JP7368217B2 - Cationic emulsion composition of polyorganosiloxane and method for producing the same - Google Patents
Cationic emulsion composition of polyorganosiloxane and method for producing the same Download PDFInfo
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- JP7368217B2 JP7368217B2 JP2019225634A JP2019225634A JP7368217B2 JP 7368217 B2 JP7368217 B2 JP 7368217B2 JP 2019225634 A JP2019225634 A JP 2019225634A JP 2019225634 A JP2019225634 A JP 2019225634A JP 7368217 B2 JP7368217 B2 JP 7368217B2
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- polyorganosiloxane
- emulsion composition
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- 239000000839 emulsion Substances 0.000 title claims description 108
- 239000000203 mixture Substances 0.000 title claims description 70
- 125000002091 cationic group Chemical group 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 64
- 125000000962 organic group Chemical group 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000003093 cationic surfactant Substances 0.000 claims description 33
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 17
- 230000001804 emulsifying effect Effects 0.000 claims description 16
- 239000000835 fiber Substances 0.000 claims description 16
- 125000005843 halogen group Chemical group 0.000 claims description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 12
- 239000002537 cosmetic Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000005871 repellent Substances 0.000 claims description 8
- 230000002940 repellent Effects 0.000 claims description 8
- 239000006082 mold release agent Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 210000004209 hair Anatomy 0.000 claims description 4
- -1 polysiloxanes Polymers 0.000 description 33
- 238000006116 polymerization reaction Methods 0.000 description 29
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 17
- 229920001296 polysiloxane Polymers 0.000 description 16
- 239000004480 active ingredient Substances 0.000 description 11
- 239000004744 fabric Substances 0.000 description 11
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 241000282320 Panthera leo Species 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 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 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 125000000913 palmityl 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])[H] 0.000 description 4
- 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 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- YSJGOMATDFSEED-UHFFFAOYSA-M behentrimonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCCCCCC[N+](C)(C)C YSJGOMATDFSEED-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 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 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 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 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000003676 hair preparation Substances 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 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 3
- 238000005342 ion exchange Methods 0.000 description 3
- 230000010534 mechanism of action Effects 0.000 description 3
- 125000001421 myristyl 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])[H] 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000005375 organosiloxane group Chemical group 0.000 description 3
- 239000002245 particle 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
- 230000000379 polymerizing effect Effects 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 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
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- PRKPGWQEKNEVEU-UHFFFAOYSA-N 4-methyl-n-(3-triethoxysilylpropyl)pentan-2-imine Chemical compound CCO[Si](OCC)(OCC)CCCN=C(C)CC(C)C PRKPGWQEKNEVEU-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- WHCKIPKZERFOAS-UHFFFAOYSA-M CCCCCCCCCCCCCCCCCCCC[N+](C)(C)C.CC(=O)[O-] Chemical compound CCCCCCCCCCCCCCCCCCCC[N+](C)(C)C.CC(=O)[O-] WHCKIPKZERFOAS-UHFFFAOYSA-M 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- DDQAGDLHARKUFX-UHFFFAOYSA-N acetic acid;methanamine Chemical compound [NH3+]C.CC([O-])=O DDQAGDLHARKUFX-UHFFFAOYSA-N 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000001204 arachidyl 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])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 1
- 125000006612 decyloxy group Chemical group 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-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
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- OROLQGYWJPKRJV-UHFFFAOYSA-M docosyl(trimethyl)azanium;acetate Chemical compound CC([O-])=O.CCCCCCCCCCCCCCCCCCCCCC[N+](C)(C)C OROLQGYWJPKRJV-UHFFFAOYSA-M 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- MRAPAFWHXSJNRN-UHFFFAOYSA-M icosyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCCCC[N+](C)(C)C MRAPAFWHXSJNRN-UHFFFAOYSA-M 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000002960 margaryl 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])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000001196 nonadecyl 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])C([H])([H])[H] 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 125000005447 octyloxy 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])O* 0.000 description 1
- 125000001117 oleyl 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])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PFPYHYZFFJJQFD-UHFFFAOYSA-N oxalic anhydride Chemical compound O=C1OC1=O PFPYHYZFFJJQFD-UHFFFAOYSA-N 0.000 description 1
- 125000002958 pentadecyl 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])[H] 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- AKLJIUURIIIOLU-UHFFFAOYSA-N silane 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound [SiH4].CO[Si](OC)(OC)CCCOC(=O)C(C)=C AKLJIUURIIIOLU-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000002562 thickening agent Substances 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
- 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
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- WDFCQTZXHUWJON-UHFFFAOYSA-M triheptyl(methyl)azanium;chloride Chemical compound [Cl-].CCCCCCC[N+](C)(CCCCCCC)CCCCCCC WDFCQTZXHUWJON-UHFFFAOYSA-M 0.000 description 1
- RNPOWDKBFLNPNV-UHFFFAOYSA-M trihexyl(methyl)azanium;chloride Chemical compound [Cl-].CCCCCC[N+](C)(CCCCCC)CCCCCC RNPOWDKBFLNPNV-UHFFFAOYSA-M 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-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
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- ILLSOFGDDPNATO-UHFFFAOYSA-M trimethyl(octadecyl)azanium;acetate Chemical compound CC([O-])=O.CCCCCCCCCCCCCCCCCC[N+](C)(C)C ILLSOFGDDPNATO-UHFFFAOYSA-M 0.000 description 1
- BFPOZPZYPNVMHU-UHFFFAOYSA-M trimethyl-[3-(trifluoromethyl)phenyl]azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC(C(F)(F)F)=C1 BFPOZPZYPNVMHU-UHFFFAOYSA-M 0.000 description 1
- UMMDBKGUDMBUSR-UHFFFAOYSA-M tris-decyl(methyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(CCCCCCCCCC)CCCCCCCCCC UMMDBKGUDMBUSR-UHFFFAOYSA-M 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/892—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a hydroxy group, e.g. dimethiconol
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/893—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by an alkoxy or aryloxy group, e.g. behenoxy dimethicone or stearoxy dimethicone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/521—Carboxylic amides (R1-CO-NR2R3), where R1, R2 and R3 are alkyl or alkenyl groups
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
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- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Cosmetics (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
本発明は、ポリオルガノシロキサンのカチオン系エマルション組成物及びその製造方法に関する。 The present invention relates to a cationic emulsion composition of polyorganosiloxane and a method for producing the same.
ポリオルガノシロキサンは、基材に処理することで平滑性や撥水性を付与できることから、繊維処理剤、離型剤、撥水剤、化粧料、毛髪用化粧料等に使用されている。中でも高重合のポリシロキサンは、平滑性の付与効果には優れている。また、これらポリシロキサンを乳化する際の界面活性剤として、４級アンモニウム塩のようなカチオン系界面活性剤を使用するとポリシロキサンの基材への吸着性が向上することも知られている。このため、高重合度のポリシロキサンをカチオン系界面活性剤で乳化したエマルションの要求が高かった。 Polyorganosiloxanes can impart smoothness and water repellency to substrates by treating them, so they are used in fiber treatment agents, mold release agents, water repellents, cosmetics, hair cosmetics, and the like. Among them, highly polymerized polysiloxanes are excellent in imparting smoothness. It is also known that when a cationic surfactant such as a quaternary ammonium salt is used as a surfactant when emulsifying these polysiloxanes, the adsorption of the polysiloxane to the base material is improved. For this reason, there has been a high demand for emulsions in which polysiloxanes with a high degree of polymerization are emulsified with cationic surfactants.
ポリシロキサンのエマルション化で一般的な方法は、ポリシロキサンと界面活性剤を乳化機の機械的なシェアで水中に乳化分散させる方法であるが、高重合度のポリシロキサンでは粘度が高すぎて均一に機械的なシェアをかけることができず、安定なエマルションを得ることはできない。 A common method for emulsifying polysiloxane is to emulsify and disperse polysiloxane and surfactant in water using the mechanical shear of an emulsifier, but polysiloxane with a high degree of polymerization has too high a viscosity and cannot be uniformly dispersed. It is not possible to apply a mechanical shear to the emulsion, making it impossible to obtain a stable emulsion.
高重合度のポリシロキサンエマルションを得る方法としては、シロキサンモノマーのエマルションを、酸又はアルカリ触媒を用いて、エマルション中で重合させる乳化重合法（特許文献１、２）が知られている。しかしながら、このような乳化重合法においては、文献記載の塩化セチルトリメチルアンモニウムに代表される４級アンモニウム塩のようなカチオン系界面活性剤を使用した場合には、重合速度が極めて遅い為に高重合度化するのに長時間を要する。工業的に実用的限界と考えられる１５０時間程度の重合を行っても、ポリシロキサンは抽出後の粘度が数万ｍＰａ・ｓレベルまでしか重合しない。 As a method for obtaining a polysiloxane emulsion with a high degree of polymerization, an emulsion polymerization method (Patent Documents 1 and 2) is known in which an emulsion of siloxane monomers is polymerized in the emulsion using an acid or alkali catalyst. However, in such an emulsion polymerization method, when a cationic surfactant such as a quaternary ammonium salt represented by cetyltrimethylammonium chloride described in the literature is used, the polymerization rate is extremely slow, resulting in high polymerization. It takes a long time to warm up. Even if polymerization is carried out for about 150 hours, which is considered to be the industrially practical limit, polysiloxane will only polymerize to a viscosity of several tens of thousands of mPa·s after extraction.
高重合度ポリシロキサンのカチオン系エマルションを得る方法として、シラノレート触媒で重合する方法（特許文献３）、アンモニウムハイドロキサイド触媒で重合する方法（特許文献４）も提案されているが、同様に重合度レベルが不十分である。 As a method for obtaining a cationic emulsion of highly polymerized polysiloxane, a method of polymerizing with a silanolate catalyst (Patent Document 3) and a method of polymerizing with an ammonium hydroxide catalyst (Patent Document 4) have also been proposed; degree level is insufficient.
また、アニオン系界面活性剤で高重合ポリシロキサンエマルションを製造した後にカチオン系界面活性剤を添加する方法（特許文献５、６）も提案されているが、アニオン系界面活性剤を併用しているので安定性に問題がある。 Additionally, a method in which a cationic surfactant is added after producing a highly polymerized polysiloxane emulsion using an anionic surfactant (Patent Documents 5 and 6) has been proposed, but anionic surfactants are also used in combination. Therefore, there is a problem with stability.
更に、２段階の温度条件で重合を行う方法（特許文献７）も提案されているが、高重合度化するには長時間の重合時間を要するといった問題がある。 Furthermore, a method (Patent Document 7) in which polymerization is carried out under two-step temperature conditions has been proposed, but there is a problem in that a long polymerization time is required to achieve a high degree of polymerization.
また近年、繊維処理剤分野において、高重合度ポリシロキサンだけでは達成が困難なレベルの洗濯耐久性を要求されることが多くなってきている。高重合度ポリシロキサンのエマルションにシリカなどの被膜補強剤を添加することによって被膜の強度を高めて耐久性を向上させる例もあるが、シリカの添加により安定性が低下してしまうことや、製造工程が増えるなどの問題もある。 In addition, in recent years, in the field of textile treatment agents, there has been an increasing demand for a level of washing durability that is difficult to achieve with high polymerization degree polysiloxanes alone. In some cases, adding a film reinforcing agent such as silica to a highly polymerized polysiloxane emulsion increases the strength of the film and improves its durability. There are also problems such as an increase in the number of steps.
本発明は、上記事情に鑑みなされたもので、粘度が３００，０００ｍＰａ・ｓ以上と高く、かつ安定性及び耐久性が良好なポリオルガノシロキサンのカチオン系エマルション組成物を提供することを目的とする。本発明は、そのようなエマルション組成物を比較的短時間で重合させることができる製造方法を提供することを目的とする。 The present invention was made in view of the above circumstances, and an object thereof is to provide a cationic emulsion composition of polyorganosiloxane that has a high viscosity of 300,000 mPa · s or more and has good stability and durability. do. An object of the present invention is to provide a manufacturing method that can polymerize such an emulsion composition in a relatively short time.
上記目的を解決するために、本発明は、
（Ａ）下記平均組成式（１）で表される、２５℃における粘度が３００，０００ｍＰａ・ｓ以上のポリオルガノシロキサン： １００質量部、
（Ｂ－１）カチオン系界面活性剤：Ｑ１
３（ＣＨ３）Ｎ＋・Ｘ－： ０．１～３０質量部、
（ここで、Ｑ１は、同一又は異種の炭素数６～３０の１価有機基、Ｘはハロゲン原子又は炭素数１～６の１価カルボキシル基である。）
（Ｂ－２）カチオン系界面活性剤：Ｑ２（ＣＨ３）３Ｎ＋・Ｘ－： ０．１～３０質量部、
（ここで、Ｑ２は、炭素数１７～３０の１価有機基、Ｘはハロゲン原子又は炭素数１～６の１価カルボキシル基である。）
（Ｃ）水： ３０～３，０００質量部
を含有してなることを特徴とするポリオルガノシロキサンのカチオン系エマルション組成物を提供する。
In order to solve the above object, the present invention
(A) 100 parts by mass of polyorganosiloxane represented by the following average composition formula (1) and having a viscosity of 300,000 mPa·s or more at 25°C,
(B-1) Cationic surfactant: Q 1 3 (CH 3 )N + ·X − : 0.1 to 30 parts by mass,
(Here, Q 1 is the same or different monovalent organic group having 6 to 30 carbon atoms, and X is a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms.)
(B-2) Cationic surfactant: Q 2 (CH 3 ) 3 N + ·X − : 0.1 to 30 parts by mass,
(Here, Q 2 is a monovalent organic group having 17 to 30 carbon atoms, and X is a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms.)
(C) Water: Provided is a cationic emulsion composition of polyorganosiloxane, characterized in that it contains 30 to 3,000 parts by mass.
このようなポリオルガノシロキサンのカチオン系エマルション組成物は、粘度が高い高重合ポリオルガノシロキサンのカチオン系エマルション組成物であり、かつ、安定性が良好であり、また耐久性も良好である。 Such a cationic emulsion composition of polyorganosiloxane is a cationic emulsion composition of highly polymerized polyorganosiloxane having a high viscosity, and has good stability and durability.
このとき、本発明のエマルション組成物は、更にノニオン系界面活性剤を含むことが好ましい。 At this time, it is preferable that the emulsion composition of the present invention further contains a nonionic surfactant.
このように、カチオン系界面活性剤の他に、ノニオン系界面活性剤を併用することでエマルションの小粒径化が容易になり、これによりエマルションの安定性の向上につながる。 In this way, by using a nonionic surfactant in addition to a cationic surfactant, it becomes easier to reduce the particle size of the emulsion, which leads to improvement in the stability of the emulsion.
また、本発明のエマルション組成物は、乾燥後に被膜を形成するものであることが好ましい。 Further, the emulsion composition of the present invention preferably forms a film after drying.
このように、本発明のエマルション化合物は、乾燥して被膜を形成することが可能である。 In this way, the emulsion compound of the present invention can be dried to form a film.
また、本発明は、上記のポリオルガノシロキサンのカチオン系エマルション組成物を含むことを特徴とする繊維処理剤を提供する。 The present invention also provides a fiber treatment agent characterized by containing the above-mentioned cationic emulsion composition of polyorganosiloxane.
また、本発明は、上記のポリオルガノシロキサンのカチオン系エマルション組成物を含むことを特徴とする離型剤を提供する。 The present invention also provides a mold release agent characterized by containing the above-mentioned cationic emulsion composition of polyorganosiloxane.
また、本発明は、上記のポリオルガノシロキサンのカチオン系エマルション組成物を含むことを特徴とする撥水剤を提供する。 The present invention also provides a water repellent characterized by containing the above-mentioned cationic emulsion composition of polyorganosiloxane.
また、本発明は、上記のポリオルガノシロキサンのカチオン系エマルション組成物を含むことを特徴とする化粧料を提供する。 The present invention also provides a cosmetic composition containing the above-mentioned cationic emulsion composition of polyorganosiloxane.
また、本発明は、上記のポリオルガノシロキサンのカチオン系エマルション組成物を含むことを特徴とする毛髪用化粧料を提供する。 The present invention also provides a hair cosmetic composition comprising the above-mentioned cationic emulsion composition of polyorganosiloxane.
このように、本発明のポリオルガノシロキサンのカチオン系エマルション組成物は、繊維処理剤、離型剤、撥水剤、化粧料、毛髪用化粧料に含まれる成分として好適に使用することができる。 Thus, the polyorganosiloxane cationic emulsion composition of the present invention can be suitably used as a component included in fiber treatment agents, mold release agents, water repellents, cosmetics, and hair cosmetics.
また、本発明は、
（Ｄ）一般式：ＨＯ－［Ｒ１
２ＳｉＯ］ｊ－Ｈで表される両末端ヒドロキシポリジオルガノシロキサン（ここで、Ｒ１は、互いに独立に、水素原子、又は、炭素数１～２０の１価有機基であり、ｊは該両末端ヒドロキシポリジオルガノシロキサンの２５℃における粘度が２，０００ｍＰａ・ｓ未満を満たす値である。）： １００質量部、
（Ｅ）下記に示されるいずれか１つ又は２つ以上のオルガノアルコキシシラン：０～２０質量部
Ｓｉ（ＯＲ３）４、Ｒ１Ｓｉ（ＯＲ３）３、Ｒ１
２Ｓｉ（ＯＲ３）２、Ｒ１
３Ｓｉ（ＯＲ３）
（ここで、Ｒ１は互いに独立に、水素原子、又は、炭素数１～２０の１価有機基であり、Ｒ３は互いに独立に、水素原子、又は、炭素数１～２０の１価有機基である。）、
（Ｂ－１）カチオン系界面活性剤：Ｑ１
３（ＣＨ３）Ｎ＋・Ｘ－： ０．１～３０質量部、
（ここで、Ｑ１は同一又は異種の炭素数６～３０の１価有機基、Ｘはハロゲン原子又は炭素数１～６の１価カルボキシル基である。）
（Ｂ－２）カチオン系界面活性剤：Ｑ２（ＣＨ３）３Ｎ＋・Ｘ－： ０．１～３０質量部、
（ここで、Ｑ２は炭素数１７～３０の１価有機基、Ｘはハロゲン原子又は炭素数１～６の１価カルボキシル基である。）
（Ｃ）水： ３０～３，０００質量部
を乳化分散させて得られるエマルションを、アルカリ触媒存在下、０～３０℃で１～１５０時間重合を行い、更に中和を行うことを特徴とするポリオルガノシロキサンのカチオン系エマルション組成物の製造方法を提供する。
Moreover, the present invention
(D) A double-terminated hydroxypolydiorganosiloxane represented by the general formula: HO-[R 1 2 SiO] j -H (where R 1 is independently a hydrogen atom or a carbon number of 1 to 20 is a monovalent organic group, and j is a value that satisfies the viscosity of the both-terminated hydroxypolydiorganosiloxane at 25°C of less than 2,000 mPa s): 100 parts by mass,
(E) Any one or more organoalkoxysilanes shown below: 0 to 20 parts by mass Si(OR 3 ) 4 , R 1 Si(OR 3 ) 3 , R 1 2 Si(OR 3 ) 2 , R 1 3 Si (OR 3 )
(Here, R 1 is independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and R 3 is independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ),
(B-1) Cationic surfactant: Q 1 3 (CH 3 )N + ·X − : 0.1 to 30 parts by mass,
(Here, Q 1 is the same or different monovalent organic group having 6 to 30 carbon atoms, and X is a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms.)
(B-2) Cationic surfactant: Q 2 (CH 3 ) 3 N + ·X − : 0.1 to 30 parts by mass,
(Here, Q 2 is a monovalent organic group having 17 to 30 carbon atoms, and X is a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms.)
(C) Water: An emulsion obtained by emulsifying and dispersing 30 to 3,000 parts by mass is polymerized at 0 to 30°C for 1 to 150 hours in the presence of an alkali catalyst, and is further neutralized. A method for producing a cationic emulsion composition of polyorganosiloxane is provided.
このようなエマルション組成物の製造方法であれば、粘度が高い高重合ポリオルガノシロキサンのカチオン系エマルション組成物であって、安定性が良好であり、また耐久性も良好であるものを、比較的短時間で重合させることができる。 With this method of producing an emulsion composition, a cationic emulsion composition of highly polymerized polyorganosiloxane with high viscosity, good stability, and good durability can be produced relatively easily. It can be polymerized in a short time.
本発明のポリオルガノシロキサンのカチオン系エマルション組成物は、粘度が高い高重合ポリオルガノシロキサンのカチオン系エマルション組成物であり、かつ、安定性が良好であり、また耐久性も良好である。また、このエマルション組成物は、単独で被膜を形成可能であり、更にその被膜の耐久性も良好とすることができる。このようなエマルション組成物は、繊維処理剤、離型剤、撥水剤、化粧料、毛髪用化粧料等として好適に用いることができる。 The cationic emulsion composition of polyorganosiloxane of the present invention is a cationic emulsion composition of highly polymerized polyorganosiloxane with high viscosity, and has good stability and durability. Further, this emulsion composition can form a film by itself, and the durability of the film can also be improved. Such an emulsion composition can be suitably used as a fiber treatment agent, a mold release agent, a water repellent, a cosmetic, a hair cosmetic, and the like.
また、本発明のポリオルガノシロキサンのカチオン系エマルション組成物の製造方法は、そのようなエマルション組成物を比較的短時間で重合させることができるので、工業的にも有用である。 Furthermore, the method for producing a cationic emulsion composition of polyorganosiloxane of the present invention is industrially useful because such an emulsion composition can be polymerized in a relatively short time.
本発明者は、上記目的を達成するために鋭意検討を重ねた結果、
（Ｄ）一般式：ＨＯ－［Ｒ１
２ＳｉＯ］ｊ－Ｈで表される両末端ヒドロキシポリジオルガノシロキサン（ここで、Ｒ１は、互いに独立に、水素原子、又は、炭素数１～２０の１価有機基であり、ｊは該両末端ヒドロキシポリジオルガノシロキサンの２５℃における粘度が２，０００ｍＰａ・ｓ未満を満たす値である。）： １００質量部、
（Ｅ）下記に示されるいずれか１つ又は２つ以上のオルガノアルコキシシラン：０～２０質量部
Ｓｉ（ＯＲ３）４、Ｒ１Ｓｉ（ＯＲ３）３、Ｒ１
２Ｓｉ（ＯＲ３）２、Ｒ１
３Ｓｉ（ＯＲ３）
（ここで、Ｒ１は互いに独立に、水素原子、又は、炭素数１～２０の１価有機基であり、Ｒ３は互いに独立に、水素原子、又は、炭素数１～２０の１価有機基である。）、
（Ｂ－１）カチオン系界面活性剤：Ｑ１
３（ＣＨ３）Ｎ＋・Ｘ－： ０．１～３０質量部、
（ここで、Ｑ１は同一又は異種の炭素数６～３０の１価有機基、Ｘはハロゲン原子又は炭素数１～６の１価カルボキシル基である。）
（Ｂ－２）カチオン系界面活性剤：Ｑ２（ＣＨ３）３Ｎ＋・Ｘ－： ０．１～３０質量部、
（ここで、Ｑ２は炭素数１７～３０の１価有機基、Ｘはハロゲン原子又は炭素数１～６の１価カルボキシル基である。）
（Ｃ）水： ３０～３，０００質量部
を乳化分散させて得られるエマルションを、アルカリ触媒存在下、０～３０℃で１～１５０時間重合を行い、更に中和を行うことにより、該エマルションを比較的短時間で重合させることができることを見出した。また、本発明者らは、これにより（Ａ）成分として、下記平均組成式（１）で表される、２５℃における粘度が３００，０００ｍＰａ・ｓ以上のポリオルガノシロキサンを含有したカチオン系エマルション組成物が得られ、このエマルション組成物は、安定性が良好であり、また耐久性も良好であることを見出し、本発明をなすに至った。
(D) A double-terminated hydroxypolydiorganosiloxane represented by the general formula: HO-[R 1 2 SiO] j -H (where R 1 is independently a hydrogen atom or a carbon number of 1 to 20 is a monovalent organic group, and j is a value that satisfies the viscosity of the both-terminated hydroxypolydiorganosiloxane at 25°C of less than 2,000 mPa s): 100 parts by mass,
(E) Any one or more organoalkoxysilanes shown below: 0 to 20 parts by mass Si(OR 3 ) 4 , R 1 Si(OR 3 ) 3 , R 1 2 Si(OR 3 ) 2 , R 1 3 Si (OR 3 )
(Here, R 1 is independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and R 3 is independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ),
(B-1) Cationic surfactant: Q 1 3 (CH 3 )N + ·X − : 0.1 to 30 parts by mass,
(Here, Q 1 is the same or different monovalent organic group having 6 to 30 carbon atoms, and X is a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms.)
(B-2) Cationic surfactant: Q 2 (CH 3 ) 3 N + ·X − : 0.1 to 30 parts by mass,
(Here, Q 2 is a monovalent organic group having 17 to 30 carbon atoms, and X is a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms.)
(C) Water: An emulsion obtained by emulsifying and dispersing 30 to 3,000 parts by mass is polymerized at 0 to 30°C for 1 to 150 hours in the presence of an alkali catalyst, and further neutralized to form an emulsion. It has been found that it is possible to polymerize in a relatively short time. The present inventors have also developed a cationic emulsion composition containing, as component (A), a polyorganosiloxane having a viscosity of 300,000 mPa·s or more at 25°C, which is represented by the following average composition formula (1). It has been found that this emulsion composition has good stability and good durability, and has led to the present invention.
このような３００，０００ｍＰａ・ｓ以上の高粘度のポリオルガノシロキサンは一般に高重合度のものである。そのため、本発明の説明の際に、高重合度ポリオルガノシロキサンのカチオン系エマルション組成物と称することがある。 Such polyorganosiloxanes having a high viscosity of 300,000 mPa·s or more generally have a high degree of polymerization. Therefore, when describing the present invention, it may be referred to as a cationic emulsion composition of highly polymerized polyorganosiloxane.
以下、本発明について実施の形態を説明するが、本発明はこれに限定されるものではない。 Embodiments of the present invention will be described below, but the present invention is not limited thereto.
まず、本発明のポリオルガノシロキサンのカチオン系エマルション組成物の各成分について説明する。 First, each component of the polyorganosiloxane cationic emulsion composition of the present invention will be explained.
［（Ａ）成分］
（Ａ）成分は、下記平均組成式（１）で表される、２５℃における粘度が３００，０００ｍＰａ・ｓ以上のポリオルガノシロキサンである。本発明のエマルション組成物において、この（Ａ）成分は、１００質量部含有される。
Component (A) is a polyorganosiloxane represented by the following average composition formula (1) and having a viscosity of 300,000 mPa·s or more at 25°C. In the emulsion composition of the present invention, this component (A) is contained in an amount of 100 parts by mass.
上記のように、Ｒ１は、互いに独立に、水素原子、又は、炭素数１～２０の１価有機基である。炭素数１～２０の１価有機基としては、直鎖、分岐鎖または環状のいずれでもよく、具体的には、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ドデシル、テトラデシル、ヘキサデシル、オクタデシル、シクロペンチル、シクロヘキシル、シクロヘプチルなどのアルキル基、フェニル、トリル、ナフチルなどのアリール基、ビニル、アリルなどのアルケニル基、或いはこれらの有機基構造中の水素原子の一部をハロゲン原子や、アミノ、アクリロキシ、メタクリロキシ、エポキシ、メルカプト等の極性基含有の有機基で置換したものなどが挙げられる。ここで、Ｒ１の８０％以上はメチル基であることが工業的及び特性的に望ましい。 As mentioned above, R 1 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The monovalent organic group having 1 to 20 carbon atoms may be linear, branched or cyclic, and specifically includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Alkyl groups such as dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, and cycloheptyl; aryl groups such as phenyl, tolyl, and naphthyl; alkenyl groups such as vinyl and allyl; or some of the hydrogen atoms in these organic group structures. Examples include those substituted with a halogen atom or an organic group containing a polar group such as amino, acryloxy, methacryloxy, epoxy, or mercapto. Here, it is desirable industrially and characteristically that 80% or more of R 1 is a methyl group.
また、上記のように、Ｒ２は、互いに独立に、上記のＲ１の選択肢から選ばれる基、又は、ヒドロキシ基、若しくは炭素数１～２０のアルコキシ基である。炭素数１～２０のアルコキシ基としては、直鎖、分岐鎖または環状のいずれでもよく、具体的には、メトキシ基、エトキシ基、プロパノキシ基、ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、オクチルオキシ基、デシルオキシ基、ドデシルオキシ基、２－エチルヘキシルオキシ基等が挙げられ、メトキシ基、エトキシ基、プロパノキシ基、ブトキシ基、ペンチルオキシ基が好ましく、メトキシ基、エトキシ基、プロパノキシ基が更に好ましい。 Furthermore, as described above, R 2 is independently a group selected from the options for R 1 above, a hydroxy group, or an alkoxy group having 1 to 20 carbon atoms. The alkoxy group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and specifically includes methoxy, ethoxy, propanoxy, butoxy, pentyloxy, hexyloxy, and octyloxy. group, decyloxy group, dodecyloxy group, 2-ethylhexyloxy group, etc., with methoxy group, ethoxy group, propanoxy group, butoxy group, and pentyloxy group being preferred, and methoxy group, ethoxy group, and propanoxy group being more preferred.
上記平均組成式（１）中に、反応性官能基が存在する場合、その反応性官能基は他の化合物と反応していても良い。具体的には、上記平均組成式（１）中にアミノ基が存在する場合、エポキシ基含有ポリオキシアルキレン化合物やエポキシ基含有アルキル化合物との開環反応をしていても良く、また、無水酢酸や、無水プロピオン酸、無水シュウ酸、無水コハク酸、無水マレイン酸、無水フタル酸、無水安息香酸といったカルボン酸無水物とのアセチル化反応をしていても良い。また、上記平均組成式（１）中にエポキシ基が存在する場合、アミノ基含有化合物と開環反応をしていても良い。なお、上記に示した反応性官能基との反応はこれらに限定されるものではない。 When a reactive functional group is present in the average compositional formula (1), the reactive functional group may react with another compound. Specifically, when an amino group exists in the above average composition formula (1), it may undergo a ring-opening reaction with an epoxy group-containing polyoxyalkylene compound or an epoxy group-containing alkyl compound, and acetic anhydride Alternatively, an acetylation reaction may be carried out with a carboxylic acid anhydride such as propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, or benzoic anhydride. Further, when an epoxy group is present in the above average compositional formula (1), it may undergo a ring-opening reaction with an amino group-containing compound. Note that the reactions with the reactive functional groups shown above are not limited to these.
上記平均組成式（１）中のａ、ｂ、ｃ、ｄは、ポリオルガノシロキサンの２５℃における粘度が３００，０００ｍＰａ・ｓ以上を満たす値であり、４００，０００ｍＰａ・ｓ以上を満たす値がより好ましく、５００，０００ｍＰａ・ｓ以上を満たす値が更に好ましい。なお、この粘度は絶対粘度であって、液状で測定できるものはそのまま、粘度が高すぎて測定できないものはトルエン溶解粘度を、回転粘度計により、２５℃で測定した値である。また、ａ≧２、ｃ＋ｄ≧１である。 In the above average compositional formula (1), a, b, c, and d are values that satisfy the viscosity of the polyorganosiloxane at 25°C of 300,000 mPa・s or more, and values that satisfy 400,000 mPa・s or more are more preferable. Preferably, a value satisfying 500,000 mPa·s or more is more preferable. Note that this viscosity is an absolute viscosity, and those that can be measured in liquid form are as-is, and those whose viscosity is too high to be measured are toluene dissolution viscosity, measured at 25 ° C. with a rotational viscometer. Further, a≧2 and c+d≧1.
上記平均組成式（１）中のｂは、典型的には５０以上、好ましくは１００以上の値を取り得る。ただし、ｃ＋ｄの値が大きい場合は架橋単位が増えるため、ｂが５０以下でも粘度が３００，０００ｍＰａ・ｓ以上となる場合もある。 b in the above average compositional formula (1) typically takes a value of 50 or more, preferably 100 or more. However, when the value of c+d is large, the number of crosslinking units increases, so even if b is 50 or less, the viscosity may be 300,000 mPa·s or more.
（Ａ）成分の具体例としては、下記平均組成式が挙げられるが、これらに限定されるものではない。下記平均組成式中、ａ、ｂ、ｃ、ｄ、ｅ、ｆは、ポリオルガノシロキサンの２５℃における粘度が３００，０００ｍＰａ・ｓ以上を満たす値であり、ａ≧２、ｃ＋ｄ≧１である。また、下記平均組成式中のｂ＋ｅ＋ｆは、典型的には５０以上、好ましくは１００以上の値を取り得る。 Specific examples of component (A) include, but are not limited to, the following average composition formula. In the average composition formula below, a, b, c, d, e, and f are values that satisfy the viscosity of the polyorganosiloxane at 25° C. of 300,000 mPa·s or more, and a≧2 and c+d≧1. Further, b+e+f in the average composition formula below typically takes a value of 50 or more, preferably 100 or more.
［（Ｂ－１）成分及び（Ｂ－２）成分］
（Ｂ－１）成分及び（Ｂ－２）成分は以下の通りである。
（Ｂ－１）カチオン系界面活性剤：Ｑ１
３（ＣＨ３）Ｎ＋・Ｘ－（ここで、Ｑ１は、同一又は異種の炭素数６～３０の１価有機基、Ｘはハロゲン原子又は炭素数１～６の１価カルボキシル基である。）
（Ｂ－２）カチオン系界面活性剤：Ｑ２（ＣＨ３）３Ｎ＋・Ｘ－（ここで、Ｑ２は、炭素数１７～３０の１価有機基、Ｘはハロゲン原子又は炭素数１～６の１価カルボキシル基である。）
[(B-1) component and (B-2) component]
The components (B-1) and (B-2) are as follows.
(B-1) Cationic surfactant: Q 1 3 (CH 3 )N +・X − (where, Q 1 is the same or different monovalent organic group having 6 to 30 carbon atoms, and X is a halogen atom) or a monovalent carboxyl group having 1 to 6 carbon atoms.)
(B-2) Cationic surfactant: Q 2 (CH 3 ) 3 N +・X − (where Q 2 is a monovalent organic group having 17 to 30 carbon atoms, and X is a halogen atom or a carbon number 1 ~6 monovalent carboxyl group)
本発明のエマルション組成物において、（Ａ）成分１００質量部に対して、（Ｂ－１）成分が０．１～３０質量部含有され、（Ｂ－２）成分が０．１～３０質量部含有される。 In the emulsion composition of the present invention, component (B-1) is contained in 0.1 to 30 parts by mass, and component (B-2) is contained in 0.1 to 30 parts by mass with respect to 100 parts by mass of component (A). Contains.
これら（Ｂ－１）成分及び（Ｂ－２）成分であるカチオン系界面活性剤は、ポリオルガノシロキサンを水中へ乳化分散させるためのものであるが、本発明者らは（Ｂ－１）及び（Ｂ－２）成分の作用機構について、乳化剤としての作用機構以外にも次のような作用機構を考えている。本発明のポリオルガノシロキサンのカチオン系エマルション組成物の製造方法において、ポリオルガノシロキサンを水中へ乳化分散した後に、アルカリ触媒を加えた際に水相に生じるＯＨ－と（Ｂ－１）及び（Ｂ－２）成分であるカチオン系界面活性剤の対イオンが交換することにより、カチオン系界面活性剤自体も触媒として作用し、その結果、より効率的に（Ａ）成分のポリオルガノシロキサンを高重合度化することができると考えられる。 These cationic surfactants, which are components (B-1) and (B-2), are for emulsifying and dispersing polyorganosiloxane in water. Regarding the mechanism of action of component (B-2), the following mechanism of action is considered in addition to the mechanism of action as an emulsifier. In the method for producing a cationic emulsion composition of polyorganosiloxane of the present invention, after emulsifying and dispersing polyorganosiloxane in water, when an alkali catalyst is added, OH -, (B-1) and (B -2) By exchanging the counter ions of the cationic surfactant component, the cationic surfactant itself acts as a catalyst, and as a result, the polyorganosiloxane component (A) can be highly polymerized more efficiently. It is thought that it can be moderated.
（Ｂ－１）成分であるカチオン系界面活性剤は、上記のように、Ｑ１ ３（ＣＨ３）Ｎ＋・Ｘ－で示されるカチオン系界面活性剤であり、Ｑ１は同一又は異種の炭素数６～３０の１価有機基であり、好ましくは７～１８の１価有機基である。Ｑ１の炭素数が６より小さい場合には、界面活性剤の親水性が強すぎて（Ａ）成分のポリオルガノシロキサンとの接触頻度が少なくなり、ポリオルガノシロキサンを高重合度化するのに長時間の重合を必要とする。また、Ｑ１の炭素数が３０より大きい場合には界面活性剤としての乳化力が弱く、安定なエマルションを得ることができない場合がある。 As mentioned above, the cationic surfactant which is the component (B-1) is a cationic surfactant represented by Q 1 3 (CH 3 )N + ·X − , where Q 1 is the same or different type. A monovalent organic group having 6 to 30 carbon atoms, preferably a monovalent organic group having 7 to 18 carbon atoms. When the number of carbon atoms in Q1 is less than 6, the hydrophilicity of the surfactant is too strong and the frequency of contact with the polyorganosiloxane of component (A) is reduced, making it difficult to increase the degree of polymerization of the polyorganosiloxane. Requires long polymerization. Furthermore, when the number of carbon atoms in Q1 is greater than 30, the emulsifying power as a surfactant is weak, and a stable emulsion may not be obtained in some cases.
Ｑ１の具体例としては、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、ヘキサデシル、ヘプタデシル、オクタデシル、ノナデシル、エイコシル、ドコサニル、シクロペンチル、シクロヘキシル、シクロヘプチルなどのアルキル基、フェニル、ベンジル、トリル、ナフチルなどのアリール基、オレイルなどのアルケニル基等が挙げられる。中でもオクチル、ドデシル、ヘキサデシル、オクタデシルが好ましい。 Specific examples of Q1 include alkyl groups such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, docosanyl, cyclopentyl, cyclohexyl, and cycloheptyl. , phenyl, benzyl, tolyl, naphthyl and other aryl groups, and oleyl and other alkenyl groups. Among these, octyl, dodecyl, hexadecyl, and octadecyl are preferred.
また、Ｘ－は、ハロゲンイオン又は炭素数１～６の１価カルボキシルイオンであり、具体的にはＣｌ－、Ｂｒ－、Ｉ－などのハロゲンイオン、ＨＣＯＯ－、ＣＨ３ＣＯＯ－、Ｃ２Ｈ５ＣＯＯ－などのカルボキシルイオンが挙げられる。中でもＣｌ－、ＨＣＯＯ－、ＣＨ３ＣＯＯ－が好ましい。 In addition, X − is a halogen ion or a monovalent carboxyl ion having 1 to 6 carbon atoms, specifically, a halogen ion such as Cl − , Br − , I − , HCOO − , CH 3 COO − , C 2 H Examples include carboxyl ions such as 5 COO - . Among them, Cl − , HCOO − and CH 3 COO − are preferable.
（Ｂ－１）成分の具体例としては、トリヘキシルメチルアンモニウムクロライド、トリヘプチルメチルアンモニウムクロライド、トリオクチルメチルアンモニウムクロライド、トリノニルメチルアンモニウムクロライド、トリデシルメチルアンモニウムクロライド、トリラウリルメチルアンモニウムクロライド、トリオクチルメチルアンモニウムアセテート、トリラウリルメチルアンモニウムアセテート等が挙げられるが、これらに限定されるものではない。 Specific examples of component (B-1) include trihexylmethylammonium chloride, triheptylmethylammonium chloride, trioctylmethylammonium chloride, trinonylmethylammonium chloride, tridecylmethylammonium chloride, trilaurylmethylammonium chloride, trioctyl Examples include, but are not limited to, methylammonium acetate and trilaurylmethylammonium acetate.
（Ｂ－１）成分のカチオン系界面活性剤の使用量としては、（Ａ）成分１００質量部に対して、０．１～３０質量部用いることができ、好ましくは０．５～２０質量部、より好ましくは１～１５質量部である。０．１質量部より少ない場合には、（Ａ）成分が重合過程で効率よく高重合度化することができない場合があり、また、３０質量部より多い場合にはエマルションの安定性が不安定になりやすい。 The amount of the cationic surfactant (B-1) used can be 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, per 100 parts by weight of component (A). , more preferably 1 to 15 parts by mass. If it is less than 0.1 parts by mass, component (A) may not be able to efficiently increase the degree of polymerization during the polymerization process, and if it is more than 30 parts by mass, the stability of the emulsion may become unstable. easy to become.
また、（Ｂ－２）成分のカチオン系界面活性剤は、上記のように、Ｑ２（ＣＨ３）３Ｎ＋・Ｘ－で示されるカチオン系界面活性剤でありエマルションの安定性を向上させることができる。ここで、Ｑ２は、炭素数１７～３０の１価有機基であり、好ましくは１８～２８の１価有機基である。Ｑ２の炭素数が１７より小さい場合には、（Ｂ－１）で示されるカチオン系界面活性剤との相溶性が悪くエマルションの安定性が低下してしまう場合がある。Ｑ２の炭素数が３０より大きい場合には、Ｑ１の場合と同様に、界面活性剤としての乳化力が弱く、安定なエマルションを得ることができない場合がある。Ｑ２のＸ－は、上記Ｑ１のＸ－と同じである。 In addition, the cationic surfactant of component (B-2) is a cationic surfactant represented by Q 2 (CH 3 ) 3 N + ·X − as described above, and improves the stability of the emulsion. be able to. Here, Q 2 is a monovalent organic group having 17 to 30 carbon atoms, preferably a monovalent organic group having 18 to 28 carbon atoms. If the number of carbon atoms in Q 2 is smaller than 17, the compatibility with the cationic surfactant represented by (B-1) may be poor, resulting in a decrease in the stability of the emulsion. When the number of carbon atoms in Q 2 is greater than 30, as in the case of Q 1 , the emulsifying power as a surfactant is weak, and a stable emulsion may not be obtained. X - in Q 2 is the same as X - in Q 1 above.
（Ｂ－２）成分の具体例としては、ステアリルトリメチルアンモニウムクロライド、イコシルトリメチルアンモニウムクロライド、ベヘニルトリメチルアンモニウムクロライド、ステアリルトリメチルアンモニウムアセテート、イコシルトリメチルアンモニウムアセテート、ベヘニルトリメチルアンモニウムアセテート等が挙げられるが、これらに限定されるものではない。 Specific examples of component (B-2) include stearyltrimethylammonium chloride, icosyltrimethylammonium chloride, behenyltrimethylammonium chloride, stearyltrimethylammonium acetate, icosyltrimethylammonium acetate, behenyltrimethylammonium acetate, etc. It is not limited to.
（Ｂ－２）成分のカチオン系界面活性剤の使用量としては、（Ａ）成分１００質量部に対して、０．１～３０質量部用いることができ、好ましくは０．５～２０質量部、より好ましくは１～１５質量部である。０．１質量部より少ない場合にはエマルションの安定性が不安定になりやすく、３０質量部より多い場合には（Ａ）成分が重合過程で効率よく高重合度化することができない場合がある。 The amount of the cationic surfactant (B-2) used can be 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, per 100 parts by weight of component (A). , more preferably 1 to 15 parts by mass. If it is less than 0.1 part by mass, the stability of the emulsion tends to become unstable, and if it is more than 30 parts by mass, component (A) may not be able to efficiently increase the degree of polymerization during the polymerization process. .
（Ｂ－１）成分は（Ｂ－２）成分と比べて疎水性が高いため、（Ａ）成分のポリオルガノシロキサンとの接触頻度が高く、より重合速度を速める効果が期待できる一方で、疎水性が高すぎて乳化能が劣る場合がある。そのため、（Ｂ－１）のみ使用する場合、エマルションの組成や、粒径、粘度、ｐＨ等の条件によってはエマルションの経時安定性が悪くなってしまう場合がある。そこで、（Ｂ－１）成分と比較して乳化能が高い（Ｂ－２）成分を併用することによって重合速度を速めたまま、エマルションの安定性を高めることができる。 Since component (B-1) is more hydrophobic than component (B-2), it comes into contact with the polyorganosiloxane of component (A) more frequently, and is expected to have the effect of increasing the polymerization rate. If the emulsifying ability is too high, the emulsifying ability may be poor. Therefore, when only (B-1) is used, the stability of the emulsion over time may deteriorate depending on the emulsion composition, particle size, viscosity, pH, and other conditions. Therefore, by jointly using component (B-2), which has a higher emulsifying ability than component (B-1), it is possible to increase the stability of the emulsion while increasing the polymerization rate.
また、本発明のポリオルガノシロキサンのカチオン系エマルション組成物においては、カチオン系界面活性剤の他に、ノニオン系界面活性剤を併用することでエマルションの小粒径化が容易になり、これによりエマルションの安定性の向上につながる。ノニオン系界面活性剤としては、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルキルフェニルエーテル、ポリオキシアルキレンアルキルエステル、ポリオキシアルキレンソルビタンアルキルエステル、ポリエチレングリコール、ポリプロピレングリコール、ジエチレングリコール等が例示され、１種単独で又は２種以上を適宜選択して用いることができる。中でも、下記一般式（２）
Ｒ４Ｏ（ＥＯ）Ｐ（ＰＯ）ｑＨ （２）
（式中、Ｒ４は、炭素原子数８～３０の直鎖又は分岐鎖のアルキル基であり、ＥＯはエチレンオキシド基、ＰＯはプロピレンオキシド基を示し、それらの配列はブロック状でもランダム状でもよい。ｐ及びｑは独立に０～１００の整数であり、ただし、ｐ＋ｑ＞０である。）で表されるものが好ましい。特には、上記一般式（２）において、Ｒ４は炭素原子数８～１８の直鎖又は分岐鎖のアルキル基が好ましく、ｐ、ｑは独立に０～２５、０＜ｐ＋ｑ≦５０が好ましい。
In addition, in the cationic emulsion composition of polyorganosiloxane of the present invention, by using a nonionic surfactant in addition to the cationic surfactant, it is easy to reduce the particle size of the emulsion. This leads to improved stability. Examples of nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ether, polyoxyalkylene alkyl ester, polyoxyalkylene sorbitan alkyl ester, polyethylene glycol, polypropylene glycol, diethylene glycol, etc. Alternatively, two or more types can be appropriately selected and used. Among them, the following general formula (2)
R 4 O (EO) P (PO) q H (2)
(In the formula, R 4 is a linear or branched alkyl group having 8 to 30 carbon atoms, EO is an ethylene oxide group, and PO is a propylene oxide group, and their arrangement may be block-like or random-like. .p and q are independently integers from 0 to 100, provided that p+q>0) is preferred. Particularly, in the above general formula (2), R 4 is preferably a linear or branched alkyl group having 8 to 18 carbon atoms, and p and q are preferably independently 0 to 25, and 0<p+q≦50.
また、エマルションの安定性を補う等の目的で、（Ｂ－１）成分及び（Ｂ－２）成分以外の第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を添加することは何ら問題ない。 In addition, for the purpose of supplementing the stability of the emulsion, cationic surfactants such as quaternary ammonium salts, alkylamine acetates, alkyl betaines, alkyl There is no problem in adding an amphoteric surfactant such as imidazoline.
［（Ｃ）成分］
本発明のエマルション組成物は、（Ｃ）成分として水を、（Ａ）成分１００質量部に対して３０～３，０００質量部、好ましくは４０～２，４００質量部配合する。水が少なすぎると油中水型エマルションとならず、多すぎると不経済である。
[(C) Component]
The emulsion composition of the present invention contains 30 to 3,000 parts by weight, preferably 40 to 2,400 parts by weight of water as component (C) per 100 parts by weight of component (A). If the water content is too small, a water-in-oil emulsion will not be obtained, and if the water content is too large, it will be uneconomical.
［エマルション組成物の製造方法］
次に、本発明のエマルション組成物の製造方法は、以下の通りである。すなわち、
（Ｄ）一般式：ＨＯ－［Ｒ１
２ＳｉＯ］ｊ－Ｈで表される両末端ヒドロキシポリジオルガノシロキサン（ここで、Ｒ１は、互いに独立に、水素原子、又は、炭素数１～２０の１価有機基であり、ｊは該両末端ヒドロキシポリジオルガノシロキサンの２５℃における粘度が２，０００ｍＰａ・ｓ未満を満たす値である。）： １００質量部、
（Ｅ）下記に示されるいずれか１つ又は２つ以上のオルガノアルコキシシラン：０～２０質量部
Ｓｉ（ＯＲ３）４、Ｒ１Ｓｉ（ＯＲ３）３、Ｒ１
２Ｓｉ（ＯＲ３）２、Ｒ１
３Ｓｉ（ＯＲ３）
（ここで、Ｒ１は互いに独立に、水素原子、又は、炭素数１～２０の１価有機基であり、Ｒ３は互いに独立に、水素原子、又は、炭素数１～２０の１価有機基である。）、
（Ｂ－１）カチオン系界面活性剤：Ｑ１
３（ＣＨ３）Ｎ＋・Ｘ－： ０．１～３０質量部、
（ここで、Ｑ１は同一又は異種の炭素数６～３０の１価有機基、Ｘはハロゲン原子又は炭素数１～６の１価カルボキシル基である。）
（Ｂ－２）カチオン系界面活性剤：Ｑ２（ＣＨ３）３Ｎ＋・Ｘ－： ０．１～３０質量部、
（ここで、Ｑ２は炭素数１７～３０の１価有機基、Ｘはハロゲン原子又は炭素数１～６の１価カルボキシル基である。）
（Ｃ）水： ３０～３，０００質量部
を乳化分散させて得られるエマルションを、アルカリ触媒存在下、０～３０℃で１～１５０時間重合を行い、更に中和を行うものである。
[Method for producing emulsion composition]
Next, the method for producing the emulsion composition of the present invention is as follows. That is,
(D) A double-terminated hydroxypolydiorganosiloxane represented by the general formula: HO-[R 1 2 SiO] j -H (where R 1 is independently a hydrogen atom or a carbon number of 1 to 20 is a monovalent organic group, and j is a value that satisfies the viscosity of the both-terminated hydroxypolydiorganosiloxane at 25°C of less than 2,000 mPa s): 100 parts by mass,
(E) Any one or more organoalkoxysilanes shown below: 0 to 20 parts by mass Si(OR 3 ) 4 , R 1 Si(OR 3 ) 3 , R 1 2 Si(OR 3 ) 2 , R 1 3 Si (OR 3 )
(Here, R 1 is independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and R 3 is independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ),
(B-1) Cationic surfactant: Q 1 3 (CH 3 )N + ·X − : 0.1 to 30 parts by mass,
(Here, Q 1 is the same or different monovalent organic group having 6 to 30 carbon atoms, and X is a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms.)
(B-2) Cationic surfactant: Q 2 (CH 3 ) 3 N + ·X − : 0.1 to 30 parts by mass,
(Here, Q 2 is a monovalent organic group having 17 to 30 carbon atoms, and X is a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms.)
(C) Water: An emulsion obtained by emulsifying and dispersing 30 to 3,000 parts by mass is polymerized in the presence of an alkali catalyst at 0 to 30°C for 1 to 150 hours, and further neutralized.
［（Ｄ）成分］
まず、（Ｄ）成分である一般式：ＨＯ－［Ｒ１
２ＳｉＯ］ｊ－Ｈで表される両末端ヒドロキシポリジオルガノシロキサン（ここで、Ｒ１は、互いに独立に、水素原子、又は、炭素数１～２０の１価有機基であり、ｊは該両末端ヒドロキシポリジオルガノシロキサンの２５℃における粘度が２，０００ｍＰａ・ｓ未満を満たす値である。）は、（Ａ）成分であるポリオルガノシロキサンの原料となるものである。
[(D) Component]
First, component (D) is a double-terminated hydroxypolydiorganosiloxane represented by the general formula: HO-[R 1 2 SiO] j -H (where R 1 is independently a hydrogen atom or a carbon is a monovalent organic group having a number of 1 to 20, and j is a value that satisfies the viscosity of the both-terminated hydroxypolydiorganosiloxane at 25°C of less than 2,000 mPa·s. It is a raw material for siloxane.
上記一般式中のｊは、典型的には１～４００という値を取り得る。 j in the above general formula can typically take a value of 1 to 400.
（Ｄ）成分の具体例としては、下記平均組成式が挙げられるが、これらに限定されるものではない。下記平均組成式中のｊ、ｋ＋ｌ、ｋ＋ｌ＋ｍは両末端ヒドロキシポリジオルガノシロキサンの２５℃における粘度が２，０００ｍＰａ・ｓ未満を満たす値である。また、下記一般式中のｊ、ｋ＋ｌ、ｋ＋ｌ＋ｍは、典型的には１～４００という値を取り得る。 Specific examples of component (D) include, but are not limited to, the following average composition formula. In the average compositional formula below, j, k+l, and k+l+m are values that satisfy the viscosity of the both-terminated hydroxypolydiorganosiloxane at 25°C of less than 2,000 mPa·s. Furthermore, j, k+l, and k+l+m in the following general formula can typically take values of 1 to 400.
［（Ｅ）成分］
（Ｅ）成分であるオルガノアルコキシシランは、（Ａ）成分となるポリオルガノシロキサンの原料となるものであり、下記一般式のいずれか１つ又は２つ以上のオルガノアルコキシシランである。
Ｓｉ（ＯＲ３）４、Ｒ１Ｓｉ（ＯＲ３）３、Ｒ１
２Ｓｉ（ＯＲ３）２、Ｒ１
３Ｓｉ（ＯＲ３）
ここで、Ｒ１は互いに独立に、水素原子、又は、炭素数１～２０の１価有機基である。炭素数１～２０の１価有機基としてはメチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ドデシル、テトラデシル、ヘキサデシル、オクタデシル、シクロペンチル、シクロヘキシル、シクロヘプチルなどのアルキル基、フェニル、トリル、ナフチルなどのアリール基、ビニル、アリルなどのアルケニル基、或いはこれらの有機基構造中の水素原子の一部をハロゲン原子や、アミノ、アクリロキシ、メタクリロキシ、エポキシ、メルカプト等の極性基含有の有機基で置換したものなどが挙げられる。ここで、Ｒ１の８０％以上はメチル基であることが工業的及び特性的に望ましい。また、Ｒ３は互いに独立に、水素原子、又は、炭素数１～２０の１価有機基である。Ｒ３の炭素数１～２０の１価有機基としては上記Ｒ１と同じであり、メチル基、エチル基、プロピル基、ブチル基が好ましく、メチル基、エチル基がさらに好ましい。
[(E) component]
The organoalkoxysilane which is the component (E) is a raw material for the polyorganosiloxane which is the component (A), and is an organoalkoxysilane having one or more of the following general formula.
Si ( OR3 ) 4 , R1Si ( OR3 ) 3 , R12Si ( OR3 ) 2 , R13Si( OR3 )
Here, R 1 is independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. Examples of monovalent organic groups having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, and cycloheptyl. , phenyl, tolyl, naphthyl, and other aryl groups; vinyl, allyl, and other alkenyl groups; Examples include those substituted with organic groups contained therein. Here, it is desirable industrially and characteristically that 80% or more of R 1 is a methyl group. Furthermore, R 3 is independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The monovalent organic group having 1 to 20 carbon atoms in R 3 is the same as R 1 above, and is preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and more preferably a methyl group or an ethyl group.
（Ｅ）成分の使用量としては、（Ｄ）成分である両末端ヒドロキシポリジオルガノシロキサン１００質量部に対し、０～２０質量部であり、好ましくは０～１５質量部である。（Ｅ）成分の配合量が多すぎると被膜化した際に脆くなってしまい耐久性が低下する場合がある。 The amount of component (E) used is 0 to 20 parts by weight, preferably 0 to 15 parts by weight, based on 100 parts by weight of the both-terminated hydroxypolydiorganosiloxane that is component (D). If the amount of component (E) is too large, the coating may become brittle and have reduced durability.
（Ｅ）成分の具体例としては、メチルトリメトキシシラン、ジメチルジメトキシシラン、フェニルトリメトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、フェニルトリエトキシシラン、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、デシルトリメトキシシラン、トリフルオロプロピルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルトリエトキシシラン、ｐ－スチリルトリメトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－アクリロキシプロピルトリメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－トリエトキシシリル－Ｎ－（１，３－ジメチル－ブチリデン）プロピルアミン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、３－ウレイドプロピルトリエトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、３－メルカプトプロピルトリメトキシシラン、ビス（トリエトキシシリルプロピル）テトラスルフィド、３－イソシアネートプロピルトリエトキシシランなどが挙げられるが、これらに限定されるものではない。 Specific examples of component (E) include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyl Trimethoxysilane, trifluoropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycid Xypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2 -(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatepropyl Examples include, but are not limited to, triethoxysilane.
［（Ｂ－１）成分、（Ｂ－２）成分、（Ｃ）成分］
本発明のエマルション組成物の製造方法で用いる（Ｂ－１）成分、（Ｂ－２）成分、（Ｃ）成分については上記と同様である。
[(B-1) component, (B-2) component, (C) component]
The components (B-1), (B-2), and (C) used in the method for producing an emulsion composition of the present invention are the same as described above.
これらの（Ｄ）成分である両末端ヒドロキシポリジオルガノシロキサン、（Ｅ）成分であるオルガノアルコキシシラン、上述した（Ｂ－１）成分及び（Ｂ－２）成分であるカチオン系界面活性剤及び（Ｃ）成分である水をホモミキサー、ホモジナイザー、コロイドミル、ホモディスパー、ラインミキサーのような乳化機を用いて均一なエマルションにした後、アルカリ触媒を添加し、０～３０℃で１～１５０時間重合を行う。 These (D) component, both terminal hydroxy polydiorganosiloxane, (E) component, organoalkoxysilane, the above-mentioned (B-1) component and (B-2) component, the cationic surfactant, and (C ) component water is made into a homogeneous emulsion using an emulsifier such as a homomixer, homogenizer, colloid mill, homodisper, or line mixer, then an alkali catalyst is added and polymerized at 0 to 30°C for 1 to 150 hours. I do.
ここで、アルカリ触媒としては、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、フッ化カリウム、アンモニア、テトラメチルアンモニウムハイドロキサイド、テトラエチルアンモニウムハイドロキサイド、テトラプロピルアンモニウムハイドロキサイド、テトラブチルアンモニウムハイドロキサイド、ベンジルトリメチルアンモニウムハイドロキサイド、テトラブチルホスホニウムハイドロキサイド、トリフロロメチルフェニルトリメチルアンモニウムハイドロキサイドなどが挙げられる。中でも、水酸化ナトリウム、水酸化カリウム、アンモニア、テトラメチルアンモニウムハイドロキサイド、テトラブチルアンモニウムハイドロキサイド、ベンジルトリメチルアンモニウムハイドロキサイド、テトラブチルホスホニウムハイドロキサイドが好ましい。 Here, the alkali catalysts include sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium fluoride, ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. oxide, benzyltrimethylammonium hydroxide, tetrabutylphosphonium hydroxide, trifluoromethylphenyltrimethylammonium hydroxide, and the like. Among these, sodium hydroxide, potassium hydroxide, ammonia, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, and tetrabutylphosphonium hydroxide are preferred.
アルカリ触媒の使用量としては、（Ｄ）成分である両末端ヒドロキシオルガノシロキサン１００質量部に対し、０．０１～５質量部であることが好ましく、０．０３～５質量部であることがさらに好ましい。 The amount of the alkali catalyst to be used is preferably 0.01 to 5 parts by mass, more preferably 0.03 to 5 parts by mass, per 100 parts by mass of the both-terminated hydroxyorganosiloxane as component (D). preferable.
なお、（Ｂ－１）及び（Ｂ－２）成分であるカチオン系界面活性剤を、イオン交換樹脂を用いて４級アンモニウムハイドロキサイドとすれば、このもの自身がアルカリ触媒成分として作用するのでアルカリ触媒を別途添加する必要はない。このように、（Ｂ－１）成分又は（Ｂ－２）成分自体をアルカリ触媒成分として作用させる場合も、本発明のエマルション組成物の製造方法における、上記（Ｄ）、（Ｅ）、（Ｂ－１）、（Ｂ－２）及び（Ｃ）成分を乳化分散させて得られるエマルションを、アルカリ触媒存在下で重合を行うことに該当する。 Note that if the cationic surfactants (B-1) and (B-2) are converted into quaternary ammonium hydroxide using an ion exchange resin, this itself acts as an alkali catalyst component. There is no need to separately add an alkaline catalyst. In this way, even when component (B-1) or component (B-2) itself acts as an alkali catalyst component, the above (D), (E), and (B This corresponds to polymerizing an emulsion obtained by emulsifying and dispersing components -1), (B-2), and (C) in the presence of an alkali catalyst.
また、重合温度は０～３０℃である。０℃より低い場合には重合の進行が遅く実用的でなく、３０℃より高い場合にはエマルションの安定性が不安定なものとなる。好ましくは５～２５℃である。また、重合時間は１～１５０時間である。１時間未満の場合には重合が不十分であり、１５０時間より長くなると工業的ではなくなる。この重合時間は、好ましくは５～１２０時間である。 Further, the polymerization temperature is 0 to 30°C. If it is lower than 0°C, polymerization progresses slowly and is not practical, and if it is higher than 30°C, the stability of the emulsion becomes unstable. Preferably it is 5 to 25°C. Further, the polymerization time is 1 to 150 hours. When the time is less than 1 hour, the polymerization is insufficient, and when it is longer than 150 hours, it is not industrially practical. This polymerization time is preferably 5 to 120 hours.
所定の重合時間後、中和することにより、重合反応を停止することができる。ここでの中和は酸性化合物で行うことができる。酸性化合物としては、塩酸、ギ酸、酢酸、プロピオン酸などが挙げられ、好ましくは、塩酸、ギ酸、酢酸である。なお、酸性化合物を使用する代わりにイオン交換樹脂を利用して中和することも可能である。 After a predetermined polymerization time, the polymerization reaction can be stopped by neutralization. Neutralization here can be performed with an acidic compound. Examples of the acidic compound include hydrochloric acid, formic acid, acetic acid, propionic acid, etc., and preferably hydrochloric acid, formic acid, and acetic acid. Note that it is also possible to neutralize using an ion exchange resin instead of using an acidic compound.
以上の方法により得られる本発明の高重合度オルガノシロキサンのカチオン系エマルション組成物は、繊維処理剤、離型剤、撥水剤、化粧品原料等として好適に用いられ、各種繊維、皮革、紙、毛髪等に処理することで優れた柔軟性、滑り性、撥水性、ボリューム感等を付与することができる。なお、繊維としては、綿、麻、絹、羊毛のような天然繊維、ポリエステル、ポリアミド、ポリアクリロニトリル、ポリエチレン、ポリプロピレン、ビニロン、ポリ塩化ビニル、スパンデックス等の合成繊維、アセテート等の半合成繊維などが挙げられるが、これらに限定されるものではない。 The cationic emulsion composition of highly polymerized organosiloxane of the present invention obtained by the above method is suitably used as a fiber treatment agent, a mold release agent, a water repellent, a raw material for cosmetics, etc., and can be used for various fibers, leather, paper, etc. By treating hair etc., it can impart excellent flexibility, slipperiness, water repellency, volume, etc. Fibers include natural fibers such as cotton, linen, silk, and wool, synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyethylene, polypropylene, vinylon, polyvinyl chloride, and spandex, and semi-synthetic fibers such as acetate. These include, but are not limited to.
本発明の高重合度オルガノシロキサンのカチオン系エマルション組成物には、各種の増粘剤、顔料、染料、浸透剤、帯電防止剤、消泡剤、難燃剤、抗菌剤、防腐剤、撥水剤、架橋剤、密着向上剤や、他のシリコーンオイル、シリコーン樹脂、シリカ、アクリル樹脂、ウレタン樹脂等を適宜配合することができる。 The cationic emulsion composition of highly polymerized organosiloxane of the present invention includes various thickeners, pigments, dyes, penetrants, antistatic agents, antifoaming agents, flame retardants, antibacterial agents, preservatives, and water repellents. , a crosslinking agent, an adhesion improver, and other silicone oils, silicone resins, silica, acrylic resins, urethane resins, etc. can be appropriately blended.
本発明の高重合度オルガノシロキサンのカチオン系エマルション組成物は、乾燥後に被膜を形成することが可能であり、繊維、紙、金属、木材、ゴム、プラスチック、ガラス等各種基材表面に処理して使用することができる。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、バーコート法、はけ塗り法等、従来公知の各種塗装法が可能である。 The cationic emulsion composition of highly polymerized organosiloxane of the present invention can form a film after drying, and can be applied to the surface of various substrates such as fiber, paper, metal, wood, rubber, plastic, and glass. can be used. Various conventionally known coating methods such as dipping, spraying, roll coating, bar coating, and brushing can be used to apply the coating onto the substrate.
以下、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、「％」は「質量％」を示す。 EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples below. In addition, in the following examples, "%" indicates "mass %".
［実施例１］
一般式：ＨＯ－［（ＣＨ３）２ＳｉＯ］ｎ－Ｈで示される両末端ヒドロキシポリジメチルシロキサン（（Ｄ）成分） ３００ｇ（ここで、ｎは約３１０であり、２５℃における粘度が１，５００ｍＰａ・ｓである）、トリエトキシフェニルシラン（（Ｅ）成分） ４．３ｇ、トリオクチルメチルアンモニウムクロライド（（Ｂ－１）成分）の有効成分７５％のＩＰＡ（イソプロピルアルコール）溶液（ＴＯＭＡＣ－７５：ライオン・スペシャリティ・ケミカルズ社製）２４．０ｇ、ベヘニルトリメチルアンモニウムクロライド（（Ｂ－２）成分）の有効成分８０％のエタノール品（リポカード２２－８０：ライオン・スペシャリティ・ケミカルズ社製）１８．０ｇ、イオン交換水（（Ｃ）成分）２３９．３ｇをホモミキサー、ディスパーを用いて均一に乳化分散することによりエマルションを得た。このエマルションに３０％アンモニア水溶液６．６ｇを添加した（アルカリ触媒）。その後、液温度を１５℃に下げ、２４時間重合を行い、酢酸７．８ｇで中和することでエマルションＡを得た。
[Example 1]
General formula: HO-[(CH 3 ) 2 SiO] n -H Both-terminated hydroxypolydimethylsiloxane (component (D)) 300 g (where n is approximately 310 and the viscosity at 25°C is 1, 500 mPa・s), 4.3 g of triethoxyphenylsilane (component (E)), and a 75% IPA (isopropyl alcohol) solution of the active ingredient of trioctylmethylammonium chloride (component (B-1)) (TOMAC-75). : manufactured by Lion Specialty Chemicals) 24.0 g, ethanol product containing 80% of the active ingredient of behenyltrimethylammonium chloride (component (B-2)) (Lipo Card 22-80: manufactured by Lion Specialty Chemicals) 18. An emulsion was obtained by uniformly emulsifying and dispersing 239.3 g of ion-exchanged water (component (C)) using a homomixer and a disper. 6.6 g of 30% ammonia aqueous solution was added to this emulsion (alkaline catalyst). Thereafter, the liquid temperature was lowered to 15° C., polymerization was carried out for 24 hours, and emulsion A was obtained by neutralizing with 7.8 g of acetic acid.
［実施例２］
実施例１のイオン交換水を２１５．３ｇに代えて、更にノニオン系乳化剤として、ポリオキシエチレンアルキルエーテルであるエマルゲン１０９Ｐ（花王社製）２４．０ｇを追加した以外は実施例１と同様にしてエマルションＢを得た。
[Example 2]
The same procedure as in Example 1 was carried out except that 215.3 g of the ion-exchanged water in Example 1 was replaced and 24.0 g of Emulgen 109P (manufactured by Kao Corporation), which is a polyoxyethylene alkyl ether, was added as a nonionic emulsifier. Emulsion B was obtained.
［実施例３］
実施例２のトリオクチルメチルアンモニウムクロライドの有効成分７５％のＩＰＡ溶液（ＴＯＭＡＣ－７５：ライオン・スペシャリティ・ケミカルズ社製）を３．０ｇに、イオン交換水を２３６．３ｇに代えた以外は実施例２と同様にしてエマルションＣを得た。
[Example 3]
Example except that the IPA solution containing 75% of the active ingredient of trioctylmethylammonium chloride in Example 2 (TOMAC-75: manufactured by Lion Specialty Chemicals) was replaced with 3.0 g, and the ion exchange water was replaced with 236.3 g. Emulsion C was obtained in the same manner as in 2.
［実施例４］
実施例２のトリオクチルメチルアンモニウムクロライドの有効成分７５％のＩＰＡ溶液（ＴＯＭＡＣ－７５：ライオン・スペシャリティ・ケミカルズ社製）を１２．０ｇに、イオン交換水を２２７．３ｇに代えた以外は実施例２と同様にしてエマルションＤを得た。
[Example 4]
Example except that the IPA solution containing 75% of the active ingredient of trioctylmethylammonium chloride in Example 2 (TOMAC-75: manufactured by Lion Specialty Chemicals) was replaced with 12.0 g and the ion exchange water was replaced with 227.3 g. Emulsion D was obtained in the same manner as in 2.
［実施例５］
実施例４における重合条件を１５℃で４８時間として重合した以外は、実施例４と同様にしてエマルションＥを得た。
[Example 5]
Emulsion E was obtained in the same manner as in Example 4, except that the polymerization conditions in Example 4 were changed to 15° C. for 48 hours.
［実施例６］
実施例４のイオン交換水を２３１．６ｇに変更し、３０％アンモニア水溶液の代わりに８５％のＫＯＨを２．３ｇを添加した以外は実施例４と同様にしてエマルションＦを得た。
[Example 6]
Emulsion F was obtained in the same manner as in Example 4, except that the ion-exchanged water in Example 4 was changed to 231.6 g, and 2.3 g of 85% KOH was added instead of the 30% ammonia aqueous solution.
［比較例１］
実施例１のトリエトキシフェニルシランを１．１ｇに、イオン交換水を２５８．７ｇに代えて、更にトリオクチルメチルアンモニウムクロライドの有効成分７５％のＩＰＡ溶液（ＴＯＭＡＣ－７５：ライオン・スペシャリティ・ケミカルズ社製）、及び、ベヘニルトリメチルアンモニウムクロライドの有効成分８０％のエタノール品（リポカード２２－８０：ライオン・スペシャリティ・ケミカルズ社製）をセチルトリメチルアンモニウムクロライドの有効成分３０％の水溶液（コータミン６０Ｗ：花王社製）２５．８ｇに代えた以外は実施例１と同様にしてエマルションＧを得た。
[Comparative example 1]
In Example 1, 1.1 g of triethoxyphenylsilane and 258.7 g of ion-exchanged water were used, and an IPA solution containing 75% of the active ingredient of trioctylmethylammonium chloride (TOMAC-75: Lion Specialty Chemicals) was added. ), and an ethanol product containing 80% of the active ingredient of behenyltrimethylammonium chloride (Lipocard 22-80: manufactured by Lion Specialty Chemicals) and an aqueous solution of 30% of the active ingredient of cetyltrimethylammonium chloride (Cortamine 60W: manufactured by Kao Corporation). Emulsion G was obtained in the same manner as in Example 1, except that 25.8 g of the emulsion was used (manufactured by Manufacturer Co., Ltd.).
［比較例２］
比較例１における重合条件を１５℃で９６時間として重合した以外は、比較例１と同様にしてエマルションＨを得た。
[Comparative example 2]
Emulsion H was obtained in the same manner as in Comparative Example 1, except that the polymerization conditions in Comparative Example 1 were changed to 15° C. for 96 hours.
［比較例３］
比較例１のトリエトキシフェニルシランを４．３ｇに、イオン交換水を２５５．５ｇに代えた以外は比較例１と同様にしてエマルションＩを得た。
[Comparative example 3]
Emulsion I was obtained in the same manner as in Comparative Example 1 except that 4.3 g of triethoxyphenylsilane and 255.5 g of ion-exchanged water were used in Comparative Example 1.
［比較例４］
比較例３のセチルトリメチルアンモニウムクロライドの有効成分３０％の水溶液（コータミン６０Ｗ：花王社製）をトリオクチルメチルアンモニウムクロライドの有効成分７５％のＩＰＡ溶液（ＴＯＭＡＣ－７５：ライオン・スペシャリティ・ケミカルズ社製）２４．０ｇに、イオン交換水を２５７．３ｇに代えた以外は比較例３と同様にしてエマルションＪを得た。
[Comparative example 4]
An aqueous solution containing 30% of the active ingredient of cetyltrimethylammonium chloride in Comparative Example 3 (Cortamine 60W: manufactured by Kao Corporation) was mixed with an IPA solution of 75% of the active ingredient of trioctylmethylammonium chloride (TOMAC-75: manufactured by Lion Specialty Chemicals). Emulsion J was obtained in the same manner as in Comparative Example 3 except that 24.0 g of ion-exchanged water was used and 257.3 g of ion-exchanged water was used.
［比較例５］
比較例４にセチルトリメチルアンモニウムクロライドの有効成分３０％の水溶液（コータミン６０Ｗ：花王社製）２５．８ｇを追加し、イオン交換水を２３１．５ｇに代えた以外は比較例４と同様にして製造したが、本組成ではエマルションＫを製造することはできなかったため物性、特性評価は行わなかった。
[Comparative example 5]
Manufactured in the same manner as Comparative Example 4, except that 25.8 g of an aqueous solution of 30% of the active ingredient of cetyltrimethylammonium chloride (Cortamine 60W: manufactured by Kao Corporation) was added to Comparative Example 4, and ion exchange water was replaced with 231.5 g. However, since it was not possible to produce Emulsion K with this composition, physical properties and characteristics were not evaluated.
［比較例６］
２５℃における粘度が８００，０００ｍＰａ・ｓの直鎖ジメチルシリコーンを３００ｇ、セチルトリメチルアンモニウムクロライドの有効成分３０％の水溶液（コータミン６０Ｗ：花王社製）２１．６ｇ、イオン交換水２３５．２ｇをホモミキサー、ディスパーを用いて均一に乳化分散することによりエマルションＬを得た。
[Comparative example 6]
300 g of linear dimethyl silicone with a viscosity of 800,000 mPa・s at 25°C, 21.6 g of a 30% aqueous solution of cetyltrimethylammonium chloride as an active ingredient (Cortamine 60W, manufactured by Kao Corporation), and 235.2 g of ion-exchanged water were mixed into a homomixer. Emulsion L was obtained by uniformly emulsifying and dispersing the mixture using a disperser.
上記実施例１～６、比較例１～６で得られたエマルションの物性、特性を下記評価方法により測定し、結果を表１、２に示した。 The physical properties and characteristics of the emulsions obtained in Examples 1 to 6 and Comparative Examples 1 to 6 were measured by the following evaluation method, and the results are shown in Tables 1 and 2.
（抽出したシリコーンの粘度）
エマルションＡ～Ｌ ３００ｇを２ＬのＩＰＡ中に撹拌しながら添加することでエマルションを破壊させてポリジオルガノシロキサンを抽出し、このポリジオルガノシロキサンを１０５℃で３時間乾燥した後、２５℃においてＢＨ型回転粘度計で粘度を測定した。なお、この粘度は液状で測定できるものはそのまま、粘度が高すぎて測定できないものは１０％トルエン溶解粘度を測定した。粘度が高すぎて液状で測定できないものの粘度は全て３００，０００ｍＰａ・ｓ以上である。
(Viscosity of extracted silicone)
Add 300 g of emulsions A to L to 2 L of IPA with stirring to break the emulsion and extract the polydiorganosiloxane. After drying this polydiorganosiloxane at 105°C for 3 hours, rotate it in a BH type at 25°C. The viscosity was measured using a viscometer. Note that the viscosity was measured as it is for those that could be measured in liquid form, and for those whose viscosity was too high to be measured, the viscosity dissolved in 10% toluene was measured. Although the viscosity is too high to be measured in liquid form, all the viscosity is 300,000 mPa·s or more.
（被膜形成の有無）
エマルションＡ～Ｌ ２０ｇをＰＰ（ポリプロピレン）トレーに分取し、２５℃で４８時間乾燥させた後、更に１０５℃で１時間乾燥させ、被膜が形成するか評価した。
○：被膜形成
×：被膜形成なし（液状のまま）
(Presence or absence of film formation)
20 g of emulsions A to L were placed on a PP (polypropylene) tray, dried at 25° C. for 48 hours, and then further dried at 105° C. for 1 hour to evaluate whether a film was formed.
○: Film formation ×: No film formation (remains liquid)
（保存安定性）
２５℃で１ヶ月静置した後の外観を目視にて評価した。
○：分離なし
△：僅かに分離
×：完全に分離
(Storage stability)
The appearance after being allowed to stand at 25° C. for one month was visually evaluated.
○: No separation △: Slight separation ×: Complete separation
（処理布の風合い）
エマルションＡ～Ｌを、ポリオルガノシロキサン濃度が１％となるようにイオン交換水で希釈し処理液を作製した。処理液にＴ／Ｃブロード布を１０秒間浸漬させた後に絞り率１００％の条件でロールを用いて絞り、１５０℃で２分間乾燥した。その後、処理布を手触評価し、未処理布と柔軟性及び平滑性を比較した。）
○：良好
×：未処理布レベル
(Texture of treated cloth)
Emulsions A to L were diluted with ion-exchanged water to give a polyorganosiloxane concentration of 1% to prepare treatment solutions. A T/C broad cloth was immersed in the treatment liquid for 10 seconds, then squeezed using a roll at a squeezing rate of 100%, and dried at 150° C. for 2 minutes. Thereafter, the treated fabric was evaluated to the touch and compared with the untreated fabric in terms of flexibility and smoothness. )
○: Good ×: Untreated cloth level
（処理布の洗濯耐久性）
エマルションＡ～Ｌを、ポリオルガノシロキサン濃度が１％となるようにイオン交換水で希釈し処理液を作製した。処理液にＴ／Ｃブロード布を１０秒間浸漬させた後に絞り率１００％の条件でロールを用いて絞り、１５０℃で２分間乾燥した。その後、処理布を半分に裁断し、片方の処理布をＪＩＳ ＬＯ２１７ １０３に準拠した手法により、洗濯機による洗濯を１回実施した後に室温で１日間乾燥した。洗濯前後の処理布の繊維表面のシリコーン残存量を蛍光Ｘ線分析装置（Ｒｉｇａｋｕ社製）にて測定し、洗濯後の残存率（％）を算出した。
(Washing durability of treated fabric)
Emulsions A to L were diluted with ion-exchanged water to give a polyorganosiloxane concentration of 1% to prepare treatment solutions. A T/C broad cloth was immersed in the treatment liquid for 10 seconds, then squeezed using a roll at a squeezing rate of 100%, and dried at 150° C. for 2 minutes. Thereafter, the treated fabric was cut in half, and one of the treated fabrics was washed once in a washing machine in accordance with JIS LO217 103, and then dried at room temperature for one day. The amount of silicone remaining on the fiber surface of the treated cloth before and after washing was measured using a fluorescent X-ray analyzer (manufactured by Rigaku), and the residual rate (%) after washing was calculated.
表１、２に示される通り、本発明の高重合度ポリオルガノシロキサンのカチオン系エマルション組成物は高粘度でも比較的短時間で重合できるとともに、被膜形成能を有していることから繊維に処理した際の耐久性に優れており、また、処理布の風合も良好である。更に、本発明の高重合度ポリオルガノシロキサンのカチオン系エマルション組成物は保存安定性にも優れている。これに対して比較例の組成により得られたカチオン系エマルション組成物は、安定性は高いものの、被膜形成能がないものや、また繊維処理した際の耐久性が劣っていたり、被膜形成能はあるものの、エマルションの安定性が低くすぐに分離してしまう。 As shown in Tables 1 and 2, the cationic emulsion composition of the highly polymerized polyorganosiloxane of the present invention can be polymerized in a relatively short time even at high viscosity, and has the ability to form a film, so it can be processed into fibers. It has excellent durability when applied, and the texture of the treated fabric is also good. Furthermore, the cationic emulsion composition of the highly polymerized polyorganosiloxane of the present invention also has excellent storage stability. On the other hand, the cationic emulsion compositions obtained with the compositions of comparative examples have high stability, but some do not have film-forming ability, have poor durability when treated with fibers, and have poor film-forming ability. However, the stability of the emulsion is low and it separates quickly.
本発明の高重合度ポリオルガノシロキサンのカチオン系エマルション組成物を繊維処理剤として用いることで、繊維に対して良好な柔軟性を付与することができ、耐久性にも優れていることから、洗濯処理後も良好な柔軟性を維持することが可能である。さらに、本発明の高重合度ポリオルガノシロキサンのカチオン系エマルション組成物を処理し乾燥させた際に形成する被膜は耐久性が高いことから、汎用性にも優れており、繊維処理剤以外にも、離型剤や撥水剤、化粧料、毛髪用化粧料等に広く応用が可能である。 By using the cationic emulsion composition of the highly polymerized polyorganosiloxane of the present invention as a fiber treatment agent, it is possible to impart good flexibility to the fibers and has excellent durability. It is possible to maintain good flexibility even after processing. Furthermore, the film formed when the cationic emulsion composition of the highly polymerized polyorganosiloxane of the present invention is treated and dried is highly durable, and therefore has excellent versatility and can be used as a non-fiber treatment agent. It can be widely applied to mold release agents, water repellents, cosmetics, hair cosmetics, etc.
Claims (11)
（Ｂ－１）カチオン系界面活性剤：Ｑ１ ３（ＣＨ３）Ｎ＋・Ｘ－： ０．１～３０質量部、
（ここで、Ｑ１は、同一又は異種の炭素数６～３０の１価有機基、Ｘはハロゲン原子又は炭素数１～６の１価カルボキシル基である。）
（Ｂ－２）カチオン系界面活性剤：Ｑ２（ＣＨ３）３Ｎ＋・Ｘ－： ０．１～３０質量部、
（ここで、Ｑ２は、炭素数１７～３０の１価有機基、Ｘはハロゲン原子又は炭素数１～６の１価カルボキシル基である。）
（Ｃ）水： ３０～３，０００質量部
を含有してなることを特徴とするポリオルガノシロキサンのカチオン系エマルション組成物。 (A) 100 parts by mass of polyorganosiloxane represented by the following average composition formula (1) and having a viscosity of 300,000 mPa·s or more at 25°C,
(B-1) Cationic surfactant: Q 1 3 (CH 3 )N + ·X − : 0.1 to 30 parts by mass,
(Here, Q 1 is the same or different monovalent organic group having 6 to 30 carbon atoms, and X is a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms.)
(B-2) Cationic surfactant: Q 2 (CH 3 ) 3 N + ·X − : 0.1 to 30 parts by mass,
(Here, Q 2 is a monovalent organic group having 17 to 30 carbon atoms, and X is a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms.)
(C) Water: A cationic emulsion composition of polyorganosiloxane, characterized in that it contains 30 to 3,000 parts by mass.
（Ｅ）下記に示されるいずれか１つ又は２つ以上のオルガノアルコキシシラン：０～２０質量部
Ｓｉ（ＯＲ３）４、Ｒ１Ｓｉ（ＯＲ３）３、Ｒ１ ２Ｓｉ（ＯＲ３）２、Ｒ１ ３Ｓｉ（ＯＲ３）
（ここで、Ｒ１は互いに独立に、水素原子、又は、炭素数１～２０の１価有機基であり、Ｒ３は互いに独立に、水素原子、又は、炭素数１～２０の１価有機基である。）、
（Ｂ－１）カチオン系界面活性剤：Ｑ１ ３（ＣＨ３）Ｎ＋・Ｘ－： ０．１～３０質量部、
（ここで、Ｑ１は同一又は異種の炭素数６～３０の１価有機基、Ｘはハロゲン原子又は炭素数１～６の１価カルボキシル基である。）
（Ｂ－２）カチオン系界面活性剤：Ｑ２（ＣＨ３）３Ｎ＋・Ｘ－： ０．１～３０質量部、
（ここで、Ｑ２は炭素数１７～３０の１価有機基、Ｘはハロゲン原子又は炭素数１～６の１価カルボキシル基である。）
（Ｃ）水： ３０～３，０００質量部
を乳化分散させて得られるエマルションを、アルカリ触媒存在下、０～３０℃で１～１５０時間重合を行い、更に中和を行うことを特徴とするポリオルガノシロキサンのカチオン系エマルション組成物の製造方法。 (D) A double-terminated hydroxypolydiorganosiloxane represented by the general formula: HO-[R 1 2 SiO] j -H (where R 1 is independently a hydrogen atom or a carbon number of 1 to 20 is a monovalent organic group, and j is a value that satisfies the viscosity of the both-terminated hydroxypolydiorganosiloxane at 25°C of less than 2,000 mPa s): 100 parts by mass,
(E) Any one or more organoalkoxysilanes shown below: 0 to 20 parts by mass Si(OR 3 ) 4 , R 1 Si(OR 3 ) 3 , R 1 2 Si(OR 3 ) 2 , R 1 3 Si (OR 3 )
(Here, R 1 is independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and R 3 is independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ),
(B-1) Cationic surfactant: Q 1 3 (CH 3 )N + ·X − : 0.1 to 30 parts by mass,
(Here, Q 1 is the same or different monovalent organic group having 6 to 30 carbon atoms, and X is a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms.)
(B-2) Cationic surfactant: Q 2 (CH 3 ) 3 N + ·X − : 0.1 to 30 parts by mass,
(Here, Q 2 is a monovalent organic group having 17 to 30 carbon atoms, and X is a halogen atom or a monovalent carboxyl group having 1 to 6 carbon atoms.)
(C) Water: An emulsion obtained by emulsifying and dispersing 30 to 3,000 parts by mass is polymerized at 0 to 30°C for 1 to 150 hours in the presence of an alkali catalyst, and is further neutralized. A method for producing a cationic emulsion composition of polyorganosiloxane.
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| JP2005089372A (en) | 2003-09-18 | 2005-04-07 | Lion Corp | Hair cosmetic |
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| JP3335842B2 (en) | 1995-08-07 | 2002-10-21 | ジーイー東芝シリコーン株式会社 | Method for producing silicone emulsion |
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| JP2001106787A (en) | 1999-10-05 | 2001-04-17 | Shin Etsu Chem Co Ltd | Method for producing organopolysiloxane emulsion |
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| JP2005179337A (en) | 2003-11-28 | 2005-07-07 | Kose Corp | Hair cosmetic |
| JP2006335792A (en) | 2005-05-31 | 2006-12-14 | Shin Etsu Chem Co Ltd | Cationic emulsion composition of high-polymerization degree organosiloxane and its manufacturing method |
| US20100178266A1 (en) | 2007-07-02 | 2010-07-15 | Momentive Performance Materials Gmbh | Process For The Manufacture Of Polyorganosiloxanes Comprising (C6-C60)-Alkylmethylsiloxy Groups And Dimethylsiloxy Groups |
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