WO2023008042A1 - 液状付加硬化型フルオロシリコーン組成物、シリコーンゴム、成形品 - Google Patents
液状付加硬化型フルオロシリコーン組成物、シリコーンゴム、成形品 Download PDFInfo
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- WO2023008042A1 WO2023008042A1 PCT/JP2022/025551 JP2022025551W WO2023008042A1 WO 2023008042 A1 WO2023008042 A1 WO 2023008042A1 JP 2022025551 W JP2022025551 W JP 2022025551W WO 2023008042 A1 WO2023008042 A1 WO 2023008042A1
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- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 229920002379 silicone rubber Polymers 0.000 title description 16
- 239000004945 silicone rubber Substances 0.000 title description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 32
- 230000006835 compression Effects 0.000 claims abstract description 30
- -1 3,3,3-trifluoropropyl group Chemical group 0.000 claims abstract description 29
- 238000007906 compression Methods 0.000 claims abstract description 29
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 19
- 229920005560 fluorosilicone rubber Polymers 0.000 claims abstract description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 11
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims abstract description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 11
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 10
- 238000007259 addition reaction Methods 0.000 claims abstract description 9
- 239000000945 filler Substances 0.000 claims abstract description 9
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- 239000010703 silicon Substances 0.000 claims description 4
- 238000001746 injection moulding Methods 0.000 abstract description 18
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract description 3
- 125000004429 atom Chemical group 0.000 abstract 1
- 238000000034 method Methods 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 238000000748 compression moulding Methods 0.000 description 8
- 238000013007 heat curing Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 125000005388 dimethylhydrogensiloxy group Chemical group 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 229910021485 fumed silica Inorganic materials 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 4
- 229910002012 Aerosil® Inorganic materials 0.000 description 3
- 229910004283 SiO 4 Inorganic materials 0.000 description 3
- WYUIWUCVZCRTRH-UHFFFAOYSA-N [[[ethenyl(dimethyl)silyl]amino]-dimethylsilyl]ethene Chemical compound C=C[Si](C)(C)N[Si](C)(C)C=C WYUIWUCVZCRTRH-UHFFFAOYSA-N 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 3
- 150000001282 organosilanes Chemical class 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- XCMSVSBUVANQIE-UHFFFAOYSA-N [SiH4].N1N=NC2=C1C=CC=C2 Chemical compound [SiH4].N1N=NC2=C1C=CC=C2 XCMSVSBUVANQIE-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 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 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 210000002374 sebum Anatomy 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- WGGNJZRNHUJNEM-UHFFFAOYSA-N 2,2,4,4,6,6-hexamethyl-1,3,5,2,4,6-triazatrisilinane Chemical compound C[Si]1(C)N[Si](C)(C)N[Si](C)(C)N1 WGGNJZRNHUJNEM-UHFFFAOYSA-N 0.000 description 1
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 description 1
- NNKJLYMBVRDUEI-UHFFFAOYSA-N chloro-tris(ethenyl)silane Chemical compound C=C[Si](Cl)(C=C)C=C NNKJLYMBVRDUEI-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 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 1
- 238000011161 development Methods 0.000 description 1
- VSYLGGHSEIWGJV-UHFFFAOYSA-N diethyl(dimethoxy)silane Chemical compound CC[Si](CC)(OC)OC VSYLGGHSEIWGJV-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000010068 moulding (rubber) Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 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 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003209 poly(hydridosilsesquioxane) Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- HUZZQXYTKNNCOU-UHFFFAOYSA-N triethyl(methoxy)silane Chemical compound CC[Si](CC)(CC)OC HUZZQXYTKNNCOU-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/5406—Silicon-containing compounds containing elements other than oxygen or nitrogen
Definitions
- the present invention relates to a liquid addition-curable fluorosilicone composition, a fluorosilicone rubber obtained by heat-curing the composition, and a molded article thereof.
- addition-curable fluorosilicone rubber compositions have been used for aircraft and vehicle-mounted rubber parts, printer parts, etc., due to their excellent gasoline and oil resistance (Patent Document 1).
- Patent Document 1 it has also been studied for mobile parts due to its resistance to sebum, and for sealing parts for fuel cell vehicles due to its acid resistance.
- Addition-curable fluorosilicone rubber compositions used for these parts are required to have a low compression set and maintain practical strength, that is, mechanical strength.
- the development of liquid addition-curable fluorosilicone rubber compositions with excellent productivity has been desired.
- Injection molding, compression molding, injection molding, etc., using molds are preferable as processing methods with excellent productivity, and liquid addition-curable fluorosilicone rubber compositions cannot be used unless they have a viscosity that can be applied to these processing methods. There was a problem.
- the present invention has been made in view of the above circumstances, and provides a liquid addition-curable fluorosilicone composition that exhibits a low compression set after heat curing, retains mechanical strength, and is particularly suitable for injection molding. and to provide a fluorosilicone rubber obtained by heat-curing the composition and a molded article thereof.
- the fluorosilicone composition targeted by the present invention contains linear polysiloxane having, as the main chain, a repeating structure of diorganosiloxane units having fluoroalkyl groups, as the main component constituting the matrix of the cured silicone rubber. do.
- a typical dimethylsilicone composition is based on linear dimethylpolysiloxane whose main chain is composed of repeating dimethylsiloxane units.
- the fluorosilicone composition aimed at by the present invention is essentially different from the dimethylsilicone composition.
- an addition-curable fluorosilicone composition which is liquid at 23°C, is surface-treated with an organosilicon compound having a trifluoropropyl group to provide reinforcing properties. It has been found that a fluorosilicone rubber having a low compression set value after heat curing and retaining mechanical strength can be obtained by blending a silica filler. Furthermore, the inventors have found that the liquid addition-curable fluorosilicone composition is suitable as a material for injection molding, compression molding and injection molding, and have completed the present invention.
- the present invention provides (A) the following general formula (1) (wherein R 1 is a group independently selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms and an aralkyl group having 7 to 12 carbon atoms, and x is 1 to 10 an integer, m is an integer from 0 to 100, and n is an integer from 1 to 800, with the proviso that 5 ⁇ m+n ⁇ 800)
- R 1 is a group independently selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms and an aralkyl group having 7 to 12 carbon atoms, and x is 1 to 10 an integer, m is an integer from 0 to 100, and n is an integer from 1 to 800, with the proviso that 5 ⁇ m+n ⁇ 800)
- B Organohydrogenpolysiloxane having two or more silicon-bonded hydrogen atoms per molecule: silicon in component (B) an amount such that
- the present invention provides a fluorosilicone rubber which is a cured product of the liquid addition-curable fluorosilicone composition, and a molded product of the silicone rubber.
- the liquid addition-curable fluorosilicone composition of the present invention provides a fluorosilicone rubber having a low compression set after heat curing and retaining mechanical strength. Since the liquid addition-curable fluorosilicone composition is suitable as a material for injection molding, compression molding and injection molding, it can contribute to improved productivity of molded articles.
- Vinyl-containing organopolysiloxane Component (A) is an organopolysiloxane having a viscosity at 25° C. of 100 to 500,000 mPa ⁇ s represented by the following general formula (1).
- R 1 is a group independently selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms and an aralkyl group having 7 to 12 carbon atoms, and x is 1 to 10 an integer
- m is an integer from 0 to 100
- n is an integer from 1 to 800, provided that 5 ⁇ m+n ⁇ 800
- each R 1 is independently a C 1-8 group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a cyclohexyl group, or the like.
- aryl groups having 6 to 12 carbon atoms such as alkyl groups, aryl groups having 6 to 12 carbon atoms such as tolyl groups, and aralkyl groups having 7 to 12 carbon atoms such as benzyl groups.
- an alkyl group having 1 to 8 carbon atoms is preferred, and a methyl group is particularly preferred.
- n is an integer of 1-800, preferably 5-750, more preferably 10-650, even more preferably 50-650, most preferably 100-650.
- (m+n) is an integer satisfying 5 ⁇ m+n ⁇ 800, preferably 10 ⁇ m+n ⁇ 680, more preferably 60 ⁇ m+n ⁇ 680, and still more preferably 120 ⁇ m+n ⁇ 680.
- the viscosity of the organopolysiloxane is characterized by being in the range of 100 to 500,000 mPa ⁇ s at 25°C, preferably in the range of 300 to 100,000 mPa ⁇ s. Within this range, the physical properties of the cured product are good and the handling workability of the composition is good. Furthermore, if the viscosity is less than 100 mPa ⁇ s, the strength of the resulting cured product will be insufficient, and if it exceeds 500,000 mPa ⁇ s, the handleability of the composition will deteriorate, which is not preferable. In the present invention, viscosity is a value measured by a rotational viscometer according to the method described in JIS K 7117-1:1999. (A) The degree of polymerization of the organopolysiloxane is such that the viscosity at 25°C falls within the above range.
- the number of siloxane units having a fluoroalkyl group is preferably 10 with respect to all siloxane units in the molecule (in particular, the total number of bifunctional siloxane units that make up the main chain (that is, n + m).
- mol % or more more preferably 20 mol % or more, and particularly preferably 30 to 100 mol %.
- the upper limit is not particularly limited, and may be 100 mol % or less, 95 mol % or less, 90 mol % or less. or less, or 80 mol % or less, which is preferable because excellent hydrocarbon solvent durability can be imparted within this range.
- Organohydrogenpolysiloxane Component (B) is an organohydrogenpolysiloxane having two or more silicon-bonded hydrogen atoms per molecule.
- the organohydrogenpolysiloxane undergoes a hydrosilylation addition reaction with component (A) and acts as a curing agent (crosslinking agent).
- curing agent crosslinking agent
- the component (B) organohydrogenpolysiloxane has 2 or more (usually 2 to 200), preferably 3 to 100, and particularly preferably 3 to 50 silicon-bonded hydrogen atoms per molecule. (that is, a hydrosilyl group represented by SiH).
- SiH silicon-bonded hydrogen atoms per molecule.
- these SiH groups are at the ends of the molecular chain (i.e., diorganohydrogensiloxy groups) and in the middle of the molecular chain (i.e., It may be located on either one or both of the non-terminally located bifunctional organohydrogensiloxane units or trifunctional hydrogensilsesquioxane units).
- a monovalent organic group bonded to a silicon atom other than a hydrogen atom bonded to a silicon atom is an aliphatically unsaturated group such as an unsubstituted or substituted alkenyl group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms.
- a bond-free monovalent hydrocarbon group can be exemplified.
- alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group and decyl group,
- Aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group; aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group; substituted with a halogen atom, such as a fluoroalkyl group such as a trifluoropropyl group.
- a methyl group or a fluoroalkyl group such as a trifluoropropyl group is preferred.
- the number (or degree of polymerization) of silicon atoms in one molecule of component (B) is preferably 2 to 300, more preferably 3 to 200, still more preferably 4 to 150.
- the component (B) is preferably liquid at room temperature (25°C).
- the viscosity of component (B) at 25° C. is preferably 0.1 to 1,000 mPa ⁇ s, more preferably 0.5 to 500 mPa ⁇ s, still more preferably 1 to 200 mPa ⁇ s. If the viscosity is too low or too high, the workability may deteriorate.
- Examples of (B) organohydrogenpolysiloxane include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris(hydrogendimethylsiloxy)methylsilane, tris (Hydrogendimethylsiloxy)phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane/dimethylsiloxane cyclic copolymer, both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both ends trimethylsiloxy group-blocked dimethylsiloxane/methyl Hydrogensiloxane copolymer, both terminal trimethylsiloxy group-blocked methylhydrogensiloxane/trifluoropropylmethylsiloxane copolymer, both terminal dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, both terminal dimethylhydrogens
- Component (B) is more preferably represented by the following formula (3).
- each R 1′ is independently a hydrogen atom, or a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. and include the groups exemplified for R 1 above.
- two or more, preferably 3 to 100, more preferably 3 to 50, of R 1' are hydrogen atoms.
- k is an integer of 2 to 200, preferably an integer of 3 to 100, more preferably an integer of 5 to 50; q is an integer of 0 to 200, preferably an integer of 1 to 100, more preferably An integer from 2 to 100. k+q is 2-300, more preferably 3-200, still more preferably 4-150.
- the amount of component (B) is such that the number ratio of silicon-bonded hydrogen atoms in component (B) to one silicon-bonded vinyl group in component (A) is 0.5 to 10, preferably 1 to It is an amount that falls within the range of five. If the amount of component (B) is less than the above lower limit, the obtained composition will not be sufficiently cured. On the other hand, if the amount of component (B) exceeds the above upper limit, the heat resistance of the resulting silicone rubber will be extremely poor.
- component (A) When a vinyl group-containing organosiloxane other than component (A), which will be described later, is included, the ratio of the number of silicon-bonded hydrogen atoms in component (B) to the number of vinyl groups bonded to silicon atoms in the composition is It is sufficient if the above range is satisfied.
- the addition reaction catalyst for component (C) is any catalyst that promotes the addition reaction between the vinyl groups in component (A) and the silicon-bonded hydrogen atoms in component (B). It may be a catalyst. Generally, a platinum group metal-based catalyst can be suitably used.
- platinum, palladium, rhodium, etc. chloroplatinic acid, alcohol-modified chloroplatinic acid, coordination compounds of chloroplatinic acid and olefins, vinylsiloxane or acetylene compounds, tetrakis (triphenylphosphine) palladium, chlorotris (triphenylphosphine) ) platinum group metals such as rhodium or compounds thereof, and platinum-based compounds are particularly preferred.
- (C) component may be used individually by 1 type, or may use 2 or more types together.
- the amount of component (C) to be blended may be an effective amount as a catalyst. ⁇ 1,000 ppm, preferably 1-500 ppm, more preferably 10-100 ppm. When this range is satisfied, the reaction rate of the addition reaction becomes appropriate, and the heat resistance of the cured product becomes good.
- (D) Reinforcing Silica Filler Component (D) is reinforcing silica surface-treated with a linear organosilicon compound having silanol groups at both ends of the molecular chain represented by the following formula (2).
- R 3 is a group independently selected from an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. Examples include those described for R 1.
- R 2 is a group represented by R 3 above or a 3,3,3-trifluoropropyl group, provided that R 2 At least one is a 3,3,3-trifluoropropyl group, p is an integer of 1 ⁇ p ⁇ 20, preferably an integer of 3-9.
- the reinforcing silica filler is essential for imparting mechanical strength to the resulting silicone rubber. If the organosilicon compound represented by the above formula (2) does not have a 3,3,3-trifluoropropyl group, the resulting cured product will be inferior in tensile strength, elongation at break and compression set.
- a reinforcing silica filler By containing a reinforcing silica filler surface-treated with a linear organosilicon compound in which both ends of the molecular chain are blocked with silanol groups, the viscosity of the present composition and the compression set of the rubber after heat curing are reduced. can be lowered.
- the reinforcing silica filler those conventionally used in silicone rubber compositions can be used, and precipitated silica (wet silica), fumed silica (dry silica), pyrogenic silica and the like are suitable. Fumed silica is particularly preferred.
- the component (D) may be surface-untreated silica previously surface-treated with the organosilicon compound of formula (2) above.
- the surface-untreated silica and the polysiloxane component that is, component (A)
- the organosilicon compound of formula (2) is added, and the mixture is heated and mixed, preferably in the presence of a small amount of water.
- the surface-untreated silica preferably used in the present invention may be dry silica (eg, Aerosil R-974, etc.) surface-treated with dimethyldichlorosilane or the like. It is preferable to further treat the surface of the dry silica surface-treated with dimethyldichlorosilane or the like with the organosilicon compound of formula (2).
- the amount of treatment when silica is surface-treated with the organosilicon compound of formula (2) is the organic It is preferable to surface-treat the silicon compound with 1 to 30 parts by mass, particularly 2 to 20 parts by mass.
- organosilanes such as trimethylchlorosilane, dimethyldichlorosilane, dimethylvinylchlorosilane, trivinylchlorosilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, dimethyldimethoxysilane, Alkoxysilanes such as diethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, vinyltris(methoxyethoxy)silane, hexamethyldisilazane, hexamethylcyclotrisilazane,
- chlorosilanes such as trimethylchlorosilane, dimethyldichlorosilane, dimethylvinylchlorosilane, trivinylchloro
- the BET specific surface area of silica before surface treatment with the organosilicon compound of formula (2) is 50 m 2 /g or more, preferably 100 to 400 m 2 /g, more preferably 150 to 350 m 2 /g. . If the specific surface area is less than 50 m 2 /g, not only is sufficient strength not obtained, but also the appearance of the rubber molded product may be poor. If it is more than 400 m 2 /g, it may become difficult to blend.
- the specific surface area of the silica after the surface treatment as determined by the BET method may also be within the above range.
- the blending amount of component (D) is 10 to 60 parts by mass, preferably 15 to 55 parts by mass, per 100 parts by mass of component (A). If the amount is less than the above lower limit, the resulting silicone rubber will not have sufficient rubber strength, and if it exceeds the above upper limit, it will be difficult to incorporate it into the composition.
- the liquid addition-curable fluorosilicone composition of the present invention may optionally contain other components other than components (A) to (D) as long as they do not impair the appearance of the molded rubber article.
- Other components include, for example, carbon black, conductive zinc oxide, conductive agents such as metal powder, nitrogen-containing compounds, acetylene compounds, phosphorus compounds, nitrile compounds, carboxylates, tin compounds, mercury compounds, hydrosilylation of sulfur compounds, etc.
- Reaction control agents heat resistance imparting agents such as iron oxide and cerium oxide, compression set improvers such as triazole compounds and benzotriazole derivatives, internal release agents such as dimethyl silicone oil, adhesion imparting agents, thixotropic agents etc.
- the liquid addition-curable fluorosilicone composition of the present invention does not contain isocyanuric acid derivatives having three trialkoxy groups per molecule.
- the liquid addition-curable fluorosilicone composition of the present invention is prepared by mixing the above components (A) to (D) and, if necessary, each optional component, with a conventional mixing agitator such as a kneader or planetary mixer, a kneader, or the like. can be prepared by uniformly mixing the above components using a conventional mixing agitator such as a kneader or planetary mixer, a kneader, or the like. can be prepared by uniformly mixing the above components using a conventional mixing agitator such as a kneader or planetary mixer, a kneader, or the like.
- a conventional mixing agitator such as a kneader or planetary mixer, a kneader, or the like.
- the composition of the present invention is characterized by being liquid at 23°C.
- the viscosity at a shear rate of 10 s ⁇ 1 at 23° C. is preferably 1,500 Pa s or less, more preferably 100 to 1,200 Pa s, and still more preferably 200 to 1,000 Pa s. 100 Pa ⁇ s. If the viscosity exceeds 1,500 Pa ⁇ s, it takes a long time to supply the material during injection, compression, and injection molding, which may significantly reduce productivity.
- the measurement of the viscosity under the shear rate was performed using a precision rotary viscometer (manufactured by Thermo Fisher Scientific).
- the liquid addition-curable fluorosilicone composition of the present invention can also be a two-pack type.
- each component may be appropriately divided so that component (B) as a cross-linking agent and component (C) as an addition reaction catalyst are not mixed in the same composition (solution A or solution B).
- a two-component composition comprising liquid A containing components (A), (C) and (D) and liquid B containing components (A), (B) and (D) It is preferable to prepare so that they can be mixed in equal mass or equal volume.
- the liquid addition-curable fluorosilicone composition of the present invention can be applied to various molding methods such as injection molding, compression molding and injection molding. Methods for molding fluorosilicone rubber by injection molding, compression molding, or injection molding are described in detail below.
- the liquid addition-curable fluorosilicone composition is divided into two liquid types, A liquid and B liquid.
- the material divided into two liquids is mixed with equal amounts of each liquid A and B, injected into a metal mold, heated in a constant temperature bath and cured to form a silicone rubber.
- a metal mold is installed in a compressor such as a press, and equal amounts of the above liquids A and B are mixed in the same manner as injection molding, injected into the mold, heated and cured to form silicone rubber. is molded.
- each A liquid and B liquid are supplied to a metering device from a material supply pump.
- the A liquid and the B liquid are combined at an equal ratio through the material supply line. Materials are mixed in the screw part and the cylinder part of the molding machine body. After that, it is injected into a mold, heated in the mold and cured to form a silicone rubber.
- the curing and molding (primary curing) conditions for the liquid addition-curable fluorosilicone composition may be the same as those for known addition reaction-curable silicone compositions. Curing and molding can be performed by heating for 3 seconds to 10 minutes, particularly 5 seconds to 5 minutes. The molded cured product may be post-cured (secondary curing) at, for example, 180 to 220° C. for about 30 minutes to 6 hours, if necessary.
- the cured product (silicone rubber) obtained from the liquid addition-curable fluorosilicone composition of the present application has a compression set of 10% or less after compression for 22 hours at 180°C, measured according to JIS K 6249:2003.
- the tensile strength of the mechanical strength is 5.0 MPa or more.
- the compression set after compression at 180°C for 22 hours at a compression rate of 25% should be 15% or less, preferably 10% or less.
- the cured product can be used as parts (molded products) such as sealing materials, O-rings, and packings.
- the mechanical strength should be 4.5 MPa or more, preferably 5.0 MPa or more.
- Fluorosilicone rubber molded articles obtained by heat-curing the liquid addition-curable fluorosilicone composition of the present invention are excellent in gasoline resistance and oil resistance. , from the viewpoint of sebum resistance, it can be suitably used for mobile parts, and from the viewpoint of acid resistance, it can be suitably used for sealing parts for fuel cell vehicles.
- the viscosity of component (A) was measured at 25° C. with a BH-type rotational viscometer (rotor No. 7, rotation speed 10 rpm).
- the viscosity of component (B) was measured at 25° C. with a BL-type rotational viscometer (rotor No. 2, rotation speed 60 rpm).
- the viscosity measurement of the composition was performed by the following method.
- the viscosity of the composition was measured at a shear rate of 10 s ⁇ 1 at 23° C. using a cone and plate measuring jig of a precision rotary viscometer (manufactured by Thermo Fisher Scientific).
- the hardness, tensile strength, elongation at break, and tear strength (angle) of the cured product were measured by the following methods.
- the composition was pre-cured at 150° C./10 minutes and then subjected to secondary vulcanization (post-curing) in a constant temperature bath at 200° C./4 hours.
- the hardness, tensile strength, elongation at break, and tear strength (angle) of the cured product were measured according to JIS K 6249:2003.
- the compression set of the cured product was measured by the following method.
- the composition was cured (pre-cured) at 150° C./15 minutes, and further secondary vulcanized (post-cured) in a constant temperature bath at 200° C./4 hours.
- the compression set of the cured product was measured after compression at 180° C. for 22 hours at a compression rate of 25% based on JIS K 6249:2003.
- component the following formula (4) A trifluoropropylmethylpolysiloxane having a viscosity of 76.6 Pa s at 25° C. [vinyl group content 4.6 ⁇ 10 ⁇ 5 mol/g] having both ends blocked with dimethylvinylsiloxy groups represented by (D) component: fumed silica (Aerosil R-974, manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 200 m 2 /g by the BET method; Organosilicon compound represented by the following formula (5) (B) Cross-linking agent: methylhydrogenpolysiloxane represented by the following formula (6) [viscosity 0.06 Pa s, SiH group weight 0.0049 mol/g] (C) platinum catalyst (Pt concentration 0.5% by mass) Reaction control agent: ethynylcyclohexanol Compression set improving agent: benzotriazole silane represented by
- Example 1 (A) 65 parts by mass of trifluoropropylmethylpolysiloxane represented by the above formula (4) [vinyl group content 4.6 ⁇ 10 ⁇ 5 mol/g], 40 parts by mass of the above fumed silica as a reinforcing silica filler , 3.3 parts by mass of the organosilicon compound represented by the above formula (5), 0.55 parts by mass of water, and 0.3 parts by mass of 1,3-divinyl-1,1,3,3-tetramethyldisilazane was mixed at 25° C. for 30 minutes, the temperature was raised to 160° C., and stirring was continued for 3 hours. Further, 55 parts by mass of trifluoropropylmethylpolysiloxane represented by the above formula (4) was added, and after mixing for 30 minutes, a silicone rubber base was obtained.
- composition 1 The viscosity of Composition 1 obtained was measured by the method described above. In addition, the composition was cured by the above method, and the hardness, tensile strength, elongation at break, tear strength (angle) and compression set of the cured product were measured. Table 1 shows the results.
- Example 2 In the preparation of the silicone rubber base of Example 1, 5.0 parts by mass of the organosilicon compound represented by the above formula (5) was added (the amount of component (D) was 31.1 parts by mass per 100 parts by mass of component (A). ) was repeated to prepare addition-curable fluorosilicone composition 2, which is liquid at 23°C. The viscosity of Composition 2 obtained was measured by the method described above. In addition, the composition was cured by the above method, and the hardness, tensile strength, elongation at break, tear strength (angle) and compression set of the cured product were measured. Table 1 shows the results.
- Example 3 In the preparation of the silicone rubber base of Example 1, 6.6 parts by mass of the organosilicon compound represented by the above formula (5) was added (the amount of component (D) was 31.1 parts by mass per 100 parts by mass of component (A). ) was repeated to prepare addition-curable fluorosilicone composition 3, which is liquid at 23°C. The viscosity of Composition 3 obtained was measured by the method described above. In addition, the composition was cured by the above method, and the hardness, tensile strength, elongation at break, tear strength (angle) and compression set of the cured product were measured. Table 1 shows the results.
- Example 1 In the preparation of the silicone rubber base of Example 1, no organosilicon compound represented by formula (5) was added (the amount of untreated fumed silica per 100 parts by weight of component (A) was 31.1 parts by weight. A) Otherwise, Example 1 was repeated to prepare addition-curable fluorosilicone composition 4, which is liquid at 23°C. The viscosity of Composition 4 obtained was measured by the method described above. In addition, the composition was cured by the above method, and the hardness, tensile strength, elongation at break, tear strength (angle) and compression set of the cured product were measured. Table 1 shows the results.
- the cured product obtained from the liquid addition-curable fluorosilicone composition of the present invention has excellent tensile strength and elongation at break, and a low compression set.
- the fluorosilicone composition of Comparative Example 1 in which silica was not surface-treated with the organosilicon compound of the present invention, exhibited particularly large compression set and poor mechanical strength.
- the liquid addition-curable fluorosilicone composition of the present invention is suitable as a material for injection molding, compression molding, and injection molding, and can contribute to improved productivity of molded products.
- the liquid addition-curable fluorosilicone composition of the present invention has a low compression set value after heat curing, and can be suitably used as rubber moldings such as sealing materials, O-rings, and packings.
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Abstract
Description
で示される、25℃の粘度100~500,000mPa・sを有するオルガノポリシロキサン
(B)ケイ素原子結合水素原子を1分子中に2個以上有するオルガノハイドロジェンポリシロキサン:(B)成分中のケイ素原子に結合した水素原子の数が(A)成分中のケイ素原子結合ビニル基1個当たり0.5~10個となる量、
(C)付加反応触媒:触媒量、及び
(D)下記一般式(2)で示される有機ケイ素化合物で表面処理した補強性シリカ充填剤
を含有することを特徴とする、23℃で液状である、付加硬化型フルオロシリコーン組成物を提供する。
さらに本発明は該液状付加硬化型フルオロシリコーン組成物の硬化物であるフルオロシリコーンゴム、及び該シリコーンゴムの成形品を提供する。
(A)ビニル基含有オルガノポリシロキサン
(A)成分は、下記一般式(1)で示される25℃の粘度が100~500,000mPa・sであるオルガノポリシロキサンである。
(B)成分は、ケイ素原子結合水素原子を1分子中に2個以上有するオルガノハイドロジェンポリシロキサンである。該オルガノハイドロジェンポリシロキサンは、(A)成分とヒドロシリル化付加反応し、硬化剤(架橋剤)として作用する。(B)成分の分子構造に特に制限はなく、例えば、直鎖状、環状、分岐状、三次元網状構造(樹脂状)等の、従来製造されている各種のオルガノハイドロジェンポリシロキサンを使用することができる。
(C)成分の付加反応触媒は、(A)成分中のビニル基と(B)成分中のケイ素原子に結合した水素原子との付加反応を促進するものであればいかなる触媒であってもよい。通常は、白金族金属系触媒が好適に使用できる。例えば、白金、パラジウム、ロジウム等や塩化白金酸、アルコール変性塩化白金酸、塩化白金酸とオレフィン類、ビニルシロキサン又はアセチレン化合物との配位化合物、テトラキス(トリフェニルホスフィン)パラジウム、クロロトリス(トリフェニルホスフィン)ロジウム等の、白金族金属又はそれらの化合物が挙げられるが、特に好ましくは白金系化合物である。(C)成分は、1種単独で用いても2種以上を併用してもよい。
(D)成分は、下記式(2)で表される分子鎖両末端にシラノール基を有する直鎖状有機ケイ素化合物で表面処理した補強性シリカである。
本発明において該補強性シリカ充填剤は、得られるシリコーンゴムに機械的強度を与えるために必須である。上記式(2)で表される有機ケイ素化合物が3,3,3-トリフルオロプロピル基を有さないと、得られる硬化物は引張強さ、切断時伸びや圧縮永久歪などが劣る。
上記補強性シリカ充填剤としては、従来からシリコーンゴム組成物に使用されているものを用いることができ、沈澱シリカ(湿式シリカ)、ヒュームドシリカ(乾式シリカ)、焼成シリカ等が好適である。特にはヒュームドシリカが好適である。
本発明の液状付加硬化型フルオロシリコーン組成物は、ゴム成形品の外観を損なわない範囲で前記(A)~(D)成分以外のその他の成分を必要に応じて含有してもよい。その他の成分とは例えば、カーボンブラック、導電性亜鉛華、金属粉等の導電剤、窒素含有化合物やアセチレン化合物、リン化合物、ニトリル化合物、カルボキシレート、錫化合物、水銀化合物、硫黄化合物等のヒドロシリル化反応制御剤、酸化鉄、酸化セリウムのような耐熱性付与剤、トリアゾール化合物、ベンゾトリアゾール誘導体等の圧縮永久歪向上剤、ジメチルシリコーンオイル等の内部離型剤、接着性付与剤、チクソ性付与剤等が挙げられる。ただし、本発明の液状付加硬化型フルオロシリコーン組成物は一分子中にトリアルコキシ基を3個有するイソシアヌル酸誘導体を含有しない。
なお、(A)成分の粘度は、25℃においてBH型回転粘度計(ロータNo.7、回転数10rpm)により測定した。(B)成分の粘度は、25℃においてBL型回転粘度計(ロータNo.2、回転数60rpm)により測定した。
組成物の粘度測定は以下の方法にて行った。
精密回転式粘度計(Thermo Fisher Scientific製)のコーン&プレートの測定治具を使用し、23℃におけるせん断速度10s-1での組成物の粘度を測定した。
組成物を150℃/10分のプレスキュアを行ったものに更に200℃/4時間恒温槽で2次加硫(ポストキュア)した。該硬化物について、JIS K 6249:2003の記載に基づき、硬さ、引張強さ、切断時伸び、及び引裂強さ(アングル)を測定した。
組成物を150℃/15分にて硬化(プレスキュア)し、更に200℃/4時間恒温槽で2次加硫(ポストキュア)した。該硬化物について、JIS K 6249:2003の記載に基づき圧縮率25%で180℃×22時間圧縮後の圧縮永久歪を測定した。
(A)成分:下記式(4)
(D)成分:BET法による比表面積が200m2/gであるヒュームドシリカ(日本アエロジル社製、アエロジルR-974)と、
下記式(5)で示される有機ケイ素化合物
反応制御剤:エチニルシクロヘキサノール
圧縮永久歪向上剤:下記式(7)で示されるベンゾトリアゾールシラン
(A)上記式(4)で示されるトリフルオロプロピルメチルポリシロキサン[ビニル基含有量4.6×10-5mol/g]65質量部、補強性シリカ充填剤として上記ヒュームドシリカ40質量部、上記式(5)で示される有機ケイ素化合物3.3質量部、水0.55質量部、及び、1,3-ジビニル-1,1,3,3-テトラメチルジシラザン0.3質量部を25℃で30分混合後、160℃に昇温し、3時間攪拌を続けた。さらに上記式(4)で表されるトリフルオロプロピルメチルポリシロキサン55質量部を添加し、30分混合後、シリコーンゴムベースを得た。
得られた組成物1について上記方法にて粘度を測定した。また、上記の方法にて組成物を硬化し、硬化物の硬さ、引張強さ、切断時伸び、引裂強さ(アングル)及び圧縮永久歪を測定した。結果を表1に示す。
実施例1のシリコーンゴムベースの調製において上記式(5)で示される有機ケイ素化合物を5.0質量部((A)成分100質量部当たりの(D)成分量は31.1質量部である)に変更した以外は実施例1を繰り返して23℃で液状である付加硬化型フルオロシリコーン組成物2を調製した。
得られた組成物2について、上記方法にて粘度を測定した。また、上記の方法にて組成物を硬化し、硬化物の硬さ、引張強さ、切断時伸び、引裂強さ(アングル)及び圧縮永久歪を測定した。結果を表1に示す。
実施例1のシリコーンゴムベースの調製において上記式(5)で示される有機ケイ素化合物を6.6質量部((A)成分100質量部当たりの(D)成分量は31.1質量部である)に変更した以外は実施例1を繰り返して23℃で液状である付加硬化型フルオロシリコーン組成物3を調製した。
得られた組成物3について、上記方法にて粘度を測定した。また、上記の方法にて組成物を硬化し、硬化物の硬さ、引張強さ、切断時伸び、引裂強さ(アングル)及び圧縮永久歪を測定した。結果を表1に示す。
実施例1のシリコーンゴムベースの調製において上記式(5)で示される有機ケイ素化合物を添加しなかった((A)成分100質量部当たりの未処理ヒュームドシリカの量は31.1質量部である)他は実施例1を繰り返して23℃で液状である付加硬化型フルオロシリコーン組成物4を調製した。
得られた組成物4について、上記方法にて粘度を測定した。また、上記の方法にて組成物を硬化し、硬化物の硬さ、引張強さ、切断時伸び、引裂強さ(アングル)及び圧縮永久歪を測定した。結果を表1に示す。
Claims (5)
- (A)下記一般式(1)
で示される、25℃の粘度100~500,000mPa・sを有するオルガノポリシロキサン
(B)ケイ素原子結合水素原子を1分子中に2個以上有するオルガノハイドロジェンポリシロキサン:(B)成分中のケイ素原子に結合した水素原子の数が(A)成分中のケイ素原子結合ビニル基1個当たり0.5~10個となる量、
(C)付加反応触媒:触媒量、及び
(D)下記一般式(2)で示される有機ケイ素化合物で表面処理した補強性シリカ充填剤
を含有することを特徴とする、23℃で液状である、付加硬化型フルオロシリコーン組成物。 - 23℃において、せん断速度10s-1での粘度が1,500Pa・s以下である、請求項1記載の付加硬化型フルオロシリコーン組成物。
- 請求項1又は2記載の付加硬化型フルオロシリコーン組成物の硬化物であるフルオロシリコーンゴム。
- JIS K 6249:2003の記載に基づき測定される180℃22時間圧縮後の圧縮永久歪が10%以下である、請求項3記載のフルオロシリコーンゴム。
- 請求項3または4記載のフルオロシリコーンゴムからなる成形体。
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JP2006022212A (ja) * | 2004-07-08 | 2006-01-26 | Shin Etsu Chem Co Ltd | フッ素ゴム組成物及びその硬化物を含む物品 |
JP2013047290A (ja) | 2011-08-29 | 2013-03-07 | Shin-Etsu Chemical Co Ltd | 液状付加硬化型フロロシリコーンゴム組成物及びその成形品 |
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JP2006022212A (ja) * | 2004-07-08 | 2006-01-26 | Shin Etsu Chem Co Ltd | フッ素ゴム組成物及びその硬化物を含む物品 |
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