WO2022234770A1 - Composition de caoutchouc de fluorosilicone, et objet moulé durci - Google Patents
Composition de caoutchouc de fluorosilicone, et objet moulé durci Download PDFInfo
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- WO2022234770A1 WO2022234770A1 PCT/JP2022/017893 JP2022017893W WO2022234770A1 WO 2022234770 A1 WO2022234770 A1 WO 2022234770A1 JP 2022017893 W JP2022017893 W JP 2022017893W WO 2022234770 A1 WO2022234770 A1 WO 2022234770A1
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- rubber composition
- mass
- fluorosilicone rubber
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- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 229920005560 fluorosilicone rubber Polymers 0.000 title claims abstract description 45
- -1 siloxane units Chemical group 0.000 claims abstract description 70
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 13
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 12
- 238000004438 BET method Methods 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 15
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 10
- 150000001451 organic peroxides Chemical class 0.000 claims description 8
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 7
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 abstract description 6
- 239000011737 fluorine Substances 0.000 abstract description 6
- 238000001723 curing Methods 0.000 description 27
- 229920002379 silicone rubber Polymers 0.000 description 18
- 239000004945 silicone rubber Substances 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000007259 addition reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 125000005388 dimethylhydrogensiloxy group Chemical group 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229920005601 base polymer Polymers 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 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
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 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
- 230000006866 deterioration Effects 0.000 description 2
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 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 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052909 inorganic silicate Inorganic materials 0.000 description 2
- 239000003550 marker Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- AGKBXKFWMQLFGZ-UHFFFAOYSA-N (4-methylbenzoyl) 4-methylbenzenecarboperoxoate Chemical compound C1=CC(C)=CC=C1C(=O)OOC(=O)C1=CC=C(C)C=C1 AGKBXKFWMQLFGZ-UHFFFAOYSA-N 0.000 description 1
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- OKIYQFLILPKULA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)F OKIYQFLILPKULA-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 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
- 125000000094 2-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
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- CXUYURWORTZPEG-UHFFFAOYSA-N tert-butyl (2-methylpropan-2-yl)oxy carbonate;hexane-1,6-diol Chemical compound OCCCCCCO.CC(C)(C)OOC(=O)OC(C)(C)C CXUYURWORTZPEG-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- 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
Definitions
- the present invention relates to fluorosilicone rubber compositions and cured moldings.
- Silicone rubber has excellent weather resistance, electrical properties, low compression set, heat resistance, and cold resistance. Widely used.
- the main chain of the base polymer consists essentially of a repeating structure of (3,3,3-trifluoropropyl)methylsiloxane units having 3,3,3-trifluoropropyl groups as side chain substituents.
- Fluorosilicone rubber compositions based on fluorosilicone have excellent solvent resistance properties, and are widely used as diaphragms, O-rings, and oil seal materials for parts of transportation equipment and petroleum-related equipment.
- fluorosilicone rubber is known to have strong roll adhesion and poor roll releasability due to the influence of the 3,3,3-trifluoropropyl group.
- Various compositions have been proposed to improve this roll releasability.
- a method of adding a perfluoroalkyl group-containing siloxane (Patent Document 1) or adding a polyorganosiloxane containing 5 to 25% by mass of vinyl groups Patent Document 2 is known.
- a method for improving roll adhesion by jointly adding 3,3,3-trifluorosilane or a partial hydrolyzed condensate thereof has also been disclosed (Patent Document 3).
- an improvement has been attempted by blending reinforcing silica surface-treated with silane or siloxane having a ⁇ -trifluoropropyl group and adding silanol-capped siloxane at both ends (Patent Document 4).
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a fluorosilicone rubber composition that is excellent in roll processability even with a high fluorine content.
- a fluorosilicone rubber composition (A) Those having two or more silicon-bonded alkenyl groups in one molecule, and the number of siloxane units having a fluoroalkyl group is 60 mol% or more of the total number of all siloxane units.
- a fluorosilicone rubber composition comprising (D) a linear fluorooxyalkylene group-containing polymer: 0.01 to 5 parts by mass, and (E) a curing agent: a curing effective amount.
- the organopolysiloxane of component (A) is linear, and both ends of the molecular chain of the organopolysiloxane are trimethylsiloxy group, dimethylvinylsiloxy group, dimethylhydroxysiloxy group, methyldivinylsiloxy group, and trimethylsiloxy group. It is preferably a group selected from vinylsiloxy groups.
- Such component (A) is more preferable as the base polymer of the fluorosilicone rubber composition of the present invention.
- the linear fluorooxyalkylene group-containing polymer of component (D) is represented by the following formula (3), (4) or (5); HOCH2O ( CF2O ) m1 ( CF2CF2O ) n1CH2OH ( 3 ) (In the formula, m1 and n1 are numbers satisfying the number average molecular weight range of 1,000 to 5,000.) CF3O ( CF2O)m2 ( CF2CF2O )n2CF3 ( 4 ) (In the formula, m2 and n2 are numbers satisfying the number average molecular weight range of 1,000 to 10,000.) HOCH2CF2O ( CF2CF2O ) n3 ( CF2O ) m3CF2CH2OH ( 5 ) (In the formula, m3 and n3 are numbers satisfying the number average molecular weight range of 1,000 to 5,000.) is preferably represented by
- Such a component (D) is more useful as the roll workability improver of the present invention.
- the curing agent of component (E) is a combination of an organohydrogenpolysiloxane and a hydrosilylation catalyst.
- the curing agent of the component (E) is an organic peroxide.
- the fluorosilicone rubber composition of the present invention can be cured satisfactorily.
- the present invention provides a cured molding made of the cured fluorosilicone rubber composition described above.
- the fluorosilicone rubber composition of the present invention provides a cured molded product made of a rubber-like elastic body by molding at the same time as heating and curing.
- a silicon atom bonded to a 3,3,3-trifluoropropyl group is contained in an amount of 60 mol% or more and an average degree of polymerization is 2,000 or more.
- organopolysiloxane, reinforcing silica, linear trifluoropropylmethylpolysiloxane having both ends blocked with trifluoropropylmethylhydroxysilyl groups, a linear fluorooxyalkylene group-containing polymer, and a curing agent The present inventors have found that a fluorosilicone rubber composition having excellent roll processability even with a high fluorine content can be obtained by blending a silicone rubber composition containing
- a fluorosilicone rubber composition (A) Those having two or more silicon-bonded alkenyl groups in one molecule, and the number of siloxane units having a fluoroalkyl group is 60 mol% or more of the total number of all siloxane units.
- organopolysiloxane having an average degree of polymerization of 2,000 or more calculated from the weight average molecular weight: 100 parts by mass, (B) reinforcing silica having a specific surface area of 50 m 2 /g or more by the BET method: 5 to 100 parts by mass; (C) linear trifluoropropylmethylpolysiloxane having both ends blocked with trifluoropropylmethylhydroxysilyl groups: 0.1 to 20 parts by mass, A fluorosilicone rubber composition containing (D) a linear fluorooxyalkylene group-containing polymer: 0.01 to 5 parts by mass, and (E) a curing agent: a curing effective amount.
- the present invention is a fluorosilicone rubber composition containing the above components (A) to (E). Each component will be described in detail below.
- Component (A) is an organopolysiloxane that is the main ingredient (base polymer) of the present composition.
- the component (A) organopolysiloxane has two or more silicon-bonded alkenyl groups in one molecule, and the number of siloxane units having a fluoroalkyl group is 60 mol% or more of the total number of all siloxane units. and having an average degree of polymerization of 2,000 or more calculated from the weight average molecular weight.
- the organopolysiloxane of component (A) has an average degree of polymerization of 2,000 or more, preferably in the range of 2,000 to 100,000, more preferably in the range of 2,000 to 50,000. is more preferred, and a range of 2,000 to 20,000 is particularly preferred. If the average degree of polymerization is less than 2000, the fluorosilicone rubber composition of the present invention will not satisfy the properties as a millable rubber, and roll kneadability and the like will be significantly deteriorated, which is not preferable.
- the average degree of polymerization is a value calculated from the polystyrene equivalent weight average molecular weight in GPC (gel permeation chromatography) analysis measured under the following conditions.
- component (A) preferably has a high degree of polymerization (high viscosity) and is a non-liquid organopolysiloxane crude rubber that does not self-flow at room temperature (25°C).
- the number of siloxane units having a fluoroalkyl group is 60 mol% or more, preferably 65 mol% or more, based on the total number of all siloxane units.
- the upper limit is not particularly limited as long as it is 100 mol % or less, preferably less than 100 mol %, more preferably 99.8 mol % or less, and may be 98 mol % or less.
- the siloxane unit having the fluoroalkyl group may have one or two fluoroalkyl groups bonded to the silicon atom.
- Component (A) is preferably represented by the following average compositional formula (1).
- R 1 n SiO (4 ⁇ n)/2 (1) (In the formula, R 1 is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 20 carbon atoms, and n is a positive number of 1.95 to 2.04. is.)
- each R 1 is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, or 1 to 20 carbon atoms. , preferably 1 to 10, more preferably 1 to 6 fluoroalkyl groups.
- Examples of monovalent hydrocarbon groups include alkyl groups such as methyl group, ethyl group, propyl group and butyl group; cycloalkyl groups such as cyclohexyl group; alkenyl groups such as vinyl group, allyl group, butenyl group and hexenyl group; Aryl groups such as a phenyl group and a tolyl group, aralkyl groups such as a ⁇ -phenylpropyl group, and the like can be mentioned. Among these, a methyl group, a vinyl group and a phenyl group are preferred, and a methyl group and a vinyl group are more preferred.
- fluoroalkyl group examples include 3,3,3-trifluoropropyl group, 3,3,4,4,4-pentafluorobutyl group, 3,3,4,4,5,5,5-heptafluoro pentyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, and the like. Among them, a 3,3,3-trifluoropropyl group is preferred.
- n is a positive number of 1.95 to 2.04, preferably a positive number of 1.98 to 2.02.
- n is in the range of 1.95 to 2.04, the resulting cured product exhibits sufficient rubber elasticity.
- the organopolysiloxane of component (A) must have two or more alkenyl groups in one molecule, preferably 2 to 50 alkenyl groups.
- the alkenyl group preferably accounts for 0.001 to 10 mol% of the total number of moles of R 1 , and more preferably 0.01 to 5 mol% of the alkenyl group.
- the alkenyl group is preferably a vinyl group or an allyl group, and particularly preferably a vinyl group.
- the structure of the organopolysiloxane of component (A) is not particularly limited, the main chain consists of repeating diorganosiloxane units (R 1 2 SiO 2/2 ), and both ends of the molecular chain are triorganosiloxy groups ( R 13 SiO 1/2 )-blocked linear diorganopolysiloxanes are preferred.
- R1 is as described above.
- Both ends of the molecular chain of the organopolysiloxane of component (A) are blocked with a group selected from trimethylsiloxy, dimethylvinylsiloxy, dimethylhydroxysiloxy, methyldivinylsiloxy, and trivinylsiloxy. preferable. These terminal groups may be the same at both ends of the molecular chain, or may be different.
- organopolysiloxanes may be used singly or in combination of two or more with different degrees of polymerization and molecular structures.
- the content of component (A) in the fluorosilicone rubber composition of the present invention is preferably 44 to 96% by mass, more preferably 50 to 90% by mass, and more preferably 60 to 80% by mass. More preferred.
- the (B) component, reinforcing silica acts as a filler that imparts excellent mechanical properties to the resulting fluorosilicone rubber composition.
- the reinforcing silica may be either precipitated silica (wet silica) or fumed silica (dry silica), and preferably has a large number of silanol groups on its surface.
- the reinforcing silica must have a specific surface area of 50 m 2 /g or more according to the BET method. It is preferably 100 to 400 m 2 /g. If the specific surface area is less than 50 m 2 /g, the reinforcing effect of the silicone rubber imparted by the component (B) will be insufficient.
- Component (B), the reinforcing silica may be used in an untreated state, or may be surface-treated with an organosilicon compound such as organopolysiloxane, organopolysilazane, chlorosilane, or alkoxysilane, if necessary. good too. Reinforcing silica may be used singly or in combination of two or more.
- the amount of reinforcing silica as component (B) is 5 to 100 parts by mass, preferably 10 to 80 parts by mass, and more preferably 20 to 70 parts by mass per 100 parts by mass of organopolysiloxane as component (A). Department. If the amount of component (B) is more than the above upper limit or less than the above lower limit, not only will the resulting fluorosilicone rubber composition be less processable, but also the silicone rubber obtained by curing the above fluorosilicone rubber composition. Mechanical properties such as tensile strength and tear strength of the cured product become insufficient.
- Component (C) a trifluoropropylmethylhydroxysilyl-blocked linear trifluoropropylmethylpolysiloxane, is used as a dispersibility improver (surface treatment agent) for reinforcing silica in the fluorosilicone rubber composition of the present invention. acts as
- Component (C) is preferably represented by the following average compositional formula (2). (Wherein, x is a positive number from 1 to 35.)
- x is a positive number of 1-35, preferably a positive number of 3-15. If x is 35 or less, the number of parts added for dispersing the reinforcing silica is appropriate, and as a result, the decrease in viscosity can be prevented and excellent roll workability, which is the object of the present invention, can be obtained.
- the amount of component (C) linear trifluoropropylmethylpolysiloxane added is 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of component (A) organopolysiloxane. Department. If the amount of component (C) added is less than 0.1 part by mass, so-called plasticity reversion will occur. The effect of improving workability cannot be obtained.
- Component (D) is a straight-chain fluorooxyalkylene group-containing polymer, and in the fluorosilicone rubber composition of the present invention, it acts as a roll processability improver for the resulting fluorosilicone rubber composition.
- a commercially available product can be used as the (D) component linear fluorooxyalkylene group-containing polymer.
- FOMBLIN manufactured by Solvay Solexis.
- FOMBLIN D2 number average molecular weight 1,500
- FOMBLIN M07 number average molecular weight 5,400
- FOMBLIN M15 number average molecular weight 9,700
- FOMBLIN Z03 number average molecular weight 4,000
- Examples of such polymers include those having structures represented by the following formulas (3), (4) and (5).
- HOCH2O ( CF2O ) m1 ( CF2CF2O ) n1CH2OH ( 3 ) (In the formula, m1 and n1 are numbers satisfying the number average molecular weight range of 1,000 to 5,000.)
- CF3O ( CF2O)m2 ( CF2CF2O )n2CF3 ( 4 ) In the formula, m2 and n2 are numbers satisfying the number average molecular weight range of 1,000 to 10,000.
- HOCH2CF2O ( CF2CF2O ) n3 ( CF2O ) m3CF2CH2OH ( 5 ) (In the formula, m3 and n3 are numbers satisfying the number average molecular weight range of 1,000 to 5,000.)
- the number average molecular weight of the component (D) is the number average molecular weight using perfluoro (polyoxypropylene ethyl ether) as a standard substance in GPC (gel permeation chromatography) analysis measured under the following conditions. Point.
- the blending amount of component (D) is 0.01 to 5 parts by mass, preferably 0.1 to 3 parts by mass, per 100 parts by mass of organopolysiloxane as component (A). If the amount of component (D) is too small, the roll processability of the fluorosilicone rubber composition will not be improved. occurs, which is economically unfavorable.
- the curing agent is not particularly limited as long as it can cure the fluorosilicone rubber composition of the present invention.
- component may be used individually by 1 type, and may use 2 or more types together.
- Component (E) includes, for example, (E-1) organic peroxide curing agent and (E-2) addition reaction type curing agent.
- the amount of component (E) is preferably 0.1 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, and still more preferably 0.2 parts by mass, based on 100 parts by mass of organopolysiloxane (A). ⁇ 10 parts by mass.
- Organic peroxide curing agent (E-1)
- the organic peroxide curing agent include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, p-methylbenzoyl peroxide, o-methyl benzoyl peroxide, 2,4-dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, di-t-butyl peroxide, t-butyl perbenzoate, 1,6 -hexanediol-bis-t-butyl peroxycarbonate and the like.
- the amount of the organic peroxide curing agent is preferably 0.1 to 10 parts by mass, particularly preferably 0.2 to 5 parts by mass, per 100 parts by mass of component (A). If the amount is 0.1 part by mass or more, curing will be sufficient, and if the amount is 10 parts by mass or less, the cured silicone rubber will not turn yellow due to decomposition residues of the organic peroxide.
- E-2) Addition Reaction Curing Agent As (E-2) addition reaction curing agent, an organohydrogenpolysiloxane and a hydrosilylation catalyst are preferably used in combination.
- the organohydrogenpolysiloxane preferably 2 or more, more preferably 3 or more, more preferably 3 to 200, still more preferably about 4 to 100 hydrogen atoms bonded to silicon atoms in one molecule ( That is, if it contains a hydrosilyl group), its structure may be linear, cyclic, branched or three-dimensional network structure.
- the hydrosilyl group may be at the end of the molecular chain, in the middle of the molecular chain, or at both.
- the organohydrogenpolysiloxane may be any organohydrogenpolysiloxane known as a cross-linking agent for addition reaction-curable silicone rubber compositions.
- an organohydrogenpolysiloxane represented by the following average compositional formula (6) can be used.
- R 2 p H q SiO (4-pq)/2 (6) R 2 is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, p is 0 ⁇ p ⁇ 3, q is 0 ⁇ q ⁇ 3, and 0 ⁇ p+q ⁇ 3.
- each R 2 is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, which does not have an aliphatic unsaturated bond.
- alkyl groups such as methyl group, ethyl group and propyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group and tolyl group, benzyl group, 2-phenylethyl group, 2-phenylpropyl group and the like. and the like.
- an alkyl group is preferred, and a 3,3,3-trifluoropropyl group in which some or all of the hydrogen atoms in the alkyl group are substituted with halogen atoms, preferably fluorine atoms, etc., 3,3,4,4, 4-pentafluorobutyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, and 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, etc. may be a fluoroalkyl group of
- p is 0 ⁇ p ⁇ 3, preferably 0.5 ⁇ p ⁇ 2.2, more preferably 1.0 ⁇ p ⁇ 2.0, and q is 0 ⁇ q ⁇ 3, preferably 0.002 ⁇ q ⁇ 1.1, more preferably 0.005 ⁇ q ⁇ 1, and p+q is 0 ⁇ p+q ⁇ 3, preferably 1 ⁇ p+q ⁇ 3, more preferably 1.002 ⁇ It is a positive number that satisfies p+q ⁇ 2.7.
- the organohydrogenpolysiloxane preferably has a viscosity at 25°C of 0.5 to 10,000 mPa ⁇ s, more preferably 1 to 300 mPa ⁇ s.
- viscosity is a value measured at 25° C. using a rotational viscometer according to the method described in JIS K 7117-1:1999.
- organohydrogenpolysiloxanes examples include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris(hydrogendimethylsiloxy)methylsilane, tris(hydrogen dimethylsiloxy)phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane/dimethylsiloxane cyclic copolymer, both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both ends trimethylsiloxy group-blocked dimethylsiloxane/methylhydrogensiloxane Copolymer, dimethylpolysiloxane blocked at both ends by dimethylhydrogensiloxy groups, dimethylsiloxane/methylhydrogensiloxane copolymer blocked at both ends by dimethylhydrogensiloxy groups, copolymer of methylhydrogensiloxane/diphenyl
- the amount of the organohydrogenpolysiloxane compounded is preferably 0.1 to 40 parts by mass per 100 parts by mass of component (A).
- the number ratio of silicon-bonded hydrogen atoms (hydrosilyl groups) is preferably in the range of 0.5 to 10, more preferably 0, per alkenyl group of component (A). A range of 7 to 5 is appropriate. If it is at least the above lower limit, cross-linking will be sufficient, and sufficient mechanical strength will be obtained. Further, when the amount is less than the above upper limit, the physical properties after curing do not deteriorate, and in particular, deterioration of the heat resistance of the silicone rubber and an increase in compression set can be prevented.
- the hydrosilylation catalyst is a catalyst for the hydrosilylation addition reaction between the alkenyl groups of component (A) and the silicon-bonded hydrogen atoms (hydrosilyl groups) of the organohydrogenpolysiloxane.
- Hydrosilylation catalysts include platinum group metal-based catalysts. There are elemental platinum group metals and compounds thereof, and conventionally known catalysts for addition reaction-curable silicone rubber compositions may be used. For example, particulate platinum metal adsorbed on a carrier such as silica, alumina or silica gel, platinum catalyst such as platinic chloride, chloroplatinic acid, alcoholic solution of chloroplatinic acid hexahydrate, palladium catalyst, rhodium catalyst, etc. platinum or platinum compounds (platinum catalysts) are preferred.
- the amount of catalyst to be added should be sufficient to promote the above addition reaction. Generally, it is used in the range of 1 mass ppm to 1 mass %, preferably 10 to 500 mass ppm, based on the organopolysiloxane of the component (A) in terms of platinum group metal content. If the amount of the catalyst is at least the above lower limit, the addition reaction will be sufficiently accelerated and curing will be sufficient. If the content is equal to or less than the above upper limit, it is economical because the effect of accelerating the reaction can be obtained according to the amount added.
- the fluorosilicone rubber composition of the present invention may optionally contain quartz powder, crystalline silica, non-reinforcing silica such as diatomaceous earth, calcium carbonate, acetylene black, furnace black, channel black, and the like.
- Heat resistance improvers such as carbon black, colorants, iron oxide and cerium oxide, flame retardant improvers such as platinum, titanium oxide and triazole compounds, acid acceptors, thermal conductivity improvers such as alumina and boron nitride, mold release agents, etc. may be added.
- the fluorosilicone rubber composition of the present invention can be obtained by uniformly mixing the above components using a mixing device such as a two-roll mill, Banbury mixer, Dow mixer (kneader), etc. (A) , (B), (C), and (D) to prepare a base compound, and then blend the (E) component.
- a mixing device such as a two-roll mill, Banbury mixer, Dow mixer (kneader), etc.
- the base compound is preferably prepared by heat treatment at 20 to 250°C, particularly 50 to 200°C, for 0.1 to 10 hours, particularly 0.1 to 5 hours.
- the fluorosilicone rubber composition of the present invention can be heat-cured and molded at the same time to obtain a cured molding consisting of a rubber-like elastic body (cured silicone rubber).
- the method for curing the fluorosilicone rubber composition is not particularly limited, but any method may be used as long as it applies sufficient heat to decompose the curing agent and vulcanize the fluorosilicone rubber composition.
- the temperature conditions for curing are usually 80 to 400° C., particularly 100 to 200° C., for 3 seconds to 160 minutes, particularly 3 seconds to 20 minutes, although they depend on the curing method.
- the molding method is not particularly limited, and for example, molding methods such as continuous vulcanization by extrusion molding, press molding (pressure molding), and injection molding can be employed. Further, if necessary, secondary vulcanization may be performed at 150 to 250° C. for about 1 to 10 hours.
- the (A) component organopolysiloxane (organopolysiloxane crude rubber) used in the examples and comparative examples is as follows.
- the mol % of siloxane units in the following is the ratio of each siloxane unit to the total number of siloxane units.
- Organopolysiloxane raw rubber 3,3,3-trifluoropropylmethylsiloxane unit 99.825 mol%, methylvinylsiloxane unit 0.125 mol%, dimethylvinylsiloxy unit 0.05 mol%, average polymerization Organopolysiloxane raw rubber with a degree of 4,000
- Example 1 (A) 100 parts by mass of organopolysiloxane raw rubber, (B) 40 parts by mass of fumed silica having a BET specific surface area of 200 m 2 /g (Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.), (C1) trifluoropropylmethyl at both ends 6.0 parts by mass of linear 3,3,3-trifluoropropylmethylpolysiloxane having a hydroxysilyl group, an average degree of polymerization of 4, and a viscosity of 15 mPa s at 25° C.
- (D1) 0.3 part by mass of a chain-shaped fluorooxyalkylene group-containing polymer (trade name “FOMBLIN D2” manufactured by Solvay Solexis, number average molecular weight: 1,500) was kneaded in a kneader and heated to 150° C. under mixing with a kneader.
- a base compound (1) was prepared by heat-treating for 2 hours.
- Example 2 A silicone rubber composition was prepared in the same manner as in Example 1, except that (D1) the linear fluorooxyalkylene group-containing polymer (trade name "FOMBLIN D2”) was added in an amount of 0.5 parts by mass. got The obtained composition was subjected to a roll workability test, which will be described later.
- D1 the linear fluorooxyalkylene group-containing polymer (trade name "FOMBLIN D2”) was added in an amount of 0.5 parts by mass. got The obtained composition was subjected to a roll workability test, which will be described later.
- Example 3 In Example 1, (D2) a linear fluorooxyalkylene group-containing polymer (trade name “FOMBLIN M07” Solvay A silicone rubber composition was obtained in the same manner as in Example 1, except that 0.3 parts by mass of Solexis, number average molecular weight: 5,400) was used. The obtained composition was subjected to a roll workability test, which will be described later.
- a linear fluorooxyalkylene group-containing polymer trade name “FOMBLIN M07” Solvay
- Example 1 a silicone rubber composition was prepared in the same manner as in Example 1 except that no linear fluorooxyalkylene group-containing polymer was added, and the resulting composition was subjected to the roll processability test described later. rice field.
- Example 2 A silicone rubber composition was prepared in the same manner as in Example 1, except that the linear trifluoropropylmethylpolysiloxane of component (C1) was replaced with 6.0 parts by mass of diphenylsilanediol as component (C2). prepared. The obtained composition was subjected to a roll workability test, which will be described later.
- Table 1 below shows the composition of each example and comparative example and the results of the roll workability test.
- the present invention is not limited to the above embodiments.
- the above-described embodiment is an example, and any device having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect is the present invention. included in the technical scope of
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Abstract
L'invention concerne une composition de caoutchouc de fluorosilicone qui comprend : (A) 100 parties en masse d'un organopolysiloxane qui possède au moins deux groupes alcényle liés à un atome de silicium dans chaque molécule, dont le nombre d'unités siloxane possédant un groupe fluoroalkyle est supérieur ou égal à 60% en moles du nombre total de l'ensemble des unités siloxane, et qui présente un degré moyen de polymérisation calculé à partir de sa masse moléculaire moyenne en poids supérieur ou égal à 2000 ; (B) 5 à 100 parties en masse d'une silice de renforcement possédant une surface spécifique supérieure ou égale à 50m2/g selon la méthode BET ; (C) 0,1 à 20 parties en masse d'un trifluoropropylméthylpolysiloxane à chaîne droite dont les deux extrémités sont bloquées par un trifluoropropylméthylhydroxysilyle ; et (D) 0,01 à 5 parties en masse d'un polymère comprenant un groupe groupe fluorooxyalkylène à chaîne droite ; et (E) une quantité efficace pour le durcissement d'un agent durcissant. Par conséquent, l'invention fournit une composition de caoutchouc de fluorosilicone excellente en termes de propriétés d'usinage au rouleau y compris en cas de teneur élevée en fluor.
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JPH05311078A (ja) * | 1992-05-11 | 1993-11-22 | Toshiba Silicone Co Ltd | フルオロシリコーンゴム組成物およびその製造方法 |
JP2020037629A (ja) * | 2018-09-03 | 2020-03-12 | 信越化学工業株式会社 | キーパッド作製用シリコーンゴム組成物及びキーパッド |
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JP2020037629A (ja) * | 2018-09-03 | 2020-03-12 | 信越化学工業株式会社 | キーパッド作製用シリコーンゴム組成物及びキーパッド |
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