JPH0326539A - Anti-corrossive painted steel plate excellent in weldability - Google Patents
Anti-corrossive painted steel plate excellent in weldabilityInfo
- Publication number
- JPH0326539A JPH0326539A JP16286889A JP16286889A JPH0326539A JP H0326539 A JPH0326539 A JP H0326539A JP 16286889 A JP16286889 A JP 16286889A JP 16286889 A JP16286889 A JP 16286889A JP H0326539 A JPH0326539 A JP H0326539A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- amount
- colloidal silica
- film layer
- zinc
- 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
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 55
- 239000010959 steel Substances 0.000 title claims abstract description 55
- 229920005989 resin Polymers 0.000 claims abstract description 78
- 239000011347 resin Substances 0.000 claims abstract description 78
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000003822 epoxy resin Substances 0.000 claims abstract description 36
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000008119 colloidal silica Substances 0.000 claims abstract description 27
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011701 zinc Substances 0.000 claims abstract description 22
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 21
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 4
- 239000000956 alloy Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 27
- 239000003431 cross linking reagent Substances 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 abstract description 40
- 239000011248 coating agent Substances 0.000 abstract description 35
- 238000000576 coating method Methods 0.000 abstract description 35
- 230000007797 corrosion Effects 0.000 abstract description 34
- 238000000034 method Methods 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 23
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 20
- 239000011651 chromium Substances 0.000 description 20
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 17
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 16
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 14
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 14
- 238000004070 electrodeposition Methods 0.000 description 14
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 14
- 238000003466 welding Methods 0.000 description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 10
- 239000004721 Polyphenylene oxide Substances 0.000 description 10
- 229910052804 chromium Inorganic materials 0.000 description 10
- 229920000570 polyether Polymers 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000009467 reduction Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000010828 elution Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- -1 zinc chrome metals Chemical class 0.000 description 5
- 241000238557 Decapoda Species 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910001297 Zn alloy Inorganic materials 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000007373 indentation Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- 241000501754 Astronotus ocellatus Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000003944 halohydrins Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000013034 phenoxy resin Substances 0.000 description 2
- 229920006287 phenoxy resin Polymers 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- SYQQWGGBOQFINV-FBWHQHKGSA-N 4-[2-[(2s,8s,9s,10r,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-3-oxo-1,2,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-2-yl]ethoxy]-4-oxobutanoic acid Chemical compound C1CC2=CC(=O)[C@H](CCOC(=O)CCC(O)=O)C[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 SYQQWGGBOQFINV-FBWHQHKGSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910018605 Ni—Zn Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229910007567 Zn-Ni Inorganic materials 0.000 description 1
- 229910007614 Zn—Ni Inorganic materials 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012261 resinous substance Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000009528 severe injury Effects 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は、特に自動車用に適した、溶接性に優れた防錆
塗装鋼板に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a rust-proof coated steel sheet with excellent weldability, which is particularly suitable for automobiles.
(従来の技術)
電気抵抗溶接可能な防錆塗装鋼板は、たとえば積雪地帯
の道路に融雪剤として散布される塩による自動車の請を
防ぐ目的で、我国においても次第に使われるようになっ
てきている。(Prior Art) Rust-prevention coated steel sheets that can be electrically resistance welded are increasingly being used in Japan, for example, to prevent automobile damage caused by salt sprayed as a snow-melting agent on roads in snow-covered areas. .
従来の溶接可能な防錆塗装鋼板としては、ジンクロメタ
ル(商品名:米国ダイヤモンド・ジャムロック社)で代
表されるジンクリッチ・ブライマーを塗装した鋼板があ
る。ジンクロメタルは、鋼板の上に亜鉛末およびクロム
酸を主戒分とする下地クロメート層(ダクロメット)と
、大量の亜鉛を含有するエポキシ樹脂からなるジンクリ
ッチ・プライマ一層(ジンクロメット)とを形成した防
錆塗装鋼板であり、冷延鋼板に比べて著しく優れた耐食
性を示す.
一般に自動車用の防錆塗装鋼板には、耐食性に加えて、
戒形加工性および溶接性が要求されるが、上述したジン
クロメタルは特に成形加工性と耐食性が十分でない.こ
れは、これらの鋼板に使用されているジンクリンチ・ブ
ライマーが溶接性確保の目的で体積%で50%前後、重
量%では約85〜90%という大量の亜鉛末を含有して
いるため、形成された塗膜が脆く、加工時に剥離を生じ
やすいためである。これにより耐食性が低下すると共に
、脱落した塗膜がプレス型に付着して傷の原因となるた
め、金型の手入れ頻度が増して作業性が悪化する.また
、ジンクリッチ・ブライマーは塗膜中ヘの水分の透過性
が大きく、これも耐食性の低下傾向につながる。塗膜剥
離および耐食性低下を軽減するには亜鉛末の量を減少さ
せることが有効であるが、塗膜の電気抵抗が増すため、
抵抗溶接が不利ないし不可能になる.
また、従来のジンクロメタルではジンクリッチブライマ
ーの焼付に250〜280゜Cという高温焼付を必要と
するため、鋼板の焼付硬化性が損なわれる欠点を有して
いた。焼付硬化性とは、ユーザーにおいてプレス等の加
工を行い、電着塗装等で焼付を行うことにより、鋼板の
降伏応力が増加する性質をいう。Conventional weldable anti-corrosion coated steel plates include steel plates coated with zinc-rich brimer such as Zinchrome Metal (trade name: Diamond Jamrock Co., Ltd., USA). Zinchrome metal is produced by forming a base chromate layer (Dacromet) containing zinc powder and chromic acid as the main ingredients, and a zinc-rich primer layer (Zinchromet) consisting of an epoxy resin containing a large amount of zinc on a steel plate. It is a steel plate with anti-corrosion coating and exhibits significantly superior corrosion resistance compared to cold-rolled steel plate. In general, anti-rust coated steel sheets for automobiles have, in addition to corrosion resistance,
Formability and weldability are required, but the zinc chrome metals mentioned above do not particularly have sufficient formability and corrosion resistance. This is because the zinc clinch/brimer used for these steel sheets contains a large amount of zinc powder, approximately 50% by volume and approximately 85-90% by weight, in order to ensure weldability. This is because the coating film is brittle and easily peels off during processing. This reduces corrosion resistance, and the paint film that falls off adheres to the press mold and causes scratches, which increases the frequency of mold maintenance and deteriorates workability. In addition, zinc-rich brimer has high moisture permeability into the coating film, which also tends to reduce corrosion resistance. Reducing the amount of zinc dust is effective in reducing paint peeling and deterioration of corrosion resistance, but it increases the electrical resistance of the paint film.
Resistance welding becomes disadvantageous or impossible. In addition, conventional zinc chrome metals require baking at a high temperature of 250 to 280°C to bake the zinc rich primer, which has the disadvantage of impairing the bake hardenability of the steel plate. Bake hardenability refers to the property that the yield stress of a steel sheet increases when the user performs processing such as pressing and bakes with electrodeposition coating or the like.
(発明が解決しようとする諜M)
本発明者らは、ジンクリンチ・ブライマーの上述した欠
点を解消すべく検討した結果、めっき鋼板を母材とし、
その上に下地層としてクロム酸とコロイダルシリカとを
含有する水性懸濁液を塗布・焼付してクロメート皮膜を
形成させた後、顔料を含有しないか、またはクロム酸塩
系顔料を含有させたポリヒドロキシボリエーテル樹脂溶
液の塗布・焼付により上層のクリアー塗膜を形或すると
、抵抗溶接可能でしかも耐食性および成形加工性に優れ
た防錆塗装鋼板が得られることを先に提案した(特開昭
63 − 69917号公報)。この鋼板は、焼付硬化
性を損なわない比較的低温での焼付が可能であるので、
得られた塗装鋼板は安定して焼付硬化性を保持している
,
さらに、本発明者らは、上記防錆塗装鋼板の改良として
、各種無機充填材および架橿剤の少なくとも1種を上層
塗膜形成用の樹脂液に配合することにより、上層・塗膜
を汎用のエポキシ樹脂もしくは変性エポキシ樹脂から形
戒でき、しかも、クロム酸塩系顔料を含有させずに優れ
た耐食性を得ることができることも提案した(特開平1
−80522号公報)。(Intelligence M to be Solved by the Invention) As a result of the inventors' study to eliminate the above-mentioned drawbacks of the zinc clinch and brimer, the present inventors found that using a plated steel plate as a base material,
After coating and baking an aqueous suspension containing chromic acid and colloidal silica as a base layer to form a chromate film, a polyester film containing no pigment or a chromate-based pigment is applied. We previously proposed that by forming the upper clear coating film by applying and baking a hydroxybolyether resin solution, it is possible to obtain a rust-proof coated steel sheet that can be resistance welded and has excellent corrosion resistance and formability. 63-69917). This steel plate can be baked at relatively low temperatures without impairing bake hardenability.
The obtained coated steel sheet stably maintains bake hardenability.Furthermore, as an improvement to the above-mentioned anti-rust coated steel sheet, the present inventors applied an upper layer of at least one of various inorganic fillers and crosslinking agents. By blending it into the resin liquid for film formation, the upper layer/coating film can be made from general-purpose epoxy resin or modified epoxy resin, and excellent corrosion resistance can be obtained without containing chromate pigments. also proposed (Unexamined Japanese Patent Publication No.
-80522).
しかし、最近、自動車用鋼板としては、より高度の溶接
作業性が要求されるようになってきており、従来の溶接
性のレベルでは対応が困難となる場合がある.特に、シ
リーズ・スポット溶接において、溶接電極のチップが樹
脂塗装面に当たるような組合わせで連続打点性を調査す
ると、不十分な結果になることがある。However, recently, steel sheets for automobiles have come to be required to have a higher level of welding workability, and it may be difficult to meet these demands with conventional weldability levels. In particular, in series spot welding, if the welding electrode tip hits the resin-coated surface in combination to investigate the continuous dot performance, the results may be unsatisfactory.
溶接性を向上させる手段として、例えば、上述のジンク
リッチ・プライマーの如く、導電粉を含有させるという
方法があるが、耐食性やプレス作業性に問題が出てくる
.その他の手段として、本発明者らが提案した、母材め
っき鋼板の表面上に上層クリアー膜厚に応じた適切な突
起を設けることにより良好な通電性を確保するという方
法もある(特願昭63 − 297886号).シかし
、この方法にも、ダルロールによる圧延などの余分な工
程を必要とするという欠点がある.
(課題を解決するための手段)
防錆塗装鋼板の下層皮膜に用いられるクロメート処理方
法は、■塗布型クロメート処理、■反応型クロメート処
理、および■電解クロメート処理の3種類に大別される
.このうち、反応型クロメート処理および電解クロメー
ト処理は、塗布型クロメート処理に比べると耐食性が劣
り、また処理条件の管理も難しい.そのため一般的には
塗布型クロメート処理が用いられている.
塗布型クロメート処理液には、ほとんどの場合、コロイ
ダルシリカなどのコロイド状物質が添加されている.こ
れは、耐食性、電着塗装性および耐クロム溶出性の改善
を目的としている。ところが、本発明者らは、クロメー
ト皮膜中および上層樹脂皮膜中のコロイド状物質が防錆
塗装鋼板の溶接性に及ぼす影響を調査した結果、クロメ
ート皮膜中のコロイド状物質の量が溶接性を大きく左右
することを見出した。One way to improve weldability is to include conductive powder, such as the zinc-rich primer mentioned above, but this poses problems in corrosion resistance and press workability. Another method proposed by the present inventors is to ensure good electrical conductivity by providing appropriate protrusions on the surface of the base plated steel sheet according to the thickness of the upper layer clear film. 63-297886). However, this method also has the disadvantage of requiring extra steps such as rolling with dull rolls. (Means for solving the problem) The chromate treatment methods used for the lower layer coating of anti-corrosion coated steel sheets are broadly divided into three types: ■ Spray-on chromate treatment, ■ Reactive chromate treatment, and ■ Electrolytic chromate treatment. Of these, reactive chromate treatment and electrolytic chromate treatment have inferior corrosion resistance compared to coating-type chromate treatment, and the treatment conditions are difficult to control. Therefore, coating-type chromate treatment is generally used. Most coated chromate treatment solutions contain colloidal substances such as colloidal silica. This is aimed at improving corrosion resistance, electrodeposition coating properties, and chromium elution resistance. However, as a result of investigating the effects of colloidal substances in the chromate film and the upper resin film on the weldability of anti-corrosion coated steel sheets, the inventors found that the amount of colloidal substances in the chromate film greatly affected the weldability. I found out that it depends.
すなわち、下層のクロメート皮膜に存在するコロイド状
物質の量が多いほど溶接性が低下し、下層にコロイド状
物質が存在しない場合には、溶接性、特にダイレクト・
スポット溶接やシリーズ・スボッ[9接の連続打点性が
大きく改善された。In other words, the greater the amount of colloidal material present in the underlying chromate film, the lower the weldability, and when no colloidal material is present in the underlying chromate film, the weldability, especially direct weldability, decreases.
The continuous welding performance of spot welding and series/spot [9 contacts has been greatly improved.
上層のクリアー皮膜中のコロイド状物質の量が溶接性に
及ぼす影響は、クロメート皮膜中のコロイド状物質の量
ほどは大きくなく、そのため上層のみにコロイダルシリ
カを含有させることにより、良好な溶接性が確保される
ことが判明した.この理由の詳細は不明であるが、同じ
コロイダルシリ力でも、クロメート皮膜中と樹脂皮膜中
では、溶接時における挙動が異なるためではないかと推
察される。つまり、クロメート皮膜中にコロイダルシリ
カが存在すると、コロイダルシリカはクロメートに比べ
てかなり高い電気抵抗を有する物質であるので、電極一
鋼板間での発熱が高くなって電極損傷が激しくなり、連
続打点性が劣化すると考えられる.それに対して、樹脂
皮膜中に存在するコロイダルシリカは、溶接時の樹脂の
熱分解に伴ってほとんどが周囲に飛敗するので、溶接性
にあまり影響を与えないものと考えられる。The amount of colloidal substances in the upper layer clear film does not have as great an effect on weldability as the amount of colloidal substances in the chromate film, so by containing colloidal silica only in the upper layer, good weldability can be achieved. It turned out that it was secured. Although the details of the reason for this are unknown, it is presumed that even with the same colloidal silica force, the behavior during welding differs between the chromate film and the resin film. In other words, if colloidal silica exists in the chromate film, since colloidal silica is a substance with considerably higher electrical resistance than chromate, heat generation between the electrode and the steel plate will increase, causing severe damage to the electrode and making continuous dots difficult. is thought to deteriorate. On the other hand, since most of the colloidal silica present in the resin film is blown away to the surroundings as the resin thermally decomposes during welding, it is considered that it does not have much of an effect on weldability.
本発明の基本的な考え方は、従来の通常の塗布型クロメ
ート処理液とは異なり、クロメート処理液にコロイド状
物質を存在させないことで溶接性を向上させ、クロメー
ト皮膜からコロイド状物質を抜いたことによる耐食性、
電着塗装性、耐クロム溶出性の低下を、クロメートの二
段還元および上層樹脂皮膜に適量のコロイダルシリカを
存在させることにより補償するというものである。この
ような組合わせの2N皮膜の各層を比較的薄くすること
よって、亜鉛末などの金属粉を混入しなくても優れた溶
接性を確保することができ、自動車用に適した溶接性に
優れた防錆塗装鋼板が得られることが判明した。The basic idea of the present invention is to improve weldability by eliminating the presence of colloidal substances in the chromate treatment liquid, and to remove the colloidal substances from the chromate film, unlike conventional conventional application-type chromate treatment liquids. Corrosion resistance due to
The reduction in electrodeposition coating properties and chromium elution resistance is compensated for by two-stage reduction of chromate and the presence of an appropriate amount of colloidal silica in the upper resin film. By making each layer of the 2N coating in this combination relatively thin, it is possible to ensure excellent weldability without mixing metal powder such as zinc dust, and it has excellent weldability suitable for automobiles. It was found that a rust-proof coated steel plate could be obtained.
本発明の要旨は、亜鉛もしくは亜鉛系合金めっき鋼板上
に、Cr3+/全CrO比が0.4 〜0.6となるよ
うに部分還元し、さらに未還元のCr”に対して1〜4
当量倍の還元剤を添加した、コロイド状物質を実質的に
含有しない塗布型のクロメート処理液の塗布および焼付
により形成した、Cr付着量として20〜100■/ボ
の下層皮膜と、樹脂液中の全樹脂固形分とコロイダルシ
リカとの合計量に対して10〜25重量%のコロイダル
シリカを添加したエポキシ樹脂をベース樹脂とする樹脂
液の塗布および焼付により形成した、膜[ 0.3〜1
.6−の上層皮膜とを有することを特徴とする、溶接性
に優れた防錆塗装鋼板である.
本発明の好適態様において、クロメート処理液に添加す
る還元剤は、多価アルコールおよび/または多価カルボ
ン酸および/またはオキシカルポン酸であり、このクロ
メート処理液は、モル比で未還元Cr’+の0.01倍
以上のシランカンブリング剤をさらに含有していてもよ
い.また、上記樹脂液はさらに、該エポキシ樹脂中のエ
ポキシ基とヒドロキシ基との合計量に対する架橋剤中の
官能基のモル比が0.1〜0.2となる量の架橋剤およ
び/または樹脂全固形分に対して50重量%以下のエポ
キシ樹脂以外の樹脂を含有していてもよい。エポキシ樹
脂は、変性エポキシ樹脂あるいは単核型および二核型の
2価フェノールから得られた1種もしくは2種以上の2
価フェノールとエピハロヒドリンとの重縮合により得ら
れたポリヒドロキシポリエーテル樹脂であってもよい。The gist of the present invention is to partially reduce a Cr3+/total CrO ratio of 0.4 to 0.6 on a zinc or zinc-based alloy coated steel sheet, and further reduce the Cr3+/total CrO ratio to 1 to 4% with respect to unreduced Cr.
A lower layer film with a Cr adhesion amount of 20 to 100 cm/bo formed by applying and baking a coating-type chromate treatment solution containing substantially no colloidal substances to which an equivalent amount of reducing agent has been added and a resin solution. A film formed by applying and baking a resin liquid based on an epoxy resin containing 10 to 25% by weight of colloidal silica based on the total amount of total resin solid content and colloidal silica.
.. This is a rust-proof coated steel sheet with excellent weldability, characterized by having an upper layer coating of 6-. In a preferred embodiment of the present invention, the reducing agent added to the chromate treatment solution is a polyhydric alcohol and/or a polycarboxylic acid and/or an oxycarboxylic acid, and the chromate treatment solution has a molar ratio of unreduced Cr'+. It may further contain a silane cambling agent of 0.01 times or more. In addition, the resin liquid further contains a crosslinking agent and/or resin in an amount such that the molar ratio of the functional groups in the crosslinking agent to the total amount of epoxy groups and hydroxyl groups in the epoxy resin is 0.1 to 0.2. It may contain resin other than epoxy resin in an amount of 50% by weight or less based on the total solid content. Epoxy resins are modified epoxy resins or one or more types of divalent phenols obtained from mononuclear and dinuclear dihydric phenols.
It may also be a polyhydroxy polyether resin obtained by polycondensation of a hydric phenol and epihalohydrin.
使用する母材鋼板が焼付硬化性を有する鋼板である場合
には、下層および上層のいずれの皮膜も200 ’C以
下の温度で焼付けることが好ましい。When the base steel plate used is a steel plate having bake hardenability, it is preferable that both the lower layer and the upper layer are baked at a temperature of 200'C or less.
(作用)
本発明において、各皮膜形戒用の処理液の組成を上述の
ように限定した理由および各威分の作用について詳述す
る。(Function) In the present invention, the reason why the composition of the treatment liquid for each film type is limited as described above and the effect of each effect will be explained in detail.
クロメー
クロメート膜はクロム酸の還元と水の蒸発により形成さ
れるが、低温において効率良く還元・造膜させるため、
次に述べる二段還元法を用いた。Chromate Chromate film is formed by reduction of chromic acid and evaporation of water, but in order to efficiently reduce and form the film at low temperature,
A two-stage reduction method described below was used.
すなわち、その一段目は、クロム酸水溶液中のクロム酸
(Cr”)を予め部分還元することである.これにより
、加熱乾燥(焼付〉時に還元するクロム酸量を減少させ
、効果的に造膜させることができる。一段目の部分還元
率としては、Cr3+/全C『[=Cr3+/(Cr”
+Cr”)]の比を0.4 〜0.6とする.0.4
未満であると還元効率が劣り、0.6を超えるとCr”
が過剰となり、処理液の安定性が損なわれる恐れがある
。That is, the first step is to partially reduce the chromic acid (Cr") in the chromic acid aqueous solution in advance. This reduces the amount of chromic acid reduced during heat drying (baking) and effectively forms a film. The first stage partial reduction rate is Cr3+/total C ``[=Cr3+/(Cr''
+Cr”)] ratio is 0.4 to 0.6.0.4
If it is less than 0.6, the reduction efficiency will be poor, and if it is more than 0.6, Cr”
may become excessive and the stability of the processing solution may be impaired.
一段目の還元に用いる還元剤は限定されるものではなく
、多価アルコール、多価カルボン酸等が用いられる。ま
た、市販の部分還元クロメート処理液を用いてもよい.
このクロメート処理液には、シランカップリング剤を添
加してもよい.シランカップリング剤は、加水分解して
ボリシロキサンを生成することにより、クロメート皮膜
を強化し、上層皮膜との密着性を向上させる。加水分解
により遊離したアルコールはクロム酸の還元剤として作
用する。使用しうるシランカップリング剤の例には、ビ
ニルトリエトキシシラン、ビニルートリス(β−メトキ
シエトキシ)シラン、T−メタクリロキシプロビルトリ
メトキシシラン、T−グリシドキシブロピルトリメトキ
シシラン、γ−アミノブロピルトリエトキシシラン、N
−β− (アξノエチル)一Tアミノブロビルトリメト
キシシラン、β−(3.4エポキシシクロヘキシル)エ
チルトリメトキシシランなどがある.シランカ7ブリン
グ剤を添加する場合、添加量は未還元クロム酸に対して
モル比で0.01倍以上とする, 0.01倍未満では
その効果が小さい.ただし、あまり多量にボ加すること
は経済的に不利であるばかりか、電着塗装性、耐食性を
も低下させる恐れがあるので、添加量は未還元クロム酸
に対するモル比で3倍以下とすることが好ましい.
クロメート処理液には、耐食性を向上させるために、全
クロム酸に対して等モル以下のリン酸を含有させてもよ
い。The reducing agent used in the first stage reduction is not limited, and polyhydric alcohols, polyhydric carboxylic acids, etc. are used. Alternatively, a commercially available partially reduced chromate treatment solution may be used. A silane coupling agent may be added to this chromate treatment solution. The silane coupling agent hydrolyzes to produce polysiloxane, thereby strengthening the chromate film and improving its adhesion with the upper layer film. The alcohol liberated by hydrolysis acts as a reducing agent for chromic acid. Examples of silane coupling agents that can be used include vinyltriethoxysilane, vinyllutris(β-methoxyethoxy)silane, T-methacryloxypropyltrimethoxysilane, T-glycidoxypropyltrimethoxysilane, γ-amino Propyltriethoxysilane, N
-β- (ξnoethyl)-T aminobrobyltrimethoxysilane, β-(3.4epoxycyclohexyl)ethyltrimethoxysilane, and the like. When adding Silanka 7 bling agent, the amount added should be at least 0.01 times the molar ratio of unreduced chromic acid; if it is less than 0.01 times, its effect will be small. However, adding too much boron is not only economically disadvantageous, but also may reduce electrodeposition coating properties and corrosion resistance, so the amount added should be no more than 3 times the molar ratio of unreduced chromic acid. That is preferable. The chromate treatment solution may contain phosphoric acid in an amount equal to or less than the same mole based on the total chromic acid in order to improve corrosion resistance.
一段目の還元がなされた処理液には、未還元のCr”に
対して1〜4当量倍の還元能力を有する量の還元剤を添
加する。この還元剤の量が1当量倍未満であると、クロ
メート皮膜の耐食性、耐クロム溶出性が不十分となり、
4当量倍を越えると、還元剤の還元作用が飽和するばか
りでなく、還元剤がクロメート皮膜中に残存して皮膜の
耐食性を阻害する。A reducing agent is added to the treatment solution that has been subjected to the first reduction in an amount that has a reducing ability of 1 to 4 times the amount of unreduced Cr. As a result, the corrosion resistance and chromium elution resistance of the chromate film become insufficient.
When the amount exceeds 4 equivalents, not only the reducing action of the reducing agent becomes saturated, but also the reducing agent remains in the chromate film, impairing the corrosion resistance of the film.
還元剤としては、多価アルコール、多価カルボン酸、お
よびオキシカルボン酸の1種もしくは2種以上を用いる
ことが好ましい。多価アルコールとしては、例えばエチ
レングリコール、プロピレングリコール、グリセリン等
がある.多価カルボン酸としては、コハク酸、グルタル
酸、アジビン酸等がある.オキシカルボン酸としては、
クエン酸、乳酸等がある.
この還元剤を添加する時期は、塗装の直前であることか
最も望ましいが、少なくとも塗装前、数日以内とする。As the reducing agent, it is preferable to use one or more of polyhydric alcohols, polycarboxylic acids, and oxycarboxylic acids. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, and glycerin. Examples of polyhydric carboxylic acids include succinic acid, glutaric acid, and adivic acid. As oxycarboxylic acid,
These include citric acid and lactic acid. The most desirable time to add this reducing agent is immediately before painting, but at least within a few days before painting.
この理由は、二段目の還元剤が添加された処理液は、放
置するとゲル化を生じ易いためである.
本発明で使用するクロメート処理液は、上述のように、
コロイダルシリカなどのコロイド状物質を実質的に含有
させない。また、クロム酸塩系あるいはその他の耐食性
顔料やリン化鉄などの導電性微粒子も含有させないこと
が好ましい。すなわち、好ましくは実質的に水溶液状の
クロメート処理液を使用する.
本発明の防錆塗装鋼板において、クロメート処理液の付
着量はクロム量として20〜100mg/rd、好まし
くは40〜70■/rI′rである。付着量が20■/
ボ未満では、耐食性が不十分となり、100■/ボを超
えると、溶接時にチップの損傷が激しくなり、溶接性が
低下する。The reason for this is that the treatment solution to which the second-stage reducing agent has been added tends to gel if left to stand. As mentioned above, the chromate treatment liquid used in the present invention is
It does not substantially contain colloidal substances such as colloidal silica. It is also preferable not to contain chromate-based or other corrosion-resistant pigments or conductive fine particles such as iron phosphide. That is, it is preferable to use a chromate treatment liquid that is substantially in the form of an aqueous solution. In the antirust coated steel sheet of the present invention, the amount of the chromate treatment solution applied is 20 to 100 mg/rd, preferably 40 to 70 .mu./rI'r in terms of chromium amount. Adhesion amount is 20■/
If it is less than 100 cm/bo, the corrosion resistance will be insufficient, and if it exceeds 100 cm/bo, the chip will be severely damaged during welding and weldability will deteriorate.
塗布は、ロールコーター、バーコーターなどの慣用手段
により実施できる。クロメート処理液の焼付は、60〜
200゜C1好ましくは100〜150゜Cで行う.焼
付温度が200゜Cを超えると鋼板の焼付硬化性が阻害
される.
圭夏皮股
上述のように形成された下層のクロメート皮膜の上に、
本発明の防錆塗装鋼板においては、エポキシ樹脂をベー
ス樹脂とし、樹脂液中の全樹脂固形分とコロイダルシリ
カとの合計量に対して10〜25重量%のコロイダルシ
リカを添加した樹脂液の塗布および焼付により、膜厚0
.3〜1.6 peaの上層皮膜が形成される.
エポキシ樹脂としては、ビスフェノールA系、ノボラン
ク系、ビスフェノールF系等の任意のグリシジルエーテ
ル型エポキシ樹脂が使用できる。Coating can be carried out by conventional means such as a roll coater or a bar coater. The baking of chromate treatment liquid is 60~
200°C1 Preferably carried out at 100 to 150°C. If the baking temperature exceeds 200°C, the bake hardenability of the steel sheet will be inhibited. On top of the lower chromate film formed as described above,
In the rust-preventing coated steel sheet of the present invention, a resin solution is applied using an epoxy resin as a base resin and adding colloidal silica in an amount of 10 to 25% by weight based on the total amount of the total resin solid content and colloidal silica in the resin solution. Due to baking and baking, the film thickness is 0.
.. An upper layer film of 3 to 1.6 pea is formed. As the epoxy resin, any glycidyl ether type epoxy resin such as bisphenol A type, novolank type, bisphenol F type can be used.
また、エポキシ樹脂中のエポキシ基およびヒドロキシル
基を乾性油脂肪酸中のカルボキシル基と反応させたエポ
キシエステル樹脂、エポキシ樹脂をイソシアネートと反
応させることにより得られるウレタン変性エポキシ樹脂
、エポキシ樹脂をアクリル酸、メタクリル酸等で変性し
たエポキシアクリレート樹脂などの変性エポキシ樹脂も
使用でき、本明細書では、これらもエポキシ樹脂に含め
る。In addition, epoxy ester resins obtained by reacting the epoxy groups and hydroxyl groups in epoxy resins with carboxyl groups in drying oil fatty acids, urethane-modified epoxy resins obtained by reacting epoxy resins with isocyanates, and epoxy resins obtained by reacting epoxy resins with acrylic acid, methacrylic acid, etc. Modified epoxy resins such as epoxy acrylate resins modified with acids or the like can also be used, and in this specification, these are also included in epoxy resins.
これらの樹脂は、低温焼付により硬化反応が起こらなく
ても塗膜がクッキングを起こさない程度に乾燥するよう
に、分子11000以上のものが望ましい.
本発明においてエポキシ樹脂の1種として好適に使用で
きるものに、ポリヒドロキシボリエーテル樹脂がある.
この樹脂は、単核型もしくは二核型の2価フェノールも
しくは単核型と二核型との混合2価フェノールを、アル
カリ触媒の存在下にほぼ等モル量のエビハロヒドリンと
重縮合させて得られる重合体である.単核型2価フェノ
ールの例はレゾルシン、ハイドロキノンおよびカテコー
ルであり、二核型フェノールの例はビスフェノールAで
あり、これらは単独で使用しても、あるいは2種以上併
用してもよい。エビハロヒドリンの代表例はエビクロロ
ヒドリンである。2価フェノールがレゾルシンとビスフ
ェノールAのモル比1/1の混合物である場合のポリヒ
ドロキシボリエーテル樹脂は下記構造式で示される反復
単位から構威される。These resins preferably have a molecular weight of 11,000 or more so that the coating film dries to an extent that cooking does not occur even if no curing reaction occurs due to low-temperature baking. Polyhydroxy polyether resin is one of the epoxy resins that can be suitably used in the present invention.
This resin is obtained by polycondensing mononuclear or dinuclear dihydric phenol or a mixed dihydric phenol of mononuclear and dinuclear type with approximately equimolar amount of shrimp halohydrin in the presence of an alkaline catalyst. It is a polymer. Examples of mononuclear dihydric phenols are resorcinol, hydroquinone and catechol, and examples of dinuclear phenol are bisphenol A, which may be used alone or in combination of two or more. A typical example of shrimp halohydrin is shrimp chlorohydrin. When the dihydric phenol is a mixture of resorcinol and bisphenol A at a molar ratio of 1/1, the polyhydroxy polyether resin is composed of repeating units represented by the following structural formula.
また、2価フェノールがレゾルシン単独である場合の樹
脂の反復単位は下記構造式で示される。Further, when the dihydric phenol is resorcinol alone, the repeating unit of the resin is shown by the following structural formula.
ボリヒド口キシボリエーテル樹脂はエポキシ樹脂と同様
の原料から製造されるので、本発明ではこれもエポキシ
樹脂の中に含めるものとする.ただし、この樹脂は、エ
ポキシ樹脂とは違って末端エポキシ基を持たず、数平均
分子量が約5000以上、好ましくは約8000〜so
,oooと通常のエポキシ樹脂よりかなり大きな熱可塑
性樹脂である.ビスフェノールAとエビクロロヒドリン
から製造したポリヒドロキシボリエーテル樹脂は米国ユ
ニオン・カーバイド社よりフェノキシ樹脂PKH}Iと
して市販されている.
上記構造式から明らかなように、ポリヒドロキシボリエ
ーテル樹脂は連鎖中に○H基と一〇一基を多数含んでい
る。通常のエポキシ樹脂も、やはり多くのOH基と一〇
一基とを連鎖内に有している。OH基は基体と水素結合
を形或するので、密着力の増大に寄与し、一〇一基は分
子内の回転を容易に生じるため、樹脂の可撓性増大に寄
与する。Since polyhyde-oxybolyether resins are manufactured from the same raw materials as epoxy resins, they are also included in the epoxy resins in the present invention. However, unlike epoxy resins, this resin does not have a terminal epoxy group and has a number average molecular weight of about 5,000 or more, preferably about 8,000 to so.
, ooo, it is a thermoplastic resin that is considerably larger than normal epoxy resin. A polyhydroxy polyether resin made from bisphenol A and shrimp chlorohydrin is commercially available as phenoxy resin PKH}I from Union Carbide Company of the United States. As is clear from the above structural formula, the polyhydroxy polyether resin contains a large number of ○H groups and 101 groups in the chain. Ordinary epoxy resins also have many OH groups and 101 groups in the chain. Since the OH group forms a hydrogen bond with the substrate, it contributes to an increase in adhesion, and since the 101 group easily causes intramolecular rotation, it contributes to an increase in the flexibility of the resin.
2価フェノールがビスフェノールAのような二核型のも
のであるよりもレゾルシンのような単核型のものである
方が、2価フェノールの分子量が小さいために、重量当
たりのこれらの官能基の個数が増大する.従って、レゾ
ルシンのような単核型2価フェノールの含有率が多いほ
ど、上記官能基の連鎖中の含有率が増大し、得られる塗
膜の密着性や可撓性が増大する傾向がある.この意味で
、ポリヒドロキシボリエーテル樹脂を使用する場合、2
価フェノールはレゾルシンのような単核型のものを少な
くとも一部、例えば、約50モル%もしくはそれ以上含
有するものが好ましい。同様に、他のエポキシ樹脂を使
用する場合であっても、樹脂中の○H基と一〇一基の個
数が多いものを使用する方が一般に有利である.
以上のようなポリヒドロキシボリエーテル樹脂を含むエ
ポキシ樹脂の1種もしくは2種以上を使用し、これを、
乾燥速度、平滑性などの要求特性を考慮して選択した適
当な有機溶剤に溶解させて塗布用の樹脂液を調製するこ
とができる。適当な溶剤としては、エポキシ樹脂用とし
て、例えば、セロソルブ類、ケトン類、エステル類、炭
化水素類、ハロゲン化炭化水素類、もしくはこれらの混
合溶剤などがある。ポリヒドロキシボリエーテル樹脂の
場合には、ケトン類、セロソルブ類、これらの混合溶媒
などが使用できる。When dihydric phenol is a mononuclear type such as resorcinol rather than a dinuclear type such as bisphenol A, because the molecular weight of dihydric phenol is smaller, the amount of these functional groups per weight is smaller. The number increases. Therefore, as the content of a mononuclear dihydric phenol such as resorcinol increases, the content of the functional groups in the chain increases, and the adhesion and flexibility of the resulting coating film tend to increase. In this sense, when using polyhydroxy polyether resin, 2
The phenol preferably contains at least a portion of a mononuclear type such as resorcinol, for example, about 50 mol% or more. Similarly, even when using other epoxy resins, it is generally more advantageous to use one with a large number of ○H groups and 101 groups in the resin. One or more types of epoxy resins including the above-mentioned polyhydroxy polyether resins are used, and this is
A resin liquid for coating can be prepared by dissolving it in an appropriate organic solvent selected in consideration of required characteristics such as drying speed and smoothness. Suitable solvents for epoxy resins include cellosolves, ketones, esters, hydrocarbons, halogenated hydrocarbons, and mixed solvents thereof. In the case of polyhydroxy polyether resin, ketones, cellosolves, mixed solvents thereof, etc. can be used.
本発明においては、上記樹脂液に、樹脂全固形分に対し
て10〜25重量%、好ましくは15〜20重量%のコ
ロイダルシリ力が添加される。このシリカは耐食性およ
び電着塗装性の向上を目的として添加される.添加量が
10重量%未満であると、これらの性能の向上効果が十
分でなく、また、25重量%を越えると、溶接性の低下
を招く。In the present invention, colloidal silica is added to the resin liquid in an amount of 10 to 25% by weight, preferably 15 to 20% by weight based on the total solid content of the resin. This silica is added to improve corrosion resistance and electrodeposition coating properties. If the amount added is less than 10% by weight, the effect of improving these properties will not be sufficient, and if it exceeds 25% by weight, weldability will deteriorate.
コロイダルシリ力の市販品の例には、日本アエロジル製
のアエロジル、デュポン製のLudox ,日産化学の
スノーテックス、触媒化戒製のカタロイドおよびオスカ
ル、旭電化製のものなどがあり、本発明に用いるのは、
表面を親有機性としたアルコールタイプのものがよい.
上記樹脂液には、耐食性の一層の向上を目的として、架
橋剤を添加してもよい。架橋剤としては、エポキシ樹脂
塗料の硬化剤として知られているものが利用でき、具体
例としては、フェノール樹脂、アミノ樹脂、ボリアミド
、アミン、ブロックイソシアネート、酸無水物などがあ
る.
架橋剤の添加量は、エポキシ樹脂中のエポキシ基および
ヒドロキシル基の合計量に対する架橋剤中の官能基のモ
ル比が0.1〜2.0の範囲内となる量である.このモ
ル比が0.1未満では、効果が小さく、2.0を超える
と、皮膜の可撓性が失われ、加工時に塗膜が割れて、耐
食性の低下を生ずる恐れがある.
樹脂液には、上記威分の他に、皮膜の種々の性能(例、
加工性、可撓性、潤滑性、電着塗装性など)をさらに改
善することを目的として、エポキシ樹脂以外の他の樹脂
、潤滑性付与剤などの各種添加剤をさらに添加してもよ
い。例えば、皮膜に可撓性を与える目的で、ブチラール
樹脂などの柔軟性の樹脂を1種の可塑剤として添加でき
る。また、電着塗装性を向上させる目的で、水溶性樹脂
を添加することができる.水溶性樹脂としては、ポリビ
ニルアルコール、ポリアクリル酸、ポリアクリルアミド
等が挙げられる。エポキシ樹脂以外の樹脂の添加量は、
あまり多くなると耐食性の低下を生ずるので、樹脂液中
の全樹脂固形分の約50重量%以下とする.また、上層
皮膜に適当量の着色顔料あるいは充填剤などを添加する
こともできる.
樹脂液の塗布モ、ロールコーター、バーコーターなどの
慣用手段により実施でき、乾燥後に膜厚0.3〜1.6
−、好ましくは0.6〜1.3 /JIの皮膜が得られ
るように塗布する.膜厚が0.3μ未満では耐食性が劣
り、1,6μを越えると溶接性が低下する.
樹脂液を塗布した後、塗膜を80〜300゜Cの温度で
焼付けて、上層皮膜を形成する.この温度範囲内で焼付
温度が高いほど架橋反応が進み、強固な皮膜を形成でき
るが、焼付硬化性の鋼板を使用した場合には、200
”C以上に加熱すると鋼板の焼付硬化性が失われるので
、焼付温度上限を200゜C以下とする。Examples of commercially available colloidal silica products include Aerosil manufactured by Nippon Aerosil, Ludox manufactured by DuPont, Snowtex manufactured by Nissan Chemical, Cataloid and Oscar manufactured by Catalyst Kai, and those manufactured by Asahi Denka, which are used in the present invention. The thing is,
An alcohol type product with an organophilic surface is best. A crosslinking agent may be added to the resin liquid for the purpose of further improving corrosion resistance. As the crosslinking agent, those known as curing agents for epoxy resin paints can be used, and specific examples include phenolic resins, amino resins, polyamides, amines, blocked isocyanates, and acid anhydrides. The amount of the crosslinking agent added is such that the molar ratio of the functional groups in the crosslinking agent to the total amount of epoxy groups and hydroxyl groups in the epoxy resin is within the range of 0.1 to 2.0. If this molar ratio is less than 0.1, the effect will be small, and if it exceeds 2.0, the flexibility of the coating will be lost and the coating may crack during processing, leading to a decrease in corrosion resistance. In addition to the above-mentioned properties, the resin liquid has various properties of the film (e.g.
In order to further improve processability, flexibility, lubricity, electrodeposition coating properties, etc., various additives such as resins other than epoxy resins and lubricity imparting agents may be further added. For example, for the purpose of imparting flexibility to the film, a flexible resin such as butyral resin can be added as a type of plasticizer. Additionally, a water-soluble resin can be added for the purpose of improving electrodeposition coating properties. Examples of water-soluble resins include polyvinyl alcohol, polyacrylic acid, polyacrylamide, and the like. The amount of resin other than epoxy resin is
If the amount is too large, the corrosion resistance will deteriorate, so the amount should be about 50% by weight or less based on the total resin solid content in the resin liquid. Additionally, an appropriate amount of coloring pigments or fillers may be added to the upper layer film. It can be carried out by conventional means such as a resin liquid coating machine, a roll coater, a bar coater, etc., and the film thickness is 0.3 to 1.6 after drying.
-, preferably 0.6 to 1.3/JI. If the film thickness is less than 0.3μ, corrosion resistance will be poor, and if it exceeds 1.6μ, weldability will decrease. After applying the resin liquid, the coating film is baked at a temperature of 80 to 300°C to form an upper layer film. Within this temperature range, the higher the baking temperature is, the more the crosslinking reaction progresses and a stronger film can be formed.
If heated above C, the bake hardenability of the steel plate will be lost, so the upper limit of baking temperature should be 200 degrees C or less.
本発明の防錆塗装鋼板では、優れた耐食性を確保するた
めに、母材として亜鉛または亜鉛合金めっき鋼板を用い
る.この亜鉛系めっきは、電気めっき、溶融亜鉛めっき
、あるいは合金化溶融亜鉛めっきのいずれでもよい.亜
鉛合金めっきの種類も特に制限されず、Zn−Ni+
Zn AQを始めとする各種の亜鉛合金めっきが利用
できる。また、2層以上の亜鉛系めっき層を有する複層
めっき鋼板も使用できる.加工性を低下させないために
は、亜鉛系めっきは比較的薄目付のものが好ましい。In the anti-rust coated steel sheet of the present invention, a zinc or zinc alloy coated steel sheet is used as the base material in order to ensure excellent corrosion resistance. This zinc-based plating may be electroplating, hot-dip galvanizing, or alloyed hot-dip galvanizing. The type of zinc alloy plating is not particularly limited, and Zn-Ni+
Various zinc alloy platings including Zn AQ can be used. Additionally, multi-layer plated steel sheets with two or more zinc-based plating layers can also be used. In order not to reduce workability, it is preferable that the zinc-based plating has a relatively thin basis weight.
本発明の防M塗装鋼板は、鋼板基体上に亜鉛系めっき層
、下層のクロメート皮膜層、上層のコロイダルシリ力含
有エポキシ樹脂皮膜層が順次積層された断面構造を有す
る。自動車用には、かかる塗装は通常は鋼板の片面のみ
に行われるが、用途によっては本発明の防錆塗装鋼板は
両面に上記塗装を設けたものでもよい.
次に本発明を実施例により説明する。実施例中、%およ
び部は特に指定のない限り重量%および重量部である。The anti-M coated steel sheet of the present invention has a cross-sectional structure in which a zinc-based plating layer, a lower chromate film layer, and an upper colloidal silica-containing epoxy resin film layer are sequentially laminated on a steel sheet substrate. For automobiles, such coating is usually applied only to one side of the steel plate, but depending on the application, the anti-corrosion coated steel plate of the present invention may be coated on both sides. Next, the present invention will be explained by examples. In the examples, percentages and parts are by weight unless otherwise specified.
(実施例〉
(a)母材
厚さ0.8 mの冷延鋼板上に片面目付量20 g /
rrTで12%Ni−Znをめっきした合金亜鉛電気
めっき鋼板を母材として使用した.このめっき鋼板は、
使用前に、日本バーカライジング製のアルカリ脱脂液で
あるファインクリーナ4336を用いて脱脂した.(b
)クロメート液
Crys 120 g / ’を含有するクロム酸水溶
液に、還元剤としてエチレングリコールを添加し、80
゜Cで6時間加熱した。反応終了後、クロム酸水溶液を
加えてCr3+/全Cr比を調整し、さらに水を加えて
、全クロム酸濃度をCrys換算で40 g/j!
(=0.4モル/l)に調整した.得られた部分還元ク
ロム酸水溶液に、使用前に還元剤として多価アルコール
であるグリセリンを添加した。また、一部のクロメート
処理液には、シランカップリング剤としてγ−グリシド
キシブロピルトリメトキシシンを添加した。(Example) (a) One side basis weight 20 g / on a cold rolled steel plate with a base material thickness of 0.8 m
An alloy zinc electroplated steel sheet plated with 12% Ni-Zn at rrT was used as the base material. This plated steel plate is
Before use, it was degreased using Fine Cleaner 4336, an alkaline degreasing liquid manufactured by Nippon Vercalizing. (b
) Ethylene glycol was added as a reducing agent to a chromic acid aqueous solution containing 120 g/' of chromate solution Crys.
Heated at °C for 6 hours. After the reaction is completed, an aqueous chromic acid solution is added to adjust the Cr3+/total Cr ratio, and water is further added to bring the total chromic acid concentration to 40 g/j in terms of Crys!
(=0.4 mol/l). Glycerin, which is a polyhydric alcohol, was added as a reducing agent to the obtained partially reduced chromic acid aqueous solution before use. In addition, γ-glycidoxypropyltrimethoxycin was added to some of the chromate treatment liquids as a silane coupling agent.
比較のために、下記樹脂液に使用したのと同じコロイダ
ルシリカを添加・分散させたクロメート処理液も用意し
た.
(C)樹脂液
冷却器ヲ備えたフラスコに、ビスフェノールAのジグリ
シジルエーテル(油化シエル社製エビコート828)
230部、レゾルシン55部、メチルエチルケトン20
0部、5N NaOH水溶液4容量部を仕込み、還流温
度においてl8時間反応させた。得られた樹脂状物質を
撹拌器内の水中に投入し、撹拌し、水中で再沈殿させ、
水不溶性の樹脂を回収した。これを減圧乾燥して、2価
フェノールがレゾルシンとビスフェノールA(モル比l
/1)である粉末状ポリヒドロキシボリエーテル樹脂(
以下、樹脂Aという)を得た。For comparison, we also prepared a chromate treatment solution in which the same colloidal silica used in the resin solution below was added and dispersed. (C) In a flask equipped with a resin liquid cooler, diglycidyl ether of bisphenol A (Ebicoat 828 manufactured by Yuka Ciel Co., Ltd.)
230 parts, 55 parts of resorcinol, 20 parts of methyl ethyl ketone
0 parts, 4 parts by volume of a 5N NaOH aqueous solution were charged, and the mixture was reacted at reflux temperature for 18 hours. The obtained resinous substance is poured into water in a stirrer, stirred, and reprecipitated in water.
A water-insoluble resin was recovered. This was dried under reduced pressure to extract dihydric phenols from resorcinol and bisphenol A (molar ratio l).
/1) Powdered polyhydroxy polyether resin (
Hereinafter referred to as resin A) was obtained.
得られた粉末樹脂を、酢酸セロソルブ/シクロヘキサノ
ンの1/1(容量比)混合溶媒に溶解させ、樹脂固形分
20重量%の樹脂液を得た。The obtained powdered resin was dissolved in a 1/1 (volume ratio) mixed solvent of cellosolve acetate/cyclohexanone to obtain a resin liquid having a resin solid content of 20% by weight.
また、別のポリヒドロキシボリエーテル樹脂として、市
販のユニオン・カーバイド社製フエノキシ樹脂PKHH
(分子i130.o00) も、上層皮膜形戒用に、
上と同様の樹脂液状で用いた(樹脂B).さらに、汎用
のエポキシ樹脂として、油化シエル社製エビコート10
09 (分子量3750)を、キシレン/メチルエチル
ケトン混合溶媒(重量比で6/4)に溶解した樹脂液も
用いたく樹脂C〉.コロイダルシリカ (触媒化威製、
オスカル1432平均粒径10〜20 mμ)、架橋剤
(樹脂AおよびBに対しては解離温度80″Cのブロッ
クイソシアネート、樹脂Cに対してはフェノール樹脂)
および可塑剤(ブチラール樹脂)の添加は、所定量を樹
脂溶液に加え、撹拌、分散させることにより行った.(
イ)塗装鋼板の調製
上記(a)の脱脂した鋼板の片面のめっき面上に、クロ
メート液(b)をバーコーターにより各種Cr付着量で
塗布し、仮温度が140゜Cとなるように30秒間加熱
して、クロメート皮膜を形成した。次いで、室温まで放
冷後、クロメート皮膜上に樹脂1 (C)をバーコータ
ーにより各種厚みで塗布し、板温度が140゜Cとなる
ように60秒間加熱して焼付を行い、樹脂塗膜を形成し
た。得られた防錆塗装鋼板について、下記試験を行って
、溶接性、耐食性、電着塗装性、およびクロム溶出性を
評価した。In addition, as another polyhydroxy polyether resin, commercially available phenoxy resin PKHH manufactured by Union Carbide Co., Ltd.
(Molecular i130.o00) is also used for the upper layer film type,
The same resin as above was used in liquid form (Resin B). Furthermore, as a general-purpose epoxy resin, Ebicoat 10 manufactured by Yuka Ciel Co., Ltd.
09 (molecular weight 3750) in a mixed solvent of xylene/methyl ethyl ketone (6/4 by weight) was also used for resin C>. Colloidal silica (made by Catalyst Kawei,
Oscar 1432 average particle size 10-20 mμ), crosslinking agent (blocked isocyanate with a dissociation temperature of 80″C for resins A and B, phenolic resin for resin C)
The plasticizer (butyral resin) was added by adding a predetermined amount to the resin solution and stirring and dispersing it. (
b) Preparation of coated steel plate Chromate solution (b) was applied to one side of the plated surface of the degreased steel plate in (a) above using a bar coater in various amounts of Cr, and heated for 30 minutes to a temporary temperature of 140°C. A chromate film was formed by heating for a second. Next, after cooling to room temperature, resin 1 (C) was applied to the chromate film in various thicknesses using a bar coater, and baked by heating for 60 seconds to a board temperature of 140°C to form a resin coating. Formed. The following tests were conducted on the obtained anti-rust coated steel sheets to evaluate weldability, corrosion resistance, electrodeposition coating properties, and chromium elution properties.
(e)試験方法
■溶接性試験:塗装面と未塗装面が接触するように2枚
の塗装鋼板を重ねた試験片に対して、交流シングルスポ
ット溶接器を使用し、先端径6.O rtrmの電極に
より、溶接電流10,OOOA、通電時間12サイクル
、加圧力200 kgfの条件でスポット溶接を行った
.溶接性は次の2種類の方法で評価した。(e) Test method ■Weldability test: An AC single spot welder was used on a test piece made by stacking two painted steel plates so that the painted and unpainted surfaces were in contact with each other, and the tip diameter was 6. Spot welding was carried out using an electrode at rtrm under the conditions of a welding current of 10, OOOA, energization time of 12 cycles, and a pressing force of 200 kgf. Weldability was evaluated using the following two methods.
A.導電の安定性: 1000打点後に100個の無作
為サンプリングを行い、局部的な電流集中により生じた
不安定な圧痕が得られた個数で評価した。A. Stability of conductivity: After 1000 dots, 100 samples were randomly sampled, and evaluation was made based on the number of unstable indentations caused by local current concentration.
第1図に、良好な圧痕と不安定な圧痕の模式図を示す。FIG. 1 shows a schematic diagram of a good impression and an unstable impression.
B.連続打点後の電極径7 1000打点後の連続打点
1ii極径を感圧紙にて測定し、下記基準で評価した。B. Electrode diameter after continuous dots 7 The diameter of continuous dots 1ii after 1000 dots was measured using pressure sensitive paper and evaluated according to the following criteria.
○:t極径<7,O m
△l極径−7.0〜8.0ffll
×:電極径〉8.0閤
■耐食性試験:耐食性試験に供する試験片は、平板およ
び直径50閣の円筒絞り加工を行ったものである。円筒
絞りのダイス肩は、その表面粗さが常に一定になるよう
に、各回ごとにトリクレン洗浄と120番エメリー祇に
よる研磨とを行った.これらの試験片を、日本バーカラ
イジング製の脱脂液FC−L4410中に43℃で2分
30秒間浸漬し、水洗後、165 ’Cで25分の空焼
きを行った。次いで、各試験片について、35℃での塩
水噴霧4時間、60℃の温風乾燥2時間、および50″
C、相対湿度95%以上の湿潤雰囲気2時間を1サイク
ルとする複合腐食試験を行い、200サイクル(試験時
間1600時間)での発生赤錆の面積率(%)で耐食性
を評価した.■電@塗装性試験:試験片を耐食性試験と
同様に脱脂した後、日本ペイント製電着塗料U−600
を用い、化戒処理冷延鋼板に20s付着する条件で電着
塗装を行い、165゜Cで25分間焼付けた。塗装外観
は下記基準で評価した.
○:良好な外観、
Δ:肌荒れの大きいもの、
×:クレーターがあるかまたは電着不能なもの。○: t pole diameter <7,0 m △l pole diameter -7.0~8.0 ffll ×: electrode diameter > 8.0 m ■ Corrosion resistance test: The test pieces used for the corrosion resistance test are a flat plate and a cylinder with a diameter of 50 mm. It has been subjected to drawing processing. The die shoulder of the cylindrical drawing was cleaned with triclean and polished with No. 120 Emery Gion each time so that the surface roughness was always constant. These test pieces were immersed in degreasing liquid FC-L4410 manufactured by Nippon Barcalizing Co., Ltd. at 43° C. for 2 minutes and 30 seconds, washed with water, and then baked at 165° C. for 25 minutes. Each specimen was then subjected to salt water spraying at 35°C for 4 hours, hot air drying at 60°C for 2 hours, and 50″
C. A composite corrosion test was conducted in which one cycle consisted of 2 hours in a humid atmosphere with a relative humidity of 95% or higher, and the corrosion resistance was evaluated by the area ratio (%) of red rust generated in 200 cycles (test time 1600 hours). ■ Electrodeposition test: After degreasing the test piece in the same way as the corrosion resistance test, apply Nippon Paint's electrocoating paint U-600.
Electrodeposition was applied to a chemically treated cold-rolled steel plate for 20 seconds, and baked at 165°C for 25 minutes. Paint appearance was evaluated using the following criteria. ○: Good appearance, Δ: Severely rough skin, ×: Craters or electrodeposition not possible.
■クロム溶出性試験:試験片を日本パーカライジング製
脱脂液PC−L4410中に43゛Cで2分30秒間浸
漬した場合、およびさらに同社製リン酸亜鉛化威処理液
PR−L3080に43゜Cで2分間浸漬した場合のそ
れぞれにおけるクロム溶出量を、蛍光X線分析により測
定した浸漬前後の塗装鋼板のクロム付着量から算出した
.
次の第1表に、下層皮膜および上層皮膜の詳細と共に、
試験結果をまとめて示す。■Chromium elution test: When the test piece was immersed in Nippon Parkerizing's degreasing liquid PC-L4410 at 43°C for 2 minutes and 30 seconds, and then in the same company's zinc phosphate treatment liquid PR-L3080 at 43°C. The amount of chromium eluted after each 2-minute immersion was calculated from the amount of chromium deposited on the coated steel sheet before and after immersion, as measured by X-ray fluorescence analysis. The details of the lower layer coating and upper layer coating are shown in Table 1 below.
The test results are summarized below.
(発明の効果)
第I表の結果から明らかなように、コロイダルシリ力を
従来のように下層クロメート皮膜に含有させると、少量
の添加でも溶接性が著しく劣化した(試験NαI6〜1
8).これに対して、コロイダルシリ力を上層の樹脂皮
膜中に存在させた本発明の防M塗装鋼板は、溶接性に優
れ、しかも耐食性、電着塗装性、クロム溶出量の結果も
遜色ない.ただし、25重景%を越える量のコロイダル
シリ力を上層皮膜中に存在させた比較例では、溶接性に
悪影響があった(試験N住24).
また、他の比較例のうち、部分還元したクロメート処理
液に還元剤を添加しないか、過剰の還元剤を添加した場
合、樹脂液へのコロイダルシリ力の添加量が少ない場合
、あるいは上下のいずれかの層の塗布量が少ない場合に
は耐食性が十分でなかった.上下のいずれかの層の塗布
量が多過ぎると、溶接性に加えて、電着塗装性も劣化し
た。(Effects of the invention) As is clear from the results in Table I, when colloidal silica was added to the lower chromate film as in the past, weldability deteriorated significantly even with a small amount of addition (tests NαI6 to 1).
8). On the other hand, the anti-M coated steel sheet of the present invention, which has colloidal silicide in the upper resin film, has excellent weldability, and also has comparable results in corrosion resistance, electrodepositability, and amount of chromium elution. However, in a comparative example in which a colloidal silica force of more than 25% was present in the upper layer film, weldability was adversely affected (Test N Sumi 24). In addition, among other comparative examples, when no reducing agent was added to the partially reduced chromate treatment solution, when an excessive amount of reducing agent was added, when the amount of colloidal silica added to the resin solution was small, or when either the upper or lower Corrosion resistance was not sufficient when the amount of coating of either layer was small. When the coating amount of either the upper or lower layer was too large, not only the weldability but also the electrodeposition coating properties deteriorated.
このように、本発明の防錆塗装鋼板は、加工性に悪影響
のある金属粉を皮膜中に存在させないにもかかわらず優
れた溶接性を確保することができ、また耐食性、電着塗
装性、クロム溶出量の点でも十分に満足すべき性能を示
す.従って、特に自動車用に適した優れた性能の防錆塗
装鋼板を比較的安価に供給することができる.As described above, the anti-corrosion coated steel sheet of the present invention can ensure excellent weldability despite the absence of metal powder that adversely affects workability in the coating, and also has excellent corrosion resistance, electrodeposition coating properties, It also shows sufficiently satisfactory performance in terms of the amount of chromium eluted. Therefore, it is possible to supply rust-proof coated steel sheets with excellent performance, especially suitable for automobiles, at a relatively low cost.
第1図(a)および(b)は、それぞれ良好な圧痕およ
び不安定な圧痕を示す模式図である.FIGS. 1(a) and (b) are schematic diagrams showing good indentations and unstable indentations, respectively.
Claims (4)
3^+/全Crの比が0.4〜0.6となるように部分
還元し、さらに未還元のCr^6^+に対して1〜4当
量倍の還元剤を添加した、コロイド状物質を実質的に含
有しない塗布型のクロメート処理液の塗布および焼付に
より形成した、Cr付着量として20〜100mg/m
^2の下層皮膜と、樹脂液中の全樹脂固形分とコロイダ
ルシリカとの合計量に対して10〜25重量%のコロイ
ダルシリカを添加したエポキシ樹脂をベース樹脂とする
樹脂液の塗布および焼付により形成した、膜厚0.3〜
1.6μmの上層皮膜とを有することを特徴とする、溶
接性に優れた防錆塗装鋼板。(1) Cr^ on zinc or zinc-based alloy plated steel sheet
A colloidal product that is partially reduced so that the ratio of 3^+/total Cr is 0.4 to 0.6, and a reducing agent that is 1 to 4 times the amount of unreduced Cr^6^+ is added. The amount of Cr deposited is 20 to 100 mg/m formed by applying and baking a coating-type chromate treatment liquid that does not substantially contain substances.
^2 By applying and baking a resin solution based on an epoxy resin containing 10 to 25% by weight of colloidal silica based on the total amount of the total resin solid content and colloidal silica in the resin solution. Formed film thickness 0.3~
A rust-proof coated steel sheet with excellent weldability, characterized by having an upper layer film of 1.6 μm.
6^+の0.01倍以上のシランカップリング剤をさら
に含有する、請求項1記載の防錆塗装鋼板。(2) The chromate treatment solution has a molar ratio of unreduced C^
The anticorrosive coated steel sheet according to claim 1, further comprising a silane coupling agent of 0.01 times or more of 6^+.
のエポキシ基およびヒドロキシル基の合計量に対する架
橋剤の官能基のモル比が0.1〜2.0となる量で含有
する、請求項1または2記載の防錆塗装鋼板。(3) The resin liquid further contains a crosslinking agent in an amount such that the molar ratio of the functional group of the crosslinking agent to the total amount of epoxy groups and hydroxyl groups in the epoxy resin is 0.1 to 2.0. Item 1 or 2. Rust-preventing coated steel plate.
の全固形分に対して50重量%以下の量でさらに含有す
る、請求項1ないし3のいずれかに記載の防錆塗装鋼板
。(4) The anticorrosive coated steel sheet according to any one of claims 1 to 3, wherein the resin liquid further contains a resin other than epoxy resin in an amount of 50% by weight or less based on the total solid content of the resin.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1162868A JPH0761698B2 (en) | 1989-06-26 | 1989-06-26 | Anticorrosion coated steel plate with excellent weldability |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1162868A JPH0761698B2 (en) | 1989-06-26 | 1989-06-26 | Anticorrosion coated steel plate with excellent weldability |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0326539A true JPH0326539A (en) | 1991-02-05 |
JPH0761698B2 JPH0761698B2 (en) | 1995-07-05 |
Family
ID=15762791
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1162868A Expired - Fee Related JPH0761698B2 (en) | 1989-06-26 | 1989-06-26 | Anticorrosion coated steel plate with excellent weldability |
Country Status (1)
Country | Link |
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JP (1) | JPH0761698B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1993001004A1 (en) * | 1991-07-11 | 1993-01-21 | Nkk Corporation | Steel sheet coated with composite organic film and excellent in outside rustproofness and brightness, and production thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61584A (en) * | 1984-06-13 | 1986-01-06 | Kawasaki Steel Corp | Method for specially chromating galvanized steel sheet having superior corrosion resistance and coatability |
JPS62152578A (en) * | 1985-12-25 | 1987-07-07 | Kawasaki Steel Corp | Manufacture of alloy plated steel of zn or zn family superb in corrosion resistance, paintability and weldability |
JPS63107781A (en) * | 1986-10-24 | 1988-05-12 | Nippon Dakuro Shamrock:Kk | Rust preventing coating method of galvanized steel plate |
JPS6456878A (en) * | 1987-08-28 | 1989-03-03 | Kobe Steel Ltd | Production of chromated steel sheet having superior coatability |
-
1989
- 1989-06-26 JP JP1162868A patent/JPH0761698B2/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61584A (en) * | 1984-06-13 | 1986-01-06 | Kawasaki Steel Corp | Method for specially chromating galvanized steel sheet having superior corrosion resistance and coatability |
JPS62152578A (en) * | 1985-12-25 | 1987-07-07 | Kawasaki Steel Corp | Manufacture of alloy plated steel of zn or zn family superb in corrosion resistance, paintability and weldability |
JPS63107781A (en) * | 1986-10-24 | 1988-05-12 | Nippon Dakuro Shamrock:Kk | Rust preventing coating method of galvanized steel plate |
JPS6456878A (en) * | 1987-08-28 | 1989-03-03 | Kobe Steel Ltd | Production of chromated steel sheet having superior coatability |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1993001004A1 (en) * | 1991-07-11 | 1993-01-21 | Nkk Corporation | Steel sheet coated with composite organic film and excellent in outside rustproofness and brightness, and production thereof |
US5429880A (en) * | 1991-07-11 | 1995-07-04 | Nkk Corporation | Organic composite coated steel sheet and a process for manufacturing the same |
Also Published As
Publication number | Publication date |
---|---|
JPH0761698B2 (en) | 1995-07-05 |
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