TWI516369B - 積層體及其硫化物 - Google Patents
積層體及其硫化物 Download PDFInfo
- Publication number
- TWI516369B TWI516369B TW100107418A TW100107418A TWI516369B TW I516369 B TWI516369 B TW I516369B TW 100107418 A TW100107418 A TW 100107418A TW 100107418 A TW100107418 A TW 100107418A TW I516369 B TWI516369 B TW I516369B
- Authority
- TW
- Taiwan
- Prior art keywords
- acrylic elastomer
- fluoroelastomer
- mass
- layer
- acrylate
- Prior art date
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- 229920000800 acrylic rubber Polymers 0.000 claims description 88
- 229920000058 polyacrylate Polymers 0.000 claims description 88
- 229920001973 fluoroelastomer Polymers 0.000 claims description 64
- 238000004132 cross linking Methods 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 38
- 229920005862 polyol Polymers 0.000 claims description 17
- 150000003077 polyols Chemical class 0.000 claims description 16
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 12
- 125000003700 epoxy group Chemical group 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims 1
- MOOUSOJAOQPDEH-UHFFFAOYSA-K cerium(iii) bromide Chemical compound [Br-].[Br-].[Br-].[Ce+3] MOOUSOJAOQPDEH-UHFFFAOYSA-K 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 58
- 239000000178 monomer Substances 0.000 description 47
- -1 acryl Chemical group 0.000 description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 21
- 229920001971 elastomer Polymers 0.000 description 17
- 238000004073 vulcanization Methods 0.000 description 17
- 239000003431 cross linking reagent Substances 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000004714 phosphonium salts Chemical class 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 239000000806 elastomer Substances 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 7
- 238000004381 surface treatment Methods 0.000 description 7
- 150000000703 Cerium Chemical class 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
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- 239000000945 filler Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
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- 235000017281 sodium acetate Nutrition 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- RSHBFZCIFFBTEW-UHFFFAOYSA-M tetrabutylazanium;thiocyanate Chemical compound [S-]C#N.CCCC[N+](CCCC)(CCCC)CCCC RSHBFZCIFFBTEW-UHFFFAOYSA-M 0.000 description 2
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- QNXQYOUWVYCTEL-UHFFFAOYSA-N 1-chloro-18,18-dimethylnonadecane Chemical compound CC(C)(C)CCCCCCCCCCCCCCCCCCl QNXQYOUWVYCTEL-UHFFFAOYSA-N 0.000 description 1
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- OTKXXJYYVZSYHT-UHFFFAOYSA-N 1h-indole-2,6-diol Chemical compound C1=C(O)C=C2NC(O)=CC2=C1 OTKXXJYYVZSYHT-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- PTJDGKYFJYEAOK-UHFFFAOYSA-N 2-butoxyethyl prop-2-enoate Chemical compound CCCCOCCOC(=O)C=C PTJDGKYFJYEAOK-UHFFFAOYSA-N 0.000 description 1
- AVANZZDGIRLSLM-UHFFFAOYSA-N 2-butoxypropyl prop-2-enoate Chemical compound CCCCOC(C)COC(=O)C=C AVANZZDGIRLSLM-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
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- ACHWNFGWACZQHU-UHFFFAOYSA-N 2-propoxyethyl prop-2-enoate Chemical compound CCCOCCOC(=O)C=C ACHWNFGWACZQHU-UHFFFAOYSA-N 0.000 description 1
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- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- REEBWSYYNPPSKV-UHFFFAOYSA-N 3-[(4-formylphenoxy)methyl]thiophene-2-carbonitrile Chemical compound C1=CC(C=O)=CC=C1OCC1=C(C#N)SC=C1 REEBWSYYNPPSKV-UHFFFAOYSA-N 0.000 description 1
- UACBZRBYLSMNGV-UHFFFAOYSA-N 3-ethoxypropyl prop-2-enoate Chemical compound CCOCCCOC(=O)C=C UACBZRBYLSMNGV-UHFFFAOYSA-N 0.000 description 1
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- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- YWACAHLWCZJQBK-UHFFFAOYSA-N 4-[1,1-dichloro-1,3,3,3-tetrafluoro-2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C1=CC(O)=CC=C1C(C(F)(Cl)Cl)(C(F)(F)F)C1=CC=C(O)C=C1 YWACAHLWCZJQBK-UHFFFAOYSA-N 0.000 description 1
- WFCQTAXSWSWIHS-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 WFCQTAXSWSWIHS-UHFFFAOYSA-N 0.000 description 1
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- 239000004971 Cross linker Substances 0.000 description 1
- VKOUCJUTMGHNOR-UHFFFAOYSA-N Diphenolic acid Chemical compound C=1C=C(O)C=CC=1C(CCC(O)=O)(C)C1=CC=C(O)C=C1 VKOUCJUTMGHNOR-UHFFFAOYSA-N 0.000 description 1
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- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- YIYBQIKDCADOSF-UHFFFAOYSA-N alpha-Butylen-alpha-carbonsaeure Natural products CCC=CC(O)=O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 description 1
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- 159000000009 barium salts Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 description 1
- WTEPWWCRWNCUNA-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 WTEPWWCRWNCUNA-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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Classifications
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- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B25/042—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/51—Elastic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
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Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Description
本發明係關於一種彈性體之積層體。
丙烯酸彈性體或其硫化物由於耐熱老化性或耐油性、機械特性、永久壓縮變形特性等物性優異,故而多用作汽車之發動機室內之軟管構件或密封構件、抗振橡膠構件等之材料。
受到近年來之廢氣對策或引擎之高功率化等之影響,業界對該等構件期待更佳之耐熱老化性。
因此,為解決上述問題,以提高橡膠零件之可靠性,考慮採用耐久性高於丙烯酸彈性體之氟彈性體。但是,氟彈性體耐寒性差且價格昂貴,因此並非適當之材料,尤其不適合同時要求價格與可靠性之汽車零件。
例如,下述專利文獻1~4中揭示有氟彈性體層與丙烯酸彈性體層之積層體。若對利用先前之材料時耐久性真正存在問題之部分積層氟彈性體,則可實質性提高耐久性。
將氟彈性體與丙烯酸彈性體製成積層體之情形時,重要的要求特性例如為各層間之接著性。於兩者之接著強度較低之情形時,有損作為積層體之可靠性,因此為獲得耐久性優異之廉價積層體,提高兩者之接著強度極為重要。
因此,目前係藉由實施如下處理,以謀求提高與成形為層狀之彈性體的接著強度:利用金屬鈉溶液對氟彈性體表面之表面處理(例如參照專利文獻1)、放電處理(例如參照專利文獻2)、電漿處理(例如參照專利文獻3)等。又,眾所周知藉由使用特定種類之氟彈性體,可使氟彈性體層與非氟彈性體層之接著性提高(例如專利文獻4)。
專利文獻1:日本專利特開平3-67637號公報
專利文獻2:日本專利特開2002-59486號公報
專利文獻3:日本專利特開2009-234216號公報
專利文獻4:日本專利特開2010-42669號公報
但是,如上述專利文獻1~3之表面處理會使製造步驟變得繁雜,導致軟管製品等積層體之製造成本上升。又,若彈性體層因表面處理而發生劣化,則會導致積層體之密封性降低。如專利文獻4般僅使用特定之氟彈性體之方法由於可使用氟彈性體之種類有限,故而難以根據積層體之用途自由地設計柔軟性等特性。
因此,本發明之主要目的在於提供一種牢固地接著複數層彈性體層之積層體。
即,本發明係關於一種積層體,其係由丙烯酸彈性體層與氟彈性體層接著而成,該丙烯酸彈性體層包含:相對於含有環氧基作為丙烯酸彈性體之交聯位(官能基)之丙烯酸彈性體100質量份、添加有1質量份以上之鎓鹽的丙烯酸彈性體組合物,該氟彈性體層包含:含有多元醇交聯劑之氟彈性體組合物。
較佳為鎓鹽為有機銨鹽及/或有機鏻鹽。
又,本發明提供一種將丙烯酸彈性體層與氟彈性體層之積層體硫化而獲得之硫化物。
根據本發明,可提供一種牢固地接著氟彈性體層與丙烯酸彈性體層之積層體。
以下詳細說明本發明,但本發明並不限定於以下所示之各實施形態。
圖1係表示本發明之積層體1之一例的剖面圖,積層體1具有丙烯酸彈性體層11與氟彈性體層12,且丙烯酸彈性體層11與氟彈性體層12經積層而接著。
雖然可使丙烯酸彈性體層11與氟彈性體層12單獨接著,但更理想為於界面處使彈性體彼此交聯之交聯接著。例如,若於將該等層重疊之狀態下進行硫化而製成硫化物,則可獲得更牢固之積層體1。硫化方法並無特別限定,可採用加壓硫化、蒸汽硫化、電子束硫化等通常之硫化方法。
硫化前,可對丙烯酸彈性體層11與氟彈性體層12中之任一者或兩者實施表面處理,根據本發明,即便不實施此種表面處理,亦可實現牢固之硫化接著性。丙烯酸彈性體層11與氟彈性體層12之層數亦無特別限定,可積層1層或2層以上之丙烯酸彈性體層11與1層或2層以上之氟彈性體層12而構成積層體1。於丙烯酸彈性體層11與氟彈性體層12分別為複數層之情形時,可交替積層丙烯酸彈性體層11與氟彈性體層12。又,可製成重疊丙烯酸彈性體層11與氟彈性體層12以外之層、例如補強纖維之結構。補強纖維係使丙烯酸彈性體層11與氟彈性體層12中之任一者或兩者密接。
丙烯酸彈性體層11係藉由將丙烯酸彈性體作為主成分,將添加有鎓鹽之丙烯酸彈性體組合物成形為層狀(膜狀)而獲得,氟彈性體層12係藉由將氟彈性體作為主成分,將添加有多元醇交聯劑之氟彈性體組合物成形為層狀(膜狀)而獲得。再者,所謂主成分,係指含量為整體之30質量%以上之成分,即丙烯酸彈性體組合物含有30質量%以上之丙烯酸彈性體,氟彈性體組合物含有30質量%以上之氟彈性體。以下,更加詳細地說明各組合物。
本發明所使用之丙烯酸彈性體係將(甲基)丙烯酸烷基酯作為主成分,使其與含有環氧基之交聯位單體共聚合而成者。視需要亦可使用使(甲基)丙烯酸烷基酯與乙酸乙烯酯、環氧基以外之交聯位單體或乙烯等共聚合而成者。再者,所謂交聯位單體,係指具有形成交聯位(交聯點)之官能基的單體(單體)。
(甲基)丙烯酸烷基酯係成為丙烯酸彈性體之骨架者,藉由選擇其種類,可調整所獲得之丙烯酸彈性體組合物之常態物性或耐寒性、耐油性等基本特性。於本發明中,(甲基)丙烯酸烷基酯與(甲基)丙烯酸酯含義相同,為包括甲基丙烯酸烷基酯(甲基丙烯酸酯)與丙烯酸烷基酯(丙烯酸酯)兩者之概念。
(甲基)丙烯酸烷基酯並無特別限定,例如有:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸2-甲基戊酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸正十二烷基酯、(甲基)丙烯酸正十八烷基酯等(甲基)丙烯酸烷基酯。
又,亦可使用丙烯酸2-甲氧基乙酯、丙烯酸2-乙氧基乙酯、丙烯酸2-正丙氧基乙酯、丙烯酸2-正丁氧基乙酯、丙烯酸3-甲氧基丙酯、丙烯酸3-乙氧基丙酯、丙烯酸2-正丙氧基丙酯、丙烯酸2-正丁氧基丙酯等丙烯酸烷氧基烷基酯,不僅可單獨使用該等,亦可將2種以上併用。
藉由調整該等不飽和單體之調配量,可調整所獲得之丙烯酸彈性體組合物或其硫化物之耐寒性或耐油性。例如藉由增大丙烯酸正丁酯之共聚合比率,可提高耐寒性,藉由增大丙烯酸乙酯之共聚合比率,可提高耐油性。
交聯位單體係視需要藉由與(甲基)丙烯酸烷基酯共聚合,而促進分子間交聯,以調整所獲得之丙烯酸彈性體之硬度或延伸特性者。交聯位單體必須為含有環氧基者,視需要可使用其他交聯位單體,例如具有活性氯基、羧基等交聯位單體。進而,亦可使用具有環氧基與其他官能基(羧基等)兩者之交聯位單體。
作為該等交聯位單體,並無特別限定,例如作為含有環氧基之交聯位單體,有丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、烯丙基縮水甘油基醚、甲基烯丙基縮水甘油基醚等。又,作為其他交聯位單體,例如有2-氯乙基乙烯醚、丙烯酸2-氯乙酯、乙烯苄基氯、氯乙酸乙烯酯、氯乙酸烯丙酯等具有活性氯基者,又,有丙烯酸、甲基丙烯酸、丁烯酸、2-戊烯酸、順丁烯二酸、反丁烯二酸、衣康酸、順丁烯二酸單烷基酯、反丁烯二酸單烷基酯、肉桂酸等含羧基者。
該等交聯位單體之添加量於丙烯酸彈性體100質量份中,較佳為0.5~10質量份,更佳為1~5質量份,尤佳為1~4質量份。若交聯位單體之添加量少於0.5質量份,則使丙烯酸彈性體組合物交聯之效果較小,導致所獲得之硫化物之強度不足。若交聯位單體之添加量超過10質量份,則所獲得之硫化物會發生硬化,導致失去橡膠彈性。
再者,所謂交聯位單體之添加量,於僅使用含有環氧基者作為交聯位單體之情形時,係指含有環氧基之交聯位單體之添加量,於使用含有環氧基者與其他交聯位單體兩者作為交聯位單體之情形時,係指含有環氧基者與其他交聯位單體之總量。
乙酸乙烯酯係於丙烯酸彈性體發生熱老化時,用以使其分子間交聯並維持丙烯酸彈性體之延伸等機械特性者,藉由調整其調配量,可調整所獲得之丙烯酸彈性體之分子間交聯。
丙烯酸彈性體受到熱或紫外線等影響時,其主鏈會被切斷,導致拉伸強度或斷裂伸長率等機械特性急遽下降者。因此,預先使易引起交聯反應之乙酸乙烯酯與丙烯酸彈性體之主鏈共聚合,於丙烯酸彈性體之主鏈被切斷時,乙酸乙烯酯可成為交聯位,使切斷之分子間再次交聯。
於使乙酸乙烯酯共聚合之情形時,其共聚合量於丙烯酸彈性體100質量份中較佳為設為20質量份以下之比例。若乙酸乙烯酯之共聚合量為該範圍,則可維持丙烯酸彈性體之耐熱老化性,並且抑制其機械特性之降低。
丙烯酸彈性體中,於無損本發明之目的之範圍內,亦可共聚合(甲基)丙烯酸烷基酯、交聯位單體、或可與乙酸乙烯酯共聚合之其他單體。作為可與乙酸乙烯酯共聚合之其他單體,並無特別限定,例如有:甲基乙烯基酮之類的烷基乙烯基酮,乙烯基乙基醚、丙烯基甲基醚等乙烯基醚及烯丙基醚,苯乙烯、α-甲基苯乙烯、氯苯乙烯、乙烯基甲苯、乙烯基萘等乙烯基芳香族化合物,丙烯腈、甲基丙烯腈等乙烯腈,丙烯醯胺、丙烯、丁二烯、異戊二烯、戊二烯、氯乙烯、偏二氯乙烯、氟乙烯、偏二氟乙烯、乙烯、丙酸乙烯酯等乙烯性不飽和化合物。
尤其是於使乙烯與丙烯酸彈性體共聚合之情形時,乙烯之共聚合量於丙烯酸彈性體100質量份中較佳為設為50質量份以下之比例。藉由共聚合乙烯,可獲得強度明顯提高之丙烯酸彈性體。
丙烯酸彈性體係藉由利用乳化聚合、懸浮聚合、溶液聚合、塊狀聚合等公知之方法共聚合上述單體而獲得。丙烯酸彈性體組合物係含有上述丙烯酸彈性體與鎓鹽者,鎓鹽並無特別限制,可列舉有機銨鹽、有機鏻鹽等。
本發明中所用之有機銨鹽並無特別限制,可列舉:氯化四正丁基銨、氯化三甲苯基銨、氯化三甲基十八烷基銨、氯化三甲基十二烷基銨、氯化三甲基十六烷基銨、氯化二甲基二(十八烷基)銨、氯化三丁基苄基銨、溴化四正丁基銨、溴化甲基三苯基銨、溴化乙基三苯基銨、溴化三甲基苯基銨、溴化三甲基苄基銨、溴化十八烷基三甲基銨、硫氰酸四丁基銨等。
本發明所使用之有機鏻鹽並無特別限制,可列舉:氯化四正丁基鏻、溴化四正丁基鏻、溴化甲基三苯基鏻、溴化乙基三苯基鏻、溴化丁基三苯基鏻、溴化己基三苯基鏻、溴化苄基三苯基鏻、氯化四苯基鏻、溴化四苯基鏻、溴化4-丁氧基苄基三苯基鏻、氯化烯丙基三丁基鏻、溴化2-丙炔基三苯基鏻、氯化甲氧丙基三丁基鏻等。
該等鎓鹽可單獨使用,或將2種以上併用。若考慮充分之接著力、加工性、柔軟性等,則鎓鹽之添加量相對於丙烯酸彈性體100質量份,較佳為1~10質量份。若鎓鹽之添加量不足1質量份,則積層體之接著力不足,而導致剝離。為獲得更適宜之硫化接著效果,鎓鹽之添加量相對於丙烯酸彈性體100質量份,更佳為2~10質量份,藉由使鎓鹽之添加量成為2質量份以上,可獲得所需之充分接著效果。
鎓鹽之添加方法並無特別限定,為了在不實施特別之表面處理之情況下獲得丙烯酸彈性體層11與氟彈性體層12之牢固之硫化接著性,較佳為如下方法:於硫化接著該等層之前,例如於丙烯酸彈性體與各種調配劑等之混練時添加鎓鹽,製成丙烯酸彈性體組合物。
丙烯酸彈性體組合物係藉由使用通常採用之橡膠混練裝置對丙烯酸彈性體、鎓鹽、視需要之交聯促進劑、填充劑等其他調配劑進行混練而獲得。作為橡膠混練裝置,可使用滾筒、混練機、班伯裏混合機、密閉混合器、雙軸擠出機等。
本發明所用之氟彈性體只要為彈性體中具有氟原子者,則無特別限定,例如有:四氟乙烯-乙烯共聚物、四氟乙烯-丙烯共聚物、氯三氟乙烯-乙烯共聚物、聚偏二氟乙烯、聚氟乙烯、偏二氟乙烯-六氟丙烯共聚物、四氟乙烯-偏二氟乙烯-六氟丙烯共聚物、四氟乙烯-偏二氟乙烯-全氟烷基乙烯基醚共聚物、四氟乙烯-偏二氟乙烯-丙烯共聚物等。
本發明所使用之氟彈性體並無特別限制,例如可使用可交聯多元醇者。
本發明所使用之氟彈性體組合物係於上述氟彈性體中調配多元醇交聯劑而成者。又,可將交聯促進劑與多元醇交聯劑一併使用。
多元醇交聯劑及交聯促進劑係用於交聯氟彈性體者。此處,所謂交聯,係利用多元醇交聯劑將氟彈性體之同一聚合物鏈或不同聚合物鏈彼此交聯者,藉由如此進行交聯,上述氟彈性體成為拉伸強度提高且具有良好之彈性者。
利用多元醇交聯劑交聯而成之交聯氟彈性體由於在交聯點具有碳-氧鍵,且具有永久壓縮變形較小、成形性優異之特徵,故而適合於本發明之積層體。
本發明中之多元醇交聯劑可使用已知通常用於氟彈性體用途之多元醇系化合物,例如使用多羥基化合物,尤其就耐熱性優異方面而言,宜使用多羥基芳香族化合物。
多羥基芳香族化合物之種類並無特別限定,例如可列舉:間苯二酚、對苯二酚、鄰苯二酚、2,2-雙(4-羥基苯基)丙烷、2,2-雙(4-羥基苯基)全氟丙烷、1,7-二羥基萘、2,7-二羥基萘、1,6-二羥基萘、4,4'-二羥基聯苯、4,4'-二羥基芪、2,6-二羥基蒽、2,2-雙(4-羥基苯基)丁烷、4,4-雙(4-羥基苯基)戊酸、2,2-雙(4-羥基苯基)四氟二氯丙烷、4,4'-二羥基二苯基碸、4,4'-二羥基二苯基酮、三(4-羥基苯基)甲烷、3,3',5,5'-四氯雙酚A、3,3',5,5'-四溴雙酚A等。該等多羥基芳香族化合物亦可為鹼金屬鹽、鹼土金屬鹽等,於使用酸將氟彈性體之共聚物凝聚之情形時,較佳為不使用上述金屬鹽。
該等中,就交聯後之氟彈性體之永久壓縮變形較小且成形性優異方面而言,較佳為多羥基化合物,就耐熱性優異之方面而言,更佳為多羥基芳香族化合物,更佳為2,2-雙(4-羥基苯基)全氟丙烷。
多元醇交聯劑之添加量相對於氟彈性體100質量份,較佳為0.2~10質量份,更佳為0.5~3質量份,更佳為1~2.5質量份。若交聯劑之添加量不足0.2質量份,則組合物交聯之效果較小,導致所獲得之硫化物之強度不足。若添加量超過10質量份,則所獲得之硫化物會發生硬化,導致失去橡膠彈性。
又,於多元醇系交聯中,較佳為使用多元醇交聯劑之同時並用交聯促進劑。若使用交聯促進劑,則藉由促進氟彈性體主鏈之脫氫氟酸反應中之分子內雙鍵之形成,可促進交聯反應。
作為多元醇系交聯之交聯促進劑,較佳為具有不易加成於氟彈性體主鏈上之性質的化合物,通常使用鎓化合物。作為鎓化合物並無特別限定,例如可列舉:四級銨鹽等銨化合物、四級鏻鹽等鏻化合物、氧鎓化合物、鋶化合物、環狀胺、單官能胺化合物等,該等中較佳為四級銨鹽、四級鏻鹽等鎓鹽。
作為交聯促進劑之鎓鹽之種類並無特別限定,例如可使用與上述丙烯酸彈性體組合物相同種類者。鎓鹽之添加方法並無特別限定,於硫化接著氟彈性體層與丙烯酸彈性體層之前、例如於氟彈性體與各種調配劑等之混練時添加鎓鹽之方法可實現牢固之硫化接著性。
交聯促進劑之添加量相對於氟彈性體100質量份,較佳為0.1~2.0質量份,更佳為0.1~1.5質量份,更佳為0.1~0.7質量份。若交聯促進劑之添加量不足0.1質量份,則無法獲得目標交聯速度之促進效果,若交聯促進劑之添加量超過2.0質量份,則交聯速度過快,易發生焦化(硫化步驟前之初期硫化)或成形不良。
又,視需要可調配氟彈性體用之通常之添加物,例如碳黑、補強劑、軟化劑、抗老化劑、硫化劑、硫化促進劑、填充劑、加工助劑、塑化劑、著色劑、穩定劑、接著助劑、吸酸劑、脫模劑、導電性賦予劑、導熱性賦予劑、表面非黏著劑、柔軟性賦予劑、耐熱性改良劑、阻燃劑等各種添加劑,亦可調配1種或1種以上之多元醇交聯劑以外之交聯劑或交聯促進劑。
氟彈性體組合物係藉由使用通常採用之橡膠混練裝置對氟彈性體、多元醇交聯劑、視需要之交聯促進劑、填充劑等其他調配劑進行混練而獲得。作為橡膠混練裝置,可使用滾筒、混練機、班伯裏混練機、密閉混合器、雙軸擠出機等。
以下,基於實施例進一步詳細說明本發明,但本發明並不受該等實施例限定。
於下述所示之條件下製作4種丙烯酸彈性體A~D。
向內容積40升之反應容器中投入部分皂化聚乙烯醇4質量%水溶液17 kg、乙酸鈉22 g,利用攪拌機預先充分混合,製成均勻懸浮液。利用氮氣置換槽內上部之空氣後,繼續攪拌,將槽內保持在55℃後,自注入口分別投入單體成分(丙烯酸乙酯5.5 kg、丙烯酸正丁酯5.5 kg、甲基丙烯酸縮水甘油酯0.15 kg)與過氧化第三丁基0.5質量%水溶液2 kg而開始聚合。反應過程中,槽內溫度保持在55℃,6小時後結束反應,獲得聚合液。
向所生成之聚合液中添加硼酸鈉0.3質量%水溶液20 kg而將聚合物固化,進行脫水及乾燥,獲得丙烯酸彈性體A。該丙烯酸彈性體A之共聚物組成為:甲基丙烯酸縮水甘油酯單體單元1.3質量份、丙烯酸乙酯單體單元50質量份、丙烯酸正丁酯單體單元50質量份。甲基丙烯酸縮水甘油酯單體之定量係將共聚物之生橡膠(硫化接著前)溶解於氯仿中,使用過氯酸乙酸溶液進行滴定而測定。其他單體單元成分係藉由核磁共振光譜法對各成分進行定量。
將作為丙烯酸彈性體之原料之單體成分之調配組成變為乙酸乙烯酯2.2 kg、丙烯酸正丁酯8.8 kg、甲基丙烯酸縮水甘油酯0.17 kg,除此以外,於與上述丙烯酸彈性體A相同之條件下獲得丙烯酸彈性體B。
該丙烯酸彈性體B之共聚物組成為乙酸乙烯酯單體單元20質量份、丙烯酸正丁酯單體單元80質量份、甲基丙烯酸縮水甘油酯單體單元1.5質量份。再者,關於丙烯酸彈性體B與下述丙烯酸彈性體C、D,甲基丙烯酸縮水甘油酯單體之定量法與其他單體單元成分之定量法係採用與上述丙烯酸彈性體A相同之方法。
向內容積40升之反應容器中投入部分皂化聚乙烯醇4質量%水溶液17 kg、乙酸鈉22 g,利用攪拌機預先充分混合,製成均勻懸浮液。利用氮氣置換槽內上部之空氣後,將乙烯壓入至槽內上部,將壓力調整至35 kg/cm2。繼續攪拌,使槽內保持在55℃後,自注入口分別投入單體成分(丙烯酸乙酯5.5 kg、丙烯酸正丁酯5.5 kg、甲基丙烯酸縮水甘油酯0.15 kg)與過氧化第三丁基0.5質量%水溶液2 kg而開始聚合。反應過程中,槽內溫度保持在55℃,6小時後結束反應,獲得聚合液。
向所生成之聚合液中添加硼酸鈉0.3質量%水溶液20 kg而使聚合物固化,進行脫水及乾燥,獲得丙烯酸彈性體C。該丙烯酸彈性體C之共聚物組成為甲基丙烯酸縮水甘油酯單體單元1.3質量份、丙烯酸乙酯單體單元50質量份、丙烯酸正丁酯單體單元47質量份、乙烯單體單元3質量份。
將作為丙烯酸彈性體之原料之單體成分之調配組成變為丙烯酸乙酯5.5 kg、丙烯酸正丁酯5.5 kg,除此以外,於與上述丙烯酸彈性體A相同之條件下獲得丙烯酸彈性體D。該丙烯酸彈性體D之共聚物組成為丙烯酸乙酯單體單元50質量份與丙烯酸正丁酯單體單元50質量份。
根據下述表1之調配組成(質量比)製作氟彈性體組合物,將該氟彈性體組合物(未硫化)成形為厚度2.5 mm,製作氟彈性體層。
[表1]
根據下述表2~4之調配組成(質量比),使用8英吋開放式滾筒混練上述丙烯酸彈性體A~D與其他材料,獲得實施例1~20、比較例1~7之丙烯酸彈性體組合物。將該等丙烯酸彈性體組合物(未硫化)成形為厚度2.5 mm,製作丙烯酸彈性體層,使該層與上述氟彈性體層密接,於蒸汽加熱式熱壓機中進行160℃×35 min之加熱處理,獲得積層體之硫化物。
[表2]
[表3]
[表4]
再者,上述表1~4所使用之調配試劑如下。
‧氟彈性體:Dai-El G558(Daikin工業股份有限公司製造,製品中含有多元醇交聯劑)
‧氧化鎂:Kyowamag 150(協和化學工業股份有限公司製造)
‧氫氧化鈣:特級試劑(和光純藥工業股份有限公司製造)
‧半補強碳黑:旭#50(Asahi Carbon股份有限公司製造)
‧高耐磨碳黑:Seast #3(Tokai Carbon股份有限公司製造)
‧抗老化劑:Nocrac CD(大內新興化學工業股份有限公司製造)
‧硬脂酸:Lunac S-90(花王股份有限公司製造)
‧溴化十八烷基三甲基銨:特級試劑(和光純藥工業股份有限公司製造)
‧硫氰酸四正丁基銨:特級試劑(和光純藥工業股份有限公司製造)
‧氯化四正丁基銨:特級試劑(和光純藥工業股份有限公司製造)
‧氯化苄基三丁基銨:特級試劑(和光純藥工業股份有限公司製造)
‧溴化四正丁基鏻:特級試劑(和光純藥工業股份有限公司製造)
‧溴化甲基三苯基鏻:特級試劑(和光純藥工業股份有限公司製造)
‧溴化乙基三苯基鏻:特級試劑(和光純藥工業股份有限公司製造)
針對所獲得之積層體之硫化物(試驗片),於以下條件下評價剝離強度。
剝離強度係使用拉伸試驗機,以50 mm/min之剝離速度進行各試驗片之T剝離試驗,測定接著強度。又,觀察剝離模式,根據以下標準進行評價。
○……材料破壞。
Δ……一部分材料破壞。
×……界面剝離。
將評價結果記載於上述表2~4。
由上述表2~4明確,本發明之積層體即使不進行特別之表面處理,氟彈性體層與丙烯酸彈性體層之硫化接著力亦較高,且具有牢固之接著強度。將實施例1~10與實施例11~21進行比較後明確得知,有機銨鹽、有機鏻鹽中之任一鎓鹽均適合本發明。
又,於比較例6、7中,雖然丙烯酸彈性體組合物含有鎓鹽,但其接著強度較低,為了獲得牢固之接著強度,須使丙烯酸彈性體之化學結構中含有環氧基(縮水甘油基)。
本發明之積層體可獲得層間接著力優異之組合物,其積層體及其硫化物可適宜地用作軟管構件、密封構件、抗振橡膠構件。
1...積層體
11...丙烯酸彈性體層
12...氟彈性體層
圖1係表示本發明之積層體之一例的剖面圖。
1...積層體
11...丙烯酸彈性體層
12...氟彈性體層
Claims (2)
- 一種積層體,其係由丙烯酸彈性體層與氟彈性體層接著而形成;該丙烯酸彈性體層包含:相對於含有環氧基之丙烯酸彈性體100質量份、添加有1質量份以上之選自由有機氯化銨、有機溴化銨、有機硫氰酸銨、有機氯化鏻、及有機溴化鏻所組成之群中之任一種以上的丙烯酸彈性體組合物;該氟彈性體層包含:含有多元醇交聯劑之氟彈性體組合物。
- 一種硫化物,其係將如請求項1之積層體硫化而獲得者。
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JP2583444B2 (ja) | 1988-06-23 | 1997-02-19 | 日本ゼオン株式会社 | ゴム積層体の製造方法 |
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