JPH02208310A - Surface-modifying composition - Google Patents
Surface-modifying compositionInfo
- Publication number
- JPH02208310A JPH02208310A JP2750489A JP2750489A JPH02208310A JP H02208310 A JPH02208310 A JP H02208310A JP 2750489 A JP2750489 A JP 2750489A JP 2750489 A JP2750489 A JP 2750489A JP H02208310 A JPH02208310 A JP H02208310A
- Authority
- JP
- Japan
- Prior art keywords
- water
- weight
- parts
- aqueous dispersion
- polysiloxane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- -1 polysiloxane Polymers 0.000 claims abstract description 89
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 79
- 239000006185 dispersion Substances 0.000 claims abstract description 62
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- 150000007514 bases Chemical class 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 229910000077 silane Inorganic materials 0.000 claims abstract description 11
- 150000007524 organic acids Chemical class 0.000 claims abstract description 7
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- 238000012986 modification Methods 0.000 claims description 17
- 230000004048 modification Effects 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 39
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 14
- 239000011248 coating agent Substances 0.000 abstract description 13
- 238000000576 coating method Methods 0.000 abstract description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 abstract description 5
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 abstract description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 abstract description 3
- 239000012263 liquid product Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 21
- 238000006116 polymerization reaction Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 239000010408 film Substances 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 8
- 238000013508 migration Methods 0.000 description 8
- 230000005012 migration Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000007651 thermal printing Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- GJCZUCLKDGABDS-UHFFFAOYSA-N 1,4-dihydroxybutane-2,3-dione Chemical compound OCC(=O)C(=O)CO GJCZUCLKDGABDS-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229910019977 (NH4)2ZrO Inorganic materials 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- MJYFYGVCLHNRKB-UHFFFAOYSA-N 1,1,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)CF MJYFYGVCLHNRKB-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- JTINZFQXZLCHNS-UHFFFAOYSA-N 2,2-bis(oxiran-2-ylmethoxymethyl)butan-1-ol Chemical compound C1OC1COCC(CO)(CC)COCC1CO1 JTINZFQXZLCHNS-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- IDUWIXCWGYJVKL-UHFFFAOYSA-N 2-(aminomethyl)propane-1,3-diol Chemical compound NCC(CO)CO IDUWIXCWGYJVKL-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- KJJPLEZQSCZCKE-UHFFFAOYSA-N 2-aminopropane-1,3-diol Chemical compound OCC(N)CO KJJPLEZQSCZCKE-UHFFFAOYSA-N 0.000 description 1
- PGYJSURPYAAOMM-UHFFFAOYSA-N 2-ethenoxy-2-methylpropane Chemical compound CC(C)(C)OC=C PGYJSURPYAAOMM-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- XYOSFLPUWVWHOA-UHFFFAOYSA-N 2-ethylidenepropane-1,3-diol;urea Chemical compound NC(N)=O.CC=C(CO)CO XYOSFLPUWVWHOA-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920002085 Dialdehyde starch Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229920001744 Polyaldehyde Polymers 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- SUPOBRXPULIDDX-UHFFFAOYSA-N [[4-amino-6-(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound NC1=NC(NCO)=NC(NCO)=N1 SUPOBRXPULIDDX-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- NTMDBTSKNAXHGK-UHFFFAOYSA-N diethylaminomethanol Chemical compound CCN(CC)CO NTMDBTSKNAXHGK-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- XQKRYBXCYCKQLL-UHFFFAOYSA-N dimethylaminomethanol Chemical compound CN(C)CO XQKRYBXCYCKQLL-UHFFFAOYSA-N 0.000 description 1
- WVJOGYWFVNTSAU-UHFFFAOYSA-N dimethylol ethylene urea Chemical compound OCN1CCN(CO)C1=O WVJOGYWFVNTSAU-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 1
- 229950005308 oxymethurea Drugs 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
- SOUMBTQFYKZXPN-UHFFFAOYSA-N trimethoxy(4-phenylbut-3-enyl)silane Chemical compound CO[Si](OC)(OC)CCC=CC1=CC=CC=C1 SOUMBTQFYKZXPN-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、末端ヒドロキシル基含有ポリシロキサン存在
下に重合性シラン化合物を含む単量体混合物を重合させ
て得られるポリシロキサングラフトポリマーの塩基性化
合物による塩の水性分散体、または、該水性分散体と水
溶性樹脂とを含んでなる表面改質組成物に関するもので
あり、フィルム、繊維、鋼板等の基材表面に塗布して、
撥水性、滑り性、耐熱性、剥離性、耐マイグレーション
性等の表面特性を賦与する組成物を提供するものである
。Detailed Description of the Invention [Industrial Application Field] The present invention relates to the basicity of a polysiloxane graft polymer obtained by polymerizing a monomer mixture containing a polymerizable silane compound in the presence of a polysiloxane containing a terminal hydroxyl group. It relates to an aqueous dispersion of a salt of a compound, or a surface modification composition comprising the aqueous dispersion and a water-soluble resin, which is applied to the surface of a substrate such as a film, fiber, or steel plate, and
The present invention provides a composition that imparts surface properties such as water repellency, slipperiness, heat resistance, peelability, and migration resistance.
近年、磁気テープ、フロッピーディスク、感熱印刷材料
等の滑り性、耐熱性、耐摩耗性等の性能に対する要求が
、電子機器の発達に併ってますます高度化しており、こ
れらの要求に応える組成物の出現が求められている。滑
り性、耐熱性、耐摩耗性等に対する要゛求に応える為、
従来より種々の改良が行われている。これらの方法には
大別して、磁気テープや感熱印刷材料の基材として用い
られるフィルム本体の改質と、表面に改質物質を塗布し
て改質を図るふたつの方向がある。In recent years, along with the development of electronic equipment, the requirements for performance such as slip properties, heat resistance, and abrasion resistance for magnetic tapes, floppy disks, thermal printing materials, etc. have become increasingly sophisticated, and compositions that meet these requirements are being developed. The appearance of things is required. In order to meet the demands for slipperiness, heat resistance, abrasion resistance, etc.
Various improvements have been made in the past. These methods can be broadly divided into two types: modification of the main body of the film used as a base material for magnetic tapes and thermal printing materials, and modification by applying a modification substance to the surface.
前者の方法としては、ポリミイトやポリスルホン等の耐
熱性樹脂フィルムを基材に用いる方法（特開昭５９−１
５２８９４号）が開示されているが、高価であり、高機
能化に必要な薄膜フィルムの入手に困難さがある。The former method uses a heat-resistant resin film such as polymite or polysulfone as a base material (Japanese Patent Laid-Open No. 59-1
No. 52894) has been disclosed, but it is expensive and it is difficult to obtain the thin film necessary for high functionality.
また、基材として最も一般的に用いられているポリエス
テルフィルムでは、ポリエステル製造時に無機粒子を生
成させる方法（特公昭３４−５１４４号）あるいはシリ
カや炭酸カルシウム等の無機粒子を添加する方法（特公
昭４２−２４０９９号、特公昭４３−１２０１３号）等
により滑り性の良いフィルムを得る方法か開示されてい
るがこれらの方法は、発生粒子の粒径の制御が難しいこ
とや、滑り性を得るには多量の無機粒子の添加が必要で
フィルムの薄膜化、透明化に問題を有するものである。In addition, for polyester film, which is most commonly used as a base material, there is a method of generating inorganic particles during polyester production (Japanese Patent Publication No. 34-5144) or a method of adding inorganic particles such as silica or calcium carbonate (Japanese Patent Publication No. 34-5144). 42-24099, Japanese Patent Publication No. 43-12013), etc., disclose methods for obtaining a film with good slipping properties, but these methods are difficult to control the particle size of the generated particles, and it is difficult to obtain slipping properties. This method requires the addition of a large amount of inorganic particles and has problems in making the film thin and transparent.
さらに末端ヒドロキシル基含有ポリシロキサンをポリエ
ステル主鎖に導入する方法（特開昭５９−１６８０２７
号）も開示されているが、基材全体にポリシロキサンが
分布する為、多量必要となり、また、磁性膜あるいはイ
ンキ層の密着性にも問題を生ずるものである。Furthermore, a method of introducing a polysiloxane containing terminal hydroxyl groups into the polyester main chain (Japanese Patent Application Laid-Open No. 59-168027
No. 2) is also disclosed, but since the polysiloxane is distributed throughout the base material, a large amount is required, and it also causes problems in the adhesion of the magnetic film or ink layer.
後者の方法としては、基材表面にシリコーン樹脂、エポ
キシ樹脂、メラミン樹脂、フッ素樹脂等を塗布して表面
を改質する方法（米国特許４３１０６００号、特公昭５
９−３９３０８号、特開昭５５−７４６７号）が開示さ
れているが、滑り性や耐熱性等改善を目的とする性質と
樹脂被膜の基材への密着性が両立しない欠点があった。The latter method involves coating the surface of the substrate with silicone resin, epoxy resin, melamine resin, fluororesin, etc. to modify the surface (U.S. Pat. No. 4,310,600, Japanese Patent Publication No. 5
No. 9-39308 and JP-A No. 55-7467), however, there was a drawback that the properties aimed at improving the slipperiness and heat resistance were not compatible with the adhesion of the resin coating to the base material.
また、アクリル変性シリコーンを用いたシリコーングラ
フト共重合を使用する方法（特開昭５８−１５４７６６
号、特開昭５８−１６４６５６号）が開示されており、
滑り性と密着性の両立が可能であるが、アクリル変性シ
リコーンの製造が煩雑で高価であるという問題点を歿す
ものである。In addition, a method using silicone graft copolymerization using acrylic modified silicone (Japanese Patent Application Laid-Open No. 58-154766
No., Japanese Patent Publication No. 58-164656) is disclosed,
Although it is possible to achieve both slipperiness and adhesion, it suffers from the problem that the production of acrylic-modified silicone is complicated and expensive.
〔発明が解決１．ようとする問題点〕
本発明は１．北米技術の有する上記問題点を解決し、簡
便な方法で基材に対する密着性を保持し、滑り性、耐熱
性、耐摩耗性の表面を与える一方本発明者らは特開昭６
１−２１５６２９号において、末端ヒドロキシル基含有
ポリシロキサン存在下に重合性シラン化合物を含む単量
体混合物を重合させて得られるポリシロキサングラフト
ポリマーを含んでなる表面改質組成物を提案した。しか
し、この表面改質組成物より得られる塗膜は使用条件に
よっては充分満足のいく緒特性を有しているが、場合に
よっては更に高度の耐熱性が要望されるものであった。[The invention solves the problem 1. Problems to be Solved] The present invention has the following problems: 1. While solving the above-mentioned problems of the North American technology and providing a surface that maintains adhesion to the base material and has slipperiness, heat resistance, and abrasion resistance in a simple manner, the present inventors have
No. 1-215629 proposed a surface modification composition comprising a polysiloxane graft polymer obtained by polymerizing a monomer mixture containing a polymerizable silane compound in the presence of a polysiloxane containing a terminal hydroxyl group. However, although the coating film obtained from this surface-modified composition has sufficiently satisfactory properties depending on the conditions of use, in some cases a higher degree of heat resistance is required.
また、実質的にはポリシロキサングラフトポリマーの有
機溶剤の溶液を含有する表面改質組成物であり、ポリエ
ステルフィルムのインラインコート法によるコーティン
グ剤等として使用を制限されたり、使用上労働衛生面の
問題を有していると共に、ポリマーの組成によっては長
期間の保存中にゲル化する不都合が生じる場合があった
。In addition, it is a surface modification composition that essentially contains a solution of a polysiloxane graft polymer in an organic solvent, and its use as a coating agent for in-line coating of polyester films is restricted, and there are occupational health issues when using it. In addition, depending on the composition of the polymer, there may be an inconvenience that it may gel during long-term storage.
また、これまでに提案されているポリシロキサングラフ
トポリマーの水分散物としては、水希釈性の有機溶剤中
でカルボキシル基およびヒドロキシル基を有するビニル
系重合体を製造し、これにヒドロキシル基もしくはアル
コキシル基を有するオルガノポリシロキサンを反応させ
、次いで水希釈して得られる水分散物（特開昭５０−９
５３８８号）や重合性不飽和基を有するオルガノポリシ
ロキサンと他のビニル系単量体を乳化剤の存在下に水媒
体中で乳化重合して得られる水分散物（特開昭５１−１
４６５２５号）などが知られている。しかしながら、こ
れらの方法では、オルガノポリシロキサンの反応性が低
い為、変性が不完全な事が多く、場合によっては反応中
に分離、凝集といった現象が生じ易い。従って、侵れた
前記性能を有するポリシロキサングラフトポリマー水性
分散体を安定に得るには組成上の制約を受けるのが実情
である。In addition, as an aqueous dispersion of a polysiloxane graft polymer that has been proposed so far, a vinyl polymer having a carboxyl group and a hydroxyl group is produced in a water-dilutable organic solvent, and then a hydroxyl group or an alkoxyl group is added to this. An aqueous dispersion obtained by reacting an organopolysiloxane having
5388) and an aqueous dispersion obtained by emulsion polymerization of an organopolysiloxane having a polymerizable unsaturated group and other vinyl monomers in an aqueous medium in the presence of an emulsifier (JP-A-51-1
No. 46525), etc. are known. However, in these methods, since the reactivity of organopolysiloxane is low, modification is often incomplete, and in some cases, phenomena such as separation and aggregation are likely to occur during the reaction. Therefore, the reality is that in order to stably obtain an aqueous polysiloxane graft polymer dispersion having the above-mentioned properties, there are compositional constraints.
本発明渚らは、このような現状に鑑み、撥水性、滑り性
、耐熱性、剥離性、耐マイグレーション性に優れ、かつ
使用上労働衛生面の問題の無い表面改質組成物について
鋭意研究した結果、本発明に到達した。In view of the current situation, the inventors of the present invention, Nagisa et al., have conducted extensive research into surface-modifying compositions that have excellent water repellency, slipperiness, heat resistance, peelability, and migration resistance, and are free from occupational health problems when used. As a result, we have arrived at the present invention.
即ち、本発明は末端ヒドロキシル基含有ポリシロキサン
（Ａ）１〜２０重量％存在下に、重合性シラン化合物（
Ｂ） ｏ、 ０５〜１０重量％、不飽和有機酸（Ｃ）１
〜３０重量％およびこれらと共重合可能な他の重合性単
量体（Ｄ）４０〜９７．９５重量％（但し、（Ａ） 、
（Ｂ） 、 （Ｃ：）および（Ｄ）成分の合計は１０
０重量％とする。）をアルコール以外の有機溶剤中で重
合させて得られる重合体の溶液に塩基性化合物および水
を加えた液状物を攪拌して得られるポリシロキサングラ
フトポリマーの塩基性化合物による塩の水性分散体およ
び水溶性樹脂を、該水性分散体１００重量部（固形分換
算）当たり該水溶性樹脂が０〜５０重量部の割合で含ん
でなる表面改質組成物に関するものである。That is, in the present invention, a polymerizable silane compound (
B) o, 05-10% by weight, unsaturated organic acid (C) 1
-30% by weight and other polymerizable monomers (D) copolymerizable with these 40-97.95% by weight (However, (A),
The total of (B), (C:) and (D) components is 10
0% by weight. ) is polymerized in an organic solvent other than alcohol, and a basic compound and water are added to a liquid solution of the polymer, which is then stirred. The present invention relates to a surface modification composition comprising a water-soluble resin in a proportion of 0 to 50 parts by weight per 100 parts by weight (in terms of solid content) of the aqueous dispersion.
本発明に用いられる末端ヒドロキシル基含有ポリシロキ
サン（Ａ）としては、末端の少なくとも一つがヒドロキ
シル基である直鎖状もしくは一部枝分れした分岐状ポリ
シロキサンであれば制限なく使用でき、現在各種のもの
が容易に入手でき、目的に応じて使用できる。The terminal hydroxyl group-containing polysiloxane (A) used in the present invention can be used without any restriction as long as it is a linear or partially branched polysiloxane in which at least one terminal has a hydroxyl group. These are easily available and can be used depending on the purpose.
この様な末端ヒドロキシル基含有ポリシロキサン（Ａ）
としては、例えば、−形式
（但し、Ｒ１及びＲ２はそれぞれ独立にハロゲン置換さ
れていてもよい一価の炭化水素基、Ｒ３は水素又はハロ
ゲン置換されていてもよい一価の炭化水素基、ｎは１以
上の整数である。）で示される直鎖状ポリシロキサンに
より代表されるが、部が枝分れした分岐状ポリシロキサ
ンも好適に使用できる。Such terminal hydroxyl group-containing polysiloxane (A)
For example, - format (where R1 and R2 are each independently an optionally halogen-substituted monovalent hydrocarbon group, R3 is hydrogen or a halogen-substituted monovalent hydrocarbon group, n is an integer of 1 or more), but branched polysiloxanes having branched parts can also be suitably used.
より具体的に言うならば、例えば、ジメチルポリシロキ
サン、メチルエチルポリシロキサン等のジアルキルポリ
シロキサン類、メチルフェニルポリシロキサン等のアル
キルアリールポリシロキサン類、ジフェニルポリシロキ
サン等のジアリールポリシロキサン類などを挙げること
ができ、これらの群から選ばれる１種又は２種以上の混
合物を使用することができる。More specifically, examples include dialkylpolysiloxanes such as dimethylpolysiloxane and methylethylpolysiloxane, alkylarylpolysiloxanes such as methylphenylpolysiloxane, and diarylpolysiloxanes such as diphenylpolysiloxane. One type or a mixture of two or more types selected from these groups can be used.
なかでも、末端に少なくとも一個のヒドロキシル基を有
する直鎖状もしくは一部枝分れした分岐状ジメチルポリ
シロキサンが安価に入手でき、しかも性能に優れたポリ
シロキサングラフトポリマーが得られるので好ましい。Among these, linear or partially branched dimethylpolysiloxanes having at least one hydroxyl group at the end are preferred because they can be obtained at low cost and provide polysiloxane graft polymers with excellent performance.
用いられるポリシロキサン（Ａ）の平均分子量としては
５００〜１５０万の範囲、好ましくは５０００〜１５０
万の範囲、さらに好ましくは２万〜１５０万の範囲のも
のが望ましい。平均分子量が５００未満では、得られる
表面改質組成物は所望の表面特性が充分発揮されない場
合があり、また、平均分子量が１５０万を超えると高粘
度となり、取り扱いおよび重合操作が難しくなる場合が
ある。The average molecular weight of the polysiloxane (A) used is in the range of 5,000 to 1,500,000, preferably 5,000 to 150,000.
A range of 10,000, more preferably 20,000 to 1,500,000 is desirable. If the average molecular weight is less than 500, the resulting surface-modified composition may not exhibit the desired surface properties sufficiently, and if the average molecular weight exceeds 1.5 million, it may become highly viscous, making handling and polymerization operations difficult. be.
末端ヒドロキシル基含有ポリシロキサン（Ａ）の使用量
は、表面特性の程度に応じて、１〜２０重量％の範囲内
で適宜法めることができる。１重量％未満の使用量では
表面特性が充分ではなく、また２０重量％を超える範囲
では基材への密着性が低下するので望ましくない。The amount of the terminal hydroxyl group-containing polysiloxane (A) to be used can be determined as appropriate within the range of 1 to 20% by weight, depending on the degree of surface properties. If the amount is less than 1% by weight, the surface properties will not be sufficient, and if it exceeds 20% by weight, the adhesion to the substrate will decrease, which is not desirable.
本発明に用いられる重合性シラン化合物（Ｂ）は、分子
中に少なくとも１個の重合性不飽和基と少なくとも１個
の前記ポリシロキサンと縮合反応し得る基とを有する化
合物であり、例えばビニルトリメトキシシラン、ビニル
トリエトキシシラン、ビニルトリブトキシシラン、ビニ
ルトリス（β−メトキシエトキシ）シラン、アリルトリ
エトキシシラン、γ−（メタ）アクリロキシプロピルト
リメトキシシラン、γ−（メタ）アクリロキシプロピル
トリエトキシシラン、γ−（メタ）アクリロキシプロピ
ルメチルジメトキシシラン、γ（メタ）アクリロキシプ
ロピルメチルエトキシシラン、γ−（メタ）アクリロキ
シプロピルトリス（β−メトキシエトキシ）シラン、２
−スチリルエチルトリメトキシシラン、（メタ）アクリ
ロキシエチルジメチル（３−トリメトキシシリルプロピ
ル）アンモニウムクロライド、ビニルトリアセトキシシ
ラン、ビニルトリクロルシランなどを挙げることができ
、これらの群から選ばれる１種または２種以上の混合物
を使用することができる。The polymerizable silane compound (B) used in the present invention is a compound having in its molecule at least one polymerizable unsaturated group and at least one group capable of condensation reaction with the polysiloxane. Methoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltris(β-methoxyethoxy)silane, allyltriethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane , γ-(meth)acryloxypropylmethyldimethoxysilane, γ(meth)acryloxypropylmethylethoxysilane, γ-(meth)acryloxypropyltris(β-methoxyethoxy)silane, 2
-Styrylethyltrimethoxysilane, (meth)acryloxyethyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, vinyltriacetoxysilane, vinyltrichlorosilane, etc., and one or two selected from these groups. Mixtures of more than one species can be used.
重合性シラン化合物（Ｂ）の使用量は０．０５〜１０重
量％の範囲内で適宜法めることができる。The amount of the polymerizable silane compound (B) to be used can be determined as appropriate within the range of 0.05 to 10% by weight.
０．０５重量％未満の使用量では、ポリシロキサン（Ａ
）と重合性シラン化合物（Ｂ）、不飽和有機酸（Ｃ）及
び重合性単量体（Ｄ）成分からなる重合物との結合が不
充分で有効量のグラフト反応が起こらず、水性分散体と
したのち未反応のポリシロキサンが層分離を起こす傾向
がある。また、１０重量％を超える範囲では、安定性が
不良となり重合時のゲル化が起こりやすくなる。In amounts less than 0.05% by weight, polysiloxane (A
) and the polymer consisting of the polymerizable silane compound (B), unsaturated organic acid (C), and polymerizable monomer (D) components are insufficient, and an effective amount of graft reaction does not occur, resulting in an aqueous dispersion. After this, unreacted polysiloxane tends to cause layer separation. Moreover, if the amount exceeds 10% by weight, stability becomes poor and gelation tends to occur during polymerization.
本発明に用いられる不飽和有機Ｓ （Ｃ）は、ポリシロ
キサン（Ａ）と前記重合物との結合を惹起してグラフト
反応を円滑に進める作用を有すると共に、得られるポリ
シロキサングラフトポリマーを水分散性とするための成
分であり、例えばアクリル酸、メタクリル酸、マレイン
酸、イタコン酸等の不飽和カルボン酸やビニルスルホン
酸、スルホエチルメタクリレート、２−アクリルアミド
−２−メチルプロパンスルホン酸等の不飽和スルホン酸
などを挙げることができ、これらの１種または２種以上
の混合物を使用することができる。The unsaturated organic S (C) used in the present invention has the effect of inducing a bond between the polysiloxane (A) and the polymer to smoothly advance the graft reaction, and also dispersing the resulting polysiloxane graft polymer in water. For example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, unsaturated carboxylic acids such as vinyl sulfonic acid, sulfoethyl methacrylate, 2-acrylamido-2-methylpropanesulfonic acid, etc. Examples include sulfonic acids, and one type or a mixture of two or more of these can be used.
不飽和有機酸（Ｃ）の使用量は１〜３０重量％、好まし
くは３〜２０重量％の範囲内で適宜法めることができる
。１重量％未満の使用量では、安定な水性分散体を得る
のが難しく、また、３０重量％を超える範囲では、得ら
れるポリマーの親水性が強くなりすぎ、安定な水分散化
が困難となるばかりでなく、得られる表面改質組成物は
耐水性に劣ったものとなる。The amount of the unsaturated organic acid (C) to be used can be determined as appropriate within the range of 1 to 30% by weight, preferably 3 to 20% by weight. If the amount used is less than 1% by weight, it is difficult to obtain a stable aqueous dispersion, and if the amount used exceeds 30% by weight, the hydrophilicity of the resulting polymer becomes too strong, making stable water dispersion difficult. Moreover, the resulting surface-modified composition has poor water resistance.
本発明に用いられる重合性単量体（Ｄ）としては、例え
ば、アクリル酸ブチル、アクリル酸２エチルヘキシル等
のアクリル酸エステル類；（メタ）アクリル酸２−ヒド
ロキシエチル、（メタ）アクリル＃２−ヒドロ午ジプロ
ピル等の（メタ）アクリル酸ヒドロキシアルキルエステ
ル類：メタクリル酸メチル、メタクリル酸ブチル等のメ
タクリル酸エステル類；酢酸ビニル、プロピオン酸ヒニ
ル等のビニルエステル類；スチレン、ビニルトルエン等
の芳香族ビニル類：アクリロニトリル、メタクリレート
リル等の不飽和ニトリル類；アクリルアミド、Ｎ−メチ
ロールアクリルアミド等の不飽和アミド類；エチレン、
プロピレン、インブチレン等のα−オレフィン類；メチ
ルビニルエーテル、エチルビニルエーテル、ｔ−ブチル
ビニルエーテル等のビニルエーテル類；塩化ビニル、塩
化ビニリデン、フッ化ビニル、フッ化ビニリデン等の含
ハロゲンα、β−下節和単量体類；（メタ）アクリル酸
トリフルオロエチル、２゜２．３．３−テトラフルオロ
プロピルアクリレート、ＬＨ，ＩＨ，２Ｈ，２Ｈ−へブ
タデカフルオロデシルアクリレート、ＬＨ，ＩＨ，５Ｈ
−オクタフルオロペンチルアクリレ−）？の含フッ素（
メタ）アクリル酸エステル類、２，３，５．６テトラフ
ルオロフエニルアクリル酸エステル、２．３，４，５．
６−ペンタフルオロフェニルメタクリル酸エステル等の
芳香族フッ素含有（メタ）アクリル酸エステル類等が挙
げられ、これらの１種または２種以上の混合物を使用す
ることができる。Examples of the polymerizable monomer (D) used in the present invention include acrylic esters such as butyl acrylate and 2-ethylhexyl acrylate; 2-hydroxyethyl (meth)acrylate, and (meth)acrylic #2- (Meth)acrylic acid hydroxyalkyl esters such as hydrodipropyl; Methacrylic acid esters such as methyl methacrylate and butyl methacrylate; Vinyl esters such as vinyl acetate and vinyl propionate; Aromatic vinyls such as styrene and vinyltoluene. Classes: Unsaturated nitrites such as acrylonitrile and methacrylaterile; Unsaturated amides such as acrylamide and N-methylolacrylamide; ethylene,
α-olefins such as propylene and imbutylene; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and t-butyl vinyl ether; halogen-containing α- and β-containing compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride, and vinylidene fluoride Monomers: trifluoroethyl (meth)acrylate, 2゜2.3.3-tetrafluoropropyl acrylate, LH, IH, 2H, 2H-hebutadecafluorodecyl acrylate, LH, IH, 5H
-octafluoropentyl acrylate)? Fluorine-containing (
meth)acrylic esters, 2,3,5.6 tetrafluorophenyl acrylic esters, 2.3,4,5.
Examples include aromatic fluorine-containing (meth)acrylic esters such as 6-pentafluorophenyl methacrylic ester, and one type or a mixture of two or more of these can be used.
重合性単量体（Ｄ）の使用量は、４０〜９７．９５重量
％の範囲内で適宜法めることができる。４０重量％未満
あるいは９７．９５重量％を超えた使用量では、前記の
ポリシロキサン（Ａ）、重合性シラン化合物（Ｂ）また
は不飽和有機酸（Ｃ）の使用量が前記した範囲より過多
あるいは過小となり、前記した如き欠点が発現するので
望ましくない。The amount of the polymerizable monomer (D) to be used can be determined as appropriate within the range of 40 to 97.95% by weight. If the amount used is less than 40% by weight or more than 97.95% by weight, the amount of the polysiloxane (A), polymerizable silane compound (B) or unsaturated organic acid (C) used is excessive or exceeds the above range. This is not desirable because it becomes too small and the above-mentioned drawbacks occur.
重合の際に使用できる有機溶剤としては、アルコール以
外の有機溶剤すなわちアルコール性ヒドロキシル基を持
たない有機溶剤であれば制限なく使用することができ、
例えば、トルエン、キシレン、ベンゼン、ヘキサン、シ
クロヘキサン、トリクロルエタン、メチルエチルケトン
、酢酸エチル、ジオキサン、セロソルブアセテート等を
挙げることができ、これらの１種または２種以上の混合
物を使用することができるが、ポリマーの溶解性、沸点
等からトルエン、キシレンが特に好ましい。As the organic solvent that can be used during polymerization, any organic solvent other than alcohol, that is, an organic solvent that does not have an alcoholic hydroxyl group, can be used without any restriction.
Examples include toluene, xylene, benzene, hexane, cyclohexane, trichloroethane, methyl ethyl ketone, ethyl acetate, dioxane, cellosolve acetate, etc. One type or a mixture of two or more of these can be used, but polymer Toluene and xylene are particularly preferred from the viewpoint of solubility, boiling point, etc.
アルコール性ヒドロキシル基を持ったアルコール系有機
溶剤、例えば、メチルアルコール、エチルアルコール、
イソプロピルアルコール等のアルコール類、メチルセロ
ソルブ、エチルセロソルブ等のセロソルブ類等はポリシ
ロキサン（Ａ）と重合性シラン化合物（Ｂ）、不飽和有
機酸（Ｃ）および重合性単量体（Ｄ）成分からなる重合
物とのグラフト反応を抑制するので重合初期から用いる
ことはできないが、グラフト反応が充分に進行した後は
添加して用いることができる。Alcohol-based organic solvents with alcoholic hydroxyl groups, such as methyl alcohol, ethyl alcohol,
Alcohols such as isopropyl alcohol, cellosolves such as methyl cellosolve, ethyl cellosolve, etc. are made from polysiloxane (A), a polymerizable silane compound (B), an unsaturated organic acid (C), and a polymerizable monomer (D). Since it suppresses the graft reaction with the polymer, it cannot be used from the initial stage of polymerization, but it can be added and used after the graft reaction has sufficiently progressed.
重合開始剤としてはアゾビスイソブチロニトリル、ベン
ゾイルパーオキシド等通常のラジカル重合開始剤を挙げ
ることができる。Examples of the polymerization initiator include common radical polymerization initiators such as azobisisobutyronitrile and benzoyl peroxide.
重合温度は通常室温から２００°Ｃ１好ましくは４０−
１２０°Ｃの範囲である。重合濃度は通常３０〜７０重
量％、好ましくは４０〜６０重量％である。The polymerization temperature is usually room temperature to 200°C, preferably 40°C.
The range is 120°C. The polymerization concentration is usually 30 to 70% by weight, preferably 40 to 60% by weight.
ポリシロキサングラフトポリマーの塩とするための塩基
性化合物は、従来から酸性物質の中和を目的に常用され
るものであれば制限なく使用することができ、例えば、
水酸化ナトリウム、水酸化カリウム、水酸化カルシウム
、アンモニア、トリメチルアミン、トリエチルアミン、
メチルジエチルアミン、ジメチルエチルアミン、モノメ
チロールジメチルアミン、モノメチロールジエチルアミ
ン、ジメチロールメチルアミン、ジメチロールエチルア
ミン等を挙げる事ができ、これらの１種又は２種以上を
使用することができる。塩基性化合物はポリシロキサン
グラフトポリマーを水分散性とするためおよび耐熱性を
高めるために用いるもので、該重合体の酸基の２０〜２
００モル％に相当する量で使用するのが好適である。２
０モル％未満の量では充分な水分散体が得られない場合
がある。特に、保存時においても良好な分散状態を保持
し、しかも塩基性化合物に由来する欠点、例えば、耐水
性の低下や変色等の弊害の見られない表面改質組成物を
得るために重合体中の酸基の５０〜１００モル％に相当
する量で添加するのが好ましい。この際、高度の分散安
定性を必要とする場合は適当な乳化剤及び／又は保護コ
ロイドを併用することもできる。As the basic compound for making the salt of the polysiloxane graft polymer, any basic compound that has been conventionally used for the purpose of neutralizing acidic substances can be used without any restriction, for example,
Sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, trimethylamine, triethylamine,
Examples include methyldiethylamine, dimethylethylamine, monomethyloldimethylamine, monomethyloldiethylamine, dimethylolmethylamine, and dimethylolethylamine, and one or more of these can be used. The basic compound is used to make the polysiloxane graft polymer water-dispersible and to improve heat resistance, and it contains 20 to 2
Preferably, it is used in an amount corresponding to 0.00 mol%. 2
If the amount is less than 0 mol%, a sufficient aqueous dispersion may not be obtained. In particular, in order to obtain a surface-modified composition that maintains a good dispersion state even during storage and does not have the disadvantages caused by basic compounds, such as decreased water resistance and discoloration, It is preferable to add it in an amount corresponding to 50 to 100 mol % of the acid groups. At this time, if a high degree of dispersion stability is required, an appropriate emulsifier and/or protective colloid may be used in combination.
添加する水の量はポリシロキサングラフトポリマー１０
０重量部に対して３０〜１０００重量部である。３０重
量部未満では水が連続相とならず、安定な水性分散体は
得られない。一方、１０００重量部を越える量を用いた
場合はポリシロキサングラフトポリマー分が稀薄となり
経済的に好ましくない。The amount of water added is 10% of the polysiloxane graft polymer.
The amount is 30 to 1000 parts by weight relative to 0 parts by weight. If the amount is less than 30 parts by weight, water will not become a continuous phase and a stable aqueous dispersion will not be obtained. On the other hand, if the amount exceeds 1000 parts by weight, the polysiloxane graft polymer content becomes diluted, which is economically undesirable.
ポリシロキサングラフトポリマーを含む液状物を攪拌し
て安定な水性分散体とするには、該液状物中の水溶性有
機溶剤の量を有機溶剤全量に対して３０〜１００重量％
とするのが好適である。In order to stir a liquid containing a polysiloxane graft polymer to form a stable aqueous dispersion, the amount of water-soluble organic solvent in the liquid should be 30 to 100% by weight based on the total amount of organic solvent.
It is preferable that
水溶性有機溶剤が３０重量％未満の量を用いた場合は、
分散粒子の沈降等が起こり、充分な水分散体が得られな
い場合がある。水溶性有機溶剤の比率を全有機溶剤中の
３０〜１００重量％とするのは水添加前又は添加後で良
いが、好ましくは添加前である。If the amount of water-soluble organic solvent used is less than 30% by weight,
Sedimentation of the dispersed particles may occur, and a sufficient aqueous dispersion may not be obtained. The ratio of the water-soluble organic solvent to 30 to 100% by weight of the total organic solvent may be adjusted before or after the addition of water, but preferably before the addition.
水溶性有機溶剤とはメチルアルコール、エチルアルコー
ル、イソプロピルアルコール等の低級アルコール類、テ
トラヒドロフラン、ジオキサン等の環状エーテル類、ア
セトン等のケトン類、メチルセロソルブ、エチルセロソ
ルブ等のセロソルブ類等の水希釈性有機溶剤である。Water-soluble organic solvents include lower alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, cyclic ethers such as tetrahydrofuran and dioxane, ketones such as acetone, and water-dilutable organic solvents such as cellosolves such as methyl cellosolve and ethyl cellosolve. It is a solvent.
重合に好ましく使用される有機溶剤の残存を考慮すると
、水溶性有機溶剤の比率は全有機溶剤中の４０〜９０重
量％とするのが好ましい。Considering the residual organic solvent preferably used in polymerization, the proportion of the water-soluble organic solvent is preferably 40 to 90% by weight based on the total organic solvent.
こうして得られるポリシロキサングラフトポリマーの塩
基性化合物による塩の水性分散体は、そのまま表面改質
組成物として好適に使用できるものであるが、使用時に
おける環境保全も考慮すれば、更に脱溶剤するのが好ま
しい。脱溶剤は従来公知の方法、例えば減圧蒸留、加熱
蒸留等により容易に行なうことができる。脱溶剤の量は
所望に応じて適宜決定されるべきものであるが、本発明
の特徴を最大に発揮させるために分散液中に含まれる９
０重量％以上に相当する量を除去するのが好ましい。The aqueous dispersion of a salt made from a basic compound of a polysiloxane graft polymer obtained in this way can be suitably used as a surface modification composition as it is, but if environmental protection is taken into consideration during use, it is necessary to further remove the solvent. is preferred. Solvent removal can be easily carried out by conventionally known methods, such as vacuum distillation and heating distillation. Although the amount of solvent removal should be appropriately determined depending on the needs, in order to maximize the characteristics of the present invention, the amount of 9 contained in the dispersion liquid is
It is preferable to remove an amount corresponding to 0% by weight or more.
本発明において、水溶性樹脂はポリシロキサングラフト
ポリマーの塩基性化合物による塩の水性分散体の成膜性
、濡れ性、密着性等を更に高めるものであり、水溶性樹
脂であれば制限なく使用することができ、例えば、ポリ
ビニルアルコール、水溶性アクリル樹脂、水溶性ポリエ
ステル樹脂、水溶性ボリアミード、水溶性ポリウレタン
樹脂ポリエチレングリコール、ポリアクリルアミド≠＃
、セルロース類、ゼラチン等を挙げることができ、これ
らの群から選ばれる１種又は２種以上の混合物を使用す
ることができ、なかでもポリビニルアルコールが特に濡
れ性に優れた表面改質組成物が得られるので好ましい。In the present invention, the water-soluble resin is used to further improve the film-forming properties, wettability, adhesion, etc. of the aqueous dispersion of the salt made from the basic compound of the polysiloxane graft polymer, and any water-soluble resin can be used without any restriction. For example, polyvinyl alcohol, water-soluble acrylic resin, water-soluble polyester resin, water-soluble polyamide, water-soluble polyurethane resin, polyethylene glycol, polyacrylamide≠#
, cellulose, gelatin, etc., and one type or a mixture of two or more selected from these groups can be used. Among them, polyvinyl alcohol is particularly suitable for surface-modifying compositions with excellent wettability. It is preferable because it can be obtained.
水溶性樹脂を使用する場合、その使用量はポリシロキサ
ングラフトポリマーの塩基性化合物による塩の水性分散
体の固形分１００重量部に対して５０重量部以下、好ま
しくは０．０１〜２０重量部、より好ましくは０．１〜
５重景置部範囲である。５０重量部より多くすると表面
改質組成物の耐水性が低下するので好ましくない。When a water-soluble resin is used, the amount used is 50 parts by weight or less, preferably 0.01 to 20 parts by weight, based on 100 parts by weight of the solid content of the aqueous dispersion of a salt made of a basic compound of a polysiloxane graft polymer. More preferably 0.1~
This is the range of the 5-fold view. If the amount exceeds 50 parts by weight, the water resistance of the surface-modifying composition decreases, which is not preferable.
ポリシロキサングラフトポリマーの塩基性化合物による
塩の水性分散体と水溶性樹脂とからなる水性樹脂組成物
は、
１、ポリシロキサングラフトポリマーの塩基性化合物に
よる塩の水性分散体と水溶性樹脂とを常温および加温下
に攪拌混合する方法。An aqueous resin composition consisting of an aqueous dispersion of a salt made of a basic compound of a polysiloxane graft polymer and a water-soluble resin is prepared by: 1. An aqueous dispersion of a salt made of a basic compound of a polysiloxane graft polymer and a water-soluble resin are heated at room temperature. and a method of stirring and mixing while heating.
２、ポリシロキサングラフトポリマーの溶液に塩基性化
合物、水および水溶性樹脂を加えた液状物を常温および
加温下に攪拌混合する方法。2. A method in which a liquid product obtained by adding a basic compound, water and a water-soluble resin to a solution of a polysiloxane graft polymer is stirred and mixed at room temperature and under heating.
のいづれかの方法によっても好ましく製造することがで
きる。It can also be preferably manufactured by any of the following methods.
また、水性樹脂組成物に併用される架橋剤としては、出
来るだけ低温で反応しうるちのが好ましく、例えばジメ
チロール尿素その他のポリメチロール尿素、ジメチロー
ルエチレン尿素、ジメチロールグリオキザールモノウレ
イン、ジメチロールグリオキザールジウレイン、ジメチ
ロールウロン、ジメチロールプロピレン尿素、１．３−
ビス（ヒドロキシメチル）−テトラヒドロ−５−ヒトロ
キシー２−ピリミジノン、ジメチロールトリアゾン、ジ
メチロールメラミンその他のポリメチロールメラミン、
ポリメチロールアセトグアナミンポリメチロールベンゾ
グアナミン等のポリメチロール化合物；グリオキザール
、グルタルアルデヒド、ジアルデヒド澱粉等のポリアル
デヒド化合物；１，８−へキサメチレンジエチレンウレ
ア、ｌ、１゜１−トリ （ｗ−アンリジニルプロピオネ
ート）メチルプロパン等のポリアジリジン化合物；ポリ
エチレングリコールのジグリシジルエーテル、グリセリ
ンジグリシジルエーテル、トリメチロールプロパンジグ
リシジルエーテル等の非イオン性水溶性エポキシ化合物
；アクリル酸もしくはメタアクリル酸のグリシジルエス
テルとアクリルアミド等の水溶性共重合体；ポリアミド
エポキシ樹脂；ホウ酸、ホウ酢塩； Ｎａ２ＺｒＳｉ０
４． Ｚｒ０Ｃａ・３Ｈ２０，ＺｒＯＳＯ４争ｎＨ２Ｏ
，Ｚｒ０（ＮＯ３）？４Ｈ２０，Ｚｒ０（ＣＯ３）２・
ｎ）１２０． Ｚｒ０（ＯＨ）２ｅｎＨ２０，Ｚｒ０（
Ｃ：２Ｈ２０２）２． （ＮＨ４）２ＺｒＯ（Ｃ’０３
）２ＺｒＳｉ０４等の化学式で表わされるジルコニウム
化合物等を使用することができる。又、必要であれば、
適当な硬化促進触媒を使用してもよい。架橋剤の使用量
は水性樹脂組成物１００重量部（固形分換算）当り１〜
３０重量部の範囲とするのが好ましい。The crosslinking agent used in combination with the aqueous resin composition is preferably one that reacts at as low a temperature as possible, such as dimethylol urea and other polymethylol ureas, dimethylol ethylene urea, dimethylol glyoxal monourein, and dimethylol glyoxal. Diurein, dimethyloluron, dimethylolpropylene urea, 1.3-
Bis(hydroxymethyl)-tetrahydro-5-hydroxy-2-pyrimidinone, dimethyloltriazone, dimethylolmelamine and other polymethylolmelamines,
Polymethylol compounds such as polymethylolacetoguanamine polymethylolbenzoguanamine; polyaldehyde compounds such as glyoxal, glutaraldehyde, dialdehyde starch; 1,8-hexamethylene diethylene urea, l, 1° 1-tri (w-antridinyl) (propionate) polyaziridine compounds such as methylpropane; nonionic water-soluble epoxy compounds such as diglycidyl ether of polyethylene glycol, glycerin diglycidyl ether, trimethylolpropane diglycidyl ether; glycidyl esters of acrylic acid or methacrylic acid; Water-soluble copolymers such as acrylamide; polyamide epoxy resin; boric acid, boric acid salt; Na2ZrSi0
4. Zr0Ca・3H20, ZrOSO4 conflict nH2O
,Zr0(NO3)? 4H20, Zr0(CO3)2・
n) 120. Zr0(OH)2enH20,Zr0(
C:2H202)2. (NH4)2ZrO(C'03
) A zirconium compound represented by a chemical formula such as 2ZrSi04 can be used. Also, if necessary,
A suitable curing accelerating catalyst may also be used. The amount of crosslinking agent used is 1 to 100 parts by weight (solid content equivalent) of the aqueous resin composition.
It is preferably in the range of 30 parts by weight.
以上のようにして得られるポリシロキサングラフトポリ
マーの塩基性化合物による塩の水性分散体は長期保存安
定性に優れると共に、撥水性、滑り性、耐熱性、剥離性
、耐マグレーション性等に優れた被膜を形成しうるちの
であり、そのまま、表面改質組成物として好適に使用で
きるものであるが、必要であればその他に公知の顔料、
トナー、滑剤、可塑剤、防錆剤、帯電防止剤、消泡剤、
粘度調節剤、湿潤剤、ＰＨ調節剤等を配合することがで
きる。また、適宜希釈することもできる。The aqueous dispersion of a salt of a basic compound of polysiloxane graft polymer obtained in the above manner has excellent long-term storage stability, as well as excellent water repellency, slipperiness, heat resistance, peelability, and anti-maglation properties. It is a pigment that forms a film and can be suitably used as it is as a surface modification composition, but if necessary, other known pigments,
Toner, lubricant, plasticizer, rust preventive agent, antistatic agent, antifoaming agent,
A viscosity modifier, wetting agent, PH modifier, etc. can be blended. It can also be diluted as appropriate.
本発明の表面改質組成物は長期保存安定性に優れると共
に、これを基材に塗布して得られた塗膜は、基材への密
着性も良好で、かつ、良好な撥水性、滑り性、耐熱性、
剥離性、耐マイグレーション性等の優れた表面特性を示
すものであり、磁気テープ、感熱印刷材料等のバックコ
ート剤、撥水剤等の繊維処理剤、粘着テープ、離型紙、
感熱孔版原紙等の剥離剤等に適用されて優れた特性を発
揮するものである。The surface-modified composition of the present invention has excellent long-term storage stability, and the coating film obtained by applying it to a substrate has good adhesion to the substrate, as well as good water repellency and slipperiness. properties, heat resistance,
It exhibits excellent surface properties such as peelability and migration resistance, and can be used as back coating agents for magnetic tapes, thermal printing materials, etc., fiber treatment agents such as water repellents, adhesive tapes, release papers, etc.
It exhibits excellent properties when applied as a release agent for heat-sensitive stencil paper, etc.
以下に実施例をあげて本発明を具体的に説明するが、こ
れらにより本発明は何ら限定を受けるものではない。尚
、例中の部はすべて重量部を示すものとする。The present invention will be specifically explained below with reference to Examples, but the present invention is not limited in any way by these examples. Note that all parts in the examples indicate parts by weight.
参考例 １
温度計、還流冷却器、滴下漏斗、窒素導入管および攪拌
機を備えた四つ目フラスコに末端ヒドロキシル基含有ポ
リシロキサンとして、平均分子量が１２００００の直鎖
状ジヒドロキシジメチルポリシロキサンの３０重量％ト
ルエン溶液１０部およびトルエン１００部を仕込み、窒
素雰囲気下、８０°Ｃに昇温した。これにメタクリル酎
メチル７０部、アクリル酸ブチル２０部、アクリル酸５
部、γ−メタクリロキシプロピルトリメトキシシラン５
部およびアゾビスイソブチロニトリル２部からなる単量
体均一溶液の２０重量％を加えて、８０°Ｃで３０分間
、初期重合を行った。次いで同温度で残りの単量体均一
溶液を２時間かけて滴下し、滴下終了後２時間３０分間
重合を継続した時、イソプロピルアルコール１０部を加
えて希釈した。引続き温度を８０℃に保持しながら１時
間３０分攪拌を続けて重合反応を継続したのち冷却して
、ポリシロキサングラフトポリマーの溶液（以下、重合
体溶液（１）という。）を得た。得られた重合体溶液（
１）４０ｍにインプロピルアルコール６０部を加えて希
釈後、２８％アンモニア水３部を攪拌下に添加し、１０
分間攪拌を継続した後、水を２３７部添加して水分散化
した。続いて内温を６０’Ｃ！に昇温しで、減圧蒸留法
により２５０部を留去して脱溶剤した後、アンモニア水
と水を加えてＰ Ｈ９，０、濃度３０％に調整し、ポリ
シロキサングラフトポリマー水性分散体（以下、水性分
散体（１）という。）を得た。得られた水性分散体（１
）は粘度１０ｃｐｓ（２５°Ｃ，Ｂ型粘度計、６０ ｒ
ｐｍ）で、−週間静置しても、分散粒子の沈降やポリシ
ロキサンの分離を起こさず安定なエマルションであった
。また、残存するインプロピルアルコールおよびトルエ
ンはそれぞれ９０ ｐｐｍ、７５０ｐｐｍであった。Reference Example 1 30% by weight of a linear dihydroxydimethylpolysiloxane having an average molecular weight of 120,000 was added as a polysiloxane containing terminal hydroxyl groups to a four-eye flask equipped with a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet tube, and a stirrer. 10 parts of toluene solution and 100 parts of toluene were charged, and the temperature was raised to 80°C under a nitrogen atmosphere. Add to this 70 parts of methyl methacrylate, 20 parts of butyl acrylate, and 5 parts of acrylic acid.
part, γ-methacryloxypropyltrimethoxysilane 5
1 part and 2 parts of azobisisobutyronitrile were added thereto, and initial polymerization was carried out at 80°C for 30 minutes. Next, the remaining monomer homogeneous solution was added dropwise over 2 hours at the same temperature, and when the polymerization was continued for 2 hours and 30 minutes after the completion of the addition, 10 parts of isopropyl alcohol was added to dilute the solution. Subsequently, stirring was continued for 1 hour and 30 minutes while the temperature was maintained at 80° C. to continue the polymerization reaction, and then cooled to obtain a solution of a polysiloxane graft polymer (hereinafter referred to as polymer solution (1)). The obtained polymer solution (
1) Add 60 parts of inpropyl alcohol to 40m to dilute it, then add 3 parts of 28% ammonia water with stirring,
After continuing stirring for a minute, 237 parts of water was added to form a water dispersion. Next, the internal temperature was 60'C! After raising the temperature to 250 parts by distillation under reduced pressure to remove the solvent, aqueous ammonia and water were added to adjust the pH to 9.0 and the concentration to 30%, and a polysiloxane graft polymer aqueous dispersion (hereinafter referred to as , aqueous dispersion (1)) was obtained. The obtained aqueous dispersion (1
) has a viscosity of 10 cps (25°C, B-type viscometer, 60 r
Even if the emulsion was allowed to stand for a week at 100 pm), the emulsion remained stable without sedimentation of the dispersed particles or separation of the polysiloxane. In addition, residual inpropyl alcohol and toluene were 90 ppm and 750 ppm, respectively.
液の保存安定性をみるために、５０℃で６ケ月間保存し
たところ、重合体溶液（１）はゲル化していたが、水性
分散体（１）は粘度変化なく安定であった。In order to check the storage stability of the liquid, it was stored at 50°C for 6 months, and the polymer solution (1) was gelatinized, but the aqueous dispersion (1) was stable without any change in viscosity.
参考例 ２
参考例１で用いたのと同様の四つロフラスコに参考例１
で用いたのと同様の末端ヒドロキシル基含有ポリシロキ
サンの３０重量％トルエン溶液３３．３部およびトル１
７１００部を仕込み、窒素雰囲気下８０℃に昇温した。Reference Example 2 Add Reference Example 1 to a four-bottle flask similar to that used in Reference Example 1.
33.3 parts of a 30% by weight toluene solution of the same terminal hydroxyl group-containing polysiloxane as used in
7100 parts were charged and the temperature was raised to 80°C under a nitrogen atmosphere.
これにメタクリル酸メチル５０部、アクリル酸ブチル２
ｏ部、アクリロニトリル２０部、アクリル酸５部、γ−
メタクリロキシプロピルトリメトキシシラン５部および
アゾビスイソブチロニトリル２部からなる単量体均一溶
液を用いて、参考例１と同様の初期重合操作および単量
体均一溶液の滴下操作を行った。単量体均一溶液の滴下
終了後３０分間重合を継続した時、エチルアルコール１
００部を加えて希釈した。更に８０°Ｃで３時間３０分
重合反応を継続したのち冷却して、ポリシロキサングラ
フトポリマーの溶液（以下、重合体溶液（２）という。To this, 50 parts of methyl methacrylate, 2 parts of butyl acrylate
o parts, 20 parts of acrylonitrile, 5 parts of acrylic acid, γ-
Using a homogeneous monomer solution consisting of 5 parts of methacryloxypropyltrimethoxysilane and 2 parts of azobisisobutyronitrile, the same initial polymerization operation and dropping operation of the homogeneous monomer solution as in Reference Example 1 were performed. When polymerization was continued for 30 minutes after the monomer homogeneous solution was added dropwise, ethyl alcohol 1
It was diluted by adding 0.00 parts. The polymerization reaction was further continued at 80° C. for 3 hours and 30 minutes, and then cooled to obtain a polysiloxane graft polymer solution (hereinafter referred to as polymer solution (2)).
）を得た。得られた重合体溶液（２）２００部に２８％
アンモニア水２．５部とする以外は参考例１と同様な操
作を行い、ポリシロキサングラフトポリマー水性分散体
（以下、水性分散体（２）という。）を得た。) was obtained. 28% to 200 parts of the obtained polymer solution (2)
A polysiloxane graft polymer aqueous dispersion (hereinafter referred to as aqueous dispersion (2)) was obtained by performing the same operation as in Reference Example 1 except that the ammonia water was 2.5 parts.
得られた水性分散体（２）は粘度７０ｃｐｓ（２５°Ｃ
，Ｂ型粘度計、６０ｒｐｍ）で−週間静置しても、分散
粒子の沈降やポリシロキサンの分離を起こさず安定なエ
マルションであった。また、残存するエチルアルコール
およびトルエンはそれぞれ２３０ｐｐｍ 、８７０ｐｐ
ｍであった。The resulting aqueous dispersion (2) had a viscosity of 70 cps (25°C
Even when the emulsion was allowed to stand for one week using a B-type viscometer (B-type viscometer, 60 rpm), the emulsion remained stable without sedimentation of the dispersed particles or separation of the polysiloxane. In addition, the remaining ethyl alcohol and toluene are 230 ppm and 870 ppm, respectively.
It was m.
参考例 ３
参考例１で用いたのと同様の四つロフラスコに末端ヒド
ロキシル基含有ポリシロキサンとして、平均分子量が４
８０００の直鎖状ジヒドロキシジメチルポリシロキサン
３部およびトルエン１００部を仕込み、窒素雰囲気下、
８０℃に昇温した。Reference Example 3 A polysiloxane having an average molecular weight of 4 was prepared as a polysiloxane containing a terminal hydroxyl group in a four-loaf flask similar to that used in Reference Example 1.
3 parts of 8000% linear dihydroxydimethylpolysiloxane and 100 parts of toluene were charged, and under a nitrogen atmosphere,
The temperature was raised to 80°C.
これにメタクリル酸メチル３０部、スチレン３０部、酢
酸ビニル２５部、アクリル酸１０部、２スチリル工チル
トリメトキシシラン５部およびアゾビスイソブチロニト
リル２部からなる単量体均一溶液を用いて、参考例１と
同様の初期重合操作および単量体均一溶液の滴下操作を
行った。単量体均一溶液の滴下終了後１５分間重合を継
続した時、イソプロピルアルコール１００部を加えて希
釈した。更に８０°Ｃで３時間４５分重合反応を継続し
たのち冷却して、ポリシロキサングラフトポリマーの溶
液（以下、重合体溶液（３）という。）を得た。得られ
た重合体溶液（３） ２００部に２８％アンモニア水２
部を攪拌下に添加し、１０分間攪拌を継続した後、水を
２３８部添加し、水分散化してポリシロキサン、グラフ
トポリマー水性分散体（以下、水性分散体（３）という
。）を得た。A homogeneous monomer solution consisting of 30 parts of methyl methacrylate, 30 parts of styrene, 25 parts of vinyl acetate, 10 parts of acrylic acid, 5 parts of 2-styryltrimethoxysilane and 2 parts of azobisisobutyronitrile was added to this. The same initial polymerization operation and dropping operation of a homogeneous monomer solution as in Reference Example 1 were performed. When the polymerization was continued for 15 minutes after the dropwise addition of the monomer homogeneous solution was completed, 100 parts of isopropyl alcohol was added to dilute the solution. The polymerization reaction was further continued at 80° C. for 3 hours and 45 minutes, and then cooled to obtain a polysiloxane graft polymer solution (hereinafter referred to as polymer solution (3)). 28% ammonia water to 200 parts of the obtained polymer solution (3)
After continuing stirring for 10 minutes, 238 parts of water was added and water-dispersed to obtain a polysiloxane graft polymer aqueous dispersion (hereinafter referred to as aqueous dispersion (3)). .
得られた水性分散体（３）は粘度７５０ｃｐｓ（２５°
Ｃ，Ｂ型粘度計、６０ｒｐｖａ）テ、−週間静置しても
、分散粒子の沈降やポリシロキサンの分離を起こさず安
定なエマルションであった。The resulting aqueous dispersion (3) had a viscosity of 750 cps (25°
C, Type B viscometer, 60 rpm) The emulsion remained stable without sedimentation of the dispersed particles or separation of the polysiloxane even after being allowed to stand for weeks.
参考例 ４
参考例２のアクリロニトリルの量を２０部から５部に、
およびアクリル酸の量を５部から２０部にする以外は参
考例２と同様な操作を行い、ポリシロキサングラフトポ
リマー水性分散体（以下、水性分散体（４）という。）
を得た。得られた水性分散体（４）は粘度２２０ｃｐｓ
（２５℃、Ｂ型粘度計、６０ ｒｐｍ ）で、−週間静
置しても分散粒子の沈降やポリシロキサンの分離を起こ
さず安定なエマルションであった。また、残存するエチ
ルアルコールおよびトルエンはそれぞれ３００ ｐｐｍ
、１ｌ１００ｐｐであった。Reference Example 4 The amount of acrylonitrile in Reference Example 2 was changed from 20 parts to 5 parts,
The same operation as in Reference Example 2 was performed except that the amount of acrylic acid was changed from 5 parts to 20 parts to obtain a polysiloxane graft polymer aqueous dispersion (hereinafter referred to as aqueous dispersion (4)).
I got it. The resulting aqueous dispersion (4) has a viscosity of 220 cps
(25° C., Type B viscometer, 60 rpm) The emulsion remained stable without sedimentation of the dispersed particles or separation of the polysiloxane even after being allowed to stand for a week. In addition, residual ethyl alcohol and toluene are each 300 ppm.
, 1l 100pp.
参考例 ５
参考例１で用いた末端ヒドロキシル基含有ポリシロキサ
ンの代わりに末端ヒドロキシル基を平均４個有し、平均
分子量が２６００００の一部枝分れした分岐状ジメチル
ポリシロキサンの３０重量％トルエン溶液を用いる以外
は参考例１と同様な操作を行い、ポリシロキサングラフ
トポリマー水性分散体（以下、水性分散体（５）という
。）を得た。得られた水性分散体（５）は粘度１２ｃｐ
ｓ（２５°Ｃ，Ｂ型粘度計、６０ｒρｆｆ１）で、−週
間静置しても、分散粒子の沈降やポリシロキサンの分離
も起こさず安定なエマルションであった。また、残存す
るイソプロピルアルコールおよびトルエンはそれぞれ７
０ｐｐｍ 、 ８００ｐｐｍであった。Reference Example 5 Instead of the terminal hydroxyl group-containing polysiloxane used in Reference Example 1, a 30% by weight toluene solution of partially branched dimethyl polysiloxane having an average of 4 terminal hydroxyl groups and an average molecular weight of 260,000 was used. The same operation as in Reference Example 1 was performed except that a polysiloxane graft polymer aqueous dispersion (hereinafter referred to as aqueous dispersion (5)) was obtained. The resulting aqueous dispersion (5) had a viscosity of 12 cp.
The emulsion remained stable, with no sedimentation of the dispersed particles or separation of the polysiloxane, even when the emulsion was allowed to stand for a week at 25° C., B-type viscometer, 60 rρff1. In addition, the remaining isopropyl alcohol and toluene are each 7
They were 0 ppm and 800 ppm.
比較参考例 １
参考例１におけるγ−メタクリロキシプロピルトリメト
キシシランを用いない以外は、参考例１と全く同様にし
て、比較用の重合体溶液（以下、比較用重合体溶液（１
）という。）を得た。得られた比較用重合体溶液（１）
１４０部にイソプロピルアルコール６０部を加えて希Ｉ
Ｒ後、２８％アンモニア水３部を攪拌下に添加し、１０
分間攪拌を接続した後、水を２３７部添加し、水分散化
して比較用の水性分散体（以下、比較用水性分散体（１
）という。）を得た。得られた比較用水性分散体（１）
は−晩静置するとポリシロキサンが上層に分離した。Comparative Reference Example 1 A comparative polymer solution (hereinafter referred to as a comparative polymer solution (1
). ) was obtained. Obtained comparative polymer solution (1)
Add 60 parts of isopropyl alcohol to 140 parts to dilute I
After R, 3 parts of 28% ammonia water was added with stirring, and 10
After stirring for a minute, 237 parts of water was added and water-dispersed to obtain a comparative aqueous dispersion (hereinafter referred to as "comparative aqueous dispersion").
). ) was obtained. Obtained comparative aqueous dispersion (1)
When the mixture was allowed to stand overnight, the polysiloxane separated into an upper layer.
比較参考例 ２
参考例１における末端ヒドロキシル基含有ポリシロキサ
ンを用いない以外は、参考例１と全く同様にして得られ
た重合体溶液３０２部に、参考例１で用いたのと同様の
末端ヒドロキシル基含有ポリシロキサンを３０重量％ト
ルエン溶液として１０部加え、よく混合して比較用の重
合体溶液（以下、比較用重合体溶液（２）という。）を
得た。得られた比較用重合体溶液（２）１４０部にイソ
プロピルアルコール６０部を加えて希釈後に２８％アン
モニア水３部を攪拌下に添加し、１０分間攪拌を継続し
た後、水を２３７部添加し、水分散化して比較用の水性
分散体（以下、比較用水性分散体（２）という。）を得
た。得られら比較用水性分散体（２）は−晩静置すると
ポリシロキサンが上層に分離した。Comparative Reference Example 2 The same terminal hydroxyl group-containing polysiloxane as used in Reference Example 1 was added to 302 parts of a polymer solution obtained in exactly the same manner as in Reference Example 1, except that the terminal hydroxyl group-containing polysiloxane in Reference Example 1 was not used. 10 parts of group-containing polysiloxane as a 30% by weight toluene solution were added and mixed well to obtain a comparative polymer solution (hereinafter referred to as comparative polymer solution (2)). After diluting 140 parts of the obtained comparative polymer solution (2) with 60 parts of isopropyl alcohol, 3 parts of 28% ammonia water was added with stirring, and after continuing stirring for 10 minutes, 237 parts of water was added. , to obtain a comparative aqueous dispersion (hereinafter referred to as comparative aqueous dispersion (2)). When the obtained comparative aqueous dispersion (2) was allowed to stand overnight, the polysiloxane separated into an upper layer.
比較参考例 ３
参考例１のアクリル酸の量を５部から０．５部にする以
外は参考例１と同様な操作を行い、比較用のポリシロキ
サングラフトポリマー水性分散体（以下、比較用水性分
散体（３）という。）を得た。得られた比較用水性分散
体（３）は−週間静置すると粒子が沈降し、上層に透明
な水層部分が分離した。Comparative Reference Example 3 The same operation as in Reference Example 1 was performed except that the amount of acrylic acid in Reference Example 1 was changed from 5 parts to 0.5 parts, and a comparative polysiloxane graft polymer aqueous dispersion (hereinafter referred to as comparative aqueous dispersion) was prepared. A dispersion (referred to as dispersion (3)) was obtained. When the obtained comparative aqueous dispersion (3) was allowed to stand for a week, the particles settled and a transparent aqueous layer was separated in the upper layer.
比較参考例 ４
参考例１で用いたのと同様の四つロフラスコに脱イオン
水２２０部とアニオン系乳化剤１部を仕込み、窒素雰囲
気下８０°Ｃに昇温した。一方で、ジメチルシロキサン
部分の分子量が１０，０００で末端がメタクリロキシプ
ロピル基とメチル基であるポリシロキサンマクロマー３
部、メタクリル酸メチル７０部、アクリル酸ブチル２０
部、アクリル酸５部、γ−メタクリロキシプロピルトリ
メトキシシラン５ｇ１ｌからなる単量体均一溶液を調整
した。この単量体均一溶液の１０重量％相当量および過
硫酸アンモニウムの１０％水溶液１ｏ部を上記四つロフ
ラスコに加えると共に、８０℃に昇温しで１０分間初期
乳化重合を行った。初期乳化重合を終了した後、同温度
で残りの単量体均一溶液を２時間かけて滴下し、更に引
き続き温度を８０°Ｃに保持しながら２時間攪拌を続行
して重合反応を継続して乳化重合反応を完結させた。こ
うして得られた比較用ポリシロキサングラフトポリマー
水性分散体（以下、水性分散体（４）という。）は静置
すると上層にポリシロキサン分が分離し、均一な水性分
散体を得られかった。Comparative Reference Example 4 220 parts of deionized water and 1 part of anionic emulsifier were charged into a four-loaf flask similar to that used in Reference Example 1, and the temperature was raised to 80°C under a nitrogen atmosphere. On the other hand, polysiloxane macromer 3 whose dimethylsiloxane moiety has a molecular weight of 10,000 and terminals are methacryloxypropyl and methyl groups.
parts, methyl methacrylate 70 parts, butyl acrylate 20 parts
A homogeneous monomer solution was prepared containing 5 parts of acrylic acid and 5 g of γ-methacryloxypropyltrimethoxysilane. An amount equivalent to 10% by weight of this homogeneous monomer solution and 10 parts of a 10% aqueous solution of ammonium persulfate were added to the four-lobe flask, and the temperature was raised to 80° C. to carry out initial emulsion polymerization for 10 minutes. After completing the initial emulsion polymerization, the remaining monomer homogeneous solution was added dropwise over 2 hours at the same temperature, and stirring was continued for 2 hours while maintaining the temperature at 80°C to continue the polymerization reaction. The emulsion polymerization reaction was completed. When the comparative polysiloxane graft polymer aqueous dispersion thus obtained (hereinafter referred to as aqueous dispersion (4)) was allowed to stand, the polysiloxane component separated into the upper layer, and a uniform aqueous dispersion could not be obtained.
実施例１〜８および比較例１〜５
参考例１〜５で得た水性分散体（１）〜（５）、比較参
考例１〜４で得た比較用水性分散体（１）〜（４）およ
び重合体溶液（１）各々の固形分１００部に第１表に示
した種類および量の水溶性樹脂と架橋剤を加え、室温で
１５分間攪拌して本発明の表面改質組成物（１）〜（８
）および比較用表面改質組酸物（１）〜（５）を調整し
た。Examples 1 to 8 and Comparative Examples 1 to 5 Aqueous dispersions (1) to (5) obtained in Reference Examples 1 to 5, comparative aqueous dispersions (1) to (4) obtained in Comparative Reference Examples 1 to 4 ) and polymer solution (1). Water-soluble resins and crosslinking agents of the types and amounts shown in Table 1 were added to 100 parts of the solid content of each, and the mixture was stirred at room temperature for 15 minutes to obtain the surface-modified composition of the present invention ( 1)～(8
) and comparative surface-modified acid compounds (1) to (5) were prepared.
能
これらの組成物について、下記に示す性≠試験方法によ
り性能評価した。評価結果は第１表に示す。なお、滑り
性と撥水性についてはガラス板の測定値も参考として示
した。The performance of these compositions was evaluated using the following test method. The evaluation results are shown in Table 1. In addition, regarding the slipperiness and water repellency, the measured values of the glass plate are also shown as a reference.
ｌ）滑り性ニガラス板上に表面改質組成物を１．５用の
厚さに塗布し、１００°Ｃで１分間乾燥後、１晩放置し
たものを試験片として、塗膜の動摩擦係数を測定するこ
とにより、滑り性を評価した。動摩擦係数は表面性測定
機（新来科学社製、ＨＥＩＤＯＮ−１４型）を用いて測
定した。l) Surface modification composition was coated on a slippery glass plate to a thickness of 1.5 mm, dried at 100°C for 1 minute, and left overnight as a test piece.The coefficient of kinetic friction of the coating film was determined. The slipperiness was evaluated by measurement. The coefficient of dynamic friction was measured using a surface property measuring device (manufactured by Shinraikagakusha, HEIDON-14 type).
２）撥水性：試験片は滑り性試験と同じものを用いた。2) Water repellency: The same test piece as used in the slip test was used.
塗膜の水に対する接触角を測定することにより撥水性を
評価した。接触角は接触角測定装置（協和界面科学社製
、ＣＡＡ型）を用い、液滴法で測定した。Water repellency was evaluated by measuring the contact angle of the coating film with water. The contact angle was measured by a droplet method using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., CAA type).
３ ） ｍ熱性： ＨＥＮ ６ ｐ−のポリエステルフ
ィルムの片面に表面改質組成物を！、５角の厚さに塗布
し、１００°Ｃで１分間乾燥後、１晩放置し、もう片面
に熱溶融性インキを塗布した。表面改質組成物の塗布面
をサーマルヘッド側にして受像紙と重ね、サーマルヘッ
ド印字試験装置（松下電子部品■製）を使用して、記録
紙に熱転写試験した。なお、試験条件は、印加電圧は２
０Ｖ、印字速度は２ミリ秒であった。耐熱性は熱転写試
験時の熱ステイツク現象の有無をフィルムの走行状態を
観察することにより評価した。3) Heat resistance: Surface modification composition on one side of HEN 6 p- polyester film! After drying at 100° C. for 1 minute, the ink was left to stand overnight, and the other side was coated with hot-melt ink. The coated surface of the surface-modifying composition was placed on an image-receiving paper with the surface facing the thermal head, and a thermal transfer test was performed on the recording paper using a thermal head printing test device (manufactured by Matsushita Electronics Parts). The test conditions were that the applied voltage was 2
0V and printing speed was 2 milliseconds. Heat resistance was evaluated by observing the running state of the film to determine whether there was a heat stick phenomenon during a thermal transfer test.
剥離性および耐マイグレーション性：上質紙に表面改質
組成物を１５川の厚さに塗布し、１３０℃で１０分間乾
燥後、室温で２時間放置して得た塗膜に、粘着テープに
チバンポリエステルテープ）を圧着した。Peelability and migration resistance: The surface-modifying composition was applied to a thickness of 15 mm on high-quality paper, dried at 130°C for 10 minutes, and then left at room temperature for 2 hours. (Van polyester tape) was crimped.
これを３５°Ｃで１週間保存した後、上質紙から粘着テ
ープを剥離し、剥離力を測定することにより剥離性を評
価した。また、その剥離した粘着テープをステンレス板
に圧着して、粘着テープの残留接着力を測定することに
より耐マイグレーション性を評価した。なお、剥離力お
よび残留接着力は１８０度剥離試験による剥離力で表わ
し、剥離速度は３０ｃｍ／分で行った。After storing this at 35°C for one week, the adhesive tape was peeled off from the high-quality paper, and the peelability was evaluated by measuring the peeling force. In addition, the peeled adhesive tape was pressure-bonded to a stainless steel plate, and the residual adhesive strength of the adhesive tape was measured to evaluate migration resistance. The peeling force and residual adhesive strength are expressed as the peeling force determined by a 180 degree peel test, and the peeling speed was 30 cm/min.
残留接着力の大小により表面改質組成物の耐マイグレー
ション性が評価できる。残留接着力が大きい場合、塗膜
の層間剥離が起こりにくく、耐マイグレーション性は良
好である。また、残留接着力の小さい場合、塗膜の層間
剥＃：（特に塗膜中のポリシロキサン成分の脱落）が容
易に起こり、耐マイグレーション性は不良である。The migration resistance of the surface-modified composition can be evaluated based on the level of residual adhesive strength. When the residual adhesive strength is large, interlayer peeling of the coating film is less likely to occur and migration resistance is good. Furthermore, when the residual adhesive strength is small, delamination of the coating film (particularly, shedding of the polysiloxane component in the coating film) easily occurs, resulting in poor migration resistance.
Claims (1)
２０重量％存在下に、重合性シラン化合物（Ｂ）０．０
５〜１０重量％、不飽和有機酸（Ｃ）１〜３０重量％お
よびこれらと共重合可能な他の重合性単量体（Ｄ）４０
〜９７．９５重量％（但し、（Ａ）、（Ｂ）、（Ｃ）お
よび（Ｄ）成分の合計は１００重量％とする。）をアル
コール系以外の有機溶剤中で重合させて得られる重合体
の溶液に、塩基性化合物および水を加えた液状物を攪拌
して得られるポリシロキサングラフトポリマーの塩基性
化合物による塩の水性分散体および水溶性樹脂を、該水
性分散体１００重量部（固形分換算）当り該水溶性樹脂
が０〜５０重量部の割合で含んでなる表面改質組成物。 ２、ポリシロキサングラフトポリマー水性分散体が塩基
性化合物の添加量をポリシロキサングラフトポリマー中
の酸基の２０〜２００モル％相当量とし、水の添加量を
ポリシロキサングラフトポリマー１００重量部に対して
３０〜１０００重量部とすると共に、水の添加前又は添
加後の該液状物中の水溶性有機溶剤の量を有機溶剤の全
量に対して３０〜１００重量％とすることにより得られ
たものである請求項１記載の表面改質組成物。 ３、ポリシロキサングラフトポリマーの塩基性化合物に
よる塩の水性分散体が水に分散した後、更に脱溶剤した
、ポリシロキサングラフトポリマーの塩基性化合物によ
る塩の水性分散体である請求項１または請求項２記載の
表面改質組成物。 ４、架橋剤を併用する請求項１〜３のいずれか１項に記
載の表面改質組成物。 ５、水溶性樹脂がポリシロキサングラフトポリマー水性
分散体１００重量部（固形分換算）に対して０．０１〜
２０重量部の割合である請求項１〜４のいずれか１項に
記載の表面改質組成物。 ６、水溶性樹脂がポリビニルアルコールである請求項１
〜５のいずれか１項に記載の表面改質組成物。[Claims] 1. Polysiloxane containing terminal hydroxyl group (A) 1-
In the presence of 20% by weight, 0.0% of polymerizable silane compound (B)
5 to 10% by weight, unsaturated organic acid (C) 1 to 30% by weight, and other polymerizable monomers copolymerizable with these (D) 40
Polymer obtained by polymerizing ~97.95% by weight (however, the total of components (A), (B), (C) and (D) is 100% by weight) in an organic solvent other than alcohol-based An aqueous dispersion of a salt of a basic compound of a polysiloxane graft polymer obtained by stirring a liquid obtained by adding a basic compound and water to the combined solution and a water-soluble resin were added to 100 parts by weight of the aqueous dispersion (solid). A surface-modifying composition comprising 0 to 50 parts by weight of the water-soluble resin. 2. In the polysiloxane graft polymer aqueous dispersion, the amount of basic compound added is equivalent to 20 to 200 mol% of the acid groups in the polysiloxane graft polymer, and the amount of water added is adjusted to 100 parts by weight of the polysiloxane graft polymer. 30 to 1000 parts by weight, and the amount of water-soluble organic solvent in the liquid before or after addition of water is 30 to 100% by weight based on the total amount of organic solvent. A surface modification composition according to claim 1. 3. An aqueous dispersion of a salt of a basic compound of a polysiloxane graft polymer is dispersed in water, and then the solvent is removed.Claim 1 or Claim 3. 2. The surface modification composition according to 2. 4. The surface modification composition according to any one of claims 1 to 3, in which a crosslinking agent is used in combination. 5. The water-soluble resin is 0.01 to 100 parts by weight (in terms of solid content) of the polysiloxane graft polymer aqueous dispersion.
Surface modification composition according to any one of claims 1 to 4, in a proportion of 20 parts by weight. 6.Claim 1, wherein the water-soluble resin is polyvinyl alcohol.
5. The surface modification composition according to any one of items 5 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1027504A JPH0778196B2 (en) | 1989-02-08 | 1989-02-08 | Surface modification composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1027504A JPH0778196B2 (en) | 1989-02-08 | 1989-02-08 | Surface modification composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02208310A true JPH02208310A (en) | 1990-08-17 |
| JPH0778196B2 JPH0778196B2 (en) | 1995-08-23 |
Family
ID=12222970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1027504A Expired - Fee Related JPH0778196B2 (en) | 1989-02-08 | 1989-02-08 | Surface modification composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0778196B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5510187A (en) * | 1993-04-27 | 1996-04-23 | Minnesota Mining And Manufacturing Company | Magnetic recording medium whose magnetic layer incorporates nonhalogenated vinyl copolymer and specified polyurethane polymer |
| US5674604A (en) * | 1995-03-31 | 1997-10-07 | Minnesota Mining And Manufacturing Company | Magnetic recording medium comprising magnetic particles, binder, and a non halogenated vinyl oligomer dispersant |
| JPH1036514A (en) * | 1996-07-26 | 1998-02-10 | Dainippon Ink & Chem Inc | Aqueous resin, its production and aqueous curable resin composition comprising the same |
| JPH1036515A (en) * | 1996-07-30 | 1998-02-10 | Dainippon Ink & Chem Inc | Aqueous resin, its production and aqueous curable resin composition comprising the same |
| GB2354765A (en) * | 1999-09-28 | 2001-04-04 | Hitachi Maxell | Dispersion composition and method for producing the same |
| JP2001271031A (en) * | 2000-03-28 | 2001-10-02 | Dainippon Toryo Co Ltd | Coating composition |
| JP2007525411A (en) * | 2003-04-14 | 2007-09-06 | ザ プロクター アンド ギャンブル カンパニー | Anhydrous silicone-modified fluorinated polymer for color transfer resistant lip cosmetic composition |
| CN113943533A (en) * | 2021-11-12 | 2022-01-18 | 上海三棵树防水技术有限公司 | High-permeability rubber asphalt waterproof coating and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61215629A (en) * | 1985-03-22 | 1986-09-25 | Nippon Shokubai Kagaku Kogyo Co Ltd | Surface modifying composition |
-
1989
- 1989-02-08 JP JP1027504A patent/JPH0778196B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61215629A (en) * | 1985-03-22 | 1986-09-25 | Nippon Shokubai Kagaku Kogyo Co Ltd | Surface modifying composition |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5510187A (en) * | 1993-04-27 | 1996-04-23 | Minnesota Mining And Manufacturing Company | Magnetic recording medium whose magnetic layer incorporates nonhalogenated vinyl copolymer and specified polyurethane polymer |
| US5674604A (en) * | 1995-03-31 | 1997-10-07 | Minnesota Mining And Manufacturing Company | Magnetic recording medium comprising magnetic particles, binder, and a non halogenated vinyl oligomer dispersant |
| JPH1036514A (en) * | 1996-07-26 | 1998-02-10 | Dainippon Ink & Chem Inc | Aqueous resin, its production and aqueous curable resin composition comprising the same |
| JPH1036515A (en) * | 1996-07-30 | 1998-02-10 | Dainippon Ink & Chem Inc | Aqueous resin, its production and aqueous curable resin composition comprising the same |
| GB2354765A (en) * | 1999-09-28 | 2001-04-04 | Hitachi Maxell | Dispersion composition and method for producing the same |
| US6627696B1 (en) | 1999-09-28 | 2003-09-30 | Hitachi Maxell, Ltd. | Dispersion composition and method for producing the same |
| GB2354765B (en) * | 1999-09-28 | 2004-02-04 | Hitachi Maxell | Dispersion composition and method for producing the same |
| US6936657B2 (en) | 1999-09-28 | 2005-08-30 | Hitachi Maxell, Ltd. | Dispersion composition and method for producing the same |
| JP2001271031A (en) * | 2000-03-28 | 2001-10-02 | Dainippon Toryo Co Ltd | Coating composition |
| JP2007525411A (en) * | 2003-04-14 | 2007-09-06 | ザ プロクター アンド ギャンブル カンパニー | Anhydrous silicone-modified fluorinated polymer for color transfer resistant lip cosmetic composition |
| CN113943533A (en) * | 2021-11-12 | 2022-01-18 | 上海三棵树防水技术有限公司 | High-permeability rubber asphalt waterproof coating and preparation method thereof |
| CN113943533B (en) * | 2021-11-12 | 2023-03-28 | 上海三棵树防水技术有限公司 | High-permeability rubber asphalt waterproof coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0778196B2 (en) | 1995-08-23 |
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