JPH01208494A - Formation of fluororesin coating film on surface of zinc, zinc alloy or galvanized material - Google Patents
Formation of fluororesin coating film on surface of zinc, zinc alloy or galvanized materialInfo
- Publication number
- JPH01208494A JPH01208494A JP3181188A JP3181188A JPH01208494A JP H01208494 A JPH01208494 A JP H01208494A JP 3181188 A JP3181188 A JP 3181188A JP 3181188 A JP3181188 A JP 3181188A JP H01208494 A JPH01208494 A JP H01208494A
- Authority
- JP
- Japan
- Prior art keywords
- fluororesin
- zinc
- film
- oxide film
- chromate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 33
- 239000011701 zinc Substances 0.000 title claims description 33
- 229910052725 zinc Inorganic materials 0.000 title claims description 33
- 229910001297 Zn alloy Inorganic materials 0.000 title claims description 17
- 239000000463 material Substances 0.000 title claims description 11
- 239000011248 coating agent Substances 0.000 title abstract description 21
- 238000000576 coating method Methods 0.000 title abstract description 21
- 230000015572 biosynthetic process Effects 0.000 title description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000010407 anodic oxide Substances 0.000 claims abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 7
- 239000010452 phosphate Substances 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000008151 electrolyte solution Substances 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 abstract description 17
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 10
- 229920002620 polyvinyl fluoride Polymers 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 abstract description 2
- 239000011247 coating layer Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- -1 phosphate anions Chemical class 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 238000007743 anodising Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 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 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- ABZUJFLWLLDHGX-UHFFFAOYSA-N disodium;oxido-(oxido(dioxo)chromio)oxy-dioxochromium;tetrahydrate Chemical compound O.O.O.O.[Na+].[Na+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O ABZUJFLWLLDHGX-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の目的〕
(産業上の利用分野)
本発明は亜鉛、亜鉛合金又は亜鉛めっき材の表面に高度
な耐食性と耐薬品性と耐熱性を付与するための、これら
基材に対する新規な弗素樹脂被膜の形成法に関する。[Detailed Description of the Invention] [Object of the Invention] (Industrial Application Field) The present invention provides a method for imparting high corrosion resistance, chemical resistance, and heat resistance to the surface of zinc, zinc alloy, or galvanized materials. This invention relates to a method for forming a novel fluororesin coating on a substrate.
(従来の技術) 従来、亜鉛、亜鉛合金又は亜鉛めっき材(以下。(Conventional technology) Conventionally, zinc, zinc alloy or galvanized material (hereinafter referred to as
亜鉛部材ということもある。)の表面に弗素樹脂被膜を
形成することは、亜鉛の溶融点が低いこと、かつ亜鉛と
弗素樹脂とが反応して密着性を阻害する化合物ができる
ため、被膜形成のための焼付温度が比較的高い弗素樹脂
の塗装は不適当とされていた。It is also called a zinc member. ) Forming a fluororesin film on the surface of the fluororesin requires a comparatively high baking temperature because the melting point of zinc is low and zinc and fluororesin react to form a compound that inhibits adhesion. Painting with high-quality fluororesin was considered inappropriate.
これに対して、特公昭51−43045号には亜鉛合金
にクロム酸処理を施し、次いでこのクロム酸塩被膜上に
特殊二重構造非粘着型の弗素樹脂塗料を塗布し、さらに
亜鉛合金の物理的性質をそこなわない140〜170℃
の比較的低温で焼付けることによリ、実用上十分な被膜
硬度と耐食性と耐薬品性とを有する弗素樹脂被膜の形成
方法が開示されている。On the other hand, in Japanese Patent Publication No. 51-43045, a zinc alloy was treated with chromic acid, a special double structure non-adhesive fluororesin paint was applied on the chromate film, and the zinc alloy was further treated with chromic acid. 140-170℃ without damaging the physical properties
A method for forming a fluororesin film having practically sufficient hardness, corrosion resistance, and chemical resistance by baking at a relatively low temperature is disclosed.
又、特公昭57−60434号には亜鉛めっき品への弗
素樹脂による保護層を被覆する方法として、亜鉛めっき
品をpH2以下で、かつ還元剤としてギ酸を含むクロム
酸溶液中で処理してクロメート層をつくり、このクロメ
ート化した物体を高弗点溶剤の中に分散したポリ弗化ビ
ニールによって被覆し、しかる後、 少なくとも100
℃の温度で熱処理し、亜鉛めっきした金属物体に弗素樹
脂の保護層を被覆する方法が開示されている。In addition, Japanese Patent Publication No. 57-60434 describes a method for coating zinc-plated products with a protective layer of fluororesin by treating the zinc-plated products with a chromate solution at pH 2 or less and containing formic acid as a reducing agent. The chromated body is coated with polyvinyl fluoride dispersed in a high fluoride point solvent and then coated with at least 100%
A method is disclosed for coating galvanized metal objects with a protective layer of fluororesin, heat treated at temperatures of .degree.
一方、弗素樹脂の被膜層によらず、陽極酸化被膜の形成
により亜鉛及び亜鉛合金の表面に耐食性、耐摩耗性の被
膜を形成することが、特公昭43−12250号に開示
されている。On the other hand, Japanese Patent Publication No. 12250/1983 discloses that a corrosion-resistant and wear-resistant film can be formed on the surface of zinc and zinc alloy by forming an anodic oxide film without using a fluororesin film layer.
これは、亜鉛及び亜鉛合金を陽極酸化するにあたり、リ
ン酸塩陰イオン、クロム酸塩陰イオンを主体とし、モリ
ブデン酸塩陰イオン、タングステン酸塩陰イオン、バナ
ジン酸塩陰イオンから選ばれる少なくとも1種の陰イオ
ン、さらにナトリウム及びカリウムから選ばれる少なく
とも1種の陽イオンとを含有する電解液を用いるもので
あり、その特徴は低電圧にて交流電解しようとするもの
である。When anodizing zinc and zinc alloys, this is mainly composed of phosphate anions, chromate anions, and at least one selected from molybdate anions, tungstate anions, and vanadate anions. An electrolytic solution containing various anions and at least one cation selected from sodium and potassium is used, and its feature is that alternating current electrolysis is carried out at low voltage.
(発明が解決しようとする問題点)
上述した従来の亜鉛、亜鉛合金又は亜鉛めっき材上に弗
素樹脂被膜を形成する方法において、前者の方法(特公
昭51−43045号)においては、デュポン社のテフ
ロンS系のような変成弗素樹脂塗料を使用しなければな
らず樹脂の選定がむずかしくかつ制限をうけること、又
この塗料は他の樹脂成分をも含んでいるので耐熱、耐食
性に劣るものである。又、後者の方法(特公昭57−6
0434号)においては、クロメート処理した後、この
クロメート被膜が完全に乾燥しない状態、即ちクロメー
ト被膜層の礼状の中空空間に水が残存する状態で弗素樹
脂の分散液中に浸漬することが条件である。(Problems to be Solved by the Invention) In the above-mentioned conventional method of forming a fluororesin film on zinc, zinc alloy, or galvanized material, the former method (Japanese Patent Publication No. 51-43045) was developed by DuPont Co., Ltd. Modified fluororesin paints such as Teflon S-based paints must be used, which makes resin selection difficult and restrictive, and since these paints also contain other resin components, they have poor heat resistance and corrosion resistance. . Also, the latter method (Special Public Interest Publication No. 57-6
No. 0434), the condition is that after the chromate treatment, the chromate film is immersed in the fluororesin dispersion in a state where the film is not completely dried, that is, water remains in the hollow space of the chromate film layer. be.
これは、残存する水が次工程での高弗点溶剤中のポリ弗
化ビニール樹脂分散液と置換するのを有利とするためで
ある。そのため作業上の制約があり。This is because it is advantageous for the remaining water to be replaced with the polyvinyl fluoride resin dispersion in the high-fluorescence point solvent in the next step. Therefore, there are constraints on the work.
電気めっきから塗装迄−貫した連続設備装置が必要であ
る。Continuous equipment that covers everything from electroplating to painting is required.
尚、上記の特公昭51−43045号及び特公昭57−
60434号の方法はいずれも、亜鉛部材上に設けられ
たクロメート被膜上への弗素樹脂の塗装であり。In addition, the above-mentioned Special Publication No. 51-43045 and Special Publication No. 57-
Both methods of No. 60434 involve coating a fluororesin on a chromate film provided on a zinc member.
クロメート被膜はゲル状となって亜鉛部材の表面に形成
されているため耐熱性に劣り、常温での耐食性において
は優れた効果を発揮するものの、弗素樹脂の本来の特性
である耐熱性を十分に発現させることができず、製品の
使用条件も自ら制限されている。Since the chromate film is formed in the form of a gel on the surface of the zinc component, it has poor heat resistance.Although it exhibits excellent corrosion resistance at room temperature, it does not fully maintain the heat resistance that is the original property of fluororesin. It cannot be expressed, and the conditions for using the product are also self-limited.
また、前記特公昭43−12250号のものは弗素樹脂
の使用を示唆するものではなく、単なる陽極酸化被膜の
形成のみでは弗素樹脂のもつ前記した諸特性を発現させ
ることができない。Further, the above-mentioned Japanese Patent Publication No. 43-12250 does not suggest the use of a fluororesin, and merely forming an anodic oxide film cannot bring out the above-mentioned properties of a fluororesin.
上記した事情に鑑み、本発明者らは鋭意検討した結果、
亜鉛部材の表面に特殊な条件で形成した陽極酸化被膜自
体が耐熱性があり、かつ弗素樹脂を強固に結合するため
弗素樹脂塗装の下地被膜として極めて優れていることを
見出し、本発明をなすに至ったものである。In view of the above circumstances, the inventors of the present invention have conducted extensive studies and found that
We have discovered that the anodic oxide film itself, which is formed under special conditions on the surface of zinc members, is heat resistant and strongly binds the fluororesin, making it extremely excellent as a base coat for fluororesin coating. This is what we have come to.
(問題点を解決するための手段)
本発明を概説すれば、本発明は、
亜鉛、亜鉛合金又は亜鉛めっき材の表面に弗素樹脂被膜
を形成するにあたり、
(1)まずpo、とじて0.1〜3モル/lのリン酸塩
。(Means for Solving the Problems) To summarize the present invention, in forming a fluororesin film on the surface of zinc, zinc alloy, or galvanized material, (1) first po, then 0. 1-3 mol/l phosphate.
CrO4として0.1〜3モル/l のクロ11酸塩を
含有し、水酸化ナトリウム又は水酸化カリウムのいずれ
か又は両者にてpH6〜11とした電解液を使用し、交
流による電気分解を行って前記亜鉛、亜鉛合金又は亜鉛
めっき材の表面に陽極酸化被膜を形成し、
(ii)次に、弗素樹脂の分散液中に浸漬して弗素樹脂
を塗布し、
(iii ) L、、かる後に少なくとも170℃の温
度で加熱処理すること、
からなる亜鉛、亜鉛合金又は亜鉛めっき材の表面に弗素
樹脂被膜を形成する方法に関するものである。Electrolysis was carried out by alternating current using an electrolytic solution containing 0.1 to 3 mol/l of chloro-11 acid salt as CrO4 and adjusted to pH 6 to 11 with either sodium hydroxide or potassium hydroxide, or both. to form an anodic oxide film on the surface of the zinc, zinc alloy or galvanized material, (ii) then apply a fluororesin by immersing it in a fluororesin dispersion, (iii) after that. The present invention relates to a method for forming a fluororesin coating on the surface of zinc, zinc alloy, or galvanized material, comprising: heat-treating at a temperature of at least 170°C.
以下、本発明の構成を詳しく説明する。Hereinafter, the configuration of the present invention will be explained in detail.
本発明の弗素樹脂被膜の形成方法が適用される亜鉛部材
としては、亜鉛又は亜鉛を主成分とする合金のダイカス
ト製品、鋳物、及び鉄鋼材の表面に亜鉛めっき層を被着
した亜鉛めっき製品等が含まれる。亜鉛めっき製品の場
合は陽極酸化処理により亜鉛層が処理液と反応するため
めっき膜厚は10μs程度以上あることが望ましい。め
っき被膜は電気めっきにより形成されたもの、或いは溶
融めっきにより形成されたものなどいずれのものであっ
ても良い。Examples of zinc members to which the method for forming a fluororesin film of the present invention is applied include die-cast products made of zinc or alloys whose main component is zinc, castings, and galvanized products in which a galvanized layer is applied to the surface of a steel material. is included. In the case of galvanized products, the zinc layer reacts with the treatment solution during the anodic oxidation treatment, so it is desirable that the plating film thickness be approximately 10 μs or more. The plating film may be formed by electroplating or hot-dip plating.
これら亜鉛部材の表面を陽極酸化するための処理液とし
ては、リン酸塩とクロム酸塩とを含む電解液が使用され
る。この場合P04として0.1〜3モル/l好ましく
は0.6〜1.0モル/lを、CrO4として0.1〜
3モル/l好ましくは0.4〜0.8モル/Ilを含む
ものが使用される。As a treatment solution for anodizing the surface of these zinc members, an electrolytic solution containing phosphate and chromate is used. In this case, P04 is 0.1 to 3 mol/l, preferably 0.6 to 1.0 mol/l, and CrO4 is 0.1 to 3 mol/l.
One containing 3 mol/l, preferably 0.4 to 0.8 mol/l is used.
また、本発明で使用する電解液は水酸化ナトリウム又は
水酸化カリウムのいずれか又は両者によりPHを6〜1
1に調節される。この場合、PHが更に高いか或いは低
くても亜鉛部材からの亜鉛の溶解量が多くなり被膜の形
成が遅くなるか或いは形成されなくなる。In addition, the electrolytic solution used in the present invention has a pH of 6 to 1 using either sodium hydroxide or potassium hydroxide, or both.
Adjusted to 1. In this case, even if the pH is higher or lower, the amount of zinc dissolved from the zinc member will increase, and the formation of the film will be delayed or will not be formed at all.
電解液には、 弗化物をF(フッ素)として0.3モル
/l以下を含有させることが好ましい。弗素の少量の含
有は被膜の形成を促進し、処理時間を短かくすることに
効果がある。It is preferable that the electrolytic solution contains 0.3 mol/l or less of fluoride as F (fluorine). Containing a small amount of fluorine is effective in promoting film formation and shortening processing time.
電解液の浴温度は30℃〜90℃の範囲、好ましくは5
0℃〜70℃の範囲内に維持するのがよい。The bath temperature of the electrolyte is in the range of 30°C to 90°C, preferably 5°C.
It is preferable to maintain the temperature within the range of 0°C to 70°C.
上記の電解液を使用し、処理すべき亜鉛部材を両方又は
一方の電極として交流電解を行う。電解時間の経過とと
もに亜鉛表面に抵抗性のある被膜が形成されて電流値が
下がる傾向があるが、電圧を上げて電流値が一定となる
ように所謂、定電流電解を行う。電流を一定に維持する
ための電圧が急速に増加すると電極表面に火花放電が発
生する。AC electrolysis is performed using the above electrolytic solution and using the zinc member to be treated as one or both electrodes. As the electrolysis time progresses, a resistive film is formed on the zinc surface and the current value tends to decrease, but so-called constant current electrolysis is performed so that the voltage is increased to keep the current value constant. When the voltage to maintain a constant current increases rapidly, a spark discharge occurs on the electrode surface.
本発明ではこの火花放電が始まる前に電解を止めること
が重要なことである。上記電解液を使用して電圧は20
V以下、望ましくは15〜L7Vに達した時に電解を止
めるのが、後の弗素樹脂分散液の塗装における下地被膜
とするために適当である。火花放電に到るまで電解を行
うと却って塗装の密着性が劣ることになる。In the present invention, it is important to stop electrolysis before this spark discharge begins. Using the above electrolyte, the voltage is 20
It is appropriate to stop the electrolysis when the voltage reaches V or less, preferably 15 to L7V, in order to form the base film in the subsequent coating of the fluororesin dispersion. If electrolysis is carried out to the point of spark discharge, the adhesion of the coating will actually deteriorate.
陽極酸化処理が終了した亜鉛部材を電解液から引き上げ
充分に水洗した後、乾燥する。After the anodizing process has been completed, the zinc member is pulled out of the electrolyte, thoroughly washed with water, and then dried.
このように陽極酸化処理して亜鉛部材の表面に生成させ
た被膜はZnCr0.、 ZnPO4,CrPO4,Z
nO。The coating formed on the surface of the zinc member by anodizing in this way is ZnCr0. , ZnPO4, CrPO4, Z
nO.
CrO3などの複合物からなるものと推定され、その表
面は褐色ないし黒色を呈し膜厚は2〜5μ程度で耐食性
、耐熱性に優れている。前記の陽極酸化被膜を″N1微
鏡で観察すると被膜には微細なりラックが生成されてお
り、これが次工程で塗装される弗素樹脂エマルジョンの
浸透性及び弗素樹脂の密着性に優れたアンカリング効果
を与えるものと推測される。It is estimated that it is made of a composite such as CrO3, and its surface is brown or black, the film thickness is about 2 to 5 microns, and it has excellent corrosion resistance and heat resistance. When the above-mentioned anodic oxide film is observed with an N1 microscope, fine racks are formed in the film, and these have an anchoring effect that improves the permeability of the fluororesin emulsion applied in the next process and the adhesion of the fluororesin. It is assumed that it gives
弗素樹脂の塗装はポリ弗化ビニール又はポリ弗化ビニリ
デンなどの弗素樹脂を適当な溶剤に溶解し20〜50%
の濃度とした分散液を用いて浸漬処理することにより行
われる。分散液から引き上げた後、必要に応じエアブロ
−により余分の樹脂を除去し、しかる後170℃〜28
0℃の温度で2〜5分間加熱処理し、後冷却して塗膜を
硬化させる。このようにして亜鉛部材の表面に密着性に
優れるとともに耐熱、耐食性に優れた弗素樹脂の塗膜が
形成される。For coating with fluororesin, dissolve fluororesin such as polyvinyl fluoride or polyvinylidene fluoride in an appropriate solvent and apply 20 to 50% of the fluororesin.
This is carried out by immersion treatment using a dispersion solution having a concentration of . After removing the resin from the dispersion, remove excess resin by air blowing if necessary, and then heat at 170°C to 28°C.
Heat treatment is performed at a temperature of 0° C. for 2 to 5 minutes, followed by cooling to harden the coating film. In this way, a fluororesin coating film with excellent adhesion, heat resistance, and corrosion resistance is formed on the surface of the zinc member.
以下、本発明を実施例に基づいて更に詳しく説明するが
、本発明の要旨を超えない限り本発明はこれら実施例の
ものに限定されない。Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples unless the gist of the present invention is exceeded.
実施例1
試料:亜鉛合金ダイカスト品(ZDC2)電解液:無水
クロム酸50g、燐酸2水素ナトリウAx 2水塩24
0gを1Ωの水に溶かし、水酸化ナトリウムを加えてp
H7とする。Example 1 Sample: Zinc alloy die-cast product (ZDC2) Electrolyte: 50 g of chromic anhydride, sodium dihydrogen phosphate Ax dihydrate 24
Dissolve 0g in 1Ω water, add sodium hydroxide and
Let's call it H7.
陽極酸化処理:浴温70℃、試料を一方の電極とし交流
電解により電流密度20A/dn+” に保って定電流
電解を行う。電圧6vより次第に増加し8分後に15V
に達したところで電解を止め試料を電解液より引上げて
水洗した後乾燥する。Anodic oxidation treatment: Constant current electrolysis is carried out at a bath temperature of 70°C, with the sample as one electrode and a current density of 20A/dn+" maintained by AC electrolysis.The voltage gradually increases from 6V to 15V after 8 minutes.
When the electrolytic solution reaches 1, the electrolysis is stopped and the sample is lifted out of the electrolyte, washed with water, and then dried.
亜鉛合金ダイカスト品の表面に薄チョコレート色の膜厚
2.0μの陽極酸化被膜が得られた。A light chocolate-colored anodic oxide film with a thickness of 2.0 μm was obtained on the surface of the zinc alloy die-cast product.
弗素樹脂塗装:ポリ弗化ビニリデンをレゾナール社製レ
イテントソルベントに30%の割合で溶解した分散液に
浸漬して塗布した後、温度250℃で5分間加熱処理し
、直ちに水中にて冷却し塗膜を硬化させた。Fluororesin coating: After applying polyvinylidene fluoride by dipping it in a dispersion of 30% dissolved in Resonal's Retentent Solvent, heat treatment at a temperature of 250°C for 5 minutes, immediately cool it in water, and apply it. The film was cured.
表面に膜厚13μのポリ弗化ビニリデンが被着した亜鉛
合金ダイカスト品が得られた。A zinc alloy die-cast product was obtained, the surface of which was coated with polyvinylidene fluoride having a thickness of 13 μm.
実施例2
試料:鋼管(外径10mm、肉厚0 、7 rm )亜
鉛めっき品。Example 2 Sample: Steel pipe (outer diameter 10 mm, wall thickness 0.7 rm) galvanized product.
電気めっきにより表面に膜厚25μの亜鉛めっき層を形
成した鋼管を用いた。A steel pipe on which a galvanized layer with a thickness of 25 μm was formed on the surface by electroplating was used.
電解液ニクロム酸ナトリウム4水塩100g、 98%
燐酸97g、弗化ナトリウム5gをIQの水に溶かし水
酸化カリウムを加えてρ旧0とする。Electrolyte Sodium dichromate tetrahydrate 100g, 98%
Dissolve 97 g of phosphoric acid and 5 g of sodium fluoride in IQ water and add potassium hydroxide to make ρ old 0.
陽極酸化処理:浴温60℃、両方の電極にそれぞれ試料
を配置し、交流電解により電流密度40A/dm”に保
って定電流電解を行う。Anodic oxidation treatment: A bath temperature is 60° C., a sample is placed on both electrodes, and constant current electrolysis is performed by maintaining the current density at 40 A/dm” by alternating current electrolysis.
電圧6vより次第に増加し5分後に17Vに達したとこ
ろで電解を止め、液より引上げ水洗した後乾燥する。The voltage gradually increases from 6 V, and when it reaches 17 V after 5 minutes, electrolysis is stopped, and the battery is pulled out of the solution, washed with water, and then dried.
亜鉛層の表面が濃黒褐色を呈し、膜厚2.5μの陽極酸
化被膜が形成された。The surface of the zinc layer exhibited a dark brown color, and an anodic oxide film with a thickness of 2.5 μm was formed.
弗素樹脂塗装:ポリ弗化ビニールをレゾナール社製レイ
テントソルベントに30%の割合で溶解した分散液に浸
漬して塗布した後、温度200℃の熱風により3分間加
熱処理後、水中にて冷却して塗fluを硬化させた。Fluororesin coating: After applying polyvinyl fluoride by dipping it in a dispersion of 30% dissolved in Resonal's Retentent Solvent, it was heated with hot air at a temperature of 200°C for 3 minutes, and then cooled in water. The coated flu was cured.
表面に膜厚13μのポリ弗化ビニールが被着した亜鉛め
っき鋼管が得られた。A galvanized steel pipe was obtained, the surface of which was coated with polyvinyl fluoride having a film thickness of 13 μm.
実施例3
試料:実施例2と同じ
電解液:実施例2と同じ
陽極酸化処理:浴温、電流条件は実施例2と同条件で電
解を行う。10分後に電圧70Vに達し火花放電が出現
した。この時電解を止めて液より取出し水洗後乾燥した
6
表面に灰緑色を呈した陽極酸化被膜が形成された。被膜
厚は5μであった。Example 3 Sample: Same electrolyte as Example 2: Same anodic oxidation treatment as Example 2: Electrolysis is performed under the same bath temperature and current conditions as Example 2. After 10 minutes, the voltage reached 70V and spark discharge appeared. At this time, the electrolysis was stopped, the sample was taken out from the solution, washed with water, and dried.A gray-green anodic oxide film was formed on the surface of the sample. The coating thickness was 5μ.
弗素樹脂塗装:実施例2と同様に処理し、陽極酸化被膜
の上層にポリ弗化ビニールを塗着させた。Fluororesin coating: Processed in the same manner as in Example 2, and polyvinyl fluoride was coated on the upper layer of the anodic oxide film.
比較例1 試料:実施例2と同じ クロメート処理:重クロム酸ナトリウム20g。Comparative example 1 Sample: Same as Example 2 Chromate treatment: 20 g of sodium dichromate.
無水クロム1.5g/l、 硫酸ナトリウム5 g
+酢酸5−をIQに溶解したクロメート液に浸漬処理し
、水洗乾燥して表面に黄色のクロメート被膜を形成させ
た。Anhydrous chromium 1.5 g/l, sodium sulfate 5 g
The sample was immersed in a chromate solution containing +acetic acid 5- dissolved in IQ, washed with water and dried to form a yellow chromate film on the surface.
弗素樹脂塗装:実施例2と同様に処理し、クロメート被
膜上にポリ弗化ビニールを塗着させた。Fluororesin coating: Processed in the same manner as in Example 2, and polyvinyl fluoride was coated on the chromate film.
実施例1〜3.比較例1で得られた各試料について亜鉛
部材上の弗素樹脂塗装の耐熱性と密着性の評価試験を行
った。試験方法ならびに試験結果は次の通りである。Examples 1-3. For each sample obtained in Comparative Example 1, an evaluation test was conducted to evaluate the heat resistance and adhesion of the fluororesin coating on the zinc member. The test method and test results are as follows.
〈試験方法〉
試料を100℃の高温槽の中に1時間保持した後、室温
にて1時間放冷することを1サイクルとし、これを5サ
イクル繰り返し行い、この試料について更に2mm角で
のとばん目セロテープ試験を行う。<Test method> One cycle is to hold the sample in a high temperature bath at 100°C for 1 hour and then let it cool for 1 hour at room temperature.This is repeated for 5 cycles, and the sample is further tested in a 2 mm square. Perform the cellophane tape test.
く試験結果〉 試験結果を、第1表にあわせて示す。Test results> The test results are also shown in Table 1.
(第1表)
〔発明の効果〕
本発明の弗素樹脂波H々を形成する方法によれば、各種
亜鉛部材の表面に極めて密着性に優れた弗景樹脂の塗膜
を形成することができ、高度な耐熱、耐食性の被覆層を
有した製品が得られる。(Table 1) [Effects of the Invention] According to the method of forming fluororesin waves H of the present invention, a fluororesin coating film with extremely excellent adhesion can be formed on the surface of various zinc members. , a product with a highly heat-resistant and corrosion-resistant coating layer can be obtained.
特許出願人 臼井国際産業株式会社代理人 弁理
士 水 野 喜 夫Patent applicant: Usui Kokusai Sangyo Co., Ltd. Agent: Yoshio Mizuno, patent attorney
Claims (1)
を形成するにあたり、 (i)まずPO_4として0.1〜3モル/lのリン酸
塩、CrO_4として0.1〜3モル/lのクロム酸塩
を含有し、水酸化ナトリウム又は水酸化カ リウムのいずれか又は両者にてpH6〜11とした電解
液を使用し、交流による電気分解 を行って前記亜鉛、亜鉛合金又は亜鉛めっ き材の表面に陽極酸化被膜を形成し、 (ii)次に、弗素樹脂の分散液中に浸漬して弗素樹脂
を塗布し、 (iii)しかる後に少なくとも170℃の温度で加熱
処理すること、 からなる亜鉛、亜鉛合金又は亜鉛めっき材の表面に弗素
樹脂被膜を形成する方法。[Claims] When forming a fluororesin film on the surface of zinc, zinc alloy, or galvanized material, (i) 0.1 to 3 mol/l phosphate as PO_4 and 0.1 to 3 mol/l as CrO_4; Using an electrolytic solution containing 3 mol/l of chromate and having a pH of 6 to 11 with either sodium hydroxide or potassium hydroxide, or both, the zinc, zinc alloy or Forming an anodic oxide film on the surface of the galvanized material, (ii) Next, applying a fluororesin by immersing it in a fluororesin dispersion, (iii) Then heat-treating at a temperature of at least 170°C. A method of forming a fluororesin film on the surface of zinc, zinc alloy, or galvanized material consisting of:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63031811A JP2930590B2 (en) | 1988-02-16 | 1988-02-16 | Method for forming a fluororesin coating on the surface of zinc, zinc alloy or galvanized material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63031811A JP2930590B2 (en) | 1988-02-16 | 1988-02-16 | Method for forming a fluororesin coating on the surface of zinc, zinc alloy or galvanized material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01208494A true JPH01208494A (en) | 1989-08-22 |
JP2930590B2 JP2930590B2 (en) | 1999-08-03 |
Family
ID=12341477
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63031811A Expired - Fee Related JP2930590B2 (en) | 1988-02-16 | 1988-02-16 | Method for forming a fluororesin coating on the surface of zinc, zinc alloy or galvanized material |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0523643A (en) * | 1991-07-19 | 1993-02-02 | Bridgestone Corp | Method for forming fluorinated resin film and article providing fluorinated resin film by the same method |
EP0749188A2 (en) * | 1995-06-13 | 1996-12-18 | Nissin Electric Company, Limited | Rotary section current transmitting mechanism |
NL1030260C2 (en) * | 2005-10-25 | 2007-04-26 | Roem Royalty B V | Sheet for use as protective cover in e.g. construction environment, has conductive layer applied to sides of substrate, and metal layer applied on surface of conductive layer, where thickness of metal layer is between specific micrometers |
CN112522764A (en) * | 2020-12-02 | 2021-03-19 | 昆明理工大学 | Preparation method of black anodic oxide film of zinc-copper-titanium alloy plate |
JP2021529883A (en) * | 2018-07-06 | 2021-11-04 | ポスコPosco | Manufacturing method of surface-treated zinc-nickel alloy electroplated steel sheet with excellent corrosion resistance and paintability |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61288099A (en) * | 1985-06-17 | 1986-12-18 | Nippon Steel Corp | Galvanized steel sheet and its surface treatment |
-
1988
- 1988-02-16 JP JP63031811A patent/JP2930590B2/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61288099A (en) * | 1985-06-17 | 1986-12-18 | Nippon Steel Corp | Galvanized steel sheet and its surface treatment |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0523643A (en) * | 1991-07-19 | 1993-02-02 | Bridgestone Corp | Method for forming fluorinated resin film and article providing fluorinated resin film by the same method |
EP0749188A2 (en) * | 1995-06-13 | 1996-12-18 | Nissin Electric Company, Limited | Rotary section current transmitting mechanism |
EP0749188A3 (en) * | 1995-06-13 | 1997-03-05 | Nissin Electric Co Ltd | Rotary section current transmitting mechanism |
US5827080A (en) * | 1995-06-13 | 1998-10-27 | Nissin Electric Co., Ltd. | Rotary section current transmitting mechanism |
NL1030260C2 (en) * | 2005-10-25 | 2007-04-26 | Roem Royalty B V | Sheet for use as protective cover in e.g. construction environment, has conductive layer applied to sides of substrate, and metal layer applied on surface of conductive layer, where thickness of metal layer is between specific micrometers |
JP2021529883A (en) * | 2018-07-06 | 2021-11-04 | ポスコPosco | Manufacturing method of surface-treated zinc-nickel alloy electroplated steel sheet with excellent corrosion resistance and paintability |
CN112522764A (en) * | 2020-12-02 | 2021-03-19 | 昆明理工大学 | Preparation method of black anodic oxide film of zinc-copper-titanium alloy plate |
CN112522764B (en) * | 2020-12-02 | 2024-03-26 | 昆明理工大学 | Preparation method of black anodic oxide film of zinc-copper-titanium alloy plate |
Also Published As
Publication number | Publication date |
---|---|
JP2930590B2 (en) | 1999-08-03 |
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