JP2018080223A - Silicone resin-containing emulsion composition and cured coat-forming substrate - Google Patents
Silicone resin-containing emulsion composition and cured coat-forming substrate Download PDFInfo
- Publication number
- JP2018080223A JP2018080223A JP2016221751A JP2016221751A JP2018080223A JP 2018080223 A JP2018080223 A JP 2018080223A JP 2016221751 A JP2016221751 A JP 2016221751A JP 2016221751 A JP2016221751 A JP 2016221751A JP 2018080223 A JP2018080223 A JP 2018080223A
- Authority
- JP
- Japan
- Prior art keywords
- group
- mass
- emulsion
- parts
- silicone resin
- 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 108
- 229920002050 silicone resin Polymers 0.000 title claims abstract description 51
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 239000000758 substrate Substances 0.000 title abstract description 11
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 51
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 35
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910000077 silane Inorganic materials 0.000 claims abstract description 25
- 239000012875 nonionic emulsifier Substances 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims description 47
- 239000011347 resin Substances 0.000 claims description 47
- 125000000524 functional group Chemical group 0.000 claims description 26
- 229920000642 polymer Polymers 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 230000007062 hydrolysis Effects 0.000 claims description 17
- 238000006460 hydrolysis reaction Methods 0.000 claims description 17
- 239000006227 byproduct Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002612 dispersion medium Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 125000005907 alkyl ester group Chemical group 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 11
- 239000000243 solution Substances 0.000 abstract description 6
- -1 9-decenyl group Chemical group 0.000 description 53
- 239000011248 coating agent Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 19
- 229940048053 acrylate Drugs 0.000 description 13
- 150000003254 radicals Chemical class 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 125000005372 silanol group Chemical group 0.000 description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000011253 protective coating Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000005215 alkyl ethers Chemical class 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- LTSWUFKUZPPYEG-UHFFFAOYSA-N 1-decoxydecane Chemical compound CCCCCCCCCCOCCCCCCCCCC LTSWUFKUZPPYEG-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229940114077 acrylic acid Drugs 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- 239000002023 wood 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
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 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
- 239000013011 aqueous formulation Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 2
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000006353 oxyethylene group Chemical group 0.000 description 2
- 239000006174 pH buffer Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- BLKRGXCGFRXRNQ-SNAWJCMRSA-N (z)-3-carbonoperoxoyl-4,4-dimethylpent-2-enoic acid Chemical compound OC(=O)/C=C(C(C)(C)C)\C(=O)OO BLKRGXCGFRXRNQ-SNAWJCMRSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- CSHOPPGMNYULAD-UHFFFAOYSA-N 1-tridecoxytridecane Chemical compound CCCCCCCCCCCCCOCCCCCCCCCCCCC CSHOPPGMNYULAD-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
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[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
- TYNDQCKMWHYOHW-UHFFFAOYSA-N 3-(4-ethenylphenyl)propyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCC1=CC=C(C=C)C=C1 TYNDQCKMWHYOHW-UHFFFAOYSA-N 0.000 description 1
- KSDYOJYWQOKMLC-UHFFFAOYSA-N 3-(4-ethenylphenyl)propyl-trimethoxysilane Chemical compound CO[Si](OC)(OC)CCCC1=CC=C(C=C)C=C1 KSDYOJYWQOKMLC-UHFFFAOYSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-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
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- PXIAXSAEMIOWHH-UHFFFAOYSA-N C(=C)CCCC[SiH2][SiH2][SiH3] Chemical compound C(=C)CCCC[SiH2][SiH2][SiH3] PXIAXSAEMIOWHH-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 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
- 150000008051 alkyl sulfates Chemical class 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
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- ZRGUXTGDSGGHLR-UHFFFAOYSA-K aluminum;triperchlorate Chemical compound [Al+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O ZRGUXTGDSGGHLR-UHFFFAOYSA-K 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002928 artificial marble Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011449 brick Substances 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
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- FQEKAFQSVPLXON-UHFFFAOYSA-N butyl(trichloro)silane Chemical compound CCCC[Si](Cl)(Cl)Cl FQEKAFQSVPLXON-UHFFFAOYSA-N 0.000 description 1
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 description 1
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- KWYZNESIGBQHJK-UHFFFAOYSA-N chloro-dimethyl-phenylsilane Chemical compound C[Si](C)(Cl)C1=CC=CC=C1 KWYZNESIGBQHJK-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- GCFAUZGWPDYAJN-UHFFFAOYSA-N cyclohexyl 3-phenylprop-2-enoate Chemical compound C=1C=CC=CC=1C=CC(=O)OC1CCCCC1 GCFAUZGWPDYAJN-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- ATGKAFZFOALBOF-UHFFFAOYSA-N cyclohexyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C1CCCCC1 ATGKAFZFOALBOF-UHFFFAOYSA-N 0.000 description 1
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 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
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 description 1
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- GQNWJCQWBFHQAO-UHFFFAOYSA-N dibutoxy(dimethyl)silane Chemical compound CCCCO[Si](C)(C)OCCCC GQNWJCQWBFHQAO-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 description 1
- KKRMHVJQWMXYBZ-UHFFFAOYSA-N dichloro-hexyl-methylsilane Chemical compound CCCCCC[Si](C)(Cl)Cl KKRMHVJQWMXYBZ-UHFFFAOYSA-N 0.000 description 1
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 1
- GNVPGBIHGALKRR-UHFFFAOYSA-N dichloro-methyl-propylsilane Chemical compound CCC[Si](C)(Cl)Cl GNVPGBIHGALKRR-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- YTDDWYQXURUACY-UHFFFAOYSA-N diethoxy-hexyl-methylsilane Chemical compound CCCCCC[Si](C)(OCC)OCC YTDDWYQXURUACY-UHFFFAOYSA-N 0.000 description 1
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 description 1
- UJTGYJODGVUOGO-UHFFFAOYSA-N diethoxy-methyl-propylsilane Chemical compound CCC[Si](C)(OCC)OCC UJTGYJODGVUOGO-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- DVYUOQXRGHUWKE-UHFFFAOYSA-N dimethyl(2-phenylethoxy)silane Chemical compound C[SiH](C)OCCC1=CC=CC=C1 DVYUOQXRGHUWKE-UHFFFAOYSA-N 0.000 description 1
- JOJYIOOVPHLXBQ-UHFFFAOYSA-N dimethyl-bis(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](C)(C)OC(C)=C JOJYIOOVPHLXBQ-UHFFFAOYSA-N 0.000 description 1
- BPXCAJONOPIXJI-UHFFFAOYSA-N dimethyl-di(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(C)OC(C)C BPXCAJONOPIXJI-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000000499 gel 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
- 238000013007 heat curing Methods 0.000 description 1
- CGQIJXYITMTOBI-UHFFFAOYSA-N hex-5-enyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCC=C CGQIJXYITMTOBI-UHFFFAOYSA-N 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- APQKDJQPCPXLQL-UHFFFAOYSA-N hexyl-dimethoxy-methylsilane Chemical compound CCCCCC[Si](C)(OC)OC APQKDJQPCPXLQL-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 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
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 230000014759 maintenance of location 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- REQXNMOSXYEQLM-UHFFFAOYSA-N methoxy-dimethyl-phenylsilane Chemical compound CO[Si](C)(C)C1=CC=CC=C1 REQXNMOSXYEQLM-UHFFFAOYSA-N 0.000 description 1
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- HLXDKGBELJJMHR-UHFFFAOYSA-N methyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(OC(C)C)OC(C)C HLXDKGBELJJMHR-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 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
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 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
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- UMSVPCYSAUKCAZ-UHFFFAOYSA-N propane;hydrochloride Chemical compound Cl.CCC UMSVPCYSAUKCAZ-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000005053 propyltrichlorosilane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- JTDPJYXDDYUJBS-UHFFFAOYSA-N quinoline-2-carbohydrazide Chemical compound C1=CC=CC2=NC(C(=O)NN)=CC=C21 JTDPJYXDDYUJBS-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl 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])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])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- SIPHWXREAZVVNS-UHFFFAOYSA-N trichloro(cyclohexyl)silane Chemical compound Cl[Si](Cl)(Cl)C1CCCCC1 SIPHWXREAZVVNS-UHFFFAOYSA-N 0.000 description 1
- HLWCOIUDOLYBGD-UHFFFAOYSA-N trichloro(decyl)silane Chemical compound CCCCCCCCCC[Si](Cl)(Cl)Cl HLWCOIUDOLYBGD-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
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- IHYCWJYGNRZAOB-UHFFFAOYSA-N trichloro(hex-5-enyl)silane Chemical compound Cl[Si](Cl)(Cl)CCCCC=C IHYCWJYGNRZAOB-UHFFFAOYSA-N 0.000 description 1
- LFXJGGDONSCPOF-UHFFFAOYSA-N trichloro(hexyl)silane Chemical compound CCCCCC[Si](Cl)(Cl)Cl LFXJGGDONSCPOF-UHFFFAOYSA-N 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- DOEHJNBEOVLHGL-UHFFFAOYSA-N trichloro(propyl)silane Chemical compound CCC[Si](Cl)(Cl)Cl DOEHJNBEOVLHGL-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- RKYSDIOEHLMYRS-UHFFFAOYSA-N triethoxy(hex-5-enyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCC=C RKYSDIOEHLMYRS-UHFFFAOYSA-N 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- UAIFZYSPVVBOPN-UHFFFAOYSA-N trimethyl(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](C)(C)C UAIFZYSPVVBOPN-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- DAOVYDBYKGXFOB-UHFFFAOYSA-N tris(2-methylpropoxy)alumane Chemical compound [Al+3].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] DAOVYDBYKGXFOB-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、シリコーン樹脂含有エマルジョン組成物、特には加水分解性基及び／又はシラノール基の縮合反応により硬化するシリコーン樹脂含有エマルジョン組成物、及び硬化被膜形成基材に関する。 The present invention relates to a silicone resin-containing emulsion composition, in particular, a silicone resin-containing emulsion composition that cures by a condensation reaction of hydrolyzable groups and / or silanol groups, and a cured film-forming substrate.
近年、環境保護及び安全な作業環境確保の観点から、塗料・コーティング剤分野において、有機溶剤系から水系へと分散媒の変更が求められている。この要求に基づき、アクリル樹脂に代表されるビニル重合性モノマーを乳化重合したエマルジョン系塗料が、優れた被膜形成性及び耐薬品性の良さからコーティング剤の基本材料として幅広く使用されている。しかしながら、この種の塗料は本質的に耐候性及び耐水性、耐熱性に劣るといった欠点を有している。 In recent years, from the viewpoint of environmental protection and ensuring a safe working environment, in the field of paints and coating agents, it is required to change the dispersion medium from an organic solvent system to an aqueous system. Based on this requirement, an emulsion-based paint obtained by emulsion polymerization of a vinyl polymerizable monomer typified by an acrylic resin is widely used as a basic material for a coating agent because of its excellent film-forming property and chemical resistance. However, this type of coating material has drawbacks such as inherently poor weather resistance, water resistance, and heat resistance.
一方、シラン化合物を加水分解・重合して得られるシリコーンレジンは、高硬度で耐候性、耐水性、耐熱性、撥水性に優れた被膜を形成する能力があるため、コーティング剤として注目されている。しかしながら、現在確立されているシリコーンレジンのエマルジョンの製造処方は何れも欠点を有している。 On the other hand, silicone resins obtained by hydrolyzing and polymerizing silane compounds are attracting attention as coating agents because of their high hardness and ability to form films with excellent weather resistance, water resistance, heat resistance, and water repellency. . However, all established formulations for silicone resin emulsions have drawbacks.
例えば、アルコキシシラン化合物を水中で加水分解させた水溶液は、数％程度の低濃度や狭いｐＨ範囲等の限られた条件でしか安定性を保てず、また多量のアルコールが副生するため、他のエマルジョンと混合した際に系が不安定になる問題を抱えている。 For example, an aqueous solution obtained by hydrolyzing an alkoxysilane compound in water can maintain stability only under limited conditions such as a low concentration of several percent or a narrow pH range, and a large amount of alcohol is produced as a by-product. When mixed with other emulsions, the system becomes unstable.
また、シリコーンレジンのポリマーを乳化してエマルジョンを得る方法は、ポリマーが液状である必要があるが、液状のポリマーは低分子量のため、乾燥後に硬化被膜を得るためには有機スズ等の有害な金属触媒や高温・長時間の乾燥工程が必要になる問題を抱えている。 In addition, the method of emulsifying a silicone resin polymer to obtain an emulsion requires that the polymer be in a liquid state, but the liquid polymer has a low molecular weight. It has a problem that requires a metal catalyst and a high-temperature, long-time drying process.
一方で、固形のシリコーンレジンを水系処方に使用するためには、トルエンやキシレン等の有機溶剤中で製造されたシリコーンレジン溶液をそのまま乳化したり、別の有機溶剤に置換した溶液を乳化してエマルジョン化する必要があるが（特許文献１、特許文献２）、この方法では水系処方でありながら有機溶剤を多く含むことになり、前述の環境保護及び安全な作業環境確保を完全に満足することはできなかった。 On the other hand, in order to use a solid silicone resin in an aqueous formulation, a silicone resin solution produced in an organic solvent such as toluene or xylene is emulsified as it is, or a solution substituted with another organic solvent is emulsified. Although it is necessary to emulsify (Patent Document 1 and Patent Document 2), this method contains a large amount of organic solvent while being an aqueous formulation, and completely satisfies the above-mentioned environmental protection and ensuring a safe working environment. I couldn't.
さらに上記の固形のシリコーンレジンからなる被膜は高硬度等の利点の反面、可撓性に劣り、基材の伸縮等によってクラックが発生する等の問題を抱えている。この問題の解決策として、アクリル樹脂等とシリコーンレジンを併用する方法が提案されているが（特許文献３、特許文献４）、実際には乾燥硬化時に双方のポリマーの相溶性が不足して相分離し、均一な被膜が得られない問題がある。またビニル重合性官能基含有アルコキシシランを、ラジカル重合性ビニルモノマーと共に、乳化重合してエマルジョンを作製する方法（特許文献５、特許文献６）が提案されているが、被膜中にシリコーン樹脂成分を多量に含有させることは難しく、そのため耐候性等の特性を向上させることができない問題がある。 Furthermore, the coating film made of the above-described solid silicone resin has advantages such as high hardness, but is inferior in flexibility, and has problems such as generation of cracks due to expansion and contraction of the substrate. As a solution to this problem, a method in which an acrylic resin or the like and a silicone resin are used in combination has been proposed (Patent Documents 3 and 4). However, in reality, the compatibility of both polymers is insufficient at the time of drying and curing. There exists a problem which isolate | separates and a uniform film cannot be obtained. In addition, a method (Patent Document 5 and Patent Document 6) in which an emulsion is prepared by emulsion polymerization of a vinyl polymerizable functional group-containing alkoxysilane together with a radical polymerizable vinyl monomer has been proposed. It is difficult to contain in a large amount, and therefore there is a problem that characteristics such as weather resistance cannot be improved.
また末端に水酸基を有するポリジオルガノシロキサンをコロイダルシリカの存在下にて重合させて得られるシリコーン水性乳濁液は、シリコーンレジンよりも柔らかいシリコーンゴム被膜を与えることが知られているが（特許文献７）、ポリジオルガノシロキサンを主原料とするために耐熱性が劣る問題があり、またコーティング剤として使用した場合には十分な硬さの被膜が得られず、耐擦傷性が劣ることも問題となっている。 Further, it is known that a silicone aqueous emulsion obtained by polymerizing a polydiorganosiloxane having a hydroxyl group at the terminal in the presence of colloidal silica gives a silicone rubber film that is softer than a silicone resin (Patent Document 7). ), Since polydiorganosiloxane is the main raw material, there is a problem that heat resistance is inferior, and when it is used as a coating agent, a film with sufficient hardness cannot be obtained, and the scratch resistance is also inferior. ing.
本発明は、上記事情に鑑みなされたもので、従来のシリコーンレジンエマルジョンに比べ環境上の問題が低減され、安定性が良好で、かつ、得られる被膜が高硬度であるシリコーン樹脂含有エマルジョン組成物、及び硬化被膜形成基材を提供することを目的とする。 The present invention has been made in view of the above circumstances, and has a silicone resin-containing emulsion composition in which environmental problems are reduced compared to conventional silicone resin emulsions, the stability is good, and the resulting coating has a high hardness. And it aims at providing a cured film formation base material.
上記課題を解決するために、本発明によれば、下記（Ａ）〜（Ｃ）成分を含有するオルガノシリコーンレジンエマルジョン（Ｉ）と、下記（Ｄ）成分のポリマーを含むエマルジョン（ＩＩ）との混合溶液であり、
（Ａ）下記平均組成式（１）で示される、２５℃で粘度が１００，０００ｍｍ２／ｓ以下のオルガノシリコーンレジン：１００質量部、
Ｒ１ ｍＳｉ（ＯＸ）ｐ（ＯＨ）ｑＯ（４−ｍ−ｐ−ｑ）／２・・・（１）
（式中、Ｒ１は非置換一価炭化水素基、ＯＸは加水分解性基であり、Ｘは１価炭化水素基を表す。ｍ，ｐ，ｑは０．５≦ｍ≦１．８、０．０５≦ｐ≦１．０、０≦ｑ≦０．５、０．０５≦ｐ＋ｑ≦１．５を満たす数である。）
（Ｂ）ノニオン系乳化剤：１〜５０質量部、
（Ｃ）水：２５〜２，０００質量部、
（Ｄ）下記一般式（２）で示されるビニル重合性官能基含有加水分解性シランと、該ビニル重合性官能基含有加水分解性シラン以外のラジカル重合性ビニルモノマーとの共重合体であり、該共重合体中の全モノマー単位に対して、下記一般式（２）で示されるビニル重合性官能基含有加水分解性シラン単位が０．０１〜１０モル％であるポリマー：（Ａ）成分１００質量部に対して１０〜１，０００質量部、
前記オルガノシリコーンレジンエマルジョン（Ｉ）は、前記（Ｂ）成分のノニオン系乳化剤以外の乳化剤を含まないものであり、かつ、加水分解性基ＯＸの加水分解による副生物であるアルコール以外の有機溶剤を含まないものであることを特徴とするシリコーン樹脂含有エマルジョン組成物を提供する。
In order to solve the above problems, according to the present invention, an organosilicone resin emulsion (I) containing the following components (A) to (C) and an emulsion (II) containing a polymer of the following component (D): A mixed solution,
(A) Organosilicone resin represented by the following average composition formula (1) and having a viscosity of 100,000 mm 2 / s or less at 25 ° C .: 100 parts by mass,
R 1 m Si (OX) p (OH) q O (4-mpq) / 2 (1)
(In the formula, R 1 represents an unsubstituted monovalent hydrocarbon group, OX represents a hydrolyzable group, X represents a monovalent hydrocarbon group, and m, p, and q are 0.5 ≦ m ≦ 1.8, Numbers satisfying 0.05 ≦ p ≦ 1.0, 0 ≦ q ≦ 0.5, and 0.05 ≦ p + q ≦ 1.5.)
(B) Nonionic emulsifier: 1 to 50 parts by mass,
(C) Water: 25-2,000 parts by mass,
(D) a copolymer of a vinyl polymerizable functional group-containing hydrolyzable silane represented by the following general formula (2) and a radical polymerizable vinyl monomer other than the vinyl polymerizable functional group-containing hydrolyzable silane; Polymer in which the vinyl polymerizable functional group-containing hydrolyzable silane unit represented by the following general formula (2) is 0.01 to 10 mol% with respect to all monomer units in the copolymer: (A) Component 100 10 to 1,000 parts by mass with respect to parts by mass,
The organosilicone resin emulsion (I) does not contain an emulsifier other than the nonionic emulsifier of the component (B), and an organic solvent other than alcohol which is a by-product by hydrolysis of the hydrolyzable group OX. A silicone resin-containing emulsion composition is provided that does not contain the silicone resin.
このような本発明のシリコーン樹脂含有エマルジョン組成物は、従来のシリコーンレジンエマルジョンに比べ環境上の問題が低減され、安定性が良好で、かつ、得られる被膜が高硬度であるシリコーン樹脂含有エマルジョン組成物となる。 The silicone resin-containing emulsion composition of the present invention has a silicone resin-containing emulsion composition in which environmental problems are reduced as compared with conventional silicone resin emulsions, the stability is good, and the resulting coating has high hardness. It becomes a thing.
またこの場合、前記エマルジョン（ＩＩ）は、分散媒が水であることが好ましい。 In this case, the emulsion (II) preferably has a dispersion medium of water.
このようなシリコーン樹脂含有エマルジョン組成物は、更に環境上の問題が低減されたものとなるために好ましい。 Such a silicone resin-containing emulsion composition is preferable because environmental problems are further reduced.
またこの場合、前記（Ｄ）成分における、前記一般式（２）で示されるビニル重合性官能基含有加水分解性シラン以外のラジカル重合性ビニルモノマーが、アルキル基の炭素数が１〜１８の（メタ）アクリル酸アルキルエステルであることが好ましい。 In this case, in the component (D), the radical polymerizable vinyl monomer other than the vinyl polymerizable functional group-containing hydrolyzable silane represented by the general formula (2) is an alkyl group having 1 to 18 carbon atoms ( A meth) acrylic acid alkyl ester is preferred.
このようなラジカル重合性ビニルモノマーであれば、シリコーン樹脂含有エマルジョン組成物から得られる被膜の耐薬品性や、可撓性が優れるために好ましい。 Such a radical polymerizable vinyl monomer is preferable because the chemical resistance and flexibility of the film obtained from the silicone resin-containing emulsion composition are excellent.
また、本発明では、前記シリコーン樹脂含有エマルジョン組成物の硬化被膜が形成された硬化被膜形成基材を提供する。 Moreover, in this invention, the cured film formation base material with which the cured film of the said silicone resin containing emulsion composition was formed is provided.
このように、本発明のシリコーン樹脂含有エマルジョン組成物の硬化被膜は、高硬度で可撓性に富み、接着性、耐候性、耐熱性も良好であり、更に優れた撥水性も有するため、様々な基材に形成することができる。 Thus, the cured film of the silicone resin-containing emulsion composition of the present invention has high hardness, high flexibility, good adhesiveness, weather resistance, heat resistance, and excellent water repellency. Can be formed on any substrate.
本発明におけるオルガノシリコーンレジンエマルジョン（Ｉ）は、耐候性、耐水性、及び耐熱性が良好で、かつ高硬度な被膜を形成するシリコーンレジンの安定なエマルジョンであり、このオルガノシリコーンレジンエマルジョン（Ｉ）と、特定のビニル重合性官能基含有加水分解性シラン０．０１〜１０モル％とその他のラジカル重合性ビニルモノマーとを共重合したポリマーを含むエマルジョン（ＩＩ）との混合溶液である本発明のシリコーン樹脂含有エマルジョン組成物は、従来のシリコーンレジンエマルジョンに比べ環境上の問題が低減され、安定性が良好で、室温又は加熱硬化後に耐候性、耐水性、耐熱性、可撓性に優れた、高硬度の被膜を得ることができる。 The organosilicone resin emulsion (I) in the present invention is a stable emulsion of a silicone resin that forms a high hardness film with good weather resistance, water resistance, and heat resistance. This organosilicone resin emulsion (I) And an emulsion (II) containing a polymer obtained by copolymerizing 0.01 to 10 mol% of a specific vinyl polymerizable functional group-containing hydrolyzable silane and another radical polymerizable vinyl monomer. The silicone resin-containing emulsion composition has reduced environmental problems compared to conventional silicone resin emulsions, has good stability, and has excellent weather resistance, water resistance, heat resistance and flexibility after room temperature or heat curing. A high hardness coating can be obtained.
本発明者は、上記目的を達成するため鋭意検討を行った結果、（Ａ）成分の下記平均組成式（１）で示される２５℃で粘度が１００，０００ｍｍ２／ｓ以下であるオルガノシリコーンレジンを含み、加水分解性基ＯＸの加水分解によって副生するアルコール以外の有機溶剤を含まないオルガノシリコーンレジンのエマルジョン（Ｉ）と、加水分解性基及び／又はシラノール基を分子中に有するラジカル重合性ビニルポリマーを主成分とするエマルジョン（ＩＩ）の混合溶液が、従来のシリコーンレジンエマルジョンに比べ環境上の問題が低減され、安定性が良好であり、得られる被膜の耐候性及び耐水性、耐熱性が良好で、高硬度の被膜を与えることを見出し、本発明を完成させた。以下、本発明のシリコーン樹脂含有エマルジョン組成物及び硬化被膜形成基材について詳細に説明する。 As a result of intensive studies to achieve the above object, the present inventor has obtained an organosilicone resin having a viscosity of not more than 100,000 mm 2 / s at 25 ° C. represented by the following average composition formula (1) of the component (A): Radical emulsion having a hydrolyzable group and / or a silanol group in the molecule and an emulsion (I) of an organosilicone resin containing no organic solvent other than alcohol by-produced by hydrolysis of hydrolyzable group OX Compared to conventional silicone resin emulsions, the mixed solution of emulsion (II) containing vinyl polymer as a main component has reduced environmental problems and good stability, and the weather resistance, water resistance, and heat resistance of the resulting coating Has been found to give a high hardness film, and the present invention has been completed. Hereinafter, the silicone resin-containing emulsion composition and the cured film-forming substrate of the present invention will be described in detail.
すなわち、本発明は、下記（Ａ）〜（Ｃ）成分を含有するオルガノシリコーンレジンエマルジョン（Ｉ）と、下記（Ｄ）成分のポリマーを含むエマルジョン（ＩＩ）との混合溶液であり、
（Ａ）下記平均組成式（１）で示される、２５℃で粘度が１００，０００ｍｍ２／ｓ以下のオルガノシリコーンレジン：１００質量部、
Ｒ１ ｍＳｉ（ＯＸ）ｐ（ＯＨ）ｑＯ（４−ｍ−ｐ−ｑ）／２ ・・・（１）
（式中、Ｒ１は非置換一価炭化水素基、ＯＸは加水分解性基であり、Ｘは１価炭化水素基を表す。ｍ，ｐ，ｑは０．５≦ｍ≦１．８、０．０５≦ｐ≦１．０、０≦ｑ≦０．５、０．０５≦ｐ＋ｑ≦１．５を満たす数である。）
（Ｂ）ノニオン系乳化剤：１〜５０質量部、
（Ｃ）水：２５〜２，０００質量部、
（Ｄ）下記一般式（２）で示されるビニル重合性官能基含有加水分解性シランと、該ビニル重合性官能基含有加水分解性シラン以外のラジカル重合性ビニルモノマーとの共重合体であり、該共重合体中の全モノマー単位に対して、下記一般式（２）で示されるビニル重合性官能基含有加水分解性シラン単位が０．０１〜１０モル％であるポリマー：（Ａ）成分１００質量部に対して１０〜１，０００質量部、
前記オルガノシリコーンレジンエマルジョン（I）は、前記（Ｂ）成分のノニオン系乳化剤以外の乳化剤を含まないものであり、かつ、加水分解性基ＯＸの加水分解による副生物であるアルコール以外の有機溶剤を含まないものであることを特徴とするシリコーン樹脂含有エマルジョン組成物である。
That is, the present invention is a mixed solution of an organosilicone resin emulsion (I) containing the following components (A) to (C) and an emulsion (II) containing a polymer of the following component (D),
(A) Organosilicone resin represented by the following average composition formula (1) and having a viscosity of 100,000 mm 2 / s or less at 25 ° C .: 100 parts by mass,
R 1 m Si (OX) p (OH) q O (4-mpq) / 2 (1)
(In the formula, R 1 represents an unsubstituted monovalent hydrocarbon group, OX represents a hydrolyzable group, X represents a monovalent hydrocarbon group, and m, p, and q are 0.5 ≦ m ≦ 1.8, Numbers satisfying 0.05 ≦ p ≦ 1.0, 0 ≦ q ≦ 0.5, and 0.05 ≦ p + q ≦ 1.5.)
(B) Nonionic emulsifier: 1 to 50 parts by mass,
(C) Water: 25-2,000 parts by mass,
(D) a copolymer of a vinyl polymerizable functional group-containing hydrolyzable silane represented by the following general formula (2) and a radical polymerizable vinyl monomer other than the vinyl polymerizable functional group-containing hydrolyzable silane; Polymer in which the vinyl polymerizable functional group-containing hydrolyzable silane unit represented by the following general formula (2) is 0.01 to 10 mol% with respect to all monomer units in the copolymer: (A) Component 100 10 to 1,000 parts by mass with respect to parts by mass,
The organosilicone resin emulsion (I) does not contain an emulsifier other than the nonionic emulsifier of the component (B), and an organic solvent other than alcohol which is a by-product by hydrolysis of the hydrolyzable group OX. It is a silicone resin containing emulsion composition characterized by not containing.
オルガノシリコーンレジンエマルジョン（Ｉ）
本発明におけるオルガノシリコーンレジンエマルジョン（Ｉ）は、下記（Ａ）〜（Ｃ）成分を含有し、下記（Ｂ）成分のノニオン系乳化剤以外の乳化剤を含まないものであり、かつ、加水分解性基ＯＸの加水分解による副生物であるアルコール以外の有機溶剤を含まないものである。
Organosilicone Resin Emulsion (I)
The organosilicone resin emulsion (I) in the present invention contains the following components (A) to (C), does not contain an emulsifier other than the nonionic emulsifier of the following (B) component, and has a hydrolyzable group. It does not contain organic solvents other than alcohol, which is a by-product of OX hydrolysis.
尚、本発明における「加水分解性基ＯＸの加水分解による副生物であるアルコール以外の有機溶剤を含まない」とは、オルガノシリコーンレジンエマルジョン（Ｉ）が加水分解性基ＯＸの加水分解による副生物であるアルコール以外の有機溶剤を全く含まない場合はもちろんのこと、実質的に加水分解性基ＯＸの加水分解による副生物であるアルコール以外の有機溶剤を含有しない場合、すなわち、意図的に含めたものはなく、安定性に影響がなく、環境上問題ない程度の微量（残渣あるいは不純物程度）の加水分解性基ＯＸの加水分解による副生物であるアルコール以外の有機溶剤が含まれる場合をも含むものである。 In the present invention, “no organic solvent other than alcohol which is a byproduct of hydrolysis of hydrolyzable group OX” means that the organosilicone resin emulsion (I) is a byproduct of hydrolysis of hydrolyzable group OX. As a matter of course, the organic solvent other than the alcohol which is a by-product of hydrolysis of the hydrolyzable group OX is not included. None, including a case where an organic solvent other than alcohol, which is a by-product of hydrolysis of hydrolyzable group OX, is contained in a trace amount (residue or impurities) that does not affect stability and has no environmental problems. It is a waste.
＜（Ａ）下記平均組成式（１）で示されるオルガノシリコーンレジン＞
本発明を構成する、加水分解性基を有する（Ａ）オルガノシリコーンレジンについて説明する。該オルガノシリコーンレジンは、下記平均組成式（１）で表される。
Ｒ１ ｍＳｉ（ＯＸ）ｐ（ＯＨ）ｑＯ（４−ｍ−ｐ−ｑ）／２ ・・・（１）
（式中、Ｒ１は非置換一価炭化水素基、ＯＸは加水分解性基であり、Ｘは１価炭化水素基を表す。ｍ，ｐ，ｑは０．５≦ｍ≦１．８、０．０５≦ｐ≦１．０、０≦ｑ≦０．５、０．０５≦ｐ＋ｑ≦１．５を満たす数である。）
<(A) Organosilicone resin represented by the following average composition formula (1)>
The (A) organosilicone resin having a hydrolyzable group constituting the present invention will be described. The organosilicone resin is represented by the following average composition formula (1).
R 1 m Si (OX) p (OH) q O (4-mpq) / 2 (1)
(In the formula, R 1 represents an unsubstituted monovalent hydrocarbon group, OX represents a hydrolyzable group, X represents a monovalent hydrocarbon group, and m, p, and q are 0.5 ≦ m ≦ 1.8, Numbers satisfying 0.05 ≦ p ≦ 1.0, 0 ≦ q ≦ 0.5, and 0.05 ≦ p + q ≦ 1.5.)
Ｒ１は非置換一価炭化水素基を表し、炭素数１〜１０のものが好ましく、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔ−ブチル基、ヘキシル基、シクロヘキシル基、オクチル基、デシル基等のアルキル基、及びビニル基、アリル基、５−ヘキセニル基、９−デセニル基などのアルケニル基、又はフェニル基等のアリール基を具体例として示すことができる。この中でも、メチル基、プロピル基、ヘキシル基、フェニル基が好ましい。特に耐候性を要求される場合はメチル基が好ましく、撥水性が求められる場合には長鎖アルキル基が好ましく、被膜に可撓性を付与する場合にはフェニル基を用いることが好ましい。また、Ｒ１は単独または複数の基を併用してもよいが、併用の場合、Ｒ１のメチル基の含有率が少なくとも８０モル％以上であることが好ましい。 R 1 represents an unsubstituted monovalent hydrocarbon group, preferably having 1 to 10 carbon atoms, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, cyclohexyl group, octyl group Specific examples include an alkyl group such as a group, a decyl group, and an alkenyl group such as a vinyl group, an allyl group, a 5-hexenyl group, and a 9-decenyl group, or an aryl group such as a phenyl group. Among these, a methyl group, a propyl group, a hexyl group, and a phenyl group are preferable. In particular, a methyl group is preferable when weather resistance is required, a long-chain alkyl group is preferable when water repellency is required, and a phenyl group is preferable when flexibility is imparted to the film. R 1 may be used alone or in combination with a plurality of groups, but in the case of use in combination, the content of methyl groups in R 1 is preferably at least 80 mol% or more.
ＯＸ基は加水分解性基を表し、Ｘは炭素数１〜６のアルキル基、アルケニル基、アリール基等の一価炭化水素基を表す。加水分解性基ＯＸの具体例としては、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔ−ブトキシ基、イソプロペノキシ基、フェノキシ基等を挙げることができる。加水分解・縮合反応性、エマルジョン中での安定性、及び原料の入手の容易さから、メトキシ基、エトキシ基を用いるのが好ましい。 The OX group represents a hydrolyzable group, and X represents a monovalent hydrocarbon group such as an alkyl group having 1 to 6 carbon atoms, an alkenyl group, or an aryl group. Specific examples of the hydrolyzable group OX include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, isopropenoxy group, phenoxy group and the like. . In view of hydrolysis / condensation reactivity, stability in emulsion, and availability of raw materials, it is preferable to use a methoxy group or an ethoxy group.
ｍ，ｐ，ｑは各々０．５≦ｍ≦１．８、０．０５≦ｐ≦１．０、０≦ｑ≦０．５、０．０５≦ｐ＋ｑ≦１．５の範囲を満たす数を表す。 m, p, and q are numbers satisfying the ranges of 0.5 ≦ m ≦ 1.8, 0.05 ≦ p ≦ 1.0, 0 ≦ q ≦ 0.5, and 0.05 ≦ p + q ≦ 1.5, respectively. Represent.
ｍが０．５未満ではＲ１の含有率が低く、被膜が硬くなりすぎ、硬化被膜にクラックが発生し易くなる。ｍが１．８を超えると、鎖状単位が多くなる結果、硬化被膜がゴム性を帯び、耐擦傷性が不足する。好ましくは、０．６≦ｍ≦１．５の範囲を満たす数である。 If m is less than 0.5, the content of R 1 is low, the film becomes too hard, and cracks are likely to occur in the cured film. When m exceeds 1.8, as a result of increasing the number of chain units, the cured film becomes rubbery and the scratch resistance is insufficient. Preferably, the number satisfies the range of 0.6 ≦ m ≦ 1.5.
架橋反応に関与する加水分解性基ＯＸは必須成分であるが、ＯＸ基の含有率を表すｐが１．０を超えると、エマルジョン中で加水分解した際に副生するアルコールが多量に発生し、エマルジョンが不安定となる。保存安定性が良好で、同時に高い硬化性も確保するためには、ｐの範囲は０．０５≦ｐ≦１．０であり、好ましくは０．２≦ｐ≦０．８の範囲である。 The hydrolyzable group OX involved in the cross-linking reaction is an essential component, but if p representing the content of the OX group exceeds 1.0, a large amount of alcohol generated as a by-product when hydrolyzed in the emulsion is generated. , The emulsion becomes unstable. In order to ensure good storage stability and at the same time to ensure high curability, the range of p is 0.05 ≦ p ≦ 1.0, preferably 0.2 ≦ p ≦ 0.8.
また、ＯＸ基以外にシラノール基が存在してもよいが、その存在量ｑは０．５以下でなければならない。この範囲を超えると、エマルジョン中で縮合反応を起こして高分子量化しやすく、エマルジョンの安定性が損なわれる。また加水分解性基とシラノール基の総数を表す（ｐ＋ｑ）は、０．０５≦ｐ＋ｑ≦１．５の範囲を満たしている必要があり、０．０５未満では硬化せず、１．５を超えると分子が小さくなり、乾燥硬化時に十分な強度の被膜が得られなくなる。 In addition to OX groups, silanol groups may be present, but the abundance q must be 0.5 or less. If it exceeds this range, a condensation reaction will easily occur in the emulsion to increase the molecular weight, and the stability of the emulsion will be impaired. Further, (p + q) representing the total number of hydrolyzable groups and silanol groups must satisfy the range of 0.05 ≦ p + q ≦ 1.5. As a result, the molecule becomes small, and a film having sufficient strength cannot be obtained at the time of drying and curing.
（Ａ）オルガノシリコーンレジンの２５℃における粘度は１００，０００ｍｍ２／ｓ以下であることが必要である。１００，０００ｍｍ２／ｓを超えると、エマルジョン製造時の撹拌混合が困難となり、粒子径が小さく安定性の高いエマルジョンが得られない。また、加水分解性基及び／又はシラノール基を有し、且つ１００，０００ｍｍ２／ｓを超える高粘度のオルガノシリコーンレジンは、保管時に縮合反応が起こると容易に固形化又はゲル化を生じるため、取扱いが困難になる。 (A) The viscosity at 25 ° C. of the organosilicone resin is required to be 100,000 mm 2 / s or less. When it exceeds 100,000 mm 2 / s, stirring and mixing at the time of producing the emulsion becomes difficult, and an emulsion having a small particle size and high stability cannot be obtained. In addition, the organosilicone resin having a hydrolyzable group and / or silanol group and having a viscosity exceeding 100,000 mm 2 / s easily solidifies or gels when a condensation reaction occurs during storage. Handling becomes difficult.
本発明における（Ａ）オルガノシリコーンレジンは、上記条件を満たしていれば、如何なる方法で製造してもよいが、加水分解性シラン化合物を水中で単純に加水分解するだけでは副生するアルコール類を除去できず、本発明における（Ａ）オルガノシリコーンレジンの製造方法としては不適当である。具体的な製造方法を以下に述べる。 The (A) organosilicone resin in the present invention may be produced by any method as long as the above conditions are satisfied. However, by simply hydrolyzing the hydrolyzable silane compound in water, alcohols that are by-produced are produced. It cannot be removed, and is not suitable as a method for producing the (A) organosilicone resin in the present invention. A specific manufacturing method will be described below.
（Ａ）成分のオルガノシリコーンレジンを製造するための原料としては、加水分解性基の種類がクロル或いはアルコキシであり、加水分解性基を１個、２個、３個又は４個含有し、上記条件を満たす有機置換基を有するシラン化合物であれば如何なるものでも使用可能である。具体的には、テトラクロルシラン、テトラメトキシシラン、テトラエトキシシラン、テトラブトキシシラン、メチルトリクロルシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリイソプロポキシシラン、メチルトリブトキシシラン、メチルトリイソプロペノキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジメチルジイソプロポキシシラン、ジメチルジブトキシシラン、ジメチルジイソプロペノキシシラン、トリメチルクロルシラン、トリメチルメトキシシラン、トリメチルエトキシシラン、トリメチルイソプロペノキシシラン、エチルトリクロルシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、プロピルトリクロルシラン、プロピルトリメトキシシラン、プロピルトリエトキシシラン、ブチルトリクロルシラン、ブチルトリメトキシシラン、ブチルトリエトキシシラン、ヘキシルトリクロルシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、デシルトリクロルシラン、デシルトリメトキシシラン、デシルトリエトキシシラン、フェニルトリクロルシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、シクロヘキシルトリクロルシラン、シクロヘキシルトリメトキシシラン、シクロヘキシルトリエトキシシラン、プロピルメチルジクロルシラン、プロピルメチルジメトキシシラン、プロピルメチルジエトキシシラン、ヘキシルメチルジクロルシラン、ヘキシルメチルジメトキシシラン、ヘキシルメチルジエトキシシラン、フェニルメチルジクロルシラン、フェニルメチルジメトキシシラン、フェニルメチルジエトキシシラン、ジフェニルジクロルシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン、ジメチルフェニルクロルシラン、ジメチルフェニルメトキシシラン、ジメチルフェニルエトキシシラン、ビニルトリクロルシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルメチルジクロルシラン、ビニルメチルジメトキシシラン、ビニルメチルジエトキシシラン、５−ヘキセニルトリクロルシラン、５−ヘキセニルトリメトキシシラン、５−ヘキセニルトリエトキシシラン、及びこれらの部分加水分解物等が使用可能なシラン化合物として挙げられるが、使用可能な有機ケイ素化合物はこれに限定されるものではない。操作性、副生物の留去のしやすさ、及び原料の入手の容易さから、メトキシシラン或いはエトキシシランを使用するのがより好ましい。これらのシラン化合物の１種または２種以上の混合物を使用してもよい。 As a raw material for producing the organosilicone resin of the component (A), the type of hydrolyzable group is chloro or alkoxy, and contains 1, 2, 3, or 4 hydrolyzable groups, Any silane compound having an organic substituent satisfying the conditions can be used. Specifically, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, methyltriisopropeno Xysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyldiisopropenoxysilane, trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropenoxysilane, ethyltrichloro Silane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrichlorosilane, propyltrimethoxysilane, propyltriet Sisilane, butyltrichlorosilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrichlorosilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrichlorosilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrichlorosilane, phenyltri Methoxysilane, phenyltriethoxysilane, cyclohexyltrichlorosilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, propylmethyldichlorosilane, propylmethyldimethoxysilane, propylmethyldiethoxysilane, hexylmethyldichlorosilane, hexylmethyldimethoxysilane, Hexylmethyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldimeth Sisilane, phenylmethyldiethoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dimethylphenylchlorosilane, dimethylphenylmethoxysilane, dimethylphenylethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane , Vinylmethyldichlorosilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, 5-hexenyltrichlorosilane, 5-hexenyltrimethoxysilane, 5-hexenyltriethoxysilane, and partial hydrolysates thereof can be used. Although mentioned as a silane compound, the organosilicon compound which can be used is not limited to this. It is more preferable to use methoxysilane or ethoxysilane from the viewpoint of operability, easiness of distilling off by-products, and availability of raw materials. One or a mixture of two or more of these silane compounds may be used.
上記加水分解性シラン化合物を加水分解して、本発明における（Ａ）オルガノシリコーンレジンを得る方法の一例を以下に説明する。即ち、トルエン、キシレン等の芳香族炭化水素、ヘキサン、オクタン等の炭化水素、メチルエチルケトン、メチルイソブチルケトン等のケトン系化合物、酢酸エチル、酢酸イソブチル等のエステル系化合物、メタノール、エタノール、イソプロパノール、ブタノール、イソブタノール、ｔ−ブタノール等のアルコール類から選ばれる有機溶剤中で加水分解する方法である。この方法の場合、できあがったオルガノシリコーンレジン溶液から、有機溶剤を常圧或いは減圧下で除く必要がある。除去工程後の有機溶剤残渣は１，０００ｐｐｍ以下であることが好ましい。 An example of a method for obtaining the (A) organosilicone resin in the present invention by hydrolyzing the hydrolyzable silane compound will be described below. That is, aromatic hydrocarbons such as toluene and xylene, hydrocarbons such as hexane and octane, ketone compounds such as methyl ethyl ketone and methyl isobutyl ketone, ester compounds such as ethyl acetate and isobutyl acetate, methanol, ethanol, isopropanol, butanol, In this method, hydrolysis is carried out in an organic solvent selected from alcohols such as isobutanol and t-butanol. In the case of this method, it is necessary to remove the organic solvent from the completed organosilicone resin solution under normal pressure or reduced pressure. The organic solvent residue after the removing step is preferably 1,000 ppm or less.
加水分解を実施するに際し、加水分解触媒を使用してもよい。加水分解触媒としては、従来公知の触媒を使用することができ、その水溶液がｐＨ２〜７の酸性を示すものを使用するのがよい。特に酸性のハロゲン化水素、カルボン酸、スルホン酸、酸性或いは弱酸性の無機塩、イオン交換樹脂等の固体酸等が好ましい。例としてはフッ化水素、塩酸、硝酸、硫酸、酢酸、マレイン酸に代表される有機カルボン酸、メチルスルホン酸、表面にスルホン酸又はカルボン酸基を有するカチオン交換樹脂等が挙げられる。加水分解触媒の量はケイ素原子上の加水分解性基１モルに対して０．００１〜１０モル％の範囲内であることが好ましい。 In carrying out the hydrolysis, a hydrolysis catalyst may be used. A conventionally well-known catalyst can be used as a hydrolysis catalyst, It is good to use what the aqueous solution shows the acidity of pH 2-7. Particularly preferred are acidic hydrogen halides, carboxylic acids, sulfonic acids, acidic or weakly acidic inorganic salts, solid acids such as ion exchange resins, and the like. Examples thereof include organic carboxylic acids represented by hydrogen fluoride, hydrochloric acid, nitric acid, sulfuric acid, acetic acid and maleic acid, methylsulfonic acid, and cation exchange resins having a sulfonic acid or carboxylic acid group on the surface. The amount of the hydrolysis catalyst is preferably in the range of 0.001 to 10 mol% with respect to 1 mol of the hydrolyzable group on the silicon atom.
＜（Ｂ）ノニオン系乳化剤＞
次に（Ｂ）成分であるノニオン系乳化剤について述べる。（Ｂ）ノニオン系乳化剤は、（Ａ）成分のオルガノシリコーンレジンを水中に乳化分散できるものであれば特に制限はなく、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンプロピレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレン脂肪酸エステル等を挙げることができるが、エマルジョン中の加水分解性基及び／又はシラノール基の保持及びエマルジョンの安定性の観点から、特にポリオキシエチレンアルキルエーテル、ポリオキシエチレンプロピレンアルキルエーテルが好ましい。
<(B) Nonionic emulsifier>
Next, the nonionic emulsifier which is (B) component is described. The (B) nonionic emulsifier is not particularly limited as long as it can emulsify and disperse the (A) component organosilicone resin in water. For example, polyoxyethylene alkyl ether, polyoxyethylene propylene alkyl ether, polyoxyethylene alkyl Phenyl ethers, polyoxyethylene fatty acid esters and the like can be mentioned. From the viewpoint of retention of hydrolyzable groups and / or silanol groups in the emulsion and stability of the emulsion, polyoxyethylene alkyl ethers, polyoxyethylene propylenes are particularly preferable. Alkyl ethers are preferred.
これらの具体例としては、ポリオキシエチレンオクチルエーテル、ポリオキシエチレンノニルエーテル、ポリオキシエチレンデシルエーテル、ポリオキシエチレンプロピレンデシルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンプロピレンラウリルエーテル、ポリオキシエチレントリデシルエーテル、ポリオキシエチレンプロピレントリデシルエーテル、ポリオキシエチレンミリスチルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンステアリルエーテル等が挙げられる。これらのノニオン系乳化剤は単独或いは２種以上を併用して使用することができる。 Specific examples thereof include polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene propylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene propylene lauryl ether, polyoxyethylene tridecyl Examples include ether, polyoxyethylene propylene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and the like. These nonionic emulsifiers can be used alone or in combination of two or more.
本発明におけるオルガノシリコーンレジンエマルジョン（Ｉ）は、（Ｂ）成分のノニオン系乳化剤以外の乳化剤を含まないものである。アルキル硫酸塩、アルキルベンゼンスルホン酸塩、アルキルスルホコハク酸塩、アルキルリン酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩等のアニオン系界面活性剤、第４級アンモニウム塩、アルキルアミン酢酸塩等のカチオン系界面活性剤、アルキルベタイン、アルキルイミダゾリン等の両性界面活性剤等を用いると、エマルジョン中で加水分解性基及び／又はシラノール基の一部が縮合反応を起こして消費されてしまい、後の乾燥硬化時の造膜性を損なうため使用することはできない。 The organosilicone resin emulsion (I) in the present invention does not contain an emulsifier other than the nonionic emulsifier as the component (B). Anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl phosphates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, quaternary ammonium salts, alkyls When cationic surfactants such as amine acetate and amphoteric surfactants such as alkylbetaines and alkylimidazolines are used, some hydrolyzable groups and / or silanol groups are consumed in the emulsion due to condensation reaction. Therefore, it cannot be used because the film-forming property at the time of subsequent drying and curing is impaired.
（Ｂ）成分の添加量としては、（Ａ）成分１００質量部に対して１〜５０質量部である必要がある。１質量部より少ないとエマルジョン化が困難であり、５０質量部より多いと被膜の硬度や耐水性、耐熱性、撥水性、透明性、基材との密着性が低下してしまう懸念がある。好ましくは２〜３０質量部、より好ましくは３〜２０質量部である。 (B) As addition amount of a component, it is necessary to be 1-50 mass parts with respect to 100 mass parts of (A) component. When the amount is less than 1 part by mass, emulsification is difficult. When the amount is more than 50 parts by mass, there is a concern that the hardness, water resistance, heat resistance, water repellency, transparency, and adhesion to the base material of the coating may be reduced. Preferably it is 2-30 mass parts, More preferably, it is 3-20 mass parts.
＜（Ｃ）水＞
本発明におけるオルガノシリコーンレジンエマルジョン（Ｉ）には、（Ｃ）成分として水が配合される。上述した（Ａ）成分及び（Ｂ）成分と混合し、常法に準じて乳化分散させることにより、オルガノシリコーンレジンエマルジョン（Ｉ）を調製することができる。この場合、（Ｃ）成分の水の含有量は（Ａ）成分１００質量部に対して２５〜２，０００質量部であり、特に５０〜１，０００質量部であることが好ましい。
<(C) Water>
In the organosilicone resin emulsion (I) in the present invention, water is blended as the component (C). The organosilicone resin emulsion (I) can be prepared by mixing with the components (A) and (B) described above and emulsifying and dispersing according to a conventional method. In this case, the water content of the component (C) is 25 to 2,000 parts by mass, and particularly preferably 50 to 1,000 parts by mass with respect to 100 parts by mass of the component (A).
更に、得られたエマルジョンの平均粒子径は、５０〜１，０００ｎｍ、特に１００〜８００ｎｍであることが好ましい。なお、本発明において、平均粒子径はベックマン・コールター株式会社製、サブミクロン粒度分布測定装置（コールターＮ４Ｐｌｕｓ）により測定することができる。 Furthermore, the average particle diameter of the obtained emulsion is preferably 50 to 1,000 nm, particularly preferably 100 to 800 nm. In the present invention, the average particle size can be measured with a submicron particle size distribution measuring device (Coulter N4Plus) manufactured by Beckman Coulter, Inc.
また、オルガノシリコーンレジンエマルジョン（Ｉ）には、上記（Ａ）〜（Ｃ）成分以外に、以下のような任意成分を添加してしてもよい。ただし、オルガノシリコーンレジンエマルジョン（Ｉ）は、加水分解性基ＯＸの加水分解による副生物であるアルコール以外の有機溶剤を含まないものである。 In addition to the above components (A) to (C), the following optional components may be added to the organosilicone resin emulsion (I). However, the organosilicone resin emulsion (I) does not contain an organic solvent other than alcohol, which is a byproduct of hydrolysis of the hydrolyzable group OX.
なお、本発明における「加水分解性基ＯＸの加水分解による副生物であるアルコール」とは、ＸＯＨ（Ｘは前述の通り）で示されるアルコール（類）であり、「加水分解性基ＯＸの加水分解による副生物であるアルコール以外の有機溶剤」とは、一般的に有機溶剤として使用される、ケトン系化合物、エステル系化合物、エーテル系化合物、ＸＯＨで示されるアルコール以外のアルコール系化合物等が挙げられる。 In the present invention, the “alcohol as a by-product by hydrolysis of the hydrolyzable group OX” is an alcohol (s) represented by XOH (X is as described above). Examples of the organic solvent other than alcohol which is a by-product by decomposition include ketone compounds, ester compounds, ether compounds, alcohol compounds other than alcohols represented by XOH, and the like, which are generally used as organic solvents. It is done.
エマルジョンの安定性を向上させるために、系内をｐＨ３〜９に調整することが好ましい。この場合、ｐＨを調整するための緩衝剤となる酸・塩基性化合物の組合せ、例えば酢酸と酢酸ナトリウム、リン酸水素二ナトリウムとクエン酸等を添加してもよい。ｐＨ領域がｐＨ３〜ｐＨ９である場合、シラノール基の縮合が進みやすくなる恐れや、エマルジョン自体の安定性が損なわれる恐れがないために好ましい。更に好ましくはｐＨ４〜８に調整するのがよい。加えて、任意成分として防腐剤、増粘剤等を添加してもよい。 In order to improve the stability of the emulsion, the inside of the system is preferably adjusted to pH 3-9. In this case, a combination of an acid / basic compound serving as a buffer for adjusting pH, for example, acetic acid and sodium acetate, disodium hydrogen phosphate and citric acid, or the like may be added. A pH range of pH 3 to pH 9 is preferred because there is no fear that the condensation of silanol groups will easily proceed and the stability of the emulsion itself is not impaired. More preferably, the pH should be adjusted to 4-8. In addition, preservatives, thickeners and the like may be added as optional components.
エマルジョン（ＩＩ）
本発明におけるエマルジョン（ＩＩ）は、下記（Ｄ）成分のポリマーを含むものである。
Emulsion (II)
The emulsion (II) in the present invention contains a polymer of the following component (D).
＜（Ｄ）ポリマー＞
（Ｄ）成分は、下記一般式（２）で示されるビニル重合性官能基含有加水分解性シランと、該ビニル重合性官能基含有加水分解性シラン以外のラジカル重合性ビニルモノマーとの共重合体であり、該共重合体中の全モノマー単位に対して、下記一般式（２）で示されるビニル重合性官能基含有加水分解性シラン単位が０．０１〜１０モル％であるポリマーである。
The component (D) is a copolymer of a vinyl polymerizable functional group-containing hydrolyzable silane represented by the following general formula (2) and a radical polymerizable vinyl monomer other than the vinyl polymerizable functional group-containing hydrolyzable silane. The vinyl polymerizable functional group-containing hydrolyzable silane unit represented by the following general formula (2) is 0.01 to 10 mol% with respect to all the monomer units in the copolymer.
（Ｄ）成分のポリマーは、オルガノシリコーンレジンエマルジョン（Ｉ）中の（Ａ）成分のオルガノシリコーンレジンに含まれる加水分解性基及び／又はシラノール基と縮合反応することができる、ＯＸ１基を分子中に含むことが必要である。この官能基導入のために、上記一般式（２）で示されるビニル重合性官能基含有加水分解性シランが共重合モノマーとして使用される。 The component (D) polymer is an OX 1 group that can undergo condensation reaction with hydrolyzable groups and / or silanol groups contained in the organosilicone resin (A) in the organosilicone resin emulsion (I). It is necessary to include inside. For this functional group introduction, a vinyl polymerizable functional group-containing hydrolyzable silane represented by the general formula (2) is used as a copolymerization monomer.
上記一般式（２）中、Ｒ１は前述の通りであり、Ｒ２は水素原子又はメチル基、Ｒ３は酸素原子及び−ＣＯＯ−基等を介在してもよい炭素数１〜１０のアルキレン基、アリーレン基、アルキレンアリーレン基等の二価の有機基、ｒは０，１又は２を示し、Ｘ１は上記Ｘと同様又は水素を示す。 In the general formula (2), R 1 is as described above, R 2 is a hydrogen atom or a methyl group, R 3 is an alkylene having 1 to 10 carbon atoms that may intervene with an oxygen atom, a —COO— group, or the like. A divalent organic group such as a group, an arylene group, and an alkylene arylene group, r represents 0, 1 or 2, and X 1 represents the same as X above or hydrogen.
Ｒ３の具体例としては、下記のものを例示することができる。
このような上記一般式（２）で示されるビニル重合性官能基含有加水分解性シランとしては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルメチルジメトキシシラン、ビニルメチルジエトキシシラン、５−ヘキセニルトリメトキシシラン、３−（メタ）アクリロキシプロピルトリメトキシシラン、３−（メタ）アクリロキシプロピルトリエトキシシラン、３−（メタ）アクリロキシプロピルメチルジメトキシシラン、３−（メタ）アクリロキシプロピルメチルジエトキシシラン、４−ビニルフェニルトリメトキシシラン、３−（４−ビニルフェニル）プロピルトリメトキシシラン、３−（４−ビニルフェニル）プロピルメチルジメトキシシラン等が挙げられる。 Examples of the vinyl-polymerizable functional group-containing hydrolyzable silane represented by the general formula (2) include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, and 5-hexenyltrisilane. Methoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxy Examples include silane, 4-vinylphenyltrimethoxysilane, 3- (4-vinylphenyl) propyltrimethoxysilane, and 3- (4-vinylphenyl) propylmethyldimethoxysilane.
上記一般式（２）で示されるビニル重合性官能基含有加水分解性シランの含有量は、（Ｄ）成分のポリマー（共重合体）中を構成する全モノマー単位に対して、０．０１〜１０モル％であり、特に０．１〜５モル％が好ましい。０．０１モル％未満だとシリコーン樹脂との反応率が下がり、均一な被膜が得られず、また耐溶剤性、耐薬品性、耐候性、耐熱性等の特性発現が不十分となる。１０モル％より多いと高架橋しすぎて、被膜にクラックが発生する場合があり不適当である。 The content of the vinyl polymerizable functional group-containing hydrolyzable silane represented by the general formula (2) is from 0.01 to all monomer units constituting the component (D) polymer (copolymer). It is 10 mol%, and 0.1 to 5 mol% is particularly preferable. If it is less than 0.01 mol%, the reaction rate with the silicone resin decreases, a uniform film cannot be obtained, and characteristics such as solvent resistance, chemical resistance, weather resistance and heat resistance become insufficient. If it is more than 10 mol%, it is not suitable because it is too highly crosslinked and cracks may occur in the coating.
上記一般式（２）で示されるビニル重合性官能基含有加水分解性シラン以外のラジカル重合性ビニルモノマーとしては、ラジカル重合が可能なものであれば特に限定されず、以下に示す従来公知のものを適用できる。（ａ）アクリル酸又はメタクリル酸のメチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、オクチル、２−エチルヘキシル、ラウリル、ステアリル又はシクロヘキシルエステル等のアルキル基の炭素数１〜１８の（メタ）アクリル酸アルキルエステル、（ｂ）アクリル酸、メタクリル酸、無水マレイン酸等のカルボキシル基又はその無水物含有ビニルモノマー、（ｃ）２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート等のヒドロキシル基含有ビニルモノマー、（ｄ）（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、ダイアセトン（メタ）アクリルアミド等のアミド基含有ビニルモノマー、（ｅ）ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート等のアミノ基含有ビニルモノマー、（ｆ）メトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート等のアルコキシ基含有ビニルモノマー、（ｇ）グリシジル（メタ）アクリレート、グリシジルアリルエーテル等のグリシジル基含有ビニルモノマー、（ｈ）酢酸ビニル、プロピオン酸ビニル等のビニルエステル系モノマー、（ｉ）スチレン、ビニルトルエン、α−メチルスチレン等の芳香族ビニルモノマー、（ｊ）（メタ）アクリロニトリル等のシアン化ビニルモノマー、（ｋ）塩化ビニル、臭化ビニル等のハロゲン化ビニルモノマー、（ｌ）ジビニルベンゼン、アリル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート等の１分子中にラジカル重合性不飽和基を２個以上含有するビニルモノマー、（ｍ）エチレンオキサイド基の数が１〜１００個の（ポリ）オキシエチレンモノ（メタ）アクリレート等の（ポリ）オキシエチレン鎖含有ビニルモノマー、（ｎ）片末端に（メタ）アクリロキシプロピル基を含有するジメチルポリシロキサン、片末端にスチリル基或いはα−メチルスチリル基を含有するジメチルポリシロキサン等の片末端にラジカル重合性官能基を有し、シロキサン単位が１〜２００個のジオルガノポリシロキサン等を具体例として例示することができ、これらの１種を単独で又は２種以上を混合して用いることができる。 The radically polymerizable vinyl monomer other than the vinyl polymerizable functional group-containing hydrolyzable silane represented by the general formula (2) is not particularly limited as long as radical polymerization is possible, and conventionally known ones shown below. Can be applied. (A) alkyl (meth) acrylate having 1 to 18 carbon atoms of alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, octyl, 2-ethylhexyl, lauryl, stearyl or cyclohexyl ester of acrylic acid or methacrylic acid Esters, (b) Carboxyl groups such as acrylic acid, methacrylic acid, and maleic anhydride or anhydride-containing vinyl monomers, (c) Hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. -Containing vinyl monomers, (d) (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, amide group-containing vinyl monomers such as diacetone (meth) acrylamide, (e) dimethylaminoethyl Amino group-containing vinyl monomers such as (meth) acrylate and diethylaminoethyl (meth) acrylate, (f) alkoxy group-containing vinyl monomers such as methoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate, (g) glycidyl (meth) acrylate Glycidyl group-containing vinyl monomers such as glycidyl allyl ether, (h) vinyl ester monomers such as vinyl acetate and vinyl propionate, (i) aromatic vinyl monomers such as styrene, vinyltoluene and α-methylstyrene, (j) Vinyl cyanide monomers such as (meth) acrylonitrile, (k) vinyl halide monomers such as vinyl chloride and vinyl bromide, (l) divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene group Vinyl monomer containing two or more radically polymerizable unsaturated groups in one molecule such as recalled di (meth) acrylate and trimethylolpropane tri (meth) acrylate, and (m) 1 to 100 ethylene oxide groups ( (Poly) oxyethylene chain-containing vinyl monomers such as poly) oxyethylene mono (meth) acrylate, (n) dimethylpolysiloxane containing a (meth) acryloxypropyl group at one end, styryl group or α-methyl at one end Specific examples include diorganopolysiloxane having a radical polymerizable functional group at one end, such as dimethylpolysiloxane containing a styryl group, and having 1 to 200 siloxane units. It can use individually or in mixture of 2 or more types.
これらの中で、上記一般式（２）で示されるビニル重合性官能基含有加水分解性シラン以外のラジカル重合性ビニルモノマーとしては、被膜の耐薬品性や可撓性の観点から、炭素数１〜１８のアルキル基を有する（メタ）アクリル酸アルキルエステルであることが好ましい。 Among these, as the radical polymerizable vinyl monomer other than the vinyl polymerizable functional group-containing hydrolyzable silane represented by the general formula (2), from the viewpoint of chemical resistance and flexibility of the film, the number of carbon atoms is one. It is preferable that it is (meth) acrylic-acid alkylester which has an alkyl group of -18.
また、（Ａ）成分１００質量部に対して、この共重合ポリマーは１０〜１，０００質量部の範囲で使用する。１０質量部未満では、造膜性及び耐薬品性が不十分となることがあり、１，０００質量部を超えると、耐候性及び耐水性が不足することがある。更に好ましくは、この共重合ポリマーを３０〜５００質量部の範囲で使用するのがよい。 Moreover, this copolymer is used in the range of 10 to 1,000 parts by mass with respect to 100 parts by mass of component (A). If it is less than 10 parts by mass, the film-forming property and chemical resistance may be insufficient, and if it exceeds 1,000 parts by mass, the weather resistance and water resistance may be insufficient. More preferably, the copolymer is used in the range of 30 to 500 parts by mass.
また（Ｄ）成分のポリマーはエマルジョン（ＩＩ）として調製した後に、（Ａ）〜（Ｃ）成分を含有するオルガノシリコーンレジンエマルジョン（Ｉ）と混合されて使用されるが、このエマルジョン（ＩＩ）の調製方法としては、上記一般式（２）で示されるビニル重合性官能基含有加水分解性シラン０．０１〜１０モル％と、その他のラジカル重合性ビニルモノマーとをラジカル共重合し、ポリマーとした後にエマルジョン化しても、上記一般式（２）で示されるビニル重合性官能基含有加水分解性シランと、その他のラジカル重合性ビニルモノマーを先に乳化し、乳化粒子中でラジカル重合によりポリマーを生成し、ポリマーのエマルジョンを調製してもよい。しかしながら、重合後はポリマーが固形化することが通常であるため、モノマーを先に乳化し、乳化粒子中で重合させる後者の方法がより好ましい。 Further, the polymer of component (D) is prepared as emulsion (II) and then mixed with organosilicone resin emulsion (I) containing components (A) to (C). As a preparation method, 0.01-10 mol% of a vinyl polymerizable functional group-containing hydrolyzable silane represented by the above general formula (2) and other radical polymerizable vinyl monomers are radically copolymerized to obtain a polymer. Even if it is emulsified later, the vinyl polymerizable functional group-containing hydrolyzable silane represented by the above general formula (2) and other radical polymerizable vinyl monomers are emulsified first, and a polymer is generated by radical polymerization in the emulsion particles. Alternatively, a polymer emulsion may be prepared. However, since the polymer is usually solidified after polymerization, the latter method in which the monomer is first emulsified and polymerized in the emulsified particles is more preferable.
ラジカル重合開始剤としては、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩、過酸化水素水、ｔ−ブチルハイドロパーオキサイド、ｔ−ブチルパーオキシマレイン酸、コハク酸パーオキシド、２，２‘−アゾビス−［２−Ｎ−ベンジルアミジノ］プロパン塩酸塩等の水溶性タイプ、ベンゾイルパーオキサイド、キュメンハイドロパーオキサイド、ジブチルパーオキサイド、ジイソプロピルパーオキシジカーボネート、クミルパーオキシネオデカノエート、クミルパーオキシオクトエート、アゾイソブチロニトリル等の油溶性タイプ、酸性亜硫酸ナトリウム、ロンガリット、アスコルビン酸等の還元剤を併用したレドックス系等を使用することができる。この重合開始剤の使用量は、上記一般式（２）で示されるビニル重合性官能基含有加水分解性シランと、その他のラジカル重合性ビニルモノマーの合計量に対して０．１〜１０質量％使用すればよく、好ましくは０．５〜５質量％使用するのがよい。 As radical polymerization initiators, persulfates such as potassium persulfate and ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxymaleic acid, succinic acid peroxide, 2,2′-azobis- Water-soluble type such as [2-N-benzylamidino] propane hydrochloride, benzoyl peroxide, cumene hydroperoxide, dibutyl peroxide, diisopropyl peroxydicarbonate, cumylperoxyneodecanoate, cumylperoxyoctoate, An oil-soluble type such as azoisobutyronitrile, a redox system using a reducing agent such as acidic sodium sulfite, Rongalite, and ascorbic acid can be used. The amount of the polymerization initiator used is 0.1 to 10% by mass based on the total amount of the vinyl polymerizable functional group-containing hydrolyzable silane represented by the general formula (2) and other radical polymerizable vinyl monomers. What is necessary is just to use, Preferably it is good to use 0.5-5 mass%.
エマルジョン（ＩＩ）の分散媒としては、水であることが好ましい。水を分散媒として用いることで、最終的に得られるシリコーン樹脂含有エマルジョン組成物は、より一層環境上の問題が低減されたものとなる。 The dispersion medium for the emulsion (II) is preferably water. By using water as a dispersion medium, the finally obtained silicone resin-containing emulsion composition has further reduced environmental problems.
（Ａ）〜（Ｃ）を含有するオルガノシリコーンレジンエマルジョン（Ｉ）と、（Ｄ）成分のポリマーを含むエマルジョン（ＩＩ）は、使用前に各々のエマルジョン同士を混合して混合溶液として使用される。混合後は室温でも加水分解性基及び／又はシラノール基の縮合反応により架橋・硬化可能であるが、硬化速度を加速するため、或いは優れた被膜特性を得るために、オルガノシリコーンレジンエマルジョン（Ｉ）とエマルジョン（ＩＩ）との混合の際に、必要に応じて、シラノール縮合触媒を添加してもよい。 The organosilicone resin emulsion (I) containing (A) to (C) and the emulsion (II) containing the polymer of the component (D) are used as a mixed solution by mixing the emulsions before use. . After mixing, it can be crosslinked and cured by condensation reaction of hydrolyzable groups and / or silanol groups even at room temperature, but in order to accelerate the curing rate or to obtain excellent film properties, organosilicone resin emulsion (I) When mixing with the emulsion (II), a silanol condensation catalyst may be added as necessary.
縮合用の硬化触媒としては従来公知のものが使用可能で、例えば水酸化リチウム、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、酢酸ナトリウム、ギ酸ナトリウム、ｎ−ヘキシルアミン、トリブチルアミン、ジアザビシクロウンデセン等の塩基性化合物類、テトライソプロピルチタネート、テトラブチルチタネート、アルミニウムトリイソブトキシド、アルミニウムトリイソプロポキシド、アルミニウムアセチルアセトナート、過塩素酸アルミニウム、塩化アルミニウム、コバルトオクチレート、コバルトアセチルアセトナート、亜鉛オクチレート、亜鉛アセチルアセトナート、鉄オクチレート、鉄アセチルアセトナート、スズアセチルアセトナート、ジブチルスズジオクチレート、ジブチルスズジラウレート、ジブチルスズオキサイド等の含金属化合物類、ｐ−トルエンスルホン酸、トリクロル酢酸などの酸性化合物類、フッ化カリウム、フッ化ナトリウム、テトラメチルアンモニウムフルオライド、六フッ化ケイ酸ソーダなどの含フッ素化合物等が挙げられる。これらの縮合触媒は、（Ａ）成分のオルガノシリコーンレジン１００質量部に対して、０．０１〜１０質量部使用するのがよい。 A conventionally known curing catalyst can be used as the condensation catalyst. For example, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, sodium formate, n-hexylamine, tributylamine, diazabicyclo Basic compounds such as undecene, tetraisopropyl titanate, tetrabutyl titanate, aluminum triisobutoxide, aluminum triisopropoxide, aluminum acetylacetonate, aluminum perchlorate, aluminum chloride, cobalt octylate, cobalt acetylacetonate, Zinc octylate, zinc acetylacetonate, iron octylate, iron acetylacetonate, tin acetylacetonate, dibutyltin dioctylate, dibutyltin dilaurate, dibutyltin Metal-containing compounds such as oxides, acidic compounds such as p-toluenesulfonic acid and trichloroacetic acid, fluorine-containing compounds such as potassium fluoride, sodium fluoride, tetramethylammonium fluoride and sodium hexafluorosilicate It is done. These condensation catalysts are preferably used in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the organosilicone resin as component (A).
このように得られた本発明のシリコーン樹脂含有エマルジョン組成物は、従来のシリコーンレジンエマルジョンに比べ環境上の問題が低減され、安定性が良好で、かつ、得られる被膜が高硬度であるシリコーン樹脂含有エマルジョン組成物となる。 The silicone resin-containing emulsion composition of the present invention thus obtained is a silicone resin in which environmental problems are reduced as compared with conventional silicone resin emulsions, the stability is good, and the resulting coating has a high hardness. It becomes a containing emulsion composition.
本発明のシリコーン樹脂含有エマルジョン組成物は、金属、セラミック系無機材料、ガラス、木材、紙製品、プラスチック等の透明又は不透明な基材表面に塗布し、室温或いは加熱して硬化させることにより硬化被膜（保護膜）を形成することができる。この硬化被膜は、高硬度で可撓性に富み、接着性、耐候性も良好であり、更に撥水性も付与することができるので、金属、セラミック、木材等の外装建材の下地処理剤、トップコート剤等の塗料、プレコートメタル等の金属表面の保護コート剤、電子写真用キャリアの帯電調節コート剤、或いは接着剤等に適している。 The silicone resin-containing emulsion composition of the present invention is applied to a transparent or opaque substrate surface such as metal, ceramic inorganic material, glass, wood, paper product, plastic, etc. and cured by heating at room temperature or heating. (Protective film) can be formed. This cured film has high hardness, high flexibility, good adhesion and weather resistance, and can also impart water repellency. Therefore, it can be used as a base treatment agent for exterior building materials such as metals, ceramics, and wood. It is suitable for coating materials such as coating agents, protective coating agents for metal surfaces such as pre-coated metals, charge control coating agents for electrophotographic carriers, or adhesives.
基材が金属の場合、鉄、ステンレス製建築構造材やアルミサッシ建材等の表面保護、或いは防食処理コーティング等の下地処理、自動車或いは電化製品用の電着塗装用コーティング、又は電子写真用キャリアに使用される磁性粉の表面保護コーティングに好適に使用することができる。 When the base material is metal, it is suitable for surface protection of iron, stainless steel building structure materials and aluminum sash building materials, etc. It can be suitably used for the surface protective coating of the magnetic powder used.
基材がプラスチックの場合、プラスチック板、磁気或いは感熱性記録用フィルム、包装用フィルム、ビニルクロス等の表面保護コーティング、或いは機能付与用バインダーとして好適に使用することができる。 When the substrate is a plastic, it can be suitably used as a plastic plate, a magnetic or heat-sensitive recording film, a packaging film, a surface protective coating such as vinyl cloth, or a function-imparting binder.
基材が木材或いは紙製品の場合、合板の表面保護コーティング、感熱記録用の表面保護、印刷表面に処理する耐水性付与コーティング等に適用できる。また撥水性も有しているため、合成皮革等の表面保護被膜としても適用することができる。耐水性印刷インキ用の水溶性バインダーとしても適用することができる。 When the substrate is a wood or paper product, it can be applied to a surface protective coating for plywood, a surface protection for thermal recording, a water-resistant coating applied to the printing surface, and the like. Moreover, since it also has water repellency, it can also be applied as a surface protective coating for synthetic leather and the like. It can also be applied as a water-soluble binder for water-resistant printing inks.
基材が無機材料の場合、モルタル、コンクリート、或いはセメント製の外装用壁材又は窯業パネル、ＡＬＣ板、サイジングボード、石膏ボード、レンガ、ガラス、陶磁器、人工大理石等の表面保護コーティング、表面処理用塗料として適用することができる。 When the base material is inorganic material, mortar, concrete or cement exterior wall or ceramic panel, ALC board, sizing board, gypsum board, brick, glass, ceramic, artificial marble surface protection coating, surface treatment It can be applied as a paint.
また接着剤のベースポリマーとしても使用することができ、他の有機樹脂又はシランカップリング剤等を添加することにより、異種の基材間の接着に有効な接着剤を得ることができる。 It can also be used as a base polymer for adhesives, and by adding other organic resins or silane coupling agents, it is possible to obtain an adhesive effective for adhesion between different substrates.
本発明のシリコーン樹脂含有エマルジョン組成物の基材への塗布方法としては、浸漬法、スプレー法、ロールコート法、刷毛塗り法等、従来公知の各種塗装法が可能である。またシリコーン樹脂含有エマルジョン組成物の塗布量は特に制限されないが、通常は乾燥後の被膜の厚さが０．１〜１，０００μｍ、特に１〜１００μｍとなる量であることが好ましい。 As a method for applying the silicone resin-containing emulsion composition of the present invention to a substrate, various conventionally known coating methods such as a dipping method, a spray method, a roll coating method, and a brush coating method are possible. The coating amount of the silicone resin-containing emulsion composition is not particularly limited, but it is usually preferable that the coating thickness after drying is 0.1 to 1,000 μm, particularly 1 to 100 μm.
以下、製造例、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、下記の例において、部は質量部、％は質量％を示す。 EXAMPLES Hereinafter, although a manufacture example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, in the following example, a part shows a mass part and% shows the mass%.
［製造例１］
平均組成式：［（ＣＨ３）１．０（Ｃ６Ｈ５）０．５Ｓｉ（ＯＣＨ３）０．７（ＯＨ）０．１Ｏ０．９］で示されるオルガノシリコーンレジン（２５℃での粘度：１００ｍｍ２／ｓ）５０質量部、ノニオン系乳化剤として「ノイゲンＸＬ−４０」（商品名：第一工業製薬社製、ポリオキシアルキレンデシルエーテル、ＨＬＢ＝１０．５）２．５質量部、「ノイゲンＸＬ−４００Ｄ」（商品名：第一工業製薬社製、ポリオキシアルキレンデシルエーテル、ＨＬＢ＝１８．４の６５％水溶液）３．５質量部及び脱イオン水４４．０質量部をホモディスパーを用いて乳化分散し、１０５℃／３時間での不揮発分が５２％、平均粒子径（ベックマン・コールター株式会社製サブミクロン粒度分布測定装置コールターＮ４Ｐｌｕｓを用いて測定）が２５０ｎｍの白色のオルガノシリコーンレジンエマルジョン（Ａ−１）を得た。Ａ−１を４０℃で１ヶ月保管した後、１０５℃で水を除去して得た不揮発分はオイル状を保っていた。またこの不揮発分のＧＰＣ測定を行い、原料オルガノシリコーンレジンと比較した結果、ほぼ同一であることを確認した。
[Production Example 1]
Average composition formula: [(CH 3 ) 1.0 (C 6 H 5 ) 0.5 Si (OCH 3 ) 0.7 (OH) 0.1 O 0.9 ]] Viscosity: 100 mm 2 / s) 50 parts by mass, “Neugen XL-40” (trade name: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene decyl ether, HLB = 10.5) 2.5 parts by mass as a nonionic emulsifier , "Neugen XL-400D" (trade name: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene decyl ether, 65% aqueous solution of HLB = 18.4) 3.5 parts by mass and deionized water 44.0 parts by mass Emulsified and dispersed using a disper, non-volatile content at 105 ° C./3 hours is 52%, average particle size (using a sub-micron particle size distribution measuring device Coulter N4Plus manufactured by Beckman Coulter, Inc.) Measurement) to obtain a 250nm white organosilicone resin emulsion (A-1). After storing A-1 at 40 ° C. for 1 month, the non-volatile content obtained by removing water at 105 ° C. kept an oily state. Moreover, GPC measurement of this non-volatile content was performed, and as a result of comparison with the raw material organosilicone resin, it was confirmed that it was almost the same.
［製造例２］
平均組成式：［（ＣＨ３）１．０Ｓｉ（ＯＣＨ３）０．２Ｏ１．４］で示されるオルガノシリコーンレジン（２５℃での粘度：３０ｍｍ２／ｓ）５０質量部、ノニオン系乳化剤として「ノイゲンＸＬ−４０」３．５質量部、「ノイゲンＸＬ−４００Ｄ」４．９質量部及び脱イオン水４１．６質量部をホモディスパーを用いて乳化分散し、１０５℃／３時間での不揮発分が４３％、平均粒子径（ベックマン・コールター株式会社製サブミクロン粒度分布測定装置コールターＮ４Ｐｌｕｓを用いて測定）が２１０ｎｍの白色のオルガノシリコーンレジンエマルジョン（Ａ−２）を得た。Ａ−２を４０℃で１ヶ月保管した後、１０５℃で水を除去して得た不揮発分はオイル状を保っていた。またこの不揮発分のＧＰＣ測定を行い、原料オルガノシリコーンレジンと比較した結果、ほぼ同一であることを確認した。
[Production Example 2]
Average composition formula: organosilicone resin represented by [(CH 3 ) 1.0 Si (OCH 3 ) 0.2 O 1.4 ] (viscosity at 25 ° C .: 30 mm 2 / s), 50 parts by mass, nonionic emulsifier As follows, 3.5 parts by weight of "Neugen XL-40", 4.9 parts by weight of "Neugen XL-400D" and 41.6 parts by weight of deionized water were emulsified and dispersed using a homodisper, and the temperature was 105 ° C / 3 hours. A white organosilicone resin emulsion (A-2) having a nonvolatile content of 43% and an average particle size (measured using a submicron particle size distribution measuring device Coulter N4Plus manufactured by Beckman Coulter, Inc.) of 210 nm was obtained. After storing A-2 at 40 ° C. for 1 month, the non-volatile content obtained by removing water at 105 ° C. kept an oily state. Moreover, GPC measurement of this non-volatile content was performed, and as a result of comparison with the raw material organosilicone resin, it was confirmed that it was almost the same.
［製造例３］
平均組成式：［（ＣＨ３）１．０（Ｃ６Ｈ５）０．５Ｓｉ（ＯＣＨ３）０．７（ＯＨ）０．１Ｏ０．９］で示されるオルガノシリコーンレジン（２５℃での粘度：１００ｍｍ２／ｓ）５０質量部、ノニオン系乳化剤として「ノイゲンＸＬ−４０」２．５質量部、「ノイゲンＸＬ−４００Ｄ」３．５質量部、アニオン系乳化剤の「ニューコール２９１Ｍ」（商品名：日本乳化剤社製、アルキルスルホコハク酸ソーダ７５％液）０．５質量部、及び脱イオン水４３．５質量部をホモディスパーを用いて乳化分散し、１０５℃／３時間での不揮発分が５２％、平均粒子径（ベックマン・コールター株式会社製サブミクロン粒度分布測定装置コールターＮ４Ｐｌｕｓを用いて測定）が２６０ｎｍの白色のオルガノシリコーンレジンエマルジョン（Ａ−３）を得た。Ａ−３を４０℃で１ヶ月保管した後、１０５℃で水を除去して得た不揮発分はべたつきのある被膜を形成し、一部はトルエンに不溶となっていた。またこの不揮発分のＧＰＣ測定を行い、原料オルガノシリコーンレジンと比較した結果、Ａ−３の不揮発分は高分子量化しており原料とは異なるピーク形状となっていた。
[Production Example 3]
Average composition formula: [(CH 3 ) 1.0 (C 6 H 5 ) 0.5 Si (OCH 3 ) 0.7 (OH) 0.1 O 0.9 ]] Viscosity: 100 mm 2 / s) 50 parts by weight, 2.5 parts by weight of “Neugen XL-40” as nonionic emulsifier, 3.5 parts by weight of “Neugen XL-400D”, “Newcol 291M” as an anionic emulsifier ( (Product name: Nippon Emulsifier Co., Ltd., alkylsulfosuccinic acid sodium 75% solution) 0.5 parts by mass and deionized water 43.5 parts by mass were emulsified and dispersed using a homodisper, and the non-volatile content at 105 ° C./3 hours. Is a white organosilicone resin emma having an average particle size (measured using a submicron particle size distribution measuring device Coulter N4Plus manufactured by Beckman Coulter, Inc.) of 260 nm. It was obtained John (A-3). After storing A-3 at 40 ° C. for 1 month, the non-volatile content obtained by removing water at 105 ° C. formed a sticky film, and a part thereof was insoluble in toluene. Moreover, as a result of GPC measurement of the non-volatile content and comparison with the raw material organosilicone resin, the non-volatile content of A-3 had a high molecular weight and had a peak shape different from that of the raw material.
［製造例４］
攪拌機、コンデンサー、温度計及び窒素ガス導入口を備えた重合容器に、脱イオン水を５４０質量部、ｐＨ緩衝剤として炭酸ソーダを０．４７質量部、ホウ酸を４．７０質量部仕込み、撹拌しながら６０℃に昇温した後、窒素置換した。これにロンガリット１．７５質量部、エチレンジアミン四酢酸二ナトリウムの１％水溶液０．１２質量部、硫酸第一鉄の１％水溶液０．０４質量部を添加すると同時に、メタクリル酸メチル３３６質量部（３．３６モル）、アクリル酸ブチル１４０質量部（１．０９モル）、γ−メタクリロキシプロピルトリメトキシシラン３３質量部（０．１３モル）、ｔ−ブチルハイドロパーオキサイド（純分６９％）２．１質量部、反応性界面活性剤アクアロンＫＨ−１０（商品名：第一工業製薬社製、ポリオキシエチレン（１０）−１−（アリルオキシメチル）アルキルエーテル硫酸アンモニウム）１４．０質量部、アクアロンＫＨ−５（商品名：第一工業製薬社製、ポリオキシエチレン（５）−１−（アリルオキシメチル）アルキルエーテル硫酸アンモニウム）７．０質量部からなる混合液を、重合容器内の温度を６０℃に保持しながら２．５時間かけて均一に添加し、更に６０℃にて２時間反応させて重合を完了させた。得られたエマルジョン（Ｂ−１）の１０５℃／３時間での不揮発分は４９．１％、ｐＨ７．１であった。
[Production Example 4]
A polymerization vessel equipped with a stirrer, a condenser, a thermometer and a nitrogen gas inlet is charged with 540 parts by mass of deionized water, 0.47 parts by mass of sodium carbonate as a pH buffer, and 4.70 parts by mass of boric acid. Then, the temperature was raised to 60 ° C., and then purged with nitrogen. At the same time, 1.75 parts by mass of Rongalite, 0.12 parts by mass of a 1% aqueous solution of disodium ethylenediaminetetraacetate and 0.04 parts by mass of a 1% aqueous solution of ferrous sulfate were added to 336 parts by mass of methyl methacrylate (3 .36 mol), 140 parts by mass of butyl acrylate (1.09 mol), 33 parts by mass of γ-methacryloxypropyltrimethoxysilane (0.13 mol), t-butyl hydroperoxide (pure content 69%) 1 part by mass, reactive surfactant Aqualon KH-10 (trade name: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene (10) -1- (allyloxymethyl) alkyl ether ammonium sulfate) 14.0 parts by mass, Aqualon KH -5 (trade name: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene (5) -1- (allyloxymethyl) alkyl ether sulfate (Monium) A mixture of 7.0 parts by mass was added uniformly over 2.5 hours while maintaining the temperature in the polymerization vessel at 60 ° C., and further reacted at 60 ° C. for 2 hours to complete the polymerization. It was. The non-volatile content of the obtained emulsion (B-1) at 105 ° C./3 hours was 49.1% and pH 7.1.
［製造例５］
攪拌機、コンデンサー、温度計及び窒素ガス導入口を備えた重合容器に、脱イオン水を５４０質量部、ｐＨ緩衝剤として炭酸ソーダを０．４７質量部、ホウ酸を４．７０質量部仕込み、撹拌しながら６０℃に昇温した後、窒素置換した。これにロンガリット１．７５質量部、エチレンジアミン四酢酸二ナトリウムの１％水溶液０．１２質量部、硫酸第一鉄の１％水溶液０．０４質量部を添加すると同時に、メタクリル酸メチル３３６質量部（３．３６モル）、アクリル酸ブチル１４０質量部（１．０９モル）、ｔ−ブチルハイドロパーオキサイド（純分６９％）２．１質量部、反応性界面活性剤アクアロンＫＨ−１０（商品名：第一工業製薬社製、ポリオキシエチレン（１０）−１−（アリルオキシメチル）アルキルエーテル硫酸アンモニウム）１４．０質量部、アクアロンＫＨ−５（商品名：第一工業製薬社製、ポリオキシエチレン（５）−１−（アリルオキシメチル）アルキルエーテル硫酸アンモニウム）７．０質量部からなる混合液を、重合容器内の温度を６０℃に保持しながら２．５時間かけて均一に添加し、更に６０℃にて２時間反応させて重合を完了させた。得られたエマルジョン（Ｂ−２）の１０５℃／３時間での不揮発分は４７．９％、ｐＨ７．２であった。
[Production Example 5]
A polymerization vessel equipped with a stirrer, a condenser, a thermometer and a nitrogen gas inlet is charged with 540 parts by mass of deionized water, 0.47 parts by mass of sodium carbonate as a pH buffer, and 4.70 parts by mass of boric acid. Then, the temperature was raised to 60 ° C., and then purged with nitrogen. At the same time, 1.75 parts by mass of Rongalite, 0.12 parts by mass of a 1% aqueous solution of disodium ethylenediaminetetraacetate and 0.04 parts by mass of a 1% aqueous solution of ferrous sulfate were added to 336 parts by mass of methyl methacrylate (3 .36 mol), 140 parts by mass of butyl acrylate (1.09 mol), 2.1 parts by mass of t-butyl hydroperoxide (69% pure), reactive surfactant Aqualon KH-10 (trade name: No. 1) Ichi Kogyo Seiyaku Co., Ltd., polyoxyethylene (10) -1- (allyloxymethyl) alkyl ether ammonium sulfate 14.0 parts by mass, Aqualon KH-5 (trade name: Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene (5 ) -1- (Allyloxymethyl) alkyl ether ammonium sulfate) 7.0 parts by mass of the mixed solution, the temperature in the polymerization vessel is kept at 60 ° C. While over 2.5 hours added uniformly to complete the polymerization by 2 hours at further 60 ° C.. The non-volatile content of the obtained emulsion (B-2) at 105 ° C./3 hours was 47.9% and pH 7.2.
（実施例１〜５、比較例１〜６）
上記製造例１〜３で調製したシリコーンレジンエマルジョンと製造例４〜５で調製した（メタ）アクリルポリマー（共重合ポリマー）のエマルジョン、及び硬化触媒として酢酸ナトリウムを表１に示す配合で混合してシリコーン樹脂含有エマルジョン組成物とした（実施例１〜５、比較例１〜６）。その後、表面が清浄な磨き鋼板にワイヤーバーを用いて硬化後の膜厚が１５μｍになるように組成物を塗工し、表１に示す条件で硬化させた後に、被膜表面の外観を目視にて、硬化性を指触によるタック感にて、被膜硬度をＪＩＳ Ｋ−５４００に準ずる鉛筆硬度にて確認した。結果を表１に示す。尚、比較例１及び２は、本発明におけるオルガノシリコーンレジンエマルジョン（Ｉ）ではないエマルジョン（Ａ−３）を用いたものであり、比較例３、４は本発明におけるエマルジョン（ＩＩ）ではないエマルジョン（Ｂ−２）を用いたものであり、比較例５、６はシリコーンレジンエマルジョン中のシリコーンレジンと、（メタ）アクリルエマルジョン中の共重合ポリマーの量が、１００質量部：１０〜１０００質量部ではないものである。
(Examples 1-5, Comparative Examples 1-6)
The silicone resin emulsion prepared in Production Examples 1 to 3 above, the emulsion of (meth) acrylic polymer (copolymer) prepared in Production Examples 4 to 5, and sodium acetate as a curing catalyst were mixed in the formulation shown in Table 1. It was set as the silicone resin containing emulsion composition (Examples 1-5, Comparative Examples 1-6). Then, the composition was applied to a polished steel plate with a clean surface using a wire bar so that the film thickness after curing was 15 μm, and after curing under the conditions shown in Table 1, the appearance of the coating surface was visually observed. Then, the curability was confirmed by a tactile sensation by finger touch, and the film hardness was confirmed by a pencil hardness according to JIS K-5400. The results are shown in Table 1. In Comparative Examples 1 and 2, the emulsion (A-3) which is not the organosilicone resin emulsion (I) in the present invention is used, and Comparative Examples 3 and 4 are emulsions which are not the emulsion (II) in the present invention. (B-2) is used, and in Comparative Examples 5 and 6, the amount of the silicone resin in the silicone resin emulsion and the copolymer polymer in the (meth) acrylic emulsion is 100 parts by mass: 10 to 1000 parts by mass. It is not.
［評価方法］
（外観／目視） ○：均一、△：ややムラあり、×：不均一
（タック感／指触） ○：なし、△：ややタックあり、×：ベタつきあり
（鉛筆硬度） ＪＩＳ Ｋ−５４００に準ずる
[Evaluation method]
(Appearance / visual observation) ○: Uniform, Δ: Somewhat uneven, ×: Non-uniform (Tack feeling / finger touch) ○: None, Δ: Somewhat tacky, ×: Sticky (pencil hardness) Conforms to JIS K-5400
表１により、実施例１〜５のシリコーン樹脂含有エマルジョン組成物は、比較例１〜６のシリコーン樹脂含有エマルジョン組成物に対して、安定性に優れるものであったため、均一な被膜を形成することができ、べたつきがない被膜を得ることができた。また、実施例１〜５のシリコーン樹脂含有エマルジョン組成物は、比較例１〜６のシリコーン樹脂含有エマルジョン組成物に対して、高硬度の被膜が得られた。 According to Table 1, since the silicone resin-containing emulsion compositions of Examples 1 to 5 were superior in stability to the silicone resin-containing emulsion compositions of Comparative Examples 1 to 6, a uniform film was formed. A film without stickiness could be obtained. Moreover, the silicone resin containing emulsion composition of Examples 1-5 obtained the coating film of high hardness with respect to the silicone resin containing emulsion composition of Comparative Examples 1-6.
なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に含有される。 The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. It is contained in the technical range.
Claims (4)
（Ａ）下記平均組成式（１）で示される、２５℃で粘度が１００，０００ｍｍ２／ｓ以下のオルガノシリコーンレジン：１００質量部、
Ｒ１ ｍＳｉ（ＯＸ）ｐ（ＯＨ）ｑＯ（４−ｍ−ｐ−ｑ）／２ ・・・（１）
（式中、Ｒ１は非置換一価炭化水素基、ＯＸは加水分解性基であり、Ｘは１価炭化水素基を表す。ｍ，ｐ，ｑは０．５≦ｍ≦１．８、０．０５≦ｐ≦１．０、０≦ｑ≦０．５、０．０５≦ｐ＋ｑ≦１．５を満たす数である。）
（Ｂ）ノニオン系乳化剤：１〜５０質量部、
（Ｃ）水：２５〜２，０００質量部、
（Ｄ）下記一般式（２）で示されるビニル重合性官能基含有加水分解性シランと、該ビニル重合性官能基含有加水分解性シラン以外のラジカル重合性ビニルモノマーとの共重合体であり、該共重合体中の全モノマー単位に対して、下記一般式（２）で示されるビニル重合性官能基含有加水分解性シラン単位が０．０１〜１０モル％であるポリマー：（Ａ）成分１００質量部に対して１０〜１，０００質量部、
前記オルガノシリコーンレジンエマルジョン（Ｉ）は、前記（Ｂ）成分のノニオン系乳化剤以外の乳化剤を含まないものであり、かつ、加水分解性基ＯＸの加水分解による副生物であるアルコール以外の有機溶剤を含まないものであることを特徴とするシリコーン樹脂含有エマルジョン組成物。 It is a mixed solution of an organosilicone resin emulsion (I) containing the following components (A) to (C) and an emulsion (II) containing a polymer of the following component (D):
(A) Organosilicone resin represented by the following average composition formula (1) and having a viscosity of 100,000 mm 2 / s or less at 25 ° C .: 100 parts by mass,
R 1 m Si (OX) p (OH) q O (4-mpq) / 2 (1)
(In the formula, R 1 represents an unsubstituted monovalent hydrocarbon group, OX represents a hydrolyzable group, X represents a monovalent hydrocarbon group, and m, p, and q are 0.5 ≦ m ≦ 1.8, Numbers satisfying 0.05 ≦ p ≦ 1.0, 0 ≦ q ≦ 0.5, and 0.05 ≦ p + q ≦ 1.5.)
(B) Nonionic emulsifier: 1 to 50 parts by mass,
(C) Water: 25-2,000 parts by mass,
(D) a copolymer of a vinyl polymerizable functional group-containing hydrolyzable silane represented by the following general formula (2) and a radical polymerizable vinyl monomer other than the vinyl polymerizable functional group-containing hydrolyzable silane; Polymer in which the vinyl polymerizable functional group-containing hydrolyzable silane unit represented by the following general formula (2) is 0.01 to 10 mol% with respect to all monomer units in the copolymer: (A) Component 100 10 to 1,000 parts by mass with respect to parts by mass,
The organosilicone resin emulsion (I) does not contain an emulsifier other than the nonionic emulsifier of the component (B), and an organic solvent other than alcohol which is a by-product by hydrolysis of the hydrolyzable group OX. A silicone resin-containing emulsion composition, which is not contained.
The cured film formation base material in which the cured film of the silicone resin containing emulsion composition as described in any one of Claims 1-3 was formed in the base-material surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016221751A JP6666827B2 (en) | 2016-11-14 | 2016-11-14 | Silicone resin-containing emulsion composition and cured film-forming substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016221751A JP6666827B2 (en) | 2016-11-14 | 2016-11-14 | Silicone resin-containing emulsion composition and cured film-forming substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2018080223A true JP2018080223A (en) | 2018-05-24 |
| JP6666827B2 JP6666827B2 (en) | 2020-03-18 |
Family
ID=62197021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016221751A Active JP6666827B2 (en) | 2016-11-14 | 2016-11-14 | Silicone resin-containing emulsion composition and cured film-forming substrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6666827B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020036073A1 (en) * | 2018-08-17 | 2020-02-20 | 信越化学工業株式会社 | Silicone resin emulsion composition, method for producing same, coating agent and coated article |
| CN117285879A (en) * | 2023-11-24 | 2023-12-26 | 江苏凯伦建材股份有限公司 | Pre-laid waterproof coiled material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10316937A (en) * | 1997-03-14 | 1998-12-02 | Matsushita Electric Works Ltd | Stainproofing silicone emulsion coating composition, its production and stainproof article coated therewith |
| JPH11293196A (en) * | 1998-04-14 | 1999-10-26 | Matsushita Electric Works Ltd | Aqueous coating resin composition and coated article using the same |
-
2016
- 2016-11-14 JP JP2016221751A patent/JP6666827B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10316937A (en) * | 1997-03-14 | 1998-12-02 | Matsushita Electric Works Ltd | Stainproofing silicone emulsion coating composition, its production and stainproof article coated therewith |
| JPH11293196A (en) * | 1998-04-14 | 1999-10-26 | Matsushita Electric Works Ltd | Aqueous coating resin composition and coated article using the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020036073A1 (en) * | 2018-08-17 | 2020-02-20 | 信越化学工業株式会社 | Silicone resin emulsion composition, method for producing same, coating agent and coated article |
| CN117285879A (en) * | 2023-11-24 | 2023-12-26 | 江苏凯伦建材股份有限公司 | Pre-laid waterproof coiled material and preparation method thereof |
| CN117285879B (en) * | 2023-11-24 | 2024-02-27 | 江苏凯伦建材股份有限公司 | Pre-laid waterproof coiled material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6666827B2 (en) | 2020-03-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0841355B1 (en) | Silicone resin-containing emulsion compositions, methods for making them, and cured films thereof | |
| JP4775543B2 (en) | Organosilicone resin emulsion composition and method for producing the same, and article formed with a film of the composition | |
| JP3414251B2 (en) | Silicone resin-containing emulsion composition, method for producing the same, and article having cured coating of the composition | |
| JP3468776B2 (en) | Aqueous curable silane / polymer composition | |
| TW557320B (en) | Ambient temperature curing coating composition | |
| EP1095953B1 (en) | Silicone-grafted vinyl copolymer emulsion composition | |
| US7886499B2 (en) | Building exterior wall-coating emulsion compositions and building exterior walls | |
| JP3437672B2 (en) | Resin composition for water-based paint and method for forming coating film excellent in stain resistance | |
| JP7474204B2 (en) | Coating composition, coating composition for furniture and building interiors, and laminate | |
| EP1772500B1 (en) | Exterior wall-coating emulsion composition and building exterior walls | |
| JP2002256035A (en) | Vinylic copolymer emulsion and coating additive | |
| JP3319353B2 (en) | Silicone resin-containing emulsion composition, method for producing the same, and article having cured coating of the composition | |
| JP2008133342A (en) | Emulsion coating agent composition and article coated therewith | |
| JP6666827B2 (en) | Silicone resin-containing emulsion composition and cured film-forming substrate | |
| JP3446567B2 (en) | Silicone resin-containing emulsion composition, article having cured coating of the composition, and method for producing the same | |
| JP3521775B2 (en) | Silicone resin-containing emulsion composition and article having cured coating of the composition | |
| JP2005325253A (en) | Emulsion composition for functional inorganic filler-containing coating | |
| JP3336922B2 (en) | Silicone resin-containing emulsion composition, method for producing the same, and article having cured coating of the composition | |
| JP3479563B2 (en) | Resin composition for paint and method for producing the same | |
| JP4484260B2 (en) | Water-based paint composition | |
| JP2841113B2 (en) | Paint composition | |
| JP4542654B2 (en) | Resin composition and use thereof | |
| JP2008138059A (en) | Organosilicone resin emulsion composition and article with coated film of the composition formed thereon | |
| JPS62158767A (en) | Water-based coating agent | |
| JP2000239331A (en) | Preparation of aqueous emulsion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20181127 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20191112 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20191119 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20200108 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200117 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20200204 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20200221 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6666827 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |