JP3607404B2 - Silicone rubber suspension and method for producing the same - Google Patents
Silicone rubber suspension and method for producing the same Download PDFInfo
- Publication number
- JP3607404B2 JP3607404B2 JP08076996A JP8076996A JP3607404B2 JP 3607404 B2 JP3607404 B2 JP 3607404B2 JP 08076996 A JP08076996 A JP 08076996A JP 8076996 A JP8076996 A JP 8076996A JP 3607404 B2 JP3607404 B2 JP 3607404B2
- Authority
- JP
- Japan
- Prior art keywords
- silicone rubber
- component
- weight
- parts
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920002379 silicone rubber Polymers 0.000 title claims description 106
- 239000004945 silicone rubber Substances 0.000 title claims description 99
- 239000000725 suspension Substances 0.000 title claims description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000000843 powder Substances 0.000 claims description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000002245 particle Substances 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000006185 dispersion Substances 0.000 claims description 18
- 125000005372 silanol group Chemical group 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims 5
- 239000000203 mixture Substances 0.000 description 39
- -1 polydimethylsiloxane Polymers 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 238000003860 storage Methods 0.000 description 11
- 239000004205 dimethyl polysiloxane Substances 0.000 description 10
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 10
- 238000010790 dilution Methods 0.000 description 8
- 239000012895 dilution Substances 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 8
- 239000004944 Liquid Silicone Rubber Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 229920002545 silicone oil Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- XAYDWGMOPRHLEP-UHFFFAOYSA-N 6-ethenyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCCC2OC21C=C XAYDWGMOPRHLEP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- 239000004166 Lanolin Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000004204 candelilla wax Substances 0.000 description 2
- 235000013868 candelilla wax Nutrition 0.000 description 2
- 229940073532 candelilla wax Drugs 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- IUJAMGNYPWYUPM-UHFFFAOYSA-N hentriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC IUJAMGNYPWYUPM-UHFFFAOYSA-N 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
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 235000019388 lanolin Nutrition 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BJAARRARQJZURR-UHFFFAOYSA-N trimethylazanium;hydroxide Chemical compound O.CN(C)C BJAARRARQJZURR-UHFFFAOYSA-N 0.000 description 2
- DSEKYWAQQVUQTP-XEWMWGOFSA-N (2r,4r,4as,6as,6as,6br,8ar,12ar,14as,14bs)-2-hydroxy-4,4a,6a,6b,8a,11,11,14a-octamethyl-2,4,5,6,6a,7,8,9,10,12,12a,13,14,14b-tetradecahydro-1h-picen-3-one Chemical compound C([C@H]1[C@]2(C)CC[C@@]34C)C(C)(C)CC[C@]1(C)CC[C@]2(C)[C@H]4CC[C@@]1(C)[C@H]3C[C@@H](O)C(=O)[C@@H]1C DSEKYWAQQVUQTP-XEWMWGOFSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- UAZLASMTBCLJKO-UHFFFAOYSA-N 2-decylbenzenesulfonic acid Chemical compound CCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O UAZLASMTBCLJKO-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- CTIFKKWVNGEOBU-UHFFFAOYSA-N 2-hexadecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O CTIFKKWVNGEOBU-UHFFFAOYSA-N 0.000 description 1
- SYSFRXFRWRDPIJ-UHFFFAOYSA-N 2-hexylbenzenesulfonic acid Chemical compound CCCCCCC1=CC=CC=C1S(O)(=O)=O SYSFRXFRWRDPIJ-UHFFFAOYSA-N 0.000 description 1
- QWHHBVWZZLQUIH-UHFFFAOYSA-N 2-octylbenzenesulfonic acid Chemical compound CCCCCCCCC1=CC=CC=C1S(O)(=O)=O QWHHBVWZZLQUIH-UHFFFAOYSA-N 0.000 description 1
- UNYKBGSYYHWZCB-UHFFFAOYSA-N 2-tetradecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O UNYKBGSYYHWZCB-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- HCMRWQFXBKKVPZ-UHFFFAOYSA-N CC(CCCCCCCCO)(C)C.C(COCCO)O Chemical compound CC(CCCCCCCCO)(C)C.C(COCCO)O HCMRWQFXBKKVPZ-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 206010016322 Feeling abnormal Diseases 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 229940092738 beeswax Drugs 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- UHWHEIKTDHONME-UHFFFAOYSA-M benzyl-decyl-dimethylazanium;hydroxide Chemical compound [OH-].CCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 UHWHEIKTDHONME-UHFFFAOYSA-M 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000012185 ceresin wax Substances 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VBVQYGNPGUXBIS-UHFFFAOYSA-M dimethyl(dioctadecyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC VBVQYGNPGUXBIS-UHFFFAOYSA-M 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- JVQOASIPRRGMOS-UHFFFAOYSA-M dodecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCC[N+](C)(C)C JVQOASIPRRGMOS-UHFFFAOYSA-M 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 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
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明はシリコーンゴムサスペンジョンおよびその製造方法に関し、詳しくは、優れた保存安定性、希釈安定性、および再分散性を有するシリコーンゴムサスペンジョン、およびその製造方法に関する。
【０００２】
【従来の技術】
シリコーンゴムサスペンジョンは、液状シリコーンゴム組成物を水または界面活性剤水溶液中に均一に分散させた後、このシリコーンゴム組成物を硬化させることにより調製されるが（特公昭５８−１７２２６号公報、特開昭６２−２４３６２１号公報、および特開平１−３０６４７１号公報参照）、このようなサスペンジョンは、水を除去してシリコーンゴム粉末をえるための過渡的な状態であり、このサスペンジョン自体の保存安定性が乏しく、シリコーンゴム粉末が分離しやすく、また、一旦分離したシリコーンゴム粉末を再び分散させて均一なサスペンジョンとすることは非常に困難であった。
【０００３】
優れた保存安定性を有するシリコーンゴムサスペンジョンとしては、シリコーンゴム粉末、ＨＬＢの数値が１０未満である非イオン系界面活性剤、ＨＬＢの数値が１０以上である非イオン系界面活性剤、および水からなるシリコーンゴムサスペンジョン（特開平５−５９２８４号公報参照）が提案されているが、二種の非イオン系界面活性剤を用いなければならないという不利があり、また、このようなサスペンジョンを多量の水で希釈した場合には、シリコーンゴム粉末が容易に分離してしまうという問題があった。
【０００４】
【発明が解決しようとする課題】
本発明者らは、上記問題を解決するために鋭意努力した結果、本発明に到達した。
すなわち、本発明の目的は、優れた保存安定性、希釈安定性、および再分散性を有するシリコーンゴムサスペンジョン、およびその製造方法を提供することにある。
【０００５】
【課題を解決するための手段】
本発明のシリコーンゴムサスペンジョンは、(Ａ)(ｉ)平均粒子径が０．１〜１，０００μｍであるシリコーンゴム粉末の表面に、(ｉｉ)表面のシラノール基密度が２個／１００Å2以上であり、かつ平均粒子径が１μｍ以下である非晶質シリカ微粉末を固着してなるシリコーンゴム粉末、(Ｂ)界面活性剤、および(Ｃ)水からなることを特徴とする。また、本発明のシリコーンゴムサスペンジョンの製造方法は、 ( ｉ ) 平均粒子径が０．１〜１，０００μｍであるシリコーンゴム粉末と ( ｉｉ ) 表面のシラノール基密度が２個／１００Å 2 以上であり、かつ平均粒子径が１μｍ以下である非晶質シリカ微粉末の水分散液を加熱した後、該水分散液から水を除去することにより、 ( Ａ ) 前記 ( ｉ ) 成分の表面に前記 ( ｉｉ ) 成分を固着してなるシリコーンゴム粉末を調製し、次いで該 ( Ａ ) 成分を、 ( Ｂ ) 界面活性剤、および ( Ｃ ) 水により分散させることを特徴とする。
【０００６】
【発明の実施の形態】
本発明のシリコーンゴムサスペンジョンおよびその製造方法を詳細に説明する。
(Ａ)成分は、(ｉ)成分の表面に(ｉｉ)成分を固着したことを特徴とするシリコーンゴム粉末である。この(ｉ)成分は、平均粒子径が０．１〜１，０００μｍの範囲内であるシリコーンゴム粉末であり、好ましくは、０．１〜２００μｍの範囲内、特に好ましくは、０．５〜８０μｍの範囲内であるシリコーンゴム粉末である。これは、(ｉ)成分の平均粒子径が０．１μｍ未満であると、その表面に(ｉｉ)成分を固着しにくいためであり、また、この平均粒子径が１，０００μｍをこえると、得られるサスペンジョンの保存安定性、希釈安定性、および再分散性が低下するためである。この(ｉ)成分の形状としては、例えば、球状、偏平状、不定形状が挙げられ、特に、球状であることが好ましい。
【０００７】
(ｉ)成分を調製する方法としては、シリコーンゴム組成物を硬化させて調製したシリコーンゴムを微粉砕する方法、液状のシリコーンゴム組成物を粉霧させながら硬化する方法、液状のシリコーンゴム組成物を水または界面活性剤水溶液中に分散させて、これをミクロミキサー、タービン翼攪拌機、ホモミキサー、コロイドミル、ホモジナイザー等の攪拌装置や超音波振動機等の混合装置により均一なシリコーンゴム組成物の水系エマルジョンとした後、この組成物を硬化させる方法が挙げられ、特に、液状のシリコーンゴム組成物を水系エマルジョンとした後、この組成物を硬化させる方法が好ましい。
【０００８】
このシリコーンゴム組成物としては、例えば、一分子中に少なくとも２個のアルケニル基を有するオルガノポリシロキサン、一分子中に少なくとも２個のケイ素原子結合水素原子を有するオルガノポリシロキサン、および白金系触媒からなる付加反応硬化型のシリコーンゴム組成物；一分子中に少なくとも２個のシラノール基を有するオルガノポリシロキサン、一分子中に少なくとも２個のケイ素原子結合水素原子を有するオルガノポリシロキサン、および有機錫化合物、有機チタン化合物等の縮合反応用触媒からなるシリコーンゴム組成物や、一分子中に少なくとも２個のシラノール基を有するオルガノポリシロキサン、少なくとも３個のケイ素原子結合の加水分解性基を有するオルガノシランもしくはその部分加水分解縮合物、および縮合反応用触媒からなるシリコーンゴム組成物等の縮合反応硬化型のシリコーンゴム組成物；アルケニル基を有するオルガノポリシロキサン、および有機過酸化物からなる有機過酸化物硬化型のシリコーンゴム組成物；その他、紫外線硬化型のシリコーンゴム組成物が挙げられる。
【０００９】
このようなシリコーンゴム組成物には、この流動性を調節したり、得られるシリコーンゴム粉末の機械的強度を向上させるための任意の成分として、沈澱シリカ、ヒュームドシリカ、焼成シリカ、ヒュームド酸化チタン等の補強性充填剤；粉砕石英、ケイ藻土、アルミノケイ酸、酸化鉄、酸化亜鉛、炭酸カルシウム等の非補強性充填剤；およびこれらの充填剤をヘキサメチルジシラザン、トリメチルクロロシラン、ポリジメチルシロキサン等の有機ケイ素化合物により表面処理した充填剤を添加することができる。また、このようなシリコーンゴム組成物には、得られるシリコーンゴム粉末の表面特性を改善するために、アリルグリシジルエーテル、ビニルシクロヘキセンモノオキサイド等のアルケニル基含有エポキシ化合物；ビニルトリメトキシシラン、ビニルトリアセトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−（２−アミノエチル）アミノプロピルトリメトキシシラン、３−メルカプトプロピルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、３−メタクリルオキシプロピルトリメトキシシラン、３−アミノプロピルメチルジメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン等のシランカップリング剤を添加することができる。また、このようなシリコーンゴム組成物には、必要に応じて、顔料、耐熱剤、難燃剤、光増感剤、および分子鎖片末端にのみケイ素原子結合水酸基を有するジオルガノポリシロキサンを添加することもできる。
【００１０】
また、(ｉｉ)成分は、表面のシラノール基密度が２個／１００Å2以上であり、かつ平均粒子径が１μｍ以下である非晶質シリカ微粉末であり、特に好ましくは、この平均粒子径が０．１〜０．００１μｍの範囲内である非晶質シリカ微粉末である。これは、表面のシラノール基密度が２個／１００Å2未満であるか、または、平均粒子径が１μｍをこえる非晶質シリカ微粉末は、(ｉ)成分の表面に強固に固着することができないためである。(ｉｉ)成分は、(ｉ)成分の表面に固着するために、この平均粒子径は当然に(ｉ)成分の平均粒子径より小さいことが必要であり、実用的には、(ｉ)成分の平均粒子径の１／１０以下であることが好ましい。ここで、(ｉｉ)成分の表面のシラノール基密度は、例えば、(ｉｉ)成分を、１２０℃、１５ｍｍＨｇ以下の加熱減圧下で、３時間乾燥した後、この(ｉｉ)成分の表面のシラノール基とリチウムアルミニウムハイドライドとを反応させることにより発生した水素ガスを定量して求めたシラノール基量と、この(ｉｉ)成分の比表面積により求めることができる。この(ｉｉ)成分の形状としては、例えば、球状、偏平状、針状、不定形状が挙げられ、特に、球状であることが好ましい。このような(ｉｉ)成分としては、例えば、シリカゾル、乾式法、電弧法、および湿式法で得られる非晶質シリカ微粉末が挙げられ、特に、乾式法で得られるヒュームドシリカであることが好ましい。
【００１１】
(Ａ)成分を調製する方法としては、例えば、シリコーンゴム組成物、好ましくは、付加反応硬化型または縮合反応硬化型のシリコーンゴム組成物を界面活性剤水溶液中に均一に分散させた後、この組成物を硬化させて調製してなる(ｉ)成分の水分散液に(ｉｉ)成分を添加して、(ｉ)成分と(ｉｉ)成分の水分散液を調製して、この水分散液を加熱した後、この水分散液から水を除去する方法；(ｉ)成分と(ｉｉ)成分を必要により少量の水の存在下に高剪断下で混合する方法が挙げられ、特に、前者の方法が好ましい。(ｉ)成分と(ｉｉ)成分の水分散液を調製した後、これを加熱することにより、水中で(ｉ)成分の表面のシラノール基、ケイ素原子結合水素原子またはケイ素原子結合アルコキシ基と(ｉｉ)成分の表面のシラノール基との相互作用により、水を除去した後、(ｉ)成分の表面に(ｉｉ)成分を強固に固着することができる。(ｉ)成分と(ｉｉ)成分の水分散液を加熱する温度としては、例えば、４０〜９５℃の範囲内であることが好ましく、特に、６０〜９０℃の範囲内であることが好ましい。(ｉ)成分と(ｉｉ)成分の水分散液から水を除去する方法としては、例えば、風乾する方法、真空乾燥機、熱風循環式オーブン、スプレードライヤー等の周知の乾燥機を用いる方法が挙げられる。(ｉ)成分と(ｉｉ)成分を高剪断下で混合する装置としては、例えば、ヘンシェルミキサー、ボールミル、オングミル、スクリーンミル、ポットミル、乳鉢、アトライター、ハイブリダイザーが挙げられ、特に、ヘンシェルミキサー等の高速回転型攪拌混合機を用いることが効率的で好ましい。
【００１２】
(ｉｉ)成分の添加量としては、(ｉ)成分の表面に固着するに十分な量であればよく、例えば、(ｉ)成分１００重量部に対して０．０１〜１００重量部の範囲内であることが好ましく、特に、０．１〜３０重量部の範囲内であることが好ましい。また、(ｉ)成分の平均粒子径が０．１〜１０μｍの範囲内である場合には、０．１１〜１５重量部の範囲内であることが好ましく、(ｉ)成分の平均粒子径が１０〜２００μｍの範囲内である場合には、０．０５〜１０重量部の範囲内であることが好ましい。
【００１３】
このようにして調製された(Ａ)成分は、(ｉ)成分の表面に(ｉｉ)成分を強固に固着しており、(Ａ)成分が剪断力を受けた場合でも、(ｉ)成分の表面から(ｉｉ)成分が容易に剥落しないという特徴がある。(ｉ)成分の表面に、(ｉｉ)成分が強固に固着していることを確認する方法としては、(Ａ)成分を水や有機溶剤等の媒体中で高剪断下に攪拌して、(ｉ)成分と(ｉｉ)成分の分離の有無により確認することができる。
【００１４】
(Ｂ)成分は、(Ａ)成分の水中での分散性を向上させるための界面活性剤である。この(Ｂ)成分としては、例えば、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルキルフェノール、ポリオキシアルキレンアルキルエステル、ポリオキシアルキレンソルビタンエステル、ポリエチレングライコール、ポリプロピレングライコール、ジエチレングライコールトリメチルノナノールのエチレンオキサイド付加物等のノニオン系界面活性剤；ヘキシルベンゼンスルホン酸、オクチルベンゼンスルホン酸、デシルベンゼンスルホン酸、ドデシルベンゼンスルホン酸、セチルベンゼンスルホン酸、ミリスチルベンゼンスルホン酸やそのナトリウム塩等のアニオン系界面活性剤；オクチルトリメチルアンモニウムヒドロキシド、ドデシルトリメチルアンモニウムヒドロキシド、ヘキサデシルトリメチルアンモニウムヒドロキシド、オクチルジメチルベンジルアンモニウムヒドロキシド、デシルジメチルベンジルアンモニウムヒドロキシド、ジオクタデシルジメチルアンモニウムヒドロキシド、牛脂トリメチルアンモニウムヒドロキシド、ヤシ油トリメチルアンモニウムヒドロキシド等のカチオン系界面活性剤が挙げられ、これら界面活性剤を２種以上混合して用いることもできる。
【００１５】
(Ｂ)成分の添加量は、(Ａ)成分を水に分散させるに十分な量であればよく、具体的には、(Ａ)成分１００重量部に対して０．１〜１００重量部の範囲内であることが好ましく、特に、１〜５０重量部の範囲内であることが好ましい。ここで、(ｉ)成分が界面活性剤水溶液中で調製されたシリコーンゴム粉末である場合には、この粉末に界面活性剤を含有もしくは付着している場合があるので、この(Ｂ)成分の添加量をこの(ｉ)成分に由来する界面活性剤の量を考慮して添加することが好ましい。
【００１６】
(Ｃ)成分の水は、(Ａ)成分を分散させるための媒体である。(Ｃ)成分の添加量は、(Ａ)成分が分散し得る量であり、任意量である。
【００１７】
本発明のシリコーンゴムサスペンジョンには、その他任意の成分として、例えば、香料、染料、顔料、レベリング剤、紫外線吸収剤、帯電防止剤、増粘剤、防腐剤を添加することができる。また、このシリコーンゴムサスペンジョンを艶出し剤として使用する場合には、これにジメチルシリコーンオイル、メチルフェニルシリコーンオイル、アルキル変性シリコーンオイル、エポキシ変性シリコーンオイル、アミノ変性シリコーンオイル、フッ化アルキル変性シリコーンオイル等のシリコーンオイル；カルナウバワックス、モンタンワックス、キャンデリラワックス（カンデリラワックス）、セレシンワックス（オゾケライト）、ビーズワックス、ウールワックス（ラノリン）、固形パラフィンワックス、流動パラフィンワックス、マイクロクリスタリンワックス、ポリエチレンワックス等の天然または合成のワックス、ステアリン酸、硬化ヒマシ油、金属石鹸等の油脂、脂肪酸、およびその誘導体等のワックス状物質、ワックス状の合成樹脂類等のワックスおよび／またはワックス状物質を添加することができる。また、このシリコーンゴムサスペンジョンを水性化粧料として利用する場合には、これに保湿剤、収斂剤を添加してもよい。また、このシリコーンゴムサスペンジョンを水性洗浄剤として使用する場合には、フッ素樹脂粉末、ナイロン樹脂粉末、ポリエステル樹脂粉末、ポリエチレン樹脂粉末、アクリル樹脂粉末、エポキシ樹脂粉末、フェノール樹脂粉末、ポリウレタン樹脂粉末等の有機樹脂粉末；炭酸カルシウム、タルク、マイカ、ベントナイト、珪藻土、シリカ、マグネシウムシリケート等のケイ酸塩、アルミナ等の無機粉末等の研磨剤もしくは滑剤を添加することができる。
【００１８】
本発明のシリコーンゴムサスペンジョンは、優れた保存安定性、希釈安定性、および再分散性を有するので、長期間の保存が可能であり、例えば、水性塗料、水性化粧料、水性洗浄剤、水性艶出し剤に用いることができる。このような水性塗料は保存安定性が優れ、艶消しされ、柔らかな感触の塗膜を形成することができ、また、このような水性化粧料は洗浄性が優れ、使用感が良好であり、このような水性洗浄剤や艶出し剤は、基材に均一に塗り伸ばしでき、拭き取りが容易であり、洗浄性が優れ、基材に良好な艶を与えることができる。
【００１９】
【実施例】
本発明のシリコーンゴムサスペンジョンおよびその製造方法を実施例により詳細に説明する。なお、実施例中の粘度は２５℃において測定した値である。また、シリコーンゴム粉末の硬度は、これを作製するために用いたシリコーンゴム組成物を７０℃で２０分間熱気中で硬化させて得られたシリコーンゴムシートをＪＩＳ Ｋ ６３０１に規定されたＪＩＳ Ａ形硬度計により測定した値である。
［シリコーンゴム粉末の平均粒子径］
光学顕微鏡に接続した画像処理装置により測定した。
［シリコーンゴムサスペンジョンの保存安定性］
シリコーンゴムサスペンジョンを室温で１日間静置して、この保存安定性を観察した。シリコーンゴム粉末の分離がほとんど観察されない場合を○、シリコーンゴム粉末の一部が分離したものの、ほとんどのシリコーンゴム粉末が均一に分散している場合を△、ほとんどのシリコーンゴム粉末が分離している場合を×として評価した。
［シリコーンゴムサスペンジョンの希釈安定性］
シリコーンゴムサスペンジョンを２倍量の水に投入して、この希釈安定性を観察した。シリコーンゴム粉末が均一に希釈されている場合を○、シリコーンゴム粉末の一部が分離したものの、ほとんどのシリコーンゴム粉末が均一に希釈されている場合を△、ほとんどのシリコーンゴム粉末が分離した場合を×として評価した。
［シリコーンゴムサスペンジョンの再分散性］
シリコーンゴムサスペンジョンを室温で１週間静置した後、分離したシリコーンゴム粉末を振とうして、この再分散性を観察した。分離したシリコーンゴム粉末が均一に分散した場合を○、分離したシリコーンゴム粉末の一部は分散しないものの、ほとんどのシリコーンゴム粉末が均一に分散した場合を△、ほとんどのシリコーンゴム粉末が分散しない場合を×として評価した。
【００２０】
［参考例１］
分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン（ビニル基当量＝８０００）５０重量部と粘度が２０センチポイズである、式：
【化１】
【００２１】
［参考例２］
参考例１で調製したシリコーンゴム粉末(Ａ)１００重量部とジメチルジクロロシランにより処理された疎水性非晶質シリカ粉末（表面のシラノール基密度＝１．２個／１００Å2、一次平均粒子径＝１６ｍμ、比表面積＝１２０ｍ2／ｇ）１０重量部をヘンシェルミキサーにより１０００ｒｐｍで２０分間混合して、表面を疎水性非晶質シリカ粉末で被覆したシリコーンゴム粉末(Ｂ)を調製した。
【００２２】
［参考例３］
分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン（ビニル基当量＝８０００）５０重量部と粘度が２０センチポイズである、式：
【化２】
【００２３】
［参考例４］
分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン（ビニル基当量＝８０００）５０重量部と粘度が２０センチポイズである、式：
【化３】
【００２４】
［実施例１、２、比較例１、２］
参考例１〜４で調製したシリコーンゴム粉末を用いて、シリコーンゴム粉末１００重量部に対して、界面活性剤としてのポリオキシエチレンノニルフェニルエーテル（ＨＬＢ＝１３．１）が４重量部、水が１０００重量部となるように４種のシリコーンゴムサスペンジョンを調製した。これらシリコーンゴムサスペンジョンの保存安定性、希釈安定性、および再分散性を観察した。これらの結果を表１に示した。
【００２５】
【表１】
【発明の効果】
本発明のシリコーンゴムサスペンジョンは、(Ａ)成分、(Ｂ)成分、および(Ｃ)成分からなり、特に、(Ａ)成分として、表面に非晶質シリカ微粉末を固着したシリコーンゴム粉末を用いているので、優れた保存安定性、希釈安定性、および再分散性を有するという特徴があり、本発明の製造方法は、このようなシリコーンゴムサスペンジョンを製造できるという特徴がある。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a silicone rubber suspension and a manufacturing method thereof, particularly, excellent storage stability, dilution stability, and silicone rubber suspension having a redispersible, and a manufacturing method thereof.
[0002]
[Prior art]
A silicone rubber suspension is prepared by uniformly dispersing a liquid silicone rubber composition in water or an aqueous surfactant solution and then curing the silicone rubber composition (Japanese Patent Publication No. 58-17226, Japanese Patent Publication No. 58-17226). Such a suspension is a transitional state for removing water to obtain a silicone rubber powder, and the storage stability of the suspension itself is described in Japanese Laid-Open Patent Publication No. 62-243621 and Japanese Laid-Open Patent Application No. 1-306471. It was very difficult to separate the silicone rubber powder, and it was very difficult to disperse the once separated silicone rubber powder to obtain a uniform suspension.
[0003]
Examples of silicone rubber suspensions having excellent storage stability include silicone rubber powder, nonionic surfactants having an HLB value of less than 10, nonionic surfactants having an HLB value of 10 or more, and water. A silicone rubber suspension (see Japanese Patent Application Laid-Open No. 5-59284) has been proposed, but there is a disadvantage that two kinds of nonionic surfactants must be used, and such a suspension is used in a large amount of water. When diluted with, the silicone rubber powder is easily separated.
[0004]
[Problems to be solved by the invention]
As a result of diligent efforts to solve the above problems, the present inventors have reached the present invention.
That is, an object of the present invention is to provide a silicone rubber suspension having excellent storage stability, dilution stability, and redispersibility, and a method for producing the same.
[0005]
[Means for Solving the Problems]
The silicone rubber suspension of the present invention has (A) (i) the surface of a silicone rubber powder having an average particle size of 0.1 to 1,000 μm, and (ii) the density of silanol groups on the surface is 2/100 2 or more. And having an average particle diameter of 1 μm or less and comprising amorphous silica fine powder, silicone rubber powder (B) a surfactant, and (C) water. The method for producing the silicone rubber suspension of the present invention comprises: ( i ) a silicone rubber powder having an average particle diameter of 0.1 to 1,000 μm and ( ii ) a density of silanol groups on the surface of 2/100 2 or more. and having an average particle diameter was heated amorphous silica micropowder aqueous dispersion of which is 1μm or less, by removing water from the aqueous dispersion, the in (a) (i) above the surface of the component ( ii ) A silicone rubber powder obtained by fixing the component is prepared, and then the component ( A ) is dispersed with ( B ) a surfactant and ( C ) water.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The silicone rubber suspension of the present invention and the production method thereof will be described in detail.
Component (A) is a silicone rubber powder characterized in that component (ii) is fixed on the surface of component (i). This component (i) is a silicone rubber powder having an average particle size in the range of 0.1 to 1,000 μm, preferably in the range of 0.1 to 200 μm, particularly preferably 0.5 to 80 μm. It is a silicone rubber powder that falls within the range. This is because when the average particle diameter of the component (i) is less than 0.1 μm, the component (ii) is difficult to adhere to the surface, and when the average particle diameter exceeds 1,000 μm, it is obtained. This is because the storage stability, dilution stability, and redispersibility of the suspension to be obtained are lowered. Examples of the shape of the component (i) include a spherical shape, a flat shape, and an indefinite shape, and a spherical shape is particularly preferable.
[0007]
The component (i) is prepared by a method of finely pulverizing a silicone rubber prepared by curing a silicone rubber composition, a method of curing while spraying a liquid silicone rubber composition, or a liquid silicone rubber composition Is dispersed in water or an aqueous surfactant solution, and this is mixed with a mixing device such as a micro mixer, a turbine blade stirrer, a homomixer, a colloid mill, a homogenizer, or an ultrasonic vibrator. A method of curing the composition after forming an aqueous emulsion is particularly preferable, and a method of curing the composition after preparing a liquid silicone rubber composition as an aqueous emulsion is particularly preferable.
[0008]
Examples of the silicone rubber composition include an organopolysiloxane having at least two alkenyl groups in one molecule, an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, and a platinum-based catalyst. Addition reaction curable silicone rubber composition; organopolysiloxane having at least two silanol groups in one molecule; organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule; and organotin compound A silicone rubber composition comprising a catalyst for condensation reaction such as an organic titanium compound, an organopolysiloxane having at least two silanol groups in one molecule, and an organosilane having at least three hydrolyzable groups of silicon atoms Or its partially hydrolyzed condensate and Condensation reaction curable silicone rubber composition such as a silicone rubber composition comprising a catalyst for reaction; Organopolysiloxane having an alkenyl group; and an organic peroxide curable silicone rubber composition comprising an organic peroxide; An ultraviolet curable silicone rubber composition is exemplified.
[0009]
In such a silicone rubber composition, precipitated silica, fumed silica, calcined silica, fumed titanium oxide are included as optional components for adjusting the fluidity and improving the mechanical strength of the resulting silicone rubber powder. Non-reinforcing fillers such as pulverized quartz, diatomaceous earth, aluminosilicate, iron oxide, zinc oxide, calcium carbonate; and these fillers as hexamethyldisilazane, trimethylchlorosilane, polydimethylsiloxane It is possible to add a filler surface-treated with an organosilicon compound such as In addition, in order to improve the surface characteristics of the obtained silicone rubber powder, such a silicone rubber composition includes an alkenyl group-containing epoxy compound such as allyl glycidyl ether and vinylcyclohexene monooxide; vinyltrimethoxysilane, vinyltriacetoxy Silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane It may be added to the silane coupling agent. Moreover, to such a silicone rubber composition, a pigment, a heat-resistant agent, a flame retardant, a photosensitizer, and a diorganopolysiloxane having a silicon atom-bonded hydroxyl group only at one end of a molecular chain are added as necessary. You can also.
[0010]
The component (ii) is an amorphous silica fine powder having a surface silanol group density of 2/100 2 or more and an average particle size of 1 μm or less. Particularly preferably, the average particle size is It is an amorphous silica fine powder in the range of 0.1 to 0.001 μm. This is because the amorphous silica fine powder having a surface silanol group density of less than 2/100 2 or an average particle diameter exceeding 1 μm cannot be firmly fixed to the surface of the component (i). Because. In order for component (ii) to adhere to the surface of component (i), this average particle size must naturally be smaller than the average particle size of component (i), and practically component (i) It is preferable that it is 1/10 or less of the average particle diameter. Here, the silanol group density on the surface of the component (ii) is, for example, that the component (ii) is dried for 3 hours at 120 ° C. under heating and reduced pressure of 15 mmHg or less, It can be determined from the amount of silanol groups determined by quantifying the hydrogen gas generated by reacting lithium aluminum hydride with the specific surface area of this component (ii). Examples of the shape of the component (ii) include a spherical shape, a flat shape, a needle shape, and an indefinite shape, and a spherical shape is particularly preferable. Examples of such component (ii) include silica sol, amorphous silica fine powder obtained by a dry method, an arc method, and a wet method, and in particular, fumed silica obtained by a dry method. preferable.
[0011]
As a method for preparing the component (A), for example, a silicone rubber composition, preferably an addition reaction curable type or condensation reaction curable type silicone rubber composition is uniformly dispersed in an aqueous surfactant solution, A component (ii) is added to an aqueous dispersion of component (i) prepared by curing the composition to prepare an aqueous dispersion of components (i) and (ii). A method of removing water from the aqueous dispersion after heating; a method of mixing the components (i) and (ii) with high shear in the presence of a small amount of water if necessary, and in particular the former The method is preferred. After preparing an aqueous dispersion of the component (i) and the component (ii), by heating this, a silanol group, a silicon atom-bonded hydrogen atom or a silicon atom-bonded alkoxy group on the surface of the component (i) and ( (ii) The component (ii) can be firmly fixed to the surface of the component (i) after removing water by the interaction with the silanol group on the surface of the component. The temperature at which the aqueous dispersion of component (i) and component (ii) is heated is, for example, preferably in the range of 40 to 95 ° C, and particularly preferably in the range of 60 to 90 ° C. Examples of the method for removing water from the aqueous dispersion of component (i) and component (ii) include a method of air drying, a method using a known dryer such as a vacuum dryer, a hot air circulation oven, and a spray dryer. It is done. Examples of the apparatus for mixing the component (i) and the component (ii) under high shear include a Henschel mixer, a ball mill, an ong mill, a screen mill, a pot mill, a mortar, an attritor, and a hybridizer. It is efficient and preferable to use a high-speed rotary stirring mixer.
[0012]
Component (ii) may be added in an amount sufficient to adhere to the surface of component (i), for example, in the range of 0.01 to 100 parts by weight per 100 parts by weight of component (i). It is preferable that it is in the range of 0.1-30 weight part especially. Moreover, when the average particle diameter of (i) component exists in the range of 0.1-10 micrometers, it is preferable to exist in the range of 0.11-15 weight part, and the average particle diameter of (i) component is When it is in the range of 10 to 200 μm, it is preferably in the range of 0.05 to 10 parts by weight.
[0013]
The component (A) thus prepared has the component (ii) firmly fixed on the surface of the component (i), and even when the component (A) is subjected to shearing force, There is a feature that the component (ii) does not easily peel off from the surface. As a method for confirming that the component (ii) is firmly fixed on the surface of the component (i), the component (A) is stirred in a medium such as water or an organic solvent under high shear, This can be confirmed by the presence or absence of separation of component i) and component (ii).
[0014]
Component (B) is a surfactant for improving the dispersibility of component (A) in water. Examples of the component (B) include polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenol, polyoxyalkylene alkyl ester, polyoxyalkylene sorbitan ester, polyethylene glycol, polypropylene glycol, and ethylene oxide of diethylene glycol trimethylnonanol. Nonionic surfactants such as adducts; anionic surfactants such as hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, myristylbenzenesulfonic acid and its sodium salt Octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium Examples include cationic surfactants such as roxide, octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, dioctadecyldimethylammonium hydroxide, beef tallow trimethylammonium hydroxide, and coconut oil trimethylammonium hydroxide. A mixture of two or more of these can also be used.
[0015]
Component (B) may be added in an amount sufficient to disperse component (A) in water. Specifically, 0.1 to 100 parts by weight per 100 parts by weight of component (A). It is preferably within the range, and particularly preferably within the range of 1 to 50 parts by weight. Here, when the component (i) is a silicone rubber powder prepared in a surfactant aqueous solution, the powder may contain or adhere to a surfactant. It is preferable to add in consideration of the amount of the surfactant derived from the component (i).
[0016]
Component (C) water is a medium for dispersing component (A). The addition amount of the component (C) is an amount that can disperse the component (A) and is an arbitrary amount.
[0017]
As the other optional components, for example, a fragrance, a dye, a pigment, a leveling agent, an ultraviolet absorber, an antistatic agent, a thickener, and an antiseptic can be added to the silicone rubber suspension of the present invention. In addition, when this silicone rubber suspension is used as a polishing agent, dimethyl silicone oil, methylphenyl silicone oil, alkyl-modified silicone oil, epoxy-modified silicone oil, amino-modified silicone oil, fluorinated alkyl-modified silicone oil, etc. Silicone oils: carnauba wax, montan wax, candelilla wax (candelilla wax), ceresin wax (ozokerite), bees wax, wool wax (lanolin), solid paraffin wax, liquid paraffin wax, microcrystalline wax, polyethylene wax, etc. Natural or synthetic waxes, stearic acid, oils and fats such as hydrogenated castor oil, metal soaps, fatty acids, and wax-like substances such as derivatives thereof, waxes Waxes and / or wax-like substance such as synthetic resins can be added. Moreover, when using this silicone rubber suspension as an aqueous cosmetic, a moisturizing agent and an astringent may be added thereto. In addition, when this silicone rubber suspension is used as an aqueous cleaning agent, fluorine resin powder, nylon resin powder, polyester resin powder, polyethylene resin powder, acrylic resin powder, epoxy resin powder, phenol resin powder, polyurethane resin powder, etc. Organic resin powder: Abrasives or lubricants such as calcium carbonate, talc, mica, bentonite, diatomaceous earth, silica, inorganic powder such as alumina, silicates such as magnesium silicate, and the like can be added.
[0018]
Since the silicone rubber suspension of the present invention has excellent storage stability, dilution stability, and redispersibility, it can be stored for a long period of time, for example, water-based paints, water-based cosmetics, water-based detergents, water-based glosses. It can be used as a dispensing agent. Such a water-based paint has excellent storage stability, is matt, and can form a soft-feeling coating film, and such water-based cosmetics have excellent detergency and good usability. Such aqueous cleaning agents and polishes can be applied evenly to the substrate, can be easily wiped off, have excellent cleaning properties, and can give the substrate a good gloss.
[0019]
【Example】
The silicone rubber suspension of the present invention and the production method thereof will be described in detail with reference to examples. In addition, the viscosity in an Example is the value measured in 25 degreeC. Further, the hardness of the silicone rubber powder is determined according to JIS A type stipulated in JIS K 6301 by a silicone rubber sheet obtained by curing the silicone rubber composition used for producing the silicone rubber composition at 70 ° C. for 20 minutes in hot air. It is a value measured with a hardness meter.
[Average particle diameter of silicone rubber powder]
Measurement was performed by an image processing apparatus connected to an optical microscope.
[Storage stability of silicone rubber suspension]
This storage stability was observed by allowing the silicone rubber suspension to stand at room temperature for 1 day. ○ when the separation of the silicone rubber powder is hardly observed, △ when the silicone rubber powder is partly dispersed but most of the silicone rubber powder is uniformly dispersed, and most of the silicone rubber powder is separated The case was evaluated as x.
[Dilution stability of silicone rubber suspension]
Silicone rubber suspension was added to twice the amount of water, and this dilution stability was observed. ○ when the silicone rubber powder is diluted uniformly, △ when the silicone rubber powder is partly separated but most silicone rubber powder is diluted uniformly, when most silicone rubber powder is separated Was evaluated as x.
[Redispersibility of silicone rubber suspension]
After the silicone rubber suspension was allowed to stand at room temperature for 1 week, the separated silicone rubber powder was shaken to observe this redispersibility. ○ when the separated silicone rubber powder is uniformly dispersed, △ when most of the silicone rubber powder is evenly dispersed although some of the separated silicone rubber powder is not dispersed, and when most of the silicone rubber powder is not dispersed Was evaluated as x.
[0020]
[Reference Example 1]
The molecular chain both ends dimethylvinylsiloxy group-blocked dimethylpolysiloxane (vinyl group equivalent = 8000) 50 parts by weight and the viscosity is 20 centipoise, the formula:
[Chemical 1]
[0021]
[Reference Example 2]
Hydrophobic amorphous silica powder treated with 100 parts by weight of the silicone rubber powder (A) prepared in Reference Example 1 and dimethyldichlorosilane (surface silanol group density = 1.2 / 100 2 , primary average particle diameter = A silicone rubber powder (B) having a surface coated with a hydrophobic amorphous silica powder was prepared by mixing 10 parts by weight of 16 mμ, specific surface area = 120 m 2 / g) with a Henschel mixer at 1000 rpm for 20 minutes.
[0022]
[Reference Example 3]
The molecular chain both ends dimethylvinylsiloxy group-blocked dimethylpolysiloxane (vinyl group equivalent = 8000) 50 parts by weight and the viscosity is 20 centipoise, the formula:
[Chemical 2]
[0023]
[Reference Example 4]
The molecular chain both ends dimethylvinylsiloxy group-blocked dimethylpolysiloxane (vinyl group equivalent = 8000) 50 parts by weight and the viscosity is 20 centipoise, the formula:
[Chemical 3]
[0024]
[Examples 1 and 2, Comparative Examples 1 and 2]
Using the silicone rubber powder prepared in Reference Examples 1 to 4, 4 parts by weight of polyoxyethylene nonylphenyl ether (HLB = 13.1) as a surfactant and 100 parts by weight of water with respect to 100 parts by weight of the silicone rubber powder. Four types of silicone rubber suspensions were prepared so as to be 1000 parts by weight. The storage stability, dilution stability, and redispersibility of these silicone rubber suspensions were observed. These results are shown in Table 1.
[0025]
[Table 1]
【The invention's effect】
The silicone rubber suspension of the present invention comprises a component (A), a component (B), and a component (C), and in particular, as the component (A), a silicone rubber powder having an amorphous silica fine powder fixed on the surface is used. since it has excellent storage stability, dilution stability, and Ri wherein there of having redispersibility, the production method of the present invention, wherein there Ru that can be produced such silicone rubber suspension.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08076996A JP3607404B2 (en) | 1996-03-08 | 1996-03-08 | Silicone rubber suspension and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08076996A JP3607404B2 (en) | 1996-03-08 | 1996-03-08 | Silicone rubber suspension and method for producing the same |
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| JPH09241511A JPH09241511A (en) | 1997-09-16 |
| JP3607404B2 true JP3607404B2 (en) | 2005-01-05 |
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1996
- 1996-03-08 JP JP08076996A patent/JP3607404B2/en not_active Expired - Lifetime
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