CA1247775A - Method for producing silicone aqueous emulsion compositions - Google Patents
Method for producing silicone aqueous emulsion compositionsInfo
- Publication number
- CA1247775A CA1247775A CA000464472A CA464472A CA1247775A CA 1247775 A CA1247775 A CA 1247775A CA 000464472 A CA000464472 A CA 000464472A CA 464472 A CA464472 A CA 464472A CA 1247775 A CA1247775 A CA 1247775A
- Authority
- CA
- Canada
- Prior art keywords
- parts
- weight
- water
- emulsion
- amino
- 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
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 14
- 239000008119 colloidal silica Substances 0.000 claims abstract description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 229910000077 silane Inorganic materials 0.000 claims abstract description 12
- 230000005070 ripening Effects 0.000 claims abstract description 8
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 7
- 239000013536 elastomeric material Substances 0.000 claims abstract description 5
- -1 polydimethylsiloxane Polymers 0.000 claims description 34
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000012874 anionic emulsifier Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 125000000129 anionic group Chemical group 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
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000010454 slate Substances 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 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
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 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 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- BRWZYZWZBMGMMG-UHFFFAOYSA-J dodecanoate tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BRWZYZWZBMGMMG-UHFFFAOYSA-J 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- YMQPOZUUTMLSEK-UHFFFAOYSA-L lead(2+);octanoate Chemical compound [Pb+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O YMQPOZUUTMLSEK-UHFFFAOYSA-L 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- 125000002004 n-butylamino group Chemical group [H]N(*)C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- XZZXKVYTWCYOQX-UHFFFAOYSA-J octanoate;tin(4+) Chemical compound [Sn+4].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O XZZXKVYTWCYOQX-UHFFFAOYSA-J 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000005628 tolylene group Chemical group 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
- 125000006839 xylylene group Chemical group 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
- C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
- C04B41/495—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as oligomers or polymers
- C04B41/4961—Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones"
- C04B41/4966—Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones" containing silicon bound to hydroxy groups, i.e. OH-blocked polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/62—Coating or impregnation with organic materials
- C04B41/64—Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00112—Mixtures characterised by specific pH values
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
Abstract
METHOD FOR PRODUCING SILICONE
AQUEOUS EMULSION COMPOSITIONS
Abstract Described is a method of producing silicone aqueous emulsion compositions which cure at room temperature by the removal of water to form elastomeric coatings or films with superior surface gloss, good adhesion to substrates, and rustproofness. The method prepares an emulsion of polydiorganosiloxane having at least two hydroxyl groups per molecule, colloidal silica or alkali metal silicate, curing catalyst, emulsifier, and water, the emulsion having a pH of from 9 to 12. After a period of ripening for a period of time, so that an elastomeric material will be formed when water is removed at room temperature, an amino-functional silane or its partial hydrolyzate is added to give the emulsion its improved properties.
AQUEOUS EMULSION COMPOSITIONS
Abstract Described is a method of producing silicone aqueous emulsion compositions which cure at room temperature by the removal of water to form elastomeric coatings or films with superior surface gloss, good adhesion to substrates, and rustproofness. The method prepares an emulsion of polydiorganosiloxane having at least two hydroxyl groups per molecule, colloidal silica or alkali metal silicate, curing catalyst, emulsifier, and water, the emulsion having a pH of from 9 to 12. After a period of ripening for a period of time, so that an elastomeric material will be formed when water is removed at room temperature, an amino-functional silane or its partial hydrolyzate is added to give the emulsion its improved properties.
Description
METHOD FOR PRO~UCING SILICONE
AQUEOUS EMULSION COMPOSITIONS
This invention relates to a method of producing silieone aqueous emulsion compositions having improved adhesion and gloss.
Due to the superior water repellency, weather resistance and rubbery elasticity of silicones, many silicone aqueous emulsion compositions which form elastomeric materials by the removal of ~ater have been proposed or provided for fiber and paper treatment and for waterproof film-forming materials for concrete t wood, slate, ete.
For example, United States Patent Number 3,004,871, issued October 7, 1961, proposes a composition eonsisting of a hydroxyl group-terminated diorganopolysiloxane, an organohydrogen polysiloxane, a polyalkylsilicate and an aliphatic aeid tin salt. Japanese Patent 57-57063 [82-57063] proposes a composition consisting of a hydroxyl group-terminated diorganopolysiloxane, a trifunctional or higher funetional silane and an aliphatic acid tin salt. United States Patent Number 4,221,688, issued September 9, 1980, proposes a composition consisting of a hydroxyl group-terrninated diorganopolysiloxane, colloidal silica and an al phatic acid tin salt. United States Patent Number 4,248,751, issued February 3, 1981, proposes a composition eonsisting of a vinyl-terminated diorganopolysiloxane, an organopolysiloxane containing Si-EI groups and a platinum compound. United States Patent Number 4,228,054, issued October 14, 1980, proposes a composition obtained from the emulsion polymerlzation of a cyclic organopolysiloxane and a functionalized organoalko~ysilane.
However r these silicone aqueous emulsion compositions have the drawbacks of a lack of adhesion or of rusting when applied to the metals used in construction, machinery and electrical appliances. As a method for imparting adhesion to silicone aqueous emulsion compositions, ~apanese Rokai Patent 58-69250 [83-69250] proposes the addition of an amino-functional silane. However, the manufacturing process is overly complicated since it requires the repeated addition of small amounts of the amino-functional silane to a colloidal silica with mixing to homogeneity in order to avoid gelation of the emulsion composition upon the addition of the amino-functional silane. This composition also has the drawback of an inferior surface gloss which degrades the appearance when it is used as a coating agent.
The inventors conducted extensive research to resolve these drawbacks. As a result, the inventors discovered a method for producing a silicone aqueous emulsion composition that would cure at room temperature with the removal of water to form an elastomeric material with a superior surface gloss, good adhesion and good rustproofness.
Summary of the Invention This invention concerns a method of producing silicone aqueous emulsion compositions which cure at room temperature by the removal of water to form an elastomeric material with a superior surface gloss, good adhesion to substrates, and good rustproofness of metallic substrates coated by the emulsion composition.
It is an object of the method of this invention to produce silicone aqueous emulsion compositions which have sup~rior gloss when coated on a substrate and dried.
It is an object of the me~hod of this invention to produce silicone aqueous emulsion compositions which have good adhesion to substrates upon which they are coated and dried.
It is an object of the method of this invention to produce silicone aqueous emulsion compositions which provide a rustproof coating over substrates upon which they are coated and dried.
It is an object of this invention to disclose a method of producing silicone aqueous emulsion compositions having the above desirable features in a simple manner.
Description of the Invention This invention concerns a method for producing silicone aqueous emulsion compositions consisting essentially of (1) adjusting a base emulsion composition which consists essentially of (A) 100 parts by weight of a polydiorganosiloxane which contains at least 2 silicon-bonded hydroxyl groups per molecule, the organic groups being monovalent halogenated hydrocarbon radicals or monovalent hydrocarbon radicals, (B) from 1 to 150 parts by weight colloidal silica or from 0.3 to 30 parts by weight alkali metal silicate, (C) fromØ01 to 10 parts by weight of a curing catalyst, said catalyst being a metal salt of an organic acid, (D) from 2 to 30 parts by weight emulsifier, and (E) water to a pH of from 9 to 12, (2) ripening at a temperature of from lO to 95C for a sufficient period of time that an elastomeric material will be formed when water is removed at room temperature, ~ 7~
and (3) adding (F) from 0.5 to 30 parts by wei~ht of an amino-functional silane of the formula (XR)nsi(OR )4-n where X is an amino-functional radical, R is a divalent hydrocarbon radical containing no more than 8 carbon atoms, R' is a monovalent hydrocarbon radical containing less than 7 carbon atoms or is selected from the group isting of -CH20C2Hs or -CH2CH20C 3 3 or its partial hydrolysis condensate.
The polydiorganosiloxane comprising component (A) imparts the character of an elastic substance to the product obtained by removing water from the emulsion.
This polydiorganosiloxane must contain at least 2 silicon-bonded hydroxyl groups per molecule and there is no specific restriction on the position of hydroxyl group substitution. Aside from the silicon-bonded hydroxyl groups, the organic groups can be either monovalent hydrocarbon radicals or halogenated monovalent hydrocarbon radicals e.g., alkyl radicals such as methyl, ethyl, propyl and butyl; alkenyl radicals such as vinyl and allyl; aryl radicals such as phenyl; aralkyl radicals such as benzyl; alkaryl radicals such as styryl and tolyl; cycloalkyl radicals such as cyclohexyl and cyclopentyl; or the above radicals in which some or all of the hydrogen atoms have been substituted by a halogen such as fluorine, chlorine or bromine such as 3,3,3-trifluoropropyl, etc. This organic group i~
usually methyl, vinyl or phenylO It is not necessary that all organic radicals be identical and generally a combination of organic radicals is present. The molecular configuration may be either linear or branched.
While there is no specific restriction on the molecular weight, a molecular weight of 5000 or greater is t~
preferable. An appropriate tensile strength can be obtained at a molecular weight of 30,000 or greater. The most favorable tensile strength and elongation can b~
obtained at a molecular weight of S0,000 or greater.
Practical examples of this polydiorganosiloxane are hydroxyl group-terminated dimethylpolysiloxanes, methylphenylpolysiloxanes, me~hyl- vinylpolysiloxanes or copolymers of dimethylsiloxane units and methylvinylsiloxane units, etc. These polydiorgano-siloxanes can be synthesized by the ring-opening polymerization of cyclic siloxanes or by the hydrolysis of linear or branched polydiorganosiloxanes which contain hydrolyzable groups such as the alkoxy radical, acyloxy radical, etc., or by the hydrolysis of one or two or more diorganohalosilanes.
The colloidal silica comprising component IB) may be either a fumed colloidal silica or a precipitated colloidal silica such as those stabilized by sodium, ammonia or aluminum ions and preferably with particle sizes of 0.0001 to 0.1 micrometres. The amount of colloidal silica used is from 1.0 to 150 parts by weight and preferably from 1.0 to 70 parts by weight per 100 parts by weight of the polydiorganosiloxane comprising component (A).
The alkali metal silicate is preferably used as the aqueous solution of a water-soluble silicate salt.
Examples of the alkali metal silicate are lithium silicate, sodium silicate, potassium silicate and rubidium silicate. It is used at from 0.3 to 30 parts by weight and preferably from 0.3 to 20 parts by weight per 100 parts by weight of the polydiorganosiloxane comprising component (A).
The curing catalyst comprising component (~) is used to cure the composition of this invention. Examples are the metal salts of organic acids such as dibutyltin dilaurate, dibutyltin diacetate, tin octanoate, dibutyltin dioctoate, tin laurate, ferric star.ooctanate, lead octanoate, lead laurate, zinc octanoate, tetrabutyl titanate and amino compounds and their hydrochlorides such as n-hexylamine and guanidine. These curing catalysts are preferably emulsified beforehand using a general emulsifier and water.
The quantity of curing catalyst used is from 0.01 to 10 parts by weight and preferably from 0.05 to 5 parts by weight per 100 parts by weight o~ polydiorganosiloxane comprising component (A).
The emulsifier comprising component (D) is used to emulsify the composition of the invention. It may be an anionic, nonionic or cationic emulsifier.
Examples of anionic emulsifiers are aliphatic acid salts, salts of sulfate esters of higher alcohols, alkylbenzenesulfonic acids, salts of alkylnaphthalene-sulfonates, alkyl phosphoric acid and salts of sulfate esters of polyethylene glycol ethers. Examples of nonionic emulsifiers are polyoxyethylene alkylphenyl ethers, sorbitan aliphatic acid esters, polyoxyethylene sorbitan aliphatic acid esters, polyoxyalkyl esters, polyoxyethylene-polyoxypropylenes and aliphatic acid monoglycerides. Examples of cationic emulsi~iers are aliphatic amine salts, quaternary ammonium salts, alkylpyridinium salts, etc. One or two or more of these emulsifiers can be used. The quantity of application is from ~ to 30 parts by weight per 100 parts by weight of polydiorganosiloxane comprising component (A).
7~
The water comprising component (E) is used to emulsify the composition and its quantity is not restricted. It is preferred that the water be from 20 to 80 percent by weight of the base emulsion composition.
The amino-functional silane or its partial hydrolysis condensate comprising component (F) causes this composition to manifest gloss and rustproofness. It has the formula (XR)nSi(OR')4-n where X is an amino-functional group such as an amino yroup, ethylamino group, n-butylamino group, cyclohexylamino group, phenylamino group, N-aminoethylamino group, or dimethylamino group; R is a divalent hydrocarbon radical containing no more than 8 carbon atoms such as methylene, ethylene, propylene, butylene, hexylene, pAenylene, cyclohexylene, tolylene, or xylylene; R' is a monovalent hydrocarbon radical containing less than 7 carbon atoms or is selected from the group consisting of -CH2OC2H5 or -CH2CH2OCH3, such as methyl, ethyl, propyl, butyl, or ethoxymethyl, and n is 1, 2, or 3. Practical examples are B-aminoethyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N-aminoethyl-gamma-aminopropylmethyldimethoxysilane, and N-aminoethyl-gamma-aminopropyltriethoxysilane. The partial hydrolysis condensate of these compounds can also be used.
Component (F) is used at from 0.5 to 30 parts by weight per 100 parts by weight of the polydiorganosiloxane comprising component (A).
To manufacture the silicone aqueous emulsion composition, a base emulsion composition composed of components (A), (B), (C), (D) and (E) is first prepared.
Numerous well-known methods may be used for this preparation. For example, a hydroxyl grGup-terminated polydimethylsiloxane can be combined with the emulsifier ... .
., ~
comprising component (D) and the water comprising component (E) and then emulsified using an emulsifier such as a homomixer, homogenizer, colloid mill, etc., followed by adding and mixing the colloidal silica or alkali metal silicate comprising component (B) and the curing catalyst comprising component (C). In another example, a cyclic polydiorganosiloxane, such as octamethylcyclotetrasiloxane, is emulsified into water using an emulsifier. An already-known ring-opening catalyst is added to the emulsion of cycllc polydiorganosiloxane and an emulsion of a hydroxyl group-terminated polydiorganosiloxane is obtained by heating the mixture. A colloidal silica or alkali metal silicate as component (B) and a curing catalyst as component (C) are then mixed with the emulsion of a hydroxyl group-terminated polydiorganosiloxane. There is no specific restriction on these methods as long as the base emulsion composition is prepared from 100 parts by weight of the hydroxyl group~containing polydiorgano-siloxane comprising component (A), from 1 to 150 parts by weight colloidal silica or from 0.3 to 30 parts by weight of the emulsifier comprising component (B) curing catalyst comprising component (C), from 2 to 30 parts by weight of the emulsifier comprising component (D), and water comprising component (E). This base emulsion composition is then adjusted to pH 9 to 12. For example, amines such as diethylamine and ethylenediamine or alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, etc., may be used for adjustment. This is followed by a particular ripening (aging period).
Ripening is carried out at a temperature which does not damage the emulsion such as at 10 to 95C and preferably 15 to 50C. The length of the period is determined by a ~7~5 the condition that an elastomexic material is formed when water is removed from the base emulsion composition. In practice, this period is 1 week or more at 25C or 4 days or more at 40C. An incomplete ripening results in gelation upon the addition of component (F). After ripening, the amino-functional silane or its hydro~yzate comprising component (F) is added and mixed in to produce the silicone aqueous emulsion composition.
The usual additives for ordinary water-base paints, e.g., thickeners, fillers, defoamers, pigments, dyes, preservatives, penetrating agents (such as aqueous ammonia), may be compounded into the silicone aqueous emulsion compositions produced by the method of this invention.
The silicone aqueous emulsion composition obtained as above has a superior stability at room temperature and cures at room temperature by the removal of water. ~ince in particular it becomes an elastomer with a superior surface gloss and rustproofness as well as an excellent adhesion for the base material with which it is in contact during the curing process, it can be widely used as a treatment agent for fiber, paper, etc.; or as a binder for inorganic materials such as glass fiber, asbestos, etc.; or as a coating material or caulking material for metals, concrete~ wood, slate, etc.
Examples follow to explain this invention further.
"~arts" in the examples denote "parts by weight."
Example 1 An emulsion containing component (A) is obtained by mixing 2 parts sodium lauryl sulfate and 70 parts water with 100 parts of a hydroxyl group-terminated polydimethylsiloxane (30 siloxane repeat units) and passing this twice through a homogenizer under 150 kg/cm2 '775 followed by the addition of 1 part dodecylbenzenesulfonic acid as the polymerization initiator to carry out an emulsion polymerization at room temperature for 16 hours.
This is then adjusted to pH 7 by adding aqueous sodium hydroxide to provide an emulsion (Emulsion A) containing a hydroxyl group-terminated polydimethylsiloxane with a molecular weight of approximately 200,000.
An emulsion containing component (C) (Emulsion C~
was prepared by mixing 10 parts sodium lauryl sulfate and ~0 parts water with 40 parts dioctyltin dilaurate and then passing this through the homogenizer.
A mixture was prepared from 100 parts Emulsion A, 1.5 parts Emulsion C and 25 parts aqueous silica containing 30 weight percent solids as component (B). A
small amount of diethylamine was then added to adjust the pH to 11 and this mixture was ripened at room temperature for 2 weeks to provide a ripened emulsion. An amino-functional silane as component (F) in the form of gamma-aminopropyltriethoxy- silane, N-beta-aminoethyl-gamma-aminopropyltrimethoxysilane or N-beta-aminoethyl-gamma-aminopropyl(methyl)dimethoxy-silane was added, as shown in Table I, to 100 parts by weight of the ripened emulsion.
For comparison, gamma-methacryloxypropyltrimethoxy-silane or gamma-glycidoxypropyltrimethoxysilane were added instead of the amino-functional silane.
These aqueous emulsions were applied to iron test plates. The gloss, rustproofness and adhesion were evaluated as follows and the table reports the results.
Gloss was measured according to ~IS K5400.6.7, 60 specular gloss. Rustproofness was judged by ob~erving the amount of rust present after treatment in a weatherometer for 1000, 2000, and 3000 hours. The adhesion was ,udged by peeling the rubbery coating material off the iron test plates using a spatula and scoring adhesion using the following categories~ or cohesive rupture of the rubbery material, 2) for peeling at the interface with considerable strength, and 3) for peeling at the interface with little strength.
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a) ~ e ~ o o O O o o e ~ ~ E. Q) E, ~ 1~ 0~ E. E
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Example 2 A mixture was prepared from 1.5 parts Emulsion C, prepared as in Example 1, and 3 parts sodium silicate added to 100 parts Emulsion A prepared as in Example 1, this was mixed to homogeneity, then ad~usted to pH 10, and ripened at room temperature for 4 weeks. Then 5 parts N-beta-aminoethylaminopropyltri- methoxysilane were added to produce an aqueous emulsion. This was applied on a fluororesin film. After the removal of water, a l mm thick rubber sheet was obtained.
The surface of this rubber sheet has excellent gloss. Its measured properties were a hardness (JIS) of 70, an elongation of 280%, a tensile strength of 22 kg/cm2 and a tear strength of 13 kg/cm2.
This aqueous emulsion presented no change after storage for one year at room temperature.
AQUEOUS EMULSION COMPOSITIONS
This invention relates to a method of producing silieone aqueous emulsion compositions having improved adhesion and gloss.
Due to the superior water repellency, weather resistance and rubbery elasticity of silicones, many silicone aqueous emulsion compositions which form elastomeric materials by the removal of ~ater have been proposed or provided for fiber and paper treatment and for waterproof film-forming materials for concrete t wood, slate, ete.
For example, United States Patent Number 3,004,871, issued October 7, 1961, proposes a composition eonsisting of a hydroxyl group-terminated diorganopolysiloxane, an organohydrogen polysiloxane, a polyalkylsilicate and an aliphatic aeid tin salt. Japanese Patent 57-57063 [82-57063] proposes a composition consisting of a hydroxyl group-terminated diorganopolysiloxane, a trifunctional or higher funetional silane and an aliphatic acid tin salt. United States Patent Number 4,221,688, issued September 9, 1980, proposes a composition consisting of a hydroxyl group-terrninated diorganopolysiloxane, colloidal silica and an al phatic acid tin salt. United States Patent Number 4,248,751, issued February 3, 1981, proposes a composition eonsisting of a vinyl-terminated diorganopolysiloxane, an organopolysiloxane containing Si-EI groups and a platinum compound. United States Patent Number 4,228,054, issued October 14, 1980, proposes a composition obtained from the emulsion polymerlzation of a cyclic organopolysiloxane and a functionalized organoalko~ysilane.
However r these silicone aqueous emulsion compositions have the drawbacks of a lack of adhesion or of rusting when applied to the metals used in construction, machinery and electrical appliances. As a method for imparting adhesion to silicone aqueous emulsion compositions, ~apanese Rokai Patent 58-69250 [83-69250] proposes the addition of an amino-functional silane. However, the manufacturing process is overly complicated since it requires the repeated addition of small amounts of the amino-functional silane to a colloidal silica with mixing to homogeneity in order to avoid gelation of the emulsion composition upon the addition of the amino-functional silane. This composition also has the drawback of an inferior surface gloss which degrades the appearance when it is used as a coating agent.
The inventors conducted extensive research to resolve these drawbacks. As a result, the inventors discovered a method for producing a silicone aqueous emulsion composition that would cure at room temperature with the removal of water to form an elastomeric material with a superior surface gloss, good adhesion and good rustproofness.
Summary of the Invention This invention concerns a method of producing silicone aqueous emulsion compositions which cure at room temperature by the removal of water to form an elastomeric material with a superior surface gloss, good adhesion to substrates, and good rustproofness of metallic substrates coated by the emulsion composition.
It is an object of the method of this invention to produce silicone aqueous emulsion compositions which have sup~rior gloss when coated on a substrate and dried.
It is an object of the me~hod of this invention to produce silicone aqueous emulsion compositions which have good adhesion to substrates upon which they are coated and dried.
It is an object of the method of this invention to produce silicone aqueous emulsion compositions which provide a rustproof coating over substrates upon which they are coated and dried.
It is an object of this invention to disclose a method of producing silicone aqueous emulsion compositions having the above desirable features in a simple manner.
Description of the Invention This invention concerns a method for producing silicone aqueous emulsion compositions consisting essentially of (1) adjusting a base emulsion composition which consists essentially of (A) 100 parts by weight of a polydiorganosiloxane which contains at least 2 silicon-bonded hydroxyl groups per molecule, the organic groups being monovalent halogenated hydrocarbon radicals or monovalent hydrocarbon radicals, (B) from 1 to 150 parts by weight colloidal silica or from 0.3 to 30 parts by weight alkali metal silicate, (C) fromØ01 to 10 parts by weight of a curing catalyst, said catalyst being a metal salt of an organic acid, (D) from 2 to 30 parts by weight emulsifier, and (E) water to a pH of from 9 to 12, (2) ripening at a temperature of from lO to 95C for a sufficient period of time that an elastomeric material will be formed when water is removed at room temperature, ~ 7~
and (3) adding (F) from 0.5 to 30 parts by wei~ht of an amino-functional silane of the formula (XR)nsi(OR )4-n where X is an amino-functional radical, R is a divalent hydrocarbon radical containing no more than 8 carbon atoms, R' is a monovalent hydrocarbon radical containing less than 7 carbon atoms or is selected from the group isting of -CH20C2Hs or -CH2CH20C 3 3 or its partial hydrolysis condensate.
The polydiorganosiloxane comprising component (A) imparts the character of an elastic substance to the product obtained by removing water from the emulsion.
This polydiorganosiloxane must contain at least 2 silicon-bonded hydroxyl groups per molecule and there is no specific restriction on the position of hydroxyl group substitution. Aside from the silicon-bonded hydroxyl groups, the organic groups can be either monovalent hydrocarbon radicals or halogenated monovalent hydrocarbon radicals e.g., alkyl radicals such as methyl, ethyl, propyl and butyl; alkenyl radicals such as vinyl and allyl; aryl radicals such as phenyl; aralkyl radicals such as benzyl; alkaryl radicals such as styryl and tolyl; cycloalkyl radicals such as cyclohexyl and cyclopentyl; or the above radicals in which some or all of the hydrogen atoms have been substituted by a halogen such as fluorine, chlorine or bromine such as 3,3,3-trifluoropropyl, etc. This organic group i~
usually methyl, vinyl or phenylO It is not necessary that all organic radicals be identical and generally a combination of organic radicals is present. The molecular configuration may be either linear or branched.
While there is no specific restriction on the molecular weight, a molecular weight of 5000 or greater is t~
preferable. An appropriate tensile strength can be obtained at a molecular weight of 30,000 or greater. The most favorable tensile strength and elongation can b~
obtained at a molecular weight of S0,000 or greater.
Practical examples of this polydiorganosiloxane are hydroxyl group-terminated dimethylpolysiloxanes, methylphenylpolysiloxanes, me~hyl- vinylpolysiloxanes or copolymers of dimethylsiloxane units and methylvinylsiloxane units, etc. These polydiorgano-siloxanes can be synthesized by the ring-opening polymerization of cyclic siloxanes or by the hydrolysis of linear or branched polydiorganosiloxanes which contain hydrolyzable groups such as the alkoxy radical, acyloxy radical, etc., or by the hydrolysis of one or two or more diorganohalosilanes.
The colloidal silica comprising component IB) may be either a fumed colloidal silica or a precipitated colloidal silica such as those stabilized by sodium, ammonia or aluminum ions and preferably with particle sizes of 0.0001 to 0.1 micrometres. The amount of colloidal silica used is from 1.0 to 150 parts by weight and preferably from 1.0 to 70 parts by weight per 100 parts by weight of the polydiorganosiloxane comprising component (A).
The alkali metal silicate is preferably used as the aqueous solution of a water-soluble silicate salt.
Examples of the alkali metal silicate are lithium silicate, sodium silicate, potassium silicate and rubidium silicate. It is used at from 0.3 to 30 parts by weight and preferably from 0.3 to 20 parts by weight per 100 parts by weight of the polydiorganosiloxane comprising component (A).
The curing catalyst comprising component (~) is used to cure the composition of this invention. Examples are the metal salts of organic acids such as dibutyltin dilaurate, dibutyltin diacetate, tin octanoate, dibutyltin dioctoate, tin laurate, ferric star.ooctanate, lead octanoate, lead laurate, zinc octanoate, tetrabutyl titanate and amino compounds and their hydrochlorides such as n-hexylamine and guanidine. These curing catalysts are preferably emulsified beforehand using a general emulsifier and water.
The quantity of curing catalyst used is from 0.01 to 10 parts by weight and preferably from 0.05 to 5 parts by weight per 100 parts by weight o~ polydiorganosiloxane comprising component (A).
The emulsifier comprising component (D) is used to emulsify the composition of the invention. It may be an anionic, nonionic or cationic emulsifier.
Examples of anionic emulsifiers are aliphatic acid salts, salts of sulfate esters of higher alcohols, alkylbenzenesulfonic acids, salts of alkylnaphthalene-sulfonates, alkyl phosphoric acid and salts of sulfate esters of polyethylene glycol ethers. Examples of nonionic emulsifiers are polyoxyethylene alkylphenyl ethers, sorbitan aliphatic acid esters, polyoxyethylene sorbitan aliphatic acid esters, polyoxyalkyl esters, polyoxyethylene-polyoxypropylenes and aliphatic acid monoglycerides. Examples of cationic emulsi~iers are aliphatic amine salts, quaternary ammonium salts, alkylpyridinium salts, etc. One or two or more of these emulsifiers can be used. The quantity of application is from ~ to 30 parts by weight per 100 parts by weight of polydiorganosiloxane comprising component (A).
7~
The water comprising component (E) is used to emulsify the composition and its quantity is not restricted. It is preferred that the water be from 20 to 80 percent by weight of the base emulsion composition.
The amino-functional silane or its partial hydrolysis condensate comprising component (F) causes this composition to manifest gloss and rustproofness. It has the formula (XR)nSi(OR')4-n where X is an amino-functional group such as an amino yroup, ethylamino group, n-butylamino group, cyclohexylamino group, phenylamino group, N-aminoethylamino group, or dimethylamino group; R is a divalent hydrocarbon radical containing no more than 8 carbon atoms such as methylene, ethylene, propylene, butylene, hexylene, pAenylene, cyclohexylene, tolylene, or xylylene; R' is a monovalent hydrocarbon radical containing less than 7 carbon atoms or is selected from the group consisting of -CH2OC2H5 or -CH2CH2OCH3, such as methyl, ethyl, propyl, butyl, or ethoxymethyl, and n is 1, 2, or 3. Practical examples are B-aminoethyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N-aminoethyl-gamma-aminopropylmethyldimethoxysilane, and N-aminoethyl-gamma-aminopropyltriethoxysilane. The partial hydrolysis condensate of these compounds can also be used.
Component (F) is used at from 0.5 to 30 parts by weight per 100 parts by weight of the polydiorganosiloxane comprising component (A).
To manufacture the silicone aqueous emulsion composition, a base emulsion composition composed of components (A), (B), (C), (D) and (E) is first prepared.
Numerous well-known methods may be used for this preparation. For example, a hydroxyl grGup-terminated polydimethylsiloxane can be combined with the emulsifier ... .
., ~
comprising component (D) and the water comprising component (E) and then emulsified using an emulsifier such as a homomixer, homogenizer, colloid mill, etc., followed by adding and mixing the colloidal silica or alkali metal silicate comprising component (B) and the curing catalyst comprising component (C). In another example, a cyclic polydiorganosiloxane, such as octamethylcyclotetrasiloxane, is emulsified into water using an emulsifier. An already-known ring-opening catalyst is added to the emulsion of cycllc polydiorganosiloxane and an emulsion of a hydroxyl group-terminated polydiorganosiloxane is obtained by heating the mixture. A colloidal silica or alkali metal silicate as component (B) and a curing catalyst as component (C) are then mixed with the emulsion of a hydroxyl group-terminated polydiorganosiloxane. There is no specific restriction on these methods as long as the base emulsion composition is prepared from 100 parts by weight of the hydroxyl group~containing polydiorgano-siloxane comprising component (A), from 1 to 150 parts by weight colloidal silica or from 0.3 to 30 parts by weight of the emulsifier comprising component (B) curing catalyst comprising component (C), from 2 to 30 parts by weight of the emulsifier comprising component (D), and water comprising component (E). This base emulsion composition is then adjusted to pH 9 to 12. For example, amines such as diethylamine and ethylenediamine or alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, etc., may be used for adjustment. This is followed by a particular ripening (aging period).
Ripening is carried out at a temperature which does not damage the emulsion such as at 10 to 95C and preferably 15 to 50C. The length of the period is determined by a ~7~5 the condition that an elastomexic material is formed when water is removed from the base emulsion composition. In practice, this period is 1 week or more at 25C or 4 days or more at 40C. An incomplete ripening results in gelation upon the addition of component (F). After ripening, the amino-functional silane or its hydro~yzate comprising component (F) is added and mixed in to produce the silicone aqueous emulsion composition.
The usual additives for ordinary water-base paints, e.g., thickeners, fillers, defoamers, pigments, dyes, preservatives, penetrating agents (such as aqueous ammonia), may be compounded into the silicone aqueous emulsion compositions produced by the method of this invention.
The silicone aqueous emulsion composition obtained as above has a superior stability at room temperature and cures at room temperature by the removal of water. ~ince in particular it becomes an elastomer with a superior surface gloss and rustproofness as well as an excellent adhesion for the base material with which it is in contact during the curing process, it can be widely used as a treatment agent for fiber, paper, etc.; or as a binder for inorganic materials such as glass fiber, asbestos, etc.; or as a coating material or caulking material for metals, concrete~ wood, slate, etc.
Examples follow to explain this invention further.
"~arts" in the examples denote "parts by weight."
Example 1 An emulsion containing component (A) is obtained by mixing 2 parts sodium lauryl sulfate and 70 parts water with 100 parts of a hydroxyl group-terminated polydimethylsiloxane (30 siloxane repeat units) and passing this twice through a homogenizer under 150 kg/cm2 '775 followed by the addition of 1 part dodecylbenzenesulfonic acid as the polymerization initiator to carry out an emulsion polymerization at room temperature for 16 hours.
This is then adjusted to pH 7 by adding aqueous sodium hydroxide to provide an emulsion (Emulsion A) containing a hydroxyl group-terminated polydimethylsiloxane with a molecular weight of approximately 200,000.
An emulsion containing component (C) (Emulsion C~
was prepared by mixing 10 parts sodium lauryl sulfate and ~0 parts water with 40 parts dioctyltin dilaurate and then passing this through the homogenizer.
A mixture was prepared from 100 parts Emulsion A, 1.5 parts Emulsion C and 25 parts aqueous silica containing 30 weight percent solids as component (B). A
small amount of diethylamine was then added to adjust the pH to 11 and this mixture was ripened at room temperature for 2 weeks to provide a ripened emulsion. An amino-functional silane as component (F) in the form of gamma-aminopropyltriethoxy- silane, N-beta-aminoethyl-gamma-aminopropyltrimethoxysilane or N-beta-aminoethyl-gamma-aminopropyl(methyl)dimethoxy-silane was added, as shown in Table I, to 100 parts by weight of the ripened emulsion.
For comparison, gamma-methacryloxypropyltrimethoxy-silane or gamma-glycidoxypropyltrimethoxysilane were added instead of the amino-functional silane.
These aqueous emulsions were applied to iron test plates. The gloss, rustproofness and adhesion were evaluated as follows and the table reports the results.
Gloss was measured according to ~IS K5400.6.7, 60 specular gloss. Rustproofness was judged by ob~erving the amount of rust present after treatment in a weatherometer for 1000, 2000, and 3000 hours. The adhesion was ,udged by peeling the rubbery coating material off the iron test plates using a spatula and scoring adhesion using the following categories~ or cohesive rupture of the rubbery material, 2) for peeling at the interface with considerable strength, and 3) for peeling at the interface with little strength.
I I i I ~ O ,a ~~ ,a a ~ ~ ~ o h ta ~1 U~ E~ Q
t~ 5 Q~ Sl S~ U7 u~ I I I ~ I o ,~-,1a I I I I ~
~IJ ~ Q
E~ C~
o I I I n a~~ aJ
U7~ O~ O
,a,a .a~1~ Q
~a S~
n 0 , co I I o :~ aJ a, ~ eo o ta Q (I~ Q
~ 0 U~
O oe QO eQO
tq ~ ~
U~ ~ O ~ O
,~ O (~Q ~Q
E~
U~ U~
U~
I I I I ~ ~~ ~0 ~ O
~ ~ Q~ (~ Qa ~-/ rlI ~ Q.
~1 1 1 1 1 1 U~~1 0 U~ ~ r~l r~ r-l ~X U~
X O ~ Q O
~ S Q. O ~I X ~ 1~
h ~:O ~ ~ O ~ ~ O S~ O X ~~- h 5~ h au Oh rl al h ~1 a) h ~h ~ O -iu~
9 ~ 1 o Q~rl O Q~ rlUl O O O
~ ~o u~ ~ O ~q ~ O E(d a) ,1 u~
~ U ~ ~ e u ~ ~
1 X E, ~I X ~1~~ ~1 ~1 X~ o o o O (a E~ O E,--O h ~ OO o o o ~:
a) ~ e ~ o o O O o o e ~ ~ E. Q) E, ~ 1~ 0~ E. E
~ .,~ Q ~ 3 o ~ o u~ -~
X E~ h I ~ ~3 td h 11~ h r-l ~1 ~ ~ Z t~ ~ Z t~ ~ tJ` h 7~
Example 2 A mixture was prepared from 1.5 parts Emulsion C, prepared as in Example 1, and 3 parts sodium silicate added to 100 parts Emulsion A prepared as in Example 1, this was mixed to homogeneity, then ad~usted to pH 10, and ripened at room temperature for 4 weeks. Then 5 parts N-beta-aminoethylaminopropyltri- methoxysilane were added to produce an aqueous emulsion. This was applied on a fluororesin film. After the removal of water, a l mm thick rubber sheet was obtained.
The surface of this rubber sheet has excellent gloss. Its measured properties were a hardness (JIS) of 70, an elongation of 280%, a tensile strength of 22 kg/cm2 and a tear strength of 13 kg/cm2.
This aqueous emulsion presented no change after storage for one year at room temperature.
Claims (6)
1. A method for producing silicone aqueous emulsion compositions consisting essentially of (1) adjusting a base emulsion composition which consists essentially of (A) 100 parts by weight of a polydiorganosiloxane which contains at least 2 silicon-bonded hydroxyl groups per molecule, the organic groups being monovalent halogenated hydrocarbon radicals or monovalent hydrocarbon radicals, (B) from 1 to 150 parts by weight colloidal silica or from 0.3 to 30 parts by weight alkali metal silicate, (C) from 0.01 to 10 parts by weight of a curing catalyst, said catalyst being a metal salt of an organic acid, (D) from 2 to 30 parts by weight emulsifier, and (E) water to a pH of from 9 to 12, (2) ripening at a temperature of from 10 to 95°C for a sufficient period of time that an elastomeric material will be formed when water is removed at room temperature, and characterizingly (3) adding (F) from 0.5 to 30 parts by weight of an amino-functional silane of the formula (XR)nSi(OR')4-n where X is an amino-functional radical, R is a divalent hydrocarbon radical containing no more than 8 carbon atoms, R' is a monovalent hydrocarbon radical containing less than 7 carbon atoms or is selected from the group consisting of -CH2OC2H5 or -CH2CH2OCH3, and n is 1, 2, or 3 or its partial hydrolysis condensate.
2. The method of claim 1 in which (A) is a polydimethylsiloxane having a molecular weight of greater than 50,000, (B) is from 1 to 70 parts by weight of colloidal silica, (C) is from 0.01 to 10 parts by weight of a dialkyltindicarboxylate, (D) is an anionic emulsifier, and (F) is an amino-functional silane where n is 1 or 2.
3. The method of claim 1 in which the adjusting step (1) consists essentially of admixing an amine.
4. The method of claim 1 in which the adjusting step (1) consists essentially of admixing alkali metal hydroxide.
5. The method of claim 4 in which the alkali metal hydroxide is sodium hydroxide.
6. The method of claim 1 in which the ripening is carried out at a temperature of from 15 to 50°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP204482/83 | 1983-10-31 | ||
| JP58204482A JPS6096650A (en) | 1983-10-31 | 1983-10-31 | Production of aqueous silicone emulsion composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1247775A true CA1247775A (en) | 1988-12-28 |
Family
ID=16491251
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000464472A Expired CA1247775A (en) | 1983-10-31 | 1984-10-02 | Method for producing silicone aqueous emulsion compositions |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4535109A (en) |
| EP (1) | EP0143541B1 (en) |
| JP (1) | JPS6096650A (en) |
| AU (1) | AU575868B2 (en) |
| BR (1) | BR8405243A (en) |
| CA (1) | CA1247775A (en) |
| DE (1) | DE3478455D1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112358802A (en) * | 2020-12-11 | 2021-02-12 | 成都新柯力化工科技有限公司 | Electroplating coating imitated nano water-based paint and preparation method thereof |
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| US4568718A (en) * | 1984-06-26 | 1986-02-04 | Dow Corning Corporation | Polydiorganosiloxane latex |
| JPH0639568B2 (en) * | 1985-04-24 | 1994-05-25 | 東レ・ダウコーニング・シリコーン株式会社 | Process for producing silicone aqueous emulsion composition |
| US4618642A (en) * | 1985-05-02 | 1986-10-21 | Dow Corning Corporation | Silicone water-based caulking material |
| US4590220A (en) * | 1985-05-24 | 1986-05-20 | Dow Corning Corporation | Method of producing a silicone water-based elastomer |
| US4618645A (en) * | 1985-05-24 | 1986-10-21 | Dow Corning Corporation | Method of producing aqueous latex of crosslinked polydiorganosiloxane |
| US4661556A (en) * | 1985-05-24 | 1987-04-28 | Dow Corning Corporation | Method of producing reinforced aqueous emulsion of polydiorganosiloxane |
| JPH066680B2 (en) * | 1985-10-30 | 1994-01-26 | 東レ・ダウコーニング・シリコーン株式会社 | Primer composition |
| US4764363A (en) * | 1986-04-04 | 1988-08-16 | The Procter & Gamble Company | Hair styling mousse |
| US4710405A (en) * | 1986-08-25 | 1987-12-01 | Dow Corning Corporation | Adhesion of silicone elastomers obtained from aqueous emulsion |
| FR2642765B1 (en) * | 1989-02-03 | 1991-04-26 | Rhone Poulenc Chimie | AQUEOUS SILICONE DISPERSION BASED ON AMINOSILANE AND / OR AMIDOSILANE CROSSLINKING TO AN ELASTOMER BY REMOVAL OF WATER |
| JP2750899B2 (en) * | 1989-06-19 | 1998-05-13 | 東レ・ダウコーニング・シリコーン株式会社 | Method for producing cyclohexylamino group-containing organopolysiloxane microemulsion |
| FR2649115B1 (en) * | 1989-06-29 | 1994-10-28 | Rhone Poulenc Chimie | AQUEOUS DISPERSION BASED ON SILICON OILS AND ORGANIC (CO) POLYMER CROSSLINKING TO AN ELASTOMER BY REMOVAL OF WATER |
| DE3932025A1 (en) * | 1989-09-26 | 1991-04-04 | Wacker Chemie Gmbh | WAESSED DISPERSIONS OF ORGANOPOLYSILOXANES |
| CA2017090A1 (en) * | 1990-05-17 | 1991-11-17 | Stephen Dunn | Coating composition |
| DE4029640A1 (en) * | 1990-09-19 | 1992-03-26 | Goldschmidt Ag Th | PREPARATION FOR WATER REPELLENT IMPREGNATION OF POROESER MINERAL BUILDING MATERIALS |
| US5205860A (en) * | 1992-01-23 | 1993-04-27 | Dow Corning Corporation | Water repellents containing organosilicon compounds |
| PL308464A1 (en) * | 1992-10-20 | 1995-07-24 | Wacker Chemie Gmbh | Aqueous binders and coating compositions |
| US5300327A (en) * | 1993-03-22 | 1994-04-05 | Dow Corning Corporation | Water repellent organosilicon compositions |
| US5548021A (en) * | 1994-10-28 | 1996-08-20 | Dow Corning Corporation | Trialkyl endcapped polyorganosiloxane emulsions |
| GB2303857B (en) * | 1995-07-28 | 1999-05-26 | Gen Electric | Cationic surfactant compatible anionic emulsion polymerized silicone emulsions |
| US5807921A (en) * | 1995-12-21 | 1998-09-15 | Dow Corning Corporation | Silicone elastomers from aqueous silicone emulsions having improved adhesion to substrates |
| GB9622095D0 (en) * | 1996-10-23 | 1996-12-18 | Armstrong John S | Process for providing coating for non-porous sufaces with useing a unique blend of silicones |
| CA2241766C (en) * | 1998-06-25 | 2003-05-06 | Csl Silicones Inc. | One-part organopolysiloxane rubber composition for use as a corrosion protection coating on metals |
| US6090885A (en) * | 1998-10-06 | 2000-07-18 | General Electric Company | Aminofunctional silicone emulsion |
| US6214928B1 (en) * | 1999-11-02 | 2001-04-10 | General Electric Company | Aqueous emulsions of amine-functionalized organopolysiloxanes and method |
| ES2283333T3 (en) * | 1999-11-17 | 2007-11-01 | Henkel Corporation | USE OF FLUID RESISTANT SILICONE COMPOSITIONS TO SEAL MAGNESIUM ALLOY COMPONENTS. |
| US20040225079A1 (en) * | 2003-05-05 | 2004-11-11 | Analytical Services And Materials Inc. | Erosion-resistant silicone coatings |
| US7033673B2 (en) * | 2003-07-25 | 2006-04-25 | Analytical Services & Materials, Inc. | Erosion-resistant silicone coatings for protection of fluid-handling parts |
| US8012544B2 (en) | 2003-10-08 | 2011-09-06 | Dow Corning Corporation | Silicone MQ resin reinforced silicone elastomer emulsions |
| DE10349082A1 (en) * | 2003-10-22 | 2005-05-25 | Wacker-Chemie Gmbh | Aqueous polymer dispersions |
| TW200704593A (en) * | 2005-04-22 | 2007-02-01 | Dow Corning Toray Co Ltd | Solution or dispersion for substarate surface treatment comprising titanium oxide doped with metallic element, method for substrate surface treatment using the same, and surface-treated material obtained therefrom |
| JP4689631B2 (en) | 2007-02-08 | 2011-05-25 | Ｙｋｋ株式会社 | Liquid-tight slide fastener and method for producing liquid-tight slide fastener |
| WO2010062674A1 (en) * | 2008-11-03 | 2010-06-03 | Dow Corning Corporation | Film forming silicone emulsions |
| EP2406323B1 (en) * | 2009-03-10 | 2013-07-24 | Dow Corning Toray Co., Ltd. | Oil-in-water silicone emulsion composition |
| JP2013203612A (en) * | 2012-03-29 | 2013-10-07 | Awaji Materia Co Ltd | Film-forming agent for superconducting bulk body, coating for superconducting bulk body, superconducting bulk body with coating, and superconducting bulk magnet |
| JP2016508179A (en) * | 2013-01-11 | 2016-03-17 | ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ | Air and water barrier |
| PL3256560T3 (en) * | 2015-02-10 | 2019-03-29 | Unilever N.V. | Hard surface treatment composition |
| US20220041867A1 (en) | 2020-08-07 | 2022-02-10 | Illinois Tool Works Inc. | Vehicle ceramic surface treatment composition and process for use thereof |
| EP4244299A1 (en) * | 2020-11-11 | 2023-09-20 | Industrial Control Development, Inc. | Aqueous silicone elastomers as roof coatings |
| AU2022303332A1 (en) | 2021-07-01 | 2024-01-04 | Illinois Tool Works Inc. | Solvent based automotive graphene surface treatmentand process for use thereof |
| AU2022300979A1 (en) | 2021-07-01 | 2024-01-04 | Illinois Tool Works Inc. | Automotive graphene surface treatment composition and process for use thereof |
| CN114381154A (en) * | 2022-01-20 | 2022-04-22 | 深圳市广田环保涂料有限公司 | Inorganic ceramic tile crack-beautifying coating and preparation method thereof |
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|---|---|---|---|---|
| CA664097A (en) * | 1963-05-28 | H. Ender Hans | Organosiloxane compositions and elastomers prepared therefrom | |
| US3004871A (en) * | 1959-07-23 | 1961-10-17 | Gen Electric | Rendering cellulosic materials non-adherent |
| US3817894A (en) * | 1972-08-10 | 1974-06-18 | Dow Corning | Silicone latex caulk |
| US4218359A (en) * | 1976-04-07 | 1980-08-19 | Wacker-Chemie Gmbh | Organopolysiloxane compositions and a process for treating organic fibers |
| JPS54131661A (en) * | 1978-04-05 | 1979-10-12 | Toray Silicone Co Ltd | Organopolysiloxane latex composition |
| US4221688A (en) * | 1978-04-28 | 1980-09-09 | Dow Corning Corporation | Silicone emulsion which provides an elastomeric product and methods for preparation |
| US4244849A (en) * | 1979-08-06 | 1981-01-13 | Dow Corning Corporation | Silicone emulsion which provides an elastomeric product and methods for preparation |
| US4248751A (en) * | 1979-08-31 | 1981-02-03 | Dow Corning Corporation | Process for producing a silicone elastomer emulsion and use thereof |
| GB2075040B (en) * | 1980-04-08 | 1983-11-23 | Dow Corning Ltd | Organopolysiloxane compositions |
| JPS5757063A (en) * | 1980-09-24 | 1982-04-06 | Hashimoto Corp | Automatic answering telephone set with tape for remote hearing reproduced in high speed |
| JPS5869250A (en) * | 1981-10-20 | 1983-04-25 | Shin Etsu Chem Co Ltd | Aqueous silicone emulsion composition |
| JPS6022018B2 (en) * | 1981-11-27 | 1985-05-30 | 信越化学工業株式会社 | Silicone aqueous emulsion composition |
| US4427811A (en) * | 1981-12-30 | 1984-01-24 | Dow Corning Corporation | Silicone elastomeric emulsion having improved shelf life |
-
1983
- 1983-10-31 JP JP58204482A patent/JPS6096650A/en active Pending
-
1984
- 1984-09-24 US US06/653,174 patent/US4535109A/en not_active Expired - Lifetime
- 1984-10-02 CA CA000464472A patent/CA1247775A/en not_active Expired
- 1984-10-17 BR BR8405243A patent/BR8405243A/en not_active IP Right Cessation
- 1984-10-19 DE DE8484307208T patent/DE3478455D1/en not_active Expired
- 1984-10-19 EP EP84307208A patent/EP0143541B1/en not_active Expired
- 1984-10-30 AU AU34842/84A patent/AU575868B2/en not_active Ceased
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112358802A (en) * | 2020-12-11 | 2021-02-12 | 成都新柯力化工科技有限公司 | Electroplating coating imitated nano water-based paint and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| AU3484284A (en) | 1985-05-09 |
| BR8405243A (en) | 1985-08-27 |
| DE3478455D1 (en) | 1989-07-06 |
| EP0143541B1 (en) | 1989-05-31 |
| US4535109A (en) | 1985-08-13 |
| EP0143541A1 (en) | 1985-06-05 |
| JPS6096650A (en) | 1985-05-30 |
| AU575868B2 (en) | 1988-08-11 |
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