JPS63176481A - Hot dip coated steel sheet having excellent pretreatability before painting and its production - Google Patents
Hot dip coated steel sheet having excellent pretreatability before painting and its productionInfo
- Publication number
- JPS63176481A JPS63176481A JP703087A JP703087A JPS63176481A JP S63176481 A JPS63176481 A JP S63176481A JP 703087 A JP703087 A JP 703087A JP 703087 A JP703087 A JP 703087A JP S63176481 A JPS63176481 A JP S63176481A
- Authority
- JP
- Japan
- Prior art keywords
- salt
- steel sheet
- hot
- plating
- painting
- 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
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 22
- 239000010959 steel Substances 0.000 title claims abstract description 22
- 238000010422 painting Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000011282 treatment Methods 0.000 claims abstract description 44
- 238000007747 plating Methods 0.000 claims abstract description 33
- 150000003839 salts Chemical class 0.000 claims abstract description 32
- 238000005507 spraying Methods 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 7
- 239000000956 alloy Substances 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 13
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 12
- 239000008397 galvanized steel Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims description 5
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 159000000014 iron salts Chemical class 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical group [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 20
- 239000010410 layer Substances 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 229910002651 NO3 Inorganic materials 0.000 abstract description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011247 coating layer Substances 0.000 abstract description 3
- 238000003618 dip coating Methods 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract description 2
- 229910007570 Zn-Al Inorganic materials 0.000 abstract 1
- 235000002639 sodium chloride Nutrition 0.000 description 24
- 230000003750 conditioning effect Effects 0.000 description 11
- 229910019142 PO4 Inorganic materials 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000010452 phosphate Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 230000005856 abnormality Effects 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 iron salt Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002515 CoAl Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241000269821 Scombridae Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 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 1
- 239000007789 gas Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 235000020640 mackerel Nutrition 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 210000001747 pupil Anatomy 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000005303 weighing Methods 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1241—Metallic substrates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
- Ceramic Engineering (AREA)
- Coating With Molten Metal (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Chemically Coating (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は塗装前処理において、リン酸塩処理やクロメー
ト処理などの化成処理を施す際に酸性もしくはアルカリ
性の処理液で鋼板表面を表面７１１１ｇしなくても化成
処理性に優れた溶融めっき鋼板およびその製造方法に関
する。Detailed Description of the Invention (Field of Industrial Application) The present invention is a pre-painting treatment in which the surface of a steel plate is coated with an acidic or alkaline treatment liquid (7111 g) when performing chemical conversion treatments such as phosphate treatment and chromate treatment. The present invention relates to a hot-dip galvanized steel sheet that has excellent chemical conversion treatment properties even without the use of a hot-dip galvanized steel sheet, and a method for manufacturing the same.
（従来技術）
溶融めっき鋼板に塗装を施す場合、前処理として、リン
酸塩処理やクロメート処理などの化成処理を施すが、こ
の化成処理を施す際、処理性を高めるために予め鋼板表
面に表面調整を施すのが一般的である０例えばリン酸塩
処理系の前処理場合には脱脂、水洗、表面？１４ｇ、、
リン酸塩処理、後処理、乾燥のように、またクロメート
処理系の前処理の場合には脱脂、水洗、表面調整、クロ
メート処理、乾燥のようにいずれも化成処理前に表面調
整を施している。(Prior art) When painting a hot-dip galvanized steel sheet, a chemical conversion treatment such as phosphate treatment or chromate treatment is applied as a pretreatment. For example, in the case of pretreatment for a phosphate treatment system, it is common to make adjustments such as degreasing, washing, and surface treatment. 14g...
Surface conditioning is performed before chemical conversion treatment, such as phosphate treatment, post-treatment, and drying, and in the case of chromate treatment-based pretreatment, such as degreasing, water washing, surface conditioning, chromate treatment, and drying. .
この表面調整の方法としては、従来より種々の方法が提
案されている。例えば化成処理がリン酸塩処理の場合に
はチタン化合物のコロイドを付着させて、それをリン酸
塩結晶の結晶核にして皮膜の生成を速め、均−ｍ密な皮
膜にするチタン吸着法（特公昭５７−１２０６７８号）
が、またクロメート処理の場合にはＣｏ、 Ｎｉ％Ｆｅ
等の金属イオンを含む処理液で処理して、これらの金属
および金属酸化物を付着させ、耐食性、塗装後の塗膜性
能を改善する方法などが知られている。Various methods have been proposed for this surface conditioning method. For example, when the chemical conversion treatment is a phosphate treatment, a titanium adsorption method (titanium adsorption method) in which a colloid of a titanium compound is attached and this is used as the crystal nucleus of the phosphate crystal to speed up the formation of the film and create a uniformly dense film. Special Publication No. 57-120678)
However, in the case of chromate treatment, Co, Ni%Fe
A known method is to treat with a treatment liquid containing metal ions, such as metal ions, to adhere these metals and metal oxides, and to improve corrosion resistance and coating performance after painting.
（発明が解決しようとする問題点）
しかしながら、このような表面ａＳの処理液は酸性かア
ルカリ性であるため、処理後洗浄を必要とする。このた
め塗装前処理設備には洗浄槽を設置し、その洗浄槽より
発生する廃液を処理しなければならなかった。また洗浄
槽に故障が生じ、洗浄が不十分であることに気付かずに
塗装してしまうと、表１１ｉｉｉ１１整処理液は酸性が
アルカリ性であるため、処理液が腐食因子になって腐食
を誘発したり、塗膜性能を低下させたりするものであっ
た。(Problems to be Solved by the Invention) However, since the treatment liquid for such a surface aS is acidic or alkaline, cleaning is required after treatment. For this reason, it was necessary to install a cleaning tank in the painting pretreatment equipment and treat the waste liquid generated from the cleaning tank. In addition, if a failure occurs in the cleaning tank and you paint without realizing that cleaning is insufficient, the treatment liquid may become a corrosion factor and induce corrosion because the acidity of the treatment liquid in Table 11iii11 is alkaline. or deteriorate the coating performance.
このようなことから、塗装前処理工程で化成処理前に表
面ｉｉｑ整処理を施さなくても化成処理性に優れた溶融
めっき鋼板が望まれていた。For these reasons, there has been a desire for a hot-dip plated steel sheet that has excellent chemical conversion treatment properties even without performing surface IIQ treatment before chemical conversion treatment in the painting pretreatment step.
（問題点を解決するための手段）
本発明者は亜鉛系または亜鉛−アルミニウム系合金の溶
融めっき鋼板表面にコバルト、ニッケル、鉄の１種また
は２種以上の酸化物皮膜を形成することにより直接化成
処理を施すことができるようにした。そしてこの酸化物
皮膜を形成する方法として、鋼板に亜鉛系または亜鉛−
アルミニウム系合金の溶融めっきを施した後、めっき付
着量を調整し、その後めっき層が１７０℃以上にあろう
ちに、またはめっき層を１７０℃以上に加熱してめっき
層表面にコバルト塩、ニッケル塩、鉄塩の１種！Ｒたは
２種以上を含む水溶液を霧化して吹付けることにより塩
を熱分解しで形成するようにした。(Means for Solving the Problems) The present inventors directly coated the surface of a zinc-based or zinc-aluminum alloy hot-dipped steel sheet by forming an oxide film of one or more of cobalt, nickel, and iron. It is now possible to perform chemical conversion treatment. As a method of forming this oxide film, zinc-based or zinc-based
After applying hot-dip plating with an aluminum alloy, adjust the amount of plating and then, while the plating layer is at 170°C or higher, or heat the plating layer to 170°C or higher and add cobalt salt or nickel salt to the surface of the plating layer. , a type of iron salt! The salt was thermally decomposed and formed by atomizing and spraying an aqueous solution containing R or two or more thereof.
本発明の酸化物皮膜は、例えばＣｏＪ４． ＣｏＯまた
はスピネル型ＣｏＡｌ□０．のように金属と酸素との化
合物、すなわち金属酸化物の皮膜であって、従来のＣｏ
、 Ｎｉ１Ｆｅ等の金属イオンを含む処理液で処理する
表面′ｖ４整で形成する金属およびその酸化物とは組成
が異なるものである。従来の表面調整により形成される
酸化物は置換めっきにより形成されるものであるので、
水酸化物のように金属の原子価が増加したものであり、
本発明の酸化物のように酸素との化合物ではない。The oxide film of the present invention may be made of, for example, CoJ4. CoO or spinel type CoAl□0. It is a film of a compound of metal and oxygen, that is, a metal oxide, as shown in the conventional Co
The composition is different from that of the metal and its oxide formed when the surface is treated with a treatment solution containing metal ions such as Ni1Fe and the like. Since the oxide formed by conventional surface conditioning is formed by displacement plating,
It is a metal with an increased valence like hydroxide,
It is not a compound with oxygen like the oxide of the present invention.
本発明において酸化物をコバルト、ニッケル、鉄の酸化
物にしたのは、これらの金属以外の酸化物（例えばＺｎ
、Ｔｉ、 Ｈ，Ｎｂなどの酸化物）はあまり効果がなか
ったり、あるいは逆効果を示したりするためである。In the present invention, oxides of cobalt, nickel, and iron are used as oxides of cobalt, nickel, and iron because oxides other than these metals (for example, Zn
, Ti, H, Nb, etc.) are not very effective or have the opposite effect.
酸化物皮膜の形成はコバルト、ニッケル、鉄の金属塩水
溶液を温度が塩の分解温度以上、すなわち１７０℃以上
であるめっき層に吹付けて塩を熱分解する方法により行
う。金属塩としてはいずれも硝酸塩が好ましい。これは
酢酸塩、硫酸塩、塩化物など他の塩でも金属酸化物皮膜
が形成されるが、大きな効果がなく、化学的にも不安定
で、溶出しやすく、また残留未反応物や分解物が腐食因
子となって、塗装前処理性を阻害するからでもある。The oxide film is formed by spraying an aqueous solution of metal salts of cobalt, nickel, and iron onto the plating layer at a temperature higher than the decomposition temperature of the salt, that is, 170° C. or higher, to thermally decompose the salt. As the metal salt, nitrates are preferred. Other salts such as acetate, sulfate, and chloride can also form a metal oxide film, but they are not very effective, are chemically unstable, are easily eluted, and are free from residual unreacted and decomposed substances. This is also because it becomes a corrosion factor and inhibits painting pretreatment properties.
水溶液の塩濃度や温度などはとくに限定はな（ｔが、濃
度は金属イオン濃度で０．１〜２０９ハロこなるよう調
整するのが好ましい。これは金属イオン濃度が０．１９
／［未満であると、めっき層表面に形成される金属酸化
物量が少なしまため、表面調整処理を必要とし、かつ未
凝固めっき層に吹付けてスパングルをミニマイズド化し
て、塗装性、外観を向上させる場合均一にミニマイズド
化できず、まｒＬ２０９／ｅを越えると、完全に分解し
な１１まため、残留塩が化成処理性を阻害し、しかも溶
解塩類特有の色が現われ、表面全体が着色されてしまう
からである。The salt concentration and temperature of the aqueous solution are not particularly limited (t is preferably adjusted so that the metal ion concentration is 0.1 to 209 halo).
If it is less than /[, the amount of metal oxide formed on the surface of the plating layer will be small, requiring surface conditioning treatment, and spraying on the unsolidified plating layer will minimize spangles, improving paintability and appearance. If it is dissolved, it cannot be minimized uniformly, and if it exceeds rL209/e, it will not be completely decomposed, and the residual salt will inhibit the chemical conversion process, and furthermore, the color peculiar to dissolved salts will appear, and the entire surface will be colored. This is because
水溶液のｐＨは５〜７にする必要がある。これはｐｌ＋
が低すぎたり、高すぎたりすると、めっき層が高温のた
め、めっき層と瞬時に反応して、工・ノチングやミクロ
的腐食を起こし、変色はもとより腐食の起点となってし
まうからである。塩として硝酸塩を使用する場合、金属
イオン濃度が０．１〜２０９７ｅとなるように水に溶解
すると、ｐＮが５〜７の弱酸性から中性になるので、ｐ
ｌ＋をとくに調整しなくてもそのまま使用することがで
きる。The pH of the aqueous solution needs to be 5-7. This is pl+
If the temperature is too low or too high, the high temperature of the plating layer will instantly react with the plating layer, causing chipping, notching, and microcorrosion, which will not only cause discoloration but also become the starting point for corrosion. When using nitrate as a salt, if it is dissolved in water to a metal ion concentration of 0.1 to 2097e, the pN will change from weakly acidic to neutral with a pN of 5 to 7.
It can be used as is without any particular adjustment of l+.
本発明では以上のように調整した水溶液を霧化してめっ
き層温度が１７０℃以上のめっき鋼板表面に吹付け、め
っき鋼板の温度により塩を熱分解し、酸化物皮膜を形成
する。この水溶液の吹付けはめっき後付着量をｉ１！！
整して溶融めっき鋼板の温度が１７０℃以上にあるうち
に行ってもよく、一旦常温に冷却された溶融めっき鋼板
を１７０℃以上に加熱して行ってもよい。特に前者の方
法によりめっき層が未凝固状態にあるうちに水溶液を吹
付けると、熱分解により生じたコバルト、ニッケル、鉄
の酸化物がめつきＩｆ４汲Ｍに拡散されて、めっき層と
一体になり、めっき層表層に強固な酸化物皮膜が形Ｊ＆
され、またスパングルも塩が核になって均一にミニマイ
ズド化されるので、非常に好都合である。スパングルを
ミニマイズド化する際従来でもリン酸塩や食塩などのミ
ニマイズドスパングル化剤を水溶液に添加することは知
られているが、本発明の場合はこのミニマイズドスパン
グル化剤の役目をコバルト塩、ニッケル塩、鉄塩にも兼
務させるのである。これらの塩とともに従来のミニマイ
ズドスパングル化剤を混合することも可能である。In the present invention, the aqueous solution prepared as described above is atomized and sprayed onto the surface of a plated steel sheet whose coating layer temperature is 170° C. or higher, and the salt is thermally decomposed by the temperature of the plated steel sheet to form an oxide film. Spraying this aqueous solution reduces the amount of adhesion after plating by i1! !
The hot-dip coating may be carried out while the temperature of the hot-dip plated steel sheet is 170°C or higher, or the hot-dip plated steel plate may be heated to 170°C or higher after being cooled to room temperature. In particular, if the aqueous solution is sprayed on the plating layer while it is in an unsolidified state using the former method, the oxides of cobalt, nickel, and iron produced by thermal decomposition will be diffused into the plated If4 M and become integrated with the plating layer. , a strong oxide film is formed on the surface of the plating layer.
In addition, the spangles are also minimized uniformly with the salt as the core, which is very convenient. It has been known in the past to add a minimized spangle agent such as phosphate or common salt to an aqueous solution when minimizing spangles, but in the case of the present invention, the role of this minimized spangle agent is replaced by cobalt salt, It also serves as a nickel salt and iron salt. It is also possible to mix conventional minimized spangling agents with these salts.
金属塩水溶液の吹付は量は金属換算で付着量が１〜１０
０ ｍｇ７輸２になるようにする。１ ｍ６７輪２未満
であると、表面調整効果が不十分であり、１００１１ｇ
／ ｍ ２を越えると、着色してしまうとともに、未
分解塩が残留する恐れがある。When spraying an aqueous metal salt solution, the amount of adhesion is 1 to 10 in terms of metal.
0mg7x2. If it is less than 1 m67 wheels, the surface conditioning effect will be insufficient and the weight will be 10011 g.
/m2, coloring may occur and undecomposed salts may remain.
水溶液を吹付けるときのめっき層温度を１７０℃以上に
するのはコバルト塩、ニッケル塩、鉄塩がこの温度以下
では短時間に効率よく熱分解しないためである。塩が硝
酸塩の場合２０℃程度でも熱分解して酸化物になるが、
温度がこのように低いと熱分解効率が低くなる。The reason why the temperature of the plating layer when spraying the aqueous solution is set to 170° C. or higher is because cobalt salts, nickel salts, and iron salts do not thermally decompose efficiently in a short time below this temperature. If the salt is a nitrate, it will thermally decompose into an oxide even at around 20℃, but
Such low temperatures result in low pyrolysis efficiency.
熱分解により生じる酸化物は塩の種類や熱分解温度によ
り異なるが、硝酸コバルトの場合ＮＯ２が発生して、瞬
時にＣｏ＝０４、ＣｏＯまたはスピネルペリＣｏ八１２
０４の単独皮膜もしくはそれらの２４１１以−りの複合
皮膜を形成する。The oxides produced by thermal decomposition vary depending on the type of salt and the thermal decomposition temperature, but in the case of cobalt nitrate, NO2 is generated and instantly changes to Co=04, CoO, or spinel peri-Co812.
A single film of 04 or a composite film of 2411 or more thereof is formed.
本発明の酸化物皮膜は化成処理の際表面調整の役割を果
し、リン酸塩皮膜生成の場合は結晶核になり、表面調整
を施さなくでも均一で緻密な皮膜を形成する。またクロ
メート処理でも処理後耐食性や塗装後の塗膜性能を向上
させる。さらに皮膜は酸素との化合物であるので、化学
的に安定し、しかもめっき層表層に溶着もしくは強固に
付着しているので、レベラーやスキンバスなどの８！ケ
戒的処理加工やクロム酸処理を施しても、容易には除去
されない。The oxide film of the present invention plays the role of surface conditioning during chemical conversion treatment, and in the case of phosphate film formation, it becomes a crystal nucleus, forming a uniform and dense film even without surface conditioning. Chromate treatment also improves corrosion resistance after treatment and coating performance after painting. Furthermore, since the film is a compound with oxygen, it is chemically stable and is welded or firmly attached to the surface of the plating layer, so it can be used as a leveler, skin bath, etc. It is not easily removed even with chemical treatment or chromic acid treatment.
なお本発明の溶融めっき鋼板は表面調整不要であるが、
従来のように表面調整を含む塗装面処理を施しても化成
処理性に問題は生じない。Although the hot-dip galvanized steel sheet of the present invention does not require surface preparation,
Even if the painted surface is treated, including surface conditioning, as in the past, no problem arises in chemical conversion treatment.
本発明の製造方法は従来より塗装に一般的に使用してい
る合金層成長抑制用にＡｌを微量添加した溶融亜鉛めっ
き鋼板はもとより、耐食性向上元素を添加した他の亜鉛
系のもの（例えばＡｌ０．１〜０．３０％、Ｍｇ０〜０
．５％、Ｐｂ ０．００２〜０．３％、残部がＺｎお
よび不可避的不純物のもの）やめつき層が亜鉛−アルミ
ニウム系合金のもの（例えばＡｌ４〜５３％、Ｍｇ ０
〜０．５％、Ｓｉ ０〜１０％、Ｐｂ ００００２〜０
．３０％、残部がＺｎおよび不可避的不純物のもの）で
も適用できる。The manufacturing method of the present invention is applicable not only to hot-dip galvanized steel sheets with a small amount of Al added to suppress alloy layer growth, which have been commonly used in painting, but also to other zinc-based steel sheets with addition of corrosion resistance improving elements (for example, Al0 .1~0.30%, Mg0~0
．． 5%, Pb 0.002-0.3%, balance Zn and unavoidable impurities) or the coating layer is a zinc-aluminum alloy (e.g. Al4-53%, Mg 0
~0.5%, Si 0-10%, Pb 00002-0
．． 30%, the balance being Zn and unavoidable impurities).
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）
実施例１
重量％で、 八ｌ ０．１７％、 Ｐｂ ０．３０
％、 Ｆｅ ０．０３％、残部Ｚｎおよび不可避的不
純物からなるめっき浴で冷延鋼板を溶融めつ外した後、
気体絞り法によりめっき付着量を２００〜２５０９／ａ
２に′？Ｉ４！！シ、第１表に示す塩の水溶液を２〜５
Ｋｇ／ｃｍ２の圧縮空気で霧化して吹付け、溶融亜鉛
めっき鋼板を製造した。(Example) Example 1 In weight%, 8l 0.17%, Pb 0.30
%, Fe 0.03%, balance Zn and unavoidable impurities.
Plating deposition amount is 200-2509/a by gas squeezing method
2′? I4! ! 2 to 5 times aqueous solution of the salt shown in Table 1
A hot-dip galvanized steel sheet was produced by atomizing and spraying with compressed air of Kg/cm2.
次にこの鋼板に表面調整を施すことなく直接第１−＆に
示す化成処理を施して、一旦皮膜形成状態を調査した後
、バーコード法でアルキッドメラミン系塗料を塗布して
、２０分間のセツティング後雰囲気温度１４０℃の熱風
循環式オープンで２５分間焼付け、塗膜／’；Ｅ３０±
２μｍの塗装鋼板とした。Next, this steel plate was directly subjected to the chemical conversion treatment shown in step 1-& without surface conditioning, and after investigating the state of film formation, an alkyd melamine paint was applied using the barcode method, and a 20-minute setting process was performed. After heating, bake for 25 minutes in an open hot air circulation system at an ambient temperature of 140°C, resulting in a coating film of /'; E30±.
A 2 μm coated steel plate was used.
この塗装鋼板の塗膜密着性と塩水噴霧試験結果を第１表
に示す。Table 1 shows the coating adhesion of this coated steel plate and the salt spray test results.
なお皮膜の化成処理性の評価および塗膜ｆｆｉ着性試験
や塩水噴ｎ試験の試験および評価は次のようにして行っ
た。The evaluation of the chemical conversion treatment property of the film, and the tests and evaluations of the paint film ffi adhesion test and the salt water spray n test were conducted as follows.
（１）化成処理性評価
リン酸塩系皮膜は走査型電子顕微鏡により結晶状態を次
の基準で評価した。(1) Evaluation of chemical conversion properties The crystalline state of the phosphate film was evaluated using a scanning electron microscope according to the following criteria.
Ｏ結晶粒度が微細（１０μｍ以下）で、均一に号数して
いる。The O crystal grain size is fine (10 μm or less) and uniformly numbered.
Δ 結晶粒度が中程度（２０〜４０μｌ１ｌ）である。Δ Crystal grain size is medium (20-40 μl 1 l).
× 結晶粒度が粗大（５０μ瞳以上）でムラがある。× Crystal grain size is coarse (50μ pupil or more) and uneven.
クロメート系皮膜は塩水噴霧試験を７２時間行い、錆の
発生状態を次の基準で評価した。The chromate film was subjected to a salt spray test for 72 hours, and the state of rust generation was evaluated using the following criteria.
◎ 鯖発生なし
○ 錆発生面積率が全体の１〜１０％
Δ 錆発生面積率が全体の１１〜３０％× 錆発生面積
率が全体の３１％以上
（２）塗膜ｆｆｉ着性
鋼素地に達する１ｍｍ角ゴバン目状切り込みをナイフで
塗膜に１００個入れた後、その切り込部分をエリクセン
試験機で６１押し出し、押し出し部にセロテープを貼り
付けて剥離する方法で剥離せずに残った塗膜を次の基準
で評価した。◎ No mackerel formation ○ Rust occurrence area ratio is 1 to 10% of the whole Δ Rust occurrence area ratio is 11 to 30% of the whole × Rust occurrence area ratio is 31% or more of the whole (2) Paint film ffi adhesion to steel substrate After making 100 1mm square goblin-shaped incisions with a knife into the coating film, extrude the incisions using an Erichsen tester, and remove the remaining coating by pasting Sellotape on the extruded area and peeling it off. The membrane was evaluated according to the following criteria.
◎ 塗膜剥離なし
○ 残り数９９〜９０個
Δ 残り数８９〜７（）個
Ｘ 残り敗６９個以下
（３）耐食性
塗膜に鋼素地に達するクロスカットを入れて、ＪＩＳ
Ｚ ２３７１に準じて塩水噴霧試験を実施し、次の基準
で評価した。◎ No peeling of paint film ○ Number of remaining 99 to 90 pieces Δ Number of remaining 89 to 7 ( ) pieces
A salt spray test was carried out according to Z 2371 and evaluated according to the following criteria.
◎ 異常なし
○ 僅かに異常が見られる
Δ かなり異常が見られる
Ｘ 著しく異常が見られる
実施例２
ＰｔＳ２表に示すような組成のめつき浴で冷延鋼板を溶
融めっきして、めっき付着量を１１５１ｇシた後、下記
のような水溶液のいず゛れかを霧化して吹付け、溶融め
っき鋼板を製造した。◎ No abnormality ○ Slight abnormality Δ Significant abnormality X Significant abnormality Example 2 A cold-rolled steel sheet was hot-dipped in a plating bath with the composition shown in the PtS2 table, and the coating weight was measured. After weighing 1151 g, one of the following aqueous solutions was atomized and sprayed to produce a hot-dip galvanized steel sheet.
（Ａ ）Ｃｏ（ＮＯ＋）２６６Ｈ２０を１０９／ｅ溶解
したＣＯ水溶液
（Ｂ ）Ｎｉ（ＮＯｚ）２・６１１２０を１０９７ｅ溶
解したＮｉ水溶液
（Ｃ）Ｆｅ（Ｎ０．）ｉ ” ９１１２０を１０９１溶
解したＦｅ水溶液
その後実施例１と同様な塗装前処理、塗装を施して、化
成処理性、塗膜密着性および耐食性を調査した。(A) CO aqueous solution with 109/e of Co(NO+)266H20 dissolved (B) Ni aqueous solution with 1097e of Ni(NOz)2.61120 dissolved (C) Fe aqueous solution with 1091 of Fe(N0.)i'' 91120 dissolved The same pre-painting treatment and painting as in Example 1 were performed, and chemical conversion treatment properties, paint film adhesion, and corrosion resistance were investigated.
第２表に吹付けた水溶液の！！ＩＩＶＡと評価結果を示
す。なお各試験の評価基準は実施例１と同じである。Of the aqueous solution sprayed in Table 2! ! IIVA and evaluation results are shown. Note that the evaluation criteria for each test are the same as in Example 1.
（発明の効果）
以上のごと（本発明の溶融めっき銅板はコバルト、ニッ
ケル、鉄等の酸化物皮膜を形成したものであるが、これ
らの金属酸化物皮膜を形成すると、塗装前処理の際表面
調整を施さなくても化成処理性は良好である。従って前
処理設備に表面調整槽を設ける必要はなく、廃液処理も
不要となり、かつ表面３！１ｇ後の洗浄不良に起因する
腐食や塗膜性能低下の問題もなくなる。(Effects of the invention) As described above (the hot-dip plated copper plate of the present invention has an oxide film of cobalt, nickel, iron, etc. formed thereon, when these metal oxide films are formed, the surface is Chemical conversion treatment properties are good even without adjustment.Therefore, there is no need to install a surface conditioning tank in the pretreatment equipment, no waste liquid treatment is required, and there is no need for corrosion or coating due to poor cleaning after 3~1g of the surface. This also eliminates the problem of performance degradation.
また金属酸化物皮膜の形成はコバルト塩、ニッケル塩、
鉄塩の水溶液を霧化してそれらの塩の熱分解温度以上の
溶融めっき鋼板に吹付ける方法により行うのであるから
簡単であり、しかも水溶液の吹付けｖｃ置としては通常
連続溶融めっき設備に設けられているスパングルのミニ
マイズド化用の吹付は装置を利用できるので、特別に設
ける必要がない。In addition, the formation of metal oxide films is possible with cobalt salts, nickel salts,
This method is simple because it involves atomizing an aqueous solution of iron salts and spraying it onto the hot-dip galvanized steel sheet at a temperature above the thermal decomposition temperature of the salts.Moreover, the aqueous solution spraying VC device is usually installed in continuous hot-dip plating equipment. Since spraying equipment can be used to minimize spangles, there is no need for special equipment.
Claims (8)
っき鋼板表面にコバルト、ニッケル、鉄の１種または２
種以上の酸化物皮膜を形成したことを特徴とする塗装前
処理性に優れた溶融めっき鋼板。(1) One or two types of cobalt, nickel, or iron are applied to the surface of hot-dip galvanized steel sheets made of zinc or zinc-aluminum alloy.
A hot-dip galvanized steel sheet with excellent pre-painting properties, characterized by the formation of an oxide film of at least 50% of the oxide film.
溶融めっきを施した後、めっき付着量を調整し、その後
めっき層が１７０℃以上にあるうちに、またはめっき層
を１７０℃以上に加熱してめっき層表面にコバルト塩、
ニッケル塩、鉄塩の１種または２種以上を含む水溶液を
霧化して吹付けることにより塩を熱分解し、めっき層表
面にコバルト、ニッケル、鉄の１種または２種以上の酸
化物皮膜を形成することを特徴とする塗装前処理性に優
れた溶融めっき鋼板の製造方法。(2) After applying hot-dip plating with zinc or zinc-aluminum alloy to a steel sheet, adjust the coating weight, and then heat the plating layer to 170°C or higher while the plating layer is still at 170°C or higher. cobalt salt on the surface of the plating layer,
By atomizing and spraying an aqueous solution containing one or more of nickel salts and iron salts, the salt is thermally decomposed to form an oxide film of one or more of cobalt, nickel, and iron on the surface of the plating layer. A method for producing a hot-dip galvanized steel sheet with excellent pre-painting properties.
る特許請求の範囲第２項に記載の塗装前処理性に優れた
溶融めっき鋼板の製造方法。(3) The method for producing a hot-dip plated steel sheet with excellent pre-painting treatment properties according to claim 2, wherein the cobalt salt is cobalt nitrate.
る特許請求の範囲第２項に記載の塗装前処理性に優れた
溶融めっき鋼板の製造方法。(4) The method for producing a hot-dip plated steel sheet with excellent pre-painting properties according to claim 2, wherein the nickel salt is nickel nitrate.
範囲第２項に記載の塗装前処理性に優れた溶融めっき鋼
板の製造方法。(5) The method for producing a hot-dip plated steel sheet with excellent pre-painting properties according to claim 2, wherein the iron salt is iron nitrate.
とを特徴とする特許請求の範囲第２〜５項のいずれかに
記載の塗装前処理性に優れた溶融めっき鋼板の製造方法
。(6) The method for producing a hot-dip galvanized steel sheet with excellent pre-painting properties according to any one of claims 2 to 5, characterized in that an aqueous solution having a pH of 5 to 7 is sprayed.
ｇ０〜０．５％、Ｐｂ０．００２〜０．３０％、残部が
Ｚｎおよび不可避的不純物からなるめっき浴で溶融めっ
きを施すことを特徴とする特許請求の範囲第２項に記載
の塗装前処理性に優れた溶融めっき鋼板の製造方法。(7) As zinc-based plating, Al0.1-0.3%, M
Pre-painting treatment according to claim 2, characterized in that hot-dip plating is performed in a plating bath consisting of 0 to 0.5% g, 0.002 to 0.30% Pb, and the balance being Zn and unavoidable impurities. A method for producing hot-dipped steel sheets with excellent properties.
〜５３％、Ｍｇ０〜０．５％、Ｓｉ０〜１０％、Ｐｂ０
．００２〜０．３０％、残部がＺｎおよび不可避的不純
物からなるめっき浴で溶融めっきを施すことを特徴とす
る特許請求の範囲第２項に記載の塗装前処理性に優れた
溶融めっき鋼板の製造方法。(8) As zinc-aluminum alloy plating, Al4
~53%, Mg0~0.5%, Si0~10%, Pb0
．． 0.002 to 0.30%, the balance being Zn and unavoidable impurities. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP703087A JPS63176481A (en) | 1987-01-14 | 1987-01-14 | Hot dip coated steel sheet having excellent pretreatability before painting and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP703087A JPS63176481A (en) | 1987-01-14 | 1987-01-14 | Hot dip coated steel sheet having excellent pretreatability before painting and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63176481A true JPS63176481A (en) | 1988-07-20 |
Family
ID=11654640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP703087A Pending JPS63176481A (en) | 1987-01-14 | 1987-01-14 | Hot dip coated steel sheet having excellent pretreatability before painting and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63176481A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011099160A (en) * | 2009-11-04 | 2011-05-19 | Daicel Finechem Ltd | Surface-treated plated steel sheet and method for production thereof |
-
1987
- 1987-01-14 JP JP703087A patent/JPS63176481A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011099160A (en) * | 2009-11-04 | 2011-05-19 | Daicel Finechem Ltd | Surface-treated plated steel sheet and method for production thereof |
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