JPH0466897B2 - - Google Patents
Info
- Publication number
- JPH0466897B2 JPH0466897B2 JP59145905A JP14590584A JPH0466897B2 JP H0466897 B2 JPH0466897 B2 JP H0466897B2 JP 59145905 A JP59145905 A JP 59145905A JP 14590584 A JP14590584 A JP 14590584A JP H0466897 B2 JPH0466897 B2 JP H0466897B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- organopolysiloxane
- parts
- dispersible
- vinyl polymer
- 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
- 229920001296 polysiloxane Polymers 0.000 claims description 49
- 229920002554 vinyl polymer Polymers 0.000 claims description 38
- 239000000178 monomer Substances 0.000 claims description 36
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000000203 mixture Substances 0.000 description 27
- 229920006163 vinyl copolymer Polymers 0.000 description 26
- 238000000034 method Methods 0.000 description 18
- -1 β- methoxyethoxy Chemical group 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000007720 emulsion polymerization reaction Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- 239000007809 chemical reaction catalyst Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000007664 blowing Methods 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 238000010556 emulsion polymerization method Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229940049964 oleate Drugs 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-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
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 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
- 239000012736 aqueous medium Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- JRRAUKXNAWPZES-UHFFFAOYSA-N iron 3-methylheptane Chemical compound [Fe].CCCCC(C)CC JRRAUKXNAWPZES-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 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
- 239000008096 xylene Substances 0.000 description 2
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- SXZSFWHOSHAKMN-UHFFFAOYSA-N 2,3,4,4',5-Pentachlorobiphenyl Chemical compound C1=CC(Cl)=CC=C1C1=CC(Cl)=C(Cl)C(Cl)=C1Cl SXZSFWHOSHAKMN-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- NGCJVMZXRCLPRQ-UHFFFAOYSA-N 2-methylidenepentanedinitrile Chemical compound N#CC(=C)CCC#N NGCJVMZXRCLPRQ-UHFFFAOYSA-N 0.000 description 1
- FCYVWWWTHPPJII-UHFFFAOYSA-N 2-methylidenepropanedinitrile Chemical compound N#CC(=C)C#N FCYVWWWTHPPJII-UHFFFAOYSA-N 0.000 description 1
- UDWIZRDPCQAYRF-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C=C UDWIZRDPCQAYRF-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 241001448862 Croton Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- YZFWTZACSRHJQD-UHFFFAOYSA-N ciglitazone Chemical compound C=1C=C(CC2C(NC(=O)S2)=O)C=CC=1OCC1(C)CCCCC1 YZFWTZACSRHJQD-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-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
- NKKMVIVFRUYPLQ-NSCUHMNNSA-N crotononitrile Chemical compound C\C=C\C#N NKKMVIVFRUYPLQ-NSCUHMNNSA-N 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000006264 diethylaminomethyl group Chemical group [H]C([H])([H])C([H])([H])N(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 125000006222 dimethylaminomethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])* 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
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 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
- 239000002609 medium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- GDGOJEMDZGZECC-UHFFFAOYSA-N n'-[(3-ethenylphenyl)methyl]-n-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCNCC1=CC=CC(C=C)=C1 GDGOJEMDZGZECC-UHFFFAOYSA-N 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- UBVMBXTYMSRUDX-UHFFFAOYSA-N n-prop-2-enyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCC=C UBVMBXTYMSRUDX-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 241000894007 species Species 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
- SOUMBTQFYKZXPN-UHFFFAOYSA-N trimethoxy(4-phenylbut-3-enyl)silane Chemical compound CO[Si](OC)(OC)CCC=CC1=CC=CC=C1 SOUMBTQFYKZXPN-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
Description
本発明は水分散性シリコン変性ビニル重合体の
製造方法に関するものである。更に詳しくは優れ
た表面潤滑性、耐熱性、耐候性、撥水性、耐水
性、機械的強度を有する水分散性シリコン変性ビ
ニル重合体の製造方法に関するものである。
従来からオルガノポリシロキサン、いわゆるシ
リコン樹脂は表面潤滑性、耐熱性、耐候性、撥水
性、耐水性が優れた材料として知られているが、
シリコン樹脂は一般に高価であることに加え、各
種の基材に対する密着性が劣る理由から多方面の
用途で他のビニル系重合体と混合して用いられて
いる。しかし、単に混合しただけでは例えば被膜
として用いた場合、初期の表面潤滑性や撥水性は
得られるが長期間の使用によりシリコン成分が被
膜の表面から徐々に消失し、効果が持続しない場
合が多い。これらの改善には、珪素系反応性基に
よる縮合反応を利用してビニル系重合体を変性す
るか若しくはシリコン樹脂に重合性不飽和基を導
入して他のビニル系単量体と共重合したいわゆる
シリコン変性ビニル重合体が有効である。しかも
該樹脂の水分散物は揮散物質が水であるために省
資源、労働衛生の観点から特に好ましいものであ
る。
これまでに提案されているシリコン変性ビニル
重合体の水分散物としては、水稀釈性の有機溶剤
中でカルボキシル基およびヒドロキシル基を有す
るビニル系重合体を製造し、これにヒドロキシル
基もしくはアルコキシル基を有するオルガノポリ
シロキサンを反応させ、次いで水稀釈して得られ
る水分散物（特開昭５−95388）や重合性不飽和
基を有するオルガノポリシロキサンと他のビニル
系重合体を乳化剤の存在下に水媒体中で乳化重合
して得られる水分散物（特開昭51−146525）など
が知られている。しかしながら、これらの方法
は、オルガノポリシロキサンの反応性が低い為、
変性が不完全な事が多く、場合によつては反応中
に分離、凝集といつた現象が生じ易い。従つて、
優れた前記性能を有する水分散性シリコン変性ビ
ニル重合体を安定に得るには組成上の制約を受け
るのが実情である。
本発明は、このような現状に鑑み、ビニル系共
重合体を得るための重合の際または重合後にオル
ガノポリシロキサンで変性を行い、優れた表面潤
滑性、耐熱性、耐候性、撥水性、耐水性、機械的
強度を有する水分散性シリコン変性ビニル重合体
を得るにあたり、ビニル系重合体の原料単量体の
一部としてオルガノポリシロキサンと反応しやす
い特定の単量体を用いるとともに、オルガノポリ
シロキサンとして反応性の高いものを用いて変性
が完全に行われるようにし、これにより分離およ
び凝集が生じにくく、組成上の制約を受けずに安
定して製造できる方法を提供することを課題とす
る。
本発明者らは、上記課題を解決するために鋭意
研究を重ねた結果、本発明に到達した。
すなわち、本発明は、
分子中に少なくとも１個の重合性不飽和基と少
なくとも１個の珪素原子に直結する加水分解性基
とを有する有機珪素単量体(A)0.1〜50重量％およ
び該単量体(A)と共重合可能なその他の重合性単量
体(B)50〜99.9重量％（ただし、(A)＋(B)＝100重量
％である。）を、
分子中に少なくとも１個の珪素原子に直結する
水素原子を有しかつ平均組成式が
The present invention relates to a method for producing a water-dispersible silicone-modified vinyl polymer. More specifically, the present invention relates to a method for producing a water-dispersible silicone-modified vinyl polymer having excellent surface lubricity, heat resistance, weather resistance, water repellency, water resistance, and mechanical strength. Organopolysiloxane, so-called silicone resin, has long been known as a material with excellent surface lubricity, heat resistance, weather resistance, water repellency, and water resistance.
Silicone resins are generally expensive and have poor adhesion to various substrates, so they are used in a mixture with other vinyl polymers for a variety of purposes. However, if simply mixed together, for example when used as a coating, initial surface lubricity and water repellency can be obtained, but the silicone component gradually disappears from the surface of the coating after long-term use, and the effect often does not last. . These improvements were achieved by modifying the vinyl polymer using a condensation reaction with silicon-based reactive groups, or by introducing polymerizable unsaturated groups into silicone resin and copolymerizing it with other vinyl monomers. So-called silicon-modified vinyl polymers are effective. Moreover, the aqueous dispersion of the resin is particularly preferable from the viewpoint of resource saving and occupational health, since the volatile substance is water. Aqueous dispersions of silicone-modified vinyl polymers that have been proposed so far include producing a vinyl polymer having carboxyl groups and hydroxyl groups in a water-dilutable organic solvent, and adding hydroxyl groups or alkoxyl groups to this. An aqueous dispersion (JP-A-5-95388) obtained by reacting an organopolysiloxane having a polymerizable unsaturated group and diluting it with water, or an organopolysiloxane having a polymerizable unsaturated group and another vinyl polymer in the presence of an emulsifier. Aqueous dispersions obtained by emulsion polymerization in an aqueous medium (Japanese Patent Application Laid-Open No. 146525/1983) are known. However, these methods are difficult to use due to the low reactivity of organopolysiloxane.
Denaturation is often incomplete, and in some cases, phenomena such as separation and aggregation are likely to occur during the reaction. Therefore,
The reality is that in order to stably obtain a water-dispersible silicone-modified vinyl polymer having the above-mentioned excellent properties, there are compositional constraints. In view of the current situation, the present invention involves modifying with organopolysiloxane during or after polymerization to obtain a vinyl copolymer, which provides excellent surface lubricity, heat resistance, weather resistance, water repellency, and water resistance. In order to obtain a water-dispersible silicone-modified vinyl polymer that has good properties and mechanical strength, a specific monomer that easily reacts with organopolysiloxane is used as part of the raw material monomers for the vinyl polymer, and The object of the present invention is to provide a method that uses a highly reactive siloxane to ensure complete modification, thereby preventing separation and aggregation, and allowing stable production without compositional constraints. . The present inventors have conducted extensive research to solve the above problems, and as a result, have arrived at the present invention. That is, the present invention provides 0.1 to 50% by weight of an organosilicon monomer (A) having at least one polymerizable unsaturated group and at least one hydrolyzable group directly bonded to a silicon atom in the molecule; At least 50 to 99.9% by weight of other polymerizable monomer (B) that can be copolymerized with monomer (A) (however, (A) + (B) = 100% by weight) is contained in the molecule. It has a hydrogen atom directly connected to one silicon atom and has an average compositional formula.
【式】（Ｒは炭素数１〜10個の置換
もしくは非置換の一価の炭化水素基であり、ａお
よびｂはそれぞれ0.2≦ａ≦2.5、0.0005≦ｂ≦1.0
でありかつａ＋ｂは0.3≦ａ＋ｂ≦3.0である。）
で表されるオルガノポリシロキサン
の存在下で共重合させるか、予め共重合させてお
いて前記オルガノポリシロキサンと反応させるよ
うにする、
水分散性シリコン変性ビニル重合体の製造方法
を、その要旨とする。
このように、本発明では、水分散性シリコン変
性ビニル重合体の一部を構成するビニル重合体部
分を得るために、重合性単量体として、分子中に
少なくとも１個の重合性不飽和基と少なくとも１
個の珪素原子に直結する加水分解性基とを有する
有機珪素単量体(A)と、これと共重合可能な他の重
合性単量体(B)とを用いるようにし、これらの共重
合によつて前記ビニル重合体部分となる水分散性
ビニル系共重合体（）を得て、この水分散性ビ
ニル系共重合体（）中に導入される前記加水分
解性基の反応性を利用して、水分散性シリコン変
性ビニル重合体の他の一部を構成する前記オルガ
ノポリシロキサン（）部分との反応性を高め、
水分散性ビニル系共重合体（）部分とオルガノ
ポリシロキサン（）部分とを、強く結合するよ
うにしているのである。
有機珪素単量体(A)としては、例えばビニルトリ
メトキシシラン、ビニルトリエトキシシラン、ビ
ニルトリブトキシシラン、ビニルトリス（β−メ
トキシエトキシ）シラン、アリルトリエトキシシ
ラン、トリメトキシシリルプロピルアリルアミ
ン、γ−（メタ）アクリロキシプロピルトリメト
キシシラン、γ−（メタ）アクリロキシプロピル
トリエトキシシラン、γ−（メタ）アクリロキシ
プロピルメチルジメトキシシラン、γ−（メタ）
アクリロキシプロピルメチルジエトキシシラン、
γ−（メタ）アクリロキシプロピルトリス（β−
メトキシエトキシ）シラン、Ｎ−Ｂ−（Ｎ−ビニ
ルベンジルアミノ）エチル−γ−アミノプロピル
トリメトキシシラン、Ｎ−ビニルベンジル−γ−
ビニルプロピルトリエトキシシラン、２−スチリ
ルエチルトリメトキシシラン、３−（Ｎ−スチリ
ルメチル−２−アミノエチルアミノ）プロピルト
リメトキシシラン、（メタ）アクリロキシエチル
ジメチル（３−トリメトキシシリルプロピル）ア
ンモニウムクロライド、ビニルトリアセテトキシ
シラン、ビニルトリクロルシランなどを挙げるこ
とができ、これらの群から選ばれる１種または２
種以上の混合物を使用することができる。本発明
において、有機珪素単量体(A)は、水分散性ビニル
系共重合体（）部分とオルガノポリシロキサン
（）部分との、反応を利用した結合に必須の成
分である。単量体混合物中の有機珪素単量体(A)の
使用量は特に限定されるものではないが、反応効
率および水分散性シリコン変性ビニル重合体の価
格を考慮すれば、好ましくは0.1〜50重量％、よ
り好ましくは0.5〜20重量％である。
本発明において有機珪素単量体(A)と共重合可能
なその他の重合性単量体(B)としては、例えばアク
リル酸、メタクリル酸、クロトン酸、マレイン
酸、フマル酸、イタコン酸などの如き不飽和カル
ボン酸；炭素数が１〜18個の直鎖状もしくは分岐
状脂肪族アルコール又は脂環式アルコールと不飽
和カルボン酸とのエステル；エチレングリコー
ル、ジエチレングリコール、プロピレングリコー
ル、グリセロール、トリメチロールプロパン、ペ
ンタエリスリトールなどの如き多価アルコールと
不飽和カルボン酸とのエステル；（メタ）アリル
アルコール、クロトンアルコールなどの如き不飽
和アルコール；多価アルコールと不飽和アルコー
ルとのエーテル；エチレン、プロピレン、ブチレ
ンなどの如きオレフイン系水素；スチレン、クロ
ルスチレン、ビニルトルエンなどの如きビニル芳
香族炭化水素；弗化ビニル、塩化ビニル、臭化ビ
ニルなどの如きビニルハライド；弗化ビニリデ
ン、塩化ビニリデン、臭化ビニリデンなどの如き
ビニリデンハライド；（メタ）系アクリロニトリ
ル、クロトンニトリル、イソプロピルシアノアク
リレート、メチレングルタルニトリル、シアン化
ビニリデンなどの如き不飽和ニトリル；酢酸、プ
ロピオン酸、酪酸、安息香酸などの如き１価カル
ボン酸のビニルエステル；メチルアルコール、エ
チルアルコール、プロピルアルコール、ブチルア
ルコールなどの如き１価アルコールのビニルエー
テル；（メタ）アクロレイン、クロトンアルデヒ
ドなどの如き不飽和アルデヒド；ジメチルアミノ
メチル（メタ）アクリレート、ジエチルアミノメ
チル（メタ）アクリレート、ジメチルアミノエチ
ル（メタ）アクリレートなどの如きアミノ基含有
（メタ）アクリレート；グリシジル（メタ）アク
リレートなどの如き不飽和グリシジルエステル；
（メタ）アリルグリシジルエーテルなどの如き不
飽和グリシジルエーテル；（メタ）アクリルアミ
ド、ジアセトンアクリルアミドなどの如き不飽和
酸アミド；メチロール化アクリルアミドなどの如
き不飽和酸アミド誘導体；ブタジエン、イソブレ
ンなどの如きジエン系炭化水素；ジビニルベンゼ
ン、ジビニルトルエンなどの如きジビニル芳香族
炭化水素などを挙げることができ、これらの群か
ら選ばれる１種または２種以上の混合物を使用す
ることができる。
水分散性ビニル系共重合体（）を得るには、
重合反応制御の容易さや最終的に得られる水分散
性シリコン変性ビニル重合体の利用形態を考慮す
れば、乳化重合法によるのが好ましい。乳化重合
法としては例えば、常圧下、自生圧力下または人
工的な加圧下に乳化剤および／または保護コロイ
ドの存在下または不存在下に重合開始剤および必
要に応じて促進剤を用いて、好ましくは不活性雰
囲気中有機珪素単量体(A)と重合性単量体(B)とを公
知の手順に従つて乳化共重合させれば良い。この
際乳化重合技術において慣用の添加剤、例えばキ
レート化剤、緩衝剤、鉱酸または有機酸の塩、PH
規制助剤、連鎖移動剤などを使用することは自由
である。また、水分散性ビニル系共重合体（）
は例えば塊状重合、有機溶剤中での溶液重合など
の乳化重合法以外の公知の重合方法によつて重合
した後、水に分散せしめることによつても得られ
る。水に分散せしめる方法としては例えば共重合
体自体が実己乳化性を有する場合はそのまま水に
配合するだけで水に分散できるし、共重合体が自
己乳化性を有しない場合は乳化剤および／または
保護コロイドの存在下に水に分散させれば良い。
本発明の水分散性シリコン変性ビニル重合体を
得るのに用いられるオルガノポリシロキサン
（）は、分子中に少なくとも１個の珪素原子に
直結する水素原子を有しかつ平均組成物が
[Formula] (R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, a and b are respectively 0.2≦a≦2.5, 0.0005≦b≦1.0
and a+b is 0.3≦a+b≦3.0. )
A method for producing a water-dispersible silicone-modified vinyl polymer, which is copolymerized in the presence of an organopolysiloxane represented by the formula, or copolymerized in advance and reacted with the organopolysiloxane, is summarized below. do. In this way, in the present invention, in order to obtain a vinyl polymer portion constituting a part of a water-dispersible silicone-modified vinyl polymer, at least one polymerizable unsaturated group is added in the molecule as a polymerizable monomer. and at least 1
An organosilicon monomer (A) having a hydrolyzable group directly bonded to silicon atoms and another polymerizable monomer (B) that can be copolymerized with the organosilicon monomer (A) are used, and these copolymerization to obtain a water-dispersible vinyl copolymer () that becomes the vinyl polymer portion, and utilize the reactivity of the hydrolyzable group introduced into this water-dispersible vinyl copolymer (). to increase the reactivity with the organopolysiloxane ( ) moiety constituting another part of the water-dispersible silicone-modified vinyl polymer,
The water-dispersible vinyl copolymer ( ) portion and the organopolysiloxane ( ) portion are strongly bonded. Examples of the organic silicon monomer (A) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltris(β-methoxyethoxy)silane, allyltriethoxysilane, trimethoxysilylpropylallylamine, γ-( Meta)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)
acryloxypropylmethyldiethoxysilane,
γ-(meth)acryloxypropyltris (β-
methoxyethoxy)silane, N-B-(N-vinylbenzylamino)ethyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-
Vinylpropyltriethoxysilane, 2-styrylethyltrimethoxysilane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane, (meth)acryloxyethyldimethyl(3-trimethoxysilylpropyl)ammonium chloride , vinyltriacetethoxysilane, vinyltrichlorosilane, etc., and one or two selected from these groups.
Mixtures of more than one species can be used. In the present invention, the organosilicon monomer (A) is an essential component for bonding the water-dispersible vinyl copolymer ( ) portion and the organopolysiloxane ( ) portion using a reaction. The amount of the organosilicon monomer (A) used in the monomer mixture is not particularly limited, but is preferably 0.1 to 50, considering the reaction efficiency and the price of the water-dispersible silicone-modified vinyl polymer. % by weight, more preferably 0.5-20% by weight. In the present invention, other polymerizable monomers (B) copolymerizable with the organosilicon monomer (A) include, for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, etc. Unsaturated carboxylic acids; esters of linear or branched aliphatic alcohols or alicyclic alcohols having 1 to 18 carbon atoms and unsaturated carboxylic acids; ethylene glycol, diethylene glycol, propylene glycol, glycerol, trimethylolpropane, Esters of polyhydric alcohols such as pentaerythritol and unsaturated carboxylic acids; unsaturated alcohols such as (meth)allyl alcohol and croton alcohol; ethers of polyhydric alcohols and unsaturated alcohols; ethylene, propylene, butylene, etc. Olefinic hydrogens such as styrene, chlorostyrene, vinyltoluene, etc.; vinyl halides such as vinyl fluoride, vinyl chloride, vinyl bromide, etc.; vinylidene fluoride, vinylidene chloride, vinylidene bromide, etc. Vinylidene halides; unsaturated nitriles such as (meth)acrylonitrile, crotonitrile, isopropyl cyanoacrylate, methylene glutaronitrile, vinylidene cyanide, etc.; vinyl esters of monovalent carboxylic acids such as acetic acid, propionic acid, butyric acid, benzoic acid, etc.; Vinyl ethers of monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, etc.; unsaturated aldehydes such as (meth)acrolein, crotonaldehyde, etc.; dimethylaminomethyl (meth)acrylate, diethylaminomethyl (meth)acrylate, dimethyl Amino group-containing (meth)acrylates such as aminoethyl (meth)acrylate; unsaturated glycidyl esters such as glycidyl (meth)acrylate;
Unsaturated glycidyl ethers such as (meth)allyl glycidyl ether; unsaturated acid amides such as (meth)acrylamide, diacetone acrylamide, etc.; unsaturated acid amide derivatives such as methylolated acrylamide; dienes such as butadiene, isobrene, etc. Hydrocarbons include divinyl aromatic hydrocarbons such as divinylbenzene and divinyltoluene, and one type or a mixture of two or more types selected from these groups can be used. To obtain a water-dispersible vinyl copolymer (),
Considering the ease of controlling the polymerization reaction and the form of use of the ultimately obtained water-dispersible silicone-modified vinyl polymer, emulsion polymerization is preferred. As an emulsion polymerization method, for example, under normal pressure, autogenous pressure or artificial pressure, in the presence or absence of an emulsifier and/or protective colloid, using a polymerization initiator and optionally an accelerator, preferably The organosilicon monomer (A) and the polymerizable monomer (B) may be emulsion copolymerized in an inert atmosphere according to a known procedure. In this case, the additives customary in emulsion polymerization technology, such as chelating agents, buffers, salts of mineral or organic acids, pH
Regulatory aids, chain transfer agents, etc. may be used freely. In addition, water-dispersible vinyl copolymer ()
It can also be obtained by polymerizing by a known polymerization method other than emulsion polymerization, such as bulk polymerization or solution polymerization in an organic solvent, and then dispersing it in water. For example, if the copolymer itself has self-emulsifying properties, it can be dispersed in water by simply blending it with water, or if the copolymer does not have self-emulsifying properties, it can be dispersed in water using an emulsifier and/or It can be dispersed in water in the presence of a protective colloid. The organopolysiloxane () used to obtain the water-dispersible silicone-modified vinyl polymer of the present invention has at least one hydrogen atom directly bonded to a silicon atom in the molecule and has an average composition of
【式】（Ｒは炭素数１〜10個の置換
もくかは非置換の一価の炭化水素基であり、ａお
よびｂはそれぞれ0.2≦ａ≦2.5、0.0005≦ｂ≦1.0
であり、かつａ＋ｂは0.3≦ａ＋ｂ≦3.0である。）
で表わされるオルガノポリシロキサンである。珪
素原子に直結する水素原子は、水分散性ビニル系
重合体（）中に含まれる珪素系加水分解性基と
の反応に必須のもので、オルガノポリシロキサン
（）１分子中に少なくとも１個、好ましくは珪
素原子100個当り１個以上含まれる事が必要であ
る。一方、珪素原子に直結する水素原子の数が珪
素原子100個当り100個を越えて多い場合は、水分
散性ビニル系共重合体（）との反応中に凝集が
起こりやすく好ましくない。１分子中に含まれる
珪素原子の数は特に制限はないが、好ましくは４
個以上2000個以下が適当であり、４個未満の場合
はシリコンの特徴が発揮されにくかつたり、2001
個以上の場合は反応性が低かつたり分離凝集する
欠点がある。オルガノポリシロキサン（）は液
状のものをそのまま、あるいは乳化剤の存在下に
水性媒体中に乳化分散した形状のものを適宜使用
できる。
本発明にかかる水分散性シリコン変性ビニル重
合体を得るための反応は、前記重合によつて得ら
れた水分散性ビニル系共重合体（）とオルガノ
ポリシロキサン（）とを混合して行つても良
く、また、オルガノポリシロキサン（）の存在
下に前記有機珪素単量体(A)およびその他の重合性
単量体(B)からなる重合性単量体混合物の重合を行
い、重合と同時に該反応に行つても良い。後者の
方法においてオルガノポリシロキサン（）を混
合する方法としては、例えば(イ)オルガノポリシロ
キサン（）を含む媒体中に該重合性単量体混合
物を滴下して重合する方法、(ロ)オルガノポリシロ
キサン（）と該重合性単量体混合物とのプレミ
ツクスを滴下して重合する方法、(ハ)オルガノポリ
シロキサン（）と該重合性単量体混合物をそれ
ぞれ別個に滴下して重合する方法など各種の方法
を採用することができる。
水分散性シリコン変性ビニル重合体は、水分散
性ビニル系共重合体（）とオルガノポリシロキ
サン（）とを常温〜100℃、好ましくは50〜85
℃の温度条件下に、反応に伴ない副生する水素を
系外に除去しながら反応して得られるが、反応時
間短縮の為には適当な反応触媒を使用する事が好
ましい。反応触媒としては、ジブチル錫ジアセテ
ート、ジブチル錫ジラウレート、酢酸第一錫、ナ
フテン酸鉛、カプリル酸亜鉛、酢酸ジルコニウ
ム、２−エチルヘキサン鉄、ナフテン酸コバルト
などの如きカルボン酸の金属塩；チタン酸テトラ
ブチルエステル、チタン酸テトラノニルエステル
およびその多量体などの如きチタン酸エステル；
水酸化リチウム、水酸化ナトリウム、水酸化カリ
ウム、ナトリウムメチラート、アンモニア、トリ
エチルアミン、トリエタノールアミンなどの如き
塩基性物質など珪素系加水分解性基と珪素原子に
直結する水素原子との縮合反応に慣用の反応触媒
が有効であり、これらの群から選ばれた１種また
は２種以上の混合物として使用できる。好ましい
触媒の使用方法としては、ジブチル錫ジアセテー
ト、カプリル酸亜鉛、２−エチルヘキサン鉄など
の如きカルボン酸の金属塩と水酸化ナトリウム、
アンモニア、トリエチルアミンなどの如き塩基性
物質を併用して用いる事である。反応触媒の使用
量については特に制限はないが、おおよその目安
として水分散性シリコン変性ビニル重合体の不揮
発分100重量部に対して0.05〜10重量部とする事
ができる。反応触媒を使用する時期は、水分散性
ビニル系共重合体（）とオルガノポリシロキサ
ン（）とを混合する前若しくは後とする事がで
きる。
水分散性ビニル系共重合体（）の重合法とし
て、乳化重合法によるのが好ましいのは前記した
通りであるが、この場合の水分散性ビニル系共重
合体（）とオルガノポリシロキサン（）との
反応は、前記と同様に乳化重合した後の水分散性
ビニル系共重合体（）とのオルガノポリシロキ
サン（）とを混合して行つてもよく、また、オ
ルガノポリシロキサン（）の存在下に水分散性
ビニル系共重合体（）を乳化重合する方法であ
つてもよい。前者の方法はオルガノポリシロキサ
ン（）成分が局在化し易く、例えば被膜とした
場合その表面により多くのオルガノポリシロキサ
ン成分を集中させることができるため、少量のオ
ルガノポリシロキサン（）を有効に活用できる
特徴がある。後者の方法における乳化重合の方法
としてはオルガノポリシロキサン（）を共存さ
せない場合と同様従来から公知のいかなる乳化重
合法も適用できる。その際前記同様乳化重合技術
において慣用の添加剤を使用する事は自由であ
る。
本発明の水分散性シリコン変性ビニル重合体
は、常温もしくは加熱条件下に揮発成分を揮散さ
せるだけで、表面潤滑性、耐熱性、耐候性、撥水
性、耐水性、機械的強度の優れたフイルムまたは
シートあるいは成型物にできる。また本発明の水
分散性シリコン変性ビニル重合体は金属類、プラ
スチツク類、木材、無機質基材などに対する被覆
剤または接着剤あるいは紙、繊維などに対する処
理剤など多方面の用途への応用が可能である。こ
の際、当該業者に公知の顔料、トーナー、架橋
剤、粘度調節剤、湿潤剤、可塑剤、防錆剤、消泡
剤、帯電防止剤などを配合する事は自由である。
本発明のの製造方法により得られた水分散性シ
リコン変性ビニル重合体は、優れた表面潤滑性、
耐熱性、耐候性、撥水性、耐水性、機械的強度と
の各種の基材に対する優れた密着性を兼備してい
る。しかも、水分散性ビニル系共重合体（）中
に含まれる珪素系加水分解性基とオルガノポリシ
ロキサン（）中に含まれる珪素原子に直結する
水素原子との反応によつて水分散性ビニル系共重
合体（）とオルガノポリシロキサン（）が結
合しているため、初期の性能を長期間保持しつづ
ける利点がある。また、反応方法の選択によつて
オルガノポリシロキサン（）を局在化させるこ
とが可能であり、例えば被膜とした場合にその表
面により多くのオルガノポリシロキサン成分を集
中させることができるため、少量のオルガノポリ
シロキサン（）を有効に活用できる。更に、本
発明の製造方法により得られた水分散性シリコン
変性ビニル重合体は水分散性ビニル系共重合体
（）が乳化重合によつても容易に製造されるた
め揮発成分を完全に水だけとすることができ、省
資源労働衛生の観点からも好ましいものである。
また、水分散性ビニル系共重合体（）とオルガ
ノポリシロキサン（）との反応に際して組成上
の制約をまつたく受けないなどの特徴を有してい
る。
以下に本発明の実施態様を実施例によつて説明
するが、本発明は以下の実施例によつて限定され
るものではない。尚、参考例、比較参考例、実施
例及び比較例中の部はすべて重量部を、また％は
すべて重量％を示すものである。又、例中で使用
したオルガノポリシロキサンは以下の通りであ
る。[Formula] (R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, a and b are respectively 0.2≦a≦2.5, 0.0005≦b≦1.0
and a+b satisfies 0.3≦a+b≦3.0. )
It is an organopolysiloxane represented by The hydrogen atom directly bonded to the silicon atom is essential for the reaction with the silicon-based hydrolyzable group contained in the water-dispersible vinyl polymer (), and at least one hydrogen atom is present in one molecule of the organopolysiloxane (). Preferably, it is necessary to contain one or more per 100 silicon atoms. On the other hand, if the number of hydrogen atoms directly bonded to silicon atoms is more than 100 per 100 silicon atoms, aggregation tends to occur during the reaction with the water-dispersible vinyl copolymer (), which is undesirable. The number of silicon atoms contained in one molecule is not particularly limited, but is preferably 4.
A suitable number is between 2000 and 2000, and if it is less than 4, the characteristics of silicon may not be fully demonstrated.
If the number is more than 1,000,000,000,000,000,000,000,000,000,000 or more, there is a drawback that the reactivity is low and that separation and aggregation occur. The organopolysiloxane () can be used as it is in liquid form or in the form of emulsification and dispersion in an aqueous medium in the presence of an emulsifier. The reaction for obtaining the water-dispersible silicone-modified vinyl polymer according to the present invention is carried out by mixing the water-dispersible vinyl copolymer () obtained by the above polymerization and the organopolysiloxane (). Alternatively, a polymerizable monomer mixture consisting of the organosilicon monomer (A) and other polymerizable monomers (B) may be polymerized in the presence of organopolysiloxane (), and simultaneously polymerized. This reaction may also be carried out. In the latter method, the method of mixing the organopolysiloxane () includes, for example, (a) a method of dropping the polymerizable monomer mixture into a medium containing the organopolysiloxane (b) and polymerizing it; There are various methods such as a method in which a premix of siloxane () and the polymerizable monomer mixture is dropped and polymerized, and (c) a method in which organopolysiloxane () and the polymerizable monomer mixture are individually dropped and polymerized. method can be adopted. The water-dispersible silicone-modified vinyl polymer is prepared by mixing the water-dispersible vinyl copolymer () and the organopolysiloxane () at room temperature to 100°C, preferably 50 to 85°C.
It is obtained by reacting at a temperature of 0.degree. C. while removing hydrogen by-produced during the reaction from the system, but it is preferable to use an appropriate reaction catalyst in order to shorten the reaction time. As reaction catalysts, metal salts of carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate, stannous acetate, lead naphthenate, zinc caprylate, zirconium acetate, iron 2-ethylhexane, cobalt naphthenate, etc.; titanic acid; Titanate esters such as tetrabutyl ester, titanate tetranonyl ester and polymers thereof;
Commonly used for condensation reactions between silicon-based hydrolyzable groups such as basic substances such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, ammonia, triethylamine, triethanolamine, etc. and hydrogen atoms directly bonded to silicon atoms. These reaction catalysts are effective, and one type or a mixture of two or more types selected from these groups can be used. Preferred catalyst uses include metal salts of carboxylic acids such as dibutyltin diacetate, zinc caprylate, iron 2-ethylhexane, and sodium hydroxide;
Basic substances such as ammonia and triethylamine are used in combination. There is no particular restriction on the amount of the reaction catalyst used, but as a rough guide, it can be 0.05 to 10 parts by weight per 100 parts by weight of the nonvolatile content of the water-dispersible silicone-modified vinyl polymer. The reaction catalyst can be used before or after mixing the water-dispersible vinyl copolymer () and the organopolysiloxane (). As mentioned above, it is preferable to use the emulsion polymerization method as the polymerization method for the water-dispersible vinyl copolymer (), but in this case, the water-dispersible vinyl copolymer () and the organopolysiloxane () The reaction with organopolysiloxane () may be carried out by mixing the water-dispersible vinyl copolymer () and organopolysiloxane () after emulsion polymerization in the same manner as above; A method of emulsion polymerization of a water-dispersible vinyl copolymer () may also be used. In the former method, the organopolysiloxane () component is easily localized, and for example, when it is formed into a film, more of the organopolysiloxane component can be concentrated on the surface, so a small amount of organopolysiloxane () can be effectively utilized. It has characteristics. As for the emulsion polymerization method in the latter method, any conventionally known emulsion polymerization method can be applied, as in the case where organopolysiloxane () is not present. In this case, as mentioned above, additives customary in emulsion polymerization technology may be used freely. The water-dispersible silicone-modified vinyl polymer of the present invention can be produced into a film with excellent surface lubricity, heat resistance, weather resistance, water repellency, water resistance, and mechanical strength simply by volatilizing the volatile components at room temperature or under heating conditions. Or it can be made into a sheet or molded product. Furthermore, the water-dispersible silicone-modified vinyl polymer of the present invention can be applied to a wide range of applications, such as coating agents or adhesives for metals, plastics, wood, inorganic substrates, etc., and treatment agents for paper, fibers, etc. be. At this time, pigments, toners, crosslinking agents, viscosity modifiers, wetting agents, plasticizers, rust preventives, antifoaming agents, antistatic agents, etc. known to those skilled in the art may be incorporated at will. The water-dispersible silicone-modified vinyl polymer obtained by the production method of the present invention has excellent surface lubricity,
It has heat resistance, weather resistance, water repellency, water resistance, mechanical strength, and excellent adhesion to various base materials. In addition, the water-dispersible vinyl copolymer () can be made into Since the copolymer () and organopolysiloxane () are bonded together, it has the advantage of maintaining its initial performance for a long period of time. In addition, it is possible to localize the organopolysiloxane () by selecting the reaction method, and for example, when it is formed into a film, more organopolysiloxane components can be concentrated on the surface, making it possible to Organopolysiloxane () can be used effectively. Furthermore, since the water-dispersible silicone-modified vinyl polymer obtained by the production method of the present invention can be easily produced by emulsion polymerization, the water-dispersible vinyl copolymer () can be easily produced by emulsion polymerization, so volatile components can be completely removed only by water. This is preferable from the viewpoint of resource saving and occupational health.
Furthermore, it has the characteristic that it is not subject to any compositional restrictions when reacting the water-dispersible vinyl copolymer () with the organopolysiloxane (). Embodiments of the present invention will be described below with reference to Examples, but the present invention is not limited to the following Examples. In the Reference Examples, Comparative Reference Examples, Examples, and Comparative Examples, all parts indicate parts by weight, and all percentages indicate weight %. The organopolysiloxanes used in the examples are as follows.
【表】
シロキサン(3) 成式
[Table] Siloxane (3) Formula
【表】
参考例 １
滴下ロート、撹拌機、不活性ガス導入管、温度
計及び還流冷却管を備えたフラスコに脱イオン水
154部、ラウリル硫酸ナトリウム１部、ポリオキ
シエチレンオレイン酸エステル（HLB＝９）３
部及び過硫酸カリウム0.4部を仕込み、ゆるやか
に窒素ガスを吹込みながら75℃に加熱し、撹拌し
て均一な水溶液とした。次にビニルトリメトキシ
シラン５部、アクリル酸３部、メチルメタクリレ
ート25部およびブチルアクリレート67部よりなる
重合性単量体混合物を２時間かけて滴下ロートよ
り滴下した。その後温度を75℃に保ちながら１時
間撹拌をつづけ、次いで室温まで冷却したのち28
％アンモニア水を加えてPHを約８に調整して不揮
発分約40％の水分散性ビニル系共重合体(1)を得
た。
参考例 ２〜４
参考例１において重合性単量体混合物、乳化
剤、重合触媒、水および中和剤を第１表に示した
通りとする以外は、同じ操作手順に従つて水分散
性ビニル系共重合体(2)〜(4)を得た。その性状を第
１表にまとめた。
参考例 ５
参考例１で使用したのと同じフラスコにイソプ
ロピルアルコール80部を仕込み、ゆるやかに窒素
ガスを吹込みながら80℃に加熱した。次にビニル
トリメトキシシラン３部、アクリル酸６部、メチ
ルメタクリレート40部、ブチルアクリレート51部
およびアゾビスイソブチロニトリル0.7部よりな
る重合性単量体混合物および重合開始剤の混合物
を４時間かけて滴下ロートより滴下した。滴下を
終了してから温度を81℃に保ちながら更に２時間
撹拌をつづけた後室温まで冷却した。次いで28％
アンモニア水５部および脱イオン水210部を加え
た後、再び加熱してイソプロピルアルコールの全
量および脱イオン水の計145部を留去してPH約
8.0、不揮発分約40％の水分散性ビニル系共重合
体(5)を得た。
比較参考例 １
参考例１において重合性単量体混合物を第１表
に示した様に本発明の範囲外とする他は、同じ操
作手順に従つて水分散性ビニル系共重合体(6)を得
た。その性状は第１表に示した通りであつた。[Table] Reference example 1 Deionized water is placed in a flask equipped with a dropping funnel, stirrer, inert gas introduction tube, thermometer and reflux condenser.
154 parts, sodium lauryl sulfate 1 part, polyoxyethylene oleate (HLB=9) 3
1 part and 0.4 part of potassium persulfate were added, heated to 75°C while slowly blowing nitrogen gas, and stirred to obtain a uniform aqueous solution. Next, a polymerizable monomer mixture consisting of 5 parts of vinyltrimethoxysilane, 3 parts of acrylic acid, 25 parts of methyl methacrylate, and 67 parts of butyl acrylate was added dropwise from the dropping funnel over a period of 2 hours. After that, stirring was continued for 1 hour while maintaining the temperature at 75℃, then after cooling to room temperature,
% ammonia water was added to adjust the pH to about 8 to obtain a water-dispersible vinyl copolymer (1) with a nonvolatile content of about 40%. Reference Examples 2 to 4 A water-dispersible vinyl-based material was prepared by following the same procedure as in Reference Example 1, except that the polymerizable monomer mixture, emulsifier, polymerization catalyst, water, and neutralizing agent were as shown in Table 1. Copolymers (2) to (4) were obtained. Its properties are summarized in Table 1. Reference Example 5 80 parts of isopropyl alcohol was charged into the same flask as used in Reference Example 1, and heated to 80°C while gently blowing nitrogen gas. Next, a mixture of a polymerizable monomer mixture consisting of 3 parts of vinyltrimethoxysilane, 6 parts of acrylic acid, 40 parts of methyl methacrylate, 51 parts of butyl acrylate, and 0.7 parts of azobisisobutyronitrile and a polymerization initiator was added over 4 hours. The mixture was added dropwise from the dropping funnel. After the dropwise addition was completed, stirring was continued for an additional 2 hours while maintaining the temperature at 81°C, and then the mixture was cooled to room temperature. followed by 28%
After adding 5 parts of ammonia water and 210 parts of deionized water, it was heated again to distill off the entire amount of isopropyl alcohol and a total of 145 parts of deionized water, and the pH was approx.
8.0, a water-dispersible vinyl copolymer (5) with a nonvolatile content of about 40% was obtained. Comparative Reference Example 1 A water-dispersible vinyl copolymer (6) was prepared by following the same procedure as in Reference Example 1, except that the polymerizable monomer mixture was outside the scope of the present invention as shown in Table 1. I got it. Its properties were as shown in Table 1.
【表】
実施例 １
参考例１で使用したのと同じフラスコに参考例
１で得た水分散性ビニル系共重合体(1)258部およ
びジブチル錫ジアセテート0.3部を仕込み撹拌し
ながら75℃に加熱した。次に平均組成式が
（CH3）1.15H0.95SiO0.95、平均分子量が2500のオル
ガノポリシロキサン(1)３部を滴下ロートより30分
間かけて滴下した。その後温度を75℃に保ちなが
ら２時間撹拌をつづけ、次いで室温まで冷却して
水分散性シリコン変性ビニル重合体(1)を得た。
実施例 ２〜５
実施例１において用いた水分散性ビニル系共重
合体、オルガノポリシロキサン、反応触媒および
反応条件を第２表に示した通りとする以外は、同
じ操作手順に従つて水分散性シリコン変性ビニル
重合体(2)〜(5)を得た。[Table] Example 1 In the same flask as used in Reference Example 1, 258 parts of the water-dispersible vinyl copolymer (1) obtained in Reference Example 1 and 0.3 part of dibutyltin diacetate were charged and heated at 75°C with stirring. heated to. Next, 3 parts of organopolysiloxane (1) having an average composition formula of (CH 3 ) 1.15 H 0.95 SiO 0.95 and an average molecular weight of 2500 was added dropwise from the dropping funnel over a period of 30 minutes. Thereafter, stirring was continued for 2 hours while maintaining the temperature at 75°C, and then the mixture was cooled to room temperature to obtain a water-dispersible silicone-modified vinyl polymer (1). Examples 2 to 5 Water dispersion was performed according to the same operating procedure as in Example 1, except that the water-dispersible vinyl copolymer, organopolysiloxane, reaction catalyst, and reaction conditions were as shown in Table 2. Silicon-modified vinyl polymers (2) to (5) were obtained.
【表】
実施例 ６
参考例１で使用したのと同じフラスコに脱イオ
ン水154部、ラウリル硫酸ナトリウム１部、ポリ
オキシエチレンオレイン酸エステル（HLB＝９）
３部、オルガノポリシロキサン(1)３部、ジブチル
錫ジラウレート0.3部及び過硫酸カリウム0.4部を
仕込みゆるやかに窒素ガスを吹込みながら75℃に
加熱し撹拌して均一な水溶液とした。次にビニル
トリメトキシシラン５部、アクリル酸３部、メチ
ルメタクリレート25部およびブチルアクリレート
67部よりなる重合性単量体混合物を２時間かけて
滴下ロートより滴下した。その後温度を75℃に保
ちながら２時間撹拌をつづけ、次いで室温まで冷
却したのち28％アンモニア水を加えてPHを約８に
調整して水分散性シリコン変性ビニル重合体(6)を
得た。
実施例 ７
参考例１で使用したのと同じフラスコに脱イオ
ン水110部、ドデシルベンゼンスルホン酸ナトリ
ウム1.0部、ソルビタンモノステアレート（HLB
＝4.7）8.0部、チタン酸テトラブチルエステル0.6
部及び過硫酸アンモニウム0.5部を仕込みゆるや
かに窒素ガスを吹込みながら75℃に加熱し、撹拌
して均一な水溶液とした。次にγ−メタクリロキ
シプロピルトリメトキシシラン３部、ヒドロキシ
エチルアクリレート10部、メチルメタクリレート
21部、エチルアクリレート66部およびオルガノポ
リシロキサン(2)６部よりなる重合性単量体および
オルガノポリシロキサンの混合物を２時間かけて
滴下ロートより滴下した。その後温度を75℃に保
ちながら２時間撹拌をつづけ、次いで室温まで冷
却して水分散性シリコン変性ビニル重合体(7)を得
た。
実施例 ８
参考例１で使用したのと同じフラスコに脱イオ
ン水154部、ラウリル硫酸ナトリウム１部、ポリ
オキシエチレンオレイン酸エステル（HLB＝９）
３部および過硫酸カリウム0.4部を仕込みゆるや
かに窒素ガスを吹込みながら75℃に加熱し、撹拌
して均一な水溶液とした。次にアクリル酸３部、
メチルメタクリレート13部およびブチルアクリレ
ート34部よりなる第１の重合性単量体混合物を１
時間かけて滴下ロートより滴下し、さらに30分間
撹拌した。ついで予め調製しておいたビニルトリ
メトキシシラン５部、メチルメタクリレート12
部、ブチルアクリレート33部、オルガノポリシロ
キサン(1)３部およびジブチル錫ジラウレート0.3
部よりなる重合性単量体、オルガノポリシロキサ
ンおよび反応触媒の混合物を１時間かけて滴下し
た。その後温度を75℃に保持し、さらに１時間撹
拌をつづけ、次いで室温まで冷却した後28％アン
モニア水を加えてPHを約８に調整して水分散性シ
リコン変性ビニル重合体(8)を得た。
実施例 ９
参考例１で使用したのと同じフラスコに脱イオ
ン水152部、ラウリル硫酸ナトリウム１部、オル
ガノポリシロキサンの水性乳化物（有効成分60
％）５部および過硫酸カリウム0.4部を仕込みゆ
るやかに窒素ガスを吹込みながら75℃に加熱し、
撹拌して均一な水溶液とした。次にビニルトリメ
トキシシラン３部、アクリル酸１部、メチルメタ
クリレート30部およびブチルアクリレート66部よ
りなる重合性単量体混合物を２時間かけて滴下ロ
ートより滴下した。次いでジブチル錫ジラウレー
ト0.3部を加えて温度を75℃に保ちながら２時間
撹拌をつづけた後冷却し、５％水酸化ナトリウム
水溶液を加えてPHを約７に調整して水分散性シリ
コン変性ビニル重合体(9)を得た。
実施例 10
実施例１〜９で得たシリコン変性ビニル重合体
をキシレンで脱脂した磨軟鋼板にNo.32バーコータ
ーで塗布し、150℃で10分間加熱乾燥した後の塗
膜の物性を第３表にまとめた。
比較例 １〜５
参考例１〜５で得た水分散性ビニル系共重合体
(1)〜(5)をオルガノポリシロキサンで変性せずにそ
のまま用いて、キシレンで脱脂した磨軟鋼板にNo.
32バーコーターで塗布し、150℃で10分間加熱乾
燥した後の塗膜の物性を第３表に示した。
比較例 ６
参考例１で使用したのと同じフラスコに比較参
考例１で得た水分散性ビニル系共重合体(6)258部
およびジブチル錫ジアセテート0.3部を仕込み撹
拌しながら75℃に加熱した。次いでオルガノポリ
シロキサン(1)３部を滴下ロートより30分間かけて
滴下した。その後温度を75℃に保ちながら２時間
撹拌をつづけた後、冷却して比較用のオルガノポ
リシロキサンを含む水分散性ビニル系共重合体を
得た。これをキシレンで脱脂した磨軟鋼板にNo.32
バーコータで塗布し、150℃で10分間加熱乾燥し
た後の塗膜の物性を第３表に示した。[Table] Example 6 In the same flask as used in Reference Example 1, 154 parts of deionized water, 1 part of sodium lauryl sulfate, and polyoxyethylene oleate (HLB = 9) were added.
3 parts of organopolysiloxane (1), 0.3 parts of dibutyltin dilaurate, and 0.4 parts of potassium persulfate were heated to 75° C. and stirred while gently blowing nitrogen gas to form a uniform aqueous solution. Next, 5 parts of vinyltrimethoxysilane, 3 parts of acrylic acid, 25 parts of methyl methacrylate and butyl acrylate.
A polymerizable monomer mixture consisting of 67 parts was added dropwise from the dropping funnel over a period of 2 hours. Thereafter, stirring was continued for 2 hours while maintaining the temperature at 75°C, and then, after cooling to room temperature, 28% ammonia water was added to adjust the pH to about 8 to obtain a water-dispersible silicone-modified vinyl polymer (6). Example 7 In the same flask used in Reference Example 1, 110 parts of deionized water, 1.0 part of sodium dodecylbenzenesulfonate, and sorbitan monostearate (HLB) were added.
= 4.7) 8.0 parts, titanate tetrabutyl ester 0.6
1 part and 0.5 part of ammonium persulfate were added, heated to 75°C while slowly blowing nitrogen gas, and stirred to obtain a uniform aqueous solution. Next, 3 parts of γ-methacryloxypropyltrimethoxysilane, 10 parts of hydroxyethyl acrylate, and methyl methacrylate.
A mixture of a polymerizable monomer and an organopolysiloxane consisting of 21 parts of ethyl acrylate, 66 parts of ethyl acrylate, and 6 parts of organopolysiloxane (2) was added dropwise from the dropping funnel over a period of 2 hours. Thereafter, stirring was continued for 2 hours while maintaining the temperature at 75°C, and then the mixture was cooled to room temperature to obtain a water-dispersible silicone-modified vinyl polymer (7). Example 8 In the same flask as used in Reference Example 1, 154 parts of deionized water, 1 part of sodium lauryl sulfate, and polyoxyethylene oleate (HLB=9) were added.
3 parts of potassium persulfate and 0.4 parts of potassium persulfate were added, heated to 75°C while slowly blowing nitrogen gas, and stirred to obtain a uniform aqueous solution. Next, 3 parts of acrylic acid,
1 of the first polymerizable monomer mixture consisting of 13 parts of methyl methacrylate and 34 parts of butyl acrylate
The mixture was added dropwise from the dropping funnel over time and stirred for an additional 30 minutes. Next, 5 parts of vinyltrimethoxysilane and 12 parts of methyl methacrylate prepared in advance
parts, butyl acrylate 33 parts, organopolysiloxane (1) 3 parts and dibutyltin dilaurate 0.3 parts
A mixture of a polymerizable monomer, an organopolysiloxane, and a reaction catalyst was added dropwise over 1 hour. Thereafter, the temperature was maintained at 75°C and stirring was continued for another hour, and then after cooling to room temperature, 28% ammonia water was added to adjust the pH to about 8 to obtain a water-dispersible silicone-modified vinyl polymer (8). Ta. Example 9 Into the same flask used in Reference Example 1, 152 parts of deionized water, 1 part of sodium lauryl sulfate, and an aqueous emulsion of organopolysiloxane (active ingredient: 60
%) and 0.4 parts of potassium persulfate and heated to 75℃ while gently blowing nitrogen gas.
Stir to obtain a homogeneous aqueous solution. Next, a polymerizable monomer mixture consisting of 3 parts of vinyltrimethoxysilane, 1 part of acrylic acid, 30 parts of methyl methacrylate, and 66 parts of butyl acrylate was added dropwise from the dropping funnel over a period of 2 hours. Next, 0.3 part of dibutyltin dilaurate was added, stirring was continued for 2 hours while maintaining the temperature at 75°C, and the mixture was cooled, and a 5% aqueous sodium hydroxide solution was added to adjust the pH to about 7 to form a water-dispersible silicone-modified vinyl polymer. Obtained combination (9). Example 10 The silicone-modified vinyl polymers obtained in Examples 1 to 9 were applied to a polished mild steel plate degreased with xylene using a No. 32 bar coater, and the physical properties of the coating film after drying by heating at 150°C for 10 minutes were evaluated. The results are summarized in 3 tables. Comparative Examples 1 to 5 Water-dispersible vinyl copolymers obtained in Reference Examples 1 to 5
Using (1) to (5) as they are without modifying them with organopolysiloxane, No.
Table 3 shows the physical properties of the coating film after coating with a 32 bar coater and heating and drying at 150°C for 10 minutes. Comparative Example 6 In the same flask as used in Reference Example 1, 258 parts of the water-dispersible vinyl copolymer (6) obtained in Comparative Reference Example 1 and 0.3 part of dibutyltin diacetate were charged and heated to 75°C with stirring. did. Next, 3 parts of organopolysiloxane (1) was added dropwise from the dropping funnel over 30 minutes. Thereafter, stirring was continued for 2 hours while maintaining the temperature at 75° C., and then cooled to obtain a water-dispersible vinyl copolymer containing organopolysiloxane for comparison. No. 32 was applied to a polished mild steel plate degreased with xylene.
Table 3 shows the physical properties of the coating film after coating with a bar coater and heating and drying at 150°C for 10 minutes.
【表】【table】
Claims (1)
少なくとも１個の珪素原子に直結する加水分解性
基とを有する有機珪素単量体(A)0.1〜50重量％お
よび該単量体(A)と共重合可能なその他の重合性単
量体(B)50〜99.9重量％（ただし、(A)＋(B)＝100重
量％である。）を、分子中に少なくとも１個の珪
素原子に直結する水素原子を有しかつ平均組成式
が 【式】（Ｒは炭素数１〜10個の置換 もしくは非置換の一価の炭化水素基であり、ａお
よびｂはそれぞれ0.2≦ａ≦2.5、0.0005≦ｂ≦1.0
でありかつａ＋ｂは0.3≦ａ＋ｂ≦3.0である。）
で表されるオルガノポリシロキサンの存在下で共
重合させるか、予め共重合させておいて前記オル
ガノポリシロキサンと反応させるようにする、 水分散性シリコン変性ビニル重合体の製造方法。[Scope of Claims] 1. 0.1 to 50% by weight of an organosilicon monomer (A) having at least one polymerizable unsaturated group and at least one hydrolyzable group directly bonded to a silicon atom in the molecule; 50 to 99.9% by weight of another polymerizable monomer (B) copolymerizable with the monomer (A) (however, (A) + (B) = 100% by weight) is contained in the molecule. It has a hydrogen atom directly connected to at least one silicon atom and has an average compositional formula of [Formula] (R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and a and b are 0.2≦a≦2.5, 0.0005≦b≦1.0, respectively
and a+b is 0.3≦a+b≦3.0. )
A method for producing a water-dispersible silicone-modified vinyl polymer, which comprises copolymerizing in the presence of an organopolysiloxane represented by the formula above, or copolymerizing in advance and reacting with the organopolysiloxane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59145905A JPS6126627A (en) | 1984-07-16 | 1984-07-16 | Water-dispersible silicon-modified vinyl polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59145905A JPS6126627A (en) | 1984-07-16 | 1984-07-16 | Water-dispersible silicon-modified vinyl polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6126627A JPS6126627A (en) | 1986-02-05 |
| JPH0466897B2 true JPH0466897B2 (en) | 1992-10-26 |
Family
ID=15395768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59145905A Granted JPS6126627A (en) | 1984-07-16 | 1984-07-16 | Water-dispersible silicon-modified vinyl polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6126627A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3820635B2 (en) * | 1996-07-26 | 2006-09-13 | 大日本インキ化学工業株式会社 | Method for producing aqueous resin dispersion or aqueous resin solution |
| JP3796826B2 (en) * | 1996-07-30 | 2006-07-12 | 大日本インキ化学工業株式会社 | Method for producing aqueous resin dispersion or aqueous resin solution |
| JP5493286B2 (en) * | 2008-04-04 | 2014-05-14 | Ｄｉｃ株式会社 | Organic-inorganic hybrid resin aqueous dispersion, curable resin composition, paint and paint |
-
1984
- 1984-07-16 JP JP59145905A patent/JPS6126627A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6126627A (en) | 1986-02-05 |
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