JP7371717B2 - Addition-curable liquid silicone rubber composition - Google Patents
Addition-curable liquid silicone rubber composition Download PDFInfo
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- JP7371717B2 JP7371717B2 JP2022058364A JP2022058364A JP7371717B2 JP 7371717 B2 JP7371717 B2 JP 7371717B2 JP 2022058364 A JP2022058364 A JP 2022058364A JP 2022058364 A JP2022058364 A JP 2022058364A JP 7371717 B2 JP7371717 B2 JP 7371717B2
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- 239000000203 mixture Substances 0.000 title claims description 55
- 229920002379 silicone rubber Polymers 0.000 title claims description 53
- 239000004944 Liquid Silicone Rubber Substances 0.000 title claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 48
- 125000003342 alkenyl group Chemical group 0.000 claims description 40
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 229920001296 polysiloxane Polymers 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910021485 fumed silica Inorganic materials 0.000 claims description 14
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims description 11
- 238000004438 BET method Methods 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000007259 addition reaction Methods 0.000 claims description 6
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 239000004945 silicone rubber Substances 0.000 description 38
- -1 chloropropyl group Chemical group 0.000 description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000004205 dimethyl polysiloxane Substances 0.000 description 23
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 23
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 21
- 238000003756 stirring Methods 0.000 description 15
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000001723 curing Methods 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 229910002012 Aerosil® Inorganic materials 0.000 description 6
- 229910002018 Aerosil® 300 Inorganic materials 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 5
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical compound [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000011417 postcuring Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000012756 surface treatment agent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000006459 hydrosilylation 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 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
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000005998 bromoethyl group Chemical group 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 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
- 238000007796 conventional method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 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
- 125000005388 dimethylhydrogensiloxy group Chemical group 0.000 description 2
- 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 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 210000002445 nipple Anatomy 0.000 description 2
- 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 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- QYXVDGZUXHFXTO-UHFFFAOYSA-L 3-oxobutanoate;platinum(2+) Chemical compound [Pt+2].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O QYXVDGZUXHFXTO-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- ZPECUSGQPIKHLT-UHFFFAOYSA-N bis(ethenyl)-dimethoxysilane Chemical compound CO[Si](OC)(C=C)C=C ZPECUSGQPIKHLT-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- VSYLGGHSEIWGJV-UHFFFAOYSA-N diethyl(dimethoxy)silane Chemical compound CC[Si](CC)(OC)OC VSYLGGHSEIWGJV-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- WKWOFMSUGVVZIV-UHFFFAOYSA-N n-bis(ethenyl)silyl-n-trimethylsilylmethanamine Chemical compound C[Si](C)(C)N(C)[SiH](C=C)C=C WKWOFMSUGVVZIV-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 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
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- HUZZQXYTKNNCOU-UHFFFAOYSA-N triethyl(methoxy)silane Chemical compound CC[Si](CC)(CC)OC HUZZQXYTKNNCOU-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、硬度上昇を抑えつつ、高強度化、特に引裂強度の高いシリコーンゴムを与えることが可能な付加硬化性液状シリコーンゴム組成物に関する。 The present invention relates to an addition-curable liquid silicone rubber composition that can provide a silicone rubber with high strength, particularly high tear strength, while suppressing an increase in hardness.
シリコーンゴムは、耐熱性、耐寒性、安全性、外観の良さ(透明性)、肌触りの良さ、更には耐久性の良さから、哺乳瓶用乳首や食品用等のヘルスケア材料、車載用のホースやガスケット材料、建築部材、繊維のコーティング材料等、幅広い分野で使用されている。 Due to its heat resistance, cold resistance, safety, good appearance (transparency), good texture, and durability, silicone rubber is used in healthcare materials such as baby bottle nipples, food products, and car hoses. It is used in a wide range of fields, including gasket materials, building materials, and fiber coating materials.
通常シリコーンゴムは強度が低く、これまでに高強度化、特に、引裂強さを向上させる多くの課題がある。しかし、従来の高強度化の方法では、シリコーンゴム組成物に対し、アルケニル基を多く有するポリオルガノシロキサンレジンを添加したり(特許文献1:特開2010-13295号公報、特許文献2:特開2015-52027号公報、特許文献3:特開2015-52026号公報)、ビニル量の多いポリオルガノシロキサンを添加したりする方法(特許文献4:特開平7-331079号公報、特許文献5:特開2011-46826号公報)が提案されているが、いずれも高ビニル価の添加剤を使用しているため、添加前の組成物に比べ、硬化後のゴムの硬さが大きく上昇してしまい、狙いの硬さに調整する事や低硬度ゴムを製造する事が困難であった。 Silicone rubber usually has low strength, and there have been many challenges to date to improve its strength, particularly its tear strength. However, conventional methods for increasing strength include adding a polyorganosiloxane resin having a large number of alkenyl groups to a silicone rubber composition (Patent Document 1: JP 2010-13295, Patent Document 2: JP No. 2015-52027, Patent Document 3: JP 2015-52026), a method of adding polyorganosiloxane with a large amount of vinyl (Patent Document 4: JP 7-331079, Patent Document 5: However, since they all use high vinyl value additives, the hardness of the rubber after curing increases significantly compared to the composition before addition. However, it was difficult to adjust the hardness to the desired hardness and to manufacture low hardness rubber.
本発明は、上記事情を改善するためになされたもので、硬度上昇を抑えつつ、高強度化、特に引裂強度の高いシリコーンゴムを与えることが可能な付加硬化性液状シリコーンゴム組成物を提供することを目的とする。 The present invention has been made in order to improve the above-mentioned situation, and provides an addition-curable liquid silicone rubber composition capable of providing a silicone rubber with high strength, particularly high tear strength, while suppressing an increase in hardness. The purpose is to
本発明者らは、上記目的を達成するため鋭意検討を行った結果、後述する(A)~(E)各成分の特定量を必須成分とした付加硬化性液状シリコーンゴム組成物において、特に(A)成分の1分子中に少なくとも2個のケイ素原子に結合したアルケニル基を有し、分子鎖両末端がトリオルガノシロキシ基で封鎖され、主鎖がジオルガノシロキサン単位の繰り返しからなる平均重合度が150~1,500の直鎖状構造を有する、25℃で液状のオルガノポリシロキサンと(B)成分の特定の置換基を有し、特定数のアルケニル基を有するかご型シルセスキオキサンとを組み合わせて用いる事により、高硬度化せずに引裂強度の高いシリコーンゴムが得られることを見出し、本発明をなすに至った。 As a result of intensive studies to achieve the above object, the present inventors have found that an addition-curable liquid silicone rubber composition containing specific amounts of each of the components (A) to (E) described below as essential components, in particular ( A) An average degree of polymerization in which each molecule of the component has at least two alkenyl groups bonded to silicon atoms, both ends of the molecular chain are blocked with triorganosiloxy groups, and the main chain consists of repeating diorganosiloxane units. an organopolysiloxane that is liquid at 25°C and has a linear structure of 150 to 1,500, and a cage-type silsesquioxane that has a specific substituent group and a specific number of alkenyl groups as component (B). It has been discovered that by using a combination of the following, a silicone rubber with high tear strength can be obtained without increasing the hardness, and the present invention has been completed.
従って、本発明は、下記に示す付加硬化性液状シリコーンゴム組成物を提供する。
〔1〕
(A)1分子中に少なくとも2個のケイ素原子に結合したアルケニル基を有し、分子鎖両末端がトリオルガノシロキシ基で封鎖され、主鎖がジオルガノシロキサン単位の繰り返しからなる平均重合度が150~1,500の直鎖状構造を有する、25℃で液状のアルケニル基含有オルガノポリシロキサン:100質量部、
(B)下記一般式(I)
で示され、(B)成分中のアルケニル基の含有量が2.0×10-5mol/g~1.5×10-3mol/gであるかご型構造を有するシルセスキオキサン:(A)成分100質量部に対し、1~100質量部、
(C)1分子中にケイ素原子に結合した水素原子を少なくとも2個有するオルガノハイドロジェンポリシロキサン:(A)成分と(B)成分の合計100質量部に対し、0.1~40質量部、
(D)BET法による比表面積が50m2/g以上であるヒュームドシリカ:(A)成分100質量部に対し、10~100質量部、
(E)付加反応触媒:(A)成分と(B)成分の合計100質量部に対し、白金族金属(質量換算)として0.1~1,000ppm
を含有することを特徴とする付加硬化性液状シリコーンゴム組成物。
〔2〕
(B)成分中のR1において、分子中の全R1の内、3~6個がビニル基であることを特徴とする〔1〕記載の付加硬化性液状シリコーンゴム組成物。
Accordingly, the present invention provides the addition-curable liquid silicone rubber composition shown below.
[1]
(A) has at least two silicon-bonded alkenyl groups in one molecule, both ends of the molecular chain are blocked with triorganosiloxy groups, and the main chain consists of repeating diorganosiloxane units; the average degree of polymerization is 100 parts by mass of an alkenyl group-containing organopolysiloxane that is liquid at 25°C and has a linear structure of 150 to 1,500;
(B) The following general formula (I)
A silsesquioxane having a cage structure and having a content of alkenyl groups in component (B) of 2.0×10 -5 mol/g to 1.5×10 -3 mol/g: ( A) 1 to 100 parts by mass per 100 parts by mass of component,
(C) Organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule: 0.1 to 40 parts by mass based on a total of 100 parts by mass of components (A) and (B),
(D) Fumed silica with a specific surface area of 50 m 2 /g or more by BET method: 10 to 100 parts by mass per 100 parts by mass of component (A),
(E) Addition reaction catalyst: 0.1 to 1,000 ppm as platinum group metal (in terms of mass) based on a total of 100 parts by mass of components (A) and (B)
An addition-curable liquid silicone rubber composition comprising:
[2]
The addition-curable liquid silicone rubber composition according to [ 1 ], wherein 3 to 6 R 1 in the molecule in the component (B) are vinyl groups.
本発明によれば、上記(A)~(E)成分の特定量の組み合わせにより、高硬度化せずに引裂強度の高いシリコーンゴムを与えることが可能な付加硬化性液状シリコーンゴム組成物を提供することができる。 According to the present invention, there is provided an addition-curable liquid silicone rubber composition that can provide a silicone rubber with high tear strength without increasing hardness by combining specific amounts of the above-mentioned components (A) to (E). can do.
〔付加硬化性液状シリコーンゴム組成物〕
本発明の付加硬化性液状シリコーンゴム組成物は、以下の(A)~(E)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。
(A)アルケニル基含有オルガノポリシロキサン
まず、(A)成分である25℃で液状のアルケニル基含有オルガノポリシロキサンは、本発明の組成物の主剤(ベースポリマー)であって、1分子中に少なくとも2個のケイ素原子に結合したアルケニル基を有し、平均重合度が1,500以下のオルガノポリシロキサンである。好ましくは、該アルケニル基を分子鎖末端に含有する。本発明の組成物において、25℃で液状の(即ち、自己流動性のある)アルケニル基含有オルガノポリシロキサンとしては、このオルガノポリシロキサン((A)成分)のみからなるものである。
[Addition-curable liquid silicone rubber composition]
The addition-curable liquid silicone rubber composition of the present invention contains the following components (A) to (E) and is liquid at room temperature (25°C). Each component will be explained in detail below.
(A) Alkenyl group-containing organopolysiloxane
First, component (A), an alkenyl group-containing organopolysiloxane that is liquid at 25°C, is the main component (base polymer) of the composition of the present invention, and contains alkenyl groups bonded to at least two silicon atoms in one molecule. It is an organopolysiloxane having an average degree of polymerization of 1,500 or less. Preferably, the alkenyl group is contained at the end of the molecular chain. In the composition of the present invention, the alkenyl group-containing organopolysiloxane that is liquid (that is, self-flowing) at 25° C. consists only of this organopolysiloxane (component (A)).
ここで、1分子中に少なくとも2個のケイ素原子に結合したアルケニル基を有するオルガノポリシロキサンとしては、下記平均組成式(IV)で示される、25℃で液状のものを用いることができる。
R3
aSiO(4-a)/2 (IV)
(式中、R3は互いに同一又は異種の炭素数1~10、好ましくは1~8の非置換又は置換の1価炭化水素基であり、aは1.5~2.8、好ましくは1.8~2.5、より好ましくは1.95~2.05の範囲の正数である。)
Here, as the organopolysiloxane having at least two silicon-bonded alkenyl groups in one molecule, one that is liquid at 25° C. and is represented by the following average composition formula (IV) can be used.
R 3 a SiO (4-a)/2 (IV)
(In the formula, R 3 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, which is the same or different from each other, and a is 1.5 to 2.8, preferably 1 (It is a positive number in the range of .8 to 2.5, more preferably 1.95 to 2.05.)
ここで、上記R3で示されるケイ素原子に結合した炭素数1~10、好ましくは1~8の非置換又は置換の1価炭化水素基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、tert-ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、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、ビニル基、アリル基、ブテニル基、ヘキセニル基、シクロヘキセニル基、オクテニル基等のアルケニル基や、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、シアノ基等で置換したもの、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、トリフロロプロピル基、シアノエチル基等が挙げられるが、全R3の90モル%以上がメチル基であることが好ましい。 Here, the unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, bonded to the silicon atom represented by R 3 above is a methyl group, an ethyl group, a propyl group, an isopropyl group. , alkyl groups such as butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, phenyl group, tolyl group, xylyl group, naphthyl group, etc. Aralkyl groups such as aryl groups, benzyl groups, phenylethyl groups, phenylpropyl groups, alkenyl groups such as vinyl groups, allyl groups, butenyl groups, hexenyl groups, cyclohexenyl groups, octenyl groups, and one of the hydrogen atoms of these groups. Examples include those partially or entirely substituted with a halogen atom such as fluorine, bromine, or chlorine, or a cyano group, such as a chloromethyl group, chloropropyl group, bromoethyl group, trifluoropropyl group, or cyanoethyl group, but all R 3 It is preferable that 90 mol% or more of the group is a methyl group.
また、R3のうち少なくとも2個はアルケニル基(炭素数2~8のものが好ましく、更に好ましくは2~6であり、特に好ましくはビニル基である。)であることが必要である。
なお、アルケニル基の含有量は、オルガノポリシロキサン中1.0×10-6mol/g~3.0×10-3mol/g、特に1.0×10-5mol/g~2.0×10-3mol/gとすることが好ましい。アルケニル基の量が、この範囲内であれば、硬度が適切な範囲内となり、優れたゴム物性を有する硬化物を得ることができる。
Furthermore, at least two of R 3 need to be alkenyl groups (preferably those having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably vinyl groups).
The content of alkenyl groups in the organopolysiloxane is 1.0 x 10 -6 mol/g to 3.0 x 10 -3 mol/g, particularly 1.0 x 10 -5 mol/g to 2.0 It is preferable to set it as x10-3 mol/g. If the amount of alkenyl groups is within this range, the hardness will be within an appropriate range and a cured product with excellent rubber properties can be obtained.
このオルガノポリシロキサンの構造は、基本的には、分子鎖両末端がトリオルガノシロキシ基で封鎖され、主鎖がジオルガノシロキサン単位の繰り返しからなる直鎖状構造を有するが、部分的には、モノオルガノシルセスキオキサン単位を有する分岐状構造や環状構造などであってもよい。 The structure of this organopolysiloxane basically has a linear structure in which both ends of the molecular chain are blocked with triorganosiloxy groups and the main chain consists of repeating diorganosiloxane units, but partially It may be a branched structure or a cyclic structure having a monoorganosilsesquioxane unit.
このアルケニル基は、分子鎖末端のケイ素原子に結合していても、分子鎖途中(分子鎖非末端)のケイ素原子に結合していてもよいが、本発明の(A)成分においては、分子鎖末端のケイ素原子(即ち、トリオルガノシロキシ基中のケイ素原子)に結合したアルケニル基を分子中に少なくとも1個、好ましくは2個以上含有することが好ましく、分子鎖途中のケイ素原子(即ち、ジオルガノシロキサン単位又はモノオルガノシルセスキオキサン単位中のケイ素原子)に結合したアルケニル基は含有していても、していなくてもよいが、分子鎖末端にアルケニル基が1個しかない場合は、少なくとも1個のアルケニル基が分子鎖途中に必要なのは言うまでもない。分子鎖末端のケイ素原子に結合したアルケニル基を少なくとも1個、好ましくは2個以上含有することで、低硬度でかつ高引裂強度のゴム硬化物が得られる。 This alkenyl group may be bonded to a silicon atom at the end of the molecular chain, or may be bonded to a silicon atom in the middle of the molecular chain (non-terminal of the molecular chain), but in component (A) of the present invention, It is preferable that the molecule contains at least one, preferably two or more, alkenyl groups bonded to the silicon atom at the end of the chain (i.e., the silicon atom in the triorganosiloxy group); The alkenyl group bonded to the silicon atom in the diorganosiloxane unit or monoorganosilsesquioxane unit may or may not be present, but if there is only one alkenyl group at the end of the molecular chain, Needless to say, at least one alkenyl group is required in the middle of the molecular chain. By containing at least one, preferably two or more alkenyl groups bonded to the silicon atom at the end of the molecular chain, a cured rubber product with low hardness and high tear strength can be obtained.
このオルガノポリシロキサンの平均重合度は、1,500以下であることが必要であり、通常100~1,500、好ましくは150~1,100である。100未満では、十分なゴム感が得られない場合があり、1,500より高いと粘度が高くなり、成形が困難になってしまう。
なお、本発明中で言及する平均重合度とは、数平均重合度のことを指し、下記条件で測定したゲルパーミエーションクロマトグラフィ(GPC)によるポリスチレンを標準物質とした平均重合度を指すこととする。
[測定条件]
展開溶媒:トルエン
流量:1mL/min
検出器:示差屈折率検出器(RI)
カラム:KF-805L×2(Shodex社製)
カラム温度:25℃
試料注入量:30μL(濃度0.2質量%のトルエン溶液)
The average degree of polymerization of this organopolysiloxane must be 1,500 or less, usually 100 to 1,500, preferably 150 to 1,100. If it is less than 100, a sufficient rubbery feel may not be obtained, and if it is more than 1,500, the viscosity becomes high and molding becomes difficult.
The average degree of polymerization referred to in the present invention refers to the number average degree of polymerization, and refers to the average degree of polymerization measured by gel permeation chromatography (GPC) under the following conditions using polystyrene as a standard material. .
[Measurement condition]
Developing solvent: toluene Flow rate: 1 mL/min
Detector: Differential refractive index detector (RI)
Column: KF-805L x 2 (manufactured by Shodex)
Column temperature: 25℃
Sample injection amount: 30 μL (toluene solution with a concentration of 0.2% by mass)
このような(A)成分のオルガノポリシロキサンとして、具体的には、分子鎖両末端ジオルガノアルケニルシロキシ基封鎖ジオルガノポリシロキサン、分子鎖両末端オルガノジアルケニルシロキシ基封鎖ジオルガノポリシロキサン、分子鎖両末端トリアルケニルシロキシ基封鎖ジオルガノポリシロキサン、分子鎖両末端トリオルガノシロキシ基封鎖ジオルガノシロキサン・オルガノアルケニルシロキサン共重合体、分子鎖両末端ジオルガノアルケニルシロキシ基封鎖ジオルガノシロキサン・オルガノアルケニルシロキサン共重合体、分子鎖の片末端がジオルガノアルケニルシロキシ基封鎖で他方の片末端がトリオルガノシロキシ基封鎖であるジオルガノシロキサン・オルガノアルケニルシロキサン共重合体などが挙げられるが、好ましくは、分子鎖両末端ジオルガノアルケニルシロキシ基封鎖ジオルガノポリシロキサン、分子鎖両末端トリオルガノシロキシ基封鎖ジオルガノシロキサン・オルガノアルケニルシロキサン共重合体及び/又は分子鎖両末端ジオルガノアルケニルシロキシ基封鎖ジオルガノシロキサン・オルガノアルケニルシロキサン共重合体である。なお、上記各シロキサン中の「オルガノ基」とは、式(II)中のR3のうち、アルケニル基を除く非置換又は置換の1価炭化水素基と同様のものを意味するものである。
(A)成分は、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 component (A) include diorganopolysiloxanes with diorganoalkenylsiloxy groups at both ends of the molecular chain, diorganopolysiloxanes with organodialkenylsiloxy groups at both ends of the molecular chains, and diorganopolysiloxanes with organodialkenylsiloxy groups at both molecular chain ends. Diorganopolysiloxane with trialkenylsiloxy groups blocked at both ends, diorganosiloxane/organoalkenylsiloxane copolymer with triorganosiloxy groups blocked at both molecular chain ends, diorganosiloxane/organoalkenylsiloxane with diorganoalkenylsiloxy groups blocked at both molecular chain ends Polymers include diorganosiloxane/organoalkenylsiloxane copolymers in which one end of the molecular chain is blocked with a diorganoalkenylsiloxy group and the other end is blocked with a triorganosiloxy group, but preferably, both ends of the molecular chain are blocked with a diorganosiloxy group. Diorganopolysiloxane endblocked with diorganoalkenylsiloxy groups, diorganosiloxane/organoalkenylsiloxane copolymer endblocked with triorganosiloxy groups at both molecular chain ends, and/or diorganosiloxane/organoalkenyl endblocked with diorganoalkenylsiloxy groups at both endpoints of the molecular chain. It is a siloxane copolymer. Incidentally, the "organo group" in each of the above siloxanes means the same group as an unsubstituted or substituted monovalent hydrocarbon group excluding an alkenyl group among R 3 in formula (II).
Component (A) may be used alone or in combination of two or more.
(B)かご型構造を有するシルセスキオキサン
(B)成分は、下記一般式(I)
で示され、分子中の全R1の内、2~7個がアルケニル基であるかご型構造を有するシルセスキオキサンであり、シリコーンゴムの補強材として使用される成分である。
(B) Silsesquioxane having a cage structure (B) component has the following general formula (I)
It is a silsesquioxane having a cage structure in which 2 to 7 of all R 1 in the molecule are alkenyl groups, and is a component used as a reinforcing material for silicone rubber.
上記式(I)中、R1は互いに同一又は異種の、炭素数2~6のアルケニル基又は上記式(II)で示されるオルガノポリシロキサン残基である。R2は互いに同一又は異種の炭素数1~6のアルキル基であり、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、ネオペンチル基等が挙げられる。中でも全R2の90モル%以上はメチル基であることが好ましい。R1は炭素数2~6のアルケニル基を含み、ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基などが挙げられ、中でもビニル基、アリル基が好ましく、R1として存在する1分子中のアルケニル基の数は2~7個であり、好ましくは3~6個である。2より少ないと硬化後のゴムの補強効果が十分に得られず、また、7より多いと(A)成分に不溶となり、ゴムの強度低下、外観不良の原因となってしまう。
上記式(II)中、R2は上記式(I)において示されたものと同じであり、Xは酸素原子、又は炭素数2~6のアルキレン基であり、好ましくはエチレン基、トリメチレン基であり、nは1~200の整数であり、好ましくは3~150である。
In the above formula (I), R 1 is the same or different alkenyl group having 2 to 6 carbon atoms or an organopolysiloxane residue represented by the above formula (II). R 2 is the same or different alkyl group having 1 to 6 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, etc. It will be done. Among these, it is preferable that 90 mol% or more of all R 2 be methyl groups. R 1 includes an alkenyl group having 2 to 6 carbon atoms, such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, etc. Among them, vinyl group and allyl group are preferable. The number of alkenyl groups is 2 to 7, preferably 3 to 6. If it is less than 2, a sufficient reinforcing effect of the cured rubber will not be obtained, and if it is more than 7, it will become insoluble in component (A), causing a decrease in the strength of the rubber and poor appearance.
In the above formula (II), R 2 is the same as shown in the above formula (I), and X is an oxygen atom or an alkylene group having 2 to 6 carbon atoms, preferably an ethylene group or a trimethylene group. n is an integer from 1 to 200, preferably from 3 to 150.
また、(B)成分のアルケニル基の含有量は、(B)成分中2.0×10-5mol/g~3.0×10-3mol/g、特に1.0×10-5mol/g~1.5×10-3mol/gとすることが好ましい。アルケニル基の量がこの範囲内であれば、硬度が適切な範囲内となり、優れたゴム物性を有する硬化物を得ることができる。 Further, the content of alkenyl group in component (B) is 2.0×10 -5 mol/g to 3.0×10 -3 mol/g, particularly 1.0×10 -5 mol/g. /g to 1.5× 10 -3 mol/g. If the amount of alkenyl groups is within this range, the hardness will be within an appropriate range and a cured product with excellent rubber properties can be obtained.
(B)成分の配合量は、(A)成分100質量部に対し、1~100質量部であり、好ましくは1~80質量部、より好ましくは1~50質量部である。1質量部よりも少なくても、100質量部より多くても十分な補強効果が得られない場合がある。
なお、(B)成分の合成方法としては、例えば、前記式(I)で示されるシルセスキオキサンにおいて、R1が全て炭素数2~6のアルケニル基であるようなシルセスキオキサンと下記式(II’)
で示される片末端ヒドロシリル基含有オルガノポリシロキサンとのヒドロシリル化反応によって合成できる。また、R1が全て炭素数2~6のアルケニル基であるようなシルセスキオキサンは市販のものを使ってもよいし、例えば、特開2009-269820号公報や特開2010-280816号公報に記載の方法で合成したものを使ってもよい。
The blending amount of component (B) is 1 to 100 parts by weight, preferably 1 to 80 parts by weight, and more preferably 1 to 50 parts by weight, per 100 parts by weight of component (A). Even if it is less than 1 part by mass or more than 100 parts by mass, a sufficient reinforcing effect may not be obtained.
In addition, as a method for synthesizing component (B), for example, in the silsesquioxane represented by the above formula (I), R 1 is all an alkenyl group having 2 to 6 carbon atoms, and the following silsesquioxane: Formula (II')
It can be synthesized by a hydrosilylation reaction with an organopolysiloxane containing a hydrosilyl group at one end. Furthermore, commercially available silsesquioxanes in which R 1 is all alkenyl groups having 2 to 6 carbon atoms may be used, and for example, silsesquioxanes such as those disclosed in JP-A No. 2009-269820 and JP-A No. 2010-280816 may be used. You may use the one synthesized by the method described in .
(C)オルガノハイドロジェンポリシロキサン
(C)成分は、1分子中にケイ素原子に結合した水素原子(Si-H基)を少なくとも2個含有するオルガノハイドロジェンポリシロキサンであり、分子中のSi-H基が前記(A)成分及び(B)成分中のアルケニル基とヒドロシリル化付加反応により架橋し、組成物を硬化させるための硬化剤として作用するものである。
(C) The organohydrogenpolysiloxane component (C) is an organohydrogenpolysiloxane containing at least two silicon-bonded hydrogen atoms (Si-H groups) in one molecule, and the Si- The H group crosslinks with the alkenyl groups in the components (A) and (B) through a hydrosilylation addition reaction, and acts as a curing agent for curing the composition.
(C)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、下記平均組成式(III)で示され、1分子中に少なくとも2個以上、好ましくは3個以上、より好ましくは3~100個、更に好ましくは3~80個のケイ素原子結合水素原子(Si-H基)を有するものが好適に用いられる。
R4
bHcSiO(4-b-c)/2 (III)
The organohydrogenpolysiloxane of component (C) is represented by the following average composition formula (III), and has at least 2 or more, preferably 3 or more, more preferably 3 to 100, and even more preferably 3 to 100 in one molecule. Those having 3 to 80 silicon-bonded hydrogen atoms (Si--H groups) are preferably used.
R 4 b H c SiO (4-bc)/2 (III)
式(III)中、R4は互いに同一又は異種の炭素数1~10、好ましくは1~8の非置換又は置換の1価炭化水素基である。R4の例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、tert-ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、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、ナフチル基等のアリール基や、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、シアノ基等で置換したもの、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、トリフロロプロピル基、シアノエチル基等を挙げることができるが、脂肪族不飽和基を有さないものが好ましい。
また、bは0.7~2.1、好ましくは0.8~2.0であり、cは0.001~1.0、好ましくは0.01~1.0であり、かつ、b+cは0.8~3.0、好ましくは1.0~2.5を満足する正数であり、オルガノハイドロジェンポリシロキサンの分子構造は、直鎖状、環状、分岐状、三次元網目状のいずれの構造であってもよい。なお、ケイ素原子に結合する水素原子は分子鎖末端、分子鎖の途中のいずれに位置していてもよく、両方に位置するものであってもよい。
In formula (III), R 4 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, which are the same or different from each other. Examples of R4 include 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. Alkyl groups such as phenyl groups, tolyl groups, aryl groups such as naphthyl groups, and those in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, chlorine, cyano groups, etc., e.g. Examples include chloromethyl group, chloropropyl group, bromoethyl group, trifluoropropyl group, cyanoethyl group, etc., but those having no aliphatic unsaturated group are preferred.
Further, b is 0.7 to 2.1, preferably 0.8 to 2.0, c is 0.001 to 1.0, preferably 0.01 to 1.0, and b+c is It is a positive number satisfying 0.8 to 3.0, preferably 1.0 to 2.5, and the molecular structure of the organohydrogenpolysiloxane can be linear, cyclic, branched, or three-dimensional network. It may be the structure of Note that the hydrogen atom bonded to the silicon atom may be located at either the end of the molecular chain, the middle of the molecular chain, or both.
(C)成分のケイ素原子に結合した水素原子(Si-H基)の含有量は、オルガノハイドロジェンポリシロキサン中、5.0×10-4~1.7×10-2mol/g、特に1.0×10-3~1.7×10-2mol/gであることが好ましい。この範囲内であれば、安定な物性を有するゴム硬化物を得ることができる。 The content of silicon-bonded hydrogen atoms (Si--H groups) in component (C) is 5.0×10 -4 to 1.7×10 -2 mol/g, particularly in the organohydrogenpolysiloxane. It is preferably 1.0×10 −3 to 1.7×10 −2 mol/g. Within this range, a cured rubber product having stable physical properties can be obtained.
このような(C)成分のオルガノハイドロジェンポリシロキサンとして、具体的には、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、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、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、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、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、(CH3)2HSiO1/2単位と(CH3)3SiO1/2単位とSiO4/2単位とからなる共重合体、(CH3)2HSiO1/2単位とSiO4/2単位とからなる共重合体や、これら例示化合物においてメチル基の一部又は全部を他のアルキル基などで置換したものなどが挙げられる。 Specific examples of the organohydrogenpolysiloxane of component (C) include methylhydrogencyclopolysiloxane, methylhydrogensiloxane/dimethylsiloxane cyclic copolymer, and methylhydrogenpolysiloxane endblocked with trimethylsiloxy groups at both ends. , dimethylsiloxane/methylhydrogensiloxane copolymer blocked with trimethylsiloxy groups at both ends, dimethylpolysiloxane blocked with dimethylhydrogensiloxy groups at both ends, dimethylsiloxane/methylhydrogensiloxane copolymer blocked with dimethylhydrogensiloxy groups at both ends, ( Copolymer consisting of CH 3 ) 2 HSiO 1/2 units, (CH 3 ) 3 SiO 1/2 units and SiO 4/2 units, (CH 3 ) 2 HSiO 1/2 units and SiO 4/2 units and copolymers consisting of these exemplified compounds, in which part or all of the methyl groups are substituted with other alkyl groups.
(C)成分のオルガノハイドロジェンポリシロキサンの配合量は、(A)成分と(B)成分の合計100質量部に対し、0.1~40質量部であり、好ましくは0.3~20質量部である。また、(C)成分のオルガノハイドロジェンポリシロキサン中のケイ素原子に結合した水素原子(Si-H基)と、(A)成分及び(B)成分中のケイ素原子に結合したアルケニル基の総量とのモル比(Si-H基/アルケニル基)が、1.0~3.0、特に1.1~2.5となる量であることが好ましい。この比が1.0以上であれば、十分な架橋密度を有するゴム硬化物となるため、表面がべたつくこともなく、3.0以下であれば、熱時で硬度が大きく上昇することもなく、硬化時に発泡するおそれもない。 The amount of organohydrogenpolysiloxane as component (C) is 0.1 to 40 parts by weight, preferably 0.3 to 20 parts by weight, based on the total of 100 parts by weight of components (A) and (B). Department. In addition, the total amount of hydrogen atoms (Si-H groups) bonded to silicon atoms in the organohydrogenpolysiloxane of component (C) and alkenyl groups bonded to silicon atoms in components (A) and (B). The molar ratio (Si--H group/alkenyl group) is preferably from 1.0 to 3.0, particularly from 1.1 to 2.5. If this ratio is 1.0 or more, the cured rubber product will have sufficient crosslinking density, so the surface will not become sticky, and if it is 3.0 or less, the hardness will not increase significantly when heated. There is no risk of foaming during curing.
(D)ヒュームドシリカ
(D)成分のヒュームドシリカは、得られるシリコーンゴムに十分な強度を与えるために必要なものである。ヒュームドシリカのBET法による比表面積は、50m2/g以上である必要があり、通常、50~400m2/g、好ましくは90~380m2/gであり、50m2/gより小さいと十分な強度が得られないばかりか、成型物の透明性も低下してしまう。また、400m2/g以下であれば、配合が容易であり、変色するようなこともない。
(D) Fumed Silica Component (D) fumed silica is necessary to impart sufficient strength to the resulting silicone rubber. The specific surface area of fumed silica by the BET method must be 50 m 2 /g or more, usually 50 to 400 m 2 /g, preferably 90 to 380 m 2 /g, and smaller than 50 m 2 /g is sufficient. Not only is it not possible to obtain sufficient strength, but the transparency of the molded product is also reduced. Moreover, if it is 400 m 2 /g or less, it is easy to blend and there is no possibility of discoloration.
(D)成分のヒュームドシリカの配合量は、(A)成分100質量部に対し、0~100質量部であり、10~100質量部が好ましく、より好ましくは10~60質量部である。配合量が100質量部より多いと粘度が高くなるため、成形が困難となってしまう。 The amount of fumed silica as component (D) is 0 to 100 parts by weight, preferably 10 to 100 parts by weight, and more preferably 10 to 60 parts by weight, per 100 parts by weight of component (A). If the blending amount is more than 100 parts by mass, the viscosity will increase, making molding difficult.
上記(D)成分のヒュームドシリカは、通常表面に疎水性処理を施したものを用いることが好ましい。表面処理をしない場合、シリコーンオイルへの分散性が悪く、シリカの凝集体が生成したり、配合が困難となったりする場合がある。シリカの表面処理は、粉体の状態で直接処理されたものでも、(A)成分との混合時にシリカ表面処理剤とともに加熱混合することにより表面処理されたものであってもよい。
通常の処理法として、一般的周知の技術により処理でき、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シリカ表面処理剤を入れ、必要に応じて不活性ガス存在下において室温あるいは熱処理にて混合処理する。場合により、触媒を使用して処理を促進してもよい。混練後、乾燥することにより処理シリカ微粉末を製造し得る。
The fumed silica of component (D) is preferably one whose surface has been subjected to hydrophobic treatment. If surface treatment is not performed, dispersibility in silicone oil may be poor, resulting in the formation of silica aggregates or difficulty in blending. The surface treatment of silica may be performed directly in the powder state or by heating and mixing it with a silica surface treatment agent when mixed with component (A).
As a normal treatment method, the treatment can be performed using a generally well-known technique. For example, the untreated fine silica powder and the silica surface treatment agent are placed in a sealed mechanical kneading device or fluidized bed at normal pressure, and if necessary, Mixing treatment is performed at room temperature or heat treatment in the presence of an active gas. Optionally, a catalyst may be used to facilitate the process. After kneading, a treated silica fine powder can be produced by drying.
シリカ表面処理剤は、上述したように(D)成分であるヒュームドシリカの表面を疎水性処理するために用いることができるものであり、シリカ表面処理剤として、具体的には、へキサメチルジシラザン、ジビニルテトラメチルジ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、ビニルトリエトキシシラン、ビニルトリメトキシシラン、トリメチルメトキシシラン、トリエチルメトキシシラン、ビニルトリス(メトキシエトキシ)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、ジビニルジメトキシシラン及びクロロプロピルトリメトキシシラン等のシラン系カップリング剤、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る。処理剤としては、特にシラン系カップリング剤又はシラザン類が好ましい。
なお、シリカ表面処理剤の使用量は、(D)成分100質量部に対し、5~75質量部であることが好ましく、5~60質量部であることがより好ましい。
As mentioned above, the silica surface treatment agent can be used to hydrophobically treat the surface of fumed silica, which is component (D), and specifically, as a silica surface treatment agent, hexamethyl Silazane such as disilazane, divinyltetramethyldisilazane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane , silane coupling agents such as trimethylmethoxysilane, triethylmethoxysilane, vinyltris(methoxyethoxy)silane, trimethylchlorosilane, dimethyldichlorosilane, divinyldimethoxysilane and chloropropyltrimethoxysilane, polymethylsiloxane, organohydrogenpolysiloxane, etc. The following organosilicon compounds can be mentioned. As the treatment agent, silane coupling agents or silazane are particularly preferred.
The amount of the silica surface treatment agent used is preferably 5 to 75 parts by weight, more preferably 5 to 60 parts by weight, per 100 parts by weight of component (D).
(E)付加反応触媒
(E)成分の付加反応触媒としては、白金黒、塩化第2白金、塩化白金酸、塩化白金酸と1価アルコールとの反応物、塩化白金酸とオレフィン類との錯体、白金ビスアセトアセテート等の白金系触媒、パラジウム系触媒、ロジウム系触媒などが挙げられる。
なお、この付加反応触媒の配合量は、触媒量とすることができ、通常、(A)及び(B)成分の合計100質量部に対し、白金族金属(質量換算)として0.1~1,000ppm、特に1~500ppm程度である。
(E) Addition reaction catalyst (E) Component addition reaction catalysts include platinum black, platinum chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, and a complex of chloroplatinic acid and olefins. , platinum-based catalysts such as platinum bisacetoacetate, palladium-based catalysts, rhodium-based catalysts, and the like.
The addition reaction catalyst can be added in a catalytic amount, and is usually 0.1 to 1 in terms of platinum group metal (in terms of mass) per 100 parts by mass of components (A) and (B) in total. ,000 ppm, especially about 1 to 500 ppm.
その他の成分
本発明の付加硬化性液状シリコーンゴム組成物に、発明の効果を損なわない限り、その他の成分として、必要に応じて、沈降シリカ、石英粉、珪藻土、炭酸カルシウムのような充填剤や、カーボンブラック、導電性亜鉛華、金属粉等の導電剤、窒素含有化合物やアセチレン化合物、リン化合物、ニトリル化合物、カルボキシレート、錫化合物、水銀化合物、硫黄化合物等のヒドロシリル化反応制御剤、酸化鉄、酸化セリウムのような耐熱剤、ジメチルシリコーンオイル等の内部離型剤、接着性付与剤、及びチクソ性付与剤等を配合することは任意である。
Other components The addition-curable liquid silicone rubber composition of the present invention may contain fillers such as precipitated silica, quartz powder, diatomaceous earth, calcium carbonate, etc., as necessary, as long as they do not impair the effects of the invention. , carbon black, conductive zinc white, conductive agents such as metal powder, hydrosilylation reaction control agents such as nitrogen-containing compounds, acetylene compounds, phosphorus compounds, nitrile compounds, carboxylates, tin compounds, mercury compounds, sulfur compounds, iron oxide, etc. , a heat resisting agent such as cerium oxide, an internal mold release agent such as dimethyl silicone oil, an adhesion imparting agent, a thixotropy imparting agent, etc. may optionally be blended.
〔調製方法〕
こうして、上述した(A)~(E)成分及び必要に応じて配合されるその他成分の各所定量を、2本ロール、ニーダー、プラネタリーミキサー等の混練機で混練することにより、容易に付加硬化性液状シリコーンゴム組成物を調製することができる。
〔成形・硬化方法〕
付加硬化性シリコーンゴム組成物の成形・硬化方法としては、常法を採用し得るが、成形法として射出成形、トランスファー成形、注入成形、圧縮成形等から目的にあった最適な手段を選択することが可能である。硬化条件としては、40~230℃で3秒~160分間程度の加熱処理(一次加硫)条件を採用し得る。また、必要に応じて任意に40~230℃で10分~24時間程度の二次加硫(ポストキュア)を行ってもよい。
[Preparation method]
In this way, by kneading predetermined amounts of each of the above-mentioned components (A) to (E) and other components blended as necessary with a kneading machine such as a two-roll, kneader, or planetary mixer, addition curing can be easily achieved. A liquid silicone rubber composition can be prepared.
[Molding/curing method]
Conventional methods can be used to mold and cure the addition-curable silicone rubber composition, but the most suitable molding method for the purpose should be selected from among injection molding, transfer molding, injection molding, compression molding, etc. is possible. As the curing conditions, heat treatment (primary vulcanization) conditions at 40 to 230° C. for about 3 seconds to 160 minutes can be adopted. Further, if necessary, secondary vulcanization (post-cure) may be optionally performed at 40 to 230°C for about 10 minutes to 24 hours.
こうして得られる本発明の付加硬化性液状シリコーンゴム組成物は、硬化後に高硬度とならずに高引裂強度を有するシリコーンゴムを与えるものであり、哺乳瓶用乳首、マスク材料等として好適に用いられる。 The addition-curable liquid silicone rubber composition of the present invention thus obtained provides a silicone rubber having high tear strength without becoming highly hard after curing, and is suitably used as nipples for baby bottles, mask materials, etc. .
以下、合成例、実施例及び比較例により本発明を具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、下記例で部は質量部を示す。また、平均重合度は、数平均重合度を示す。 Hereinafter, the present invention will be specifically explained with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples. In addition, in the following examples, parts indicate parts by mass. Moreover, the average degree of polymerization indicates the number average degree of polymerization.
[合成例1]
温度計、還流管、滴下ロート及び機械撹拌装置を備えた500mlのセパラブルフラスコに、下記式(V)
で示される化合物B1(1分子当たりの平均ビニル基数:4.3個、ビニル基量0.000440mol/g)を79.7g得た。
[Synthesis example 1]
The following formula (V) was added to a 500 ml separable flask equipped with a thermometer, reflux tube, dropping funnel and mechanical stirring device.
79.7 g of Compound B1 (average number of vinyl groups per molecule: 4.3, amount of vinyl groups 0.000440 mol/g) represented by the formula was obtained.
[合成例2]
温度計、還流管、滴下ロート及び機械撹拌装置を備えた500mlのセパラブルフラスコに、合成例1の式(V)で示される化合物9.0g(0.0074mol)、トルエン30.0g及び白金の1,3-ジビニルテトラメチルジシロキサン錯体のトルエン溶液(白金濃度:0.5質量%)0.057gを入れ、80℃に加熱した。次いで、下記式(VIII)
で示される化合物B2(1分子当たりの平均ビニル基数:4.5個、ビニル基量0.000256mol/g)を124.8g得た。
[Synthesis example 2]
In a 500 ml separable flask equipped with a thermometer, reflux tube, dropping funnel, and mechanical stirrer, 9.0 g (0.0074 mol) of the compound represented by formula (V) of Synthesis Example 1, 30.0 g of toluene, and platinum were added. 0.057 g of a toluene solution of 1,3-divinyltetramethyldisiloxane complex (platinum concentration: 0.5% by mass) was added and heated to 80°C. Then, the following formula (VIII)
124.8 g of compound B2 (average number of vinyl groups per molecule: 4.5, amount of vinyl groups 0.000256 mol/g) represented by the formula was obtained.
[実施例1]
両末端がジメチルビニルシロキシ基で封鎖された平均重合度が750であるジメチルポリシロキサン(A1)60部、BET法による比表面積が300m2/gであるヒュームドシリカ(D1)(日本アエロジル社製、アエロジル300)40部、ヘキサメチルジシラザン8部、水2.0部を25℃で30分混合後、150℃に昇温し、3時間撹拌を続け、冷却し、シリコーンゴムベースを得た。
このシリコーンゴムベース100部に、上記ジメチルポリシロキサン(A1)30部、両末端がジメチルビニルシロキシ基で封鎖された平均重合度が450であるジメチルポリシロキサン(A2)15部、合成例1のビニル基を有するかご型シルセスキオキサン(B1)5部を入れ、30分撹拌を続けた後、更に架橋剤として両末端がトリメチルシロキシ基で封鎖され側鎖にSi-H基を平均35個有するメチルハイドロジェン・ジメチルポリシロキサン(C1)(平均重合度100、Si-H基量0.0055mol/g)を2.0部、反応制御剤としてエチニルシクロヘキサノール0.05部を添加し、15分撹拌を続けて、シリコーンゴム混合物を得た。
なお、この混合物において、総Si-H基量と総ビニル基量のモル比(Si-H基/ビニル基)は1.8である。
[Example 1]
60 parts of dimethylpolysiloxane (A1) with an average degree of polymerization of 750, both ends of which are blocked with dimethylvinylsiloxy groups, fumed silica (D1) with a specific surface area of 300 m 2 /g by the BET method (manufactured by Nippon Aerosil Co., Ltd.) , Aerosil 300), 8 parts of hexamethyldisilazane, and 2.0 parts of water were mixed at 25°C for 30 minutes, heated to 150°C, continued stirring for 3 hours, and cooled to obtain a silicone rubber base. .
To 100 parts of this silicone rubber base, 30 parts of the above-mentioned dimethylpolysiloxane (A1), 15 parts of dimethylpolysiloxane (A2) having an average degree of polymerization of 450 and having both ends blocked with dimethylvinylsiloxy groups, and the vinyl of Synthesis Example 1. After adding 5 parts of cage-type silsesquioxane (B1) having groups and continuing stirring for 30 minutes, both ends are further blocked with trimethylsiloxy groups as a crosslinking agent and the side chains have an average of 35 Si-H groups. Added 2.0 parts of methylhydrogen-dimethylpolysiloxane (C1) (average degree of polymerization 100, Si-H group amount 0.0055 mol/g) and 0.05 part of ethynylcyclohexanol as a reaction control agent, and heated for 15 minutes. Stirring was continued to obtain a silicone rubber mixture.
In this mixture, the molar ratio between the total amount of Si--H groups and the total amount of vinyl groups (Si--H groups/vinyl groups) is 1.8.
このシリコーンゴム混合物中に、(E)成分として1,3-ジビニル-1,1,3,3-テトラメチルジシロキサン白金錯体のジメチルシロキサン溶液(Pt濃度1質量%)0.10部((A)成分と(B)成分の合計100質量部に対し、白金族金属(質量換算)として956.5ppmに相当)を混合してシリコーンゴム組成物とした。該組成物を120℃/10分のプレスキュア後、オーブン内で150℃/1時間のポストキュアを行って得られた硬化物について、JIS K 6253-3:2012に基づき、デュロメータタイプAにおける硬さ、JIS K 6251:2010に基づき、引張強さ及び切断時伸び、JIS K 6252-1:2015に基づき、クレセント形及びトラウザ形試験片で引裂強さを測定した結果を表1に示した。
In this silicone rubber mixture, 0.10 parts of a dimethylsiloxane solution (Pt concentration 1% by mass) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex as component (E) ((A A platinum group metal (equivalent to 956.5 ppm in terms of mass) was mixed with a total of 100 parts by mass of components () and (B) to prepare a silicone rubber composition. After press-curing the composition at 120°C for 10 minutes, post-curing the composition at 150°C for 1 hour in an oven. Table 1 shows the results of measuring the tensile strength and elongation at break based on JIS K 6251:2010, and the tear strength of crescent-shaped and trousers-shaped test pieces based on JIS K 6252-1:2015.
[実施例2]
両末端がジメチルビニルシロキシ基で封鎖された平均重合度が750であるジメチルポリシロキサン(A1)60部、BET法による比表面積が300m2/gであるヒュームドシリカ(D1)(日本アエロジル社製、アエロジル300)40部、ヘキサメチルジシラザン8部、水2.0部を25℃で30分混合後、150℃に昇温し、3時間撹拌を続け、冷却し、シリコーンゴムベースを得た。
このシリコーンゴムベース100部に、上記ジメチルポリシロキサン(A1)30部、両末端がジメチルビニルシロキシ基で封鎖された平均重合度が450であるジメチルポリシロキサン(A2)15部、合成例2のビニル基を有するかご型シルセスキオキサン(B2)5部を入れ、30分撹拌を続けた後、更に架橋剤として両末端がトリメチルシロキシ基で封鎖され側鎖にSi-H基を平均35個有するメチルハイドロジェン・ジメチルポリシロキサン(C1)(平均重合度100、Si-H基量0.0055mol/g)を1.7部、反応制御剤としてエチニルシクロヘキサノール0.05部を添加し、15分撹拌を続けて、シリコーンゴム混合物を得た。
なお、この混合物において、総Si-H基量と総ビニル基量のモル比(Si-H基/ビニル基)は1.8である。
[Example 2]
60 parts of dimethylpolysiloxane (A1) with an average degree of polymerization of 750, both ends of which are blocked with dimethylvinylsiloxy groups, fumed silica (D1) with a specific surface area of 300 m 2 /g by the BET method (manufactured by Nippon Aerosil Co., Ltd.) , Aerosil 300), 8 parts of hexamethyldisilazane, and 2.0 parts of water were mixed at 25°C for 30 minutes, heated to 150°C, continued stirring for 3 hours, and cooled to obtain a silicone rubber base. .
To 100 parts of this silicone rubber base, 30 parts of the above dimethylpolysiloxane (A1), 15 parts of dimethylpolysiloxane (A2) having an average degree of polymerization of 450 and having both ends blocked with dimethylvinylsiloxy groups, and the vinyl of Synthesis Example 2. After adding 5 parts of cage-type silsesquioxane (B2) having groups and continuing stirring for 30 minutes, both ends are further blocked with trimethylsiloxy groups as a crosslinking agent and the side chains have an average of 35 Si-H groups. Added 1.7 parts of methylhydrogen-dimethylpolysiloxane (C1) (average degree of polymerization 100, Si-H group amount 0.0055 mol/g) and 0.05 part of ethynylcyclohexanol as a reaction control agent, and heated for 15 minutes. Stirring was continued to obtain a silicone rubber mixture.
In this mixture, the molar ratio between the total amount of Si--H groups and the total amount of vinyl groups (Si--H groups/vinyl groups) is 1.8.
このシリコーンゴム混合物中に、(E)成分として1,3-ジビニル-1,1,3,3-テトラメチルジシロキサン白金錯体のジメチルシロキサン溶液(Pt濃度1質量%)0.10部((A)成分と(B)成分の合計100質量部に対し、白金族金属(質量換算)として956.5ppmに相当)を混合してシリコーンゴム組成物とした。該組成物を120℃/10分のプレスキュア後、オーブン内で150℃/1時間のポストキュアを行って得られた硬化物について、JIS K 6253-3:2012に基づき、デュロメータタイプAにおける硬さ、JIS K 6251:2010に基づき、引張強さ及び切断時伸び、JIS K 6252-1:2015に基づき、クレセント形及びトラウザ形試験片で引裂強さを測定した結果を表1に示した。
In this silicone rubber mixture, 0.10 parts of a dimethylsiloxane solution (Pt concentration 1% by mass) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex as component (E) ((A A platinum group metal (equivalent to 956.5 ppm in terms of mass) was mixed with a total of 100 parts by mass of components () and (B) to prepare a silicone rubber composition. After press-curing the composition at 120°C for 10 minutes, post-curing the composition at 150°C for 1 hour in an oven. Table 1 shows the results of measuring the tensile strength and elongation at break based on JIS K 6251:2010, and the tear strength of crescent-shaped and trousers-shaped test pieces based on JIS K 6252-1:2015.
[実施例3]
両末端がジメチルビニルシロキシ基で封鎖された平均重合度が750であるジメチルポリシロキサン(A1)60部、BET法による比表面積が300m2/gであるヒュームドシリカ(D1)(日本アエロジル社製、アエロジル300)40部、ヘキサメチルジシラザン8部、水2.0部を25℃で30分混合後、150℃に昇温し、3時間撹拌を続け、冷却し、シリコーンゴムベースを得た。
このシリコーンゴムベース100部に、上記ジメチルポリシロキサン(A1)30部、合成例2のビニル基を有するかご型シルセスキオキサン(B2)20部を入れ、30分撹拌を続けた後、更に架橋剤として両末端がトリメチルシロキシ基で封鎖され側鎖にSi-H基を平均35個有するメチルハイドロジェン・ジメチルポリシロキサン(C1)(平均重合度100、Si-H基量0.0055mol/g)を2.7部、反応制御剤としてエチニルシクロヘキサノール0.05部を添加し、15分撹拌を続けて、シリコーンゴム混合物を得た。
なお、この混合物において、総Si-H基量と総ビニル基量のモル比(Si-H基/ビニル基)は1.8である。
[Example 3]
60 parts of dimethylpolysiloxane (A1) with an average degree of polymerization of 750, both ends of which are blocked with dimethylvinylsiloxy groups, fumed silica (D1) with a specific surface area of 300 m 2 /g by the BET method (manufactured by Nippon Aerosil Co., Ltd.) , Aerosil 300), 8 parts of hexamethyldisilazane, and 2.0 parts of water were mixed at 25°C for 30 minutes, heated to 150°C, continued stirring for 3 hours, and cooled to obtain a silicone rubber base. .
To 100 parts of this silicone rubber base, 30 parts of the above dimethylpolysiloxane (A1) and 20 parts of the vinyl group-containing cage-type silsesquioxane (B2) of Synthesis Example 2 were added, and after continued stirring for 30 minutes, further crosslinking was performed. As an agent, methylhydrogen dimethylpolysiloxane (C1) is blocked with trimethylsiloxy groups at both ends and has an average of 35 Si-H groups in the side chain (average degree of polymerization 100, amount of Si-H groups 0.0055 mol/g). 2.7 parts of and 0.05 parts of ethynylcyclohexanol as a reaction control agent were added, and stirring was continued for 15 minutes to obtain a silicone rubber mixture.
In this mixture, the molar ratio between the total amount of Si--H groups and the total amount of vinyl groups (Si--H groups/vinyl groups) is 1.8.
このシリコーンゴム混合物中に、(E)成分として1,3-ジビニル-1,1,3,3-テトラメチルジシロキサン白金錯体のジメチルシロキサン溶液(Pt濃度1質量%)0.10部((A)成分と(B)成分の合計100質量部に対し、白金族金属(質量換算)として956.5ppmに相当)を混合してシリコーンゴム組成物とした。該組成物を120℃/10分のプレスキュア後、オーブン内で150℃/1時間のポストキュアを行って得られた硬化物について、JIS K 6253-3:2012に基づき、デュロメータタイプAにおける硬さ、JIS K 6251:2010に基づき、引張強さ及び切断時伸び、JIS K 6252-1:2015に基づき、クレセント形及びトラウザ形試験片で引裂強さを測定した結果を表1に示した。
In this silicone rubber mixture, 0.10 parts of a dimethylsiloxane solution (Pt concentration 1% by mass) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex as component (E) ((A A platinum group metal (equivalent to 956.5 ppm in terms of mass) was mixed with a total of 100 parts by mass of components () and (B) to prepare a silicone rubber composition. After press-curing the composition at 120°C for 10 minutes, post-curing the composition at 150°C for 1 hour in an oven. Table 1 shows the results of measuring the tensile strength and elongation at break based on JIS K 6251:2010, and the tear strength of crescent-shaped and trousers-shaped test pieces based on JIS K 6252-1:2015.
[比較例1]
両末端がジメチルビニルシロキシ基で封鎖された平均重合度が750であるジメチルポリシロキサン(A1)60部、BET法による比表面積が300m2/gであるヒュームドシリカ(D1)(日本アエロジル社製、アエロジル300)40部、ヘキサメチルジシラザン8部、水2.0部を25℃で30分混合後、150℃に昇温し、3時間撹拌を続け、冷却し、シリコーンゴムベースを得た。
このシリコーンゴムベース100部に、上記ジメチルポリシロキサン(A1)30部、両末端がジメチルビニルシロキシ基で封鎖された平均重合度が450であるジメチルポリシロキサン(A2)20部を入れ、30分撹拌を続けた後、更に架橋剤として両末端がトリメチルシロキシ基で封鎖され側鎖にSi-H基を平均35個有するメチルハイドロジェン・ジメチルポリシロキサン(C1)(平均重合度100、Si-H基量0.0055mol/g)を1.4部、反応制御剤としてエチニルシクロヘキサノール0.05部を添加し、15分撹拌を続けて、シリコーンゴム混合物を得た。
なお、この混合物において、総Si-H基量と総ビニル基量のモル比(Si-H基/ビニル基)は1.8である。
[Comparative example 1]
60 parts of dimethylpolysiloxane (A1) with an average degree of polymerization of 750, both ends of which are blocked with dimethylvinylsiloxy groups, fumed silica (D1) with a specific surface area of 300 m 2 /g by the BET method (manufactured by Nippon Aerosil Co., Ltd.) , Aerosil 300), 8 parts of hexamethyldisilazane, and 2.0 parts of water were mixed at 25°C for 30 minutes, heated to 150°C, continued stirring for 3 hours, and cooled to obtain a silicone rubber base. .
To 100 parts of this silicone rubber base, 30 parts of the above dimethylpolysiloxane (A1) and 20 parts of dimethylpolysiloxane (A2), which has both ends blocked with dimethylvinylsiloxy groups and has an average degree of polymerization of 450, were added and stirred for 30 minutes. Then, as a crosslinking agent, methylhydrogen dimethylpolysiloxane (C1), which has both ends blocked with trimethylsiloxy groups and has an average of 35 Si-H groups in the side chain (average degree of polymerization 100, Si-H groups), was used as a crosslinking agent. 0.0055 mol/g) and 0.05 part of ethynylcyclohexanol as a reaction control agent were added, and stirring was continued for 15 minutes to obtain a silicone rubber mixture.
In this mixture, the molar ratio between the total amount of Si--H groups and the total amount of vinyl groups (Si--H groups/vinyl groups) is 1.8.
このシリコーンゴム混合物中に、(E)成分として1,3-ジビニル-1,1,3,3-テトラメチルジシロキサン白金錯体のジメチルシロキサン溶液(Pt濃度1質量%)0.10部((A)成分と(B)成分の合計100質量部に対し、白金族金属(質量換算)として956.5ppmに相当)を混合してシリコーンゴム組成物とした。該組成物を120℃/10分のプレスキュア後、オーブン内で150℃/1時間のポストキュアを行って得られた硬化物について、JIS K 6253-3:2012に基づき、デュロメータタイプAにおける硬さ、JIS K 6251:2010に基づき、引張強さ及び切断時伸び、JIS K 6252-1:2015に基づき、クレセント形及びトラウザ形試験片で引裂強さを測定した結果を表1に示した。
In this silicone rubber mixture, 0.10 parts of a dimethylsiloxane solution (Pt concentration 1% by mass) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex as component (E) ((A A platinum group metal (equivalent to 956.5 ppm in terms of mass) was mixed with a total of 100 parts by mass of components () and (B) to prepare a silicone rubber composition. After press-curing the composition at 120°C for 10 minutes, post-curing the composition at 150°C for 1 hour in an oven. Table 1 shows the results of measuring the tensile strength and elongation at break based on JIS K 6251:2010, and the tear strength of crescent-shaped and trousers-shaped test pieces based on JIS K 6252-1:2015.
[比較例2]
両末端がジメチルビニルシロキシ基で封鎖された平均重合度が750であるジメチルポリシロキサン(A1)60部、BET法による比表面積が300m2/gであるヒュームドシリカ(D1)(日本アエロジル社製、アエロジル300)40部、ヘキサメチルジシラザン8部、水2.0部を25℃で30分混合後、150℃に昇温し、3時間撹拌を続け、冷却し、シリコーンゴムベースを得た。
このシリコーンゴムベース100部に、上記ジメチルポリシロキサン(A1)30部、両末端がジメチルビニルシロキシ基で封鎖された平均重合度が450であるジメチルポリシロキサン(A2)15部、室温で固体の(CH3)3SiO1/2単位、CH2=CH(CH3)2SiO1/2単位及びSiO2単位からなる樹脂質共重合体[((CH3)3SiO1/2単位+CH2=CH(CH3)2SiO1/2単位)/SiO2単位=0.9(モル比)、ビニル基含有量=0.0008mol/g、Mn=3,700]5部を入れ、30分撹拌を続けた後、更に架橋剤として両末端がトリメチルシロキシ基で封鎖され側鎖にSi-H基を平均35個有するメチルハイドロジェン・ジメチルポリシロキサン(C1)(平均重合度100、Si-H基量0.0055mol/g)を2.6部、反応制御剤としてエチニルシクロヘキサノール0.05部を添加し、15分撹拌を続けて、シリコーンゴム混合物を得た。
なお、この混合物において、総Si-H基量と総ビニル基量のモル比(Si-H基/ビニル基)は1.8である。
[Comparative example 2]
60 parts of dimethylpolysiloxane (A1) with an average degree of polymerization of 750, both ends of which are blocked with dimethylvinylsiloxy groups, fumed silica (D1) with a specific surface area of 300 m 2 /g by the BET method (manufactured by Nippon Aerosil Co., Ltd.) , Aerosil 300), 8 parts of hexamethyldisilazane, and 2.0 parts of water were mixed at 25°C for 30 minutes, heated to 150°C, continued stirring for 3 hours, and cooled to obtain a silicone rubber base. .
To 100 parts of this silicone rubber base, 30 parts of the above-mentioned dimethylpolysiloxane (A1), 15 parts of dimethylpolysiloxane (A2) with an average degree of polymerization of 450, which is blocked at both ends with dimethylvinylsiloxy groups, and ( A resinous copolymer consisting of CH 3 ) 3 SiO 1/2 units, CH 2 =CH(CH 3 ) 2 SiO 1/2 units, and SiO 2 units [((CH 3 ) 3 SiO 1/2 units + CH 2 = 5 parts of CH (CH 3 ) 2 SiO 1/2 units)/SiO 2 units = 0.9 (mole ratio), vinyl group content = 0.0008 mol/g, Mn = 3,700] and stirred for 30 minutes. Then, as a crosslinking agent, methylhydrogen dimethylpolysiloxane (C1), which has both ends blocked with trimethylsiloxy groups and has an average of 35 Si-H groups in the side chain (average degree of polymerization 100, Si-H groups), was used as a crosslinking agent. 0.0055 mol/g) and 0.05 part of ethynylcyclohexanol as a reaction control agent were added, and stirring was continued for 15 minutes to obtain a silicone rubber mixture.
In this mixture, the molar ratio between the total amount of Si--H groups and the total amount of vinyl groups (Si--H groups/vinyl groups) is 1.8.
このシリコーンゴム混合物中に、(E)成分として1,3-ジビニル-1,1,3,3-テトラメチルジシロキサン白金錯体のジメチルシロキサン溶液(Pt濃度1質量%)0.10部((A)成分と(B)成分の合計100質量部に対し、白金族金属(質量換算)として1004.5ppmに相当)を混合してシリコーンゴム組成物とした。該組成物を120℃/10分のプレスキュア後、オーブン内で150℃/1時間のポストキュアを行って得られた硬化物について、JIS K 6253-3:2012に基づき、デュロメータタイプAにおける硬さ、JIS K 6251:2010に基づき、引張強さ及び切断時伸び、JIS K 6252-1:2015に基づき、クレセント形及びトラウザ形試験片で引裂強さを測定した結果を表1に示した。 In this silicone rubber mixture, 0.10 parts of a dimethylsiloxane solution (Pt concentration 1% by mass) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex as component (E) ((A A platinum group metal (equivalent to 1004.5 ppm in terms of mass) was mixed with a total of 100 parts by mass of components () and (B) to prepare a silicone rubber composition. After press-curing the composition at 120°C for 10 minutes, post-curing the composition at 150°C for 1 hour in an oven. Table 1 shows the results of measuring the tensile strength and elongation at break based on JIS K 6251:2010, and the tear strength of crescent-shaped and trousers-shaped test pieces based on JIS K 6252-1:2015.
[比較例3]
両末端がジメチルビニルシロキシ基で封鎖された平均重合度が750であるジメチルポリシロキサン(A1)60部、BET法による比表面積が300m2/gであるヒュームドシリカ(D1)(日本アエロジル社製、アエロジル300)40部、ヘキサメチルジシラザン8部、水2.0部を25℃で30分混合後、150℃に昇温し、3時間撹拌を続け、冷却し、シリコーンゴムベースを得た。
このシリコーンゴムベース100部に、上記ジメチルポリシロキサン(A1)30部、両末端がジメチルビニルシロキシ基で封鎖された平均重合度が450であるジメチルポリシロキサン(A2)15部、合成例1の式(V)の化合物5部を入れ、30分撹拌を続けた。しかし、式(V)の化合物が不溶であり、白色固体として析出したため、これ以上の検討は断念した。
[Comparative example 3]
60 parts of dimethylpolysiloxane (A1) with an average degree of polymerization of 750, both ends of which are blocked with dimethylvinylsiloxy groups, fumed silica (D1) with a specific surface area of 300 m 2 /g by the BET method (manufactured by Nippon Aerosil Co., Ltd.) , Aerosil 300), 8 parts of hexamethyldisilazane, and 2.0 parts of water were mixed at 25°C for 30 minutes, heated to 150°C, continued stirring for 3 hours, and cooled to obtain a silicone rubber base. .
To 100 parts of this silicone rubber base, 30 parts of the above dimethylpolysiloxane (A1), 15 parts of dimethylpolysiloxane (A2) whose both ends are blocked with dimethylvinylsiloxy groups and whose average degree of polymerization is 450, and the formula of Synthesis Example 1. 5 parts of compound (V) was added and stirring was continued for 30 minutes. However, since the compound of formula (V) was insoluble and precipitated as a white solid, further investigation was abandoned.
Claims (2)
(B)下記一般式(I)
で示され、(B)成分中のアルケニル基の含有量が2.0×10-5mol/g~1.5×10-3mol/gであるかご型構造を有するシルセスキオキサン:(A)成分100質量部に対し、1~100質量部、
(C)1分子中にケイ素原子に結合した水素原子を少なくとも2個有するオルガノハイドロジェンポリシロキサン:(A)成分と(B)成分の合計100質量部に対し、0.1~40質量部、
(D)BET法による比表面積が50m2/g以上であるヒュームドシリカ:(A)成分100質量部に対し、10~100質量部、
(E)付加反応触媒:(A)成分と(B)成分の合計100質量部に対し、白金族金属(質量換算)として0.1~1,000ppm
を含有することを特徴とする付加硬化性液状シリコーンゴム組成物。 (A) has at least two silicon-bonded alkenyl groups in one molecule, both ends of the molecular chain are blocked with triorganosiloxy groups, and the main chain consists of repeating diorganosiloxane units; the average degree of polymerization is 100 parts by mass of an alkenyl group-containing organopolysiloxane that is liquid at 25°C and has a linear structure of 150 to 1,500;
(B) The following general formula (I)
A silsesquioxane having a cage structure and having a content of alkenyl groups in component (B) of 2.0×10 -5 mol/g to 1.5×10 -3 mol/g: ( A) 1 to 100 parts by mass per 100 parts by mass of component,
(C) Organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule: 0.1 to 40 parts by mass based on a total of 100 parts by mass of components (A) and (B),
(D) Fumed silica with a specific surface area of 50 m 2 /g or more by BET method: 10 to 100 parts by mass per 100 parts by mass of component (A),
(E) Addition reaction catalyst: 0.1 to 1,000 ppm as platinum group metal (in terms of mass) based on a total of 100 parts by mass of components (A) and (B)
An addition-curable liquid silicone rubber composition comprising:
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JP2008156578A (en) | 2006-12-26 | 2008-07-10 | Momentive Performance Materials Japan Kk | Addition reaction-curable silicone composition and semiconductor device |
JP2013108063A (en) | 2011-10-25 | 2013-06-06 | Central Glass Co Ltd | Siloxane-based composition and cured product thereof, and use thereof |
JP2014098146A (en) | 2012-10-18 | 2014-05-29 | Central Glass Co Ltd | Curable composition containing silica particles, cured product thereof, and semiconductor sealing material using the same |
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JP2007031619A (en) | 2005-07-28 | 2007-02-08 | Nagase Chemtex Corp | Resin composition for optical element sealing use |
JP2008156578A (en) | 2006-12-26 | 2008-07-10 | Momentive Performance Materials Japan Kk | Addition reaction-curable silicone composition and semiconductor device |
JP2013108063A (en) | 2011-10-25 | 2013-06-06 | Central Glass Co Ltd | Siloxane-based composition and cured product thereof, and use thereof |
JP2014098146A (en) | 2012-10-18 | 2014-05-29 | Central Glass Co Ltd | Curable composition containing silica particles, cured product thereof, and semiconductor sealing material using the same |
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