JP7047901B2 - Additive curable liquid silicone rubber composition for air bags and air bags - Google Patents
Additive curable liquid silicone rubber composition for air bags and air bags Download PDFInfo
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- JP7047901B2 JP7047901B2 JP2020516102A JP2020516102A JP7047901B2 JP 7047901 B2 JP7047901 B2 JP 7047901B2 JP 2020516102 A JP2020516102 A JP 2020516102A JP 2020516102 A JP2020516102 A JP 2020516102A JP 7047901 B2 JP7047901 B2 JP 7047901B2
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- silicone rubber
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- 239000000203 mixture Substances 0.000 title claims description 81
- 229920002379 silicone rubber Polymers 0.000 title claims description 50
- 239000004944 Liquid Silicone Rubber Substances 0.000 title claims description 29
- 239000000654 additive Substances 0.000 title claims description 4
- 230000000996 additive effect Effects 0.000 title claims description 4
- -1 siloxane unit Chemical group 0.000 claims description 78
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 77
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000000843 powder Substances 0.000 claims description 37
- 239000000377 silicon dioxide Substances 0.000 claims description 35
- 125000003342 alkenyl group Chemical group 0.000 claims description 34
- 229910052710 silicon Inorganic materials 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 27
- 229920001296 polysiloxane Polymers 0.000 claims description 27
- 239000012756 surface treatment agent Substances 0.000 claims description 24
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 23
- 239000004744 fabric Substances 0.000 claims description 21
- 239000010703 silicon Substances 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 125000000524 functional group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000005046 Chlorosilane Substances 0.000 claims description 9
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 9
- 238000004438 BET method Methods 0.000 claims description 8
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 6
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 6
- 150000003609 titanium compounds Chemical class 0.000 claims description 5
- 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 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000003755 zirconium compounds Chemical class 0.000 claims description 4
- OWMFJACZEUJGTQ-UHFFFAOYSA-N [dimethyl-(trimethylsilylamino)silyl]ethene Chemical compound C[Si](C)(C)N[Si](C)(C)C=C OWMFJACZEUJGTQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 3
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 claims description 3
- ZIFXYFOVERKZLG-UHFFFAOYSA-N chloro-methyl-(2-phenylethenyl)silane Chemical compound C[SiH](Cl)C=CC1=CC=CC=C1 ZIFXYFOVERKZLG-UHFFFAOYSA-N 0.000 claims description 3
- MAYIDWCWWMOISO-UHFFFAOYSA-N dichloro-bis(ethenyl)silane Chemical compound C=C[Si](Cl)(Cl)C=C MAYIDWCWWMOISO-UHFFFAOYSA-N 0.000 claims description 3
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 claims description 3
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 3
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 3
- NCLNPSIKIBQDBM-UHFFFAOYSA-N [[[bis(ethenyl)-methylsilyl]amino]-ethenyl-methylsilyl]ethene Chemical compound C=C[Si](C=C)(C)N[Si](C)(C=C)C=C NCLNPSIKIBQDBM-UHFFFAOYSA-N 0.000 claims description 2
- 238000013006 addition curing Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 description 23
- 239000004945 silicone rubber Substances 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 14
- 239000004205 dimethyl polysiloxane Substances 0.000 description 14
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 14
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 14
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000001723 curing Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 150000003377 silicon compounds Chemical class 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 125000003700 epoxy group Chemical group 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000006087 Silane Coupling Agent Substances 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 125000005388 dimethylhydrogensiloxy group Chemical group 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910002012 Aerosil® Inorganic materials 0.000 description 4
- 229910002018 Aerosil® 300 Inorganic materials 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 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 4
- 238000004898 kneading Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 4
- 239000012763 reinforcing filler Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 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 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 2
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004593 Epoxy Substances 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
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 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 2
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 229940093858 ethyl acetoacetate Drugs 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
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- 239000011261 inert gas Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000005375 organosiloxane group Chemical group 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
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 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 2
- 229960005235 piperonyl butoxide Drugs 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
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- 239000005020 polyethylene terephthalate Substances 0.000 description 2
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- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 125000005369 trialkoxysilyl 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
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- 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
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- 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
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- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ASGKDLGXPOIMTM-UHFFFAOYSA-N diethoxy-methyl-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](C)(OCC)OCC)CCC2OC21 ASGKDLGXPOIMTM-UHFFFAOYSA-N 0.000 description 1
- QUSVCBQRCPWRBV-UHFFFAOYSA-N diethoxy-methyl-[2-(7-oxabicyclo[4.1.0]heptan-5-yl)ethyl]silane Chemical compound CCO[Si](C)(OCC)CCC1CCCC2OC12 QUSVCBQRCPWRBV-UHFFFAOYSA-N 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 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
- SLQTWNAJXFHMHM-UHFFFAOYSA-N dimethoxy-methyl-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](C)(OC)OC)CCC2OC21 SLQTWNAJXFHMHM-UHFFFAOYSA-N 0.000 description 1
- TUYGQPLOWCVRDY-UHFFFAOYSA-N dimethoxy-methyl-[2-(7-oxabicyclo[4.1.0]heptan-5-yl)ethyl]silane Chemical compound CO[Si](C)(OC)CCC1CCCC2OC12 TUYGQPLOWCVRDY-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 1
- YAPKLBSSEAZLGL-UHFFFAOYSA-N ethoxy(propyl)silane Chemical compound CCC[SiH2]OCC YAPKLBSSEAZLGL-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
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000005417 glycidoxyalkyl group Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000001867 hydroperoxy group Chemical group [*]OO[H] 0.000 description 1
- FGOLZCPMTWJPOU-UHFFFAOYSA-N hydroxy-dimethyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C)O FGOLZCPMTWJPOU-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002688 maleic acid derivatives 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
- 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
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 230000002093 peripheral effect Effects 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
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].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 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
- 239000012215 seam sealant Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- FPLNVLLOPKZBQX-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-5-yl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCC1CCCC2OC12 FPLNVLLOPKZBQX-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- HUZZQXYTKNNCOU-UHFFFAOYSA-N triethyl(methoxy)silane Chemical compound CC[Si](CC)(CC)OC HUZZQXYTKNNCOU-UHFFFAOYSA-N 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R21/00—Arrangements or fittings on vehicles for protecting or preventing injuries to occupants or pedestrians in case of accidents or other traffic risks
- B60R21/02—Occupant safety arrangements or fittings, e.g. crash pads
- B60R21/16—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags
- B60R21/23—Inflatable members
- B60R21/235—Inflatable members characterised by their material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Air Bags (AREA)
- Paints Or Removers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、エアーバッグを作製するのに好適なエアーバッグ用付加硬化型液状シリコーンゴム組成物及びエアーバッグに関する。 The present invention relates to an addition-curable liquid silicone rubber composition for an air bag and an air bag suitable for producing an air bag.
従来、繊維表面にゴム被膜を形成させることを目的としたエアーバッグ用シリコーンゴム組成物が提案されている。シリコーンゴム被膜を有するエアーバッグは気密性及び低燃焼速度性に優れるため、自動車等のエアーバッグとして好適に用いられている。 Conventionally, a silicone rubber composition for an air bag has been proposed for the purpose of forming a rubber film on the fiber surface. An air bag having a silicone rubber film is excellent in airtightness and low combustion speed, and is therefore suitably used as an air bag for automobiles and the like.
このようなエアーバッグ用シリコーンゴム組成物としては、組成物のチキソ比を適正なものにすることにより、コーティング材の基布への塗工性に優れた付加硬化型液状シリコーンゴム組成物（特開２００８－０７４８８１号公報：特許文献１）や、レジン状ポリシロキサンを含有し、シロキサン成分をシリカ、表面処理剤、水とともに事前に混合することで、低燃焼速度性に優れた付加硬化型液状シリコーンゴム組成物（特開２０１３－２０９５１７号公報：特許文献２）、及び、Ｑ単位を含有する分岐鎖オルガノポリシロキサンをベースポリマーとする付加硬化型シリコーンゴム組成物を基布にコーティングすることにより気密性に優れたエアーバッグを製造する方法（特表２０１３－５１６５２１号公報：特許文献３）などが開示されている。 As such a silicone rubber composition for an air bag, an addition-curable liquid silicone rubber composition having excellent coatability to a base cloth of a coating material by making the composition ratio appropriate (specially). Kai 2008-074881A: Additive-curing liquid containing resin-like polysiloxane and premixed with silica, surface treatment agent, and water to have excellent low combustion rate. By coating the base cloth with a silicone rubber composition (Japanese Patent Laid-Open No. 2013-209517: Patent Document 2) and an addition-curable silicone rubber composition using a branched-chain organopolysiloxane containing a Q unit as a base polymer. A method for producing an air bag having excellent airtightness (Japanese Patent Laid-Open No. 2013-516521: Patent Document 3) and the like are disclosed.
しかし、フロントピラーからルーフサイドに沿って収納され、衝突時や車両の転倒時に頭部の保護や飛び出しを防ぐために一定膨脹時間を維持することが要求されるカーテンエアーバッグは、近年、エアーバッグモジュールの低重量化及びコンパクト化のためにコーティング材の薄膜化が求められており、これらの組成物を基布にコーティングして製造したエアーバッグは、インフレーターガスの洩れを抑え、膨脹時間の持続性を十分に満足させるものではなかった。 However, in recent years, curtain airbags, which are stored along the roof side from the front pillars and are required to maintain a constant expansion time to protect the head and prevent popping out in the event of a collision or a vehicle tipping over, have become an air bag module. In order to reduce the weight and compactness of the air bag, it is required to reduce the thickness of the coating material, and the air bag manufactured by coating the base fabric with these compositions suppresses the leakage of inflator gas and sustains the expansion time. Was not fully satisfactory.
本発明は、上記事情に鑑みてなされたものであって、エアーバッグの展開時にインフレーターガスの洩れを抑え、膨脹時間の持続性に優れたエアーバッグ用付加硬化型液状シリコーンゴム組成物及びエアーバッグを提供することを目的とする。 The present invention has been made in view of the above circumstances, and is an addition-curable liquid silicone rubber composition for an air bag and an air bag, which suppresses leakage of inflator gas when the air bag is deployed and has excellent durability of expansion time. The purpose is to provide.
本発明者らは、上記目的を達成するべく鋭意検討を行った結果、後述する（Ａ）～（Ｆ）成分を必須成分とした液状シリコーンゴム組成物において、特に（Ｄ）成分のケイ素原子に結合したアルケニル基を含有する表面処理剤で（Ｃ）成分のＢＥＴ法比表面積が５０ｍ2／ｇ以上であるシリカ微粉末を表面処理したものを含有させることにより、この液状シリコーンゴム組成物をエアーバッグ用基布表面に所定量塗布し、これを加熱硬化させて得られるエアーバッグが、エアーバッグの展開時にインフレーターガスの洩れを抑え、膨脹時間の持続性に優れたものであることを見出し、本発明をなすに至った。As a result of diligent studies to achieve the above object, the present inventors have made a liquid silicone rubber composition containing the components (A) to (F) described later as essential components, particularly the silicon atom of the component (D). This liquid silicone rubber composition is air-treated by containing a surface-treated silica fine powder having a BET method specific surface area of the component (C) of 50 m 2 / g or more, which is a surface treatment agent containing a bonded alkenyl group. We found that an air bag obtained by applying a predetermined amount to the surface of the base cloth for a bag and heating and curing it suppresses leakage of inflator gas when the air bag is deployed, and has excellent durability of expansion time. This has led to the present invention.
従って、本発明は、下記エアーバッグ用付加硬化型液状シリコーンゴム組成物及びエアーバッグを提供する。
１．（Ａ）１分子中に２個以上のケイ素原子に結合したアルケニル基を含有する重合度が１００～２，０００のオルガノポリシロキサン：１００質量部、
（Ｂ）１分子中に少なくとも２個のケイ素原子に結合した水素原子（ＳｉＨ基）を含有するオルガノハイドロジェンポリシロキサン：本成分中に含まれるＳｉＨ基が、（Ａ）成分及び下記（Ｄ）成分中に含まれるケイ素原子結合アルケニル基の合計１モル当たり、１～１０モルとなる量、
（Ｃ）ＢＥＴ法比表面積が５０ｍ2／ｇ以上であるシリカ微粉末：１～５０質量部、
（Ｄ）１分子中にビニル基を１個以上有するクロロシラン類、シラザン類、及び下記式（１）又は（２）で表わされる有機ケイ素化合物から選ばれるものである表面処理剤（但し、（Ａ）成分を除く。また、上記シラザン類のうち、１，３－ジビニル－１，１，３，３－テトラメチルジシラザン及び１，１，３，３－テトラビニル－１，３－ジメチルジシラザンを除く。）
（Ｅ）ヒドロシリル化反応用触媒：（Ａ）～（Ｄ）の合計質量に対して、触媒金属元素の質量換算で１～５００ｐｐｍ、
（Ｆ）接着性付与官能基を含有する有機ケイ素化合物（但し、（Ａ）、（Ｂ）、（Ｄ）成分を除く。）：０．１～１０質量部
を必須成分とすることを特徴とするエアーバッグ用付加硬化型液状シリコーンゴム組成物。
２．（Ｄ）成分の、１分子中にビニル基を１個以上有するクロロシラン類が、ジメチルビニルクロロシラン、メチルビニルジクロロシラン、ビニルトリクロロシラン、ジビニルジクロロシラン、及びメチルフェニルビニルクロロシランから選ばれるものである上記１に記載のエアーバッグ用付加硬化型液状シリコーンゴム組成物。
３．（Ｄ）成分の、１分子中にビニル基を１個以上有するシラザン類が、１－ビニル－１，１，３，３，３－ペンタメチルジシラザン、及び１，１，１，３，５，５，５－ヘプタメチル－３－ビニルトリシラザンから選ばれるものである上記１に記載のエアーバッグ用付加硬化型液状シリコーンゴム組成物。
４．（Ｆ）成分が、アルケニル基及び／又はＳｉＨ基を含む場合、組成物中の（Ａ）成分、（Ｄ）成分、及び（Ｆ）成分中に含まれるケイ素原子結合アルケニル基の合計１モル当たり、（Ｂ）成分及び（Ｆ）成分中に含まれるＳｉＨ基の合計量が１～１０モルとなる量が配合されてなる上記１～３のいずれかに記載のエアーバッグ用付加硬化型液状シリコーンゴム組成物。
５．更に、（Ｇ）成分として、有機チタニウム化合物、有機ジルコニウム化合物、及び有機アルミニウム化合物から選ばれる少なくとも１種の縮合触媒を、（Ａ）成分１００質量部に対して、０．１～５質量部含有することを特徴とする上記１～４のいずれかに記載のエアーバッグ用付加硬化型液状シリコーンゴム組成物。
６．エアーバッグ用基布上に、上記１～５のいずれかに記載のエアーバッグ用付加硬化型液状シリコーンゴム組成物の硬化被膜を有することを特徴とするエアーバッグ。
Therefore, the present invention provides the following addition-curable liquid silicone rubber composition for air bag and air bag.
1. 1. (A) Organopolysiloxane having a degree of polymerization of 100 to 2,000 containing an alkenyl group bonded to two or more silicon atoms in one molecule: 100 parts by mass,
(B) Organohydrogenpolysiloxane containing a hydrogen atom (SiH group) bonded to at least two silicon atoms in one molecule: The SiH group contained in this component is the component (A) and the following (D). An amount of 1 to 10 mol per 1 mol of the total silicon atom-bonded alkenyl groups contained in the component,
(C) BET method Silica fine powder having a specific surface area of 50 m 2 / g or more: 1 to 50 parts by mass,
(D) A surface treatment agent selected from chlorosilanes and silazanes having one or more vinyl groups in one molecule, and an organosilicon compound represented by the following formula (1) or (2) (however, (A). ) Components are excluded. Of the above silazanes, 1,3-divinyl-1,1,3,3-tetramethyldisilazane and 1,1,3,3-tetravinyl-1,3-dimethyldisilazane are excluded. Except for. )
(E) Catalyst for hydrosilylation reaction: 1 to 500 ppm in terms of mass of the catalyst metal element with respect to the total mass of (A) to (D).
(F) Organosilicon compound containing an adhesive-imparting functional group (excluding the components (A), (B) and (D)): 0.1 to 10 parts by mass as an essential component. Additive curable liquid silicone rubber composition for air bags.
2. 2. Chlorosilanes having one or more vinyl groups in one molecule of the component (D) are selected from dimethylvinylchlorosilane, methylvinyldichlorosilane, vinyltrichlorosilane, divinyldichlorosilane, and methylphenylvinylchlorosilane. The addition-curable liquid silicone rubber composition for an air bag according to 1.
3. 3. The silazanes having one or more vinyl groups in one molecule of the component (D) are 1-vinyl-1,1,3,3,3-pentamethyldisilazane and 1,1,1,3,5. , 5,5-Heptamethyl-3-vinyltrisilazane, the addition-curable liquid silicone rubber composition for an air bag according to 1 above.
4 . When the component (F) contains an alkenyl group and / or a SiH group, a total of 1 mol of the silicon atom-bonded alkenyl group contained in the component (A), the component (D), and the component (F) in the composition. , The addition-curable liquid silicone for an air bag according to any one of 1 to 3 above, wherein the total amount of SiH groups contained in the component (B) and the component (F) is 1 to 10 mol. Rubber composition.
5 . Further, as the component (G), at least one condensation catalyst selected from an organic titanium compound, an organic zirconium compound, and an organoaluminum compound is contained in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the component (A). The addition-curable liquid silicone rubber composition for an air bag according to any one of 1 to 4 above.
6 . An air bag characterized by having a cured film of the addition-curable liquid silicone rubber composition for an air bag according to any one of 1 to 5 above on a base cloth for an air bag.
本発明によれば、エアーバッグの展開時にインフレーターガスの洩れが抑制され、膨脹時間の持続性に優れたエアーバッグ用付加硬化型液状シリコーンゴム組成物、及びこの組成物を基布にコーティング、硬化してなる機械的強度にも優れたエアーバッグが得られる。 According to the present invention, an addition-curing liquid silicone rubber composition for an air bag, which suppresses leakage of inflator gas when the air bag is deployed and has excellent durability of expansion time, and a coating and curing of this composition on a base fabric. An air bag with excellent mechanical strength can be obtained.
以下、本発明につき、更に詳しく説明する。なお、本明細書中において、粘度は、２５℃において、ＪＩＳ Ｋ ７１１７－１：１９９９に記載の方法で回転粘度計により測定した値である。また、重合度は、トルエンを展開溶媒としてＧＰＣ（ゲルパーミエーションクロマトグラフィ）分析におけるポリスチレン換算の重量平均重合度（重量平均分子量）として求めた値である。 Hereinafter, the present invention will be described in more detail. In the present specification, the viscosity is a value measured by a rotational viscometer by the method described in JIS K 7117-1: 1999 at 25 ° C. The degree of polymerization is a value obtained as a polystyrene-equivalent weight average degree of polymerization (weight average molecular weight) in GPC (gel permeation chromatography) analysis using toluene as a developing solvent.
＜付加硬化型液状シリコーンゴム組成物＞
本発明のエアーバッグ用付加硬化型液状シリコーンゴム組成物は、以下の（Ａ）～（Ｆ）成分を含有してなるものであって、室温（２５℃）で液状のものである。以下、各成分について詳細に説明する。<Additional curing type liquid silicone rubber composition>
The addition-curable liquid silicone rubber composition for an air bag of the present invention contains the following components (A) to (F) and is liquid at room temperature (25 ° C.). Hereinafter, each component will be described in detail.
［（Ａ）成分］
（Ａ）成分のオルガノポリシロキサンは、１分子中にケイ素原子に結合したアルケニル基を２個以上含有する２５℃で液状のオルガノポリシロキサンであり、本発明にかかる組成物のベースポリマー（主剤）である。[(A) component]
The organopolysiloxane as a component (A) is an organopolysiloxane liquid at 25 ° C. containing two or more alkenyl groups bonded to silicon atoms in one molecule, and is a base polymer (main agent) of the composition according to the present invention. Is.
（Ａ）成分の分子構造としては、例えば、直鎖状、環状、分岐鎖状等が挙げられるが、主鎖が基本的にジオルガノシロキサン単位の繰り返しからなり、分子鎖両末端がトリオルガノシロキシ基で封鎖された直鎖状のジオルガノポリシロキサンが好ましい。また、（Ａ）成分のオルガノポリシロキサンの分子構造が直鎖状又は分岐鎖状である場合、該オルガノポリシロキサンの分子中においてアルケニル基が結合するケイ素原子の位置は、分子鎖末端（即ち、トリオルガノシロキシ基）及び分子鎖途中（即ち、分子鎖非末端に位置する２官能性のジオルガノシロキサン単位又は３官能性のモノオルガノシルセスキオキサン単位）のどちらか一方でも両方でもよい。（Ａ）成分として、特に好ましいものは、少なくとも分子鎖両末端のケイ素原子に結合したアルケニル基を含有する直鎖状のジオルガノポリシロキサンである。 Examples of the molecular structure of the component (A) include linear, cyclic, branched chain, etc., but the main chain basically consists of repeating diorganosiloxane units, and both ends of the molecular chain are triorganosyloxy. Linear diorganopolysiloxanes sealed with a group are preferred. When the molecular structure of the organopolysiloxane component (A) is linear or branched, the position of the silicon atom to which the alkenyl group is bonded in the molecule of the organopolysiloxane is the terminal of the molecular chain (that is, that is, Either one or both of the triorganosyloxy group) and the middle of the molecular chain (that is, the bifunctional diorganosiloxane unit or the trifunctional monoorganosylsesquioxane unit located at the non-terminal of the molecular chain) may be used. Particularly preferred as the component (A) is a linear diorganopolysiloxane containing at least an alkenyl group bonded to silicon atoms at both ends of the molecular chain.
（Ａ）成分中のケイ素原子に結合したアルケニル基としては、例えば、通常、炭素数２～８、好ましくは炭素数２～４のものが挙げられる。その具体例としては、ビニル基、アリル基、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基、シクロヘキセニル基、ヘプテニル基等が挙げられ、特にビニル基であることが好ましい。 Examples of the alkenyl group bonded to the silicon atom in the component (A) include those having 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms. Specific examples thereof include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclohexenyl group, a heptenyl group and the like, and a vinyl group is particularly preferable.
（Ａ）成分中のケイ素原子に結合したアルケニル基の含有量は、ケイ素原子に結合した１価の有機基（即ち、非置換若しくは置換の１価炭化水素基）全体に対して、０．００１～１０モル％であることが好ましく、特に０．０１～５モル％程度であることが好ましい。 The content of the alkenyl group bonded to the silicon atom in the component (A) is 0.001 with respect to the entire monovalent organic group bonded to the silicon atom (that is, the unsubstituted or substituted monovalent hydrocarbon group). It is preferably about 10 mol%, and particularly preferably about 0.01 to 5 mol%.
（Ａ）成分のアルケニル基以外のケイ素原子に結合する１価の有機基としては、例えば、互いに同一又は異種の非置換若しくは置換の、通常、炭素数１～１２、好ましくは炭素数１～１０の１価炭化水素基が挙げられる。１価の有機基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、シクロヘキシル基、ヘプチル基等のアルキル基；フェニル基、トリル基、キシリル基、ナフチル基等のアリール基；ベンジル基、フェネチル基等のアラルキル基；クロロメチル基、３－クロロプロピル基、３，３，３－トリフルオロプロピル基等のハロゲン置換アルキル基などが挙げられ、特に、メチル基、フェニル基であることが好ましい。 The monovalent organic group bonded to the silicon atom other than the alkenyl group of the component (A) is, for example, the same or different substituents, usually 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms. The monovalent hydrocarbon group of is mentioned. Specific examples of the monovalent organic group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group and a heptyl group; a phenyl group, a trill group, a xsilyl group and a naphthyl group. Alaryl groups such as benzyl group and phenethyl group; halogen-substituted alkyl groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group, and the like, in particular, methyl group. , Preferably a phenyl group.
（Ａ）成分の重合度は、１００～２，０００であり、より好ましくは１５０～１，５００である。重合度が１００よりも低いと、得られるシリコーンゴムの機械的特性が悪くなることがあり、また重合度が２，０００より大きいと、得られるシリコーンゴム組成物の粘度が高くなり、コーティング作業性が悪化することがある。 The degree of polymerization of the component (A) is 100 to 2,000, more preferably 150 to 1,500. If the degree of polymerization is lower than 100, the mechanical properties of the obtained silicone rubber may deteriorate, and if the degree of polymerization is greater than 2,000, the viscosity of the obtained silicone rubber composition becomes high, and the coating workability is increased. May get worse.
（Ａ）成分のオルガノポリシロキサンの具体例としては、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖メチルビニルポリシロキサン、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端ジメチルビニルシロキシ基封鎖メチルビニルポリシロキサン、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端ジビニルメチルシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端ジビニルメチルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、分子鎖両末端トリビニルシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端トリビニルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、及びこれらのオルガノポリシロキサンの２種以上からなる混合物が挙げられる。
（Ａ）成分のオルガノポリシロキサンは、１種単独で用いても２種以上を併用してもよい。Specific examples of the organopolysiloxane of the component (A) include a trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer at both ends of the molecular chain, a trimethylsiloxy group-blocked methylvinylpolysiloxane at both ends of the molecular chain, and trimethyl at both ends of the molecular chain. Syroxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, molecular chain double-ended dimethylvinyl syroxy group-blocked dimethylpolysiloxane, molecular chain double-ended dimethylvinylsiloxy group-blocked methylvinylpolysiloxane, molecular chain double-ended dimethylvinyl Syloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain double-ended dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, molecular chain double-ended divinylmethylsiloxy group-blocked dimethylpolysiloxane, molecule Divinylmethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer at both ends of the chain, trivinylsiloxy group-blocked dimethylpolysiloxane at both ends of the molecular chain, trivinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer at both ends of the molecular chain, And a mixture of two or more of these organopolysiloxanes.
The organopolysiloxane of the component (A) may be used alone or in combination of two or more.
［（Ｂ）成分］
（Ｂ）成分のオルガノハイドロジェンポリシロキサンは、主に（Ａ）成分中のアルケニル基とヒドロシリル化付加反応し、架橋剤（硬化剤）として作用するものである。
（Ｂ）成分の分子構造としては、例えば、直鎖状、環状、分岐鎖状、三次元網状（樹脂状）構造等各種のものが挙げられるが、１分子中に少なくとも２個、好ましくは３個以上のケイ素原子に結合した水素原子（ＳｉＨ基）を有する必要があり、通常２～３００個、好ましくは３～２００個、より好ましくは４～１００個のＳｉＨ基を有することが望ましく、２５℃で液状のものが使用される。このようなＳｉＨ基は、分子鎖末端、分子鎖途中のいずれに位置していてもよく、またこの両方に位置するものであってもよい。[(B) component]
The organohydrogenpolysiloxane of the component (B) mainly reacts with the alkenyl group in the component (A) by hydrosilylation addition reaction and acts as a cross-linking agent (curing agent).
Examples of the molecular structure of the component (B) include various structures such as linear, cyclic, branched chain, and three-dimensional network (resin-like) structures, and at least two, preferably three, are included in one molecule. It is necessary to have a hydrogen atom (SiH group) bonded to one or more silicon atoms, and it is usually preferable to have 2 to 300, preferably 3 to 200, more preferably 4 to 100 SiH groups, 25. Liquid ones are used at ° C. Such a SiH group may be located at the end of the molecular chain or in the middle of the molecular chain, or may be located at both of them.
このオルガノハイドロジェンポリシロキサンとしては、下記平均組成式（３）で示されるものを用いることができる。
式（３）中、Ｒ3は互いに同一又は異種の、アルケニル基等の脂肪族不飽和結合を除く、好ましくは炭素数１～１０の、ケイ素原子に結合した非置換若しくは置換の１価炭化水素基であり、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、シクロヘキシル基、オクチル基、ノニル基、デシル基等のアルキル基、フェニル基、トリル基、キシリル基、ナフチル基等のアリール基、ベンジル基、フェニルエチル基、フェニルプロピル基等のアラルキル基や、これらの基の水素原子の一部又は全部をフッ素、臭素、塩素等のハロゲン原子で置換したもの、例えばクロロメチル基、クロロプロピル基、ブロモエチル基、トリフルオロプロピル基等が挙げられる。Ｒ3としては、好ましくはアルキル基、アリール基であり、より好ましくはメチル基、フェニル基である。また、ａは０．７～２．１、ｂは０．００１～１．０で、かつａ＋ｂが０．８～３．０を満足する正数であり、好ましくはａは１．０～２．０、ｂは０．０１～１．０で、かつａ＋ｂが１．５～２．５を満足する正数である。In formula (3), R 3 is an unsubstituted or substituted monovalent hydrocarbon bonded to a silicon atom, preferably having 1 to 10 carbon atoms, excluding aliphatic unsaturated bonds such as alkenyl groups, which are the same or different from each other. 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, decyl group and the like. Alkyl group such as alkyl group, phenyl group, trill group, xylyl group, naphthyl group, aralkyl group such as benzyl group, phenylethyl group and phenylpropyl group, and some or all of the hydrogen atoms of these groups are fluorine. Examples thereof include those substituted with a halogen atom such as bromine and chlorine, such as a chloromethyl group, a chloropropyl group, a bromoethyl group and a trifluoropropyl group. R 3 is preferably an alkyl group or an aryl group, and more preferably a methyl group or a phenyl group. Further, a is 0.7 to 2.1, b is 0.001 to 1.0, and a + b is a positive number satisfying 0.8 to 3.0, preferably a is 1.0 to 2. .0 and b are 0.01 to 1.0, and a + b is a positive number satisfying 1.5 to 2.5.
このような（Ｂ）成分のオルガノハイドロジェンポリシロキサンとしては、１，１，３，３－テトラメチルジシロキサン、１，３，５，７－テトラメチルシクロテトラシロキサン、トリス（ハイドロジェンジメチルシロキシ）メチルシラン、トリス（ハイドロジェンジメチルシロキシ）フェニルシラン、メチルハイドロジェンシクロポリシロキサン、メチルハイドロジェンシロキサン・ジメチルシロキサン環状共重合体、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサン、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン・ジフェニルシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖メチルハイドロジェンポリシロキサン、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・ジフェニルシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖メチルフェニルポリシロキサン、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジフェニルポリシロキサンや、これらの各例示化合物において、メチル基の一部又は全部がエチル基、プロピル基等の他のアルキル基で置換されたもの、式：Ｒ4 3ＳｉＯ0.5で示されるシロキサン単位と式：Ｒ4 2ＨＳｉＯ0.5で示されるシロキサン単位と式：ＳｉＯ2で示されるシロキサン単位からなるオルガノシロキサン共重合体、式：Ｒ4 2ＨＳｉＯ0.5で示されるシロキサン単位と式：ＳｉＯ2で示されるシロキサン単位からなるオルガノシロキサン共重合体、式：Ｒ4ＨＳｉＯで示されるシロキサン単位と式：Ｒ4ＳｉＯ1.5で示されるシロキサン単位若しくは式：ＨＳｉＯ1.5で示されるシロキサン単位からなるオルガノシロキサン共重合体、及びこれらのオルガノポリシロキサンの２種以上からなる混合物が挙げられる。上記式中のＲ4はアルケニル基以外の１価炭化水素基であり、前記Ｒ3と同様の基が例示される。Examples of the organohydrogenpolysiloxane of the component (B) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and tris (hydrogendimethylsiloxy). Methylsilane, Tris (hydrogendimethylsiloxy) phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane / dimethylsiloxane cyclic copolymer, trimethylsiloxy group-sealed methylhydrogenpolysiloxane at both ends of the molecular chain, trimethyl at both ends of the molecular chain Syloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain double-ended trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane / methylphenylsiloxane copolymer, molecular chain double-ended trimethylsiloxy group-blocked dimethylsiloxane / methylhydro Gensiloxane / diphenylsiloxane copolymer, molecular chain double-ended dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane, molecular chain double-ended dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, molecular chain double-ended dimethylhydrogensiloxy group-blocked dimethyl Siloxane / Methylhydrogensyloxy group-blocked dimethylhydroxyloxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer, dimethylhydrogensiloxy group-blocked dimethylsiloxane / diphenylsiloxane copolymer at both ends of the molecular chain, molecule In the dimethylhydrogensiloxy group-blocked methylphenylpolysiloxane at both ends of the chain, the dimethylhydrogensiloxy group-blocked diphenylpolysiloxane at both ends of the molecular chain, and in each of these exemplary compounds, part or all of the methyl group is an ethyl group, a propyl group, etc. Substituted with another alkyl group, an organosiloxane consisting of a siloxane unit represented by the formula: R 4 3 SiO 0.5 and a siloxane unit represented by the formula: R 4 2 HSiO 0.5 and a siloxane unit represented by the formula: SiO 2 . Copolymer, formula: siloxane unit represented by R 4 2 HSiO 0.5 and formula: organosiloxane copolymer consisting of siloxane unit represented by SiO 2 , formula: siloxane unit represented by formula: R 4 HSiO and formula: R 4 SiO Siloxane unit represented by 1.5 or formula: Organoshi consisting of siloxane unit represented by HSiO 1.5 Examples thereof include a losane copolymer and a mixture of two or more of these organopolysiloxanes. R 4 in the above formula is a monovalent hydrocarbon group other than the alkenyl group, and the same group as R 3 is exemplified.
（Ｂ）成分の配合量は、（Ａ）成分及び後述する（Ｄ）成分中に含まれるケイ素原子結合アルケニル基の合計１モル（又は個）に対して、（Ｂ）成分中に含まれるＳｉＨ基が１～１０モル（又は個）、好ましくは１．２～９モル（又は個）、より好ましくは１．５～８モル（又は個）となる量である。
（Ａ）成分及び（Ｄ）成分中に含まれるケイ素原子結合アルケニル基の合計１モルに対して、（Ｂ）成分中に含まれるＳｉＨ基が１モル未満であると、組成物は十分に硬化せず、またこれが１０モルを超えると、得られるシリコーンゴム硬化物の耐熱性が極端に劣ることがある。
（Ｂ）成分のオルガノハイドロジェンポリシロキサンは、１種単独で用いても２種以上を併用してもよい。The blending amount of the component (B) is SiH contained in the component (B) with respect to a total of 1 mol (or pieces) of the silicon atom-bonded alkenyl groups contained in the component (A) and the component (D) described later. The amount of the group is 1 to 10 mol (or pieces), preferably 1.2 to 9 mol (or pieces), and more preferably 1.5 to 8 mol (or pieces).
When the SiH group contained in the component (B) is less than 1 mol with respect to a total of 1 mol of the silicon atom-bonded alkenyl groups contained in the component (A) and the component (D), the composition is sufficiently cured. If it does not exceed 10 mol, the heat resistance of the obtained cured silicone rubber product may be extremely inferior.
As the component (B), organohydrogenpolysiloxane may be used alone or in combination of two or more.
［（Ｃ）成分］
（Ｃ）成分のシリカ微粉末は、補強性充填剤として作用する。即ち、本発明にかかる組成物から得られるシリコーンゴム硬化物に強度を付与するもので、シリカ微粉末を補強性充填剤として使用することにより、本発明に必要な強度を満足するコーティング膜を形成することが可能となる。かかるシリカ微粉末は、比表面積（ＢＥＴ法）が５０ｍ2／ｇ以上であり、好ましくは５０～４００ｍ2／ｇ、より好ましくは１００～３００ｍ2／ｇであることが必要であり、比表面積が５０ｍ2／ｇ未満では、満足するような強度特性を付与することができない。[(C) component]
The silica fine powder of the component (C) acts as a reinforcing filler. That is, it imparts strength to the cured silicone rubber obtained from the composition according to the present invention, and by using silica fine powder as a reinforcing filler, a coating film satisfying the strength required for the present invention is formed. It becomes possible to do. The specific surface area (BET method) of the silica fine powder needs to be 50 m 2 / g or more, preferably 50 to 400 m 2 / g, more preferably 100 to 300 m 2 / g, and the specific surface area is high. If it is less than 50 m 2 / g, it is not possible to impart satisfactory strength characteristics.
このようなシリカ微粉末としては、比表面積が上記範囲内であることを条件として、従来からシリコーンゴムの補強性充填剤として使用されている公知のものでよく、例えば、煙霧質シリカ（ヒュームドシリカ）、沈降シリカ（湿式シリカ）などが挙げられる。 The silica fine powder may be a known silica fine powder that has been conventionally used as a reinforcing filler for silicone rubber, provided that the specific surface area is within the above range. For example, fumes silica (fumed). Silica), precipitated silica (wet silica) and the like.
上記補強性シリカ微粉末は、例えば、クロロシラン、アルコキシシラン、オルガノシラザン等の（通常、加水分解性の）有機ケイ素化合物などの表面処理剤で、表面が疎水化処理されたシリカ微粉末を用いることができる。その場合、これらのシリカ微粉末は、予め粉体の状態で、表面処理剤により、直接表面疎水化処理されたものを用いてもよいし、シリコーンオイル（例えば、上記（Ａ）成分のアルケニル基含有オルガノポリシロキサン）との混練時に表面処理剤を添加して、表面疎水化処理したものを用いてもよい。
なお、ここで用いられる表面処理剤は、後述する（Ｄ）成分のケイ素原子に結合したアルケニル基を含有する表面処理剤と比較して、アルケニル基を有さないものである点で明確に区別される。The reinforcing silica fine powder is a surface treatment agent such as an organosilicon compound (usually hydrolyzable) such as chlorosilane, alkoxysilane, and organosilazane, and the surface of the silica fine powder is hydrolyzed. Can be done. In that case, as these fine silica powders, those which have been directly surface-hydrophobicized with a surface treatment agent in the state of powder in advance may be used, or silicone oil (for example, the alkenyl group of the component (A) above). A surface treatment agent may be added at the time of kneading with the contained organopolysiloxane) to make the surface hydrophobic.
The surface treatment agent used here is clearly distinguished in that it does not have an alkenyl group as compared with a surface treatment agent containing an alkenyl group bonded to a silicon atom of the component (D) described later. Will be done.
（Ｃ）成分の通常の処理法として、公知の技術により表面処理することができ、例えば、常圧で密閉された機械混練装置又は流動層に上記未処理のシリカ微粉末と表面処理剤とを入れ、必要に応じて不活性ガス存在下において、室温（２５℃）あるいは熱処理（加熱）下にて混合処理することができる。場合により、水又は触媒（加水分解促進剤等）を使用して表面処理を促進してもよい。混練後、乾燥することにより、表面処理シリカ微粉末を製造し得る。表面処理剤の配合量は、その表面処理剤の被覆面積から計算される量以上であればよい。 As a usual treatment method for the component (C), the surface can be treated by a known technique. For example, the untreated silica fine powder and the surface treatment agent are applied to a mechanical kneading device or a fluidized bed sealed at normal pressure. It can be added and mixed if necessary in the presence of an inert gas at room temperature (25 ° C.) or heat treatment (heating). In some cases, water or a catalyst (hydrolysis accelerator, etc.) may be used to accelerate the surface treatment. After kneading, the surface-treated silica fine powder can be produced by drying. The blending amount of the surface treatment agent may be an amount calculated from the covering area of the surface treatment agent or more.
表面処理剤として、具体的には、へキサメチルジシラザン、１，１，３，３，５，５－ヘキサメチルシクロトリシラザン等のシラザン類、メチルトリメトキシシラン、エチルトリメトキシシラン、プロピルトリメトキシシラン、ブチルトリメトキシシラン、ジメチルジメトキシシラン、ジエチルジメトキシシラン、トリメチルメトキシシラン、トリエチルメトキシシラン、トリメチルクロロシラン、ジメチルジクロロシラン、クロロプロピルトリメトキシシラン、トリメチルシラノール及びヒドロキシペンタメチルジシロキサン等のシランカップリング剤、ポリメチルシロキサン、オルガノハイドロジェンポリシロキサン等の有機ケイ素化合物が挙げられ、これらで表面処理した疎水性シリカ微粉末を用いることができる。表面処理剤としては、特にシランカップリング剤又はシラザン類が好ましい。 Specific examples of the surface treatment agent include hexamethyldisilazane, silazans such as 1,1,3,3,5,5-hexamethylcyclotrisilazane, methyltrimethoxysilane, ethyltrimethoxysilane, and propyltri. Silane couplings such as methoxysilane, butyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, trimethylchlorosilane, dimethyldichlorosilane, chloropropyltrimethoxysilane, trimethylsilanol and hydroxypentamethyldisiloxane. Examples thereof include organic silicon compounds such as agents, polymethylsiloxane, and organohydrogenpolysiloxane, and hydrophobic silica fine powder surface-treated with these can be used. As the surface treatment agent, a silane coupling agent or silazanes are particularly preferable.
（Ｃ）成分の配合量は、（Ａ）成分のオルガノポリシロキサン１００質量部に対して、１～５０質量部であり、好ましくは１０～３０質量部である。配合量が少なすぎると、本発明に必要な強度が得られず、配合量が多すぎると、組成物の粘度が高くなり、流動性が低下してコーティング作業が悪化することがある。
（Ｃ）成分の微粉末シリカは、１種単独で用いても２種以上を併用してもよい。The blending amount of the component (C) is 1 to 50 parts by mass, preferably 10 to 30 parts by mass with respect to 100 parts by mass of the organopolysiloxane of the component (A). If the blending amount is too small, the strength required for the present invention cannot be obtained, and if the blending amount is too large, the viscosity of the composition may increase, the fluidity may decrease, and the coating operation may deteriorate.
The fine powder silica of the component (C) may be used alone or in combination of two or more.
［（Ｄ）成分］
（Ｄ）成分のケイ素原子に結合したアルケニル基を含有する表面処理剤は、シリコーンゴム組成物の硬化物の強度向上剤として作用する。[(D) component]
The surface treatment agent containing an alkenyl group bonded to the silicon atom of the component (D) acts as a strength improving agent for the cured product of the silicone rubber composition.
（Ｄ）成分としては、１分子中にビニル基を１個以上有するクロロシラン類、シラザン類、及び下記式（１）又は（２）で表わされる有機ケイ素化合物から選ばれるものが挙げられる。
１分子中にビニル基を１個以上有するクロロシラン類の具体例としては、ジメチルビニルクロロシラン、メチルビニルジクロロシラン、ビニルトリクロロシラン、ジビニルジクロロシラン、メチルフェニルビニルクロロシランなどが挙げられ、また１分子中にビニル基を１個以上有するシラザン類の具体例としては、１，３－ジビニル－１，１，３，３－テトラメチルジシラザン、１，１，３，３－テトラビニル－１，３－ジメチルジシラザン、１－ビニル－１，１，３，３，３－ペンタメチルジシラザン、１，１，１，３，５，５，５－ヘプタメチル－３－ビニルトリシラザン等が挙げられるが、特に１，３－ジビニル－１，１，３，３－テトラメチルジシラザンが好ましい。 Specific examples of chlorosilanes having one or more vinyl groups in one molecule include dimethylvinylchlorosilane, methylvinyldichlorosilane, vinyltrichlorosilane, divinyldichlorosilane, methylphenylvinylchlorosilane, and the like. Specific examples of the silazanes having one or more vinyl groups include 1,3-divinyl-1,1,3,3-tetramethyldisilazane and 1,1,3,3-tetravinyl-1,3-dimethyl. Examples thereof include disilazan, 1-vinyl-1,1,3,3,3-pentamethyldisilazan, 1,1,1,3,5,5,5-heptamethyl-3-vinyltrisilazane, and the like. 1,3-Divinyl-1,1,3,3-tetramethyldisilazane is preferable.
式（１）又は（２）において、Ｒ1の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ヘキシル基、オクチル基、デシル基等のアルキル基、フェニル基、トリル基、キシリル基、ナフチル基等のアリール基、シクロヘキシル基等のシクロアルキル基、ベンジル基、フェニルエチル基等のアラルキル基等が挙げられるが、中でもメチル基が好ましい。In the formula (1) or (2), specific examples of R 1 include 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, an octyl group, a decyl group and the like. Examples thereof include an aryl group such as an alkyl group, a phenyl group, a trill group, a xylyl group and a naphthyl group, a cycloalkyl group such as a cyclohexyl group, an aralkyl group such as a benzyl group and a phenylethyl group, and a methyl group is preferable.
式（１）又は（２）において、Ｒ2の具体例としては、水素原子、又はメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ヘキシル基等のアルキル基が挙げられるが、中でも水素原子又はメチル基が好ましい。In the formula (1) or (2), specific examples of R 2 include a hydrogen atom or an alkyl such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group and a hexyl group. A group may be mentioned, but a hydrogen atom or a methyl group is preferable.
式（１）又は（２）において、ｎは０～５０の整数、好ましくは０～２０の整数である。また、式（２）において、ｍは１～５０の整数、好ましくは１～１０の整数である。 In the formula (1) or (2), n is an integer of 0 to 50, preferably an integer of 0 to 20. Further, in the formula (2), m is an integer of 1 to 50, preferably an integer of 1 to 10.
本発明では、（Ｄ）成分のケイ素原子に結合したアルケニル基を含有する表面処理剤を（Ｃ）成分のシリカ微粉末と混合し、６０～２００℃で加熱処理することにより、（Ｃ）成分のシリカ微粉末の表面上に（Ｄ）成分の表面処理剤が充分に供給されて、処理されるので、得られるシリコーンゴム組成物の硬化物は本発明に必要な強度を得ることができる。その場合、上述したように、例えば、（Ｃ）成分のシリカ微粉末を、予め粉体の状態で、（Ｄ）成分の表面処理剤と混合し、加熱処理されるようにしてもよいし、（Ｃ）成分のシリカ微粉末とシリコーンオイル（例えば、上記（Ａ）成分のアルケニル基含有オルガノポリシロキサン）との混合時に（Ｄ）成分の表面処理剤を添加して、加熱処理されるようにしてもよい。 In the present invention, the surface treatment agent containing an alkenyl group bonded to the silicon atom of the component (D) is mixed with the silica fine powder of the component (C) and heat-treated at 60 to 200 ° C. to obtain the component (C). Since the surface treatment agent of the component (D) is sufficiently supplied and treated on the surface of the silica fine powder of the above, the obtained cured product of the silicone rubber composition can obtain the strength required for the present invention. In that case, as described above, for example, the silica fine powder of the component (C) may be mixed with the surface treatment agent of the component (D) in the state of powder in advance and heat-treated. When the silica fine powder of the component (C) and the silicone oil (for example, the alkenyl group-containing organopolysiloxane of the component (A) above) are mixed, a surface treatment agent of the component (D) is added so as to be heat-treated. You may.
（Ｄ）成分の表面処理剤で（Ｃ）成分のシリカ微粉末の表面処理をシリコーンオイル中で行う方法としては、例えば、（Ａ）成分の一部と、（Ｃ）成分、（Ｄ）成分の全部とを６０℃未満の温度で混合した後に６０～２００℃で熱処理することで表面処理することができる。その際にビニル基を含まないクロロシラン類やシラザン類などの表面処理剤を同時に混合してもよい。また場合により、水又は触媒（加水分解促進剤等）を使用して表面処理を促進してもよい。 As a method of performing the surface treatment of the silica fine powder of the component (C) in the silicone oil with the surface treatment agent of the component (D), for example, a part of the component (A), the component (C), and the component (D) are used. The surface can be treated by mixing all of the above with a temperature of less than 60 ° C. and then heat-treating at 60 to 200 ° C. At that time, a surface treatment agent such as chlorosilanes or silazanes containing no vinyl group may be mixed at the same time. In some cases, water or a catalyst (hydrolysis accelerator or the like) may be used to promote the surface treatment.
（Ｃ）成分のシリカ微粉末を、予め粉体の状態で、（Ｄ）成分の表面処理剤と混合し、加熱処理する方法は、例えば、常圧で密閉された機械混練装置又は流動層に上記（Ｃ）成分のシリカ微粉末と（Ｄ）成分の表面処理剤とを入れ、必要に応じて不活性ガス存在下において、６０℃未満の温度で混合した後に６０～２００℃にて加熱処理することで表面処理することができる。その際にビニル基を含まないクロロシラン類やシラザン類などの表面処理剤を同時に混合してもよい。また場合により、水又は触媒（加水分解促進剤等）を使用して表面処理を促進してもよい。 The method of mixing the silica fine powder of the component (C) in the powder state in advance with the surface treatment agent of the component (D) and heat-treating it is, for example, in a mechanical kneading device or a fluidized layer sealed at normal pressure. The silica fine powder of the component (C) and the surface treatment agent of the component (D) are added, and if necessary, mixed at a temperature of less than 60 ° C. in the presence of an inert gas, and then heat-treated at 60 to 200 ° C. By doing so, the surface can be treated. At that time, a surface treatment agent such as chlorosilanes or silazanes containing no vinyl group may be mixed at the same time. In some cases, water or a catalyst (hydrolysis accelerator or the like) may be used to promote the surface treatment.
（Ｄ）成分の配合量は、（Ｃ）成分のシリカ微粉末１００質量部に対して、０．０１～５質量部、好ましくは０．０５～４．５質量部、より好ましくは０．１０～４質量部である。（Ｄ）成分の配合量が、０．０１質量部よりも少ないと充分な補強効果を得られないことがあり、５質量部よりも多いと組成物の硬化物の硬さが極端に高くなり、機械的特性が極端に悪化することがある。
（Ｄ）成分は、１種単独で用いても２種以上を併用してもよい。The blending amount of the component (D) is 0.01 to 5 parts by mass, preferably 0.05 to 4.5 parts by mass, and more preferably 0.10 with respect to 100 parts by mass of the silica fine powder of the component (C). ~ 4 parts by mass. If the blending amount of the component (D) is less than 0.01 parts by mass, a sufficient reinforcing effect may not be obtained, and if it is more than 5 parts by mass, the hardness of the cured product of the composition becomes extremely high. , Mechanical properties may be extremely deteriorated.
The component (D) may be used alone or in combination of two or more.
［（Ｅ）成分］
（Ｅ）成分のヒドロシリル化反応用触媒は、主に（Ａ）成分中のケイ素原子に結合したアルケニル基と（Ｂ）成分中のＳｉＨ基との付加反応を促進するものである。このヒドロシリル化反応用触媒は、特に限定されず、例えば、白金、パラジウム、ロジウム等の白金族金属；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化合物等が挙げられ、好ましくは白金族金属化合物である。[(E) component]
The catalyst for the hydrosilylation reaction of the component (E) mainly promotes the addition reaction between the alkenyl group bonded to the silicon atom in the component (A) and the SiH group in the component (B). The catalyst for the hydrosilylation reaction is not particularly limited, and for example, platinum group metals such as platinum, palladium, and rhodium; platinum chloride acid; alcohol-modified platinum chloride acid; platinum chloride acid, and olefins, vinylsiloxane, or acetylene compounds. Coordination compounds; Platinum group metal compounds such as tetrakis (triphenylphosphine) palladium and chlorotris (triphenylphosphine) rhodium are mentioned, and platinum group metal compounds are preferable.
（Ｅ）成分の配合量は、触媒としての有効量であればよいが、（Ａ）～（Ｄ）成分の合計量に対して、触媒金属元素の質量換算で、好ましくは１～５００ｐｐｍ、より好ましくは１０～１００ｐｐｍである。この配合量が少なすぎると付加反応が著しく遅くなったり、組成物が硬化しなかったりすることがあり、この配合量が多すぎると硬化物の耐熱性が低下することがある。
（Ｅ）成分の付加反応触媒は、１種単独で用いても２種以上を併用してもよい。The blending amount of the component (E) may be an effective amount as a catalyst, but is preferably 1 to 500 ppm in terms of the mass of the catalyst metal element with respect to the total amount of the components (A) to (D). It is preferably 10 to 100 ppm. If this blending amount is too small, the addition reaction may be significantly slowed down or the composition may not be cured, and if this blending amount is too large, the heat resistance of the cured product may be lowered.
The addition reaction catalyst of the component (E) may be used alone or in combination of two or more.
［（Ｆ）成分］
（Ｆ）成分は、接着性付与官能基を含有する有機ケイ素化合物であり、接着性付与官能基としては、エポキシ基、ケイ素原子結合アルコキシ基（アルコキシシリル基）、ヒドロシリル基、イソシアネート基、アクリル基、メタクリル基などが挙げられ、シリコーンゴム組成物のエアーバッグ用基布に対する接着性を発現・向上させるために添加するものである。
有機ケイ素化合物としては、このような接着性付与官能基を有するものであれば、いかなる有機ケイ素化合物でも使用できるが、１分子中にエポキシ基とケイ素原子結合アルコキシ基とをそれぞれ１個以上有する有機ケイ素化合物であることが好ましく、接着発現性の観点からは、少なくとも１個のエポキシ基と少なくとも１個のケイ素原子結合アルコキシ基（例えば、トリアルコキシシリル基、オルガノジアルコキシシリル基等）とを有する有機ケイ素化合物、例えば、オルガノシラン、又はケイ素原子数が２～１００個、好ましくは４～５０個程度の環状若しくは直鎖状のオルガノシロキサンであって、少なくとも１個のエポキシ基と少なくとも２個のケイ素原子結合アルコキシ基とを有するものがより好ましい。[(F) component]
The component (F) is an organic silicon compound containing an adhesive-imparting functional group, and the adhesive-imparting functional group includes an epoxy group, a silicon atom-bonded alkoxy group (alkoxysilyl group), a hydrosilyl group, an isocyanate group, and an acrylic group. , Methacyl groups and the like, and are added in order to develop and improve the adhesiveness of the silicone rubber composition to the base cloth for an air bag.
As the organic silicon compound, any organic silicon compound can be used as long as it has such an adhesive-imparting functional group, but it is an organic compound having one or more epoxy groups and one or more silicon atom-bonded alkoxy groups in one molecule. It is preferably a silicon compound, and has at least one epoxy group and at least one silicon atom-bonded alkoxy group (for example, a trialkoxysilyl group, an organodialkoxysilyl group, etc.) from the viewpoint of adhesion development. An organic silicon compound, for example, an organosilane, or a cyclic or linear organosiloxane having 2 to 100, preferably 4 to 50, silicon atoms, with at least one epoxy group and at least two. Those having a silicon atom-bonded alkoxy group are more preferable.
エポキシ基は、例えば、グリシドキシプロピル基等のグリシドキシアルキル基；２，３－エポキシシクロヘキシルエチル基、３，４－エポキシシクロヘキシルエチル基等のエポキシ含有シクロヘキシルアルキル基等の形で、ケイ素原子に結合していることが好ましい。
ケイ素原子結合アルコキシ基は、ケイ素原子と結合して、例えば、トリメトキシシリル基、トリエトキシシリル基等のトリアルコキシシリル基；メチルジメトキシシリル基、エチルジメトキシシリル基、メチルジエトキシシリル基、エチルジエトキシシリル基等のアルキルジアルコキシシリル基等を形成していることが好ましい。The epoxy group is, for example, a silicon atom in the form of a glycidoxyalkyl group such as a glycidoxypropyl group; an epoxy-containing cyclohexylalkyl group such as a 2,3-epoxycyclohexylethyl group or a 3,4-epoxycyclohexylethyl group. It is preferable that it is bound to.
The silicon atom-bonded alkoxy group is bonded to a silicon atom to form, for example, a trialkoxysilyl group such as a trimethoxysilyl group or a triethoxysilyl group; a methyldimethoxysilyl group, an ethyldimethoxysilyl group, a methyldiethoxysilyl group, or an ethyldi. It is preferable to form an alkyldialkoxysilyl group such as an ethoxysilyl group.
また、（Ｆ）成分は、１分子中にエポキシ基及びケイ素原子結合アルコキシ基以外の官能性基として、例えば、ビニル基等のアルケニル基、アクリル基、（メタ）アクリロキシ基、イソシアネート基、及びヒドロシリル基（ＳｉＨ基）からなる群より選択される少なくとも１種の官能性基を有してもよい。 Further, the component (F) contains a functional group other than the epoxy group and the silicon atom-bonded alkoxy group in one molecule, for example, an alkenyl group such as a vinyl group, an acrylic group, a (meth) acryloxy group, an isocyanate group, and a hydrosilyl. It may have at least one functional group selected from the group consisting of groups (SiH groups).
（Ｆ）成分の有機ケイ素化合物としては、例えば、γ－グリシドキシプロピルトリエトキシシラン、γ－グリシドキシプロピルメチルジエトキシシラン、（３，４－エポキシシクロヘキシルエチル）トリメトキシシラン、（３，４－エポキシシクロヘキシルエチル）トリエトキシシラン、（３，４－エポキシシクロヘキシルエチル）メチルジメトキシシラン、（３，４－エポキシシクロヘキシルエチル）メチルジエトキシシラン、（２，３－エポキシシクロヘキシルエチル）トリエトキシシラン、（２，３－エポキシシクロヘキシルエチル）メチルジメトキシシラン、（２，３－エポキシシクロヘキシルエチル）メチルジエトキシシラン等のエポキシ基含有シランカップリング剤（即ち、エポキシ官能性基含有オルガノアルコキシシラン）又はビニルトリメトキシシラン等のビニル基含有シランカップリング剤又は、３－アクリロキシプロピルトリメトキシシラン等のアクリル基含有シランカップリング剤又は、３－イソシアネートプロピルエトキシシラン等のイソシアネート基含有のシランカップリング剤又はトリアリルイソシアヌレートのメトキシシリル変性体等のシランカップリング剤の他、下記の化学式で示される環状オルガノポリシロキサン、又は直鎖状オルガノポリシロキサン等の有機ケイ素化合物、これらの２種以上の混合物、あるいはこれらの１種若しくは２種以上の部分加水分解縮合物等が挙げられる。 Examples of the organic silicon compound as the component (F) include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, (3,4-epoxycyclohexylethyl) trimethoxysilane, and (3). 4-Epoxycyclohexylethyl) triethoxysilane, (3,4-epoxycyclohexylethyl) methyldimethoxysilane, (3,4-epoxycyclohexylethyl) methyldiethoxysilane, (2,3-epoxycyclohexylethyl) triethoxysilane, Epoxy group-containing silane coupling agents such as (2,3-epoxycyclohexylethyl) methyldimethoxysilane, (2,3-epoxycyclohexylethyl) methyldiethoxysilane (ie, epoxy functional group-containing organoalkoxysilanes) or vinyltri. A vinyl group-containing silane coupling agent such as methoxysilane, an acrylic group-containing silane coupling agent such as 3-acryloxypropyltrimethoxysilane, or an isocyanate group-containing silane coupling agent or tri such as 3-isocyanoxide propylethoxysilane. In addition to a silane coupling agent such as a methoxysilyl modified product of allyl isocyanurate, a cyclic organopolysiloxane represented by the following chemical formula, an organic silicon compound such as a linear organopolysiloxane, a mixture of two or more thereof, or a mixture thereof. Examples thereof include one or more of these partially hydrolyzed condensates.
（Ｆ）成分の配合量は、（Ａ）成分のオルガノポリシロキサン１００質量部に対して、０．１～１０質量部であり、好ましくは０．２５～５質量部である。配合量が０．１質量部未満であると、得られる組成物が充分な接着力を有しないことがある。配合量が１０質量部を超えると、組成物のチキソ性が高くなり、流動性が低下し、コーティング作業性が悪化することがある。 The blending amount of the component (F) is 0.1 to 10 parts by mass, preferably 0.25 to 5 parts by mass with respect to 100 parts by mass of the organopolysiloxane of the component (A). If the blending amount is less than 0.1 parts by mass, the obtained composition may not have sufficient adhesive strength. If the blending amount exceeds 10 parts by mass, the thixotropic property of the composition becomes high, the fluidity decreases, and the coating workability may deteriorate.
また、（Ｆ）成分がアルケニル基及び／又はＳｉＨ基を含む場合、組成物中の（Ａ）成分、（Ｄ）成分、及び（Ｆ）成分中に含まれるケイ素原子結合アルケニル基の合計１モル（又は個）に対する（Ｂ）成分及び（Ｆ）成分中に含まれるＳｉＨ基の合計量は、１～１０モル（又は個）、好ましくは１．２～９モル（又は個）、より好ましくは１．５～８モル（又は個）である。組成物中のケイ素原子結合アルケニル基１モルに対して、ＳｉＨ基が１モル未満であると、組成物は十分に硬化せず、十分な接着力を有しない場合がある。一方、これが１０モルを超えると、得られるシリコーンゴム硬化物の耐熱性が極端に劣り、接着力が向上しにくくなり、コスト的に高いものとなり、不経済となりやすい。
（Ｆ）成分は、１種単独で用いても２種以上を併用してもよい。When the component (F) contains an alkenyl group and / or a SiH group, a total of 1 mol of the silicon atom-bonded alkenyl group contained in the component (A), the component (D), and the component (F) in the composition. The total amount of SiH groups contained in the component (B) and the component (F) with respect to (or the individual) is 1 to 10 mol (or individual), preferably 1.2 to 9 mol (or individual), more preferably. 1.5-8 mol (or pieces). If the SiH group is less than 1 mol with respect to 1 mol of the silicon atom-bonded alkenyl group in the composition, the composition may not be sufficiently cured and may not have sufficient adhesive strength. On the other hand, if this exceeds 10 mol, the heat resistance of the obtained cured silicone rubber is extremely inferior, the adhesive strength is difficult to improve, the cost is high, and it tends to be uneconomical.
The component (F) may be used alone or in combination of two or more.
［その他の成分］
本発明にかかる組成物には、前記（Ａ）～（Ｆ）成分以外にも、本発明の目的を損なわない範囲で、その他の任意の成分を配合することができる。その具体例としては、以下のものが挙げられる。これらのその他の成分は、各々、１種単独で用いても２種以上を併用してもよい。[Other ingredients]
In addition to the above-mentioned components (A) to (F), any other component may be added to the composition according to the present invention as long as the object of the present invention is not impaired. Specific examples thereof include the following. Each of these other components may be used alone or in combination of two or more.
［（Ｇ）成分］
（Ｇ）成分の縮合触媒は、有機チタニウム化合物、有機ジルコニウム化合物、及び有機アルミニウム化合物から選ばれる少なくとも１種であり、接着促進のために、（Ｆ）成分中の接着性付与官能基の縮合助触媒として作用するものである。（Ｇ）成分の具体例としては、例えば、チタンテトライソプロポキシド、チタンテトラノルマルブトキシド、チタンテトラ－２－エチルヘキソキシド等の有機チタン酸エステル、チタンジイソプロポキシビス（アセチルアセトネート）、チタンジイソプロポキシビス（エチルアセトアセテート）、チタンテトラアセチルアセトネート等の有機チタンキレート化合物等のチタン系縮合助触媒（チタニウム化合物）、ジルコニウムテトラノルマルプロポキシド、ジルコニウムテトラノルマルブトキシド等の有機ジルコニウムエステル、ジルコニウムトリブトキシモノアセチルアセトネート、ジルコニウムモノブトキシアセチルアセトネートビス（エチルアセトアセテート）、ジルコニウムテトラアセチルアセトネート等の有機ジルコニウムキレート化合物等のジルコニウム系縮合助触媒（ジルコニウム化合物）、アルミニウムセカンダリーブトキシド等の有機アルミニウム酸エステル、アルミニウムトリスアセチルアセトネート、アルミニウムビスエチルアセトアセテートモノアセチルアセトネート、アルミニウムトリスエチルアセトアセテート等の有機アルミニウムキレート化合物等のアルミニウム系縮合助触媒が挙げられる。[(G) component]
The condensation catalyst of the component (G) is at least one selected from an organic titanium compound, an organic zirconium compound, and an organoaluminum compound, and helps to condense the adhesive-imparting functional group in the component (F) in order to promote adhesion. It acts as a catalyst. Specific examples of the component (G) include organic titanium acid esters such as titanium tetraisopropoxide, titanium tetranormalbutoxide, and titanium tetra-2-ethylhexoxide, and titanium diisopropoxybis (acetylacetonate). Titanium-based condensation co-catalysts (titanium compounds) such as titanium diisopropoxybis (ethylacetacetate) and organic titanium chelate compounds such as titanium tetraacetylacetonate, organic zirconium esters such as zirconium tetranormal propoxide and zirconium tetranormal butoxide, Organic zirconium-based condensation co-catalysts such as zirconium tributoxymonoacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetoacetate), zirconium tetraacetylacetonate and other organic zirconium chelate compounds, and organic such as aluminum secondary butoxide. Examples thereof include aluminum-based condensation co-catalysts such as organic aluminum chelate compounds such as aluminum acid ester, aluminum tris acetylacetonate, aluminum bisethyl acetoacetate monoacetyl acetonate, and aluminum tris ethyl acetoacetate.
（Ｇ）成分の有機チタニウム化合物、有機ジルコニウム化合物、及び有機アルミニウム化合物は、必要に応じて配合される任意成分であり、その配合量は、（Ａ）成分１００質量部に対して、通常５質量部以下（０．０１～５質量部）程度でよいが、（Ｇ）成分を配合する場合には、好ましくは０．１～５質量部、より好ましくは０．２～２質量部である。配合量が０．１質量部未満であると、得られる硬化物は高温高湿下での接着耐久性が低下しやすくなることがあり、配合量が５質量部を超えると、得られる硬化物は耐熱性が低下しやすくなることがある。
（Ｇ）成分は１種単独で用いても２種以上を併用してもよい。The organic titanium compound, the organic zirconium compound, and the organic aluminum compound of the component (G) are optional components to be blended as necessary, and the blending amount thereof is usually 5 mass by mass with respect to 100 parts by mass of the component (A). It may be about 10 parts by mass or less (0.01 to 5 parts by mass), but when the component (G) is blended, it is preferably 0.1 to 5 parts by mass, and more preferably 0.2 to 2 parts by mass. If the blending amount is less than 0.1 parts by mass, the obtained cured product may easily deteriorate in adhesive durability under high temperature and high humidity, and if the blending amount exceeds 5 parts by mass, the obtained cured product may be easily deteriorated. May tend to have reduced heat resistance.
The component (G) may be used alone or in combination of two or more.
・反応制御剤
反応制御剤は、（Ｅ）成分のヒドロシリル化反応用触媒に対して、硬化抑制効果を有する化合物であれば、特に限定されず、公知のものを用いることができる。その具体例としては、トリフェニルホスフィンなどのリン含有化合物；トリブチルアミン、テトラメチルエチレンジアミン、ベンゾトリアゾールなどの窒素含有化合物；硫黄含有化合物；アセチレンアルコール類等のアセチレン系化合物；アルケニル基を２個以上含む化合物；ハイドロパーオキシ化合物；マレイン酸誘導体などが挙げられる。-Reaction control agent The reaction control agent is not particularly limited as long as it is a compound having a curing inhibitory effect on the hydrosilylation reaction catalyst of the component (E), and known ones can be used. Specific examples thereof include phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine and benzotriazole; sulfur-containing compounds; acetylene-based compounds such as acetylene alcohols; and two or more alkenyl groups. Compounds; hydroperoxy compounds; maleic acid derivatives and the like can be mentioned.
反応制御剤による硬化抑制効果の度合は、その反応制御剤の化学構造によって異なるため、反応制御剤の添加量は、使用する反応制御剤の各々について、最適な量に調整することが好ましい。最適な量の反応制御剤を添加することにより、組成物は室温での長期貯蔵安定性及び硬化性に優れたものとなる。 Since the degree of the curing inhibitory effect of the reaction control agent varies depending on the chemical structure of the reaction control agent, it is preferable to adjust the addition amount of the reaction control agent to an optimum amount for each of the reaction control agents to be used. By adding the optimum amount of the reaction control agent, the composition becomes excellent in long-term storage stability and curability at room temperature.
・非補強性充填剤
（Ｃ）成分のシリカ微粉末以外の充填剤として、例えば、結晶性シリカ（例えば、ＢＥＴ法比表面積が５０ｍ2／ｇ未満の石英粉）、有機樹脂製中空フィラー、ポリメチルシルセスキオキサン微粒子（いわゆるシリコーンレジンパウダー）、ヒュームド二酸化チタン、酸化マグネシウム、酸化亜鉛、酸化鉄、水酸化アルミニウム、炭酸マグネシウム、炭酸カルシウム、炭酸亜鉛、カーボンブラック、ケイ藻土、タルク、カオリナイト、ガラス繊維等の充填剤；これらの充填剤をオルガノアルコキシシラン化合物、オルガノクロロシラン化合物、オルガノシラザン化合物、低分子量シロキサン化合物等の有機ケイ素化合物により表面疎水化処理した充填剤；シリコーンゴムパウダー；シリコーンレジンパウダーなどが挙げられる。-Non-reinforcing filler As a filler other than the silica fine powder of the component (C), for example, crystalline silica (for example, quartz powder having a BET method specific surface area of less than 50 m 2 / g), an organic resin hollow filler, and poly. Methylsilsesquioxane fine particles (so-called silicone resin powder), fumed titanium dioxide, magnesium oxide, zinc oxide, iron oxide, aluminum hydroxide, magnesium carbonate, calcium carbonate, zinc carbonate, carbon black, coconut soil, talc, kaolinite , Glass fiber and other fillers; fillers in which these fillers are surface-hydrophobicized with organic silicon compounds such as organoalkoxysilane compounds, organochlorosilane compounds, organosilazane compounds, and low molecular weight siloxane compounds; silicone rubber powders; silicone resins. Examples include powder.
・その他の成分
その他にも、例えば、１分子中に１個のケイ素原子結合水素原子を含有し、他の官能性基を含有しないオルガノポリシロキサン、１分子中に１個のケイ素原子結合アルケニル基を含有し、他の官能性基を含有しないオルガノポリシロキサン、ケイ素原子結合水素原子もケイ素原子結合アルケニル基も他の官能性基も含有しない無官能性のオルガノポリシロキサン（いわゆるジメチルシリコーンオイル）、有機溶剤、クリープハードニング防止剤、可塑剤、チキソ性付与剤、顔料、染料、防かび剤などを配合することができる。-Other components In addition, for example, an organopolysiloxane containing one silicon atom-bonded hydrogen atom in one molecule and not containing other functional groups, and one silicon atom-bonded alkenyl group in one molecule. Organopolysiloxane containing, and containing no other functional groups, non-functional organopolysiloxane (so-called dimethylsilicone oil) containing no silicon atom-bonded hydrogen atom, silicon atom-bonded alkenyl group, or other functional group. Organic solvents, creep hardening inhibitors, plasticizers, thioxane-imparting agents, pigments, dyes, antifungal agents and the like can be blended.
＜付加硬化型液状シリコーンゴム組成物の調製＞
上記（Ａ）～（Ｆ）成分の他、（Ｇ）成分等、必要に応じて配合されるその他の成分を均一に混合することにより、付加硬化型液状シリコーンゴム組成物を調製することができる。
こうして得られる付加硬化型液状シリコーンゴム組成物は、２５℃で液状の組成物であり、ＪＩＳ Ｋ ７１１７－１：１９９９に記載の方法で測定した２５℃における粘度は、１，０００～１，０００，０００ｍＰａ・ｓであり、好ましくは１０，０００～３００，０００ｍＰａ・ｓである。この粘度範囲内であれば、エアーバッグ用基布に塗工する際に、塗工むらや硬化後の密着不足などが生じにくいため、好適に用いることができる。<Preparation of Additive Curing Liquid Silicone Rubber Composition>
In addition to the above components (A) to (F), an addition-curable liquid silicone rubber composition can be prepared by uniformly mixing other components to be blended as needed, such as the component (G). ..
The addition-curable liquid silicone rubber composition thus obtained is a composition liquid at 25 ° C., and the viscosity at 25 ° C. measured by the method described in JIS K 7117-1: 1999 is 1,000 to 1,000. It is 000 mPa · s, preferably 10,000 to 300,000 mPa · s. If the viscosity is within this range, uneven coating and insufficient adhesion after curing are unlikely to occur when the base cloth for an air bag is coated, so that it can be suitably used.
＜エアーバッグ用基布＞
本発明において、上記組成物の硬化物からなるシリコーンゴム層が形成されるエアーバッグ用基布（繊維布からなる基材）としては、公知のものが用いられ、その具体例としては、６，６－ナイロン、６－ナイロン、アラミド繊維などの各種ポリアミド繊維、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）などの各種ポリエステル繊維などの各種合成繊維の織生地が挙げられる。<Base cloth for air bag>
In the present invention, a known base cloth (base material made of a fiber cloth) for forming a silicone rubber layer made of a cured product of the above composition is used, and specific examples thereof include 6, Examples thereof include woven fabrics of various polyamide fibers such as 6-nylon, 6-nylon and aramid fibers, and various synthetic fibers such as various polyester fibers such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).
＜エアーバッグの製造方法＞
上記付加硬化型液状シリコーンゴム組成物を、エアーバッグ用基布（繊維布からなる基材）の少なくとも一方の表面、特には一方の表面に塗布した後、乾燥炉などで加熱硬化することにより、シリコーンゴム層（硬化物層）を形成させることができる。このようにして得たエアーバッグ用シリコーンゴムコーティング基布を用いて、エアーバッグを製造することができる。<Manufacturing method of air bag>
The addition-curable liquid silicone rubber composition is applied to at least one surface of a base cloth for an air bag (a base material made of a fiber cloth), particularly to one surface, and then heat-cured in a drying furnace or the like. A silicone rubber layer (cured product layer) can be formed. An air bag can be manufactured by using the silicone rubber-coated base cloth for an air bag thus obtained.
ここで、付加硬化型液状シリコーンゴム組成物をエアーバッグ用基布（繊維布からなる基材）にコーティングする方法としては、常法を採用することができるが、ナイフコーターによるコーティングが好ましい。コーティング層の厚さ（又は表面塗布量）は、通常１０～１００ｇ／ｍ2、好ましくは１２～９０ｇ／ｍ2、より好ましくは１５～８０ｇ／ｍ2とすることができる。Here, as a method of coating the addition-curable liquid silicone rubber composition on the base cloth for an air bag (a base material made of a fiber cloth), a conventional method can be adopted, but coating with a knife coater is preferable. The thickness (or surface coating amount) of the coating layer can be usually 10 to 100 g / m 2 , preferably 12 to 90 g / m 2 , and more preferably 15 to 80 g / m 2 .
付加硬化型液状シリコーンゴム組成物は、公知の硬化条件下で公知の硬化方法により硬化させることができる。具体的には、例えば、１００～２００℃において、１～３０分加熱することにより、該組成物を硬化させることができる。 The addition-curable liquid silicone rubber composition can be cured by a known curing method under known curing conditions. Specifically, for example, the composition can be cured by heating at 100 to 200 ° C. for 1 to 30 minutes.
このようにして製造された少なくとも一方の表面にシリコーンゴム層を有するエアーバッグ用基布（エアーバッグ用シリコーンゴムコーティング基布）をエアーバッグに加工する際は、少なくともエアーバッグの内面側がシリコーンゴムでコーティングされている２枚の平織布の外周部同士を接着剤で貼り合わせ、かつその接着剤層を縫い合わせて作製する方法が挙げられる。また、予め袋織りして作製されたエアーバッグ用基布の少なくとも内側に、上記のように、付加硬化型液状シリコーンゴム組成物を所定のコーティング量でコーティングし、所定の硬化条件下で硬化させる方法を採ってもよい。なお、ここで用いる接着剤には、公知のものを用いることができるが、シームシーラントと呼ばれるシリコーン系接着剤が接着力や接着耐久性などの面から好適である。 When processing an air bag base cloth (silicone rubber coated base cloth for an air bag) having a silicone rubber layer on at least one surface manufactured in this way into an air bag, at least the inner surface side of the air bag is made of silicone rubber. Examples thereof include a method in which the outer peripheral portions of two coated plain woven fabrics are bonded to each other with an adhesive, and the adhesive layers are sewn together. Further, as described above, the addition-curable liquid silicone rubber composition is coated with a predetermined coating amount on at least the inside of the air bag base fabric prepared by weaving in a bag in advance, and cured under a predetermined curing condition. You may take the method. As the adhesive used here, known adhesives can be used, but a silicone-based adhesive called seam sealant is suitable in terms of adhesive strength and adhesive durability.
以下、調製例及び実施例と比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、粘度は回転粘度計により測定した。また、組成物に係る部は質量部を意味し、室温は２５℃を意味する。 Hereinafter, the present invention will be specifically described with reference to Preparation Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. The viscosity was measured with a rotary viscometer. Further, the part related to the composition means a mass part, and the room temperature means 25 ° C.
［調製例１］
粘度が約３０，０００ｍＰａ・ｓであり、平均重合度が７５０である分子鎖両末端ビニルジメチルシロキシ基封鎖ジメチルポリシロキサン（Ａ１）６０部、へキサメチルジシラザン８部、下記（４）式で表されるビニル基を有するポリシロキサン（Ｄ１）０．８部、水２部、及びＢＥＴ法による比表面積が約３００ｍ2／ｇであるシリカ微粉末（Ｃ）（商品名：アエロジル３００、日本アエロジル社製）４０部を、ニーダー中で１時間混合した。その後、へキサメチルジシラザン８部を投入し、さらに１時間混合した。次にニーダー内の温度を１５０℃に昇温し、引き続き２時間混合した。次いで、該温度を１００℃まで降温した後、粘度が約３０，０００ｍＰａ・ｓであり、平均重合度が７５０である分子鎖両末端ビニルジメチルシロキシ基封鎖ジメチルポリシロキサン（Ａ１）３０部を添加し、均一になるまで混合することで、ベースコンパウンド（１）を得た。
60 parts of vinyldimethylsiloxy group-blocked dimethylpolysiloxane (A1) at both ends of the molecular chain having a viscosity of about 30,000 mPa · s and an average degree of polymerization of 750, 8 parts of hexamethyldisilazane, according to the following formula (4). 0.8 part of polysiloxane (D1) having a vinyl group, 2 parts of water, and silica fine powder (C) having a specific surface area of about 300 m 2 / g by the BET method (trade name: Aerosil 300, Nippon Aerosil) 40 parts (manufactured by the company) were mixed in a kneader for 1 hour. Then, 8 parts of hexamethyldisilazan was added, and the mixture was further mixed for 1 hour. Next, the temperature in the kneader was raised to 150 ° C., and the mixture was continued for 2 hours. Then, after the temperature was lowered to 100 ° C., 30 parts of vinyl dimethylsiloxy group-sealed dimethylpolysiloxane (A1) having a viscosity of about 30,000 mPa · s and an average degree of polymerization of 750 was added. , The base compound (1) was obtained by mixing until uniform.
［調製例２］
粘度が約３０，０００ｍＰａ・ｓであり、平均重合度が７５０である分子鎖両末端ビニルジメチルシロキシ基封鎖ジメチルポリシロキサン（Ａ１）６０部、へキサメチルジシラザン８部、下記（５）式で表される片末端にビニル基を有するポリシロキサン（Ｄ２）０．５８部、水２部、及びＢＥＴ法による比表面積が約３００ｍ2／ｇであるシリカ微粉末（Ｃ）（商品名：アエロジル３００、日本アエロジル社製）４０部を、ニーダー中で１時間混合した。その後、へキサメチルジシラザン８部を投入し、さらに１時間混合した。次にニーダー内の温度を１５０℃に昇温し、引き続き２時間混合した。次いで、該温度を１００℃まで降温した後、粘度が約３０，０００ｍＰａ・ｓであり、平均重合度が７５０である分子鎖両末端ビニルジメチルシロキシ基封鎖ジメチルポリシロキサン（Ａ１）３０部を添加し、均一になるまで混合することで、ベースコンパウンド（２）を得た。
60 parts of vinyldimethylsiloxy group-blocked dimethylpolysiloxane (A1) at both ends of the molecular chain having a viscosity of about 30,000 mPa · s and an average degree of polymerization of 750, 8 parts of hexamethyldisilazane, according to the following formula (5). 0.58 parts of polysiloxane (D2) having a vinyl group at one end, 2 parts of water, and silica fine powder (C) having a specific surface area of about 300 m 2 / g by the BET method (trade name: Aerosil 300). , Nippon Aerosil Co., Ltd.) 40 parts were mixed in a kneader for 1 hour. Then, 8 parts of hexamethyldisilazan was added, and the mixture was further mixed for 1 hour. Next, the temperature in the kneader was raised to 150 ° C., and the mixture was continued for 2 hours. Then, after the temperature was lowered to 100 ° C., 30 parts of vinyl dimethylsiloxy group-sealed dimethylpolysiloxane (A1) having a viscosity of about 30,000 mPa · s and an average degree of polymerization of 750 was added. , The base compound (2) was obtained by mixing until uniform.
［調製例３］
粘度が約３０，０００ｍＰａ・ｓであり、平均重合度が７５０である分子鎖両末端ビニルジメチルシロキシ基封鎖ジメチルポリシロキサン（Ａ１）６０部、へキサメチルジシラザン８部、１，３－ジビニル－１，１，３，３－テトラメチルジシラザン（Ｄ３）０．１部、水２部、及びＢＥＴ法による比表面積が約３００ｍ2／ｇであるシリカ微粉末（Ｃ）（商品名：アエロジル３００、日本アエロジル社製）４０部を、ニーダー中で１時間混合した。その後、へキサメチルジシラザン８部を投入し、さらに１時間混合した。次にニーダー内の温度を１５０℃に昇温し、引き続き２時間混合した。次いで、該温度を１００℃まで降温した後、粘度が約３０，０００ｍＰａ・ｓであり、平均重合度が７５０である分子鎖両末端ビニルジメチルシロキシ基封鎖ジメチルポリシロキサン（Ａ１）３０部を添加し、均一になるまで混合することで、ベースコンパウンド（３）を得た。[Preparation Example 3]
Molecular chain double-ended vinyl dimethylsiloxy group-sealed dimethylpolysiloxane (A1) 60 parts, hexamethyldisilazane 8 parts, 1,3-divinyl- with a viscosity of about 30,000 mPa · s and an average degree of polymerization of 750. 1,1,3,3-Tetramethyldisilazane (D3) 0.1 part, water 2 parts, and silica fine powder (C) having a specific surface area of about 300 m 2 / g by the BET method (trade name: Aerosil 300) , Nippon Aerosil Co., Ltd.) 40 parts were mixed in a kneader for 1 hour. Then, 8 parts of hexamethyldisilazan was added, and the mixture was further mixed for 1 hour. Next, the temperature in the kneader was raised to 150 ° C., and the mixture was continued for 2 hours. Then, after the temperature was lowered to 100 ° C., 30 parts of vinyl dimethylsiloxy group-sealed dimethylpolysiloxane (A1) having a viscosity of about 30,000 mPa · s and an average degree of polymerization of 750 was added. , The base compound (3) was obtained by mixing until uniform.
［調製例４］
粘度が約３０，０００ｍＰａ・ｓであり、平均重合度が７５０である分子鎖両末端ビニルジメチルシロキシ基封鎖ジメチルポリシロキサン（Ａ１）６０部、へキサメチルジシラザン８部、水２部、およびＢＥＴ法による比表面積が約３００ｍ2／ｇであるシリカ微粉末（Ｃ）（商品名：アエロジル３００、日本アエロジル社製）４０部を、ニーダー中で１時間混合した。その後、へキサメチルジシラザン８部を投入し、さらに１時間混合した。次にニーダー内の温度を１５０℃に昇温し、引き続き２時間混合した。次いで、該温度を１００℃まで降温した後、粘度が約３０，０００ｍＰａ・ｓであり、平均重合度が７５０である分子鎖両末端ビニルジメチルシロキシ基封鎖ジメチルポリシロキサン（Ａ１）３０部を添加し、均一になるまで混合することで、ベースコンパウンド（４）を得た。[Preparation Example 4]
60 parts of vinyldimethylsiloxy group-blocked dimethylpolysiloxane (A1) with a viscosity of about 30,000 mPa · s and an average degree of polymerization of 750, 8 parts of hexamethyldisilazane, 2 parts of water, and BET. 40 parts of silica fine powder (C) (trade name: Aerosil 300, manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of about 300 m 2 / g according to the method was mixed in a kneader for 1 hour. Then, 8 parts of hexamethyldisilazan was added, and the mixture was further mixed for 1 hour. Next, the temperature in the kneader was raised to 150 ° C., and the mixture was continued for 2 hours. Then, after the temperature was lowered to 100 ° C., 30 parts of vinyl dimethylsiloxy group-sealed dimethylpolysiloxane (A1) having a viscosity of about 30,000 mPa · s and an average degree of polymerization of 750 was added. , The base compound (4) was obtained by mixing until uniform.
［実施例１］
調製例１で得られたベースコンパウンド（１）１１０部に、粘度が約１００，０００ｍＰａ・ｓであり、平均重合度が１，０００である分子鎖両末端ビニルジメチルシロキシ基封鎖ジメチルポリシロキサン（Ａ２）５９．５部、架橋剤として粘度が１２ｍＰａ・ｓであり、平均重合度が１８である分子鎖両末端及び分子鎖非末端にケイ素原子に結合した水素原子を有する分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖のジメチルシロキサン・メチルハイドロジェンシロキサン共重合体（Ｂ）（ＳｉＨ基量０．００３５ｍｏｌ／ｇ）８．５部（ＳｉＨ基／ビニル基＝５．５ｍｏｌ／ｍｏｌ）、γ－グリシドキシプロピルトリメトキシシラン（Ｆ）０．９部、１－エチニルシクロヘキサノール０．０７５部、塩化白金酸／１，３－ジビニルテトラメチルジシロキサン錯体を白金原子含有量として１質量％含有するジメチルポリシロキサン溶液（Ｅ）０．２８部、及びジルコニウムテトラアセチルアセトネート（Ｇ）０．２６部を１時間混合して、組成物Ａ（粘度２００Ｐａ・ｓ）を調製した。次に組成物Ａに関して、硬化物のゴム物性及び内圧保持性を試験した結果を表１に示す。[Example 1]
110 parts of the base compound (1) obtained in Preparation Example 1 has a molecular chain double-ended vinyldimethylsiloxy group-sealed dimethylpolysiloxane (A2) having a viscosity of about 100,000 mPa · s and an average degree of polymerization of 1,000. ) 59.5 parts, dimethylhydrogen at both ends of the molecular chain having a hydrogen atom bonded to a silicon atom at both ends of the molecular chain and non-terminal of the molecular chain having a viscosity of 12 mPa · s as a cross-linking agent and an average degree of polymerization of 18. Dimethylsiloxane / methylhydrogensiloxane copolymer (B) (SiH group amount 0.0035 mol / g) 8.5 parts (SiH group / vinyl group = 5.5 mol / mol), γ-glycidoxy Dimethylpolysiloxane containing 0.9 part of propyltrimethoxysilane (F), 0.075 part of 1-ethynylcyclohexanol, and 1% by mass of platinum chloride acid / 1,3-divinyltetramethyldisiloxane complex as the platinum atom content. 0.28 part of the solution (E) and 0.26 part of zirconium tetraacetylacetonate (G) were mixed for 1 hour to prepare a composition A (viscosity 200 Pa · s). Next, Table 1 shows the results of testing the rubber physical characteristics and internal pressure retention of the cured product with respect to the composition A.
＜内圧保持性試験方法＞
得られた液状シリコーンゴム組成物をナイフコーターで６６ナイロン基布（２１０デニール）から製造した袋織りエアーバッグの片面に５０ｇ／ｍ2になるように均一にコーティングし、オーブン中で、１８０℃で３分間加熱して硬化させた。その後、もう一方の面も同様にシリコーンコーティングを行い、１８０℃で３分間加熱硬化させることで袋織りエアーバッグを作製した。このエアーバッグを用いて、内圧保持性試験を行った。内圧保持性試験は、エアーバッグを１００ｋＰａの圧力で膨張させ、３０秒後の残存圧力を測定し、この値により評価した。<Internal pressure retention test method>
The obtained liquid silicone rubber composition was uniformly coated on one side of a bag-woven air bag manufactured from 66 nylon base cloth (210 denier) with a knife coater so as to be 50 g / m 2 , and then in an oven at 180 ° C. It was cured by heating for 3 minutes. Then, the other surface was similarly coated with silicone and heat-cured at 180 ° C. for 3 minutes to prepare a bag-woven air bag. An internal pressure retention test was performed using this air bag. In the internal pressure retention test, the air bag was inflated at a pressure of 100 kPa, and the residual pressure after 30 seconds was measured and evaluated by this value.
＜硬化物のゴム物性の測定方法＞
調製した組成物を１５０℃で５分プレスキュアーして２．０ｍｍ厚のシートを作製し、このシートについて、ＪＩＳ Ｋ ６２４９：２００３記載の方法で、硬さ、切断時伸び、引張強さ、引裂強さを測定した。結果を表１に示す。<Measuring method of rubber physical properties of cured product>
The prepared composition was press-cured at 150 ° C. for 5 minutes to prepare a sheet having a thickness of 2.0 mm, and the sheet was subjected to hardness, elongation at cutting, tensile strength, and tear by the method described in JIS K 6249: 2003. The strength was measured. The results are shown in Table 1.
［実施例２］
実施例１のベースコンパウンド（１）を調製例２で調製したベースコンパウンド（２） に同質量部で置き換えたこと以外は同様にして組成物Ｂ（ＳｉＨ基／ビニル基＝５．５ｍｏｌ／ｍｏｌ、粘度１９０Ｐａ・ｓ）を調製し、実施例１と同様に硬化物のゴム物性及び内圧保持性を試験した結果を表１に示す。[Example 2]
Composition B (SiH group / vinyl group = 5.5 mol / mol, except that the base compound (1) of Example 1 was replaced with the base compound (2) prepared in Preparation Example 2 by the same mass part, Table 1 shows the results of preparing a viscosity of 190 Pa · s) and testing the rubber physical properties and internal pressure retention of the cured product in the same manner as in Example 1.
［参考例１］
実施例１のベースコンパウンド（１）を調製例３で調製したベースコンパウンド（３）に同質量部で置き換えたこと以外は同様にして組成物Ｃ（ＳｉＨ基／ビニル基＝５．５ｍｏｌ／ｍｏｌ、粘度１９０Ｐａ・ｓ）を調製し、実施例１と同様に硬化物のゴム物性及び内圧保持性を試験した結果を表１に示す。
[ Reference example 1 ]
Composition C (SiH group / vinyl group = 5.5 mol / mol, except that the base compound (1) of Example 1 was replaced with the base compound (3) prepared in Preparation Example 3 by the same mass part, Table 1 shows the results of preparing a viscosity of 190 Pa · s) and testing the rubber physical properties and internal pressure retention of the cured product in the same manner as in Example 1.
［比較例１］
実施例１のベースコンパウンド（１）を調製例４で調製したベースコンパウンド（４） に同質量部で置き換えたこと以外は同様にして組成物Ｄ（ＳｉＨ基／ビニル基＝６．５ｍｏｌ／ｍｏｌ、粘度１８０Ｐａ・ｓ）を調製し、実施例１と同様に硬化物のゴム物性及び内圧保持性を試験した結果を表１に示す。[Comparative Example 1]
Composition D (SiH group / vinyl group = 6.5 mol / mol, except that the base compound (1) of Example 1 was replaced with the base compound (4) prepared in Preparation Example 4 by the same mass part, Table 1 shows the results of preparing a viscosity of 180 Pa · s) and testing the rubber physical properties and internal pressure retention of the cured product in the same manner as in Example 1.
［比較例２］
比較例１で調製した組成物Ｄに上記（４）式で表されるビニル基含有のポリシロキサン（Ｄ１）０．８部を２５℃で１５分混合し、組成物Ｅ（ＳｉＨ基／ビニル基＝５．５ｍｏｌ／ｍｏｌ、粘度２２０Ｐａ・ｓ）を調製し、実施例１と同様に硬化物のゴム物性及び内圧保持性を試験した結果を表１に示す。[Comparative Example 2]
0.8 part of the vinyl group-containing polysiloxane (D1) represented by the above formula (4) was mixed with the composition D prepared in Comparative Example 1 at 25 ° C. for 15 minutes, and the composition E (SiH group / vinyl group) was mixed. = 5.5 mol / mol, viscosity 220 Pa · s) was prepared, and the results of testing the rubber physical characteristics and internal pressure retention of the cured product in the same manner as in Example 1 are shown in Table 1.
Claims (6)
（Ｂ）１分子中に少なくとも２個のケイ素原子に結合した水素原子（ＳｉＨ基）を含有するオルガノハイドロジェンポリシロキサン：本成分中に含まれるＳｉＨ基が、（Ａ）成分及び下記（Ｄ）成分中に含まれるケイ素原子結合アルケニル基の合計１モル当たり、１～１０モルとなる量、
（Ｃ）ＢＥＴ法比表面積が５０ｍ2／ｇ以上であるシリカ微粉末：１～５０質量部、
（Ｄ）１分子中にビニル基を１個以上有するクロロシラン類、シラザン類、及び下記式（１）又は（２）で表わされる有機ケイ素化合物から選ばれるものである表面処理剤（但し、（Ａ）成分を除く。また、上記シラザン類のうち、１，３－ジビニル－１，１，３，３－テトラメチルジシラザン及び１，１，３，３－テトラビニル－１，３－ジメチルジシラザンを除く。）
（Ｅ）ヒドロシリル化反応用触媒：（Ａ）～（Ｄ）の合計質量に対して、触媒金属元素の質量換算で１～５００ｐｐｍ、
（Ｆ）接着性付与官能基を含有する有機ケイ素化合物（但し、（Ａ）、（Ｂ）、（Ｄ）成分を除く。）：０．１～１０質量部
を必須成分とすることを特徴とするエアーバッグ用付加硬化型液状シリコーンゴム組成物。 (A) Organopolysiloxane having a degree of polymerization of 100 to 2,000 containing an alkenyl group bonded to two or more silicon atoms in one molecule: 100 parts by mass,
(B) Organohydrogenpolysiloxane containing a hydrogen atom (SiH group) bonded to at least two silicon atoms in one molecule: The SiH group contained in this component is the component (A) and the following (D). An amount of 1 to 10 mol per 1 mol of the total silicon atom-bonded alkenyl groups contained in the component,
(C) BET method Silica fine powder having a specific surface area of 50 m 2 / g or more: 1 to 50 parts by mass,
(D) A surface treatment agent selected from chlorosilanes and silazanes having one or more vinyl groups in one molecule, and an organosilicon compound represented by the following formula (1) or (2) (however, (A). ) Components are excluded. Of the above silazanes, 1,3-divinyl-1,1,3,3-tetramethyldisilazane and 1,1,3,3-tetravinyl-1,3-dimethyldisilazane are excluded. Except for. )
(E) Catalyst for hydrosilylation reaction: 1 to 500 ppm in terms of mass of the catalyst metal element with respect to the total mass of (A) to (D).
(F) Organosilicon compound containing an adhesive-imparting functional group (excluding the components (A), (B) and (D)): 0.1 to 10 parts by mass as an essential component. Additive curable liquid silicone rubber composition for air bags.
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| JP2010083946A (en) | 2008-09-30 | 2010-04-15 | Shin-Etsu Chemical Co Ltd | Silicone composition for use in covering, and covered film covered with cured film of the same |
| JP2013087203A (en) | 2011-10-19 | 2013-05-13 | Shin-Etsu Chemical Co Ltd | Liquid silicone rubber coating composition, curtain airbag, and method for manufacturing the curtain airbag |
| JP2013516520A (en) | 2009-12-30 | 2013-05-13 | ダウ コーニング コーポレーション | Silicone coating composition for airbags |
| JP2015085271A (en) | 2013-10-31 | 2015-05-07 | 信越化学工業株式会社 | Production method of silicone air bag and improvement method of blocking resistance |
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| JP2010083946A (en) | 2008-09-30 | 2010-04-15 | Shin-Etsu Chemical Co Ltd | Silicone composition for use in covering, and covered film covered with cured film of the same |
| JP2013516520A (en) | 2009-12-30 | 2013-05-13 | ダウ コーニング コーポレーション | Silicone coating composition for airbags |
| JP2013087203A (en) | 2011-10-19 | 2013-05-13 | Shin-Etsu Chemical Co Ltd | Liquid silicone rubber coating composition, curtain airbag, and method for manufacturing the curtain airbag |
| JP2015085271A (en) | 2013-10-31 | 2015-05-07 | 信越化学工業株式会社 | Production method of silicone air bag and improvement method of blocking resistance |
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