JPH01162780A - Zinc phosphate treatment of surface of metal for coating - Google Patents
Zinc phosphate treatment of surface of metal for coatingInfo
- Publication number
- JPH01162780A JPH01162780A JP32173787A JP32173787A JPH01162780A JP H01162780 A JPH01162780 A JP H01162780A JP 32173787 A JP32173787 A JP 32173787A JP 32173787 A JP32173787 A JP 32173787A JP H01162780 A JPH01162780 A JP H01162780A
- Authority
- JP
- Japan
- Prior art keywords
- treatment
- zinc phosphate
- tungsten
- ion
- 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.)
- Pending
Links
- 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 title claims abstract description 50
- 229910000165 zinc phosphate Inorganic materials 0.000 title claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
- 239000002184 metal Substances 0.000 title claims abstract description 32
- 238000000576 coating method Methods 0.000 title claims abstract description 31
- 239000011248 coating agent Substances 0.000 title claims abstract description 26
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 28
- 239000010937 tungsten Substances 0.000 claims abstract description 28
- -1 m- nitrobenzenesulfonate ion Chemical class 0.000 claims abstract description 26
- 230000002378 acidificating effect Effects 0.000 claims abstract description 25
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 25
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940085991 phosphate ion Drugs 0.000 claims abstract description 8
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims abstract description 6
- 229940005654 nitrite ion Drugs 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 37
- 229910052742 iron Inorganic materials 0.000 claims description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 21
- 239000011701 zinc Substances 0.000 claims description 21
- 229910052725 zinc Inorganic materials 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 238000007654 immersion Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 238000007598 dipping method Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 150000003658 tungsten compounds Chemical class 0.000 claims description 10
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 8
- 229910001437 manganese ion Inorganic materials 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 5
- 229910001453 nickel ion Inorganic materials 0.000 claims description 5
- 239000007769 metal material Substances 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 25
- 238000004070 electrodeposition Methods 0.000 abstract description 19
- 150000003839 salts Chemical class 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 13
- 239000007788 liquid Substances 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 206010039509 Scab Diseases 0.000 abstract description 11
- 239000008367 deionised water Substances 0.000 abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 abstract description 3
- 239000010953 base metal Substances 0.000 abstract 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 abstract 1
- 239000007921 spray Substances 0.000 description 17
- 239000002585 base Substances 0.000 description 11
- 125000002091 cationic group Chemical group 0.000 description 9
- 239000003973 paint Substances 0.000 description 8
- 238000010422 painting Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- 229910001335 Galvanized steel Inorganic materials 0.000 description 6
- 239000008397 galvanized steel Substances 0.000 description 6
- 239000008399 tap water Substances 0.000 description 6
- 235000020679 tap water Nutrition 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 229920000180 alkyd Polymers 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229940005989 chlorate ion Drugs 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013527 degreasing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 230000002747 voluntary effect Effects 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241000237858 Gastropoda Species 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- KHPLPBHMTCTCHA-UHFFFAOYSA-N ammonium chlorate Chemical compound N.OCl(=O)=O KHPLPBHMTCTCHA-UHFFFAOYSA-N 0.000 description 1
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000001177 diphosphate Substances 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- UCDPMNSCCRBWIC-UHFFFAOYSA-N orthosulfamuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)NC=2C(=CC=CC=2)C(=O)N(C)C)=N1 UCDPMNSCCRBWIC-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- LJRGBERXYNQPJI-UHFFFAOYSA-M sodium;3-nitrobenzenesulfonate Chemical compound [Na+].[O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 LJRGBERXYNQPJI-UHFFFAOYSA-M 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LEMQFBIYMVUIIG-UHFFFAOYSA-N trifluoroborane;hydrofluoride Chemical compound F.FB(F)F LEMQFBIYMVUIIG-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/42—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
技 術 分 野
本発明は塗装用金属表面のリン酸亜鉛処理方法に関わり
、さらに詳しくは電着塗装、就中カチオン型電着塗装後
装した、塗膜密着性、耐食性、特に温塩水性、スキャブ
性に優れたタングステン含有リン酸亜鉛皮膜を形成する
処理方法に関するものである。[Detailed Description of the Invention] Technical Field The present invention relates to a method for treating metal surfaces for painting with zinc phosphate, and more specifically, to improve the adhesion and corrosion resistance of coatings applied after electrocoating, especially cationic electrocoating. In particular, the present invention relates to a treatment method for forming a tungsten-containing zinc phosphate film having excellent warm salt water resistance and scabability.
従 来 技 術
塗装用の金属前処理としてリン酸亜鉛皮膜fヒ成処理が
古くから行われており、その処理手段としてスプレー法
、浸漬法あるいはそれらの組み合わせが採用されている
。スプレー法は設備コスト、生産効率などの点で有利で
あるが、他方袋部などをもつ複雑な物品に対しては未処
理部分を生じたり、スプレーのはね返りによる皮膜化成
不良か発生し易いという欠点がある。また浸漬法では設
備が大きくなるという欠点があるが、他方袋tlI造部
などをもつ複雑な物品に対しても、スプレー処理では皮
膜を形成しない部分にも均一な皮膜を形成できるという
利点がある。BACKGROUND OF THE INVENTION Zinc phosphate coating annealing has been used for a long time as a metal pretreatment for painting, and spraying, dipping, or a combination thereof has been adopted as the treatment method. The spray method is advantageous in terms of equipment costs and production efficiency, but on the other hand, it has the disadvantages that it tends to leave untreated areas on complex items such as bags, and is prone to poor film formation due to spray splashing. There is. In addition, the immersion method has the disadvantage of requiring large equipment, but on the other hand, the spray treatment has the advantage of being able to form a uniform film even on areas where no film will be formed, even for complex articles with bag tlI structures. .
通常浸漬法によるリン酸亜鉛皮膜化成では処理液の亜鉛
イオン濃度が2〜4ζ/又程度と大で、処理粂件も高温
(60〜90℃)、長時間(3〜10分)でしか皮膜化
成できず、しかも得られた皮4膜は高々膜量(3〜5+
;/m2)で、且つ皮膜の質が悪く、塗装下地、就中電
着塗装下地としては密着性、耐食性および塗膜外観が悪
く不適当とされている。When forming a zinc phosphate film using the normal dipping method, the concentration of zinc ions in the treatment solution is as high as 2 to 4ζ/m, and the coating can only be formed at high temperatures (60 to 90°C) and for a long period of time (3 to 10 minutes). It could not be chemically formed, and the four films obtained had a film amount of at most (3 to 5+
/m2) and the quality of the film is poor, making it unsuitable as a base for painting, particularly as a base for electrodeposition coating, due to its poor adhesion, corrosion resistance, and appearance.
また近年自動車部門などで腐食環境下で充分な防錆力を
もつものが要求されるため、電着塗料もアニオン型から
カチオン型に代わりつつあり、この場合には塗料焼付時
に塗膜の収縮が大きくリン酸亜41膜にかなりの力がか
かるため、カチオン型電着塗装下地のリン酸亜鉛皮膜自
体の強度も大でなければならず、従来の処理浴による処
理では電着塗装、就中カチオン電着塗装に適した下地は
得られないとされていた。In addition, in recent years, the automobile sector and other industries require materials with sufficient rust prevention power in corrosive environments, so electrocoating paints are also changing from anionic to cationic paints, which cause shrinkage of the coating film during baking. Since a considerable amount of force is applied to the sub-41 phosphate film, the strength of the zinc phosphate film itself, which is the base for the cationic electrodeposition coating, must be strong. It was believed that it was not possible to obtain a suitable base for electrodeposition coating.
このような状況下にあって、最近特開昭55−1077
84号に処理浴の亜鉛イオン、リン酸イオンおよび亜硝
酸イオンなどの皮膜(ヒ成促進剤濃度を制御することに
より低温短時間の浸漬法で、低皮膜量のしかも均−緻密
な密着性、耐食性に優れたリン酸亜鉛皮膜を得ることが
でき、電着塗装用下地として充分使用に耐えうる皮膜の
形成法が提案されるに至り、にわかに浸漬法が脚光を浴
びるに至った。すなわち同特開昭発明においては、亜鉛
イオンを 0.5〜1.5 g/9に、またリン酸イオ
ンを5〜30gQ! 、亜硝酸イオンを0.01〜0.
2 g/ズに制御しこれらを主成分とする酸性リン酸亜
鉛処理液でちって金属表面を40〜70℃で15〜12
0秒間浸漬処理し、次いでスラ・ソジ除去の目的で上記
と同じ処理液、処理温度で2〜60秒間スプレー処理す
ることにより 1.5〜3g/m2の低皮膜量で、均一
緻密な電着塗装に適した下地を形成させるものである。Under these circumstances, recently Japanese Patent Application Laid-Open No. 55-1077
No. 84 is coated with zinc ions, phosphate ions, nitrite ions, etc. in the treatment bath (by controlling the concentration of the arsenal accelerator, a low-temperature, short-time immersion method is used to produce a low coating amount, uniform and dense adhesion, A method for forming a zinc phosphate film with excellent corrosion resistance that can be used as a base for electrodeposition coating was proposed, and the dipping method suddenly came into the spotlight. In the Kaisho invention, zinc ions were added at 0.5-1.5 g/9, phosphate ions were added at 5-30 g/9, and nitrite ions were added at 0.01-0.
The metal surface was heated at 40 to 70°C for 15 to 12 g/sec with an acidic zinc phosphate treatment solution containing these as the main ingredients.
By immersion treatment for 0 seconds and then spray treatment for 2 to 60 seconds using the same treatment solution and treatment temperature as above for the purpose of removing slugs and dirt, a uniform and dense electrical coating with a low film amount of 1.5 to 3 g/m2 was obtained. It forms a base suitable for coating.
その後、主として自動車工業界で塗装後の耐食性をさら
に向上させる目的でボディー素材として片面だけ亜鉛ま
たは合金化亜鉛メツキした鋼材が使用され始め、前記処
理浴による浸漬処理では鉄系表面では問題はないが、亜
鉛系表面に対してはカチオン型電着塗装後の耐塩水噴霧
性が不充分であるとか、中塗り、上塗り後の二次密着性
か鉄系表面の場合に比し大幅に劣る問題がクローズア・
・ノブされ、これに対処するため、例えば特開昭57−
152472号の如く亜鉛イオン、リン酸イオン、およ
び皮膜化成促進剤濃度の制御された浴に、マンガンイオ
ン0.6〜3g/Jおよび/またはニッケルイオン0.
1〜4g/lを含有せしめる技術、あるいは処理温度を
下げる目的でマンガンイオンと共にフッ素イオン0.0
5g/、R以上を加える技術(特公昭61−36588
号)が開発されてきた。After that, steel materials plated with zinc or alloyed zinc on only one side began to be used as body materials mainly in the automobile industry for the purpose of further improving the corrosion resistance after painting, and although immersion treatment in the treatment bath described above poses no problem on iron-based surfaces, For zinc-based surfaces, there are problems such as insufficient salt spray resistance after cationic electrodeposition coating, and secondary adhesion after intermediate and top coatings that are significantly inferior to iron-based surfaces. Closer
・In order to deal with this, for example, Japanese Patent Application Laid-open No. 1987-
No. 152472, 0.6 to 3 g/J of manganese ions and/or 0.6 g/J of nickel ions are added to a bath with controlled concentrations of zinc ions, phosphate ions, and film formation promoters.
Technology to contain 1 to 4 g/l or 0.0 fluorine ion together with manganese ion for the purpose of lowering the processing temperature.
Technology to add 5g/R or more (Special Publication No. 61-36588
) has been developed.
このように鉄系表面に対しても、あるいは鉄系表面と亜
鉛系表面を同時に有する金属表面に対しても、浸漬法に
よるリン酸亜鉛処理で電着塗装に適した化成皮膜を提供
することができるようになり、建材、小物物品などに限
らず、自動車ボディー、自動車部品など広範な、鉄、亜
鉛およびそれらの合金表面を有する物品の耐食性改善を
主目的としたリン酸亜鉛化成°処理に浸漬法が確固たる
暴君を確立するに至っている。しかしながら近年、自動
車ボディーの耐食性に対する要求品質はますます高度に
なってきており、例えば外板部の傷から塩水、乾湿気象
条件変化を繰り返し受ける際、鉄面に発生するカサブタ
状の錆(スキャブコロージョン)の防止、より高度の耐
温塩水性などが強く望まれ現行のリン酸亜鉛処理法では
かがる要求に対処し得なくなりつつある。In this way, it is possible to provide a chemical conversion film suitable for electrodeposition coating on iron-based surfaces, or on metal surfaces that have both an iron-based surface and a zinc-based surface, by zinc phosphate treatment using the dipping method. It is now possible to immerse a wide range of products, including not only building materials and small items, but also car bodies and parts, in zinc phosphate chemical conversion treatment, which is aimed at improving the corrosion resistance of a wide range of items with iron, zinc, and their alloy surfaces. The law has come to establish a determined tyranny. However, in recent years, the quality requirements for corrosion resistance of automobile bodies have become more and more sophisticated. There are strong demands for prevention of corrosion (corrosion) and higher resistance to warm salt water, and the current zinc phosphate treatment methods are becoming unable to meet these demands.
他方、鋼製家具などでは依然、主としてスプレー処理が
主流であるが、しかしこの分野でも防錆性向上を目的と
して亜鉛鋼板の導入がけがられており、これらについて
も密着性や耐食性において必ずしも満足されていない。On the other hand, spray treatment is still the mainstream for steel furniture, etc., but even in this field, galvanized steel sheets are being introduced for the purpose of improving rust prevention, and the adhesion and corrosion resistance of these sheets are not always satisfactory. Not yet.
さらに前処理による耐スキャブ性や温塩水性の向上が望
まれている。Furthermore, it is desired to improve scab resistance and hot salt water resistance through pretreatment.
発明が解決しようとする問題点
そこで、鉄面あるいは鉄面と亜鉛面を合わせ有する金属
表面のリン酸亜鉛処理方法であって、塗装、就中電着塗
装に適した耐食性化成皮膜を与えうるだけでなく、鉄面
の耐スキャブ性、鉄面および亜鉛面の耐温塩水性が特段
に改善され、また電着塗装板に中塗り、上塗りを施した
際の二次密着性もさらに改善される処理方法が要望され
ておりかかる課題に応えることが本発明目的である。Problems to be Solved by the Invention Therefore, a method for treating a metal surface with iron surface or a combination of iron and zinc surfaces with zinc phosphate, which can provide a corrosion-resistant chemical conversion film suitable for painting, especially electrodeposition coating, is proposed. In addition, the scab resistance of steel surfaces and the hot salt water resistance of iron and zinc surfaces are significantly improved, and the secondary adhesion when applying intermediate and top coats to electrodeposited boards is also further improved. There is a need for a processing method, and it is an object of the present invention to meet this problem.
問題点を解決するための手段
本発明に従えば上記目的が、金属表面を、可溶性タング
ステン化合物をタングステンとして0.05〜20.0
g/l含む酸性リン酸亜鉛処理水溶液で処理することを
特徴とする金属表面のリン酸亜鉛処理方法により達成せ
られる。本発明にあっては鉄系表面または鉄系表面と亜
鉛系表面を合わせ有する金属表面を対象とする場合に最
も有効であるが、これに限らず亜鉛系表面単独に対して
も同様の目的でもって処理できることは言うまでもない
。すなわち本発明は上記いずれの態様の金属表面をも処
理の対象とするものである。Means for Solving the Problems According to the present invention, the above object is achieved by forming a metal surface with a tungsten compound of 0.05 to 20.0
This is achieved by a method for treating metal surfaces with zinc phosphate, which is characterized in that the metal surface is treated with an acidic zinc phosphate treatment aqueous solution containing g/l. The present invention is most effective when targeting an iron-based surface or a metal surface having a combination of an iron-based surface and a zinc-based surface, but is not limited to this, and the same purpose can be applied to a zinc-based surface alone. Needless to say, it can be handled with ease. That is, the present invention targets metal surfaces of any of the above embodiments.
本発明処理方法の実用的に有利な一具木例を示すと次の
通りである。金属表面をまずアルカリ性脱脂剤で温度3
0〜6〔1℃で2分間スプレーおよび/または浸漬処理
して脱脂し、次いで水道水で水洗し、次いで浸漬処理の
場合は表面調整剤で室温で10〜30秒間スプレーおよ
び/または浸漬処理し、次いで上述の本発明酸性リン酸
亜鉛処理水溶液で温度30〜70℃で15秒間以上浸漬
およびスプレー処理し、次いで水道水そして脱イオン水
で水洗すればよい。An example of a tree that is practically advantageous for the treatment method of the present invention is as follows. First, treat the metal surface with an alkaline degreaser at temperature 3.
0 to 6 [Degrease by spraying and/or dipping at 1°C for 2 minutes, then washing with tap water, and then spraying and/or dipping with a surface conditioner for 10 to 30 seconds at room temperature in the case of dipping. Then, it may be immersed and sprayed in the above-mentioned acidic zinc phosphate treatment aqueous solution of the present invention at a temperature of 30 to 70° C. for 15 seconds or more, and then washed with tap water and deionized water.
本願を浸漬処理で用いる場合には本発明処理液の主成分
である亜鉛イオンは0.1〜2.0 g/J2 、好ま
しくはOj〜1.5 g/アでよい。O,1g/1未満
では鉄系表面に均一なリン酸亜鉛皮膜が生成せず、スゲ
の多い、一部ブルーカラー状の皮膜が生成する。また2
、(Ig/lを超えると均一なリン酸亜鉛皮膜は生成す
るが、表面の該皮膜はアルカリに溶解し易い皮膜になり
易く、特にカチオン電着時にさらされるアルカリ雰囲気
によって皮膜溶解し易くなる。その結果、一般に耐温塩
水性が低下し、特に鉄系表面の場合耐スキャブ性が劣f
ヒするなど、所望の性能が得られないので電着塗装、特
にカチオン電着塗装下地としては不適当である。リン酸
イオンは5〜40g/又、好ましくは10〜30g/ρ
である。5g/美未満では不均一皮膜を形成し易く、ま
た40g/pを超えても本発明以上の効果は期待できず
、薬品の使用量が多くなって経済的に不利である。可溶
性タングステン化合物はタングステンとして0.05〜
20.0g/J 、好ましくは0.05〜IO,ogJ
。When the present invention is used in immersion treatment, the amount of zinc ion, which is the main component of the treatment liquid of the present invention, may be 0.1 to 2.0 g/J2, preferably Oj to 1.5 g/A. If O is less than 1 g/1, a uniform zinc phosphate film will not be formed on the iron-based surface, and a partially blue-colored film with many ridges will be formed. Also 2
, (If it exceeds Ig/l, a uniform zinc phosphate film will be formed, but the film on the surface tends to be a film that is easily dissolved in alkali, and in particular, the film is easily dissolved by the alkaline atmosphere exposed during cationic electrodeposition. As a result, the resistance to hot salt water generally decreases, and the scab resistance is particularly poor in the case of iron-based surfaces.
It is not suitable for use as a base for electrodeposition coatings, especially cationic electrodeposition coatings, because the desired properties such as scorching cannot be obtained. Phosphate ion is 5 to 40g/, preferably 10 to 30g/ρ
It is. If it is less than 5 g/p, a non-uniform film is likely to be formed, and if it exceeds 40 g/p, no effect greater than that of the present invention can be expected, and the amount of chemicals used increases, which is economically disadvantageous. Soluble tungsten compound is 0.05~ as tungsten
20.0g/J, preferably 0.05~IO,ogJ
.
より好ましくは0,1〜3.0 g/Jlである。0.
05g/以下ではリン酸亜鉛皮膜の改質が不充分であり
、耐スキャブ性や耐温塩水性が向上しない。一方、20
gA2を超えると皮膜反応に寄与する以上のタングステ
ンの量となり、本発明以上の効果は期待できず、またス
ラッジも多くなり、好ましくない。More preferably 0.1 to 3.0 g/Jl. 0.
If the amount is less than 0.05 g/l, the modification of the zinc phosphate film is insufficient, and the scab resistance and hot salt water resistance are not improved. On the other hand, 20
If it exceeds gA2, the amount of tungsten will be more than it contributes to the film reaction, and no effect greater than that of the present invention can be expected, and the amount of sludge will increase, which is not preferable.
皮膜化成促進剤としては、亜硝酸イオン0.O1〜0.
5 g/、2 、好ましくは0.01〜11.4 g/
l 、TO−ニトロベンゼンスルホン酸イオン0.05
〜’5g/0.好ましくは0.1〜4g/又および過酸
化水素(H2O2100%換算)0.5〜10g/l、
好ましくは1〜8 g/lから選ばれる少なくとも1種
でよい。これらの促進剤が規定量に達しないと鉄系表面
で充分な皮膜化成ができず黄精などになり、また規定量
を超えると鉄系表面にブルーカラー状の不均一皮膜を形
成し易い。As a film formation accelerator, nitrite ion 0. O1~0.
5 g/, 2, preferably 0.01 to 11.4 g/
l, TO-nitrobenzenesulfonic acid ion 0.05
~'5g/0. Preferably 0.1 to 4 g/l and hydrogen peroxide (calculated as 100% H2O2) 0.5 to 10 g/l,
Preferably, at least one type selected from 1 to 8 g/l may be used. If these accelerators do not reach a specified amount, sufficient film formation cannot be achieved on the iron-based surface, resulting in yellowing, and if the amount exceeds the specified amount, a blue-collar uneven film tends to be formed on the iron-based surface.
これら主成分の供給源としては例えば亜鉛イオンは酸化
亜鉛、炭酸亜鉛、硝酸亜鉛などでよく、リン酸イオンは
リン酸、リン酸亜鉛、リン酸マンカンなどでよく、可溶
性タングステン化合物はタングステン酸ソーダ、タング
ステン酸アンモンなどでよく、皮膜化成促進剤は亜硝酸
ソーダ、亜硝酸アンモン、m−ニトロベンゼンスルホン
酸ソーダ過酸化水素水などでよい。As sources of these main components, for example, zinc ions can be zinc oxide, zinc carbonate, zinc nitrate, etc., phosphate ions can be phosphoric acid, zinc phosphate, mankan phosphate, etc., and soluble tungsten compounds can be sodium tungstate, sodium tungstate, etc. Ammonium tungstate may be used, and the film formation accelerator may be sodium nitrite, ammonium nitrite, sodium m-nitrobenzenesulfonate, hydrogen peroxide solution, or the like.
またスプレー処理の場合、塗装下地用リン酸亜鉛皮膜の
金属表面への化成を良好ならしめ、加えて従来の処理液
に比して亜硝酸塩の消費を 172以下に軽減し、副生
物スラッジを改質し、さらにはその発生量を 173〜
1/4に軽減することを目的とし化成処理中の該処理液
におけるリン酸イオン濃度を少なくとも5g/、1、亜
硝酸イオン0.02〜0.5g/、ill、亜鉛イオン
濃度を少なくとも Qjg/ズ、リン酸イオン:硝酸イ
オンのモル重量比率をl:07〜1.3、およびリン酸
イオン:亜鉛イオンのモル比率を1 : 0.116以
下に維持して、該処理液のp)Iが3.3〜3゜8であ
る範囲において処理することが例えば特公昭55−55
90号に提案され注目されているが、このような処理剤
でも、また通常のスプレー用のリン酸亜鉛処理液に対し
ても、本発明に従い可溶性タングステン化合物をタング
ステンとして少なくとも0.05〜20g/ノの濃度範
囲で含有せしめることにより、所期効果と共に耐スキャ
ブ性、耐温塩水性、密着性、就中亜鉛系表面の密着を格
段に向上せしめることが可能である。In addition, in the case of spray treatment, it improves the conversion of the zinc phosphate film for the paint base onto the metal surface, reduces nitrite consumption to 172 or less compared to conventional treatment solutions, and improves by-product sludge. 173~
For the purpose of reducing the concentration to 1/4, the phosphate ion concentration in the treatment solution during chemical conversion treatment is at least 5 g/, 1, the nitrite ion concentration is at least 0.02 to 0.5 g/ill, and the zinc ion concentration is at least Qjg/. p) I of the treatment liquid by maintaining the molar weight ratio of phosphate ions: nitrate ions to 1:07 to 1.3 and the molar ratio of phosphate ions:zinc ions to 1:0.116 or less. For example, according to Japanese Patent Publication No. 55-55,
No. 90 proposed and attracting attention, in accordance with the present invention, a soluble tungsten compound of at least 0.05 to 20 g/as tungsten is added to such a treatment agent, and also to a normal zinc phosphate treatment solution for spraying. By containing it in the above concentration range, it is possible to significantly improve scab resistance, hot salt water resistance, adhesion, especially adhesion to zinc-based surfaces, as well as the desired effects.
また、本発明処理液は上記主成分の他に、マンガンイオ
ン、ニッケルイオン、フッ素イオン、硝酸イオンおよび
塩素酸イオンなどを含んでいてよい。マンガンイオン、
二・・7ケルイオンは0.Ig/f1以上でよく、フ・
ソ素イオンは0〜4 g/9 、好ましくはo、i〜2
.0 g/J、硝酸イオンは0〜15g/ア、好ましく
は2〜IOg/、(、塩素酸イオンは0〜2.Og/又
未満、好ましくは0.2〜1.5 g/、Qでよい。こ
れらの成分は単独、または2種以上組み合わされて含有
されてよい。これらの成分の供給源としては例えばマン
ガンイオンは炭酸マンガン、硝酸マンガン、塩化マンガ
ン、リン酸マンガンなどでよく、ニッケルイオンでは炭
酸ニッケル、硝酸ニッケル、塩化ニッケル、リン酸ニッ
ケル、水酸化ニッケルなどでよく、フッ素イオンはフッ
酸、ホウフッ化水素酸、ケイフッ化水素酸、それらの金
属塩などでよく、硝酸イオンは硝酸ソーダ、硝酸アンモ
ン、硝酸亜鉛、硝酸マンガン、硝酸ニッケルなどでよく
塩素酸イオンは塩素酸ソーダ、塩素酸アンモンなどでよ
い。In addition to the above main components, the treatment liquid of the present invention may also contain manganese ions, nickel ions, fluorine ions, nitrate ions, chlorate ions, and the like. manganese ion,
2...7 Kelion is 0. Ig/f1 or higher is sufficient;
The sodium ion is 0 to 4 g/9, preferably o, i to 2
.. 0 g/J, nitrate ions from 0 to 15 g/A, preferably 2 to IOg/, (chlorate ions from 0 to 2.0 g/J, preferably 0.2 to 1.5 g/, Q) These components may be contained alone or in combination of two or more.As sources of these components, for example, manganese ions may be manganese carbonate, manganese nitrate, manganese chloride, manganese phosphate, etc., and nickel ions may be used. In this case, nickel carbonate, nickel nitrate, nickel chloride, nickel phosphate, nickel hydroxide, etc. may be used, the fluorine ion may be hydrofluoric acid, hydrofluoroboric acid, hydrofluorosilicic acid, or their metal salts, etc., and the nitrate ion may be sodium nitrate. , ammonium nitrate, zinc nitrate, manganese nitrate, nickel nitrate, etc., and the chlorate ion may be sodium chlorate, ammonium chlorate, etc.
本発明処理液による処理温度は30〜70℃1好ましく
は35〜60℃であってよい。低温でありすぎると皮膜
化成性が悪く、長時間の処理を要することになる。高温
でありすぎると皮膜1ヒ成促進剤の分解および処理液の
沈澱発生などで処理液のバランスがくずれ易く、良好な
皮膜が得られ難い。The treatment temperature using the treatment liquid of the present invention may be 30 to 70°C, preferably 35 to 60°C. If the temperature is too low, the film formation properties will be poor and a long treatment time will be required. If the temperature is too high, the balance of the treatment solution is likely to be lost due to the decomposition of the coating 1 arsenal accelerator and the occurrence of precipitation in the treatment solution, making it difficult to obtain a good coating.
処理時間は15秒以上、好ましくは30〜120秒間で
よい。短時間でありすぎると所望結晶を有する皮膜が充
分に形成されない。尚、自動車ボディーの如く複雑な形
状を有する品物を処理する場合には、実用上浸漬処理と
スプレー処理を組み合わせることが好ましく、その場合
、例えば先ず15秒以上、好ましくは30〜120秒間
浸漬処理し、次いで2秒間以上、好ましくは5〜45秒
間スプレー処理すればよい。尚、浸漬処理時に付着した
スラ・ソジを洗い落とすには、スプレー処理は可能な限
り長時間であることが好ましい。従って本発明による処
理には浸漬処理、スプレー処理およびそれらの組み合わ
せの処理態様も包含されるものである。The treatment time may be 15 seconds or more, preferably 30 to 120 seconds. If the time is too short, a film having the desired crystals will not be sufficiently formed. In addition, when treating an article with a complicated shape such as an automobile body, it is practically preferable to combine immersion treatment and spray treatment. , then spray treatment for 2 seconds or more, preferably 5 to 45 seconds. Incidentally, in order to wash off the slurry and dirt that adhered during the immersion treatment, it is preferable that the spray treatment last as long as possible. Therefore, the treatment according to the present invention includes treatment modes such as dipping treatment, spray treatment, and combinations thereof.
本発明はまた、上述の構成からなる処理液を提供する濃
厚処理剤にかかる。この濃厚処理剤にあっては、亜鉛イ
オン供給源、リン酸イオン供給源をイオン形態での重量
で、可溶性タングステン化合物供給源をタングステンと
しての重量で、その重量比が亜鉛イオンニリン酸イオン
:可溶性タングステン化合物(Wとして)=1:2.5
〜400;0.025〜200となるように混合して調
製した(A)液と促進剤液である (B)mとの2液で
構成され、これらを希釈し適宜混合することにより、前
記組成の処理液が容易に調製せられる。尚、(A)液に
は主成分以外の他のイオン洪給源、すなわちマンガンイ
オン、ニッケルイオン、フッ素イオン、硝酸イオンおよ
び塩素酸イオン洪給源などを添加することかできる。但
し、塩素酸イオン源は(A)液でなり(B)液に添加し
てよく、特に(A)液にマンガンイオン供給源を添加す
る場合には塩素酸イオン源は(B)Mに添加することが
好ましい。尚、可溶性タングステン化合物供給源は使用
比率がタングステンとしての重量で上記亜鉛イオン:タ
ングステン化合物=1:0゜025〜200となるよう
に亜鉛イオン供給源と混合したものを (B)液に添加
してもよい。The present invention also relates to a concentrated processing agent that provides a processing liquid having the above-mentioned composition. In this concentrated treatment agent, the weight of the zinc ion source and the phosphate ion source is in ionic form, and the soluble tungsten compound source is the weight of tungsten, and the weight ratio is zinc ion diphosphate ion: soluble tungsten. Compound (as W) = 1:2.5
~400; It is composed of two liquids, liquid (A) prepared by mixing to give a concentration of 0.025 to 200, and (B)m, which is an accelerator liquid. By diluting these and mixing them appropriately, the A processing solution having the same composition can be easily prepared. In addition, other ion sources other than the main component, such as manganese ions, nickel ions, fluorine ions, nitrate ions, and chlorate ions, can be added to the solution (A). However, the chlorate ion source is liquid (A) and may be added to liquid (B). In particular, when a manganese ion supply source is added to liquid (A), the chlorate ion source is added to (B) M. It is preferable to do so. In addition, the soluble tungsten compound source is mixed with the zinc ion source so that the ratio of zinc ion to tungsten compound is 1:0°025 to 200 by weight as tungsten and added to the solution (B). You can.
尚、上記の処理剤と処理条件で金属表面に処理を行い得
られたタングステン含有リン酸亜鉛皮膜については、そ
の中にタングステンが0.1重量5!6以上含まれてい
る場合、この発明の効果が確実であることが確かめられ
ている。In addition, regarding the tungsten-containing zinc phosphate film obtained by treating the metal surface with the above-mentioned treatment agent and treatment conditions, if it contains 0.1 weight 5!6 or more of tungsten, this invention does not apply. It has been confirmed that it is effective.
以上の構成からなる本発明によれば、鉄系表面のみなら
ず亜鉛系と鉄系表面の両者を同時に有する金属表面に対
して、塗装下地、特に電着塗装下地、就中カチオン型電
着塗装下地として耐食性、特に耐スキャブ性が格段に優
れ、亜鉛系表面、鉄系表面、亜鉛系・鉄系を同時に有す
る金属表面など全般について耐湯塩水性、密着性共に充
分な効果を示す皮膜を形成することができる。According to the present invention having the above configuration, a coating base, especially an electrodeposition coating base, especially a cationic electrodeposition coating, can be applied to not only an iron-based surface but also a metal surface having both a zinc-based surface and an iron-based surface at the same time. As a base, it has excellent corrosion resistance, especially scab resistance, and forms a film that exhibits sufficient hot and salt water resistance and adhesion on all types of surfaces, including zinc-based surfaces, iron-based surfaces, and metal surfaces that contain zinc and iron at the same time. can do.
以下、実施例により本発明を説明する。The present invention will be explained below with reference to Examples.
実施例1〜7、実施例10および比較例1〜7(1)処
理対象金属:
(イ)合金化溶融亜鉛:合金化溶融亜鉛メツキ鋼板(ロ
)電気亜鉛:電気亜鉛メツキ鋼板
(ハ)合金化電気亜鉛:合金化電気亜鉛メツキ鋼板(ニ
)冷延鋼板
(2)酸性リン酸亜鉛処理水溶液:
第1表に示す組成を有する15種のものを使用(3)処
理工程
上記4種((1)の(イ)〜く二))の金属表面をそれ
ぞれ同時に以下の工程に従って処理。Examples 1 to 7, Example 10 and Comparative Examples 1 to 7 (1) Metals to be treated: (a) Alloyed molten zinc: Alloyed molten galvanized steel sheet (b) Electrolytic zinc: electrolytic galvanized steel sheet (c) Alloy Electrolytic zinc alloying: Alloyed electrogalvanized steel sheet (d) Cold rolled steel sheet (2) Acidic zinc phosphate treatment aqueous solution: 15 types having the composition shown in Table 1 were used (3) Treatment process The metal surfaces of 1) (a) to 2)) are treated simultaneously according to the following steps.
(4)各処理条件
(a)脱脂;
アルカリ性脱脂剤(日本ペイント社製[リドリン5D2
50 、.2重量%濃度)を使用し、40℃で2分間浸
漬処理する。(4) Each treatment condition (a) Degreasing; Alkaline degreaser (manufactured by Nippon Paint Co., Ltd. [Ridrin 5D2
50,. 2% concentration by weight) and immersion treatment at 40°C for 2 minutes.
(b)水洗: 水道水を使用し、室温で15秒間水洗する。(b) Washing with water: Rinse with tap water for 15 seconds at room temperature.
(C)表面調整:
表面調整剤(日本ペイント社製「フイキソヂン5N−5
4,0,1重量%濃度)を使用し、室温で15秒間浸漬
処理する。(C) Surface conditioning: Surface conditioning agent (“Fixodin 5N-5” manufactured by Nippon Paint Co., Ltd.)
4, 0, 1 wt% concentration) and immersion treatment for 15 seconds at room temperature.
(d)化成:
上記酸性リン酸亜鉛処理水溶液を使用し、第1表に示す
温度(52℃または40℃)で120秒間浸漬処理する
。(d) Chemical formation: Using the above acidic zinc phosphate treatment aqueous solution, immersion treatment is performed for 120 seconds at the temperature shown in Table 1 (52°C or 40°C).
(e)水洗: 水道水を使用し、室温で15秒間水洗する。(e) Washing with water: Rinse with tap water for 15 seconds at room temperature.
(f)純水洗: イオン交換水を使用し、室温で15秒間浸漬処理する。(f) Pure water washing: Dip in ion-exchanged water for 15 seconds at room temperature.
(g)乾燥:
100℃の熱風で10分間乾燥する。尚、このようにし
て得られた化成処理板の外観と化成膜重量を測定する。(g) Drying: Dry with hot air at 100°C for 10 minutes. Incidentally, the appearance and weight of the chemical conversion film of the chemical conversion treated plate thus obtained were measured.
(h)塗装:
カチオン型電着塗料(日本ペイント社製、「パワート・
ツブロー80グレー」)を焼1寸乾燥膜厚20μになる
よう塗装しく電圧180V、通電時間3分)、180℃
で30分間焼付る。得られる電着塗装板の一部を温塩水
浸漬試験に供する。残りの電着塗装板に中塗塗料(日本
ペイント社製「オルガTO4811グレー」、メラミン
アルキド樹脂系)を焼付乾燥膜厚30μになるようにス
プレー塗装し、140℃で20分間焼付る。(h) Painting: Cationic electrodeposition paint (manufactured by Nippon Paint Co., Ltd., “Powert
Bake 1 inch of "Tsuburo 80 Gray") to a dry film thickness of 20 μm. Voltage: 180 V, energizing time: 3 minutes), 180°C.
Bake for 30 minutes. A portion of the electrodeposited plate obtained is subjected to a warm salt water immersion test. An intermediate coating ("Olga TO4811 Gray" manufactured by Nippon Paint Co., Ltd., melamine alkyd resin system) was spray-coated on the remaining electrodeposited plate to a dry film thickness of 30 μm, and baked at 140° C. for 20 minutes.
次いで上塗塗料(日本ペイント社製「オルガTO630
ドーパ−ホワイト」、メラミンアルキド樹脂系)を焼付
乾燥膜厚40μになるようにスプレー塗装し 140℃
で20分間焼付け、全体で3コート3ベークの塗装板を
得る。これを密着性試験とスキャブ試験に供する。Next, top coat paint (Olga TO630 manufactured by Nippon Paint Co., Ltd.
Doper White, melamine alkyd resin) was spray-painted to a baked dry film thickness of 40μ at 140℃.
Bake for 20 minutes to obtain a painted board with 3 coats and 3 bakes in total. This is subjected to an adhesion test and a scab test.
実施例8.9および比較例8.9
(1)処理対象金属:
(イ)合金化溶融亜鉛二合金化溶融亜鉛メツキ鋼板(+
7>電気亜鉛:電気亜鉛メツキ鋼板(ハ)合金化電気亜
鉛;合金化電気亜鉛メツキ鋼板(ニ)冷延鋼板
(2)酸性リン酸亜鉛処理水溶液:
第1表に示す組成を有する4種のものを使用(3)処理
工程
上記4種((1)の(イ)〜(ニ))の金属表面をそれ
ぞれ同時に以下の工程に従って処理。Example 8.9 and Comparative Example 8.9 (1) Metals to be treated: (a) Alloyed hot-dip galvanized steel sheet (+
7> Electrolytic zinc: Electrolytic galvanized steel sheet (c) Alloyed electrolytic zinc; Alloyed electrolytic galvanized steel sheet (d) Cold rolled steel sheet (2) Acidic zinc phosphate treatment aqueous solution: 4 types having the composition shown in Table 1 (3) Treatment process The four types of metal surfaces ((1) (a) to (d)) are treated simultaneously according to the following steps.
(a)脱脂:
アルカリ性脱脂剤(日本ペイント社製[リドリン510
2.+ 、2重量%濃度)を使用し、ト℃で2分間スプ
レー処理する。(a) Degreasing: Alkaline degreaser (manufactured by Nippon Paint Co., Ltd. [Ridrin 510
2. +, 2% concentration by weight) for 2 minutes at 7°C.
(b)水洗;
水道水分使用し、室温で15秒間水洗する、(C)化成
:
上記酸性リン酸亜鉛処理水溶液を使用し、スプレー圧0
.7kg、/cm 、55℃で120秒間スプレー処
理する。(b) Water washing: Use tap water and wash with water for 15 seconds at room temperature. (C) Chemical formation: Use the above acidic zinc phosphate treated aqueous solution and spray pressure 0.
.. Spray at 7 kg,/cm 2 at 55° C. for 120 seconds.
(d)水洗: 水道水を使用し、室温で15秒間水洗する。(d) Washing with water: Rinse with tap water for 15 seconds at room temperature.
(e)純水洗: イオン交換水を使用し、室温で15秒間浸漬処理する。(e) Pure water washing: Dip in ion-exchanged water for 15 seconds at room temperature.
(f)乾燥:
+00℃の熱風で10分間乾燥する。尚、このようにし
て得られた化成処理板の外観と化成膜重量を測定する。(f) Drying: Dry with hot air at +00°C for 10 minutes. Incidentally, the appearance and weight of the chemical conversion film of the chemical conversion treated plate thus obtained were measured.
(g)塗装:
カチオン型電着塗料(日本ペイント社製、「パワートッ
プU−80グレー」)を焼付乾燥膜厚20μになるよう
塗装しく電圧180■、通電時間3分)、180℃で3
0分間焼1する。得られる電着塗装板の一部を温塩水浸
漬試験に供する。残りの電着塗装板に中塗塗料(日本ペ
イント社製「オルガTO4811グレー」、メラミンア
ルキド樹脂系)を焼付乾燥膜厚30μになるようにスプ
レー塗装し、140℃で20分間焼付る。次いで上塗塗
料(日本ペイント社製[オルガTO630ドーパ−ホワ
イト」、メラミンアルキド樹脂系)を焼付乾燥膜厚40
μになるようにスプレー塗装し 140℃で20分間焼
付け、全体で3コート3ベークの塗装板を得る。これを
密着性試験とスキャブ試験に供する。(g) Painting: Apply cationic electrodeposition paint (manufactured by Nippon Paint Co., Ltd., "Power Top U-80 Gray") to a dry film thickness of 20 μm (voltage: 180 cm, current application time: 3 minutes) at 180°C.
Bake for 0 minutes. A portion of the electrodeposited plate obtained is subjected to a warm salt water immersion test. An intermediate coating ("Olga TO4811 Gray" manufactured by Nippon Paint Co., Ltd., melamine alkyd resin system) was spray-coated on the remaining electrodeposited plate to a dry film thickness of 30 μm, and baked at 140° C. for 20 minutes. Next, a top coat (Olga TO630 Doper White manufactured by Nippon Paint Co., Ltd., melamine alkyd resin system) is baked to a dry film thickness of 40 mm.
Spray paint the plate so that it is μ and bake it for 20 minutes at 140°C to obtain a coated board with 3 coats and 3 bakes. This is subjected to an adhesion test and a scab test.
試験結果:
上記各実施例、比較例により得られた各種試験板につい
て各種試験を実施し、その結果を第2表に示した。尚、
各試験方法は以下に示す。Test Results: Various tests were conducted on the various test plates obtained in the above Examples and Comparative Examples, and the results are shown in Table 2. still,
Each test method is shown below.
(^〉温塩水浸漬試験
電着塗装板に鋭利なカッターで力・ソトを入れ、5%、
55℃の食塩水中に480時間浸漬した後、カット部に
粘着テープを貼着した後剥離し、塗膜の最大剥離中を測
定する。(^〉Warm salt water immersion test Apply force and tension with a sharp cutter to the electrodeposition coated plate, 5%
After 480 hours of immersion in saline solution at 55° C., an adhesive tape is attached to the cut portion and then peeled off, and the maximum peeling of the coating film is measured.
<8)密着性試験:
塗装板を40℃の脱イオン水に20日間漫潰した後、こ
れに1開間隔と21111間隔のゴバン目(100個)
を鋭利なカッターで形成し、その各面に粘着テープを貼
着した峻これらを制mして、塗装板に残っているゴバン
目塗膜の数を数える。<8) Adhesion test: After soaking the painted board in deionized water at 40°C for 20 days, it was coated with grids (100 pieces) with 1 and 21111 spacing.
The number of rough coatings remaining on the painted board was counted by cutting a sharp strip using a sharp cutter and applying adhesive tape to each side of the strip.
(C)スキャブ試験
塗装板に鋭利なカッターでカットを入れ、次いでこの塗
装板を5%塩水噴霧試験(JIS−Z−2371,24
時間)→湿潤試験(温度40℃、相対湿度85%、12
0時間)→室内放N(24時間)を1サイクルとして1
0サイクルの腐食試験(以後スキャブ試験という)に付
した。試験後の塗面の塗膜異常(糸錆・フクレなど)の
最大中を調べた。(C) Scab test A cut was made on the painted board with a sharp cutter, and then the painted board was subjected to a 5% salt spray test (JIS-Z-2371, 24
time) → Humidity test (temperature 40℃, relative humidity 85%, 12
0 hours)→Indoor discharge N (24 hours) is considered as 1 cycle.
It was subjected to a 0-cycle corrosion test (hereinafter referred to as a scab test). The maximum number of paint film abnormalities (thread rust, blisters, etc.) on the painted surface after the test was investigated.
(以下余白)
手続補正書(自発)
1.事件の表示
昭和62年特許願第321737号
2、発明の名称
塗装用金属表面のリン酸亜鉛処理方法
3、補正をする者
事件との関係 特許出願人
住所 大阪市大淀区大淀北2丁目1番2号名称 日本ペ
イント株式会社
代表者 佐々木 −雄
4、代理人
住所 〒540大阪市東区京橋3丁目57番地ビル・リ
バーセンター6階
−(自発)
7、補正の対象 明細書の特許請求の範囲の欄、ならび
に発明の詳細な説明の欄
8 補正の内容 別紙の通り
1、特許請求の範囲を下記の通り訂正する「(1)金属
表面を、可溶性タングステン化合物をタングステンとし
て0.05〜20.Og&含む酸性リン酸亜鉛処理水酸
液で処理することを特徴とする金属表面のリン酸亜鉛処
理方法。(Left below) Procedural amendment (voluntary) 1. Display of the case 1986 Patent Application No. 321737 2 Title of the invention Method for treating zinc phosphate on metal surfaces for painting 3 Person making the amendment Relationship to the case Patent applicant address 2-1 Oyodokita, Oyodo-ku, Osaka City No. 2 Name: Nippon Paint Co., Ltd. Representative: Yu Sasaki 4, Agent address: 6th floor, River Center Building, 3-57 Kyobashi, Higashi-ku, Osaka 540 (voluntary) 7. Subject of amendment: Claims in the specification Column and Detailed Description of the Invention Column 8 Contents of the Amendment As per Attachment 1, the claims are amended as follows: ``(1) The metal surface is 0.05 to 20.Og & A method for treating a metal surface with zinc phosphate, the method comprising treating a metal surface with an acidic zinc phosphate treatment hydroxide solution.
(2) 1lKH面ヲ亜鉛イオ70.1〜2.0g/j
l!、リン酸イオン5〜40g/i、可溶性タングステ
ン化合物をタングステンとして0,05〜2o、Og/
Lおよび皮膜化成促進剤を主成分として含む酸性リン酸
亜鉛処理水溶液で処理することを特徴とする特許請求の
範囲第1項記載の方法。(2) 1lKH surface zinc ion 70.1-2.0g/j
l! , phosphate ion 5-40g/i, soluble tungsten compound as tungsten 0.05-2o, Og/i
The method according to claim 1, characterized in that the treatment is carried out with an acidic zinc phosphate treatment aqueous solution containing L and a film formation accelerator as main components.
(3)処理方式が浸漬処理である特許請求の範囲第2項
記載の方法。(3) The method according to claim 2, wherein the treatment method is immersion treatment.
(4)皮膜化成促進剤が亜硝酸イオン0.O1〜0.5
g/jl!、、m−ニトロベンゼンスルホン酸イオン0
.05〜5g/lおよび過酸化水素0.5〜IOg/i
!からj■ばれる少なくとも1種である特許請求の範囲
第2項記載の方法。(4) Film formation accelerator contains nitrite ion 0. O1~0.5
g/jl! ,, m-nitrobenzenesulfonic acid ion 0
.. 05-5g/l and hydrogen peroxide 0.5-IOg/i
! The method according to claim 2, wherein at least one of the following is used.
(5)酸性リン酸亜鉛処理水溶液がマンカンイオンを最
大3g/Lまで含む特許請求の範囲第2項記載の方法。(5) The method according to claim 2, wherein the acidic zinc phosphate treated aqueous solution contains mankan ions up to 3 g/L.
(6)酸性リン酸亜鉛処理水溶液が、フ・・I素イオン
を最大4g/必まで含む特許請求の範囲第5項記載の方
法。(6) The method according to claim 5, wherein the acidic zinc phosphate treatment aqueous solution contains up to 4 g/required of F...I ions.
(7)酸性リン酸亜鉛処理水溶液が二・・Iケルイオン
を最大4gzZまで含む特許請求の範囲第5項記載の方
法。(7) The method according to claim 5, wherein the acidic zinc phosphate treatment aqueous solution contains up to 4 gzZ of di...I Kel ions.
(8)酸性リン酸亜鉛処理水溶液が硝酸イオン15 g
、/i以下および/または塩素酸イオン2g、711未
満を含む特許請求の範囲第2項記載の方法(9)処理温
度が30〜70℃である特許請求の範囲第1項記載の方
法、
(lO)浸漬処理が、先ず15秒以上の浸漬処理、次い
でスプレー処理の組合せからなる特許請求の範囲第3項
記載の方法。(8) Acidic zinc phosphate treated aqueous solution contains 15 g of nitrate ions
, /i or less and/or 2 g of chlorate ions, method (9) according to claim 2, wherein the treatment temperature is 30 to 70°C, ( 4. The method of claim 3, wherein the dipping treatment comprises a combination of first dipping for 15 seconds or more and then spraying.
(II)金属表面が鉄系表面、亜鉛系表面、♂るいは鉄
系表面と亜鈴系表面とを同時に有するものである特許請
求の範囲第2項記載の方法5(12)亜鉛イオン源、リ
ン酸イオン源およびタングステンイオン源(Wとして)
を1:2.5〜400 :0.025〜200の重量比
で含む(A)成分と皮膜化成促進剤を含む(B)成分と
からなる、上記第2項の酸性リン酸亜鉛処理水溶液を希
釈により調整するための2液型濃厚処理剤。(II) Method 5 (12) Zinc ion source according to claim 2, wherein the metal surface has an iron-based surface, a zinc-based surface, a ferrous surface, or an iron-based surface and a dumbbell-based surface at the same time. Acid ion source and tungsten ion source (as W)
The acidic zinc phosphate treated aqueous solution of item 2 above, consisting of component (A) containing 1:2.5 to 400:0.025 to 200 and component (B) containing a film formation accelerator. A two-part concentrated processing agent that can be adjusted by dilution.
(13)Wを(B)に添加する2液型濃厚処理剤(14
)亜鉛イオン0.1〜2.0 gL 、リン酸イオン5
〜40号ρ 、可溶性タングステンイオンfヒ合物をタ
ングステンとして0.05〜20 、0 g/Lおよび
皮膜化成促進剤を主成分として含む酸性リン酸亜鉛処理
水溶液で処理して得られるタングステン含有リン酸亜鉛
皮膜を有する金属材。(13) Two-component concentrated processing agent (14) in which W is added to (B)
) Zinc ion 0.1-2.0 gL, phosphate ion 5
- No. 40 ρ, tungsten-containing phosphorus obtained by treating with an acidic zinc phosphate treatment aqueous solution containing 0.05 to 20,0 g/L of soluble tungsten ion f arsenide as tungsten and a film formation accelerator as a main component. Metal material with acid zinc coating.
(15)タングステン含有リン酸亜鉛皮膜のタングステ
ン含量が0.1 重量%以上である特許請求の範囲第
14項記載の金属材。」
2、明細書第16頁の2〜4行に
「上記亜鉛イオン:タングステン・・・・・・混合した
ものをB液に添加し」
とあるを
V上記亜鈴イオン:タングステン化合物=1:0.00
25〜200となるように(B)液に添加し」と訂正す
る。(15) The metal material according to claim 14, wherein the tungsten content of the tungsten-containing zinc phosphate film is 0.1% by weight or more. 2. On page 16 of the specification, lines 2 to 4, it says, ``Add the above zinc ion: tungsten...mixture to liquid B.'' .00
Add it to solution (B) so that it has a concentration of 25 to 200.''
3、明細書第18頁の下より5〜4行に「化成膜重量」 とあるを r化成皮膜重量j と訂正する、3. "Chemical coating weight" in lines 5-4 from the bottom of page 18 of the specification A certain thing r Chemical conversion coating weight j to correct,
Claims (15)
ステンとして0.05〜20.0g/l含む酸性リン酸
亜鉛処理水溶液で処理することを特徴とする金属表面の
リン酸亜鉛処理方法。(1) A method for treating a metal surface with zinc phosphate, which comprises treating the metal surface with an acidic zinc phosphate treatment aqueous solution containing a soluble tungsten compound of 0.05 to 20.0 g/l of tungsten.
ン酸イオン5〜40g/l、可溶性タングステン化合物
をタングステンとして0.05〜20.0g/lおよび
皮膜化成促進剤を主成分として含む酸性リン酸亜鉛処理
水溶液で処理することを特徴とする特許請求の範囲第1
項記載の方法。(2) The main components of the metal surface are zinc ions of 0.1 to 2.0 g/l, phosphate ions of 5 to 40 g/l, soluble tungsten compounds of 0.05 to 20.0 g/l of tungsten, and a film formation accelerator. Claim 1, characterized in that the treatment is performed with an acidic zinc phosphate treatment aqueous solution containing
The method described in section.
記載の方法。(3) The method according to claim 2, wherein the treatment method is immersion treatment.
g/l、m−ニトロベンゼンスルホン酸イオン0.05
〜5g/lおよび過酸化水素0.5〜10g/lから選
ばれる少なくとも1種である特許請求の範囲第2項記載
の方法、(4) Film formation accelerator is nitrite ion 0.01-0.5
g/l, m-nitrobenzenesulfonic acid ion 0.05
5 g/l and at least one selected from hydrogen peroxide 0.5 to 10 g/l, the method according to claim 2,
大3g/lまで含む特許請求の範囲第2項記載の方法。(5) The method according to claim 2, wherein the acidic zinc phosphate treated aqueous solution contains manganese ions up to 3 g/l.
大4g/lまで含む特許請求の範囲第5項記載の方法。(6) The method according to claim 5, wherein the acidic zinc phosphate treatment aqueous solution contains fluorine ions up to 4 g/l.
大4g/lまで含む特許請求の範囲第5項記載の方法。(7) The method according to claim 5, wherein the acidic zinc phosphate treatment aqueous solution contains nickel ions up to 4 g/l.
l以下および/または塩素酸イオン2g/l未満を含む
特許請求の範囲第2項記載の方法。(8) Acidic zinc phosphate treated aqueous solution contains 15 g of nitrate ions/
1 and/or less than 2 g/l of chlorate ions.
1項記載の方法。(9) The method according to claim 1, wherein the treatment temperature is 30 to 70°C.
でスプレー処理の組み合わせからなる特許請求の範囲第
3項記載の方法。(10) The method according to claim 3, wherein the dipping treatment comprises a combination of first dipping treatment for 15 seconds or more and then spraying treatment.
系表面とを同時に有するものである特許請求の範囲第2
項記載の方法。(11) Claim 2 in which the metal surface has an iron-based surface or an iron-based surface and a zinc-based surface at the same time.
The method described in section.
テンイオン源(Wとして)を1:2.5〜400:0.
025〜200の重量比で含む(A)成分と、皮膜化成
促進剤を含む(B)成分とからなる、上記第2項の酸性
リン酸亜鉛処理水溶液を希釈により調製するための2液
型濃厚処理剤。(12) Zinc ion source, phosphate ion source and tungsten ion source (as W) in a ratio of 1:2.5 to 400:0.
A two-component concentrated solution for preparing by dilution the acidic zinc phosphate treatment aqueous solution of item 2 above, which consists of component (A) contained in a weight ratio of 0.025 to 200 and component (B) containing a film formation accelerator. Processing agent.
ン5〜40g/l、可溶性タングステンイオン化合物を
タングステンとして0.05〜20.0g/lおよび皮
膜化成促進剤を主成分として含む酸性リン酸亜鉛処理水
溶液で処理して得られるタングステン含有リン酸亜鉛皮
膜を有する金属材。(14) Contains zinc ion 0.1 to 2.0 g/l, phosphate ion 5 to 40 g/l, soluble tungsten ion compound as tungsten 0.05 to 20.0 g/l, and film formation accelerator as main components. A metal material having a tungsten-containing zinc phosphate film obtained by treatment with an acidic zinc phosphate treatment solution.
ン含量が0.1重量%以上である特許請求の範囲第14
項記載の金属材。(15) Claim 14, wherein the tungsten content of the tungsten-containing zinc phosphate coating is 0.1% by weight or more.
Metal materials listed in section.
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP32173787A JPH01162780A (en) | 1987-12-18 | 1987-12-18 | Zinc phosphate treatment of surface of metal for coating |
CA000586120A CA1333683C (en) | 1987-12-18 | 1988-12-16 | Process for phosphating metal surfaces |
EP88202896A EP0321059B1 (en) | 1987-12-18 | 1988-12-16 | Process for phosphating metal surfaces |
AU27023/88A AU610313B2 (en) | 1987-12-18 | 1988-12-16 | Process for phosphating metal surfaces |
ES88202896T ES2092983T3 (en) | 1987-12-18 | 1988-12-16 | PROCEDURE TO PHOSPHATE WITH A ZINC A METALLIC SURFACE. |
DE8888202896T DE3875459T2 (en) | 1987-12-18 | 1988-12-16 | METHOD FOR PHOSPHATING METAL SURFACES. |
KR1019880016866A KR890010273A (en) | 1987-12-18 | 1988-12-17 | Phosphate treatment on metal surfaces |
US07/532,241 US5039363A (en) | 1987-12-18 | 1990-05-30 | Process for phosphating metal surfaces |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP32173787A JPH01162780A (en) | 1987-12-18 | 1987-12-18 | Zinc phosphate treatment of surface of metal for coating |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH01162780A true JPH01162780A (en) | 1989-06-27 |
Family
ID=18135881
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP32173787A Pending JPH01162780A (en) | 1987-12-18 | 1987-12-18 | Zinc phosphate treatment of surface of metal for coating |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH01162780A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5221370A (en) * | 1989-06-15 | 1993-06-22 | Nippon Paint Co., Ltd. | Method for forming zinc phosphate film on metal surface |
JP2002212751A (en) * | 2001-01-17 | 2002-07-31 | Nippon Paint Co Ltd | Metal surface treatment method |
JP2012126941A (en) * | 2010-12-14 | 2012-07-05 | Jfe Steel Corp | Steel sheet having excellent corrosion resistance and method for manufacturing the same |
-
1987
- 1987-12-18 JP JP32173787A patent/JPH01162780A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5221370A (en) * | 1989-06-15 | 1993-06-22 | Nippon Paint Co., Ltd. | Method for forming zinc phosphate film on metal surface |
JP2002212751A (en) * | 2001-01-17 | 2002-07-31 | Nippon Paint Co Ltd | Metal surface treatment method |
JP4658339B2 (en) * | 2001-01-17 | 2011-03-23 | 日本ペイント株式会社 | Metal surface treatment method |
JP2012126941A (en) * | 2010-12-14 | 2012-07-05 | Jfe Steel Corp | Steel sheet having excellent corrosion resistance and method for manufacturing the same |
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