it is necessary that both ends of the molecular chain are blocked with a hydrolyzable silyl group and / or a silanol group. That is, due to the presence of this hydrolyzable group, such a polymer is hydrolyzed and polycondensed by the presence of moisture, or by the presence of a silanol group, it is subjected to condensation crosslinking with a curing agent and / or a curing catalyst to cure the rubber elastic body. Form things. This hydrolyzable silyl group is a group in which at least one hydrolyzable group is bonded to a silicon atom. Examples of the hydrolyzable group include a carboxyl group, a ketoxime group, an alkoxy group, an alkenoxy group, an amino group, and an aminoxy group. And an amide group. These hydrolyzable groups bonded to the silicon atom are not limited to one, and two or three hydrolyzable groups may be bonded to the same silicon atom. Further, naturally, other organic groups may be bonded to the silicon atom to which these hydrolyzable groups are bonded. Examples of such organic groups include alkyl groups such as a methyl group, an ethyl group, and a propyl group. A group, a cycloalkyl group such as a cyclohexyl group, an alkenyl group such as a vinyl group or an allyl group, an aryl group such as a phenyl group or a tolyl group, or a group in which the hydrogen atoms of these groups are partially substituted with halogen atoms, for example, A chloromethyl group, a 3,3,3-trifluoropropyl group, etc. can be illustrated.
（Ｄ）成分としての分子鎖両末端が加水分解性シリル基及び／又はシラノール基で封鎖されたジオルガノポリシロキサンとしては、具体的には例えば下記一般式（９）：
で表されるものが適当である。
Specific examples of the diorganopolysiloxane having both ends of the molecular chain as the component (D) blocked with hydrolyzable silyl groups and / or silanol groups include, for example, the following general formula (9):
Is suitable.
ここで、前記Ｒ11〜Ｒ13としては、前記加水分解性シリル基に関して例示した加水分解性基以外の有機基を挙げることができる。更に、ｎは、このジオルガノポリシロキサンが、２５℃において２５〜１，０００，０００ｍＰａ・ｓの範囲の粘度を有するものであることから、通常、１０以上の整数である。 Here, as said R < 11 > -R < 13 >, organic groups other than the hydrolysable group illustrated regarding the said hydrolysable silyl group can be mentioned. Furthermore, n is an integer of usually 10 or more because the diorganopolysiloxane has a viscosity in the range of 25 to 1,000,000 mPa · s at 25 ° C.
上記Ｒ11〜Ｒ13の置換又は非置換の一価炭化水素基としては、これは特に炭素数１〜１２のものが好ましく、その具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等のアルキル基；シクロペンチル基、シクロヘキシル基、シクロヘプチル基等のシクロアルキル基；フェニル基、トリル基、キシリル基、ナフチル基等のアリール基；ベンジル基、フェニルエチル基、フェニルプロピル基等のアラルキル基；及びこれらの基の水素原子の一部又は全部をフッ素、塩素、臭素等のハロゲン原子等で置換したクロロメチル基、ブロモエチル基、クロロプロピル基、トリフルオロプロピル基、３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル基等が挙げられる。
As the substituted or unsubstituted monovalent hydrocarbon group for R 11 to R 13 , this is particularly preferably one having 1 to 12 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Alkyl groups such as butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group; cycloalkyl such as cyclopentyl group, cyclohexyl group and cycloheptyl group An aryl group such as a phenyl group, a tolyl group, a xylyl group, or a naphthyl group; an aralkyl group such as a benzyl group, a phenylethyl group, or a phenylpropyl group; and a part or all of the hydrogen atoms of these groups are fluorine, chlorine, Chloromethyl group, bromoethyl group, chloropropyl group, trifluoropropyl group substituted with halogen atoms such as
また、（Ｄ）成分としての分子鎖両末端が加水分解性シリル基及び／又はシラノール基で封鎖された主鎖がパーフルオロアルキレン構造及び／又はパーフルオロポリエーテル構造からなる直鎖状ポリマーとしては、具体的には例えば下記一般式（１０）で表されるものが適当である。
Ｙ−［Ｒ14−（Ｒｆ−Ｒ15）a−Ｒｆ−Ｒ14］−Ｙ （１０）
〔式中、Ｒｆはパーフルオロアルキレン基、二価のパーフルオロポリエーテル基又はパーフルオロアルキレン基と二価のパーフルオロポリエーテル基の組み合わせからなる二価の基であり、Ｒ14及びＲ15は同一でも異なってもよく、置換又は非置換の二価炭化水素基（但し、該炭化水素基は酸素原子、窒素原子及びケイ素原子の１種又は２種以上を含んでもよい。）であり、ａは０以上の整数であり、Ｙは加水分解性シリル基及び／又はシラノール基である。〕
In addition, as a linear polymer in which the main chain in which both ends of the molecular chain as component (D) are blocked with hydrolyzable silyl groups and / or silanol groups has a perfluoroalkylene structure and / or a perfluoropolyether structure, Specifically, for example, those represented by the following general formula (10) are suitable.
Y- [R 14 - (Rf- R 15) a -Rf-R 14] -Y (10)
[Wherein, Rf is a perfluoroalkylene group, a divalent perfluoropolyether group or a divalent group comprising a combination of a perfluoroalkylene group and a divalent perfluoropolyether group, and R 14 and R 15 are They may be the same or different and are substituted or unsubstituted divalent hydrocarbon groups (provided that the hydrocarbon group may contain one or more of oxygen, nitrogen and silicon atoms), and a. Is an integer of 0 or more, and Y is a hydrolyzable silyl group and / or silanol group. ]
上記一般式（１０）において、Ｒｆにより表されるパーフルオロアルキレン基としては、例えば、一般式：−ＣpＦ2p−（但し、ｐは１〜１０の整数であり、好ましくは１〜６の整数である。）で示す直鎖状又は分岐状のものが挙げられる。 In the general formula (10), examples of the perfluoroalkylene group represented by Rf include, for example, the general formula: —C p F 2p — (p is an integer of 1 to 10, preferably 1 to 6. It is an integer.
また、Ｒｆにより表される二価のパーフルオロポリエーテル基としては、一般式：−（Ｒｆ’−Ｏ）q−（式中、複数のＲｆ’は同一又は異なり、炭素原子数１〜６、好ましくは炭素原子数１〜３の直鎖状又は分岐状のパーフルオロアルキレン基であり、ｑは１〜５００の整数、好ましくは２〜４００の整数、更に好ましくは１０〜２００の整数である。）で示すものが挙げられる。上記式：−（Ｒｆ’−Ｏ）q−の構造単位の具体例としては、−ＣＦ2Ｏ−、−ＣＦ2ＣＦ2Ｏ−、−ＣＦ2ＣＦ2ＣＦ2Ｏ−、−ＣＦ（ＣＦ3）ＣＦ2Ｏ−、−ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ−、−ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ−、及び−Ｃ（ＣＦ3）2Ｏ−等が挙げられる。特に好ましいのは、−ＣＦ2Ｏ−、−ＣＦ2ＣＦ2Ｏ−、−ＣＦ2ＣＦ2ＣＦ2Ｏ−及び−ＣＦ（ＣＦ3）ＣＦ2Ｏ−である。
In addition, as the divalent perfluoropolyether group represented by Rf, the general formula: — (Rf′—O) q — (wherein a plurality of Rf ′ are the same or different and have 1 to 6 carbon atoms, Preferably it is a C1-C3 linear or branched perfluoroalkylene group, q is an integer of 1-500, preferably an integer of 2-400, more preferably an integer of 10-200. ). The formula :-( Rf'-O) q - Specific examples of the
上記一般式（１０）において、Ｒ14及びＲ15は、炭素原子数１〜２０の置換又は非置換の二価炭化水素基が好ましく、特に炭素原子数２〜１０の二価炭化水素基が好ましい。具体的には、メチレン基、エチレン基、プロピレン基、メチルエチレン基、ブチレン基、ヘキサメチレン基等のアルキレン基；シクロヘキシレン基等のシクロアルキレン基；フェニレン基、トリレン基、キシリレン基、ナフチレン基、ビフェニレン基等のアリーレン基；これらの基の水素原子の一部又は全部をハロゲン原子で置換した基；及び置換又は非置換のアルキレン基とアリーレン基の組み合わせが例示される。 In the general formula (10), R 14 and R 15 are preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, and particularly preferably a divalent hydrocarbon group having 2 to 10 carbon atoms. . Specifically, alkylene groups such as methylene group, ethylene group, propylene group, methylethylene group, butylene group and hexamethylene group; cycloalkylene groups such as cyclohexylene group; phenylene group, tolylene group, xylylene group, naphthylene group, Examples include arylene groups such as biphenylene groups; groups in which some or all of the hydrogen atoms in these groups have been substituted with halogen atoms; and combinations of substituted or unsubstituted alkylene groups and arylene groups.
Ｒ14及びＲ15は、その構造中に酸素原子、窒素原子及びケイ素原子の１種又は２種以上を含んでもよい。この場合、酸素原子、窒素原子及びケイ素原子は、それぞれ、−Ｏ−又は−ＣＯ−結合；−ＮＲ’−結合〔Ｒ’は、水素原子、アリール基又は炭素原子数１〜８、特に１〜６のアルキル基である。〕として、下記に示すような直鎖状又は環状のオルガノシロキシ基、オルガノシリレン基として炭化水素基内に又は炭化水素基の末端に存在することができる。 R 14 and R 15 may contain one or more of oxygen atom, nitrogen atom and silicon atom in the structure. In this case, the oxygen atom, the nitrogen atom, and the silicon atom are each an —O— or —CO— bond; —NR′—bond [R ′ is a hydrogen atom, an aryl group, or a carbon atom number of 1 to 8, particularly 1 to 6 alkyl groups. ] Can be present in the hydrocarbon group or at the end of the hydrocarbon group as a linear or cyclic organosiloxy group or organosilylene group as shown below.
上記のＲ”としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等のアルキル基；シクロペンチル基、シクロヘキシル基、シクロヘプチル基等のシクロアルキル基；ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、イソブテニル基、ヘキセニル基、シクロヘキセニル基等のアルケニル基；フェニル基、トリル基、キシリル基、ナフチル基等のアリール基；ベンジル基、フェニルエチル基、フェニルプロピル基等のアラルキル基；及びこれらの基の水素原子の一部又は全部をハロゲン原子で置換した基（例えば、クロロメチル基、ブロモエチル基、クロロプロピル基、トリフルオロプロピル基）が挙げられる。 As R ″ above, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group An alkyl group such as cyclopentyl group, cyclohexyl group and cycloheptyl group; an alkenyl group such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, hexenyl group and cyclohexenyl group; Aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group; aralkyl groups such as benzyl group, phenylethyl group, phenylpropyl group; and groups in which some or all of hydrogen atoms of these groups are substituted with halogen atoms (For example, chloromethyl group, bromoethyl group, chloropropyl group, Fluoropropyl group).
該含フッ素ポリマー（１０）の両末端に有する加水分解性シリル基及び又はシラノール基としては、例えば、一般式：−ＳｉＲ”3-bＸb（ここで、Ｘは加水分解性基及び／又は水酸基であり、Ｒ”は前記と同じ意味であり、ｂは１〜３の整数である。）で示されるものがある。上記一般式の加水分解性基Ｘとしては、上記したものと同様の基が挙げられるが、好ましくはカルボキシル基、ケトオキシム基、アルコキシ基、アルケノキシ基、アミノ基、アミノキシ基、アミド基及びフッ素、塩素、臭素、ヨウ素等のハロゲン原子を例示することができる。 Examples of the hydrolyzable silyl group and / or silanol group at both ends of the fluoropolymer (10) include, for example, the general formula: —SiR ″ 3-b X b (where X is a hydrolyzable group and / or A hydroxyl group, R ″ has the same meaning as described above, and b is an integer of 1 to 3). Examples of the hydrolyzable group X of the above general formula include the same groups as described above, but preferably a carboxyl group, a ketoxime group, an alkoxy group, an alkenoxy group, an amino group, an aminoxy group, an amide group, fluorine, chlorine. And halogen atoms such as bromine and iodine.
（Ｄ）成分の直鎖状化合物は、２５℃において、通常２５〜１，０００，０００ｍＰａ・ｓ、好ましくは１００〜１００，０００ｍＰａ・ｓの粘度であればよい。この粘度が低すぎると物理的強度に優れた硬化物が得られないことがある。逆に、粘度が高すぎると、得られる組成物の粘度が高く、その結果、組成物の使用時における作業性が悪くなることがある。 (D) The linear compound of a component should just be the viscosity of 25-1,000,000 mPa * s normally at 25 degreeC, Preferably it is 100-100,000 mPa * s. If the viscosity is too low, a cured product having excellent physical strength may not be obtained. On the other hand, when the viscosity is too high, the viscosity of the resulting composition is high, and as a result, workability during use of the composition may deteriorate.
（Ｅ）成分は、上記（Ｄ）成分を縮合架橋させる硬化剤及び／又は硬化触媒であるが、ここで（Ｄ）成分を縮合架橋させる硬化剤としては、下記一般式（１１），（１２）又は（１３）で表されるように、水分を必要とせずにＳｉ−ＯＨ基と縮合反応するＳｉ−ＯＹ基を分子中に２個以上有する有機ケイ素化合物が挙げられる。 The component (E) is a curing agent and / or a curing catalyst that condenses and crosslinks the component (D). The curing agents that condense and crosslink the component (D) are the following general formulas (11) and (12 ) Or (13), an organosilicon compound having two or more Si—OY groups in the molecule that undergo a condensation reaction with a Si—OH group without the need for moisture may be mentioned.
ここで、Ｙは下記に示す基から選ばれる一価の有機基であり、いずれもＳｉ−ＯＹ基としてＳｉ−ＯＨ基と縮合反応するものである。 Here, Y is a monovalent organic group selected from the following groups, all of which are condensed with a Si—OH group as a Si—OY group.
また、Ｒ16は一価の有機基であり、これは置換又は非置換の一価炭化水素基、特に炭素数１〜１２のものが好ましく、その具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等のアルキル基；シクロペンチル基、シクロヘキシル基、シクロヘプチル基等のシクロアルキル基；フェニル基、トリル基、キシリル基、ナフチル基等のアリール基；ベンジル基、フェニルエチル基、フェニルプロピル基等のアラルキル基；ビニル基、アリル基、プロペニル基、ブテニル基等のアルケニル基；及びこれらの基の水素原子の一部又は全部をフッ素、塩素、臭素等のハロゲン原子等で置換したクロロメチル基、ブロモエチル基、クロロプロピル基、トリフルオロプロピル基、３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル基等が挙げられる。 R 16 is a monovalent organic group, which is preferably a substituted or unsubstituted monovalent hydrocarbon group, particularly one having 1 to 12 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, and a propyl group. Group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and other alkyl groups; cyclopentyl group, cyclohexyl group, cycloheptyl group Cycloalkyl groups such as phenyl groups, tolyl groups, xylyl groups, naphthyl groups, etc .; aralkyl groups such as benzyl groups, phenylethyl groups, phenylpropyl groups; vinyl groups, allyl groups, propenyl groups, butenyl groups, etc. An alkenyl group; and a group in which some or all of the hydrogen atoms in these groups are substituted with halogen atoms such as fluorine, chlorine, bromine, etc. Romechiru group, bromoethyl group, chloropropyl group, trifluoropropyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, and the like.
更に、Ｒ16は下記一般式
Ｒｆ2−Ｒ14−
で示されるものでもよい。ここで、Ｒｆ2は一価のフッ素化ポリエーテル基であり、上記Ｒｆの片末端がＣＦ3Ｏ−、ＣＦ3ＣＦ2Ｏ−、ＣＦ3ＣＦ2ＣＦ2Ｏ−、（ＣＦ3）2ＣＦＯ−、ＣＦ3ＣＦ2ＣＦ2ＣＦ2Ｏ−等で封鎖された構造のものが例示される。Ｒ14は上記の通りの意味を有する。
Furthermore, R 16 is represented by the following general formula Rf 2 -R 14 -
It may be shown by. Here, Rf 2 is a monovalent fluorinated polyether group, and one end of Rf is CF 3 O—, CF 3 CF 2 O—, CF 3 CF 2 CF 2 O—, (CF 3 ) 2 CFO. - those of CF 3 CF 2 CF 2 CF 2 O- blocked with such structure is illustrated. R 14 has the meaning as described above.
なお、Ｒｆ、Ｒ14は前記の通りであり、また、式（１１），（１２），（１３）において、ｅは２又は３、ｆは１，２又は３、ｇは２又は３である。 Incidentally, Rf, R 14 are as defined above, also, the formula (11), (12), in (13), e is 2 or 3, f is 1, 2 or 3, g is 2 or 3 .
上記（Ｄ）成分を縮合架橋させる硬化剤としての（Ｅ）成分の有機ケイ素化合物は、架橋剤として機能するもので、１種単独で用いてもよく、又は２種以上を同時に用いてもよい。（Ｄ）成分と（Ｅ）成分の配合量比は、（Ｄ）成分中のＳｉ−ＯＨ基のモル量と（Ｅ）成分中のＳｉ−ＯＹ基のモル量との比が、Ｓｉ−ＯＹ／Ｓｉ−ＯＨ＝０．２〜５．０、好ましくは０．５〜３．０となるようにすればよい。 The organosilicon compound of component (E) as a curing agent that condenses and crosslinks component (D) functions as a crosslinking agent and may be used alone or in combination of two or more. . The blending ratio of the component (D) and the component (E) is such that the ratio of the molar amount of Si-OH groups in the component (D) to the molar amount of Si-OY groups in the component (E) is Si-OY. /Si-OH=0.2-5.0, preferably 0.5-3.0.
また、（Ｄ）成分を縮合架橋させる（Ｅ）成分の硬化触媒は、上記Ｓｉ−ＯＨ基とＳｉ−ＯＹ基の縮合反応を促進する作用を有するものである。この促進剤としては、例えば、鉛−２−エチルオクトエート、ジブチルスズジメトキシド、ジブチルスズジアセテート、ジブチルスズジラウレート、ブチルスズトリ−２−エチルヘキソエート、鉄−２−エチルヘキソエート、コバルト−２−エチルヘキソエート、マンガン−２−エチルヘキソエート、亜鉛−２−エチルヘキソエート、カプリル酸第１スズ、ナフテン酸スズ、オレイン酸スズ、ブチル酸スズ、ナフテン酸チタン、ナフテン酸亜鉛、ナフテン酸コバルト、ステアリン酸亜鉛、トリフルオロ酢酸アンモニウム塩、トリフルオロ酢酸−ジエチルアミン塩等の有機カルボン酸の金属塩又はアミン塩；パラトルエンスルホン酸、トリフルオロ酢酸、トリクロロ酢酸、ピクリン酸などの有機酸；テトラブチルチタネート、テトラ−２−エチルヘキシルチタネート、トリエタノールアミンチタネート、テトラ（イソプロペニルオキシ）チタネート等の有機チタン酸エステル；オルガノシロキシチタン、β−カルボニルチタン等の有機チタン化合物；アルコキシアルミニウム化合物；３−アミノプロピルトリエトキシシラン、Ｎ−（トリメトキシシリルプロピル）エチレンジアミン等のアミノアルキル基置換アルコキシシラン；ヘキシルアミン、リン酸ドデシルアミン等のアミン化合物及びその塩；ベンジルトリエチルアンモニウムアセテート等の第４級アンモニウム塩；酢酸カリウム、酢酸ナトリウム、シュウ酸リチウム等の低級脂肪酸のアルカリ金属塩；ジメチルヒドロキシルアミン、ジエチルヒドロキシルアミン等のジアルキルヒドロキシルアミン；及び、テトラメチルグアニジン、グアニジル基を含有するシラン及びシロキサンのグアニジル化合物を挙げることができる。これらの中で、スズ化合物、チタン化合物、有機酸及びグアニジル化合物が好ましく、特にグアニジル化合物が組成物を迅速に硬化させると共に、得られる硬化物の接着性を改善する点でより好ましい。これらは１種単独でも２種以上を組み合わせてもよい。 Further, the curing catalyst of the component (E) that condenses and crosslinks the component (D) has an action of promoting the condensation reaction of the Si—OH group and the Si—OY group. Examples of the accelerator include lead-2-ethyl octoate, dibutyltin dimethoxide, dibutyltin diacetate, dibutyltin dilaurate, butyltin tri-2-ethylhexoate, iron-2-ethylhexoate, cobalt-2- Ethylhexoate, manganese-2-ethylhexoate, zinc-2-ethylhexoate, stannous caprylate, tin naphthenate, tin oleate, tin butyrate, titanium naphthenate, zinc naphthenate, naphthene Metal salts or amine salts of organic carboxylic acids such as cobalt acid, zinc stearate, ammonium trifluoroacetate, trifluoroacetic acid-diethylamine salt; organic acids such as paratoluenesulfonic acid, trifluoroacetic acid, trichloroacetic acid, picric acid; Tetrabutyl titanate, tetra-2-ethyl Organic titanates such as hexyl titanate, triethanolamine titanate, tetra (isopropenyloxy) titanate; organotitanium compounds such as organosiloxytitanium and β-carbonyltitanium; alkoxyaluminum compounds; 3-aminopropyltriethoxysilane, N- (Trimethoxysilylpropyl) aminoalkyl group-substituted alkoxysilanes such as ethylenediamine; amine compounds such as hexylamine and dodecylamine phosphate and salts thereof; quaternary ammonium salts such as benzyltriethylammonium acetate; potassium acetate, sodium acetate, sulphate Alkali metal salts of lower fatty acids such as lithium acid; dialkylhydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine; and tetramethylguanidi And guanidyl compounds of silane and siloxane containing guanidyl groups. Among these, a tin compound, a titanium compound, an organic acid, and a guanidyl compound are preferable, and in particular, a guanidyl compound is more preferable in terms of rapidly curing the composition and improving adhesiveness of the obtained cured product. These may be used alone or in combination of two or more.
（Ｅ）成分の硬化触媒の量は、（Ｄ）成分又は（Ｄ）成分と硬化剤としての（Ｅ）成分の有機ケイ素化合物との合計１００質量部に対して、通常０．０１〜５質量部であり、好ましくは０．０５〜２質量部である。 The amount of the (E) component curing catalyst is usually 0.01 to 5 mass with respect to 100 parts by mass of the (D) component or the (D) component and the organosilicon compound of the (E) component as a curing agent. Part, preferably 0.05 to 2 parts by mass.
（Ｆ）成分のカルボニル基含有有機化合物は、後述する（Ｇ）成分のアミノ基含有有機化合物と反応して、硬化剤として作用する水を組成物中の深部に発生させるものである。かかる有機化合物としては、大気中の水分の存在により生じる架橋反応に平行して、（Ｆ）成分の化合物と（Ｇ）成分の化合物とが、脱水縮合反応を行い、これによって組成物中の深部に水分を生じるような反応を示す反応性のカルボニル基を有するものであれば、任意のものを使用することができるが、一般的には、アセトン、メチルエチルケトン、アセトフェノンなどのケトン類、酢酸エチル、酢酸ブチル、プロピオン酸メチル、アクリル酸エチル、ブチロラクトンなどのエステル類、ジメチルフォルムアミド、ジエチルアセトアミド、ブチロラクタムなどのアミド類、酢酸、プロピオン酸、安息香酸などのカルボン酸類、及びこれらを官能基として有するシランカップリング剤、その他、Ｃ＝Ｏ基を有するポリマー、オリゴマーなどが例示される。本発明においては、（Ｆ）成分の反応時における立体障害性の見地から、特にカルボニル基のα位の炭素原子が１級、２級又は芳香族環の一部であるものが好適に使用される。このα位の炭素原子が、通常の３級の炭素原子である場合には、アミノ基との反応性に劣り、所望の効果が得られない場合がある。また、これらの化合物は１種類に限定される必要はなく、２種類以上の使用も可能である。 The carbonyl group-containing organic compound of component (F) reacts with the amino group-containing organic compound of component (G) described later to generate water acting as a curing agent in the deep part of the composition. As such an organic compound, in parallel with the crosslinking reaction caused by the presence of moisture in the air, the compound (F) and the compound (G) undergo a dehydration condensation reaction, whereby a deep portion in the composition is obtained. As long as it has a reactive carbonyl group that exhibits a reaction that generates water, any one can be used, but in general, ketones such as acetone, methyl ethyl ketone, acetophenone, ethyl acetate, Esters such as butyl acetate, methyl propionate, ethyl acrylate and butyrolactone, amides such as dimethylformamide, diethylacetamide and butyrolactam, carboxylic acids such as acetic acid, propionic acid and benzoic acid, and silanes having these as functional groups Coupling agents, other polymers with C = O groups, oligomers, etc. It is shown. In the present invention, from the viewpoint of steric hindrance during the reaction of the component (F), in particular, those in which the carbon atom at the α-position of the carbonyl group is a primary, secondary or aromatic ring are preferably used. The When the α-position carbon atom is a normal tertiary carbon atom, the reactivity with the amino group is inferior, and the desired effect may not be obtained. Moreover, these compounds do not need to be limited to one type, and two or more types can be used.
なお、この（Ｆ）成分の配合量は、そのカルボニル基（Ｃ＝Ｏ基）量が（Ｄ）成分１００ｇ当たり、０．００１〜１モルの範囲、好ましくは０．０１〜０．１モルの範囲とすることが好ましい。０．００１モル未満では充分な深部硬化性が発現せず、１モルを超えると得られる弾性体硬化物が目的とする物性を示さなくなる場合がある。 The amount of component (F) is such that the amount of carbonyl group (C═O group) is in the range of 0.001 to 1 mol, preferably 0.01 to 0.1 mol, per 100 g of component (D). It is preferable to be in the range. If it is less than 0.001 mol, sufficient deep part curability will not be exhibited, and if it exceeds 1 mol, the resulting cured elastomer may not exhibit the desired physical properties.
（Ｇ）成分のアミノ基含有有機化合物は、先に述べた通り、（Ｆ）成分と反応して硬化剤として作用する水を組成物中の深部に発生させる。かかる有機化合物としては、（Ｆ）成分の化合物と（Ｇ）成分の化合物とが、脱水縮合反応を行い、これによって組成物中の深部に水分を生じるような反応を示す反応性のアミノ基を有するものであれば、任意のものを使用することができるが、一般的には、メチルアミン、エチルアミン、ブチルアミン、エチレンジアミン、アニリンなどのアミン類、γ−アミノプロピルトリエトキシシランなどのＮＨ2基を官能基として有するシランカップリング剤、ＮＨ2基を有するポリマー、オリゴマーなどが例示される。本発明においては、（Ｆ）成分の反応時における立体障害性の見地から、特にアミノ基のα位の炭素原子が１級、２級又は芳香族環の一部であるものが好適に使用される。このα位の炭素原子が、通常の３級の炭素原子である場合には、カルボニル基との反応性に劣り、所望の効果が得られない場合がある。また、これらの化合物は１種類に限定される必要はなく、２種類以上の使用も可能である。 As described above, the amino group-containing organic compound (G) reacts with the component (F) to generate water acting as a curing agent in the deep part of the composition. As such an organic compound, a reactive amino group exhibiting a reaction in which the compound of the component (F) and the compound of the component (G) undergo a dehydration condensation reaction, thereby generating moisture in the deep part of the composition. Any one can be used as long as it has, but generally, amines such as methylamine, ethylamine, butylamine, ethylenediamine, and aniline, and NH 2 groups such as γ-aminopropyltriethoxysilane are used. Examples thereof include silane coupling agents having functional groups, polymers having NH 2 groups, and oligomers. In the present invention, from the viewpoint of steric hindrance during the reaction of the component (F), those in which the carbon atom at the α-position of the amino group is part of a primary, secondary or aromatic ring are preferably used. The When the α-position carbon atom is a normal tertiary carbon atom, the reactivity with the carbonyl group is poor and the desired effect may not be obtained. Moreover, these compounds do not need to be limited to one type, and two or more types can be used.
なお、この（Ｇ）成分の配合量は、そのアミノ基（ＮＨ2基）量が（Ｄ）成分１００ｇ当たり、０．００１〜１モルの範囲、好ましくは０．０１〜０．１モルの範囲とすることが好ましい。０．００１モル未満では充分な深部硬化性が発現せず、１モルを超えると得られる弾性体硬化物が目的とする物性を示さなくなる場合がある。 The blending amount of the component (G) is such that the amino group (NH 2 group) amount is in the range of 0.001 to 1 mol, preferably in the range of 0.01 to 0.1 mol, per 100 g of the component (D). It is preferable that If it is less than 0.001 mol, sufficient deep part curability will not be exhibited, and if it exceeds 1 mol, the resulting cured elastomer may not exhibit the desired physical properties.
その他の成分として、硬化物の物性を調整する等のために、種々の配合剤を添加することも可能である。例えば、メチルトリメトキシシラン、メチルトリプロペノキシシラン、ビニルトリブタノキシムシラン、メチルトリアセトキシシラン等の保存安定剤；煙霧質シリカ、沈降性シリカ、二酸化チタン、酸化アルミニウム、石英粉末、炭素粉末、タルク、ベントナイト等の補強剤；アスベスト、ガラス繊維、有機繊維等の繊維質充填剤；顔料、染料等の着色剤；ベンガラ、酸化セリウム等の耐熱性向上剤；耐寒性向上剤；脱水剤；防錆剤；β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルメチルジエトキシシラン、γ−クロロプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−イソシアナートプロピルトリエトキシシラン等の接着性向上剤；トリオルガノシロキシ単位及びＳｉＯ2単位よりなる網状ポリシロキサン等の液状補強剤が挙げられる。 As other components, various compounding agents can be added in order to adjust the physical properties of the cured product. For example, storage stabilizers such as methyltrimethoxysilane, methyltripropenoxysilane, vinyltributanoximesilane, methyltriacetoxysilane; fumed silica, precipitated silica, titanium dioxide, aluminum oxide, quartz powder, carbon powder, talc Reinforcing agents such as bentonite; fibrous fillers such as asbestos, glass fibers and organic fibers; colorants such as pigments and dyes; heat resistance improvers such as bengara and cerium oxide; cold resistance improvers; dehydrating agents; Agent: β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-chloropropyl Trimethoxysilane, γ-mercaptopropyltrimethoxysila , Adhesion promoting agent such as γ- isocyanate propyl triethoxysilane; liquid reinforcing agents reticulated polysiloxane consisting triorganosiloxy units and SiO 2 units and the like.
なお、本発明においては、（Ｆ）成分と（Ｇ）成分とが前述したように反応して深部硬化剤である水を生成することが重要であるから、（Ｆ）成分と（Ｇ）成分とは、このような反応が速やかに生じるものが選択使用されることは勿論であり、また任意的に使用される各種配合剤も、かかる水分の生成を阻害しないように選択使用される。 In the present invention, since it is important that the component (F) and the component (G) react as described above to produce water as a deep curing agent, the component (F) and the component (G) Of course, those that cause such a reaction to be promptly used are selected and used, and various compounding agents that are optionally used are also selected and used so as not to inhibit the generation of such moisture.
上記２液縮合架橋型組成物を２液型として調製する場合には、上記した（Ｄ）成分及び（Ｅ）成分を含み、（Ｆ），（Ｇ）成分を含まない場合、（Ｄ）成分を含む液（ｉ）と、（Ｅ）成分を含む液剤（ｉｉ）との２液梱包とし、硬化物を使用する時にこれら２液を混合する。即ち、上記両液剤（ｉ）及び（ｉｉ）の混合物を塗布し、該混合物を介在させた状態で上記（ａ）、（ｂ）を貼り合わせることにより、水分を必要とせずにＳｉ−ＯＨ基とＳｉ−ＯＹ基の反応で上記組成物を硬化すると共に、上記（ａ）、（ｂ）を接合して目的の複合物品を製造することができる。 When preparing the two-component condensation-crosslinking type composition as a two-component type, when the component (D) and the component (E) are included and the component (F) and (G) are not included, the component (D) The liquid (i) containing the liquid (i) and the liquid agent (ii) containing the component (E) are packed in two liquids, and these two liquids are mixed when the cured product is used. That is, by applying a mixture of the both liquids (i) and (ii) and bonding the above (a) and (b) with the mixture intervening, Si—OH group can be obtained without requiring moisture. The composition can be cured by the reaction of Si and OY groups, and (a) and (b) can be joined to produce the desired composite article.
また、上記した（Ｄ），（Ｅ），（Ｆ）及び（Ｇ）成分を含む組成物の場合、（Ｆ）成分を含む液剤（ｉ）と（Ｇ）成分を含む液剤（ｉｉ）とが別包装されてなる２液縮合架橋型の液状シリコーンゴム組成物又は液状パーフルオロポリエーテル系含フッ素ゴム組成物であって、硬化物を使用する時にこれら２液を混合する。なお、上記した（Ｄ），（Ｅ）成分は、それぞれ上記液剤（ｉ），（ｉｉ）に適宜配合すればよく、その配合形態は限定されない。通常は、（Ｄ），（Ｅ）及び（Ｆ）成分からなる液剤（ｉ）と（Ｄ）及び（Ｇ）成分からなる液剤（ｉｉ）との２液縮合架橋型の液状シリコーンゴム組成物又は液状パーフルオロポリエーテル系含フッ素ゴム組成物が好ましい。この場合も、上記両液剤（ｉ）及び（ｉｉ）の混合物を塗布し、該混合物を介在させた状態で上記（ａ）、（ｂ）を貼り合わせ、上記（Ｆ），（Ｇ）成分の混合により生成した水分で上記組成物を硬化すると共に、上記（ａ）、（ｂ）を接合することにより目的の複合物品を製造することができる。 Moreover, in the case of the composition containing said (D), (E), (F), and (G) component, the liquid agent (i) containing (F) component and the liquid agent (ii) containing (G) component are included. A two-pack condensation-crosslinked liquid silicone rubber composition or a liquid perfluoropolyether-based fluorine-containing rubber composition separately packaged, and these two liquids are mixed when a cured product is used. In addition, what is necessary is just to mix | blend the above-mentioned (D) and (E) component with the said liquid agent (i) and (ii), respectively, and the compounding form is not limited. Usually, a two-component condensation-crosslinking type liquid silicone rubber composition comprising a solution (i) comprising the components (D), (E) and (F) and a solution (ii) comprising the components (D) and (G) or A liquid perfluoropolyether fluorine-containing rubber composition is preferred. Also in this case, the mixture of both the liquids (i) and (ii) is applied, the above (a) and (b) are bonded together with the mixture interposed, and the components (F) and (G) are combined. While hardening the said composition with the water | moisture content produced | generated by mixing, the target composite article can be manufactured by joining said (a) and (b).
このような２液型は、２液を例えば二連カートリッジに同体積ずつ梱包し、ミキサー付きノズルより混合押出しするというように１：１に配分することも可能であるので、作業しやすいという効果がある。混合時の温度は、室温〜６０℃の範囲がよい。 Such a two-pack type is advantageous in that it is easy to work because it is possible to distribute two liquids in the same volume, for example, in a double cartridge, and mix and extrude from a nozzle with a mixer. There is. The temperature during mixing is preferably in the range of room temperature to 60 ° C.
なお、上記接着剤として使用する２液縮合架橋型の液状シリコーンゴム組成物の塗布量は、適宜選定されるが、硬化した状態で０．０１〜１．０ｍｍ、特に０．０５〜０．５ｍｍの厚さとなるように塗布することが好ましい。 The coating amount of the two-component condensation-crosslinking liquid silicone rubber composition used as the adhesive is appropriately selected, but is 0.01 to 1.0 mm, particularly 0.05 to 0.5 mm in a cured state. It is preferable to apply so that the thickness becomes.
図１に示すようなゴムキャップ（薬栓）のような成形品を加工するには、耐薬品性と柔軟性が必要な部分には含フッ素ゴム成形品２を用い、柔軟性が不要な部分はプラスチックなどの異種材料１とする。この異種材料１及び／又は含フッ素ゴム成形品２の接着部分にヘラ等を用いて２液縮合架橋タイプの液状ゴム組成物３を塗布し、含フッ素ゴム成形品と異種材料を固定して室温で放置するだけで硬化し、本発明の物品が得られる。
To process molded products such as rubber caps (medicinal plugs) as shown in Fig. 1, use fluorine-containing rubber molded
図２は、異種材料１との２層ゴムシートを加工する場合であり、厚さ調整を行い、架橋した含フッ素ゴム成形品（シート）２もしくは異種材料１のどちらか一面に接着剤として作用する２液縮合架橋タイプの液状ゴム組成物３を塗布してエアーの混入に注意しながら張り合わせ、同様に室温で放置して物品が得られる。シート状の大きな面積に液状ゴム組成物３を塗布する場合は、スクリーン印刷やバーコート等が工業的には好ましい。
FIG. 2 shows a case where a two-layer rubber sheet with a
図３は、３層構造の物品を加工する場合であり、図２の製造方法と全く同様に製造できる。 FIG. 3 shows a case where an article having a three-layer structure is processed, and can be manufactured in exactly the same manner as the manufacturing method of FIG.
図２及び図３の構造にする場合、異種材料１をポリイミドやポリエステルなどの樹脂フィルムとすると、含フッ素ゴム成形品２の変形に追従できる柔軟性のあるシート加工品とすることができる。
2 and 3, if the
室温での放置時間は、形状や温度により一定でないが、湿度に関係なく２４時間程度放置すれば、２液縮合タイプのゴム組成物を硬化させることができるので、工業的な生産性も問題ない。 The standing time at room temperature is not constant depending on the shape and temperature, but if left for about 24 hours regardless of humidity, the two-component condensation type rubber composition can be cured, so there is no problem in industrial productivity. .
本発明の物品は、種々の用途に利用することができる。即ち、耐油性を要求される自動車用ゴム部品、具体的にはフューエル・レギュレーター用ダイヤフラム、パルセーションダンパ用ダイヤフラム、オイルプレッシャースイッチ用ダイヤフラム、ＥＧＲ用ダイヤフラムなどのダイヤフラム類、キャニスタ用バルブ、パワーコントロール用バルブなどのバルブ類、クイックコネクタ用Ｏ−リング、インジェクター用Ｏ−リングなどのＯ−リング類、あるいは、オイルシール、シリンダヘッド用ガスケットなどのシール材など、化学プラント用ゴム部品、具体的にはポンプ用ダイヤフラム、バルブ類、Ｏ−リング類、ホース類、パッキン類、オイルシール、ガスケットなどのシール材など、インクジェットプリンタ用ゴム部品、半導体製造ライン用ゴム部品、具体的には薬品が接触する機器用のダイヤフラム、弁、Ｏ−リング、パッキン、ガスケットなどのシール材など、低摩擦耐磨耗性を要求されるバルブなど、分析、理化学機器用ゴム部品、具体的にはポンプ用ダイヤフラム、弁、シール部品（Ｏ−リング、パッキンなど）、医療機器用ゴム部品、具体的にはポンプ、バルブ、ジョイントなど、また、テント膜材料、シーラント、成型部品、押し出し部品、被覆材、複写機ロール材料、電気用防湿コーティング材、センサー用ポッティング材、燃料電池用シール材、積層ゴム布などに有用である。 The article of the present invention can be used for various applications. In other words, rubber parts for automobiles that require oil resistance, specifically diaphragms for fuel regulators, diaphragms for pulsation dampers, diaphragms for oil pressure switches, diaphragms for EGR, canister valves, power control, etc. Rubber parts for chemical plants, such as valves such as valves, O-rings such as O-rings for quick connectors and O-rings for injectors, or sealing materials such as oil seals and cylinder head gaskets, specifically Diaphragms for pumps, valves, O-rings, hoses, packings, oil seals, rubber parts for ink jet printers, rubber parts for semiconductor production lines, and more specifically equipment that comes into contact with chemicals Die for Rubber parts for analysis and physics and chemistry equipment such as valves that require low friction and wear resistance, such as sealing materials such as frams, valves, O-rings, packings, gaskets, etc. Specifically, diaphragms for valves, valves, seal parts (O-rings, packing, etc.), rubber parts for medical equipment, specifically pumps, valves, joints, etc., tent film materials, sealants, molded parts, extruded parts, coating materials, copier roll materials, electrical It is useful for moisture-proof coating materials, potting materials for sensors, sealing materials for fuel cells, laminated rubber cloths, etc.
以下、実施例、参考例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。
実施例、参考例及び比較例で用いられるゴム成形品及び接着剤
下記組成物からなる２ｍｍ厚プレス成形シートを作成した。
（パーフルオロポリエーテル系含フッ素ゴム成形品）
含フッ素ゴム組成物（Ｉ）：ＳＩＦＥＬ５７０１（信越化学工業（株）製、（Ａ）〜（Ｃ）成分含有、付加架橋・ミラブルタイプ組成物標準配合）
含フッ素ゴム組成物（ＩＩ）：ＳＩＦＥＬ３５１１（信越化学工業（株）製、（Ａ）〜（Ｃ）成分含有、ＬＩＭＳタイプ組成物標準配合）
EXAMPLES Hereinafter, although an Example , a reference example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
Rubber molded products and adhesives used in Examples, Reference Examples and Comparative Examples 2 mm thick press-molded sheets composed of the following compositions were prepared.
(Perfluoropolyether fluorine-containing rubber molded product)
Fluorine-containing rubber composition (I): SIFEL5701 (manufactured by Shin-Etsu Chemical Co., Ltd., containing components (A) to (C), addition crosslinking / millable type composition standard composition)
Fluorine-containing rubber composition (II): SIFEL 3511 (manufactured by Shin-Etsu Chemical Co., Ltd., containing components (A) to (C), LIMS type composition standard formulation)
以上、２品種の組成物は、いずれも疎水化表面処理シリカを含有し、そのシリカ含有量は５〜３０質量％の範囲の組成物、下記の１品種はシリカ含有０％の組成物である。
含フッ素ゴム組成物（ＩＩＩ）：上記含フッ素ゴム組成物（ＩＩ）において、シリカを含まないもの
（２液タイプ縮合架橋液状ゴム接着剤）
２液タイプ液状シリコーンゴム組成物（Ｉ）：Ｘ−３１−２３３１Ａ／Ｂ：（信越化学工業（株）製、（Ｄ）〜（Ｇ）成分含有）
２液タイプ液状シリコーンゴム組成物（ＩＩ）：ＫＥ６６（信越化学工業（株）製、（Ｄ）〜（Ｅ）成分含有、（Ｅ）成分としてＣＡＴ−ＲＣを２部添加）、（Ｆ），（Ｇ）成分無含有）
２液状タイプパーフルオロポリエーテル系含フッ素ゴム組成物：ＳＩＦＥＬ７５０（信越化学工業（株）製、（Ｄ）〜（Ｇ）成分含有）
（１液タイプ縮合架橋液状シリコーンゴム接着剤）
液状シリコーンゴム組成物：シーラントマスター３００（信越化学工業（株）製、（Ｄ），〜（Ｅ）成分含有、（Ｆ），（Ｇ）成分無含有）
（異種材料）
アルミニウム試験片、ステンレス試験片、ガラス繊維強化エポキシ樹脂試験片（以上３種はケーディーエス社製テストピース）
ポリイミド０．１ｍｍフィルム：カプトン（デュポン社製）
As described above, the two types of compositions both contain hydrophobized surface-treated silica, the silica content is a composition in the range of 5 to 30% by mass, and the following one type is a composition containing 0% silica. .
Fluorine-containing rubber composition (III): The above-mentioned fluorine-containing rubber composition (II) which does not contain silica (two-component type condensation-crosslinking liquid rubber adhesive)
Two-component liquid silicone rubber composition (I): X-31-2331 A / B: (Shin-Etsu Chemical Co., Ltd., (D) to (G) component contained)
Two-component liquid silicone rubber composition (II): KE66 (manufactured by Shin-Etsu Chemical Co., Ltd., containing (D) to (E) components, adding 2 parts of CAT-RC as component (E)), (F), (G) No component)
2-liquid type perfluoropolyether-based fluorine-containing rubber composition: SIFEL750 (manufactured by Shin-Etsu Chemical Co., Ltd., containing components (D) to (G))
(1 liquid type condensation crosslinking liquid silicone rubber adhesive)
Liquid silicone rubber composition: Sealant master 300 (manufactured by Shin-Etsu Chemical Co., Ltd., containing (D), (E) component, (F), (G) component free)
(Different materials)
Aluminum test piece, stainless steel test piece, glass fiber reinforced epoxy resin test piece (the above three are test pieces made by KDS)
Polyimide 0.1 mm film: Kapton (manufactured by DuPont)
（評価用成形品の製造）
図２に示す構造の成形品を得るために下記の工程で製造を行った。
（１）パーフルオロポリエーテル系含フッ素ゴム成形品に液状ゴム組成物を０．２〜０．５ｍｍの厚さでバーコートにより塗布する。
（２）もう一方の異種材料をエアーの混入に注意しながら張り合わせる。
（３）張り合わせたシートを２３℃，湿度５０％の環境に４８時間放置後に評価を行う。
(Manufacture of molded products for evaluation)
In order to obtain a molded article having the structure shown in FIG.
(1) A liquid rubber composition is applied to a perfluoropolyether-based fluorine-containing rubber molded article at a thickness of 0.2 to 0.5 mm by bar coating.
(2) The other dissimilar materials are bonded together while paying attention to air mixing.
(3) The laminated sheet is evaluated after being left in an environment of 23 ° C. and 50% humidity for 48 hours.
［接着性評価方法］
（１）剥離状態：液状ゴム組成物の硬化物にカッターナイフで切込みを入れて引き剥がしたときの界面のゴムのはがれ具合を評価した。
[Adhesion evaluation method]
(1) Peeled state: The degree of rubber peeling at the interface when the cured product of the liquid rubber composition was cut with a cutter knife and peeled off was evaluated.
○：液状ゴム組成物の硬化物が凝集破壊して材料界面は安定
△：ごく一部分の界面で凝集破壊するが、大部分の液状ゴム組成物が未硬化
×：全く接着せず、界面から容易に剥離
［実施例１〜６、参考例１、比較例１］
表１に示す組み合わせでゴム成形品シートと異種材料を張り合わせ、評価を行った。実施例で示すシリカ含有パーフルオロポリエーテル系含フッ素ゴム成形品は、（Ｄ）〜（Ｇ）成分含有２液タイプ縮合架橋液状ゴム組成物を用いて異種材料と安定に接着可能であった。比較例１に示すシリカを含有しないパーフルオロポリエーテル系含フッ素ゴム成形品は、含フッ素ゴム組成物の成形品界面で容易に剥離してしまった。
○: The cured material of the liquid rubber composition is agglomerated and destroyed, and the material interface is stable. Δ: The material is agglomerated and destroyed at a small part of the interface, but most of the liquid rubber composition is uncured. [Examples 1 to 6, Reference Example 1 , Comparative Example 1]
A rubber molded product sheet and a different material were bonded together in the combinations shown in Table 1 and evaluated. The silica-containing perfluoropolyether-based fluorine-containing rubber molded product shown in the examples could be stably bonded to different materials using the (D) to (G) component-containing two-component type condensation-crosslinked liquid rubber composition. The perfluoropolyether-based fluorine-containing rubber molded product containing no silica shown in Comparative Example 1 was easily peeled off at the molded product interface of the fluorine-containing rubber composition.
［比較例２，３］
表２で示すように、（Ｆ），（Ｇ）成分を含まず空気の水分により硬化する１液縮合架橋タイプ液状シリコーンゴム組成物は、気体透過性の小さい２種類の材料であるパーフルオロポリエーテル系含フッ素ゴム成形品とステンレスやポリイミドでは液状ゴム組成物の端部は硬化しているものの中央部のほとんどは未硬化であり、実用に耐えるものとならなかった。
[Comparative Examples 2 and 3]
As shown in Table 2, the one-liquid condensation-crosslinking type liquid silicone rubber composition that does not contain the components (F) and (G) and is cured by moisture in the air is a perfluoropolyester that is two kinds of materials having low gas permeability. With ether-based fluorine-containing rubber molded products and stainless steel or polyimide, the end of the liquid rubber composition is cured, but most of the center is uncured and cannot be practically used.
１ 異種材料
２ パーフルオロポリエーテル系フッ素ゴム
３ ２液縮合架橋型液状ゴム組成物
DESCRIPTION OF
Claims (8)
（ｃ）（Ｄ）下記一般式（９）：
で示される分子鎖両末端が加水分解性シリル基及び／又はシラノール基で封鎖されたジオルガノポリシロキサン、及び
（Ｅ）上記（Ｄ）成分を縮合架橋させる硬化剤及び／又は硬化触媒
を含む組成物を必須成分とし、（Ｄ）成分を含む液剤（ｉ）と（Ｅ）成分を含む液剤（ｉｉ）とが別包装されてなる２液縮合架橋型の液状シリコーンゴム組成物の硬化物を介して接着されてなることを特徴とするゴム物品。 (A) a perfluoropolyether-based fluorine-containing rubber molded product containing silica as a filler , and (b) a different material other than a silicone rubber molded product ,
(C) (D) The following general formula (9):
A diorganopolysiloxane in which both ends of the molecular chain represented by are blocked with hydrolyzable silyl groups and / or silanol groups, and
(E) Curing agent and / or curing catalyst for condensation crosslinking of component (D)
Curing of a two-component condensation-crosslinking type liquid silicone rubber composition in which a liquid composition (i) containing the component (D) and a liquid agent (ii) containing the component (E) are separately packaged. A rubber article which is bonded through an object.
（ｃ）（Ｄ）下記一般式（９）：(C) (D) The following general formula (9):
で示される分子鎖両末端が加水分解性シリル基及び／又はシラノール基で封鎖されたジオルガノポリシロキサン、A diorganopolysiloxane in which both ends of the molecular chain represented by are blocked with hydrolyzable silyl groups and / or silanol groups,
（Ｅ）上記（Ｄ）成分を縮合架橋させる硬化剤及び／又は硬化触媒、(E) a curing agent and / or a curing catalyst for condensation-crosslinking the component (D).
（Ｆ）カルボニル基を有する化合物、及び(F) a compound having a carbonyl group, and
（Ｇ）アミノ基を有する化合物(G) Compound having amino group
を含む組成物を必須成分とし、（Ｆ）成分を含む液剤（ｉ）と（Ｇ）成分を含む液剤（ｉｉ）とが別包装されてなる２液縮合架橋型の液状シリコーンゴム組成物の硬化物を介して接着されてなることを特徴とするゴム物品。Curing of a two-component condensation-crosslinking type liquid silicone rubber composition in which a liquid composition (i) containing the component (F) and a liquid composition (ii) containing the component (G) are separately packaged. A rubber article which is bonded through an object.
（Ａ）分子中に少なくとも２個のアルケニル基を有し、かつ主鎖中に二価のパーフルオロアルキレン構造又は二価のパーフルオロポリエーテル構造を有するパーフルオロ化合物の前記アルケニル基の一部に、分子中に少なくとも２個のヒドロシリル基を有するアルケニル基と付加反応可能な化合物が付加してなるポリマー、
（Ｂ）シリカ、及び
（Ｃ）分子中にヒドロシリル基を有する付加反応可能な架橋剤又はパーオキサイド架橋剤を前記（Ａ）成分を硬化させるのに十分な量
を含有してなる架橋性フッ素ゴム組成物を硬化させてなるものであることを特徴とする請求項１又は２記載のゴム物品。 The above (a) perfluoropolyether-based fluorine-containing rubber molded product is
(A) a part of the alkenyl group of the perfluoro compound having at least two alkenyl groups in the molecule and having a divalent perfluoroalkylene structure or a divalent perfluoropolyether structure in the main chain; A polymer formed by adding a compound capable of addition reaction with an alkenyl group having at least two hydrosilyl groups in the molecule,
Crosslinkable fluororubber comprising (B) silica, and (C) an addition-reactive crosslinker having a hydrosilyl group in the molecule or a peroxide crosslinker sufficient to cure the component (A) The rubber article according to claim 1 or 2 , wherein the rubber article is obtained by curing the composition.
（Ｄ）下記一般式（９）：
で示される分子鎖両末端が加水分解性シリル基及び／又はシラノール基で封鎖されたジオルガノポリシロキサン、
（Ｅ）上記（Ｄ）成分を縮合架橋させる硬化剤及び／又は硬化触媒、
（Ｆ）カルボニル基を有する化合物、及び
（Ｇ）アミノ基を有する化合物
を含む組成物を必須成分とし、（Ｆ）成分を含む液剤（ｉ）と（Ｇ）成分を含む液剤（ｉｉ）とが別包装されてなる２液縮合架橋型の液状シリコーンゴム組成物又は液状パーフルオロポリエーテル系含フッ素ゴム組成物の上記両液剤（ｉ）及び（ｉｉ）の混合物を塗布し、該混合物を介在させた状態で上記（ａ）、（ｂ）を貼り合わせ、上記（Ｆ），（Ｇ）成分の混合により生成した水分で上記組成物を硬化すると共に、上記（ａ）、（ｂ）を接合することを特徴とするゴム物品の製造方法。 (A) Perfluoropolyether-based fluorine-containing rubber molded products containing silica as a filler and / or (b) different materials other than silicone rubber molded products,
(D) The following general formula (9):
In shown both molecular chain terminals are are blocked with a hydrolyzable silyl group and / or silanol groups di organopolysiloxane down,
(E) a curing agent and / or a curing catalyst for condensation-crosslinking the component (D).
A composition containing (F) a compound having a carbonyl group and (G) a compound having an amino group is an essential component, and a solution (i) containing the component (F) and a solution (ii) containing the component (G) Apply the mixture of the two liquid agents (i) and (ii) of the two-pack condensation-crosslinked liquid silicone rubber composition or liquid perfluoropolyether-based fluorine-containing rubber composition separately packaged, and interpose the mixture. The above (a) and (b) are bonded together, and the composition is cured with moisture generated by mixing the above (F) and (G) components, and the above (a) and (b) are joined. A method for producing a rubber article.
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| CN102260398A (en) * | 2011-07-13 | 2011-11-30 | 成都晨光博达橡塑有限公司 | Premixed fluororubber gum with improved thermal tear resistance and preparation method thereof |
| CN107603083A (en) * | 2017-09-30 | 2018-01-19 | 成都晨光博达橡塑有限公司 | A kind of high heat conduction fluorubber premixing glue and preparation method thereof |
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| JP4725730B2 (en) | 2006-03-01 | 2011-07-13 | 信越化学工業株式会社 | Manufacturing method of rubber article in which silicone rubber molded product and fluorine-based elastomer are integrated |
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| CN107603083A (en) * | 2017-09-30 | 2018-01-19 | 成都晨光博达橡塑有限公司 | A kind of high heat conduction fluorubber premixing glue and preparation method thereof |
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