JPS63248872A - Composition for treating metallic surface - Google Patents
Composition for treating metallic surfaceInfo
- Publication number
- JPS63248872A JPS63248872A JP8110787A JP8110787A JPS63248872A JP S63248872 A JPS63248872 A JP S63248872A JP 8110787 A JP8110787 A JP 8110787A JP 8110787 A JP8110787 A JP 8110787A JP S63248872 A JPS63248872 A JP S63248872A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- acrylic resin
- weight
- cationic
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 47
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 31
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 28
- 239000010959 steel Substances 0.000 claims abstract description 28
- 125000002091 cationic group Chemical group 0.000 claims abstract description 25
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 17
- 229920001577 copolymer Polymers 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000004069 aziridinyl group Chemical group 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 239000011701 zinc Substances 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 39
- 238000004381 surface treatment Methods 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 20
- 229910000851 Alloy steel Inorganic materials 0.000 claims description 8
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 5
- 229910052681 coesite Inorganic materials 0.000 abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract 2
- 229910045601 alloy Inorganic materials 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000010408 film Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 15
- 238000000576 coating method Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 11
- -1 ethylene, propylene Chemical group 0.000 description 11
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 230000000903 blocking effect Effects 0.000 description 10
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 239000003431 cross linking reagent Substances 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 239000004908 Emulsion polymer Substances 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 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
- 125000000129 anionic group Chemical group 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007739 conversion coating Methods 0.000 description 2
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 2
- ORHSGYTWJUDWKU-UHFFFAOYSA-N dimethoxymethyl(ethenyl)silane Chemical compound COC(OC)[SiH2]C=C ORHSGYTWJUDWKU-UHFFFAOYSA-N 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- PZWQOGNTADJZGH-SNAWJCMRSA-N (2e)-2-methylpenta-2,4-dienoic acid Chemical compound OC(=O)C(/C)=C/C=C PZWQOGNTADJZGH-SNAWJCMRSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- PRPINYUDVPFIRX-UHFFFAOYSA-N 1-naphthaleneacetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CC=CC2=C1 PRPINYUDVPFIRX-UHFFFAOYSA-N 0.000 description 1
- VYONOYYDEFODAJ-UHFFFAOYSA-N 2-(1-Aziridinyl)ethanol Chemical compound OCCN1CC1 VYONOYYDEFODAJ-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
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- UWHCZFSSKUSDNV-UHFFFAOYSA-N 3-(aziridin-1-yl)propanoic acid;2-ethyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound OC(=O)CCN1CC1.OC(=O)CCN1CC1.OC(=O)CCN1CC1.CCC(CO)(CO)CO UWHCZFSSKUSDNV-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
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- QGJPEZISMDKYLK-HSSWLXNDSA-N Myxalamid C Chemical compound CC\C=C(/C)[C@H](O)[C@H](C)\C=C(/C)\C=C\C=C/C=C/C=C(\C)C(=O)N[C@@H](C)CO QGJPEZISMDKYLK-HSSWLXNDSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- FYAMXEPQQLNQDM-UHFFFAOYSA-N Tris(1-aziridinyl)phosphine oxide Chemical compound C1CN1P(N1CC1)(=O)N1CC1 FYAMXEPQQLNQDM-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- YETKGQMGLZKKGE-UHFFFAOYSA-N acetic acid;chromium Chemical compound [Cr].CC(O)=O YETKGQMGLZKKGE-UHFFFAOYSA-N 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XTSFUENKKGFYNX-UHFFFAOYSA-N bis(aziridin-1-yl)methanone Chemical compound C1CN1C(=O)N1CC1 XTSFUENKKGFYNX-UHFFFAOYSA-N 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- JNNKWUPPLJTSSJ-UHFFFAOYSA-N chloromethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCl JNNKWUPPLJTSSJ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000004185 ester group Chemical group 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
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- YVOQADGLLJCMOE-UHFFFAOYSA-N n-[6-(aziridine-1-carbonylamino)hexyl]aziridine-1-carboxamide Chemical compound C1CN1C(=O)NCCCCCCNC(=O)N1CC1 YVOQADGLLJCMOE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- IUCJMVBFZDHPDX-UHFFFAOYSA-N tretamine Chemical compound C1CN1C1=NC(N2CC2)=NC(N2CC2)=N1 IUCJMVBFZDHPDX-UHFFFAOYSA-N 0.000 description 1
- 229950001353 tretamine Drugs 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は鉄、鋼、合金鋼、亜鉛、亜鉛合金から選ばれる
少なくとも一種の金属表面処理用組成物に関するもので
ある。詳しくは、金属表面に高耐食性や塗装下地性を付
与し、金属表面への密着性、深絞り加工性、耐溶剤性、
潤滑性に優れ、かつ耐ブロッキング性にも優れた鉄、鋼
、合金鋼、亜鉛、亜鉛合金から選ばれる少なくとも一種
の金属表面処理用組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a composition for treating the surface of at least one metal selected from iron, steel, alloy steel, zinc, and zinc alloy. In detail, we provide high corrosion resistance and paint base properties to metal surfaces, adhesion to metal surfaces, deep drawability, solvent resistance,
The present invention relates to a composition for treating the surface of at least one metal selected from iron, steel, alloy steel, zinc, and zinc alloy, which has excellent lubricity and anti-blocking properties.
（従来の技術）
従来、金属表面に耐食性を付与したり塗料との密着性を
向上させるための塗装下地性を付与する目的でクロム酸
塩処理あるいはリン酸塩処理が行われている。(Prior Art) Conventionally, chromate treatment or phosphate treatment has been carried out for the purpose of imparting corrosion resistance to metal surfaces and providing a coating base for improving adhesion with paint.
この内、クロム酸塩処理方法では耐食性はかなり良好で
あるが塗装下地性や深絞り加工性が不充分であり、又リ
ン酸塩処理方法では耐食性や深絞り加工性が不充分等の
欠点を有している。これらの改良方法として種々の方法
が提案されているが、性能、作業性において問題点を有
している。Among these, the chromate treatment method has fairly good corrosion resistance, but the coating base properties and deep drawing workability are insufficient, and the phosphate treatment method has disadvantages such as insufficient corrosion resistance and deep drawing workability. have. Various methods have been proposed to improve these methods, but they have problems in performance and workability.
このようなことから、特開昭５７−１４３３５９号、及
び特開昭６０−２２１４５０号に、水分散シリカ、ジア
ルコキシシラン及び／又は、トリアルコキシシラン化合
物の加水分解物、陽イオン性樹脂及び／又は両性イオン
性樹脂並びにクロム化合物の特定比率からなる金属表面
処理用組成物などが提案されている。For this reason, JP-A-57-143359 and JP-A-60-221450 disclose hydrolyzates of water-dispersed silica, dialkoxysilane and/or trialkoxysilane compounds, cationic resins and/or Alternatively, a metal surface treatment composition comprising a specific ratio of an amphoteric ionic resin and a chromium compound has been proposed.
（発明が解決しようとする問題点）
特開昭６０−２２１４５０号に提案された、金属表面処
理用組成物は、たしかに、耐食性、作業性、絞り加工性
、耐ブロッキング性に優れるが、一方で、耐溶剤性、潤
滑性、硬さ、塗装下地性においては、かならずしも満足
のいくものではなかった。(Problems to be Solved by the Invention) The composition for metal surface treatment proposed in JP-A No. 60-221450 is certainly excellent in corrosion resistance, workability, drawing workability, and blocking resistance, but on the other hand, , solvent resistance, lubricity, hardness, and coating base properties were not always satisfactory.
従って本発明は、特開昭６０−２２１４５０号に提案さ
れた金属表面処理用組成物の特徴をそのまま生かし、さ
らに耐溶剤性、潤滑性、硬さ、塗装下地性にも優れた金
属表面処理用組成物の製造方法を提供するものである。Therefore, the present invention utilizes the characteristics of the metal surface treatment composition proposed in JP-A No. 60-221450, and further provides a metal surface treatment composition with excellent solvent resistance, lubricity, hardness, and coating base properties. A method for producing a composition is provided.
（問題点を解決するための手段）
本発明は、鉄、鋼、合金鋼、亜鉛、亜鉛合金から選ばれ
る少なくとも一種の金属表面処理用組成物１１当り、
（Ａ）水分散性シリカ（Ｉ）をＳ ｉ Ｏ２に換算して
０．５〜２５０ｇの範囲の量、
（Ｂ）重合性不飽和基を有する７”ルコキシシラン化合
物（ａ）０．１〜１０重量％型
巣合性不飽和カルボン酸（ｂ）０〜２０重量％、
アルキル基の炭素数が１〜８である（メタ）アクリル酸
アルキルエステル（ｃ）２０〜９９重量％、
これらと共重合可能な単量体（ｄ）０〜４０７Ｔ！量％
、
［ただし、（ａ）、（ｂ）、（ｃ）および（ｄ）の合計
は１００重量％である６］からなる単量体成分を多段乳
化重合して得られる芯部分のＴｇが１５℃以上であり、
最外殻部分のＴｇが１０℃以下である多層構造共重合体
から誘導される陽イオン性及び／又は両性イオン性アク
リル系樹脂（ＩＩ）を０．５〜６００ｇの範囲の量、
（Ｃ）Ｔｇが１０℃以上である陽イオン性及び／又は両
性イオン性アクリル系樹脂（ＩＩ［）を０〜６００ｇの
範囲の量、
（Ｄ）陽イオン性及び／又は両性イオン性カルボキシル
化ポリオレフィン系樹脂（ＩＶ ）を０゜５〜６００ｇ
の範囲の量、
（ただし、（Ａ）（Ｂ）（Ｃ）および（Ｄ）の合計が、
７００ｇを超えない範囲）
（Ｅ）多官能のアジリジニル基を有する化合物を樹脂に
対する固形物の比率で０．１〜１０重量％、
を含有することを特徴とする金属表面処理用組成物に関
するものである。(Means for Solving the Problems) The present invention provides at least one metal surface treatment composition 11 selected from iron, steel, alloy steel, zinc, and zinc alloy, comprising: (A) water-dispersible silica (I); (B) 7" lukoxysilane compound having a polymerizable unsaturated group (a) 0.1 to 10% by weight of nesting unsaturated carboxylic acid (b) 0 to 20% by weight, (meth)acrylic acid alkyl ester whose alkyl group has 1 to 8 carbon atoms (c) 20 to 99% by weight, monomer copolymerizable with these (d) 0 to 407T!Amount%
, [However, the total of (a), (b), (c) and (d) is 100% by weight 6] The core portion obtained by multi-stage emulsion polymerization of the monomer component has a Tg of 15°C. That's all,
An amount in the range of 0.5 to 600 g of a cationic and/or amphoteric acrylic resin (II) derived from a multilayer structure copolymer whose outermost shell portion has a Tg of 10° C. or less; (C) An amount in the range of 0 to 600 g of a cationic and/or amphoteric acrylic resin (II[) having a Tg of 10° C. or higher, (D) a cationic and/or amphoteric carboxylated polyolefin resin ( IV) 0゜5~600g
amount within the range of (provided that the sum of (A), (B), (C), and (D) is
(within a range not exceeding 700 g) (E) A composition for metal surface treatment characterized by containing a compound having a polyfunctional aziridinyl group in a ratio of 0.1 to 10% by weight of solids to resin. be.
本発明に用いられる（Ａ）水分散性シリカ（Ｉ）とは、
一般に使用されているケイ酸の縮合体でコロイダルシリ
カであり、粒子径が２〜５０ｍμのものが好ましい、こ
の様な水分散性シリカ（Ｉ）としては例えば市販品とし
て、「スノーテックス０」 「スノーテックスＮ」 「
スノーテックスＮＣ８」 「スノーテックス２０」 Ｃ
スノーテックスＣ」「スノーテックスＳ」 「スノーテ
ックスＳＳ」「スノーテックスＸＳ、（以上、８産化学
工業（株）ｖ）、ｒｃａｔａｌｏｉｄ ＳＮ」「Ｃａ
ｔａｌｏｉｄ ５ｉ−３５０Ｊ ｒｃａｔａｌｏｉ
ｄＳｉ−５００Ｊ（以上、触媒化成工業（株）Ｖ）等が
ある。又、表面処理されたコロイダルシソ力例えばアル
ミン酸で処理されなｒｃａｔａｌｏｉｄｓＡ」 （触媒
化成工業（株）製）等も用いることができる。これらは
そのまま用いてもよいし、金属表面処理用組成物中での
その分散性を高めるためには、本発明の池の必須成分で
あるアクリル系樹脂（ＩＩ）あるいは第４級アンモニム
塩等のアミン類であらかじめ水分散性シリカ（Ｉ）の表
面処理をしなり、エチレンイミン等のアジリジン誘導体
を水分散性シリカ（Ｉ）表面上にグラフトさせて用いて
もよい、 水分散性シリカ（Ｉ）は、本発明の金属表面
処理用組成物ＩＪ！当り０６５〜２５０ｇの範囲の量含
有される。０．５ｇ未満の量では耐食性等の効果が不充
分であり、逆に２５０ｇを超えて用いると加工性が悪く
なり、いずれも好ましくない。The (A) water-dispersible silica (I) used in the present invention is:
Colloidal silica is a condensation product of silicic acid that is commonly used, and preferably has a particle size of 2 to 50 mμ. Examples of such water-dispersible silica (I) include commercially available products such as “Snowtex 0” and “Snowtex 0”. Snowtex N""
Snowtex NC8” “Snowtex 20” C
Snowtex C", "Snowtex S", "Snowtex SS", "Snowtex
taloid 5i-350J rcataloi
Examples include dSi-500J (all manufactured by Catalysts & Chemicals Co., Ltd. V). Furthermore, surface-treated colloidal cataboloids such as ``Cataloids A'' (manufactured by Catalysts Kasei Kogyo Co., Ltd.) which have not been treated with aluminic acid can also be used. These may be used as they are, but in order to improve their dispersibility in the composition for metal surface treatment, acrylic resin (II) or quaternary ammonium salt, etc., which are essential components of the pond of the present invention, may be used. Water-dispersible silica (I) may be used by pre-surface treatment of water-dispersible silica (I) with amines and grafting an aziridine derivative such as ethyleneimine onto the surface of water-dispersible silica (I). is the metal surface treatment composition IJ! of the present invention. The content ranges from 0.65 to 250 g per serving. If the amount is less than 0.5 g, effects such as corrosion resistance will be insufficient, and if it is used in excess of 250 g, processability will deteriorate, and both are not preferred.
本発明に用いられる（Ｂ）アクリル系樹脂（Ｉ（）とは
、重合性不飽和基を有するアルコキシシラン化合物（ａ
）０．１〜１０重量％、重合性不飽和カルボン酸くｂ）
０〜２０ｆ！量％、アルキル基の炭素数が１〜８である
（メタ）アクリル酸アルキルエステル（Ｃ）２０〜９９
ｆ！量％、これらと共重合可能な単量体（ｄ）０〜４０
重量％（但し、（ａ）、（ｂ）、（ｃ）及び（ｄ）の合
計は１００重量％である。）からなる単量体成分を多段
乳化重合して得られる芯部分のＴｇが１５℃以上であり
、最外殻部分のＴｇが１０°Ｃ以下である多層構造共重
合体から誘導される陽イオン性及び／又は両性イオン性
アクリル系樹脂である。ここでぃう多段乳化重合とは、
まず、前記単量体成分の中から、一部成分をその重合体
のＴｇが１５℃以上となるように選び、この一部成分を
第１段目として公知の乳化重合法で乳化重合し、得られ
た重合体（これを芯部分という）の存在下に、残りの単
量体成分を用いて第２段目以降の乳化重合を逐次行う方
法である。この際、第２段目以降は第１段目で使用した
残りの単量体成分を全量用いることによって２段重合と
してもよく、あるいは適宜分割することによって３段以
上の重合としてもよい。The acrylic resin (B) used in the present invention (I()) is an alkoxysilane compound having a polymerizable unsaturated group (a
) 0.1 to 10% by weight, polymerizable unsaturated carboxylic acid b)
0~20f! Amount %, (meth)acrylic acid alkyl ester (C) in which the alkyl group has 1 to 8 carbon atoms, 20 to 99
f! Amount %, monomer (d) copolymerizable with these 0 to 40
% by weight (however, the total of (a), (b), (c) and (d) is 100% by weight)) The core portion obtained by multi-stage emulsion polymerization has a Tg of 15 It is a cationic and/or amphoteric acrylic resin derived from a multilayer structure copolymer having a temperature of 10° C. or higher and a Tg of the outermost shell portion of 10° C. or lower. What is multi-stage emulsion polymerization?
First, from among the monomer components, some components are selected so that the Tg of the polymer is 15 ° C. or more, and this part is emulsion polymerized as the first stage by a known emulsion polymerization method, In this method, in the presence of the obtained polymer (this is referred to as a core portion), the remaining monomer components are used to sequentially perform emulsion polymerization in the second and subsequent stages. At this time, from the second stage onward, the remaining monomer components used in the first stage may be used in their entirety to perform two-stage polymerization, or by appropriately dividing the polymerization to three or more stages.
そして最終段目の組成の重合体を最外殻部分という０本
発明では最外殻部分のＴｇは１０℃以下であることが必
要である。多段乳化重合としては一般には２段〜３段の
重合が用いられ、又、芯部分とその他の部分の比率は１
０：９０から９０＝１０の重量比の範囲で重合させるこ
とが好ましい。In the present invention, the polymer having the composition of the final stage is referred to as the outermost shell portion. In the present invention, the Tg of the outermost shell portion must be 10° C. or less. Generally, two to three stages of polymerization are used as multistage emulsion polymerization, and the ratio of the core part to the other parts is 1.
It is preferable to polymerize at a weight ratio of 0:90 to 90=10.
この様な方法によって得られた重合体を本発明では多層
構造共重合体と称する。A polymer obtained by such a method is referred to as a multilayer structure copolymer in the present invention.
本発明の多層構造共重合体を構成する重合体単量体成分
の具体的な例は、アルコキシシラン化合物（ａ）として
は、ビニルジメトキシメチルシラン、ビニルトリス（β
−メトキシエトキシ）シラン、ビニルトリエトキシシラ
ン、ビニルトリメトキシシラン、γ−メタアクリロキシ
プロピルトリメトキシシラン、γ−メタアクリロキシプ
ロピルメチルジメトキシシラン等をあげることができる
。Specific examples of polymer monomer components constituting the multilayer structure copolymer of the present invention include vinyldimethoxymethylsilane, vinyltris (β
-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and the like.
これら単量体の１種又は２種以上の混合物が単量体成分
全体の０．１〜１０重量％用いられる。０゜１重量％未
満では基材への密着性や架橋性が不充分であるし、また
、１（ｌ量％を超える量では架橋が進みすぎ加工性等に
悪影響を及ぼし経済的でもない。One type or a mixture of two or more of these monomers is used in an amount of 0.1 to 10% by weight based on the total monomer component. If it is less than 0.1% by weight, the adhesion to the substrate and crosslinking properties will be insufficient, and if it exceeds 1 (1%) by weight, crosslinking will proceed too much, adversely affecting processability, etc., and it will not be economical.
重合性不飽和カルボン酸（ｂ）の代表的な例としては、
アクリル酸、メタアクリル酸、イタコン酸等をあげるこ
とができる。これら単量体の１種又は２種以上の°混合
物が単量体全体の０〜２０重量％用いられる９重合性不
飽和カルボン酸は樹脂に両性イオン性を付与したり、又
後反応によって陽イオン性を導入するための単量体とし
て使用されるが、２０重量％をこえると樹脂の耐水性が
わるくなり好ましくない。Typical examples of polymerizable unsaturated carboxylic acids (b) include:
Examples include acrylic acid, methacrylic acid, and itaconic acid. The 9-polymerizable unsaturated carboxylic acid, in which one or a mixture of two or more of these monomers is used in an amount of 0 to 20% by weight based on the total monomers, can impart zwitterionicity to the resin or can be cationized by post-reaction. It is used as a monomer to introduce ionicity, but if it exceeds 20% by weight, the water resistance of the resin will deteriorate, which is not preferable.
アルキル基の炭素数が１〜８である（メタ）アクリル酸
アルキルエステル（Ｃ）の代表的な例としては、アクリ
ル酸メチル、アクリル酸エチル、アクリル酸ブチル、ア
クリル酸２−エチルヘキシル、メタアクリル酸メチル、
メタアクリル酸エチル、メタアクリル酸プロピル、メタ
アクリル酸ブチル等をあげることができる。これら単量
体の１種又は２種以上の混合物が単量体成分全体の２０
〜・９９重量％用いられる。Typical examples of (meth)acrylic acid alkyl esters (C) in which the alkyl group has 1 to 8 carbon atoms include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methacrylic acid. methyl,
Examples include ethyl methacrylate, propyl methacrylate, and butyl methacrylate. One type or a mixture of two or more of these monomers accounts for 20% of the total monomer component.
~・99% by weight is used.
これらと共重合可能な単量体（ｄ）としては、エチレン
、プロピレン、イソブチレン等のα−オレフィン類、塩
化ビニル、臭化ビニル等のハロゲン化ビニル、アクリロ
ニトリル、メタアクリロニトリル等のシアン化ビニル、
酢塩ビニル、プロピオン酸ビニル等のビニルニスデル類
、スチレン、ビニルトルエン、α−メチルスチレン等の
芳香族ビニル、塩化ビニリデン、弗化ビニリデン等のハ
ロゲン化ビニリデン、ジメチルアミノエチルアクリレー
ト、ジエチルアミノエチルアクリレート、ジメチルアミ
ノエチルメタアクリレート、ジエチルアミノエチルメタ
アクリレート、グリシジルアクリレート、アクリルアミ
ド、メタアクリルアミド、Ｎ−メチロールアクリルアミ
ド等をあげることができる。これら単量体の１種又は２
種以上が多層構造共重合体を陽イオン性及び／又は両性
イオン性にし、且つ芯部分と最外殻部分のＴｇに対する
要求を満たすための必要に応じて単量体成分全体の０〜
４０重量％用いられる。多層構造共重合体は、分子中に
加水分解性の珪素化合物を含む特殊なアクリル系樹脂で
あるが、さらに芯部分のＴｇが１５℃以上であり、且つ
最外殻部分のＴｇが１０’Ｃ以下であることが重要であ
る。ここで示しなＴｇとは共重合体のガラス転移点を示
し、その値は実際に測定することが好ましいが、他の方
法として、フ、ｒ ックス（Ｆｏｘ）のｒＢｕＪ］。Monomers (d) copolymerizable with these include α-olefins such as ethylene, propylene, and isobutylene; vinyl halides such as vinyl chloride and vinyl bromide; vinyl cyanides such as acrylonitrile and methacrylonitrile;
Vinyl nitrides such as vinyl acetate and vinyl propionate, aromatic vinyls such as styrene, vinyltoluene, and α-methylstyrene, vinylidene halides such as vinylidene chloride and vinylidene fluoride, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, and dimethylamino Examples include ethyl methacrylate, diethylaminoethyl methacrylate, glycidyl acrylate, acrylamide, methacrylamide, and N-methylolacrylamide. One or two of these monomers
In order to make the multilayer structure copolymer cationic and/or zwitterionic and to satisfy the requirements for the Tg of the core portion and the outermost shell portion, the amount of 0 to 100% of the total monomer components may be
40% by weight is used. The multilayer structure copolymer is a special acrylic resin containing a hydrolyzable silicon compound in the molecule, and the Tg of the core portion is 15°C or higher, and the Tg of the outermost shell portion is 10'C. It is important that: The Tg shown here indicates the glass transition point of the copolymer, and it is preferable to actually measure its value, but as another method, it is possible to measure the value using the Tg (Fox's rBuJ).
Ａｍ、Ｐｈｙｓｉｃｓ Ｓｏｃ、Ｊ １巻３号１２３
頁（１９５６年）に記載のごとく算出することができる
。芯部分のＴｇが１５°Ｃ未満であると得られる塗膜の
強度も弱く、加熱によって塗膜が柔かくなりすぎる傾向
がある。そのなめ組成物が塗布された金属材料は、例え
ばそれが鋼板であればコイルとして巻取られた時にブロ
ッキングを起しやすく、作業上問題がある。ｆ＆外殻部
分はＴｇが１０℃以下である必要がある。１０℃を超え
ると金属材料に塗布された時、低温で成膜しにくく、膜
欠陥ができやすくて充分な性能が期待できない場合が多
い、アクリル系樹脂（ＩＩ）は、このような多層構造共
重合体から誘導される分子中に陽イオン性窒素を有する
ものである。その代表的な陽イオン性樹脂として例えば
次の第（１）〜（３）の各項に示した樹脂をあげること
ができる。Am, Physics Soc, J Volume 1 No. 3 123
(1956). If the Tg of the core portion is less than 15°C, the strength of the resulting coating film will be low, and the coating film will tend to become too soft when heated. If the metal material coated with the licking composition is, for example, a steel plate, it is likely to cause blocking when wound up into a coil, which poses a problem in terms of work. The f& outer shell portion must have a Tg of 10°C or less. Acrylic resin (II), when applied to metal materials at temperatures exceeding 10°C, is difficult to form into a film at low temperatures, tends to cause film defects, and is often unable to provide sufficient performance. It has cationic nitrogen in the molecule derived from a polymer. Typical cationic resins include, for example, the resins listed in items (1) to (3) below.
（１）ジアルキルアミノアルキル（メタ）アクリレート
等のアミノエステル基を含有するビニル化合物、ビニル
ピリジン、ビニルイミダゾールあるいはそれらの塩類等
の陽イオン性窒素含有ビニル化合物から選ばれた１種又
は２種以上を共重合することにより得られた樹脂、
（２）グリシジル（メタ）アクリレートやクロルメチル
メタアクリレートを共重合させたアクリル系樹脂をジメ
チルアミン、ジエチルアミン、エチレンジアミン等で陽
イオン化した樹脂、（３）ｐ−クロルメチルスチレンを
共重合させたアクリル系樹脂とアミン及び／又はポリア
ミンとの反応によって得られるアミノメチル基を含む樹
脂。また、両性イオン性樹脂とは分子中に陽イオン性窒
素と陰イオン性のカルボキシル基とを有する樹脂であっ
て、例えば次の第（４）〜（６）の各項に示した樹脂を
あげることができる、（４）前記第（１）〜（３）項の
陽イオン樹脂に公知の方法で（例えばクロム酢酸等を用
いて）陰イオン性基であるカルボキシル基を導入した樹
脂、（５）カルボキシル基含有の（メタ）アクリル系樹
脂とエチレンイミン、グロピレンイミン、ヒドロキシエ
チルエチレンイミン、シアンエチルエチレンイミン等の
アジリジン化合物やグリシジルアミンまたはその塩等の
塩基性窒素含有アルキル化剤との反応によって得られる
両性イオン基を含有する樹脂、
（６）ジアルキルアミノアルキル（メタ）アクリレート
、ビニルピリジン、ビニルイミダゾールあるいはそれら
の基間等の塩基性窒素含有ビニル化合物から選ばれた１
種又は２種以上と、（メタ）アクリル酸、クロトン酸あ
るいはマレイン酸等のカルボキシル基含有ビニル化合物
の１種又は２種以上を必須成分として得られた共重合体
、等があげられる。(1) One or more types selected from vinyl compounds containing an amino ester group such as dialkylaminoalkyl (meth)acrylate, and cationic nitrogen-containing vinyl compounds such as vinylpyridine, vinylimidazole, or their salts. Resin obtained by copolymerization, (2) Resin obtained by cationizing an acrylic resin copolymerized with glycidyl (meth)acrylate or chloromethyl methacrylate with dimethylamine, diethylamine, ethylenediamine, etc., (3) p- A resin containing aminomethyl groups obtained by reacting an acrylic resin copolymerized with chloromethylstyrene and an amine and/or a polyamine. In addition, an amphoteric ionic resin is a resin having cationic nitrogen and anionic carboxyl group in the molecule, and includes, for example, the resins shown in the following items (4) to (6). (4) A resin in which a carboxyl group, which is an anionic group, is introduced into the cationic resin of items (1) to (3) above by a known method (for example, using chromium acetic acid, etc.), (5) ) Obtained by the reaction of a (meth)acrylic resin containing a carboxyl group with a basic nitrogen-containing alkylating agent such as an aziridine compound such as ethyleneimine, glopyleneimine, hydroxyethylethyleneimine, or cyanethylethyleneimine, or glycidylamine or its salt. (6) 1 selected from basic nitrogen-containing vinyl compounds such as dialkylaminoalkyl (meth)acrylate, vinylpyridine, vinylimidazole, or between these groups;
Examples include copolymers obtained by using as essential components one or more types of carboxyl group-containing vinyl compounds such as (meth)acrylic acid, crotonic acid, or maleic acid.
これらのアクリル系（Ｍ脂（ＩＩ）のなかでも、第（１
）項や第（５）項で示した樹脂が本発明における樹脂（
ＩＩ）として特に有効なものである。Among these acrylic (M fat (II)), the
) and (5) are the resins (
It is particularly effective as II).
本発明においては、アクリル系樹脂（ＩＩ＞としては、
前記第（１）項〜第（６）項に例示した如く各種の陽イ
オン性樹脂及び／又は両性イオン性樹脂を用いることが
できる。In the present invention, the acrylic resin (II>) is
Various cationic resins and/or amphoteric ionic resins can be used as exemplified in items (1) to (6) above.
しかし、陽イオン性樹脂の場合、通常公知の方法例えば
コロイド滴定法、電導症滴定法等によって測定した陽イ
オン性窒素の量が、該樹脂１ｇ当り０．０１〜５ミリモ
ルの範囲の量であることが。However, in the case of cationic resins, the amount of cationic nitrogen measured by commonly known methods such as colloid titration, conductivity titration, etc. is in the range of 0.01 to 5 mmol per 1 g of the resin. That's it.
望ましい。desirable.
また、両性イオン性樹脂の場合、陽イオン性窒素の量及
び陰イオン化しうるカルボキシル基の量（これらの量も
コロイド滴定法、電導症滴定法等によって測定できる。In the case of amphoteric ionic resins, the amount of cationic nitrogen and the amount of carboxyl groups that can be anionized (these amounts can also be measured by colloid titration, conductivity titration, etc.).
）が、該樹脂１ｇ当りそれぞれ０．０１〜５ミリモルの
範囲の量であることが望ましい、この範囲をはずれると
金属表面処理用組成物としての効果が不充分であり好ま
しくない。) is desirably in the range of 0.01 to 5 mmol per 1 g of the resin. If it deviates from this range, the effect as a metal surface treatment composition will be insufficient and is therefore undesirable.
アクリル系樹脂（ＩＩ）を本発明で用いるに際しては、
そのまま用いてもよく、あるいは陽イオン性窒素の１部
又は全部を塩酸、硝酸、リン酸、ギ酸等の鉱酸もしくは
有機酸の塩又は第４級アンモニウム塩として用いたり、
あるいはアンモニア、アミン、ポリアミン等の塩基性物
質を加えて用いることもできる。アクリル系樹脂（ＩＩ
）は、本発明の金属表面処理用組成物１１当り０．５〜
６００ｇ、好ましくは１〜４００ｇの範囲の置台まれる
ものである。When using the acrylic resin (II) in the present invention,
It may be used as it is, or part or all of the cationic nitrogen may be used as a salt or quaternary ammonium salt of a mineral or organic acid such as hydrochloric acid, nitric acid, phosphoric acid, or formic acid,
Alternatively, a basic substance such as ammonia, amine, polyamine, etc. can be added and used. Acrylic resin (II
) is 0.5 to 11 per metal surface treatment composition of the present invention.
The weight is 600 g, preferably 1 to 400 g.
次に必要に応じて添加されるアクリル系樹脂（Ｉｌｒ）
とは、Ｔｇが１０℃以上である陽イオン性及び／又は両
性イオン性アクリル系樹脂であり、従来公知の各種乳化
重合方法によって得られるもので、代表的な例としては
前記第（１）〜（６）の各項に記載した様な樹脂が用い
られるが、その中でも前記第（１）項又は第（５）項に
示す様な樹脂が好ましい、ただ、前記アクリル系樹脂（
Ｉｆ）の様に多層構造を持つ必要はない、アクリル系樹
脂（Ｉ［）に於て、陽イオン性窒素の量は該樹脂１ｇ当
り０．０１〜３ミリモル、さらには０．０１〜１ミリモ
ルの範囲の量であることが好ましい。Next, acrylic resin (Ilr) added as necessary
is a cationic and/or amphoteric acrylic resin with a Tg of 10°C or higher, which can be obtained by various conventionally known emulsion polymerization methods, and typical examples include the above-mentioned (1) to The resins listed in each item (6) are used, but among them, the resins shown in item (1) or item (5) are preferable. However, the acrylic resin (
In the acrylic resin (I[), which does not need to have a multilayer structure like If), the amount of cationic nitrogen is 0.01 to 3 mmol, more preferably 0.01 to 1 mmol, per 1 g of the resin. Preferably, the amount is in the range of .
又、両性イオン性樹脂の場合、陽イオン性窒素の量及び
陰イオン化しうるカルボキシル基の量が該樹脂１ｇ当り
それぞれ０．０１〜３ミリモルさらには０．０１〜１ミ
リモルの範囲の量であることが好ましい。この範囲をは
ずれると、金属表面処理用組成物としての効果が不充分
であり好ましくない。アクリル系樹脂（ＩＩ［）は、金
属表面処理用組成物１１当り０〜６００ｇの範囲の置台
有されるが、処理された鋼板をコイルに巻取った時に耐
ブロッキング性を向上させる働きがあり、また架橋が少
なく熱可塑性をもっているため、絞り加工性を向上させ
る働きもある。さらに塗膜の耐水性を向上させる働きも
ある。Further, in the case of an amphoteric ionic resin, the amount of cationic nitrogen and the amount of anionizable carboxyl group are each in the range of 0.01 to 3 mmol, more preferably 0.01 to 1 mmol, per 1 g of the resin. It is preferable. If it is outside this range, the effect as a metal surface treatment composition will be insufficient, which is not preferable. The acrylic resin (II [) is used in a range of 0 to 600 g per metal surface treatment composition 11, and has the function of improving blocking resistance when the treated steel plate is wound into a coil. Furthermore, since it has little crosslinking and is thermoplastic, it also works to improve drawing workability. It also works to improve the water resistance of the paint film.
本発明において用いられる（Ｄ）カルボキシル化オレフ
ィン系樹脂（ＩＶ ）としては、（１）エチレン系炭化
水素（例えばエチレン、プロピレン、ブテン、インブチ
レン等）の１種または２種以上と、カルボキシル基含有
単量体（例えばアクリル酸、メタクリル酸、マレイン酸
等）の１８または２種以上を必須モノマーとする共重合
体くブロック共重合体およびランダム共重合体を包含）
、または
（２）カルボキシル基含有単量体のポリマーとエチレン
系炭化水素のポリマーとのブロック共重合体であって、
カルボキシル基を３〜３０重量％含有するオレフィン系
樹脂である。具体的には、例えばエチレン−アクリル酸
共重合体、エチレン−メタクリル酸共重合体、エチレン
−マレイン酸共重合体、エチレン−ビニルアルコール−
アクリル酸共重合体、エチレン−酢酸ビニル−アクリル
酸共重合体、エチレン−プロピレン−アクリル酸共重合
体、エチレン−アクリル酸−メタクリル酸共重合体、プ
ロピレン−アクリル酸共重合体、プロピレン−マレイン
酸共重合体、インブチレン−アクリル酸共重合体、また
はポリアクリル酸−ポリエチレン・ブロック共重合体等
が挙げられる。かかる共重合体にあって、そのカルボキ
シル基含有量は上述の如き一定範囲に設定されているこ
とが必要で、化成処理皮膜との密着性はカルボキシル基
含有量が増加するにつれて良好となる。即ち、含有量が
、３％未満では、化成処理皮膜との密着性が悪く、また
３０％を超えると、当該高分子皮膜の耐水性が低下し且
つクロムの溶出を招くことがある。このように、上記適
性範囲を逸脱すると、高度の耐食性は得られない。さら
に、当該共重合体の分子量範囲について、ある程度に規
制する必要があると考えられるが、一般にその分子量を
直接測定することは困器なため、分子量に関係するメル
トインデックス（Ｍｌ）値で代替することができる。し
かし、このＭＩ値も当該共重合体の種類、カルボキシル
基含有単量体の種類およびカルボキシル基含有量によっ
て異なるため一般的に記述することはできないが、例え
ばアクリル酸のモノマー比率が２０％のエチレン−アク
リル酸共重合体の場合では、１９０±１°Ｃ１２１６０
±１０ｇの条件でＭＩ値は２００〜６００ ｄ ｇ ／
ｍ ｉ ｎのものが好適である。The (D) carboxylated olefin resin (IV) used in the present invention includes (1) one or more ethylene hydrocarbons (e.g. ethylene, propylene, butene, imbutylene, etc.) and a carboxyl group-containing Copolymers (including block copolymers and random copolymers) in which 18 or 2 or more monomers (e.g. acrylic acid, methacrylic acid, maleic acid, etc.) are essential monomers)
, or (2) a block copolymer of a carboxyl group-containing monomer polymer and an ethylene hydrocarbon polymer,
It is an olefin resin containing 3 to 30% by weight of carboxyl groups. Specifically, for example, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-maleic acid copolymer, ethylene-vinyl alcohol-
Acrylic acid copolymer, ethylene-vinyl acetate-acrylic acid copolymer, ethylene-propylene-acrylic acid copolymer, ethylene-acrylic acid-methacrylic acid copolymer, propylene-acrylic acid copolymer, propylene-maleic acid Examples include copolymers, inbutylene-acrylic acid copolymers, and polyacrylic acid-polyethylene block copolymers. The carboxyl group content of such a copolymer must be set within a certain range as described above, and the adhesion to the chemical conversion coating becomes better as the carboxyl group content increases. That is, if the content is less than 3%, the adhesion with the chemical conversion coating will be poor, and if it exceeds 30%, the water resistance of the polymer coating will decrease and chromium may be leached. As described above, if the above suitable range is exceeded, a high degree of corrosion resistance cannot be obtained. Furthermore, it is thought that it is necessary to regulate the molecular weight range of the copolymer to a certain extent, but since it is generally difficult to directly measure the molecular weight, the melt index (Ml) value, which is related to the molecular weight, is used instead. be able to. However, this MI value also varies depending on the type of copolymer, the type of carboxyl group-containing monomer, and the carboxyl group content, so it cannot be generally described. - In case of acrylic acid copolymer, 190±1°C12160
MI value is 200 to 600 d g / under ±10 g condition.
min is preferred.
カルボキシル化オレフィン系樹脂（ＩＶ）は、０゜５〜
６００ｇの範囲の置台有される。用いられる形態として
は、水分散型にしたディスパージョンタイプのものが、
使いやすい。The carboxylated olefin resin (IV) has a temperature of 0°5 to
It has a stand with a weight range of 600g. The form used is a dispersion type that is water-dispersed.
easy to use.
本発明において、架橋剤として用いられる（Ｅ）アジリ
ジニル基を有する化合物は、２個以上のアジリジニル基
を有する化合物、たとえば、１．６＝へキサメチレンジ
エチレンウレア、ジフェニルメタン−ビス−４，４−−
Ｎ、Ｎ−−ジエチレンウレア、２，２−ビスヒドロキシ
メチルブタノール−トリスＣ３−（１−アジリジニル）
プロピオネート〕、トリエチレンメラミン、トリス−１
−アジリジニルホスフィンオキサイド、２．４−ジエチ
レンウレアトルイジン、２，４．６−１リエチレンイミ
ノ）−ｓｙｍ−）リアジン、ω−アジリジニルプロピオ
ン酸−２，２−ジヒドロキシメチル−ブタノール−トリ
エステル、２．４．６−トリス（２−メチル−１−アジ
リジル）−ｓｙｍ−トリアジン、２，４．６−トリス〈
２−エチル−１−アジリジル）−ｓｙｍ−トリアジン、
ビス（２−エチル−１−アジリジル）ベンゼン−１゜３
−ジカルボン酸アミド、トリス（２−エチル−１−アジ
リジル）ベンゼン−１，３，５−トリカルボン酸アミド
、ビス（２−エチル−１−アジリジル）セバシン酸アミ
ド、２．４−ジエチレンウレイドトルエン、１．１−一
カルボニルーｂｉｓ−二チレンイミン、ポリメチレン（
Ｃ２−Ｃ４）−ｂｉｓ−エチレンユリア、Ｎ、Ｎ−−ｂ
ｉｓ−（４，６−ジエチレンイミノ−１，３，５−トリ
アジン−２−イル）−へキサメチレンジアミノ等を例示
できる。In the present invention, (E) a compound having an aziridinyl group used as a crosslinking agent is a compound having two or more aziridinyl groups, such as 1.6=hexamethylene diethylene urea, diphenylmethane-bis-4,4--
N,N--diethyleneurea, 2,2-bishydroxymethylbutanol-trisC3-(1-aziridinyl)
propionate], triethylene melamine, tris-1
-Aziridinylphosphine oxide, 2,4-diethyleneureatluidine, 2,4.6-1lyethylenimino)-sym-)riazine, ω-aziridinylpropionic acid-2,2-dihydroxymethyl-butanol-triester , 2.4.6-tris(2-methyl-1-aziridyl)-sym-triazine, 2,4.6-tris<
2-ethyl-1-aziridyl)-sym-triazine,
Bis(2-ethyl-1-aziridyl)benzene-1゜3
-dicarboxylic acid amide, tris(2-ethyl-1-aziridyl)benzene-1,3,5-tricarboxylic acid amide, bis(2-ethyl-1-aziridyl)sebacic acid amide, 2,4-diethyleneureidotoluene, 1 .1-1-carbonyl-bis-dethyleneimine, polymethylene (
C2-C4)-bis-ethylene urea, N, N--b
Examples include is-(4,6-diethyleneimino-1,3,5-triazin-2-yl)-hexamethylene diamino.
アジリジニル基を有する化合物の添加量は、樹脂に対す
る固形分の比率で、０．１〜１０重量％の範囲で、各樹
脂組成物ごとに、またそれぞれのアジリジニル基を有す
る化合物ごとに定める。The amount of the compound having an aziridinyl group to be added is determined for each resin composition and for each compound having an aziridinyl group in the range of 0.1 to 10% by weight as a solid content ratio to the resin.
これらの架橋剤は、樹脂と反応あるいは、混合して用い
るが、耐溶剤性や、耐水性等を、向上させる働きがある
。These crosslinking agents are used by reacting or mixing with the resin, and have the function of improving solvent resistance, water resistance, etc.
本発明の金属表面処理用組成物が使用できる金属として
は、鉄、鋼、合金鋼、亜鉛、亜鉛合金が挙げられる。ま
た鉄、鋼、合金鋼、亜鉛、亜鉛合金から選ばれる少なく
とも一種を被覆した金属被覆物に対して用いることがで
きる。またこれらの被塗物の形状としては、板状、パイ
プ状、線状等の種々の形状のものを使用することができ
る本発明の金属表面処理用組成物の使用方法は、常温〜
１５０℃好ましくは常温〜・７０℃の被塗物金属の表面
にハゲ塗り、スプレー塗布、ロール塗布、浸漬等の方法
で塗布後、常温以上の温度で数秒〜数分間乾燥するだけ
でよい、その際、得られる塗膜の膜厚は０．１〜５μ程
度の薄膜で十分な効果が得られる。このようにして得ら
れた本発明の金属表面処理用組成物の塗膜は、一般に塗
装前処理工程で行なわれている付着油分除去の脱脂工程
においてもほとんど剥離せず、したがってリン酸塩処理
工程を省略することができる。Metals that can be used with the metal surface treatment composition of the present invention include iron, steel, alloy steel, zinc, and zinc alloys. It can also be used for metal coatings coated with at least one selected from iron, steel, alloy steel, zinc, and zinc alloys. In addition, various shapes such as a plate, a pipe, and a line can be used as the shape of the object to be coated.The metal surface treatment composition of the present invention can be used at room temperature to
After coating the surface of the metal to be coated at 150°C, preferably room temperature to 70°C, by a method such as bald coating, spray coating, roll coating, or dipping, it is sufficient to dry the coating at a temperature above room temperature for a few seconds to several minutes. In this case, a sufficient effect can be obtained with a thin film of about 0.1 to 5 μm in thickness. The coating film of the metal surface treatment composition of the present invention obtained in this way hardly peels off even in the degreasing step for removing adhering oil, which is generally performed in the pre-painting treatment step, and therefore, it does not peel off during the phosphate treatment step. can be omitted.
本発明の鉄、鋼、合金鋼、亜鉛、亜鉛合金から選ばれる
少なくとも一種の金属表面処理用組成物は、金属表面へ
の直接的な表面処理用として使用できる特徴を有するも
のである。さらに従来のリン酸塩処理板へのクロメート
シーリングにかわる後処理用としても使用できる。また
従来のクロメート処理板へ使用し、より高い耐食性で塗
装下地性を付与するシーリング剤として使用できる。At least one metal surface treatment composition selected from iron, steel, alloy steel, zinc, and zinc alloy according to the present invention has the characteristic that it can be used for direct surface treatment of metal surfaces. It can also be used as a post-treatment alternative to conventional chromate sealing on phosphate-treated boards. It can also be used as a sealant for conventional chromate-treated boards to provide higher corrosion resistance and base properties for painting.
（実 施 例）
以下、本発明を具体例によりさらに詳細に説明するが、
本発明が実施例により何ら制限されるものではない。な
お、！！！造例および実施例中の％は重量％を示す４
両性イオン性アクリル系樹脂（ＩＩ）の製造間製造例１
撹拌器、還流冷却器、温度計、窒素導入管及び滴下ロー
トを備えたフラスコに脱イオン水４６６部とアニオン系
乳化剤２部を加えると共に７０’Ｃに昇温しな０次に、
過硫酸アンモニウム２部を加えた後、スチレン２８．０
部、メチルメタアクリレート２７．５部、ブチルアクリ
レート３９部、アクリル酸６部及びビニルトリメトキシ
シラン０゜５部からなる単量体混合物を１時間にわたり
加え、第１段目の乳化重合を行った。添加後さらに１時
間重合した後、スチレン３０部、ブチルアクリレート６
０部、アクリル酸９部及びビニルジメトキシメチルシラ
ン１部からなる単量体混合物を１時間にわたり加えて第
２段目（最外殻部分を構成）の乳化重合を行い、芯部分
のＴｇ約１９℃、最外殻部背約−１２℃の多層構造重合
体を得た。次にこの重合体にエチレンイミン７部と脱イ
オン水１６部を加え、５０℃で３時間反応後アンモニア
で中和してｐＨ９，０とし、固形分３０％を有する両性
イオン性アクリル系樹脂（ＩＩ）を得た。(Example) The present invention will be explained in more detail using specific examples below.
The present invention is not limited in any way by the examples. In addition,! ! ! % in Preparation Examples and Examples indicates % by weight 4 During the production of zwitterionic acrylic resin (II) Production Example 1 In a flask equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen introduction tube and a dropping funnel. Next, add 466 parts of deionized water and 2 parts of anionic emulsifier and raise the temperature to 70'C.
After adding 2 parts of ammonium persulfate, styrene 28.0
A monomer mixture consisting of 27.5 parts of methyl methacrylate, 39 parts of butyl acrylate, 6 parts of acrylic acid, and 0.5 parts of vinyltrimethoxysilane was added over 1 hour to perform the first stage emulsion polymerization. . After further polymerization for 1 hour, 30 parts of styrene and 6 parts of butyl acrylate were added.
A monomer mixture consisting of 0 parts, 9 parts of acrylic acid, and 1 part of vinyldimethoxymethylsilane was added over 1 hour to perform emulsion polymerization of the second stage (constituting the outermost shell part), and the Tg of the core part was about 19. A multilayered polymer having a temperature of about -12°C at the outermost shell was obtained. Next, 7 parts of ethyleneimine and 16 parts of deionized water were added to this polymer, and after reacting at 50°C for 3 hours, it was neutralized with ammonia to a pH of 9.0. II) was obtained.
製造例２
製造例１と同様の方法により、第１段目メチルメタアク
リレート５４．５部、ブチルアクリレート３９部、アク
リル酸６部及びγ−メタアクリロキシプロピルトリメト
キシシラン０．５部がらなり、第２段目はメチルメタア
クリレート１２部、ブチルアクリレート８１部、アクリ
ル酸６部及びγ−メタアクリロキシプロピルトリメトキ
シシラン１部からなる、芯部分のＴｇが約２１℃、最外
殻部背約−３６℃である多層構造重合体を合成した後、
エチレンイミン３．６ｓで陽イオン化反応を行い、アン
モニアで中和後固形分３０％、ｐＨ９，０の両性イオン
性アクリル系樹脂（Ｉｔ）を得な。Production Example 2 By the same method as Production Example 1, the first stage consisted of 54.5 parts of methyl methacrylate, 39 parts of butyl acrylate, 6 parts of acrylic acid, and 0.5 parts of γ-methacryloxypropyltrimethoxysilane, The second stage consists of 12 parts of methyl methacrylate, 81 parts of butyl acrylate, 6 parts of acrylic acid, and 1 part of γ-methacryloxypropyltrimethoxysilane. After synthesizing the multilayer structure polymer at -36°C,
A cationization reaction was carried out with ethyleneimine for 3.6 seconds, and after neutralization with ammonia, a zwitterionic acrylic resin (It) with a solid content of 30% and a pH of 9.0 was obtained.
製造例３
製造例１と同様の方法により、第１段目メチルメタアク
リレート５５部、ブチルアクリレート３９部、アクリル
酸５．５部及びγ−メタアクリロキシプロピルトリメト
キシシラン０．５部からなり、第２段目はメチルメタア
クリレート４部、ブチルアクリレート８１部、アクリル
酸１４部及びγ−メタアクリロキシプロピルトリメトキ
シシラン１部からなる、芯部分のＴｇが約２４℃、最外
殻部背約−３５℃である多層構造重合体を合成した後、
エチレンイミン６部で陽イオン化反応を行い、アンモニ
アで中和後固形分３０％、ＰＨ９゜０の両性イオン性ア
クリル系樹脂（ＩＩ）を得た。Production Example 3 By the same method as Production Example 1, the first stage consisted of 55 parts of methyl methacrylate, 39 parts of butyl acrylate, 5.5 parts of acrylic acid, and 0.5 parts of γ-methacryloxypropyltrimethoxysilane, The second stage consists of 4 parts of methyl methacrylate, 81 parts of butyl acrylate, 14 parts of acrylic acid, and 1 part of γ-methacryloxypropyltrimethoxysilane, the Tg of the core part is about 24°C, and the height of the outermost shell part is about 24°C. After synthesizing the multilayer structure polymer at -35°C,
A cationization reaction was carried out with 6 parts of ethyleneimine, and after neutralization with ammonia, a zwitterionic acrylic resin (II) having a solid content of 30% and a pH of 9.0 was obtained.
両性イオン性アクリル系樹脂（ＩＩＩ）の製造間製造例
４
メチルメタアクリレート６０部、２−エチルへキシルア
クリレート３８．８部及びアクリル酸１゜２部より得ら
れたＴｇが約１３℃である固形分４０％の乳化重合物１
００部とエチレンイミン０゜２８部とを反応後、アンモ
ニアで中和して固形分４０％、ｐＨ８，５の両性イオン
性アクリル系樹脂（ＩＩ［）を得た。Production example 4 during production of zwitterionic acrylic resin (III) Solid with Tg of about 13°C obtained from 60 parts of methyl methacrylate, 38.8 parts of 2-ethylhexyl acrylate and 1.2 parts of acrylic acid. 40% emulsion polymer 1
After reacting 0.00 parts with 0.28 parts of ethyleneimine, the mixture was neutralized with ammonia to obtain an amphoteric ionic acrylic resin (II[) having a solid content of 40% and a pH of 8.5.
製造例５
２−エチルへキシルアクリレート３７部、スチレン５８
部、アクリル酸５部より得られたＴｇが約１５°Ｃであ
る固形分４０％の乳化重合物１００部とエチレンイミン
１．１部とを反応後、アンモニアで中和して固形分４０
％、ｐｌ（８，５の両性イオン性アクリル系樹脂（ＩＩ
Ｉ）を得た。Production Example 5 37 parts of 2-ethylhexyl acrylate, 58 parts of styrene
After reacting 100 parts of an emulsion polymer with a solid content of 40% and having a Tg of about 15°C obtained from 5 parts of acrylic acid and 1.1 parts of ethyleneimine, the mixture was neutralized with ammonia to obtain a solid content of 40°C.
%, pl (8,5 zwitterionic acrylic resin (II
I) was obtained.
製造例６
メチルメタアクリレート５８．５部、２−エチルへキシ
ルアクリレート３７．５部及びアクリル酸４部より得ら
れなＴｇが約１５°Ｃである固形分４０％の乳化重合物
１００部とエチレンイミン０゜９５部とを反応後、アン
モニアで中和して固形分４０％、ｐｌ（８，５の両性イ
オン性アクリル系樹脂（ＩＩＩ）を得た。Production Example 6 100 parts of an emulsion polymer with a solid content of 40% and having a Tg of about 15°C obtained from 58.5 parts of methyl methacrylate, 37.5 parts of 2-ethylhexyl acrylate and 4 parts of acrylic acid, and ethylene After reacting with 0.95 parts of imine, it was neutralized with ammonia to obtain an amphoteric ionic acrylic resin (III) with a solid content of 40% and a pl (8.5).
両性イオン性カルボキシル化オレフィン系樹脂（１ｖ）
の製造例
製造例７
固形分２５％で、カルボキシル基を約２０モル％含有す
るカルボキシル化ポリエチレン樹脂のディスパージョン
（商品名：ザイクセンＡ 製鉄化学工業（株）製）１０
０部を脱イオン水で固形分２０％に希釈後、エチレンイ
ミン１部と反応させ、アンモニアで中和して固形分２０
％、ｐ Ｈ１０。Zwitterionic carboxylated olefin resin (1v)
Production Example Production Example 7 Dispersion of carboxylated polyethylene resin having a solid content of 25% and containing about 20 mol% of carboxyl groups (trade name: Zaixen A manufactured by Steel Chemical Industry Co., Ltd.) 10
After diluting 0 part with deionized water to a solid content of 20%, it was reacted with 1 part of ethyleneimine and neutralized with ammonia to a solid content of 20%.
%, pH 10.
０の両性イオン性カルボキシル化オレフィン樹脂（ＩＶ
）を得た。0 zwitterionic carboxylated olefin resin (IV
) was obtained.
製造例８
固形分２５％で、カルボキシル基を２０モル％含有する
カルボキシル化ポリエチレン樹脂のディスパージョン〈
商品名：プリマコール４９８３ダウケミカル（株）製）
１００部を脱イオン水で固形分２０％に希釈後、エチレ
ンイミン１部と反応させ、アンモニアで中和して固形分
２０％、ｐＨｌ０．Ｏの両性イオン性カルボキシル化オ
レフィン系樹脂（ＩＶ ）を得た。Production Example 8 Dispersion of carboxylated polyethylene resin with solid content of 25% and containing 20 mol% of carboxyl groups
Product name: Primacol 4983 (manufactured by Dow Chemical Co.)
After diluting 100 parts with deionized water to a solid content of 20%, it was reacted with 1 part of ethyleneimine and neutralized with ammonia to give a solid content of 20% and a pH of 0. A zwitterionic carboxylated olefin resin (IV) of O was obtained.
製造例９
固形分２７％のエチレン−メタクリル酸アイオノマー（
商品名：ケミパールＳ−１００三井石油化学工業（株）
製）１００部を脱イオン水で固形分２０％に希釈後、エ
チレンイミン０．３部と反応させ、アンモニアで中和し
て固形分２０％、ｐＨ１０，０の両性イオン性カルボキ
シル化オレフィン樹脂（ＩＶ ）を得た。Production Example 9 Ethylene-methacrylic acid ionomer with a solid content of 27% (
Product name: Chemipearl S-100 Mitsui Petrochemical Industries, Ltd.
After diluting 100 parts of 20% solids with deionized water, it was reacted with 0.3 parts of ethyleneimine, and neutralized with ammonia to obtain a zwitterionic carboxylated olefin resin with a solids content of 20% and a pH of 10.0. IV) was obtained.
実施例１
製造例７で得られたカルボキシル化オレフィン系樹脂（
ＩＶ）７０部、製造例１で得られたアクリル系樹脂（Ｕ
）１５部、製造例４で得られたアクリル系樹脂（■）４
部、及び脱イオン水１１部を混合し、次いで、架橋剤と
して、ジフェニルメタン−ビス−４，４−−Ｎ、Ｎ″−
ジエチレンウレア（商品名：ＤＺ−２２Ｎ２５％白色水
分散液日本触媒化学工業（株）製）０．７部を加え、５
０”Ｃで１２時間反応後、水分散性シリカ（Ｉ）（商品
名ニスノーテックスＣ，５ｉｎ２２０％品）３３部を加
え、金属表面処理用組成物を得た。この組成物を板厚０
．６市のクロメート処理された市販の電気亜鉛めっき鋼
板（商品名ニシンコート、新日本製鉄（株）製）に膜厚
２．０μになる様にスプレー塗布後、１００°Ｃで６０
秒間乾燥を行い、表面処理板を得た。Example 1 Carboxylated olefin resin obtained in Production Example 7 (
IV) 70 parts, acrylic resin obtained in Production Example 1 (U
) 15 parts, acrylic resin obtained in Production Example 4 (■) 4
and 11 parts of deionized water, and then diphenylmethane-bis-4,4--N,N''- as a crosslinking agent.
Add 0.7 part of diethylene urea (trade name: DZ-22N 25% white aqueous dispersion manufactured by Nippon Shokubai Chemical Co., Ltd.), and
After reacting at 0"C for 12 hours, 33 parts of water-dispersible silica (I) (trade name Nisnortex C, 5in 220% product) was added to obtain a composition for metal surface treatment.
．． After spray coating a commercially available chromate-treated electrogalvanized steel sheet (trade name: Nishin Coat, manufactured by Nippon Steel Corporation) to a film thickness of 2.0μ, it was heated at 100°C for 60 minutes.
Drying was performed for seconds to obtain a surface-treated board.
実施例２
製造例７で得られたカルボキシル化オレフィン系樹脂（
ＩＶ）７０部、製造例２で得られたアクリル系樹脂（Ｉ
［）１５部、製造例５で得られたアクリル系樹脂（■）
４部、及び脱イオン水１１部を混合し、次いで、架橋剤
として、１．６−ヘキサメチレンジエチレンウレア（商
品名：Ｈ２−２２日本触媒化学工業（株）製）ｏ、１部
を加え、５０℃で１２時間反応後、水分散性シリカ＜Ｉ
＞（商品名：Ｃａｔａｌｏｉｄ ５ｉ−３５０Ｓ ｉ
Ｏ２３０％品）２０部を加え、金属表面処理用組成物を
得な、この組成物を板厚０．６＋ｎｓ＋のクロメート処
理された市販の電気ｇ！鉛めっき鋼板（商品名ニシンコ
ート、新日本製鉄（株）製）に膜厚２．０μになる様に
スプレー塗布後、１００″Ｃで６０秒間乾燥を行い、表
面処理板を得た。Example 2 Carboxylated olefin resin obtained in Production Example 7 (
IV) 70 parts, acrylic resin obtained in Production Example 2 (I
[) 15 parts, acrylic resin obtained in Production Example 5 (■)
4 parts and 11 parts of deionized water were mixed, and then 1 part of 1,6-hexamethylene diethylene urea (trade name: H2-22 manufactured by Nippon Shokubai Chemical Co., Ltd.) was added as a crosslinking agent, After reaction at 50°C for 12 hours, water-dispersible silica<I
＞(Product name: Cataloid 5i-350S i
Add 20 parts of O2 (30% product) to obtain a composition for metal surface treatment, and apply this composition to a commercially available chromate-treated electric g! A lead-plated steel plate (trade name: Nishin Coat, manufactured by Nippon Steel Corporation) was spray-coated to a film thickness of 2.0 μm, and then dried at 100″C for 60 seconds to obtain a surface-treated plate.
実施例３
製造例７で得られたカルボキシル化オレフィン系樹脂（
ＩＶ）７０部、製造例３で得られたアクリル系樹脂（Ｉ
［）１５部、ａ造例６で得られたアクリル系樹脂（■）
４部、及び脱イオン水１１部を混合し、次いで、架橋剤
として、２．２−ビスヒドロキシメチルブタノール−ト
リス［３−（１−アジリジニル）プロピオネート］（商
品名：ＰＺ−３３日本触媒化学工業（株）製］０．１部
を加え、５０°Ｃで１２時間反応後、水分散性シリカ（
■）（商品名ニスノーテックスＸ Ｓ 、 Ｓ ｉＯ２
２０％品）３３部を加え、金属表面処理用組成物を得た
。この組成物を板厚０．６關のクロメート処理された市
販の電気亜鉛めっき鋼板（商品名ニシンコート、新日本
製鉄（株）製）に膜厚２．０μになる様にスプレー塗布
後、１００℃で６０秒間乾燥を行い、表面処理板を得な
。Example 3 Carboxylated olefin resin obtained in Production Example 7 (
IV) 70 parts, acrylic resin obtained in Production Example 3 (I
[) 15 parts, a Acrylic resin obtained in Formation Example 6 (■)
4 parts and 11 parts of deionized water, and then, as a crosslinking agent, 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate] (trade name: PZ-33 Nippon Shokubai Chemical Co., Ltd.) Co., Ltd.] was added, and after reacting at 50°C for 12 hours, water-dispersible silica (
■) (Product name: Nisnortex X S, S iO2
20% product) was added to obtain a composition for metal surface treatment. This composition was sprayed onto a commercially available electrogalvanized steel sheet (trade name Nishin Coat, manufactured by Nippon Steel Corporation) that had been chromate-treated and had a thickness of 0.6 μm to a film thickness of 2.0 μm. Dry at ℃ for 60 seconds to obtain a surface-treated board.
実施例４
製造例８で得られたカルボキシル化オレフィン系樹脂（
ＩＶ）７０部、製造例３で得られたアクリル系樹脂（Ｉ
Ｉ）１５部、製造例５で得られたアクリル系樹脂（■）
４部、及び脱イオン水１１部を混合し、次いで、架橋剤
として、１．６−ヘキサメチレンジエチレンウレア（商
品名：Ｈ２−２２日本触媒化学工業（株）製）０．１部
を加え、５０°Ｃで１２時間反応後、水分散性シリカ（
Ｉ）（商品名ニスノーテックスＸ Ｓ 、 Ｓ ｉＯ２
２０％品）３３部を加え、金属表面処理用組成物を得た
。Example 4 Carboxylated olefin resin obtained in Production Example 8 (
IV) 70 parts, acrylic resin obtained in Production Example 3 (I
I) 15 parts, acrylic resin obtained in Production Example 5 (■)
4 parts and 11 parts of deionized water were mixed, and then 0.1 part of 1,6-hexamethylene diethylene urea (trade name: H2-22 manufactured by Nippon Shokubai Chemical Co., Ltd.) was added as a crosslinking agent. After reacting at 50°C for 12 hours, water-dispersible silica (
I) (Product name: Nisnortex X S, SiO2
20% product) was added to obtain a composition for metal surface treatment.
この組成物を板厚０．６ｍｍのクロメート処理された市
販の電気亜鉛めっき鋼板（商品名ニシンコート、新日本
製鉄（株）製）に膜厚２．０μになる様にスプレー塗布
後、１００℃で６０秒間乾燥を行い、表面処理板を得た
。This composition was sprayed onto a chromate-treated commercially available electrogalvanized steel sheet (trade name Nishin Coat, manufactured by Nippon Steel Corporation) with a thickness of 0.6 mm to a film thickness of 2.0 μm, and then heated to 100°C. The plate was dried for 60 seconds to obtain a surface-treated plate.
実施例５
製造例９で得られたカルボキシル化オレフィン系樹脂（
ＩＶ）７０部、製造例２で得られたアクリル系樹脂（Ｉ
Ｉ）１５部、製造例５で得られたアクリル系樹脂（■）
４部、及び脱イオン水１１部を混合し、次いで、架橋剤
として、２．４−ジエチレンウレアトルイジン０．１５
部を加え５０°Ｃで１２時間反応後、水分散性シリカ（
Ｉ）（商品名：Ｃａｔａｌｏｉｄ ５ｔ−５００Ｓｉ
０２２０％品）３３部を加え、金属表面処理用組成物を
得た。Example 5 Carboxylated olefin resin obtained in Production Example 9 (
IV) 70 parts, acrylic resin obtained in Production Example 2 (I
I) 15 parts, acrylic resin obtained in Production Example 5 (■)
and 11 parts of deionized water, and then 0.15 parts of 2,4-diethyleneureatluidine as a crosslinking agent.
After reacting at 50°C for 12 hours, water-dispersible silica (
I) (Product name: Cataloid 5t-500Si
0220% product) was added to obtain a composition for metal surface treatment.
この組成物を板厚０．６ｍ＋のクロメート処理された市
販の電気亜鉛めっき鋼板（商品名ニシンコート、新日本
製鉄（株）製）に膜厚２．０μになる様にスプレー塗布
後、１００°Ｃで６０秒間乾燥を行い、表面処理板を得
た。This composition was sprayed onto a chromate-treated commercially available electrogalvanized steel sheet (trade name: Nishin Coat, manufactured by Nippon Steel Corporation) with a thickness of 0.6m+ to a film thickness of 2.0μ, and then heated at 100°. It was dried at C for 60 seconds to obtain a surface-treated board.
比較例１
製造例３で得られた、アクリル系樹脂（■）２６７部、
製造例４で得られた、アクリル系樹脂（Ｉ）２００部及
びさらに、水分散性シリカ（Ｉ）（商品名：スノーテツ
クスＣ、Ｓ ｉ ０２２０％品）２００部及び５％無水
クロム酸１０部を加えて全体を脱イオン水で１１にする
ことにより、金属表面処理用組成物を得た。この組成物
を板厚０．６柑のクロメート処理された市販の電気亜鉛
めっき鋼板（商品名ニシンコート、新日本製鉄（株）製
）に膜厚２．０μになる様にスプレー塗布後、１００°
Ｃで６０秒間乾燥を行い、表面処理板を得た。Comparative Example 1 267 parts of acrylic resin (■) obtained in Production Example 3,
200 parts of the acrylic resin (I) obtained in Production Example 4, and further 200 parts of water-dispersible silica (I) (trade name: Snowtex C, S i 02 20% product) and 10 parts of 5% chromic anhydride. In addition, the whole was made up to 11 with deionized water to obtain a composition for metal surface treatment. This composition was spray-coated to a film thickness of 2.0 μm on a commercially available electrogalvanized steel sheet (trade name: Nishin Coat, manufactured by Nippon Steel Corporation) that had been chromate-treated and had a thickness of 0.6 μm. °
It was dried at C for 60 seconds to obtain a surface-treated board.
比軸例２
製造例７で得られたカルボキシル化オレフィン系樹脂（
ＩＶ）７０部に製造例２で得られたアクリル系樹脂（Ｉ
Ｉ）１５部及び製造例５で得られたアクリル系樹脂（■
）４部、及び脱イオン水１１部を混合し、さらに、水分
散性シリカ（■）：（商品名ニスノーテックスＸ Ｓ
、 Ｓ ｉＯ２２０％品）３３部を加え、金属表面処理
用組成物を得た。Ratio Example 2 Carboxylated olefin resin obtained in Production Example 7 (
IV) 70 parts of the acrylic resin obtained in Production Example 2 (I
I) 15 parts and the acrylic resin obtained in Production Example 5 (■
) and 11 parts of deionized water, and further water-dispersible silica (■): (Product name: Nisnortex X S
, 33 parts of SiO2 (20% product) was added to obtain a composition for metal surface treatment.
この組成物を板厚０．６關のクロメート処理された市販
の電気亜鉛めっき鋼板（商品名ニシンコート、新日本製
鉄（株）製）に膜厚２．０μになる様にスプレー塗布後
、１００°Ｃで６０秒間乾燥を行い、表面処理板を得た
。This composition was sprayed onto a commercially available electrogalvanized steel sheet (trade name Nishin Coat, manufactured by Nippon Steel Corporation) that had been chromate-treated and had a thickness of 0.6 μm to a film thickness of 2.0 μm. Drying was performed at °C for 60 seconds to obtain a surface-treated board.
比較例３
製造例３で得られたアクリル系樹脂（Ｕ）３３部、製造
例４で得られたアクリル系樹脂（■）２５部、脱イオン
水４２部、及び架橋剤としてＤＺ＝２２Ｎを１．０部加
え、５０℃で１２時間反応後、水分散性シリカ（■）（
商品名ニスノーテックスＣ、Ｓ ｉＯ２２０％品）３３
部を加え、金属表面処理用組成物を得た。この組成物を
板厚０゜６關のクロメート処理された市販の電気亜鉛め
っき鋼板（商品名ニシンコート、新日本製鉄（株）製）
に膜厚２．０μになる様にスプレー塗布後、１００℃で
６０秒間乾燥を行い、表面処理板を得た。Comparative Example 3 33 parts of the acrylic resin (U) obtained in Production Example 3, 25 parts of the acrylic resin (■) obtained in Production Example 4, 42 parts of deionized water, and 1 part of DZ=22N as a crosslinking agent. After adding .0 parts and reacting at 50°C for 12 hours, water-dispersible silica (■) (
Product name: Varnish Notex C, SiO2 20% product) 33
A composition for metal surface treatment was obtained. A commercially available electrogalvanized steel sheet (trade name: Nishin Coat, manufactured by Nippon Steel Corporation) that has been chromate-treated with this composition has a thickness of 0°6.
After spray coating to a film thickness of 2.0 μm, drying was performed at 100° C. for 60 seconds to obtain a surface-treated board.
これら得られた処理板の試験結果を表−１に示した。The test results of these treated plates are shown in Table 1.
なお評価は、次のようにして行った。The evaluation was performed as follows.
■耐溶剤性二石油ベンジンをしみ込ませたガーゼに、５
００ｇの荷重をかけ１０往復
ラビングテストした。■Gauze impregnated with solvent-resistant di-petroleum benzine, 5
A 10-reciprocating rubbing test was performed with a load of 0.00 g applied.
◎・・・変化なし、
○・・・すり疵あり、
Δ・・・一部溶出、
×・・・溶出
■１次耐食性：ＪＩＳＺ−２３７１により５００時間塩
水噴霧試験を行い、白錆発
生面積を％で評価した。◎... No change, ○... Scratches present, Δ... Partially eluted, ×... Eluted ■Primary corrosion resistance: A salt spray test was conducted for 500 hours according to JIS Z-2371, and the area where white rust occurred was determined. It was evaluated in %.
■絞り加工性： ５０ｍ＋ｏＸ ５０ｍｍの角頭を用い
、シワおさえ５００１ｑｒで３０間の深さ
まで絞り加工後に脱脂し、粘着テ
ープを圧着後はがしてその内面を
評価した。■Drawing workability: Using a square head of 50m+oX 50mm, the workpiece was drawn to a depth of 30m with a wrinkle suppressor of 5001qr, degreased, and the adhesive tape was crimped and peeled off to evaluate its inner surface.
◎・・・ハクリなし、 ○・・・はとんどハクリなし、 Δ・・・一部はくり、 ×・・・全面はくり。◎・・・No peeling, ○...There is almost no peeling, Δ...partly peeled off, ×... Fully peeled off.
■密着性：エリクセン試験機 １０ｗ押出し後、セロファンチー プを圧着させた後、これをはがし、 １０点（満点）法で評価した。■Adhesion: Erichsen tester Cellophane tea after 10W extrusion After crimping the tape, peel it off. Evaluation was made using a 10-point (full score) system.
■塗料密＠性：市販のメラミン−アルキッド樹脂ＰＷＣ
５０％を膜厚的２５μにな
る様に１３０℃Ｘ２０分間焼付け
したのち、３０分、湧水処理し、
１１ＩｌＩＩ幅１０ＸＩＯの基盤目を入れたのち、エリ
クセ２７間押出し後、
セロファンテープを圧着させたの
ちこれをはがし、１０点く満点）
法で評価した。■Paint density: Commercially available melamine-alkyd resin PWC
50% was baked at 130℃ for 20 minutes to a film thickness of 25μ, then treated with spring water for 30 minutes, and a base grain of 11IlII width 10XIO was put in. After extruding for 27 minutes with elixir, cellophane tape was crimped. This was later peeled off and evaluated using the 10-point scale.
■耐ブロッキング性二両面に金属表面処理剤用組成物を
塗布した処理板を、５０關
Ｘ５０鴎の大きさに切断し、４枚
重ねて５０℃で１０００ｋＩｒ／−の
圧力下で２０分間圧着後、そのブ
ロッキング性を測定した。■ Blocking resistance A treated plate coated with a composition for metal surface treatment agent on both sides was cut into a size of 50 x 50 pieces, stacked in four pieces and pressed together at 50℃ for 20 minutes under a pressure of 1000 kIr/-. , and its blocking properties were measured.
◎・・・ブロッキングなし、 Ｏ・・・ややブロッキングあり、 △・・・一部塗膜がブロッキングして はがれる。◎・・・No blocking, O: Slight blocking, △・・・Part of the coating film is blocking. It peels off.
Ｘ・・・全面ブロッキング ■潤滑性：動摩擦係数の測定 ＡＳＴＭ Ｄ−１８９４により測定 ■硬度 ：鉛筆硬度 塗膜用鉛筆引っかき試験機を用い、 １．０±０．０５ｋｇの荷重をかけ、 日塗検検査済引っかき試験用鉛筆で塗 面を引っかき、きす跡の残らないとき の鉛筆の硬さ。X...Full blocking ■Lubricity: Measurement of dynamic friction coefficient Measured according to ASTM D-1894 ■Hardness: Pencil hardness Using a paint film pencil scratch tester, Apply a load of 1.0±0.05kg, Painted with a scratch test pencil When you scratch the surface and no scratch marks remain The hardness of the pencil.
（発明の効果）
本発明の鉄、鋼、合金鋼、亜鉛、亜鉛合金から選ばれる
少なくとも一種の金属表面処理用組成物は、実施例から
も明らかなように、
（１）オレフィン樹脂の導入により、耐溶剤性、絞り加
工性、塗装密着性、潤滑性、硬度を向上させ、（２）さ
らに、架橋剤としてアジリジニル基を有する化合物の添
加により、耐溶剤性と耐ブロッキング性を、その他の性
能を低下させることなく、向上させ、
極めて性能の良い表面処理金属板を作製することができ
る効果を有するものである。(Effects of the Invention) As is clear from the examples, the at least one metal surface treatment composition selected from iron, steel, alloy steel, zinc, and zinc alloy of the present invention has the following effects: (1) By introducing an olefin resin. (2) Furthermore, by adding a compound having an aziridinyl group as a crosslinking agent, solvent resistance and blocking resistance are improved, and other properties are improved. This has the effect of improving the surface-treated metal plate without degrading it, and making it possible to produce a surface-treated metal plate with extremely good performance.
Claims (1)
なくとも一種の金属表面処理用組成物１ｌ当り、 （Ａ）水分散性シリカ（ I ）をＳｉＯ＿２に換算して
０．５〜２５０ｇの範囲の量、 （Ｂ）重合性不飽和基を有するアルコキシシラン化合物
（ａ）０．１〜１０重量％、 重合性不飽和カルボン酸（ｂ）０〜２０重量％、 アルキル基の炭素数が１〜８である（メタ）アクリル酸
アルキルエステル（ｃ）２０〜９９重量％、 これらと共重合可能な単量体（ｄ）０〜４０重量％、 ［ただし、（ａ）、（ｂ）、（ｃ）および（ｄ）の合計
は１００重量％である。］ からなる単量体成分を多段乳化重合して得られる芯部分
のＴｇが１５℃以上であり、最外殻部分のＴｇが１０℃
以下である多層構造共重合体から誘導される陽イオン性
及び／又は両性イオン性アクリル系樹脂（II）を０．５
〜６００ｇの範囲の量、 （Ｃ）Ｔｇが１０℃以上である陽イオン性及び／又は両
性イオン性アクリル系樹脂（III）を０〜６００ｇの範
囲の量、 （Ｄ）陽イオン性及び／又は両性イオン性カルボキシル
化ポリオレフィン系樹脂（IV）を０．５〜６００ｇの範
囲の量、 （ただし、（Ａ）（Ｂ）（Ｃ）および（Ｄ）の合計が、
７００ｇを超えない範囲） （Ｅ）多官能のアジリジニル基を有する化合物を樹脂に
対する固形物の比率で０．１〜１０重量％、 を含有することを特徴とする金属表面処理用組成物。(1) 0.5 to 250 g of (A) water-dispersible silica (I) in terms of SiO_2 per 1 liter of at least one metal surface treatment composition selected from iron, steel, alloy steel, zinc, and zinc alloy; (B) an alkoxysilane compound having a polymerizable unsaturated group (a) 0.1 to 10% by weight; a polymerizable unsaturated carboxylic acid (b) 0 to 20% by weight; the number of carbon atoms in the alkyl group is 1 to 8 (meth)acrylic acid alkyl ester (c) 20 to 99% by weight, a monomer copolymerizable with these (d) 0 to 40% by weight, [However, (a), (b), The sum of (c) and (d) is 100% by weight. ] The Tg of the core portion obtained by multistage emulsion polymerization of the monomer component consisting of is 15°C or higher, and the Tg of the outermost shell portion is 10°C.
0.5 cationic and/or zwitterionic acrylic resin (II) derived from the following multilayer copolymer:
(C) an amount of cationic and/or amphoteric acrylic resin (III) having a Tg of 10° C. or more in a range of 0 to 600 g; (D) a cationic and/or zwitterionic acrylic resin (III); Zwitterionic carboxylated polyolefin resin (IV) in an amount ranging from 0.5 to 600 g (provided that the sum of (A), (B), (C), and (D) is
700 g) (E) A composition for metal surface treatment, comprising: (E) a compound having a polyfunctional aziridinyl group in a ratio of 0.1 to 10% by weight of solids to resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8110787A JPS63248872A (en) | 1987-04-03 | 1987-04-03 | Composition for treating metallic surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8110787A JPS63248872A (en) | 1987-04-03 | 1987-04-03 | Composition for treating metallic surface |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63248872A true JPS63248872A (en) | 1988-10-17 |
Family
ID=13737156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8110787A Pending JPS63248872A (en) | 1987-04-03 | 1987-04-03 | Composition for treating metallic surface |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63248872A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085566C (en) * | 1995-01-31 | 2002-05-29 | 株式会社神户制钢所 | Metal plate coated with resin and production method thereof |
| JP2008179754A (en) * | 2006-12-27 | 2008-08-07 | Asahi Kagaku Kogyo Co Ltd | Coating fluid and clear-coated steel sheet |
| JP2009270034A (en) * | 2008-05-09 | 2009-11-19 | Asahi Kasei Chemicals Corp | Water-based resin composition |
| JP2009270035A (en) * | 2008-05-09 | 2009-11-19 | Asahi Kasei Chemicals Corp | Water base resin composition for clear paint |
| WO2013047880A1 (en) * | 2011-09-30 | 2013-04-04 | ダイキン工業株式会社 | Composition and coated article |
| WO2018040374A1 (en) * | 2016-08-29 | 2018-03-08 | 常熟市诺信达机械设备有限公司 | Cloth laying machine for industrial production |
-
1987
- 1987-04-03 JP JP8110787A patent/JPS63248872A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085566C (en) * | 1995-01-31 | 2002-05-29 | 株式会社神户制钢所 | Metal plate coated with resin and production method thereof |
| JP2008179754A (en) * | 2006-12-27 | 2008-08-07 | Asahi Kagaku Kogyo Co Ltd | Coating fluid and clear-coated steel sheet |
| JP2009270034A (en) * | 2008-05-09 | 2009-11-19 | Asahi Kasei Chemicals Corp | Water-based resin composition |
| JP2009270035A (en) * | 2008-05-09 | 2009-11-19 | Asahi Kasei Chemicals Corp | Water base resin composition for clear paint |
| WO2013047880A1 (en) * | 2011-09-30 | 2013-04-04 | ダイキン工業株式会社 | Composition and coated article |
| JP2013082925A (en) * | 2011-09-30 | 2013-05-09 | Daikin Industries Ltd | Composition, and coated article |
| WO2018040374A1 (en) * | 2016-08-29 | 2018-03-08 | 常熟市诺信达机械设备有限公司 | Cloth laying machine for industrial production |
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