JPH04261454A - Polyorganosiloxane-based emulsion - Google Patents
Polyorganosiloxane-based emulsionInfo
- Publication number
- JPH04261454A JPH04261454A JP4217191A JP4217191A JPH04261454A JP H04261454 A JPH04261454 A JP H04261454A JP 4217191 A JP4217191 A JP 4217191A JP 4217191 A JP4217191 A JP 4217191A JP H04261454 A JPH04261454 A JP H04261454A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polyorganosiloxane
- parts
- emulsion
- meth
- 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.)
- Granted
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 47
- 229920000642 polymer Polymers 0.000 claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 125000005375 organosiloxane group Chemical group 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 6
- 125000005370 alkoxysilyl group Chemical group 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 150000001721 carbon Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 50
- 238000000576 coating method Methods 0.000 abstract description 19
- 239000011248 coating agent Substances 0.000 abstract description 18
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 6
- 230000000379 polymerizing effect Effects 0.000 abstract description 6
- AJTVQQFMXNOEIE-UHFFFAOYSA-N CO[SiH](OC)CC1=CC=C(C=C)C=C1 Chemical compound CO[SiH](OC)CC1=CC=C(C=C)C=C1 AJTVQQFMXNOEIE-UHFFFAOYSA-N 0.000 abstract description 5
- 238000009833 condensation Methods 0.000 abstract description 5
- 230000005494 condensation Effects 0.000 abstract description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 3
- 125000005907 alkyl ester group Chemical group 0.000 abstract description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 43
- 239000000203 mixture Substances 0.000 description 23
- 239000004816 latex Substances 0.000 description 20
- 229920000126 latex Polymers 0.000 description 20
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 19
- 229920002554 vinyl polymer Polymers 0.000 description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- -1 dimethylvinylsilyl group Chemical group 0.000 description 13
- 239000003995 emulsifying agent Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 229910001873 dinitrogen Inorganic materials 0.000 description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 229920000578 graft copolymer Polymers 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000010559 graft polymerization reaction Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 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 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000004567 concrete Substances 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000004996 alkyl benzenes Chemical class 0.000 description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- UXBOFOZEKHESIO-UHFFFAOYSA-N 2-(4-ethenylphenyl)ethyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCC1=CC=C(C=C)C=C1 UXBOFOZEKHESIO-UHFFFAOYSA-N 0.000 description 2
- FTGQNVPMXAOYSD-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 4-ethenylbenzoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C1=CC=C(C=C)C=C1 FTGQNVPMXAOYSD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- HRKQOINLCJTGBK-UHFFFAOYSA-L dioxidosulfate(2-) Chemical compound [O-]S[O-] HRKQOINLCJTGBK-UHFFFAOYSA-L 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 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 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000010454 slate Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- UZRFZKPJHQYZGZ-UHFFFAOYSA-N (3-ethenylphenyl)-diphenyl-(3-triethoxysilylpropyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=C(C=C)C=CC=1)(CCC[Si](OCC)(OCC)OCC)C1=CC=CC=C1 UZRFZKPJHQYZGZ-UHFFFAOYSA-N 0.000 description 1
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- UUGXDEDGRPYWHG-UHFFFAOYSA-N (dimethylamino)methyl 2-methylprop-2-enoate Chemical compound CN(C)COC(=O)C(C)=C UUGXDEDGRPYWHG-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NMIKUVSQOXIPLN-UHFFFAOYSA-N 2-(3-ethenylphenyl)ethyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCC1=CC=CC(C=C)=C1 NMIKUVSQOXIPLN-UHFFFAOYSA-N 0.000 description 1
- GSQIVVSEVORPJF-UHFFFAOYSA-N 2-(butylamino)ethyl prop-2-enoate Chemical compound CCCCNCCOC(=O)C=C GSQIVVSEVORPJF-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- DFWPREUTILPHQS-UHFFFAOYSA-N 2-amino-2-cyanopropanamide Chemical compound N#CC(N)(C)C(N)=O DFWPREUTILPHQS-UHFFFAOYSA-N 0.000 description 1
- UGIJCMNGQCUTPI-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate Chemical compound NCCOC(=O)C=C UGIJCMNGQCUTPI-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-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
- RZRUOQGLPXQNBX-UHFFFAOYSA-N 2-methyl-n-[3-(methylamino)propyl]prop-2-enamide Chemical compound CNCCCNC(=O)C(C)=C RZRUOQGLPXQNBX-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- RINDUYMVZWQJDB-UHFFFAOYSA-N 4-amino-2-methylidenebutanamide Chemical compound NCCC(=C)C(N)=O RINDUYMVZWQJDB-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 101100232079 Arabidopsis thaliana HSR4 gene Proteins 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- IUMSDRXLFWAGNT-UHFFFAOYSA-N Dodecamethylcyclohexasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 IUMSDRXLFWAGNT-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- GADGMZDHLQLZRI-VIFPVBQESA-N N-(4-aminobenzoyl)-L-glutamic acid Chemical compound NC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 GADGMZDHLQLZRI-VIFPVBQESA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- GKDXBEQZAULDTI-UHFFFAOYSA-N [diethoxy(ethyl)silyl]oxy-(4-ethenylphenyl)-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC(C=C)=CC=1)(O[Si](CC)(OCC)OCC)C1=CC=CC=C1 GKDXBEQZAULDTI-UHFFFAOYSA-N 0.000 description 1
- RBVFNSJEHOOOSX-UHFFFAOYSA-N [dimethoxy(methyl)silyl]-(2-ethenylphenyl)-dimethylsilane Chemical compound CO[Si](C)(OC)[Si](C)(C)C1=CC=CC=C1C=C RBVFNSJEHOOOSX-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- GSFNTDSEFPQLJR-UHFFFAOYSA-N benzyl-ethenyl-dimethoxysilane Chemical compound CO[Si](C=C)(OC)CC1=CC=CC=C1 GSFNTDSEFPQLJR-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- HAURRGANAANPSQ-UHFFFAOYSA-N cis-2,4,6-Trimethyl-2,4,6-triphenylcyclotrisiloxane Chemical compound O1[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si]1(C)C1=CC=CC=C1 HAURRGANAANPSQ-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- UJTGYJODGVUOGO-UHFFFAOYSA-N diethoxy-methyl-propylsilane Chemical compound CCC[Si](C)(OCC)OCC UJTGYJODGVUOGO-UHFFFAOYSA-N 0.000 description 1
- WQTNGCZMPUCIEX-UHFFFAOYSA-N dimethoxy-methyl-prop-2-enylsilane Chemical compound CO[Si](C)(OC)CC=C WQTNGCZMPUCIEX-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- HTSRFYSEWIPFNI-UHFFFAOYSA-N ethyl-dimethoxy-methylsilane Chemical compound CC[Si](C)(OC)OC HTSRFYSEWIPFNI-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- QUPCNWFFTANZPX-UHFFFAOYSA-M paramenthane hydroperoxide Chemical compound [O-]O.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-M 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical compound CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- NNLPAMPVXAPWKG-UHFFFAOYSA-N trimethyl(1-methylethoxy)silane Chemical compound CC(C)O[Si](C)(C)C NNLPAMPVXAPWKG-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、ポリオルガノシロキサ
ン系重合体の水性分散体の存在下に、単量体成分を重合
して得られる、耐候性、密着性、耐水性、耐熱性に優れ
たポリオルガノシロキサン系エマルジョンに関する。[Industrial Application Field] The present invention is a polyorganosiloxane polymer that has excellent weather resistance, adhesion, water resistance, and heat resistance, and is obtained by polymerizing monomer components in the presence of an aqueous dispersion of a polyorganosiloxane polymer. The present invention relates to a polyorganosiloxane emulsion.
【０００２】0002
【従来の技術】近年、環境保全および安全衛生のため、
塗料の無公害化が強く要望されており、従来の溶剤型塗
料の水系化が行われつつある。そのため、水性塗料の用
途が拡大され、それにともなって水性塗料への要求性能
が高度になっている。この要求性能のなかで、塗膜の耐
久性は大きな解決課題として常に問題提起されている。
従来の水性塗料は、耐候性において劣り、塗膜表面の劣
化にともない、光沢を失ったり変色したりし、劣化が著
しい場合には塗膜が剥離する場合がある。また、密着性
、耐水性においても劣るため、基材と塗膜の間に水が侵
入することによって膨れが生じる。例えば、外装用塗料
の場合、これらの問題は非常に重要となる。これらの問
題点を解決するために、例えば特開昭５８−１８０５６
３号公報には、アクリル系共重合体エマルジョンにシリ
コン樹脂エマルジョンを配合したものを塗料主成分とし
て用いることが提案されている。しかしながら、アクリ
ル系共重合体エマルジョンとシリコン樹脂エマルジョン
との相溶性が悪く、塗膜形成時に分離してしまい、充分
な塗膜強度が得られない。[Prior Art] In recent years, for environmental protection and safety and health,
There is a strong demand for pollution-free paints, and conventional solvent-based paints are being replaced with water-based paints. Therefore, the uses of water-based paints have expanded, and the performance requirements for water-based paints have become more sophisticated. Among these required performances, the durability of the coating film is always being raised as a major problem to be solved. Conventional water-based paints have poor weather resistance, and as the surface of the paint film deteriorates, it loses its gloss or changes color, and if the deterioration is significant, the paint film may peel off. Furthermore, since the adhesion and water resistance are poor, blistering occurs due to water entering between the base material and the coating film. For example, in the case of exterior paints, these issues become very important. In order to solve these problems, for example, Japanese Patent Application Laid-Open No. 58-18056
Publication No. 3 proposes the use of a mixture of an acrylic copolymer emulsion and a silicone resin emulsion as the main component of the paint. However, the compatibility between the acrylic copolymer emulsion and the silicone resin emulsion is poor and they separate during coating film formation, making it impossible to obtain sufficient coating film strength.
【０００３】また、特開昭６２−２６７３７４号公報に
おいては、デシルトリメトキシシランなどのオルガノア
ルコキシシランの存在下に、ビニル系単量体を乳化重合
したものを塗料主成分として用いることが提案されてい
る。しかしながら、安定した分散体が得られず、充分な
耐候性、密着性、耐水性が得られない。耐候性の問題を
解決するための一つの手段として、ポリオルガノシロキ
サン系共重合体とビニル系単量体とのグラフト共重合体
を塗料主成分として用いることが考えられる。このグラ
フト共重合体の製造方法として、例えば特開昭６１−１
０６６１４号公報、特開昭６２−８１４１２号公報、特
開平１−９８６０９号公報などが提案されている。しか
しながら、これらの共重合体を水性塗料に用いた場合、
ポリオルガノシロキサン系共重合体とビニル系単量体と
の相溶性が不充分なため充分な耐候性が得られず、例え
ば外装塗料などの厳しい外的条件下には適さない。[0003] Furthermore, in JP-A No. 62-267374, it is proposed to use a vinyl monomer emulsion polymerized in the presence of an organoalkoxysilane such as decyltrimethoxysilane as the main component of a paint. ing. However, a stable dispersion cannot be obtained, and sufficient weather resistance, adhesion, and water resistance cannot be obtained. One possible means to solve the problem of weather resistance is to use a graft copolymer of a polyorganosiloxane copolymer and a vinyl monomer as the main component of the paint. As a method for producing this graft copolymer, for example, JP-A-61-1
06614, Japanese Patent Application Laid-Open No. 62-81412, Japanese Patent Application Laid-open No. 1-98609, etc. have been proposed. However, when these copolymers are used in water-based paints,
Since the compatibility between the polyorganosiloxane copolymer and the vinyl monomer is insufficient, sufficient weather resistance cannot be obtained, making it unsuitable for severe external conditions such as exterior paints.
【０００４】0004
【発明が解決しようとする課題】本発明は、以上のよう
な従来技術の課題を背景になされたもので、水性塗料に
用いた場合、塗膜に優れた耐候性、密着性、耐水性、耐
熱性を付与し、また水性塗料以外の用途に用いた場合に
も同様の優れた性質を有するエマルジョンを提供するこ
とにある。Problems to be Solved by the Invention The present invention was made against the background of the problems of the prior art as described above, and it provides a coating film with excellent weather resistance, adhesion, water resistance, and The object of the present invention is to provide an emulsion that has heat resistance and also has similar excellent properties when used in applications other than water-based paints.
【０００５】[0005]
【課題を解決するための手段】本発明は、オルガノシロ
キサン（Ｉ）に、グラフト交叉剤（ＩＩ） を（Ｉ）と
（ＩＩ） 成分の合計量に対し０．０２〜２０重量％共
縮合して得られるポリオルガノシロキサン系重合体（Ｉ
ＩＩ）１〜９０重量部（固形分）の水性分散体の存在下
に、（ａ）アルキル基の炭素数が１〜１０の（メタ）ア
クリル酸アルキルエステル１９．５〜９９．５重量％、
（ｂ）エチレン系不飽和カルボン酸０．５〜１５重量％
、および（ｃ）これらと共重合可能な他の単量体０〜８
０％〔ただし、（ａ）＋（ｂ）＋（ｃ）＝１００重量％
〕からなる単量体成分（ＩＶ） ９９〜１０重量部〔た
だし、（ＩＩＩ）＋（ＩＶ） ＝１００重量部〕を重合
することによって得られるポリオルガノシロキサン系エ
マルジョンを提供するものである。[Means for Solving the Problems] The present invention comprises cocondensing organosiloxane (I) with grafting agent (II) in an amount of 0.02 to 20% by weight based on the total amount of components (I) and (II). The polyorganosiloxane polymer (I
II) In the presence of 1 to 90 parts by weight (solid content) of an aqueous dispersion, (a) 19.5 to 99.5% by weight of a (meth)acrylic acid alkyl ester whose alkyl group has 1 to 10 carbon atoms;
(b) Ethylenically unsaturated carboxylic acid 0.5-15% by weight
, and (c) other monomers copolymerizable with these 0 to 8
0% [However, (a) + (b) + (c) = 100% by weight
The present invention provides a polyorganosiloxane emulsion obtained by polymerizing 99 to 10 parts by weight of monomer component (IV) [where (III) + (IV) = 100 parts by weight].
【０００６】本発明に使用されるオルガノシロキサン（
Ｉ）は、例えば一般式Ｒ１ ｍ ＳｉＯ（４−ｍ）／２
（式中、Ｒ１ は置換または非置換の１価の炭化水素
基であり、ｍは０〜３の整数を示す）で表される構造単
位を有するものであり、直鎖状、分岐状または環状構造
を有するが、好ましくは環状構造を有するオルガノシロ
キサンである。このオルガノシロキサン（Ｉ）の有する
置換または非置換の１価の炭化水素基としては、例えば
メチル基、エチル基、プロピル基、ビニル基、フェニル
基、およびそれらをハロゲン原子またはシアノ基で置換
した置換炭化水素基などを挙げることができる。また、
前記平均組成式中、ｎの値は０〜３の整数である。Organosiloxane used in the present invention (
I) has the general formula R1 m SiO(4-m)/2, for example
(wherein, R1 is a substituted or unsubstituted monovalent hydrocarbon group, m is an integer of 0 to 3), and has a linear, branched or cyclic structural unit. structure, preferably an organosiloxane having a cyclic structure. The substituted or unsubstituted monovalent hydrocarbon group possessed by this organosiloxane (I) includes, for example, a methyl group, an ethyl group, a propyl group, a vinyl group, a phenyl group, and substitutions thereof with a halogen atom or a cyano group. Examples include hydrocarbon groups. Also,
In the average compositional formula, the value of n is an integer of 0 to 3.
【０００７】オルガノシロキサン（Ｉ）の具体例として
は、ヘキサメチルシクロトリシロキサン、オクタメチル
シクロテトラシロキサン、デカメチルシクロペンタシロ
キサン、ドデカメチルシクロヘキサシロキサン、トリメ
チルトリフェニルシクロトリシロキサンなどの環状化合
物のほかに、直鎖状あるいは分岐状のオルガノシロキサ
ンを挙げることができる。なお、このオルガノシロキサ
ン（Ｉ）は、あらかじめ縮合された、例えばポリスチレ
ン換算の重量平均分子が５００〜１０，０００程度のポ
リオルガノシロキサンであってもよい。また、オルガノ
シロキサン（Ｉ）が、ポリオルガノシロキサンである場
合、その分子鎖末端は、例えば水酸基、アルコキシ基、
トリメチルシリル基、ジメチルビニルシリル基、メチル
フェニルビニルシリル基、メチルジフェニルシリル基な
どで封鎖されていてもよい。Specific examples of organosiloxane (I) include cyclic compounds such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and trimethyltriphenylcyclotrisiloxane. Examples include linear or branched organosiloxanes. The organosiloxane (I) may be a precondensed polyorganosiloxane having, for example, a weight average molecular weight of about 500 to 10,000 in terms of polystyrene. In addition, when organosiloxane (I) is a polyorganosiloxane, the molecular chain terminal thereof may be, for example, a hydroxyl group, an alkoxy group,
It may be blocked with a trimethylsilyl group, dimethylvinylsilyl group, methylphenylvinylsilyl group, methyldiphenylsilyl group, or the like.
【０００８】次に、本発明で使用されるグラフト交叉剤
（ＩＩ） は、例えば次のものを挙げることができる。
■化２[0008] Next, examples of the grafting agent (II) used in the present invention include the following. ■ Chemical 2
【化２】
（式中、Ｒ２ は水素原子または炭素数１〜６のアルキ
ル基、ｎは０〜１２の整数、好ましくは０を示す）で表
される不飽和基と、アルコキシシリル基とをあわせ持つ
グラフト交叉剤
■Ｒ３ ｐ ＳｉＯ（３−ｐ）／２ （式中、Ｒ３ は
ビニル基またはアリル基、ｐは０〜２の整数を示す。）
具体例；ビニルメチルジメトキシシラン、テトラビニル
テトラメチルシクロシロキサン、アリルメチルジメトキ
シシラン。
■ＨＳＲ４ ＳｉＲ５ ｑ Ｏ（３−ｑ）／２ （式中
、Ｒ４ は炭素数１〜１８の２価または３価の飽和脂肪
族炭化水素基、Ｒ５ は炭素数１〜６の脂肪族不飽和基
を含有しない１価の炭化水素基であり、ｑは０〜２の整
数を示す。）具体例；γ−メルカプトプロピルメチルジ
メトキシシラン
（式中、Ｒ６ は水素原子、メチル基、エチル基、プロ
ピル基またはフェニル基、ｒは１〜６の整数、ｓは０〜
２の整数を示す。）
具体例；γ−メタクリロキシプロピルメチルジメトキシ
シラン
これらのグラフト交叉剤（ＩＩ） のうち、特に好まし
くは前記■で表される不飽和基とアルコキシシリル基と
をあわせ持つ化合物である。[Formula 2] (wherein, R2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n is an integer of 0 to 12, preferably 0) and an alkoxysilyl group. Concomitant graft cross-agent ■R3 p SiO(3-p)/2 (In the formula, R3 is a vinyl group or an allyl group, and p is an integer from 0 to 2.)
Specific examples: vinylmethyldimethoxysilane, tetravinyltetramethylcyclosiloxane, allylmethyldimethoxysilane. ■HSR4 SiR5 q O(3-q)/2 (wherein, R4 is a divalent or trivalent saturated aliphatic hydrocarbon group having 1 to 18 carbon atoms, and R5 is an aliphatic unsaturated group having 1 to 6 carbon atoms. is a monovalent hydrocarbon group containing no or phenyl group, r is an integer of 1 to 6, s is 0 to
Indicates an integer of 2. ) Specific example: γ-methacryloxypropylmethyldimethoxysilane Among these grafting agents (II), particularly preferred are compounds having both an unsaturated group and an alkoxysilyl group represented by (1) above.
【０００９】この■グラフト交叉剤について、さらに詳
述すると、前記一般式のＲ２ としては、水素原子また
は炭素数１〜６のアルキル基であるが、水素原子または
炭素数１〜２のアルキル基が好ましく、さらに好ましく
は水素原子またはメチル基である。これらの■グラフト
交叉剤としては、具体的にはｐ−ビニルフェニルメチル
ジメトキシシラン、２−（ｍ−ビニルフェニル）エチル
メチルジメトキシシラン、１−（ｍ−ビニルフェニル）
メチルジメチルイソプロポキシシラン、２−（ｐ−ビニ
ルフェニル）エチルメチルジメトキシシラン、３−（ｐ
−ビニルフェノキシ）プロピルメチルジエトキシシラン
、３−（ｐ−ビニルベンゾイロキシ）プロピルメチルジ
メトキシシラン、１−（ｏ−ビニルフェニル）−１，１
，２−トリメチル−２，２−ジメトキシジシラン、１−
（ｐ−ビニルフェニル）−１，１−ジフェニル−３−エ
チル−３，３−ジエトキシジシロキサン、ｍ−ビニルフ
ェニル−〔３−（トリエトキシシリル）プロピル〕ジフ
ェニルシラン、〔３−（ｐ−イソプロペニルベンゾイル
アミノ）プロピル〕フェニルジプロポキシシランなどの
ほか、これらの混合物を挙げることができる。■グラフ
ト交叉剤としては、好ましくはｐ−ビニルフェニルメチ
ルジメトキシシラン、２−（ｐ−ビニルフェニル）エチ
ルメチルジメトキシシラン、３−（ｐ−ビニルベンゾイ
ロキシ）プロピルメチルジメトキシシランであり、さら
に好ましくはｐ−ビニルフェニルメチルジメトキシシラ
ンである。この■グラフト交叉剤を用いたものは、グラ
フト率の高いものが得られ、従って一段と優れた本発明
の目的とするエマルジョンが得られる。To explain this (1) graft cross-agent in more detail, R2 in the above general formula is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Preferably, a hydrogen atom or a methyl group is more preferable. Specific examples of these graft cross-agents include p-vinylphenylmethyldimethoxysilane, 2-(m-vinylphenyl)ethylmethyldimethoxysilane, and 1-(m-vinylphenyl).
Methyldimethylisopropoxysilane, 2-(p-vinylphenyl)ethylmethyldimethoxysilane, 3-(p-vinylphenyl)ethylmethyldimethoxysilane,
-vinylphenoxy)propylmethyldiethoxysilane, 3-(p-vinylbenzoyloxy)propylmethyldimethoxysilane, 1-(o-vinylphenyl)-1,1
, 2-trimethyl-2,2-dimethoxydisilane, 1-
(p-vinylphenyl)-1,1-diphenyl-3-ethyl-3,3-diethoxydisiloxane, m-vinylphenyl-[3-(triethoxysilyl)propyl]diphenylsilane, [3-(p- Examples include isopropenylbenzoylamino)propyl]phenyldipropoxysilane, as well as mixtures thereof. ■ The grafting cross-agent is preferably p-vinylphenylmethyldimethoxysilane, 2-(p-vinylphenyl)ethylmethyldimethoxysilane, or 3-(p-vinylbenzoyloxy)propylmethyldimethoxysilane, more preferably p-vinylphenylmethyldimethoxysilane. When this (1) graft cross-agent is used, a high grafting rate can be obtained, and therefore a much more excellent emulsion, which is the object of the present invention, can be obtained.
【００１０】以上のグラフト交叉剤（ＩＩ） の使用割
合は、（Ｉ）成分と（ＩＩ） 成分の合計量中、０．０
２〜２０重量％、好ましく０．１〜１０重量％、さらに
好ましく０．５〜５重量％であり、０．２重量％未満で
は得られるポリオルガノシロキサン系重合体（ＩＩＩ）
と単量体成分（ＩＶ） とのグラフト重合において高い
グラフト率が得られず、その結果、塗膜としての充分な
強度が得られない。一方、グラフト交叉剤（ＩＩ） の
割合が２０重量％を超えると、グラフト率は増大するが
、グラフト交叉剤（ＩＩ） の増加とともに重合体が低
分子量となり、その結果、塗膜としての充分な強度が得
られない。The proportion of the above-mentioned graft cross-agent (II) used is 0.0 in the total amount of components (I) and (II).
2 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, and if it is less than 0.2% by weight, the resulting polyorganosiloxane polymer (III)
In the graft polymerization of the monomer component (IV) and the monomer component (IV), a high grafting ratio cannot be obtained, and as a result, sufficient strength as a coating film cannot be obtained. On the other hand, when the proportion of the grafting agent (II) exceeds 20% by weight, the grafting rate increases, but as the amount of the grafting agent (II) increases, the polymer becomes lower in molecular weight, and as a result, it becomes insufficient to form a coating film. Strength cannot be obtained.
【００１１】ポリオルガノシロキサン系重合体（ＩＩＩ
）は、前記オルガノシロキサン（Ｉ）とグラフト交叉剤
（ＩＩ） とを、例えばアルキルベンゼンスルホン酸な
どの乳化剤の存在下にホモミキサーなどを用いて剪断混
合し、縮合させることによって製造することができる。
この乳化剤は、オルガノシロキサンの乳化剤として作用
するほか、縮合開始剤となる。この乳化剤の使用量は、
（Ｉ）成分および（ＩＩ） 成分の合計量に対して、通
常、０．１〜５重量％、好ましくは０．３〜３重量％程
度である。なお、この際の水の使用量は、（Ｉ）成分お
よび（ＩＩ） 成分合計量１００重量部に対して、通常
、１００〜５００重量部、好ましくは２００〜４００重
量部である。また、縮合温度は、通常、５〜１００℃で
ある。なお、このようにして得られるポリオルガノシロ
キサン系重合体（ＩＩＩ）のポリスチレン換算重量平均
分子量は、好ましく３０，０００〜１，０００，０００
、さらに好ましく５０，０００〜３００，０００程度で
あり、３０，０００未満では得られる塗膜の強度が不充
分であり、一方１，０００，０００を超えると密着性が
低下する。Polyorganosiloxane polymer (III
) can be produced by shear mixing the organosiloxane (I) and the grafting agent (II) using a homomixer in the presence of an emulsifier such as alkylbenzenesulfonic acid, and condensing the mixture. This emulsifier acts as an emulsifier for organosiloxane and also serves as a condensation initiator. The amount of emulsifier used is
It is usually about 0.1 to 5% by weight, preferably about 0.3 to 3% by weight, based on the total amount of component (I) and component (II). The amount of water used in this case is usually 100 to 500 parts by weight, preferably 200 to 400 parts by weight, based on 100 parts by weight of the total amount of components (I) and (II). Moreover, the condensation temperature is usually 5 to 100°C. The polyorganosiloxane polymer (III) thus obtained preferably has a weight average molecular weight in terms of polystyrene of 30,000 to 1,000,000.
, more preferably about 50,000 to 300,000. If it is less than 30,000, the strength of the resulting coating film will be insufficient, while if it exceeds 1,000,000, the adhesion will decrease.
【００１２】本発明のポリオルガノシロキサン系エマル
ジョンは、このようにして得られるポリオルガノシロキ
サン系重合体（ＩＩＩ）の水性分散体の存在下に、（ａ
）アルキル基の炭素数が１〜１０の（メタ）アクリル酸
アルキルエステル（ｂ）エチレン系不飽和カルボン酸、
および（ｃ）これらと共重合可能な他の単量体からなる
単量体成分（ＩＶ） を重合することによって得られる
。The polyorganosiloxane emulsion of the present invention is prepared by dispersing (a) in the presence of the aqueous dispersion of the polyorganosiloxane polymer (III) thus obtained.
) (meth)acrylic acid alkyl ester whose alkyl group has 1 to 10 carbon atoms (b) ethylenically unsaturated carboxylic acid,
and (c) obtained by polymerizing monomer component (IV) consisting of another monomer copolymerizable with these.
【００１３】ここで、単量体成分（ＩＶ） を構成する
（ａ）アルキル基の炭素数が１〜１０の（メタ）アクリ
ル酸アルキルエステルとしては、例えば（メタ）アクリ
ル酸メチル、（メタ）アクリルアクリル酸エチル、（メ
タ）アクリル酸ｎ−プロピル、（メタ）アクリル酸ｉ−
プロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）ア
クリル酸ｉ−ブチル、（メタ）アクリル酸ｎ−アミル、
（メタ）アクリル酸ｉ−アミル、（メタ）アクリル酸ヘ
キシル、（メタ）アクリル酸２−エチルヘキシル、（メ
タ）アクリル酸オクチル、（メタ）アクリル酸ｉ−ノニ
ル、（メタ）アクリル酸デシル、ヒドロキシメチル（メ
タ）アクリレート、ヒドロキシエチル（メタ）アクリレ
ートなどが挙げられる。これらの（ａ）（メタ）アクリ
ル酸アルキルエステルは、１種単独でも、あるいは２種
以上を併用することもできる。この（ａ）（メタ）アク
リル酸アルキルエステルは、得られるエマルジョンに弾
性、強度、接着力を与えるために必須の成分であり、そ
の割合は、単量体成分（ＩＶ） 中、１９．５〜９９．
５重量％、好ましくは３０〜９９重量％、さらに好まし
くは４０〜９８重量％であり、１９．５重量％未満では
弾性、強度に劣り、一方９９．５重量％を超えると重合
系の安定性が劣り、また接着力などが劣り好ましくない
。[0013] Examples of the (meth)acrylic acid alkyl ester in which the alkyl group (a) has 1 to 10 carbon atoms constituting the monomer component (IV) include, for example, methyl (meth)acrylate, (meth)acrylate, Acrylic ethyl acrylate, n-propyl (meth)acrylate, i-(meth)acrylate
Propyl, n-butyl (meth)acrylate, i-butyl (meth)acrylate, n-amyl (meth)acrylate,
i-amyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, i-nonyl (meth)acrylate, decyl (meth)acrylate, hydroxymethyl Examples include (meth)acrylate and hydroxyethyl (meth)acrylate. These (a) (meth)acrylic acid alkyl esters can be used alone or in combination of two or more. This (meth)acrylic acid alkyl ester (a) is an essential component for imparting elasticity, strength, and adhesive strength to the resulting emulsion, and its proportion in the monomer component (IV) is from 19.5 to 99.
5% by weight, preferably 30 to 99% by weight, more preferably 40 to 98% by weight; less than 19.5% by weight results in poor elasticity and strength, while more than 99.5% by weight deteriorates the stability of the polymerization system. It is not preferable because it has poor adhesive strength and poor adhesion.
【００１４】また、単量体成分（ＩＶ） を構成する（
ｂ）エチレン性不飽和カルボン酸としては、例えばイタ
コン酸、（メタ）アクリル酸、フマル酸、マレイン酸、
クロトン酸などが挙げられ、好ましくは（メタ）アクリ
ル酸である。これらの（ｂ）エチレン性不飽和カルボン
酸は、１種単独でも、あるいは２種以上を併用すること
もできる。この（ｂ）エチレン性不飽和カルボン酸は、
得られるエマルジョンの安定性と耐水性のバランスを高
水準に保つために必須の成分であって、その使用量は、
単量体成分（ＩＶ） 中、０．５〜１５重量％、好まし
くは０．５〜１０重量％であり、０．５重量％未満では
得られるエマルジョンの安定性が低下し、一方１５重量
％を超えると耐水性に劣るものとなる。[0014] Furthermore, monomer component (IV) is composed of (
b) Examples of ethylenically unsaturated carboxylic acids include itaconic acid, (meth)acrylic acid, fumaric acid, maleic acid,
Examples include crotonic acid, and (meth)acrylic acid is preferred. These (b) ethylenically unsaturated carboxylic acids may be used alone or in combination of two or more. This (b) ethylenically unsaturated carboxylic acid is
It is an essential component to maintain a high level of balance between stability and water resistance of the resulting emulsion, and its usage amount is as follows:
Monomer component (IV) 0.5 to 15% by weight, preferably 0.5 to 10% by weight; less than 0.5% by weight reduces the stability of the resulting emulsion; If it exceeds this, the water resistance will be poor.
【００１５】さらに、（ｃ）これらと共重合可能な他の
単量体としては、例えば１，３−ブタジエン、イソプレ
ン、２−クロル−１，３−ブタジエンなどの脂肪族共役
ジエン；スチレン、α−メチルスチレン、ビニルトルエ
ンなどの芳香族ビニル化合物；（メタ）アクリルアミド
、Ｎ−メチロールアクリルアミドなどのエチレン性不飽
和カルボン酸のアルキルアミド；酢酸ビニル、プロピオ
ン酸ビニルなどのカルボン酸ビニルエステル；エチレン
系不飽和ジカルボン酸の、酸無水物、モノアルキルエス
テル、モノアミド類；アミノエチルアクリレート、ジメ
チルアミノエチルアクリレート、ブチルアミノエチルア
クリレートなどのエチレン系不飽和カルボン酸のアミノ
アルキルエステル；アミノエチルアクリルアミド、ジメ
チルアミノメチルメタクリルアミド、メチルアミノプロ
ピルメタクリルアミドなどのエチレン系不飽和カルボン
酸のアミノアルキルアミド；（メタ）アクリロニトリル
、α−クロルアクリロニトリルなどのシアン化ビニル系
化合物；グリシジル（メタ）アクリレートなどの不飽和
脂肪族グリシジルエステルなどを挙げることができるが
、好ましくは１，３−ブタジエン、スチレン、アクリロ
ニトリル、α−メチルスチレンなどである。これらの（
ｃ）共重合可能な他の単量体は、１種単独でもあるいは
２種以上を併用することができる。（ｃ）共重合可能な
他の単量体の使用量は、単量体成分（ＩＶ） 中、０〜
８０重量％、好ましくは２０〜６０重量％であり、８０
重量％を超えると造膜性の低下、成膜後の変色、塗膜の
収縮などの問題があり好ましくない。Furthermore, (c) other monomers copolymerizable with these include, for example, aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and 2-chloro-1,3-butadiene; styrene, α - Aromatic vinyl compounds such as methylstyrene and vinyltoluene; Alkylamides of ethylenically unsaturated carboxylic acids such as (meth)acrylamide and N-methylolacrylamide; Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; Acid anhydrides, monoalkyl esters, monoamides of saturated dicarboxylic acids; aminoalkyl esters of ethylenically unsaturated carboxylic acids such as aminoethyl acrylate, dimethylaminoethyl acrylate, butylaminoethyl acrylate; aminoethyl acrylamide, dimethylaminomethyl methacrylate Aminoalkylamides of ethylenically unsaturated carboxylic acids such as amides and methylaminopropyl methacrylamide; vinyl cyanide compounds such as (meth)acrylonitrile and α-chloroacrylonitrile; unsaturated aliphatic glycidyl esters such as glycidyl (meth)acrylate Preferable examples include 1,3-butadiene, styrene, acrylonitrile, and α-methylstyrene. these(
c) Other copolymerizable monomers may be used alone or in combination of two or more. (c) The amount of the other copolymerizable monomer used is 0 to 0 in monomer component (IV).
80% by weight, preferably 20-60% by weight, and 80% by weight, preferably 20-60% by weight.
If it exceeds % by weight, problems such as a decrease in film-forming properties, discoloration after film formation, and shrinkage of the coating film are undesirable.
【００１６】ポリオルガノシロキサン系重合体（ＩＩＩ
）の水性分散体存在下で単量体成分（ＩＶ） を重合す
る際の仕込み組成は、（ＩＩＩ）成分（固形分換算）が
１〜９０重量部、好ましくは３〜５０重量部、さらに好
ましくは５〜３０重量部であり、（ＩＶ） 成分が９９
〜１重量部、好ましくは９７〜５０重量部、さらに好ま
しくは９５〜７０重量部〔ただし、（ＩＩＩ）＋（ＩＶ
） ＝１００重量部〕である。ここで、ポリオルガノシ
ロキサン系重合体（ＩＩＩ）が１重量部未満では、充分
な耐候性、密着性、耐水性が得られず、一方９０重量部
を超えると、塗膜としての充分な強度が得られず、また
成膜性も悪化する。Polyorganosiloxane polymer (III
) The charging composition for polymerizing monomer component (IV) in the presence of an aqueous dispersion of component (III) (in terms of solid content) is 1 to 90 parts by weight, preferably 3 to 50 parts by weight, more preferably 3 to 50 parts by weight. is 5 to 30 parts by weight, and the component (IV) is 99
~1 part by weight, preferably 97 to 50 parts by weight, more preferably 95 to 70 parts by weight [However, (III) + (IV
) = 100 parts by weight]. If the polyorganosiloxane polymer (III) is less than 1 part by weight, sufficient weather resistance, adhesion and water resistance cannot be obtained, while if it exceeds 90 parts by weight, sufficient strength as a coating film cannot be obtained. In addition, the film formability deteriorates.
【００１７】なお、このようにして得られるポリオルガ
ノシロキサン系エマルジョンを構成する重合体〔グラフ
ト共重合体のほか、グラフトされていない（共）重合体
を含む〕のグラフト率は、通常、５重量％以上、好まし
くは１０重量％以上、さらに好ましくは３０重量％以上
程度である。このように、ポリオルガノシロキサン系エ
マルジョンを構成する重合体のグラフト率が高いと、グ
ラフト共重合体とグラフトしなかった（共）重合体との
間の界面接着力が増大し、成膜時に塗膜として充分な強
度が得られる。[0017] The grafting ratio of the polymer [including the graft copolymer and non-grafted (co)polymer] constituting the polyorganosiloxane emulsion thus obtained is usually 5% by weight. % or more, preferably 10% by weight or more, more preferably 30% by weight or more. In this way, when the grafting rate of the polymer constituting the polyorganosiloxane emulsion is high, the interfacial adhesion between the graft copolymer and the non-grafted (co)polymer increases, and the coating during film formation increases. Sufficient strength can be obtained as a membrane.
【００１８】本発明のポリオルガノシロキサン系エマル
ジョンを製造するに際しては、ポリオルガノシロキサン
系重合体（ＩＩＩ）の水性分散体に、単量体成分（ＩＶ
） を通常のラジカル重合によってグラフト重合するこ
とによって得られる。また、ラジカル重合開始剤として
は、例えばクメンハイドロパーオキサイド、ジイソプロ
ピルベンゼンハイドロパーオキサイド、パラメンタンハ
イドロパーオキサイドなどの有機ハイドロパーオキサイ
ド類からなる酸化剤と、含糖ピロリン酸鉄処方、スルホ
キシレート処方、含糖ピロリン酸鉄処方／スルホキシレ
ート処方の混合処方などの還元剤との組み合わせによる
レドックス系の開始剤；過硫酸カリウム、過硫酸アンモ
ニウムなどの過硫酸塩；アゾビスイソブチロニトリル、
ジメチル−２，２′−アゾビスイソブチレート、２−カ
ルバモイルアザイソブチロニトリルなどのアゾ化合物；
ベンゾイルパーオキサイド、ラウロイルパーオキサイド
などの有機過酸化物などを挙げることができ、好ましく
は前記レドックス系の開始剤である。これらのラジカル
重合開始剤の使用量は、使用される単量体成分（ＩＶ）
１００重量部に対し、通常、０．０５〜５重量部、好
ましくは０．１〜２重量部程度である。When producing the polyorganosiloxane emulsion of the present invention, the monomer component (IV) is added to the aqueous dispersion of the polyorganosiloxane polymer (III).
) is obtained by graft polymerization using normal radical polymerization. In addition, as a radical polymerization initiator, for example, an oxidizing agent consisting of an organic hydroperoxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, para-menthane hydroperoxide, a sugar-containing iron pyrophosphate formulation, or a sulfoxylate formulation. , a redox initiator in combination with a reducing agent such as a mixed formulation of sugar-containing iron pyrophosphate formulation/sulfoxylate formulation; persulfates such as potassium persulfate and ammonium persulfate; azobisisobutyronitrile,
Azo compounds such as dimethyl-2,2'-azobisisobutyrate and 2-carbamoylazaisobutyronitrile;
Examples include organic peroxides such as benzoyl peroxide and lauroyl peroxide, and the redox-based initiators are preferred. The amount of these radical polymerization initiators to be used depends on the monomer component (IV) used.
It is usually about 0.05 to 5 parts by weight, preferably about 0.1 to 2 parts by weight per 100 parts by weight.
【００１９】この際のラジカル重合法としては、乳化重
合によって実施することが好ましい。乳化重合に際して
は、公知の乳化剤、前記ラジカル開始剤、連鎖移動剤な
どが使用される。ここで、乳化剤としては、ドデシルベ
ンゼンスルホン酸ナトリウム、ラウリル硫酸ナトリウム
、ジフェニルエーテルジスルホン酸ナトリウム、コハク
酸ジアルカリエステルスルホン酸ナトリウムなどのアニ
オン系乳化剤、あるいはポリオキシエチレンアルキルエ
ステル、ポリオキシエチレンアルキルアリルエーテルな
どのノニオン系乳化剤の１種または２種以上を挙げるこ
とができる。乳化剤の使用量は、単量体成分（ＩＶ）
に対して、通常、０．１〜１０重量％、好ましくは０．
１〜５重量％程度である。連鎖移動剤としては、ｔ−ド
デシルメルカプタン、オクチルメルカプタン、ｎ−テト
ラデシルメルカプタン、ｎ−ヘキシルメルカプタンなど
のメルカプタン類；四塩化炭素、臭化エチレンなどのハ
ロゲン化合物が、単量体成分（ＩＶ） に対して、通常
、０．０２〜１重量％使用される。乳化重合に際しては
、ラジカル重合開始剤、乳化剤、連鎖移動剤などのほか
に、必要に応じて各種電解質、ｐＨ調整剤などを併用し
て、単量体成分（ＩＶ） １００重量部に対して、通常
、水を１００〜５００重量部と、前記ラジカル重合開始
剤、乳化剤、連鎖移動剤などを前記範囲内の量を使用し
、重合温度５〜１００℃、好ましくは５０〜９０℃、重
合時間０．１〜１０時間の条件で乳化重合される。なお
、この乳化重合の場合は、オルガノシロキサン（Ｉ）と
グラフト交叉剤（ＩＩ）との縮合によって得られる、ポ
リオルガノシロキサン系重合体（ＩＩＩ）を含有する水
性分散体に、直接、単量体成分（ＩＶ） およびラジカ
ル開始剤を加えることによって実施することが好ましい
。As the radical polymerization method in this case, it is preferable to carry out emulsion polymerization. During emulsion polymerization, known emulsifiers, the aforementioned radical initiators, chain transfer agents, and the like are used. Here, as the emulsifier, anionic emulsifiers such as sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium diphenyl ether disulfonate, sodium dialkali succinate sulfonate, polyoxyethylene alkyl ester, polyoxyethylene alkyl allyl ether, etc. One or more nonionic emulsifiers may be used. The amount of emulsifier used is the monomer component (IV)
, usually 0.1 to 10% by weight, preferably 0.1 to 10% by weight.
It is about 1 to 5% by weight. Examples of chain transfer agents include mercaptans such as t-dodecylmercaptan, octylmercaptan, n-tetradecylmercaptan, and n-hexylmercaptan; halogen compounds such as carbon tetrachloride and ethylene bromide; On the other hand, it is usually used in an amount of 0.02 to 1% by weight. During emulsion polymerization, in addition to radical polymerization initiators, emulsifiers, chain transfer agents, etc., various electrolytes, pH adjusters, etc. are used in combination as necessary, and for 100 parts by weight of monomer component (IV), Usually, 100 to 500 parts by weight of water, the radical polymerization initiator, emulsifier, chain transfer agent, etc. are used in amounts within the above ranges, the polymerization temperature is 5 to 100°C, preferably 50 to 90°C, and the polymerization time is 0. Emulsion polymerization is carried out for 1 to 10 hours. In the case of this emulsion polymerization, the monomer is directly added to the aqueous dispersion containing the polyorganosiloxane polymer (III) obtained by condensation of the organosiloxane (I) and the grafting agent (II). It is preferably carried out by adding component (IV) and a radical initiator.
【００２０】また、前記各単量体（ａ）〜（ｃ）成分の
添加方法は特に制限されるものではなく、一括添加法、
連続添加法あるいは分割添加法などの任意の方法が採用
される。さらに、得られるエマルジョンの重合転化率は
、９９．５％以上であることが好ましい。さらに、本発
明のポリオルガノシロキサン系エマルジョンを得るに際
して、シード重合を採用する場合には、ポリオルガノシ
ロキサン系重合体（ＩＩＩ）をシード粒子とし、これに
単量体成分（ＩＶ） を加えて乳化重合すればよい。以
上のようにして得られるポリオルガノシロキサン系エマ
ルジョンのポリスチレン換算重量平均分子量は、特に限
定されないが、皮膜の弾性・強度や接着性から好ましく
は５０，０００〜２，０００，０００、さらに好ましく
は１００，０００〜５００，０００であり、５０，００
０未満では弾性、強度が不充分であり、一方２，０００
，０００を超えると接着力が低下するので好ましくない
。[0020] The method of adding each of the monomers (a) to (c) is not particularly limited, and may include a bulk addition method,
Any method such as a continuous addition method or a divided addition method may be employed. Furthermore, the polymerization conversion rate of the resulting emulsion is preferably 99.5% or more. Furthermore, when seed polymerization is employed to obtain the polyorganosiloxane emulsion of the present invention, the polyorganosiloxane polymer (III) is used as seed particles, and the monomer component (IV) is added thereto to emulsify. All it has to do is polymerize. The polystyrene equivalent weight average molecular weight of the polyorganosiloxane emulsion obtained as described above is not particularly limited, but is preferably from 50,000 to 2,000,000, more preferably from 100,000 to 2,000,000 in view of the elasticity/strength and adhesiveness of the film. ,000 to 500,000 and 50,00
If it is less than 0, the elasticity and strength are insufficient; on the other hand, if it is less than 2,000
,000 is not preferable because the adhesive strength decreases.
【００２１】また、本発明のポリオルガノシロキサン系
エマルジョンは、塗膜に優れた耐熱性や表面の強度・耐
候性を付与するために、該エマルジョンを構成する重合
体〔グラフト共重合体およびグラフトしていない（共）
重合体を含む〕の示差熱分析計により測定されるガラス
転移温度の最も高い値は、通常、８０℃以下、好ましく
は−６０℃〜＋６０℃、さらに好ましくは−３０℃〜＋
３０℃である。このガラス転移温度は、ポリオルガノシ
ロキサン系重合体（ＩＩＩ）と単量体成分（ＩＶ） の
仕込み組成、あるいは単量体成分（ＩＶ） 中の単量体
の組成を調整することによって適宜、決定される。なお
、本発明のポリオルガノシロキサン系エマルジョンの粒
子径は、好ましくは３００〜６，０００Å、さらに好ま
しくは１，０００〜６，０００Åの粒子が全粒子の８０
重量％以上である粒子径分布を持つことは望ましい。粒
子径分布をこのような範囲にあるようになすと、造膜性
がよく、系の安定性が保たれ、かつ物性のバランスが取
れるという効果を奏する。ここで、このエマルジョンの
粒子径の調整は、乳化剤の量、重合温度などを調整する
ことにより容易に実施することができる。[0021] In addition, the polyorganosiloxane emulsion of the present invention contains polymers [graft copolymer and graft copolymer] constituting the emulsion in order to impart excellent heat resistance, surface strength and weather resistance to the coating film. Not (joint)
The highest value of the glass transition temperature measured by a differential thermal analyzer (containing a polymer) is usually 80°C or lower, preferably -60°C to +60°C, more preferably -30°C to +
The temperature is 30°C. This glass transition temperature is determined as appropriate by adjusting the charging composition of the polyorganosiloxane polymer (III) and the monomer component (IV) or the composition of the monomers in the monomer component (IV). be done. The particle diameter of the polyorganosiloxane emulsion of the present invention is preferably 300 to 6,000 Å, more preferably 80 to 6,000 Å of the total particles.
It is desirable to have a particle size distribution that is greater than or equal to % by weight. When the particle size distribution is within this range, it is possible to achieve good film-forming properties, maintain system stability, and balance physical properties. Here, the particle size of this emulsion can be easily adjusted by adjusting the amount of emulsifier, polymerization temperature, etc.
【００２２】また、本発明のポリオルガノシロキサン系
エマルジョンの固形分濃度は、通常、２０〜７０重量％
、好ましくは３０〜６０重量％程度である。以上のよう
にして得られる本発明のポリオルガノシロキサン系エマ
ルジョンは、優れた耐候性、密着性、耐水性を有するも
のであり、特に水性塗料に用いた場合、一層優れた効果
が発揮される。本発明のポリオルガノシロキサン系エマ
ルジョンは、クリヤー塗料、着色塗料双方に使用でき、
木材、紙、合成樹脂、ガラス、金属、コンクリート、モ
ルタル、セメント、スレート、大理石、陶磁器、セッコ
ウ、皮革などのあらゆる基材に塗布することができる。
従って、本発明のエマルジョンは、多種の用途に使用可
能であるが、水性塗料として、特に建築内装・外装用、
鋼構造物用、コンクリート構造物用、屋根用、建材用、
ＰＣＭ用、自動車塗装用、缶コート用、アルミコーティ
ング用に好適である。また、水性塗料以外に、粘着剤用
、フロアーポリッシュ用、セメント混和剤用、カーペッ
トバッキング剤用、シーラント用、紙・繊維コーティン
グおよび含浸用としても使用できる。Further, the solid content concentration of the polyorganosiloxane emulsion of the present invention is usually 20 to 70% by weight.
, preferably about 30 to 60% by weight. The polyorganosiloxane emulsion of the present invention obtained as described above has excellent weather resistance, adhesion, and water resistance, and particularly when used in a water-based paint, even more excellent effects are exhibited. The polyorganosiloxane emulsion of the present invention can be used for both clear paints and colored paints,
It can be applied to all substrates including wood, paper, synthetic resin, glass, metal, concrete, mortar, cement, slate, marble, ceramics, gypsum, and leather. Therefore, the emulsion of the present invention can be used for a variety of purposes, but it can be used as a water-based paint, especially for interior and exterior buildings.
For steel structures, concrete structures, roofs, building materials,
Suitable for PCM, automobile painting, can coating, and aluminum coating. In addition to water-based paints, it can also be used for adhesives, floor polishes, cement admixtures, carpet backing agents, sealants, paper/fiber coatings, and impregnation.
【００２３】[0023]
【実施例】以下、実施例を挙げて本発明をさらに詳細に
説明する。なお、実施例中の部および％は、特に断らな
い限り重量部および重量％である。また、実施例中、各
種の測定項目は、下記に従った。
ガラス転移温度（Ｔｇ）
ガラス転移温度（Ｔｇ）は、理学電気（株）製の示差走
査熱量分析計（ＤＳＣ）を用い、次の条件で測定した。
■サンプルの約５ｇをガラス板に薄く引き伸ばし、２５
℃で７日間乾燥させ、ポリマーフィルムを得た。
■得られた乾燥フィルムのＴｇを測定した。単位は、℃
である。
条件；昇温速度 ２０℃／分
雰囲気 チッ素ガス
サンプル量 ２０ｍｇ
グラフト率
グラフト重合生成物の一定量（Ｘ）をアセトン中に投入
し、振とう機で２時間振とうし、遊離の重合体を溶解さ
せる。次いで、遠心分離機を用いて回転数２３，０００
ｒｐｍで３０分間遠心分離し、不溶分を得る。次に、真
空乾燥機を用いて１２０℃で１時間乾燥させ、不溶分重
量（Ｙ）を得、次式によりグラフト率を算出するもので
ある。
グラフト率（％）＝｛（Ｙ）−〔（Ｘ）×（グラフト重
合生成物中の（ＩＩＩ）成分分率〕｝×１００／｛（Ｘ
）×〔グラフト重合生成物中の（ＩＩＩ）成分の成分分
率〕｝粒子径
大塚電子（株）製、ＬＰＡ３１００ Ｌａｓｅｒ
Ｐａｒｔｉｃｌｅ Ａｎａｌｙｚｅｒ によって粒
子径分布を測定し、粒子径が３００〜８，０００Åにあ
る粒子の全粒子中の％を求めた。[Examples] The present invention will be explained in more detail below with reference to Examples. Note that parts and % in the examples are parts by weight and % by weight unless otherwise specified. In addition, various measurement items in the examples were as follows. Glass Transition Temperature (Tg) Glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC) manufactured by Rigaku Denki Co., Ltd. under the following conditions. ■Spread approximately 5g of the sample thinly on a glass plate, and
It was dried at ℃ for 7 days to obtain a polymer film. (2) The Tg of the obtained dry film was measured. The unit is ℃
It is. Conditions: Temperature increase rate: 20°C/min Atmosphere: Nitrogen gas sample amount: 20mg Graft ratio: A certain amount (X) of the graft polymerization product was placed in acetone and shaken for 2 hours with a shaker to remove the free polymer. Dissolve. Next, the rotation speed was 23,000 using a centrifuge.
Centrifuge at rpm for 30 minutes to obtain insoluble matter. Next, it is dried at 120° C. for 1 hour using a vacuum dryer to obtain the weight of insoluble matter (Y), and the grafting rate is calculated using the following formula. Grafting rate (%) = {(Y) - [(X) x ((III) component fraction in graft polymerization product]) x 100/{(X
)×[Component fraction of component (III) in graft polymerization product]} Particle size LPA3100 Laser manufactured by Otsuka Electronics Co., Ltd.
The particle size distribution was measured using a Particle Analyzer, and the percentage of particles having a particle size of 300 to 8,000 Å to all particles was determined.
【００２４】耐候性試験
サンシャインウエザーメーター〔スガ試験機（株）製、
Ｄｅｗ ＣｙｃｌｅＷＥＬ−ＳＵＮ−ＤＣ型〕（６３
℃）を用い、３００時間暴露後、光沢保持率、黄変度を
測定した。ここで、光沢は、ＪＩＳ Ｋ５４００に基
づき、６０°鏡面光沢度を測定した。光沢保持率の単位
は、％である。また、黄変度は、ＳＭカラーコンピュー
ター〔スガ試験機（株）製、ＳＭ−５−１Ｓ−３Ｂ型〕
を用いて測定した。黄変度の単位は、ΔＹＩ である。
密着性
ＪＩＳ Ｋ５４００の碁盤目試験により測定し、下記
に示す定められた評価点数によって判定を行った。
評価点数＝１０；切り傷の１本ごとが、細くて両側が滑
らかで、切り傷の交点と正方形の一目一目に剥がれがな
い。
評価点＝８；切り傷の交点に僅かな剥がれがあって、正
方形の一目一目に剥がれがなく、欠損部の面積は全正方
形の５％以内。
評価点＝６；切り傷の両側と交点とに剥がれがあって、
欠損部の面積は全正方形面積の５〜１５％。
評価点＝４；切り傷による剥がれの幅が広く、欠損部の
面積は全正方形面積の１５〜３５％。
評価点＝２；切り傷による剥がれの幅は４点よりも広く
、欠損部の面積は全正方形面積の３５〜６５％。
評価点＝０；剥がれの面積は、全正方形面積の６５％以
上。
耐水性試験
蒸留水（２０℃）に２４時間浸漬した後の塗膜の状態に
よって判定した。（塗料膜厚＝５００μｍ）◎・・・優
秀
○・・・良好
△・・・普通
×・・・悪い
耐熱性試験
ギヤオーブン中で１２０℃で２４時間の熱処理を行い、
その後の熱変色を肉眼で観察した。（塗料膜厚＝５００
μｍ）
○・・・熱変色なし。
△・・・熱変色が若干ある。
×・・・熱変色がおおいにある。Weather resistance test Sunshine weather meter [manufactured by Suga Test Instruments Co., Ltd.]
Dew CycleWEL-SUN-DC type] (63
After exposure for 300 hours, gloss retention and yellowing degree were measured. Here, the gloss was measured as 60° specular gloss based on JIS K5400. The unit of gloss retention is %. In addition, the degree of yellowing was measured using an SM color computer [manufactured by Suga Test Instruments Co., Ltd., type SM-5-1S-3B].
Measured using The unit of yellowing degree is ΔYI. Adhesion was measured by a JIS K5400 checkerboard test, and judged based on the prescribed evaluation scores shown below. Evaluation score = 10; Each cut is thin and smooth on both sides, and there is no peeling at the intersection of the cuts and the square. Evaluation score = 8; There is slight peeling at the intersection of the cuts, there is no peeling at every glance of the square, and the area of the defective part is within 5% of the total square. Evaluation score = 6; There was peeling on both sides of the cut and at the intersection,
The area of the defective part is 5-15% of the total square area. Evaluation score = 4: The width of the peeling due to the cut is wide, and the area of the defective part is 15 to 35% of the total square area. Evaluation score = 2: The width of the peeling due to the cut is wider than the score 4, and the area of the defective part is 35 to 65% of the total square area. Evaluation score = 0; peeling area is 65% or more of the total square area. Water Resistance Test Judgment was made based on the state of the coating film after being immersed in distilled water (20°C) for 24 hours. (Paint film thickness = 500 μm) ◎... Excellent ○... Good △... Fair
Subsequent thermal discoloration was observed with the naked eye. (Paint film thickness = 500
μm) ○...No thermal discoloration. △...There is some thermal discoloration. ×...There is a lot of thermal discoloration.
【００２５】参考例１（ポリオルガノシロキサン系重合
体ラテックスの製造）
ｐ−ビニルフェニルメチルジメトキシシラン１．５部お
よびオクタメチルシクロテトラシロキサン９８．５部を
混合し、これをドデシルベンゼンスルホン酸２．０部を
溶解した蒸溜水３００部中に入れ、ホモミキサーにより
３分間撹拌して乳化分散させた。この混合液を、コンデ
ンサー、チッ素導入口および撹拌機を備えたセパラブル
フラスコに移し、撹拌混合しながら９０℃で６時間加熱
し、５℃で２４時間冷却することによって縮合を完結さ
せた。得られたポリオルガノシロキサン系重合体ラテッ
クスを、炭酸ナトリウム水溶液でｐＨ７に中和した。Reference Example 1 (Production of polyorganosiloxane polymer latex) 1.5 parts of p-vinylphenylmethyldimethoxysilane and 98.5 parts of octamethylcyclotetrasiloxane were mixed, and this was mixed with 2.5 parts of dodecylbenzenesulfonic acid. 0 part was dissolved in 300 parts of distilled water, and stirred for 3 minutes using a homomixer to emulsify and disperse. This liquid mixture was transferred to a separable flask equipped with a condenser, a nitrogen inlet, and a stirrer, heated at 90°C for 6 hours while stirring and mixing, and cooled at 5°C for 24 hours to complete condensation. The obtained polyorganosiloxane polymer latex was neutralized to pH 7 with an aqueous sodium carbonate solution.
【００２６】実施例１〜２、比較例１〜６コンデンサー
、チッ素導入口および撹拌機を備えたセパラブルフラス
コに、イオン交換水７０部と、前記ポリオルガノシロキ
サン系重合体ラテックスと、重合開始剤０．３部を仕込
み、気相部を１５分間チッ素ガスで置換し、８０℃に昇
温した。別容器で、イオン交換水３０部と、ポリオキシ
エチレンアルキルフェニルエーテルサルフェートアンモ
ニウム塩１．０部と、アルキルベンゼンスルホン酸ナト
リウム０．５部と、表１〜２に示す各ビニル系単量体と
を混合攪拌し、プレ乳化物を作り、４時間かけて前記フ
ラスコ中に滴下した。滴下中は、チッ素ガスを導入しな
がら、８０℃で反応を行った。滴下終了後、さらに８５
℃で２時間攪拌して反応を終了させた。
その後、２５℃まで冷却し、アンモニア水でｐＨ７に調
整した。なお、ポリオルガノシロキサン系重合体ラテッ
クスと、各ビニル系単量体の仕込み量は、表１〜３のと
おりである。
実施例３
実施例１と同様のセパラブルフラスコに、イオン交換水
７０部と、参考例１で得られたポリオルガノシロキサン
系重合体ラテックスと、表１に示す各ビニル系単量体と
を仕込み、気相部を１５分間チッ素ガスで置換したのち
、１時間攪拌した。８０℃に昇温後、重合開始剤０．３
部を加え、２時間攪拌を続け、反応を行ったのち、さら
に８５℃で２時間攪拌して反応を終了させた。反応中は
、チッ素ガスを導入しながら行った。２５℃まで冷却し
、アンモニア水でｐＨ７に調整した。なお、ポリオルガ
ノシロキサン系重合体ラテックスと、各ビニル系単量体
の仕込み量は、表１のとおりである。
実施例４
実施例１と同様のセパラブルフラスコに、イオン交換水
７０部と、重合開始剤０．３部を仕込み、気相部を１５
分間チッ素ガスで置換したのち、８０℃に昇温させた。
別容器で、イオン交換水３０部と、参考例１で得られた
ポリオルガノシロキサン系重合体ラテックスと、表１に
示す各ビニル系単量体とを混合攪拌し、プレ乳化物を作
り、４時間かけて前記フラスコ中に滴下した。滴下中は
、チッ素ガスを導入しながら、８０℃で反応を行った。
滴下終了後、さらに８５℃で２時間攪拌して反応を終了
させた。その後、２５℃まで冷却し、アンモニア水でｐ
Ｈ７に調整した。なお、ポリオルガノシロキサン系重合
体ラテックスと、各ビニル系単量体の仕込み量は、表１
のとおりである。
実施例５
実施例１と同様のセパラブルフラスコに、イオン交換水
７０部と、参考例１で得られたポリオルガノシロキサン
系重合体ラテックスと、表１に示すビニル系単量体（Ａ
）と、重合開始剤０．３部を仕込み、気相部を１５分間
チッ素ガスで置換したのち、８０℃に昇温させた。
別容器で、イオン交換水３０部と、ポリオキシエチレン
アルキルフェニルエーテルサルフェートアンモニウム塩
１．０部と、アルキルベンゼンスルホン酸ナトリウム０
．５部と、表１に示すビニル系単量体（Ｂ）とを混合攪
拌し、プレ乳化物を作り、４時間かけて前記フラスコ中
に滴下した。滴下中は、チッ素ガスを導入しながら、８
０℃で反応を行った。滴下終了後、さらに８５℃で２時
間攪拌して反応を終了させた。その後、２５℃まで冷却
し、アンモニア水でｐＨ７に調整した。なお、ポリオル
ガノシロキサン系重合体ラテックスと、各ビニル系単量
体（Ａ）〜（Ｂ）の仕込み量は、表１のとおりである。Examples 1 to 2, Comparative Examples 1 to 6 Into a separable flask equipped with a condenser, a nitrogen inlet, and a stirrer, 70 parts of ion-exchanged water and the polyorganosiloxane polymer latex were added to initiate polymerization. 0.3 part of the agent was charged, the gas phase was replaced with nitrogen gas for 15 minutes, and the temperature was raised to 80°C. In a separate container, 30 parts of ion-exchanged water, 1.0 part of polyoxyethylene alkylphenyl ether sulfate ammonium salt, 0.5 part of sodium alkylbenzene sulfonate, and each vinyl monomer shown in Tables 1 and 2 were added. The mixture was mixed and stirred to form a pre-emulsion, which was added dropwise into the flask over 4 hours. During the dropwise addition, the reaction was carried out at 80° C. while introducing nitrogen gas. After the completion of dripping, another 85
The reaction was completed by stirring at ℃ for 2 hours. Thereafter, the mixture was cooled to 25° C. and adjusted to pH 7 with aqueous ammonia. The amounts of the polyorganosiloxane polymer latex and each vinyl monomer to be charged are shown in Tables 1 to 3. Example 3 In a separable flask similar to Example 1, 70 parts of ion-exchanged water, the polyorganosiloxane polymer latex obtained in Reference Example 1, and each vinyl monomer shown in Table 1 were charged. After replacing the gas phase with nitrogen gas for 15 minutes, the mixture was stirred for 1 hour. After raising the temperature to 80℃, add 0.3 of polymerization initiator
After stirring was continued for 2 hours to carry out the reaction, the reaction was further stirred at 85° C. for 2 hours to complete the reaction. During the reaction, nitrogen gas was introduced. The mixture was cooled to 25°C and adjusted to pH 7 with aqueous ammonia. The amounts of the polyorganosiloxane polymer latex and each vinyl monomer are shown in Table 1. Example 4 In a separable flask similar to Example 1, 70 parts of ion-exchanged water and 0.3 parts of polymerization initiator were charged, and the gas phase was reduced to 15 parts.
After purging with nitrogen gas for a minute, the temperature was raised to 80°C. In a separate container, 30 parts of ion-exchanged water, the polyorganosiloxane polymer latex obtained in Reference Example 1, and each vinyl monomer shown in Table 1 were mixed and stirred to prepare a pre-emulsion. It was added dropwise into the flask over time. During the dropwise addition, the reaction was carried out at 80° C. while introducing nitrogen gas. After the dropwise addition was completed, the mixture was further stirred at 85° C. for 2 hours to complete the reaction. After that, it was cooled to 25°C and plucked with ammonia water.
Adjusted to H7. The amounts of the polyorganosiloxane polymer latex and each vinyl monomer are shown in Table 1.
It is as follows. Example 5 In a separable flask similar to Example 1, 70 parts of ion-exchanged water, the polyorganosiloxane polymer latex obtained in Reference Example 1, and the vinyl monomer (A
) and 0.3 part of a polymerization initiator were charged, and after replacing the gas phase with nitrogen gas for 15 minutes, the temperature was raised to 80°C. In a separate container, 30 parts of ion-exchanged water, 1.0 part of polyoxyethylene alkylphenyl ether sulfate ammonium salt, and 0 parts of sodium alkylbenzene sulfonate.
．． 5 parts of the vinyl monomer (B) shown in Table 1 were mixed and stirred to form a pre-emulsion, which was then dropped into the flask over 4 hours. During the dropping, while introducing nitrogen gas,
The reaction was carried out at 0°C. After the dropwise addition was completed, the mixture was further stirred at 85° C. for 2 hours to complete the reaction. Thereafter, the mixture was cooled to 25° C. and adjusted to pH 7 with aqueous ammonia. The amounts of the polyorganosiloxane polymer latex and each of the vinyl monomers (A) to (B) are shown in Table 1.
【００２７】比較例７
実施例１と同様のセパラブルフラスコに、イオン交換水
７０部と、重合開始剤０．３部を仕込み、気相部を１５
分間チッ素ガスで置換したのち、８０℃に昇温させた。
別容器で、イオン交換水３０部と、ポリオキシエチレン
アルキルフェニルエーテルサルフェートアンモニウム塩
１．０部と、アルキルベンゼンスルホン酸ナトリウム０
．５部と、表２に示す各ビニル系単量体とを混合攪拌し
、プレ乳化物を作り、４時間かけて前記フラスコ中に滴
下した。滴下中は、チッ素ガスを導入しながら、８０℃
で反応を行った。滴下終了後、さらに８５℃で２時間攪
拌して反応を終了させた。その後、２５℃まで冷却し、
アンモニア水でｐＨ７に調整した。この共重合体ラテッ
クスと参考例１で得られたポリオルガノシロキサン系重
合体ラテックスを混合した。各ビニル系単量体の仕込み
量、およびポリオルガノシロキサン系重合体ラテックス
の混合量は表３に示すとおりである。
比較例８
ポリオルガノシロキサン系重合体ラテックスとして、ｐ
−ビニルフェニルメチルジメトキシシランを加えない以
外は、参考例１と同様にして得たものを用い、またビニ
ル系単量体を表３の仕込み組成にする以外は、実施例１
と同様にして重合した。結果を表３に示す。
比較例９〜１０
ポリオルガノシロキサン系重合体ラテックスの量を変更
する以外は、実施例１と同様にして重合した。結果を表
３に示す。Comparative Example 7 Into a separable flask similar to Example 1, 70 parts of ion-exchanged water and 0.3 parts of polymerization initiator were charged, and the gas phase was reduced to 15 parts.
After purging with nitrogen gas for a minute, the temperature was raised to 80°C. In a separate container, 30 parts of ion-exchanged water, 1.0 part of polyoxyethylene alkylphenyl ether sulfate ammonium salt, and 0 parts of sodium alkylbenzene sulfonate.
．． 5 parts and each vinyl monomer shown in Table 2 were mixed and stirred to form a pre-emulsion, which was dropped into the flask over 4 hours. During dropping, the temperature was maintained at 80°C while introducing nitrogen gas.
The reaction was carried out. After the dropwise addition was completed, the mixture was further stirred at 85° C. for 2 hours to complete the reaction. Then, cool to 25℃,
The pH was adjusted to 7 with aqueous ammonia. This copolymer latex and the polyorganosiloxane polymer latex obtained in Reference Example 1 were mixed. The amount of each vinyl monomer charged and the amount of polyorganosiloxane polymer latex mixed are as shown in Table 3. Comparative Example 8 As a polyorganosiloxane polymer latex, p
-Example 1 was obtained in the same manner as in Reference Example 1 except that vinyl phenylmethyldimethoxysilane was not added, and the charging composition of the vinyl monomer was changed to Table 3.
Polymerization was carried out in the same manner. The results are shown in Table 3. Comparative Examples 9-10 Polymerization was carried out in the same manner as in Example 1, except that the amount of polyorganosiloxane polymer latex was changed. The results are shown in Table 3.
【００２８】試験例
実施例１〜５、比較例１〜１０で得られたエマルジョン
を用いて、下記配合処方に従って水性塗料を得た。結果
を併せて表１〜３に示す。
水性塗料配合処方
（部） 酸化チタン〔石原産業（株
）製、タイペークＲ−６３０）
２７ 分散剤（Ｒｏｈｍ ＆ Ｈａａｓ社製、
オロタン７３１ＳＤ） ５ 増粘
剤〔フジケミカル（株）製、Ａ−５０００〕
２ 可塑剤（イ
ーストマン・ケミカル社製、テキサノール）
３ イオン交換水
３
ポリオルガノシロキサン系重合体エマルジョン（固
形分濃度４９．３％）６０（以下余白）Test Examples Using the emulsions obtained in Examples 1 to 5 and Comparative Examples 1 to 10, water-based paints were obtained according to the following formulation. The results are also shown in Tables 1 to 3. Water-based paint formulation
(Part) Titanium oxide [manufactured by Ishihara Sangyo Co., Ltd., Taipeiku R-630]
27 Dispersant (manufactured by Rohm & Haas,
Orotane 731SD) 5 Thickener [manufactured by Fuji Chemical Co., Ltd., A-5000]
2 Plasticizer (Texanol, manufactured by Eastman Chemical Company)
3 Ion exchange water
3
Polyorganosiloxane polymer emulsion (solid content concentration 49.3%) 60 (blank below)
【００２９】[0029]
【表１】[Table 1]
【００３０】[0030]
【表２】[Table 2]
【００３１】[0031]
【表３】[Table 3]
【００３２】なお、表１〜３における＊１〜＊７は、次
のような化合物である。
＊１）ｎＢＡ＝アクリル酸ｎ−ブチル
＊２）２ＥＨＡ＝アクリル酸２−エチルヘキシル＊３）
ＭＭＡ＝メタクリル酸メチル
＊４）ＳＴ＝スチレン
＊５）ＡＮ＝アクリロニトリル
＊６）ＡＡ＝アクリル酸
＊７）ＩＡ＝イタコン酸Note that *1 to *7 in Tables 1 to 3 are the following compounds. *1) nBA = n-butyl acrylate *2) 2EHA = 2-ethylhexyl acrylate *3)
MMA = methyl methacrylate *4) ST = styrene *5) AN = acrylonitrile *6) AA = acrylic acid *7) IA = itaconic acid
【００３３】表１から明らかなように、実施例１〜５は
、本発明の範囲のエマルジョンを用いた水性塗料の例で
あり、本発明の目的とする水性塗料が得られている。
これに対し、表２〜３から明らかなように、比較例１は
、（メタ）アクリル酸アルキルエステルの使用量が本発
明の範囲未満の例であり、密着性、耐候性に劣る。
比較例２は、（メタ）アクリル酸アルキルエステルの使
用量が本発明の範囲を超え、かつエチレン性不飽和カル
ボン酸の使用量が本発明の範囲未満の例であり、密着性
、耐水性、耐熱性に劣る。比較例３は、エチレン系不飽
和カルボン酸の使用量が本発明の範囲未満の例であり、
耐水性、耐熱性に劣る。比較例４は、エチレン系不飽和
カルボン酸の使用量が本発明の範囲を超える例であり、
耐水性に劣る。比較例５は、示差熱分析法により測定さ
れる重合体のガラス転移温度の最も高い値が本発明の範
囲を超える例であり、耐熱性に劣る。比較例６は、（メ
タ）アクリル酸アルキルエステルおよびエチレン系不飽
和カルボン酸を用いていない例であり、密着性、耐水性
に劣る。比較例７は、表３に示したビニル系単量体を共
重合した共重合体ラテックスとポリオルガノシロキサン
系重合体ラテックスを混合した例であり、耐候性、密着
性に劣る。比較例８は、グラフト交叉剤を共縮合してい
ないポリオルガノシロキサン系重合体ラテックスを用い
た例であり、耐候性、密着性に劣る。比較例９は、ポリ
オルガノシロキサン系重合体ラテックスの量が本発明の
範囲未満の例であり、光沢保持率、耐水性、耐熱性に劣
る。比較例１０は、ポリオルガノシロキサン系重合体ラ
テックスの量が本発明の範囲を超える例であり、耐水性
に劣る。As is clear from Table 1, Examples 1 to 5 are examples of water-based paints using emulsions within the scope of the present invention, and the water-based paints targeted by the present invention were obtained. On the other hand, as is clear from Tables 2 and 3, Comparative Example 1 is an example in which the amount of (meth)acrylic acid alkyl ester used is less than the range of the present invention, and the adhesiveness and weather resistance are poor.
Comparative Example 2 is an example in which the amount of (meth)acrylic acid alkyl ester used exceeds the range of the present invention and the amount of ethylenically unsaturated carboxylic acid used is less than the range of the present invention, and the adhesion, water resistance, Poor heat resistance. Comparative Example 3 is an example in which the amount of ethylenically unsaturated carboxylic acid used is less than the range of the present invention,
Poor water resistance and heat resistance. Comparative Example 4 is an example in which the amount of ethylenically unsaturated carboxylic acid used exceeds the range of the present invention,
Poor water resistance. Comparative Example 5 is an example in which the highest value of the glass transition temperature of the polymer measured by differential thermal analysis exceeds the range of the present invention, and is inferior in heat resistance. Comparative Example 6 is an example in which (meth)acrylic acid alkyl ester and ethylenically unsaturated carboxylic acid are not used, and the adhesiveness and water resistance are poor. Comparative Example 7 is an example in which a copolymer latex obtained by copolymerizing the vinyl monomers shown in Table 3 and a polyorganosiloxane polymer latex are mixed, and the weather resistance and adhesion are poor. Comparative Example 8 is an example in which a polyorganosiloxane polymer latex without co-condensed with a graft cross-agent is used, and the weather resistance and adhesion are poor. Comparative Example 9 is an example in which the amount of polyorganosiloxane-based polymer latex is less than the range of the present invention, and is inferior in gloss retention, water resistance, and heat resistance. Comparative Example 10 is an example in which the amount of polyorganosiloxane-based polymer latex exceeds the range of the present invention, and the water resistance is poor.
【００３４】[0034]
【発明の効果】本発明のポリオルガノシロキサン系エマ
ルジョンは、ポリオルガノシロキサン系重合体の水性分
散体の存在下に、ビニル系単量体を重合し、かつ示差熱
分析法により測定される重合体のガラス転移温度の最も
高い値が８０℃以下になるように調整することによって
得られる。本発明のポリオルガノシロキサン系エマルジ
ョンは、特に水性塗料に用いた場合、優れた性能を発揮
する。本発明のポリオルガノシロキサン系エマルジョン
は、クリヤー塗料、着色塗料双方の適しており、例えば
コンクリート、モルタル、スレートなどの無機基材へ塗
装した場合、その優れた耐候性により塗膜表面の劣化を
防ぎ、また優れた密着性、耐水性により浸水による塗膜
の膨れを防ぐことができる。本発明のポリオルガノシロ
キサン系エマルジョンは、多種の用途に使用が可能であ
り、水性塗料としては、建築内装・外装用塗料、鋼構造
物用塗料、コンクリート構造物用塗料、家庭用塗料、屋
根用塗料、床用塗料、プラスチック用塗料、皮革用塗料
、金属用塗料、紙用塗料などに好適である。また、本発
明のポリオルガノシロキサン系エマルジョンは、水性塗
料以外に、粘着剤用、フロアーポリッシュ用、セメント
混和剤用、カーペットバッキング剤用、シーラント用、
紙・繊維コーティングおよび含浸用としても使用できる
。Effects of the Invention The polyorganosiloxane emulsion of the present invention is obtained by polymerizing a vinyl monomer in the presence of an aqueous dispersion of a polyorganosiloxane polymer, and the resulting polymer is determined by differential thermal analysis. This can be obtained by adjusting the highest glass transition temperature of 80° C. or lower. The polyorganosiloxane emulsion of the present invention exhibits excellent performance especially when used in water-based paints. The polyorganosiloxane emulsion of the present invention is suitable for both clear paints and colored paints. For example, when applied to inorganic substrates such as concrete, mortar, and slate, its excellent weather resistance prevents deterioration of the paint film surface. Also, its excellent adhesion and water resistance prevent the coating film from blistering due to water intrusion. The polyorganosiloxane emulsion of the present invention can be used for a variety of purposes, and water-based paints include architectural interior and exterior paints, steel structure paints, concrete structure paints, household paints, and roof paints. Suitable for paints, floor paints, plastic paints, leather paints, metal paints, paper paints, etc. In addition to water-based paints, the polyorganosiloxane emulsion of the present invention can also be used for adhesives, floor polishes, cement admixtures, carpet backing agents, sealants, etc.
It can also be used for paper/fiber coating and impregnation.
Claims (2)
ト交叉剤（ＩＩ） を（Ｉ）と（ＩＩ） 成分の合計量
に対し０．０２〜２０重量％共縮合して得られるポリオ
ルガノシロキサン系重合体（ＩＩＩ）１〜９０重量部（
固形分）の水性分散体の存在下に、（ａ）アルキル基の
炭素数が１〜１０の（メタ）アクリル酸アルキルエステ
ル１９．５〜９９．５重量％、（ｂ）エチレン系不飽和
カルボン酸０．５〜１５重量％、および（ｃ）これらと
共重合可能な他の単量体０〜８０％〔ただし、（ａ）＋
（ｂ）＋（ｃ）＝１００重量％〕からなる単量体成分（
ＩＶ） ９９〜１０重量部〔ただし、（ＩＩＩ）＋（Ｉ
Ｖ） ＝１００重量部〕を重合することによって得られ
るポリオルガノシロキサン系エマルジョン。[Claim 1] A polyorganosiloxane polymer obtained by cocondensing organosiloxane (I) with a grafting agent (II) in an amount of 0.02 to 20% by weight based on the total amount of components (I) and (II). Combined (III) 1 to 90 parts by weight (
In the presence of an aqueous dispersion of (solid content), (a) 19.5 to 99.5% by weight of (meth)acrylic acid alkyl ester whose alkyl group has 1 to 10 carbon atoms, (b) ethylenically unsaturated carbon 0.5 to 15% by weight of acid, and (c) 0 to 80% of other monomers copolymerizable with these [however, (a) +
(b)+(c)=100% by weight]
IV) 99 to 10 parts by weight [However, (III) + (I
V) = 100 parts by weight].
１】 （式中、Ｒ２ は水素原子または炭素数１〜６のアルキ
ル基、ｎは０〜１２の整数を示す）で表される不飽和基
とアルコキシシリル基とを合わせ持つ化合物である請求
項１記載のポリオルガノシロキサン系エマルジョン。[Claim 2] The graft crossover agent (II) is represented by the following formula: [Formula 1] (wherein R2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 0 to 12) The polyorganosiloxane emulsion according to claim 1, which is a compound having both an unsaturated group and an alkoxysilyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4217191A JP2934328B2 (en) | 1991-02-15 | 1991-02-15 | Polyorganosiloxane emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4217191A JP2934328B2 (en) | 1991-02-15 | 1991-02-15 | Polyorganosiloxane emulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04261454A true JPH04261454A (en) | 1992-09-17 |
| JP2934328B2 JP2934328B2 (en) | 1999-08-16 |
Family
ID=12628527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4217191A Expired - Lifetime JP2934328B2 (en) | 1991-02-15 | 1991-02-15 | Polyorganosiloxane emulsion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2934328B2 (en) |
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|---|---|---|---|---|
| JPH07196750A (en) * | 1993-12-29 | 1995-08-01 | Takemoto Oil & Fat Co Ltd | Coating composition |
| JPH083253A (en) * | 1994-06-16 | 1996-01-09 | Mitsubishi Rayon Co Ltd | Preparation of coating emulsion |
| JPH083512A (en) * | 1994-06-16 | 1996-01-09 | Mitsubishi Rayon Co Ltd | Resin composition for coating and production thereof |
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