JP4636233B2 - Conductive silicone rubber composition and method for producing the same - Google Patents
Conductive silicone rubber composition and method for producing the same Download PDFInfo
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- JP4636233B2 JP4636233B2 JP2004234462A JP2004234462A JP4636233B2 JP 4636233 B2 JP4636233 B2 JP 4636233B2 JP 2004234462 A JP2004234462 A JP 2004234462A JP 2004234462 A JP2004234462 A JP 2004234462A JP 4636233 B2 JP4636233 B2 JP 4636233B2
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- silicone rubber
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- 239000000203 mixture Substances 0.000 title claims description 51
- 229920002379 silicone rubber Polymers 0.000 title claims description 47
- 239000004945 silicone rubber Substances 0.000 title claims description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- 229920001296 polysiloxane Polymers 0.000 claims description 27
- 125000003342 alkenyl group Chemical group 0.000 claims description 24
- 239000006229 carbon black Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims description 12
- 238000007259 addition reaction Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 32
- -1 chloropro Group Chemical group 0.000 description 29
- 229920001971 elastomer Polymers 0.000 description 23
- 239000005060 rubber Substances 0.000 description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 17
- 235000019241 carbon black Nutrition 0.000 description 15
- 239000004205 dimethyl polysiloxane Substances 0.000 description 15
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 15
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 15
- 230000006835 compression Effects 0.000 description 13
- 238000007906 compression Methods 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000006230 acetylene black Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000006232 furnace black Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000004020 conductor Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000006231 channel black Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 229910021485 fumed silica Inorganic materials 0.000 description 4
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910002012 Aerosil® Inorganic materials 0.000 description 3
- 238000004438 BET method Methods 0.000 description 3
- 229910004283 SiO 4 Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000012756 surface treatment agent Substances 0.000 description 3
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 3
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 239000004944 Liquid Silicone Rubber Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 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
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 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
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 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
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 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
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000005011 phenolic resin Substances 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
- 230000000704 physical effect Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical group C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical group C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 1
- OTXLVWBYXUCELR-UHFFFAOYSA-N 2-ethenyl-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C(=C)[Si]1(O[SiH](O[SiH](O[SiH](O1)C)C)C)C OTXLVWBYXUCELR-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
- 229920000049 Carbon (fiber) Polymers 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
- 239000004640 Melamine resin Substances 0.000 description 1
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- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
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- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 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
- 229920000180 alkyd Polymers 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical class C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
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- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
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- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、製造ロットによる電気抵抗率の変動が小さく、かつ圧縮永久歪が小さいゴム硬化物が得られる室温で液状の導電性シリコーンゴム組成物及びその製造方法に関する。 The present invention relates to a conductive silicone rubber composition that is liquid at room temperature, and a method for producing the same, in which a cured rubber having a small change in electrical resistivity depending on the production lot and a small compression set can be obtained.
従来、電気絶縁性を示すゴム状物質に導電性材料を配合した導電性ゴムは種々知られており、例えば、導電性材料としてカーボンブラック等を配合し、電気抵抗率を10Ω・m〜10kΩ・mの範囲にした導電性ゴムが、広い分野で応用されている。 Conventionally, various conductive rubbers in which a conductive material is blended with a rubber-like substance exhibiting electrical insulation properties are known. For example, carbon black or the like is blended as a conductive material, and the electrical resistivity is 10Ω · m to 10 kΩ · Conductive rubber having a range of m is applied in a wide range of fields.
一方、電気絶縁性ゴム状物質の一つであるシリコーンゴムは、耐熱性、耐寒性、耐候性に優れ、電気絶縁性ゴムとして多く利用されているが、他のゴム状物質と同様に導電性材料を添加することで、導電性ゴムとしても実用化されている。また、抵抗値を安定化する方法としては、特開平8−20725号公報(特許文献1)で導電性亜鉛華を配合する方法や、特開平3−195752号公報(特許文献2)に記載されている通り、シリコーンパウダーの添加などが知られている。しかしながら、これらはいずれもシリコーンミラブルゴムに配合されたもので、液状組成物で効果があるものではなかった。 On the other hand, silicone rubber, which is one of the electrically insulating rubbery substances, is excellent in heat resistance, cold resistance and weather resistance, and is widely used as an electrically insulating rubber, but it is conductive like other rubbery substances. It is also put into practical use as a conductive rubber by adding materials. Further, as a method for stabilizing the resistance value, a method of blending conductive zinc white in JP-A-8-20725 (Patent Document 1) and JP-A-3-1955752 (Patent Document 2) are described. As you can see, the addition of silicone powder is known. However, these were all blended with silicone millable rubber and were not effective in the liquid composition.
導電性シリコーンゴムに添加する導電性材料としては、例えば、カーボンブラックやグラファイト、銀,ニッケル,銅等の各種金属粉、各種非導電性粉体や短繊維表面を銀等の金属で処理したもの、炭素繊維,金属繊維などを混合したものが、シリコーンゴムがもつ特異な特性を損なうことなく、その導電性材料の種類及び充填量により、シリコーンゴムの電気抵抗率を10MΩ・m〜10-1Ω・m程度まで低下させ得ることから頻繁に使用されている。 Examples of the conductive material added to the conductive silicone rubber include various metal powders such as carbon black, graphite, silver, nickel and copper, various non-conductive powders, and short fiber surfaces treated with a metal such as silver. A mixture of carbon fiber, metal fiber, etc. has an electrical resistivity of 10 MΩ · m to 10 −1 depending on the type and filling amount of the conductive material without impairing the unique properties of silicone rubber. It is frequently used because it can be reduced to about Ω · m.
しかしながら、液状シリコーンゴムにこれら各種カーボンブラックや金属粉を配合した場合、10MΩ・m〜10Ω・mという低導電及び半導電領域では電気抵抗率のバラツキが極めて大きくなり、電気抵抗率を安定化させることは困難であった。これは成形条件により導電性粒子の分散性が著しく変化することが原因であると考えられる。 However, when these various carbon blacks and metal powders are blended with liquid silicone rubber, the variation in electrical resistivity becomes extremely large in the low conductive and semiconductive regions of 10 MΩ · m to 10Ω · m, and the electrical resistivity is stabilized. It was difficult. This is considered to be because the dispersibility of the conductive particles varies significantly depending on the molding conditions.
ところが、最近においては、OA機器の部品、特に乾式複写機における帯電ロール、現像ロール、紙送りロール、定着ロール、加圧ロール、除電ロール、クリーニングロール、オイル塗布ロール等のゴムロールとして低導電及び半導電ロールの必要性が高まり、この領域での電気抵抗率変動が少なく、安定した電気抵抗率を示す導電性ロールが求められている。 In recent years, however, low conductivity and semi-conductive materials are used as rubber rolls for OA equipment parts, particularly charging rolls, developing rolls, paper feed rolls, fixing rolls, pressure rolls, static elimination rolls, cleaning rolls, and oil application rolls in dry copying machines. There is a growing need for conductive rolls, and there is a need for conductive rolls that exhibit stable electrical resistivity with little variation in electrical resistivity in this region.
本発明は、上記事情に鑑みなされたもので、低導電及び半導電領域での電気抵抗率の変動が小さく、かつ圧縮永久歪も小さい導電性シリコーンゴム組成物及びその製造方法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 provides a conductive silicone rubber composition having a small variation in electrical resistivity in a low conductive and semiconductive region and a small compression set, and a method for producing the same. Objective.
本発明者は、上記目的を達成するため鋭意検討を重ねた結果、付加反応硬化型液状のオルガノポリシロキサン組成物に、導電性材料としてのカーボンブラックに加え、付加反応基を有した高分子量のシロキサンポリマーを配合することで、10MΩ・m〜10Ω・mという低導電及び半導電領域において安定した体積抵抗率が得られ、かつ圧縮永久歪が小さいシリコーンゴム組成物が得られること、更にカーボンブラックを高分子量ポリマーと同時に混練することで、カーボンブラックが十分にシロキサン中に分散し、より安定した導電性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 inventor, as a result of addition reaction curable liquid organopolysiloxane composition, in addition to carbon black as a conductive material, high molecular weight having an addition reactive group. By blending a siloxane polymer, a silicone rubber composition having a low volume conductivity of 10 MΩ · m to 10 Ω · m and a stable volume resistivity in a semiconductive region and having a small compression set can be obtained. By kneading together with the high molecular weight polymer, it was found that carbon black was sufficiently dispersed in siloxane and more stable conductivity was obtained, and the present invention was made.
従って、本発明は、
(A)一分子中に少なくとも2個の、分子鎖途中の珪素原子に結合したアルケニル基を含有する重合度が100〜800の液状オルガノポリシロキサン:97〜70質量部、
(B)一分子中に少なくとも2個の珪素原子と結合するアルケニル基を含有する重合度が2,000〜30,000の生ゴム状オルガノポリシロキサン:3〜30質量部、
(但し、(A),(B)成分の合計は100質量部である。)
(C)一分子中に少なくとも2個の珪素原子と結合する水素原子を含有するオルガノハイドロジェンポリシロキサン:0.1〜30質量部、
(D)カーボンブラック:0.5〜50質量部、
(E)付加反応触媒:触媒量
を含有してなり、室温で液状であり、電子写真式画像形成装置のロール用であることを特徴とする導電性シリコーンゴム組成物、及び(B)成分の全量と(D)成分の全量及び(A)成分の一部を予め混合し、その後に(A)成分の残量及び(C),(E)成分を加えて更に混合することを特徴とする上記導電性シリコーンゴム組成物の製造方法を提供する。
Therefore, the present invention
(A) Liquid organopolysiloxane having a polymerization degree of 100 to 800 containing at least two alkenyl groups bonded to silicon atoms in the middle of the molecular chain in one molecule: 97 to 70 parts by mass,
(B) Raw rubber-like organopolysiloxane having a degree of polymerization of 2,000 to 30,000 containing an alkenyl group bonded to at least two silicon atoms in one molecule: 3 to 30 parts by mass
(However, the total of the components (A) and (B) is 100 parts by mass.)
(C) Organohydrogenpolysiloxane containing hydrogen atoms bonded to at least two silicon atoms in one molecule: 0.1 to 30 parts by mass
(D) Carbon black: 0.5 to 50 parts by mass,
(E) Addition reaction catalyst: a conductive silicone rubber composition containing a catalytic amount, liquid at room temperature, and used for a roll of an electrophotographic image forming apparatus , and (B) component The total amount of the total amount of the component (D) and a part of the component (A) are mixed in advance, and then the remaining amount of the component (A) and the components (C) and (E) are added and further mixed. A method for producing the conductive silicone rubber composition is provided.
本発明の導電性シリコーンゴム組成物は、低導電及び半導電領域での電気抵抗率が安定で、特に製造ロットによる電気抵抗率のバラツキが少なく安定していると共に、圧縮永久歪が小さいという優れた特徴をもつものであり、画像形成装置のロール、特に現像ロール用材料として好適である。 The conductive silicone rubber composition of the present invention has stable electrical resistivity in the low conductivity and semiconducting regions, and is particularly stable with little variation in electrical resistivity due to production lots and low compression set. Therefore, it is suitable as a roll for an image forming apparatus, particularly as a material for a developing roll.
本発明の導電性シリコーンゴム組成物は、下記(A)〜(E)成分を含有してなる室温で液状のものである。
(A)一分子中に少なくとも2個の珪素原子と結合するアルケニル基を含有する重合度が800以下のオルガノポリシロキサン
(B)一分子中に少なくとも2個の珪素原子と結合するアルケニル基を含有する重合度が2,000以上のオルガノポリシロキサン
(C)一分子中に少なくとも2個の珪素原子と結合する水素原子を含有するオルガノハイドロジェンポリシロキサン
(D)カーボンブラック
(E)付加反応触媒
The conductive silicone rubber composition of the present invention is liquid at room temperature containing the following components (A) to (E).
(A) Organopolysiloxane containing an alkenyl group bonded to at least two silicon atoms in one molecule and having a polymerization degree of 800 or less (B) Containing an alkenyl group bonded to at least two silicon atoms in one molecule Organohydrogenpolysiloxane (D) carbon black (E) addition reaction catalyst containing hydrogen atoms bonded to at least two silicon atoms in one molecule of organopolysiloxane (C) having a polymerization degree of 2,000 or more
(A)成分の一分子中に少なくとも2個の珪素原子と結合するアルケニル基を含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(1)で示されるものを用いることができる。 As the organopolysiloxane containing an alkenyl group bonded to at least two silicon atoms in one molecule of the component (A), those represented by the following average composition formula (1) can be used.
R1 aSiO(4-a)/2 (1)
式中、R1は互いに同一又は異種の炭素数1〜10、好ましくは1〜8の非置換又は置換一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。
R 1 a SiO (4-a) / 2 (1)
In the formula, R 1 is an unsubstituted or substituted monovalent hydrocarbon group having the same or different carbon number of 1 to 10, preferably 1 to 8, and a is 1.5 to 2.8, preferably 1.8. It is a positive number in the range of ˜2.5, more preferably 1.95 to 2.05.
ここで、上記R1で示される珪素原子に結合した非置換又は置換の一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、プロペニル基、イソプロペニル基、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R1の90%以上がメチル基であることが好ましい。 Here, as the unsubstituted or substituted monovalent hydrocarbon group bonded to the silicon atom represented by R 1 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, Pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, alkyl group such as decyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, phenylethyl group, phenylpropyl Aralkyl groups such as groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, hexenyl groups, cyclohexenyl groups, octenyl groups and other alkenyl groups, and some or all of the hydrogen atoms of these groups are fluorine. Substituted with halogen atoms such as bromine, chlorine, cyano groups, etc., such as chloromethyl group, chloropro Group, bromoethyl group, trifluoropropyl group, but cyanoethyl group and the like, Preferably, at least 90% of all R 1 is a methyl group.
また、R1のうち少なくとも2個(通常、2〜50個)、好ましくは2〜20個、より好ましくは2〜10個はアルケニル基(炭素数2〜8のものが好ましく、更に好ましくは炭素数2〜6のものであり、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。このアルケニル基の含有量は、オルガノポリシロキサン中1.0×10-5〜1.0×10-2mol/g、特に2.0×10-5〜5.0×10-3mol/gとすることが好ましい。アルケニル基の量が1.0×10-5mol/gより少ないと架橋が不十分でゲル状になってしまう場合があり、また1.0×10-2mol/gより多いと架橋密度が高くなりすぎて、脆いゴムとなってしまうおそれがある。 In addition, at least 2 (usually 2 to 50) of R 1 , preferably 2 to 20, more preferably 2 to 10 are alkenyl groups (preferably having 2 to 8 carbon atoms, more preferably carbon. 2 to 6 and particularly preferably a vinyl group). The content of the alkenyl group is 1.0 × 10 −5 to 1.0 × 10 −2 mol / g, particularly 2.0 × 10 −5 to 5.0 × 10 −3 mol / g in the organopolysiloxane. It is preferable that May crosslink with the amount of alkenyl groups is less than 1.0 × 10 -5 mol / g becomes insufficient gel, also the crosslinking density is more than 1.0 × 10 -2 mol / g There is a possibility that the rubber becomes too high and becomes brittle rubber.
なお、このアルケニル基は、分子鎖末端の珪素原子に結合していても、分子鎖途中の珪素原子に結合していても、両者に結合していてもよい。 The alkenyl group may be bonded to a silicon atom at the end of the molecular chain, may be bonded to a silicon atom in the middle of the molecular chain, or may be bonded to both.
本発明のオルガノポリシロキサンの構造は、基本的に主鎖部分がR1 2SiO2/2で示される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R1 3SiO1/2で示されるトリオルガノシロキシ基で封鎖された直鎖状構造を有することが好ましいが、部分的には分岐状の構造、環状構造などであってもよい。 The structure of the organopolysiloxane of the present invention basically consists of repeating diorganosiloxane units whose main chain portion is represented by R 1 2 SiO 2/2 and whose molecular chain ends are represented by R 1 3 SiO 1/2 . It preferably has a linear structure blocked with a triorganosiloxy group, but may be partially branched or cyclic.
また、このオルガノポリシロキサンの分子量については、重合度が800以下、好ましくは100〜700で、室温(25℃)で液状(通常、25℃で100〜500,000mPa・s、好ましくは1,000〜100,000mPa・s程度)でなければならない。重合度が800を超えると、粘度が高くなりすぎて、成形圧力により抵抗がバラついたり、成形自体が困難になってしまう。なお、重合度の下限値としては、50以上、特に100以上であることが好ましい。 The organopolysiloxane has a molecular weight of 800 or less, preferably 100 to 700, and liquid at room temperature (25 ° C.) (usually 100 to 500,000 mPa · s at 25 ° C., preferably 1,000). ˜100,000 mPa · s). When the degree of polymerization exceeds 800, the viscosity becomes too high, resistance varies depending on the molding pressure, and molding itself becomes difficult. In addition, as a lower limit of a polymerization degree, it is preferable that it is 50 or more, especially 100 or more.
次に、(B)成分の一分子中に少なくとも2個の珪素原子と結合するアルケニル基を含有する平均重合度が2,000以上のオルガノポリシロキサンとしては、下記平均組成式(2)で示されるものを用いることができる。 Next, an organopolysiloxane having an average degree of polymerization of 2,000 or more and containing an alkenyl group bonded to at least two silicon atoms in one molecule of the component (B) is represented by the following average composition formula (2). Can be used.
R2 bSiO(4-b)/2 (2)
式中、R2は互いに同一又は異種の炭素数1〜10、好ましくは1〜8の非置換又は置換一価炭化水素基であり、bは1.8〜2.5、好ましくは1.9〜2.1、より好ましくは1.95〜2.05、更に好ましくは1.98〜2.01の範囲の正数である。
R 2 b SiO (4-b) / 2 (2)
In the formula, R 2 is the same or different, unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and b is 1.8 to 2.5, preferably 1.9. To 2.1, more preferably 1.95 to 2.05, and still more preferably a positive number in the range of 1.98 to 2.01.
ここで、上記R2で示される珪素原子に結合した非置換又は置換の一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、プロペニル基、イソプロペニル基、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R2の90%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 bonded to the silicon atom represented by R 2 includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, Pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, alkyl group such as decyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, phenylethyl group, phenylpropyl Aralkyl groups such as groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, hexenyl groups, cyclohexenyl groups, octenyl groups and other alkenyl groups, and some or all of the hydrogen atoms of these groups are fluorine. Substituted with halogen atoms such as bromine, chlorine, cyano groups, etc., such as chloromethyl group, chloropro Group, bromoethyl group, trifluoropropyl group, but cyanoethyl group and the like, it is preferable more than 90% of the total R 2 is a methyl group.
また、R2のうち少なくとも2個(通常、2〜30個)、好ましくは2〜20個、より好ましくは2〜10個はアルケニル基(炭素数2〜8のものが好ましく、更に好ましくは炭素数2〜6のものであり、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。このアルケニル基の含有量は、オルガノポリシロキサン中1.0×10-6〜1.0×10-2mol/g、特に5.0×10-6〜1.0×10-3mol/gとすることが好ましい。アルケニル基の量が1.0×10-6mol/gより少ないと硬化後、未反応あるいは架橋点を持たないポリマーがブリードしてしまう場合がある。また1.0×10-2mol/gより多いと架橋密度が高くなりすぎて、脆いゴムとなってしまうおそれがある。 In addition, at least 2 (usually 2 to 30) of R 2 , preferably 2 to 20, more preferably 2 to 10 are alkenyl groups (preferably having 2 to 8 carbon atoms, more preferably carbon. 2 to 6 and particularly preferably a vinyl group). The alkenyl group content in the organopolysiloxane is 1.0 × 10 −6 to 1.0 × 10 −2 mol / g, particularly 5.0 × 10 −6 to 1.0 × 10 −3 mol / g. It is preferable that If the amount of the alkenyl group is less than 1.0 × 10 −6 mol / g, a polymer which has not reacted or has no crosslinking point may bleed after curing. On the other hand, when the amount is more than 1.0 × 10 −2 mol / g, the crosslinking density becomes too high and the rubber may be brittle.
なお、このアルケニル基は、分子鎖末端の珪素原子に結合していても、分子鎖途中の珪素原子に結合していても、両者に結合していてもよい。 The alkenyl group may be bonded to a silicon atom at the end of the molecular chain, may be bonded to a silicon atom in the middle of the molecular chain, or may be bonded to both.
本発明のオルガノポリシロキサンの構造は、基本的に主鎖部分がR2 2SiO2/2で示される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R2 3SiO1/2で示されるトリオルガノシロキシ基で封鎖された直鎖状構造を有することが好ましいが、部分的には分岐状の構造、環状構造などであってもよい。 The structure of the organopolysiloxane of the present invention basically consists of repeating diorganosiloxane units whose main chain portion is represented by R 2 2 SiO 2/2 and whose molecular chain ends are represented by R 2 3 SiO 1/2 . It preferably has a linear structure blocked with a triorganosiloxy group, but may be partially branched or cyclic.
また、このオルガノポリシロキサンの分子量については、重合度が2,000以上、好ましくは4,000以上で、室温(25℃)で生ゴム状でなければならない。重合度が2,000未満では、増粘効果が不十分で、カーボンブラックを十分に分散させ、安定した体積抵抗率を得ることが困難になってしまう。なお、重合度の上限値としては、30,000以下、特に20,000以下であることが好ましい。 The molecular weight of the organopolysiloxane should be a degree of polymerization of 2,000 or more, preferably 4,000 or more, and a raw rubber at room temperature (25 ° C.). When the degree of polymerization is less than 2,000, the thickening effect is insufficient, and it becomes difficult to sufficiently disperse carbon black and obtain a stable volume resistivity. In addition, as an upper limit of a polymerization degree, it is preferable that it is 30,000 or less, especially 20,000 or less.
この生ゴム状オルガノポリシロキサンである(B)成分の配合量は、(A)成分と(B)成分の合計量に対し、3〜30質量%、好ましくは5〜25質量%となる量である。3質量%より少ないと十分な増粘効果が得られず、30質量%を超える量では、粘度が高すぎて成形が困難になるばかりでなく、圧縮永久歪も高くなってしまう。 The blending amount of component (B), which is this raw rubber-like organopolysiloxane, is 3-30% by mass, preferably 5-25% by mass, based on the total amount of component (A) and component (B). . If the amount is less than 3% by mass, a sufficient thickening effect cannot be obtained. If the amount exceeds 30% by mass, the viscosity is too high and molding becomes difficult, and the compression set is also increased.
本発明の(C)成分は、一分子中に珪素原子と結合する水素原子(Si−H基)を少なくとも2個、好ましくは3個以上有するオルガノハイドロジェンポリシロキサンであり、分子中のSi−H基が前記(A),(B)成分中の珪素原子に結合した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。 The component (C) of the present invention is an organohydrogenpolysiloxane having at least 2, preferably 3 or more hydrogen atoms (Si-H groups) bonded to silicon atoms in one molecule. The H group crosslinks with the alkenyl group bonded to the silicon atom in the components (A) and (B) by a hydrosilylation addition reaction, and acts as a curing agent for curing the composition.
この(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(3)で示されるものを用いることができる。
R3 cHdSiO(4-c-d)/2 (3)
(式中、R3は炭素数1〜10、好ましくは1〜8の非置換又は置換の一価炭化水素基である。またcは、0.7〜2.1、dは0.001〜1.0で、かつc+dは0.8〜3.0を満足する正数である。)
As the organohydrogenpolysiloxane of component (C), those represented by the following average composition formula (3) can be used.
R 3 c H d SiO (4-cd) / 2 (3)
(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, c is 0.7 to 2.1, and d is 0.001 to 0.001. 1.0 and c + d is a positive number satisfying 0.8 to 3.0.)
ここで、R3の非置換又は置換の一価炭化水素基としては、R1で例示したものと同様のものを挙げることができるが、脂肪族不飽和基(アルケニル基)を有しないものが好ましく、特に、メチル基、フェニル基、トリフロロプロピル基が好ましい。また、cは0.8〜2.0、dは0.01〜1.0、c+dは1.0〜2.5を満たす正数であることが好ましい。 Examples of the unsubstituted or substituted monovalent hydrocarbon group of R 3, there may be mentioned the same ones as exemplified for R 1, it is having no aliphatic unsaturated group (alkenyl group) Particularly preferred are a methyl group, a phenyl group, and a trifluoropropyl group. Further, c is preferably a positive number satisfying 0.8 to 2.0, d being 0.01 to 1.0, and c + d being 1.0 to 2.5.
本発明のオルガノハイドロジェンポリシロキサンは、1分子中に少なくとも2個(通常、2〜300個)、好ましくは3個以上(通常、3〜100個)、より好ましくは3〜50個の珪素原子結合水素原子(Si−H基)を有するものである。 The organohydrogenpolysiloxane of the present invention has at least 2 (usually 2 to 300), preferably 3 or more (usually 3 to 100), more preferably 3 to 50 silicon atoms in one molecule. It has a bonded hydrogen atom (Si-H group).
この珪素原子結合水素原子(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0.001〜0.017mol/g、特に0.002〜0.015mol/gとすることが好ましい。珪素原子結合水素原子(Si−H基)の量が少なすぎると架橋が不十分でゲル状になってしまう場合があり、また多すぎると架橋密度が高くなりすぎて、脆いゴムとなってしまうおそれがある。 The silicon atom-bonded hydrogen atom (Si—H group) content is preferably 0.001 to 0.017 mol / g, particularly 0.002 to 0.015 mol / g in the organohydrogenpolysiloxane. If the amount of silicon atom-bonded hydrogen atoms (Si-H groups) is too small, the crosslinking may be insufficient and gelation may occur, and if too large, the crosslinking density becomes too high, resulting in a brittle rubber. There is a fear.
なお、この珪素原子に結合する水素原子(Si−H基)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 addition, the hydrogen atom (Si—H group) bonded to the silicon atom may be located at either the molecular chain end or in the middle of the molecular chain, or may be located at both.
本発明の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。この場合、一分子中の珪素原子の数(又は重合度)は2〜300個、特に4〜150個程度の室温(25℃)で液状(通常、25℃で1,000mPa・s以下、好ましくは0.1〜500mPa・s程度)のものが好適に用いられる。 The molecular structure of the organohydrogenpolysiloxane of the present invention may be any of linear, cyclic, branched, and three-dimensional network structures. In this case, the number (or degree of polymerization) of silicon atoms in one molecule is 2 to 300, particularly about 4 to 150 room temperature (25 ° C.) and liquid (usually 1,000 mPa · s or less at 25 ° C., preferably Is preferably about 0.1 to 500 mPa · s).
上記(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、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、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、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シロキサン・ジフェニルシロキサン共重合体、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シロキサン・ジフェニルシロキサン・ジメチルシロキサン共重合体、(CH3)2HSiO1/2単位とSiO4/2単位とから成る共重合体、(CH3)2HSiO1/2単位と(CH3)3SiO1/2単位とSiO4/2単位とから成る共重合体、(CH3)2HSiO1/2単位とSiO4/2単位と(C6H5)SiO3/2単位とから成る共重合体などが挙げられる。 Examples of the organohydrogenpolysiloxane of the component (C) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, trimethylsiloxy group-blocked methylhydrogen at both ends. Polysiloxane, Trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, both ends dimethylhydrogensiloxy group-capped dimethylpolysiloxane, Both ends dimethylhydrogensiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer , Trimethylsiloxy group-capped methylhydrogensiloxane / diphenylsiloxane copolymer, both ends trimethylsiloxy group-capped methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane Hexane copolymer, and (CH 3) 2 HSiO copolymer comprising a 1/2 units and SiO 4/2 units, and, (CH 3) 2 HSiO 1/2 units and (CH 3) 3 SiO 1/2 units Examples thereof include a copolymer composed of SiO 4/2 units, a copolymer composed of (CH 3 ) 2 HSiO 1/2 units, SiO 4/2 units, and (C 6 H 5 ) SiO 3/2 units. .
こ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質量部に対して0.1〜30質量部、特に0.3〜20質量部であることが好ましい。0.1質量部未満では架橋が不十分で、目的とするロールとしてのゴム物性が得られず、30質量部を超えると圧縮永久歪が増大してしまう。また、こ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),(B)成分中の珪素原子に結合したアルケニル基に対する(C)成分中の珪素原子結合水素原子(Si−H基)の量がモル比で、通常0.3〜10.0、好ましくは0.5〜5.0となる量で配合することもできる。 The compounding amount of the organohydrogenpolysiloxane is preferably 0.1 to 30 parts by mass, particularly preferably 0.3 to 20 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). If the amount is less than 0.1 parts by mass, crosslinking is insufficient, and the desired physical properties of rubber as a roll cannot be obtained. If the amount exceeds 30 parts by mass, compression set increases. The amount of the organohydrogenpolysiloxane is the amount of silicon atom-bonded hydrogen atoms (Si-H groups) in the component (C) relative to the alkenyl groups bonded to silicon atoms in the components (A) and (B). Can be blended in an amount of usually 0.3 to 10.0, preferably 0.5 to 5.0, in molar ratio.
(D)成分のカーボンブラックとしては、通常、導電性ゴム組成物に常用されているものを使用し得、例えば、アセチレンブラック、コンダクティブファーネスブラック(CF)、スーパーコンダクティブファーネスブラック(SCF)、エクストラコンダクティブファーネスブラック(XCF)、コンダクティブチャンネルブラック(CC)、1,500℃程度の高温で熱処理されたファーネスブラックやチャンネルブラック等を挙げることができる。 As the carbon black of component (D), those commonly used in conductive rubber compositions can be used, such as acetylene black, conductive furnace black (CF), super conductive furnace black (SCF), and extra conductive. Examples thereof include furnace black (XCF), conductive channel black (CC), furnace black and channel black that have been heat-treated at a high temperature of about 1,500 ° C.
具体的に、アセチレンブラックとしては、電化アセチレンブラック(電気化学社製),シャウニガンアセチレンブラック(シャウニガンケミカル社製)等が、コンダクティブファーネスブラックとしては、コンチネックスCF(コンチネンタルカーボン社製),バルカンC(キャボット社製)等が、スーパーコンダクティブファーネスブラックとしては、コンチネックスSCF(コンチネンタルカーボン社製),バルカンSC(キャボット社製)等が、エクストラコンダクティブファーネスブラックとしては、旭HS−500(旭カーボン社製),バルカンXC−72(キャボット社製)等が、コンダクティブチャンネルブラックとしては、コウラックスL(デグッサ社製)等が例示され、また、ファーネスブラックの一種であるケッチェンブラックEC及びケッチェンブラックEC−600JD(ケッチェンブラックインターナショナル社製)を用いることもできる。 Specifically, as acetylene black, electrified acetylene black (manufactured by Electrochemical Co., Ltd.), Shaunigan acetylene black (manufactured by Shaunigan Chemical Co., Ltd.), etc., and as conductive furnace black, Continex CF (manufactured by Continental Carbon) , Vulcan C (manufactured by Cabot), etc., Superconductive furnace black, Continex SCF (manufactured by Continental Carbon), Vulcan SC (manufactured by Cabot), etc., as extra-conductive furnace black, Asahi HS-500 ( Asahi Carbon Co., Ltd.), Vulcan XC-72 (Cabot Co., Ltd.), etc., examples of the conductive channel black include Kourax L (Degussa Co., Ltd.), and Ketjen, a kind of furnace black. It is also possible to use a rack EC and Ketchen black EC-600JD (manufactured by Ketchen Black International Co., Ltd.).
なお、これらのうちでは、アセチレンブラックが不純物含有率が少ない上、発達した二次ストラクチャー構造を有することから導電性に優れており、本発明において特に好適に用いられる。また、その卓越した比表面積から低充填量でも優れた導電性を示すケッチェンブラックECやケッチェンブラックEC−600JD等も好ましく使用できる。 Of these, acetylene black has a low impurity content and has a developed secondary structure structure, so that it has excellent conductivity and is particularly preferably used in the present invention. Moreover, Ketjen Black EC, Ketjen Black EC-600JD, etc. which show the outstanding electroconductivity also with the low filling amount from the outstanding specific surface area can be used preferably.
なお、これらカーボンブラックは、表面疎水化処理したものを使用してもよい。表面処理剤としては、ステアリン酸エチルなどの脂肪酸エステル、テトラブチルチタネートなどの有機チタン酸エステル類、トリアルコキシビニルシランなどのシラン及びシラン系カップリング剤、ヘキサメチルジシラザンなどのシラザン類、両末端ヒドロキシシロキサンなどの有機官能基含有シロキサン類、オクタメチルシクロテトラシロキサンなどの低分子シリコーンなど、表面処理剤として公知なものであればいかなるものでもよい。 These carbon blacks may be those subjected to surface hydrophobization treatment. Surface treatment agents include fatty acid esters such as ethyl stearate, organic titanates such as tetrabutyl titanate, silanes such as trialkoxyvinyl silane and silane coupling agents, silazanes such as hexamethyldisilazane, and hydroxy groups at both ends. Any known surface treatment agent may be used, such as organic functional group-containing siloxanes such as siloxane and low molecular silicones such as octamethylcyclotetrasiloxane.
(D)成分であるカーボンブラックの配合量としては、上述した(A)成分と(B)成分のオルガノポリシロキサン合計量100質量部に対して0.5〜50質量部、好ましくは1〜30質量部、より好ましくは1〜20質量部である。添加量が0.5質量部未満では所望の導電性を得ることができず、50質量部を超えると、配合が困難であるばかりか、ゴム物性も著しく低下してしまう。なお、上記(D)成分の配合量は、本シリコーンゴム組成物の硬化物(シリコーンゴム)の体積抵抗率を10MΩ・m〜10Ω・mとする量であることが好ましい。 (B) As compounding quantity of carbon black which is a component, it is 0.5-50 mass parts with respect to 100 mass parts of organopolysiloxane total amount of (A) component and (B) component mentioned above, Preferably it is 1-30. It is 1 part by mass, more preferably 1 to 20 parts by mass. If the addition amount is less than 0.5 parts by mass, desired conductivity cannot be obtained. If the addition amount exceeds 50 parts by mass, not only the compounding is difficult, but also the physical properties of the rubber are remarkably lowered. The blending amount of the component (D) is preferably such that the volume resistivity of the cured product (silicone rubber) of the silicone rubber composition is 10 MΩ · m to 10 Ω · m.
このカーボンブラックの添加・混合方法は、(A)〜(E)成分と同時に添加することも可能であるが、好ましくは、より粘度の高い状態で予め分散させた状態のものに、液状オイル((A)成分の液状オルガノポリシロキサン)を添加して成形し易いように粘度を調整する方法が好ましい。具体的には、まずカーボンブラックの全量及び(B)成分の生ゴム状シロキサンの全量及び(A)成分の液状シロキサンの一部を混合し、カーボンブラックを十分に分散させる。なお、この時、表面処理剤を加えたり、100℃〜180℃くらいの加熱をしながら混合してもよい。混合後、残りの(A)成分、及びその他の成分を加え、再度十分に攪拌することにより所望の粘度を有する液状のシリコーンゴム組成物を得ることができる。 The carbon black can be added and mixed at the same time as the components (A) to (E). Preferably, however, liquid oil ( A method of adjusting the viscosity so as to be easily molded by adding (A) component liquid organopolysiloxane is preferred. Specifically, first, the total amount of carbon black, the total amount of raw rubber siloxane of component (B) and a part of liquid siloxane of component (A) are mixed, and the carbon black is sufficiently dispersed. At this time, a surface treatment agent may be added or mixed while heating at about 100 ° C. to 180 ° C. After mixing, the remaining component (A) and other components are added, and sufficiently stirred again to obtain a liquid silicone rubber composition having a desired viscosity.
(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、パラジウム系触媒、ロジウム系触媒などの白金族金属触媒が挙げられる。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るが、通常、金属分として(A)成分及び(B)成分の合計質量に対して0.5〜1,000ppm、特に1〜500ppm程度配合することが好ましい。 (E) Component addition reaction catalysts include platinum black, platinous chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and olefins, platinum bisacetoacetate, Examples thereof include platinum group metal catalysts such as palladium catalysts and rhodium catalysts. In addition, although the compounding quantity of this addition reaction catalyst can be made into a catalyst quantity, it is 0.5-1,000 ppm with respect to the total mass of (A) component and (B) component as a metal content normally, especially 1-. It is preferable to blend about 500 ppm.
本発明の導電性シリコーンゴム組成物には、必要に応じて、シリカヒドロゲル(含水けい酸)、シリカエアロゲル(無水けい酸−煙霧質シリカ)等の補強性シリカ充填剤、クレイ、炭酸カルシウム、ケイソウ土、二酸化チタン等の充填剤、低分子シロキサンエステル、シラノール、例えばジフェニルシランジオール等の分散剤、酸化鉄、酸化セリウム、オクチル酸鉄等の耐熱性向上剤、エチニルシクロヘキサノールなどのアセチレンアルコール、テトラビニルテトラメチルシクロテトラシロキサンなどの環状ビニルシロキサン、ベンゾトリアゾールなどのトリアゾール化合物等の反応制御剤、接着性や成形加工性を向上させるための各種カーボンファンクショナルシラン、難燃性を付与させるハロゲン化合物などを本発明の目的を損なわない範囲で添加混合してもよい。 In the conductive silicone rubber composition of the present invention, if necessary, a reinforcing silica filler such as silica hydrogel (hydrous silicic acid), silica airgel (anhydrous silicic acid-fumed silica), clay, calcium carbonate, diatomaceous earth. Soil, filler such as titanium dioxide, low molecular siloxane ester, silanol, dispersant such as diphenylsilanediol, heat resistance improver such as iron oxide, cerium oxide, iron octylate, acetylene alcohol such as ethynylcyclohexanol, tetra Reaction control agents such as cyclic vinylsiloxanes such as vinyltetramethylcyclotetrasiloxane, triazole compounds such as benzotriazole, various carbon functional silanes for improving adhesion and moldability, halogen compounds that impart flame retardancy, etc. The purpose of the present invention is not impaired It may be added and mixed in circumference.
本発明の導電性シリコーンゴム組成物の室温(25℃)における粘度は、好ましくは30〜600Pa・s、より好ましくは50〜500Pa・sの範囲である。30Pa・s未満では体積抵抗率が安定しない場合があり、600Pa・sを超える粘度では、成形時の圧力が高くなりすぎて、やはり体積抵抗率が安定しなくなってしまう場合がある。なお、本発明において、粘度はBH型、BS型等の回転粘度計などにより測定することができる。 The viscosity at room temperature (25 ° C.) of the conductive silicone rubber composition of the present invention is preferably 30 to 600 Pa · s, more preferably 50 to 500 Pa · s. If the viscosity is less than 30 Pa · s, the volume resistivity may not be stable. If the viscosity exceeds 600 Pa · s, the pressure during molding becomes too high, and the volume resistivity may not be stable. In the present invention, the viscosity can be measured by a rotational viscometer such as BH type and BS type.
本発明の導電性シリコーンゴム組成物は、これを硬化させてなるシリコーンゴムの体積抵抗率が、好ましくは10MΩ・m〜10Ω・m、より好ましくは100kΩ・m〜10Ω・mとなるものである。体積抵抗率が10Ω・m未満では現像ロールとして使用した場合、画像が不鮮明になるおそれがあり、10MΩ・mより大きいと現像ロールとして使用できない場合がある。ここで、体積抵抗率はSRIS(日本ゴム協会標準規格)2301−1969に準じて測定することができる。 The volume resistivity of the silicone rubber obtained by curing the conductive silicone rubber composition of the present invention is preferably 10 MΩ · m to 10 Ω · m, more preferably 100 kΩ · m to 10 Ω · m. . When the volume resistivity is less than 10 Ω · m, the image may be unclear when used as a developing roll. When the volume resistivity is larger than 10 MΩ · m, the developing roll may not be used. Here, the volume resistivity can be measured according to SRIS (Japan Rubber Association Standard) 2301-1969.
このような安定した低導電及び半導電が得られる本発明の導電性シリコーンゴム組成物は、電気・電子部品、自動車用部品、事務機用部品など各種の導電性を必要とする用途に使用できるが、特に複写機、プリンター、ファクシミリなどの電子写真式画像形成装置のロール用として好適に用いられる。このようなロールとしては、帯電ロール、現像ロール、転写ロール、定着ロールなどがあるが、中でも特に現像ロール用として好適である。 The conductive silicone rubber composition of the present invention that provides such a stable low conductivity and semiconductivity can be used for applications requiring various conductivity such as electrical / electronic components, automotive components, and office machine components. However, it is particularly suitably used as a roll for electrophotographic image forming apparatuses such as copying machines, printers, and facsimiles. Examples of such a roll include a charging roll, a developing roll, a transfer roll, and a fixing roll.
ここで、現像ロールとしては、芯体の外周に本発明の導電性シリコーンゴム層を設けたもので、更にその周囲にトナーと接触する表層を有するものがより効果的である。 Here, as the developing roll, it is more effective to provide the conductive silicone rubber layer of the present invention on the outer periphery of the core body and further to have a surface layer in contact with the toner around it.
芯体は特に制限はなく、各種金属や樹脂からなる中実又は中空の芯体が用いられ、例えば、金属としては、鉄、銅、洋白、ステンレススチールなどが例示され、また樹脂としては、ポリエチレン、ポリアミド、ポリアセタール、ポリカーボネート、ポリエチレンテレフタレート、ポリイミド、ポリアミドイミド、ポリエステル、フェノール樹脂、エポキシ樹脂、アクリル樹脂、メタクリル樹脂などが例示される。 The core is not particularly limited, and a solid or hollow core made of various metals and resins is used. For example, examples of the metal include iron, copper, white, stainless steel, etc. Examples include polyethylene, polyamide, polyacetal, polycarbonate, polyethylene terephthalate, polyimide, polyamideimide, polyester, phenol resin, epoxy resin, acrylic resin, and methacrylic resin.
この芯体外周にシリコーンゴム層を形成する方法としては特に制限はなく、公知の方法を採用することができ、一般には芯体上にコーティング、あるいは予め芯体を金型中央に設置し、金型壁面と芯体の間にシリコーンゴム組成物を注入あるいは射出により成形する方法などがある。なお、芯体とシリコーンゴム層の間には必要に応じてプライマーを塗布したり、接着剤層を設けてもよい。
ここで、上記シリコーンゴム組成物の硬化条件としては、室温(25℃)〜250℃、特に80〜220℃で30秒〜4時間、とりわけ120〜200℃で1分〜1時間、次いで150〜250℃、特に160〜200℃で30分〜12時間、特に1〜6時間の後硬化(ポストキュアー)を行うことが好ましい。
The method for forming the silicone rubber layer on the outer periphery of the core body is not particularly limited, and a known method can be adopted. Generally, coating is performed on the core body, or the core body is previously placed in the center of the mold, There is a method in which a silicone rubber composition is molded between the mold wall surface and the core body by injection or injection. A primer or an adhesive layer may be provided between the core and the silicone rubber layer as necessary.
Here, the curing conditions for the silicone rubber composition are room temperature (25 ° C.) to 250 ° C., particularly 80 to 220 ° C. for 30 seconds to 4 hours, particularly 120 to 200 ° C. for 1 minute to 1 hour, and then 150 to Post-curing is preferably performed at 250 ° C., particularly 160 to 200 ° C. for 30 minutes to 12 hours, particularly 1 to 6 hours.
また、トナーと接触する表層としては、ポリエステル樹脂、ポリエーテル樹脂、フッ素樹脂、エポキシ樹脂、ポリアミド樹脂、アクリル樹脂、アクリルウレタン樹脂、ウレタン樹脂、アルキッド樹脂、フェノール樹脂、メラミン樹脂、尿素樹脂、及びこれらの混合物等が挙げられる。この表層には、必要に応じて、カーボンブラック等の充填材、オイル等の可塑剤、帯電制御剤等の添加剤を、適宜添加して差し支えない。この表層をシリコーンゴム層の周囲に形成する方法も特に制限はなく、例えば、コーティング、インモールドコート法、或いは予め円筒状に形成されたシュリンクチューブを加熱収縮させて被覆する方法などが適宜選択される。なお、シリコーンゴム層とこれら表層との間に必要に応じてプライマー層、接着剤層を設けることもできる。 Further, the surface layer in contact with the toner includes polyester resin, polyether resin, fluororesin, epoxy resin, polyamide resin, acrylic resin, acrylic urethane resin, urethane resin, alkyd resin, phenol resin, melamine resin, urea resin, and these And the like. If necessary, additives such as fillers such as carbon black, plasticizers such as oil, and charge control agents may be appropriately added to the surface layer. The method for forming the surface layer around the silicone rubber layer is not particularly limited, and for example, a coating method, an in-mold coating method, or a method in which a shrink tube previously formed in a cylindrical shape is coated by heating and shrinking is appropriately selected. The In addition, a primer layer and an adhesive layer can be provided between the silicone rubber layer and these surface layers as necessary.
以下、実施例と比較例を示して本発明を具体的に説明するが、本発明は下記実施例に限定されるものではない。なお、以下の例において部はいずれも質量部を示す。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following Example. In the following examples, all parts are parts by mass.
[実施例1]
両末端がトリメチルシロキシ基で封鎖され側鎖にビニル基を有するジメチルポリシロキサンA(重合度600、ビニル基含有量0.0001mol/g)40部、両末端がトリメチルシロキシ基で封鎖され側鎖にビニル基を有する生ゴム状ジメチルポリシロキサンB(重合度8,000、ビニル基含有量0.00008mol/g)10部、BET法による比表面積が110m2/gである疎水化処理されたヒュームドシリカ(R−972、日本アエロジル社製)1部、アセチレンブラック(デンカブラックHS−100、電気化学工業社製)3部をプラネタリーミキサーに入れ、30分間撹拌を続けた後、3本ロールに1回通した。これをプラネタリーミキサーに戻した後、更にジメチルポリシロキサンAを50部加えて、30分間攪拌を継続した。その後、架橋剤として両末端及び側鎖にSi−H基を有するメチルハイドロジェンポリシロキサン(重合度17、Si−H量0.0060mol/g)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、白金触媒(Pt濃度1%)0.1部を添加し、15分間撹拌を続けてシリコーンゴム組成物を得た。この組成物の室温(25℃)での粘度をBH型粘度計、ローター7番を使用し、10rpmの条件で測定し、結果を表1に記した。
[Example 1]
40 parts of dimethylpolysiloxane A (polymerization degree 600, vinyl group content 0.0001 mol / g) having both ends blocked with trimethylsiloxy groups and vinyl groups in the side chains, both ends blocked with trimethylsiloxy groups and side chains Hydrophobic fumed silica having 10 parts of raw rubber-like dimethylpolysiloxane B having a vinyl group (degree of polymerization 8,000, vinyl group content 0.00008 mol / g) and a specific surface area of 110 m 2 / g by BET method (R-972, manufactured by Nippon Aerosil Co., Ltd.) 1 part and acetylene black (Denka Black HS-100, manufactured by Denki Kagaku Kogyo Co., Ltd.) 3 parts were put into a planetary mixer and stirred for 30 minutes. I passed through. After returning this to the planetary mixer, 50 parts of dimethylpolysiloxane A was further added, and stirring was continued for 30 minutes. Thereafter, 2.6 parts of methylhydrogenpolysiloxane having Si—H groups at both ends and side chains as a crosslinking agent (polymerization degree 17, Si—H amount 0.0060 mol / g), and ethynylcyclohexanol 0 as a reaction control agent 0.05 part and 0.1 part of platinum catalyst (Pt concentration 1%) were added and stirring was continued for 15 minutes to obtain a silicone rubber composition. The viscosity of this composition at room temperature (25 ° C.) was measured under the condition of 10 rpm using a BH viscometer and rotor No. 7, and the results are shown in Table 1.
このシリコーンゴム組成物を120℃で10分間プレス成形し、更に200℃の乾燥機で4時間ポストキュアを行った後、ゴム硬度、圧縮永久歪、体積抵抗率を測定し、表1に記した。なお、測定は、2mmのシートからJIS K6249に準じて硬度測定を行い、直径29mm×高さ12.7mmの円柱成形物から180℃×22時間、25%圧縮により圧縮永久歪を測定した。体積抵抗率の測定は、SRIS(日本ゴム協会標準規格)2301−1969に準じて測定した。なお、製造ロットによる体積抵抗率のバラツキを見るために、同組成、同製造法で10回組成物を製造し、同じ方法で硬化させたシートから体積抵抗率を測定した結果を表2に記した(即ち、体積抵抗率についてのみ合計11回測定した。)。 This silicone rubber composition was press-molded at 120 ° C. for 10 minutes and further subjected to post-cure with a dryer at 200 ° C. for 4 hours. Then, the rubber hardness, compression set, and volume resistivity were measured and listed in Table 1. . In addition, the hardness was measured according to JIS K6249 from a 2 mm sheet, and the compression set was measured from a cylindrical molded product having a diameter of 29 mm × height of 12.7 mm by 180% × 22 hours and 25% compression. The volume resistivity was measured according to SRIS (Japan Rubber Association Standard) 2301-1969. In addition, in order to see the variation in the volume resistivity depending on the production lot, the results of measuring the volume resistivity from the sheet produced 10 times by the same composition and the same production method and cured by the same method are shown in Table 2. (Ie, a total of 11 measurements were made only for volume resistivity).
[参考例1]
両末端がジメチルビニルシロキシ基で封鎖されたジメチルポリシロキサンC(重合度200)40部、両末端がトリメチルシロキシ基で封鎖され側鎖にビニル基を有する生ゴム状ジメチルポリシロキサンD(重合度5,000、ビニル基含有量0.00022mol/g)20部、アセチレンブラック(デンカブラックHS−200、電気化学工業社製)2.3部、白色導電性酸化チタンET−500W(石原産業(株)製)5部をプラネタリーミキサーに入れ、30分間撹拌を続けた後、3本ロールに1回通した。その後プラネタリーミキサーに戻し、更にジメチルポリシロキサンCを40部添加して30分間攪拌を続けた。その後、架橋剤として側鎖のみにSi−H基を有するメチルハイドロジェンポリシロキサン(重合度50、Si−H量0.0045mol/g)4.0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、白金触媒(Pt濃度1%)0.1部を添加し、15分間撹拌を続けてシリコーンゴム組成物を得た。この組成物の室温(25℃)での粘度をBH型粘度計、ローター7番を使用し、10rpmの条件で測定し、結果を表1に記した。
[Reference Example 1]
40 parts of dimethylpolysiloxane C (polymerization degree 200) blocked at both ends with dimethylvinylsiloxy groups, raw rubber-like dimethylpolysiloxane D (polymerization degree 5) with both ends blocked with trimethylsiloxy groups and vinyl groups in the side chains 000, vinyl group content 0.00022 mol / g) 20 parts, acetylene black (Denka Black HS-200, manufactured by Denki Kagaku Kogyo Co., Ltd.) 2.3 parts, white conductive titanium oxide ET-500W (produced by Ishihara Sangyo Co., Ltd.) ) 5 parts were put into a planetary mixer and stirred for 30 minutes, and then passed once through three rolls. Thereafter, the mixture was returned to the planetary mixer, 40 parts of dimethylpolysiloxane C was further added, and stirring was continued for 30 minutes. Thereafter, 4.0 parts of methylhydrogenpolysiloxane having a Si—H group only in the side chain as a crosslinking agent (polymerization degree 50, Si—H amount 0.0045 mol / g), 0.05% ethynylcyclohexanol as a reaction control agent Part, platinum catalyst (Pt concentration 1%) 0.1 part was added and stirring was continued for 15 minutes to obtain a silicone rubber composition. The viscosity of this composition at room temperature (25 ° C.) was measured under the condition of 10 rpm using a BH viscometer and rotor No. 7, and the results are shown in Table 1.
このシリコーンゴム組成物から実施例1と同様にゴム硬度、圧縮永久歪、体積抵抗率を測定した結果を表1に記した。また、製造ロットによる体積抵抗率についても同様に表2に記した。 The results of measuring the rubber hardness, compression set, and volume resistivity from this silicone rubber composition in the same manner as in Example 1 are shown in Table 1. Further, the volume resistivity according to the production lot is also shown in Table 2.
[実施例2]
実施例1のジメチルポリシロキサンA(重合度600、ビニル基含有量0.0001mol/g)40部、実施例1の生ゴム状ジメチルポリシロキサンB(重合度8,000、ビニル基含有量0.00008mol/g)10部、BET法による比表面積が110m2/gである疎水化処理されたヒュームドシリカ(R−972、日本アエロジル社製)1部、アセチレンブラック(デンカブラックHS−100、電気化学工業社製)1.5部、ファーネスブラック(ケッチェンEC600JD、ライオン社製)0.5部をプラネタリーミキサーに入れ、150℃に昇温し、1時間撹拌を続けた後、3本ロールに1回通した。これをプラネタリーミキサーに戻し、室温に冷却後、更に参考例1のジメチルポリシロキサンCを50部加えて、30分間攪拌を継続した。その後、架橋剤として両末端及び側鎖にSi−H基を有するメチルハイドロジェンポリシロキサン(重合度17、Si−H量0.0060mol/g)3.5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、白金触媒(Pt濃度1%)0.1部を添加し、15分間撹拌を続けてシリコーンゴム組成物を得た。この組成物の室温(25℃)での粘度をBH型粘度計、ローター7番を使用し、10rpmの条件で測定し、結果を表1に記した。
[Example 2]
40 parts of dimethylpolysiloxane A of Example 1 (degree of polymerization 600, vinyl group content 0.0001 mol / g), raw rubbery dimethylpolysiloxane B of Example 1 (degree of polymerization 8,000, vinyl group content 0.00008 mol) / G) 10 parts, 1 part of a hydrophobized fumed silica (R-972, manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 110 m 2 / g by BET method, acetylene black (Denka Black HS-100, Electrochemistry) 1.5 parts of Kogyo Kogyo Co., Ltd. and 0.5 part of Furnace Black (Ketjen EC600JD, Lion) were put in a planetary mixer, heated to 150 ° C., stirred for 1 hour, and then 1 in 3 rolls. I passed through. This was returned to the planetary mixer, cooled to room temperature, 50 parts of dimethylpolysiloxane C of Reference Example 1 was further added, and stirring was continued for 30 minutes. Thereafter, 3.5 parts of methylhydrogenpolysiloxane having a Si—H group at both ends and side chains as a crosslinking agent (polymerization degree 17, Si—H amount 0.0060 mol / g), and ethynylcyclohexanol 0 as a reaction control agent 0.05 part and 0.1 part of a platinum catalyst (Pt concentration 1%) were added and stirring was continued for 15 minutes to obtain a silicone rubber composition. The viscosity of this composition at room temperature (25 ° C.) was measured under the condition of 10 rpm using a BH viscometer and rotor No. 7, and the results are shown in Table 1.
このシリコーンゴム組成物から実施例1と同様にゴム硬度、圧縮永久歪、体積抵抗率を測定した結果を表1に記した。また、製造ロットによる体積抵抗率についても同様に表2に記した。 The results of measuring the rubber hardness, compression set, and volume resistivity from this silicone rubber composition in the same manner as in Example 1 are shown in Table 1. Further, the volume resistivity according to the production lot is also shown in Table 2.
[比較例1]
両末端がトリメチルシロキシ基で封鎖され側鎖にビニル基を有するジメチルポリシロキサンE(重合度1,000、ビニル基含有量0.00009mol/g)40部、実施例1の生ゴム状ジメチルポリシロキサンB(重合度8,000、ビニル基含有量0.00008mol/g)10部、BET法による比表面積が110m2/gである疎水化処理されたヒュームドシリカ(R−972、日本アエロジル社製)1部、アセチレンブラック(デンカブラックHS−100、電気化学工業社製)3部をプラネタリーミキサーに入れ、30分間撹拌を続けた後、3本ロールに1回通した。これをプラネタリーミキサーに戻した後、更にジメチルポリシロキサンBを50部加えて、30分間攪拌を継続した。その後、架橋剤として両末端及び側鎖にSi−H基を有するメチルハイドロジェンポリシロキサン(重合度17、Si−H量0.0060mol/g)2.1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、白金触媒(Pt濃度1%)0.1部を添加し、15分間撹拌を続けてシリコーンゴム組成物を得た。この組成物の室温(25℃)での粘度をBH型粘度計、ローター7番を使用し、10rpmの条件で測定し、結果を表1に記した。
[Comparative Example 1]
40 parts of dimethylpolysiloxane E having both ends blocked with trimethylsiloxy groups and vinyl groups in the side chains (polymerization degree 1,000, vinyl group content 0.00009 mol / g), raw rubber-like dimethylpolysiloxane B of Example 1 (Polymerization degree 8,000, vinyl group content 0.00008 mol / g) 10 parts, hydrophobized fumed silica having a specific surface area of 110 m 2 / g by BET method (R-972, manufactured by Nippon Aerosil Co., Ltd.) 1 part and 3 parts of acetylene black (Denka Black HS-100, manufactured by Denki Kagaku Kogyo Co., Ltd.) were placed in a planetary mixer and stirred for 30 minutes, and then passed once through 3 rolls. After returning this to the planetary mixer, 50 parts of dimethylpolysiloxane B was further added, and stirring was continued for 30 minutes. Thereafter, 2.1 parts of methylhydrogenpolysiloxane having a Si—H group at both ends and side chains as a crosslinking agent (polymerization degree 17, Si—H amount 0.0060 mol / g), and ethynylcyclohexanol 0 as a reaction control agent 0.05 part and 0.1 part of platinum catalyst (Pt concentration 1%) were added and stirring was continued for 15 minutes to obtain a silicone rubber composition. The viscosity of this composition at room temperature (25 ° C.) was measured under the condition of 10 rpm using a BH viscometer and rotor No. 7, and the results are shown in Table 1.
このシリコーンゴム組成物から実施例1と同様にゴム硬度、圧縮永久歪、体積抵抗率を測定した結果を表1に記した。また、製造ロットによる体積抵抗率についても同様に表2に記した。 The results of measuring the rubber hardness, compression set, and volume resistivity from this silicone rubber composition in the same manner as in Example 1 are shown in Table 1. Further, the volume resistivity according to the production lot is also shown in Table 2.
[比較例2]
参考例1のジメチルポリシロキサンC(重合度200)60部、アセチレンブラック(デンカブラックHS−200、電気化学工業社製)2.3部、白色導電性酸化チタンET−500W(石原産業(株)製)5部をプラネタリーミキサーに入れ、30分間撹拌を続けた後、3本ロールに1回通した。その後プラネタリーミキサーに戻し、更にジメチルポリシロキサンCを40部添加して30分間攪拌を続けた。その後、架橋剤として側鎖のみにSi−H基を有するメチルハイドロジェンポリシロキサン(重合度50、Si−H量0.0045mol/g)3.6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、白金触媒(Pt濃度1%)0.1部を添加し、15分間撹拌を続けてシリコーンゴム組成物を得た。この組成物の室温(25℃)での粘度をBH型粘度計、ローター7番を使用し、10rpmの条件で測定し、結果を表1に記した。
[Comparative Example 2]
60 parts of dimethylpolysiloxane C (degree of polymerization 200) of Reference Example 1, 2.3 parts of acetylene black (Denka Black HS-200, manufactured by Denki Kagaku Kogyo Co., Ltd.), white conductive titanium oxide ET-500W (Ishihara Sangyo Co., Ltd.) 5 parts) was put into a planetary mixer and stirred for 30 minutes, and then passed once through three rolls. Thereafter, the mixture was returned to the planetary mixer, 40 parts of dimethylpolysiloxane C was further added, and stirring was continued for 30 minutes. Thereafter, 3.6 parts of methylhydrogenpolysiloxane having a Si—H group only in the side chain as a crosslinking agent (polymerization degree 50, Si—H amount 0.0045 mol / g), and ethynylcyclohexanol 0.05 as a reaction control agent Part, platinum catalyst (Pt concentration 1%) 0.1 part was added and stirring was continued for 15 minutes to obtain a silicone rubber composition. The viscosity of this composition at room temperature (25 ° C.) was measured under the condition of 10 rpm using a BH viscometer and rotor No. 7, and the results are shown in Table 1.
このシリコーンゴム組成物から実施例1と同様にゴム硬度、圧縮永久歪、体積抵抗率を測定した結果を表1に記した。また、製造ロットによる体積抵抗率についても同様に表2に記した。 The results of measuring the rubber hardness, compression set, and volume resistivity from this silicone rubber composition in the same manner as in Example 1 are shown in Table 1. Further, the volume resistivity according to the production lot is also shown in Table 2.
Claims (8)
(B)一分子中に少なくとも2個の珪素原子と結合するアルケニル基を含有する重合度が2,000〜30,000の生ゴム状オルガノポリシロキサン:3〜30質量部、
(但し、(A),(B)成分の合計は100質量部である。)
(C)一分子中に少なくとも2個の珪素原子と結合する水素原子を含有するオルガノハイドロジェンポリシロキサン:0.1〜30質量部、
(D)カーボンブラック:0.5〜50質量部、
(E)付加反応触媒:触媒量
を含有してなり、室温で液状であり、電子写真式画像形成装置のロール用であることを特徴とする導電性シリコーンゴム組成物。 (A) Liquid organopolysiloxane having a polymerization degree of 100 to 800 containing at least two alkenyl groups bonded to silicon atoms in the middle of the molecular chain in one molecule: 97 to 70 parts by mass,
(B) Raw rubber-like organopolysiloxane having a degree of polymerization of 2,000 to 30,000 containing an alkenyl group bonded to at least two silicon atoms in one molecule: 3 to 30 parts by mass
(However, the total of the components (A) and (B) is 100 parts by mass.)
(C) Organohydrogenpolysiloxane containing hydrogen atoms bonded to at least two silicon atoms in one molecule: 0.1 to 30 parts by mass
(D) Carbon black: 0.5 to 50 parts by mass,
(E) Addition reaction catalyst: A conductive silicone rubber composition comprising a catalytic amount, liquid at room temperature , and used for a roll of an electrophotographic image forming apparatus .
(B)一分子中に少なくとも2個の珪素原子と結合するアルケニル基を含有する重合度が2,000〜30,000の生ゴム状オルガノポリシロキサン:3〜30質量部、
(但し、(A),(B)成分の合計は100質量部である。)
(C)一分子中に少なくとも2個の珪素原子と結合する水素原子を含有するオルガノハイドロジェンポリシロキサン:0.1〜30質量部、
(D)カーボンブラック:0.5〜50質量部、
(E)付加反応触媒:触媒量
を含有してなり、室温で液状であることを特徴とする導電性シリコーンゴム組成物の製造方法であって、(B)成分の全量と(D)成分の全量及び(A)成分の一部を予め混合し、その後に(A)成分の残量及び(C),(E)成分を加えて更に混合することを特徴とする導電性シリコーンゴム組成物の製造方法。 (A) Liquid organopolysiloxane having a polymerization degree of 100 to 800 containing at least two alkenyl groups bonded to silicon atoms in the middle of the molecular chain in one molecule: 97 to 70 parts by mass,
(B) Raw rubber-like organopolysiloxane having a degree of polymerization of 2,000 to 30,000 containing an alkenyl group bonded to at least two silicon atoms in one molecule: 3 to 30 parts by mass
(However, the total of the components (A) and (B) is 100 parts by mass.)
(C) Organohydrogenpolysiloxane containing hydrogen atoms bonded to at least two silicon atoms in one molecule: 0.1 to 30 parts by mass
(D) Carbon black: 0.5 to 50 parts by mass,
(E) Addition reaction catalyst: A method for producing a conductive silicone rubber composition comprising a catalytic amount and being liquid at room temperature, wherein the total amount of component (B) and component (D) A conductive silicone rubber composition characterized by mixing the whole amount and a part of the component (A) in advance, and then adding the remaining amount of the component (A) and the components (C) and (E) and further mixing. Production method.
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JP4678331B2 (en) * | 2006-05-17 | 2011-04-27 | 信越化学工業株式会社 | Method for producing silicone rubber molded article and addition curable liquid silicone rubber composition used therefor |
JP5377846B2 (en) * | 2007-11-09 | 2013-12-25 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Thermosetting silicone rubber composition |
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JP6477520B2 (en) * | 2016-01-25 | 2019-03-06 | 信越化学工業株式会社 | Method for producing addition curable liquid conductive silicone rubber composition, office machine roll and office machine belt |
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