JPH08252886A - Method for producing fluororesin coating - Google Patents
Method for producing fluororesin coatingInfo
- Publication number
- JPH08252886A JPH08252886A JP7354017A JP35401795A JPH08252886A JP H08252886 A JPH08252886 A JP H08252886A JP 7354017 A JP7354017 A JP 7354017A JP 35401795 A JP35401795 A JP 35401795A JP H08252886 A JPH08252886 A JP H08252886A
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- fluororesin coating
- etching
- coating
- aqueous solution
- 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
- 238000000576 coating method Methods 0.000 title claims abstract description 18
- 239000011248 coating agent Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 30
- 239000010935 stainless steel Substances 0.000 claims abstract description 30
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000011780 sodium chloride Substances 0.000 claims abstract description 7
- 239000011247 coating layer Substances 0.000 claims abstract description 5
- 238000005530 etching Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 230000003373 anti-fouling effect Effects 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000002161 passivation Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 238000005422 blasting Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000000945 filler 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
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GVEHJMMRQRRJPM-UHFFFAOYSA-N chromium(2+);methanidylidynechromium Chemical compound [Cr+2].[Cr]#[C-].[Cr]#[C-] GVEHJMMRQRRJPM-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000866 electrolytic etching Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Abstract
(57)【要約】
【目的】 ステンレスに撥水性，非粘着性，防汚性を付
与し，しかも強固な密着性と耐熱性を有する弗素樹脂被
覆物を得る。
【構成】 硫酸と塩化ナトリウムの混合水溶液を用い，
１５℃以下の温度でステンレスを電解エッチングし，こ
の上に弗素樹脂の被覆層を設ける。(57) [Summary] [Purpose] To obtain a fluororesin coating that imparts water repellency, non-adhesiveness, and antifouling property to stainless steel, and has strong adhesion and heat resistance. [Composition] Using a mixed aqueous solution of sulfuric acid and sodium chloride,
Stainless steel is electrolytically etched at a temperature of 15 ° C. or lower, and a fluororesin coating layer is provided on this.
Description
【０００１】[0001]
【産業上の利用分野】本願発明は，ステンレスに被覆材
料の弗素樹脂の特性を付与し，しかも強固な密着性を有
する被覆物の製造方法，特に，ステンレスに撥水性，非
粘着性，防汚性を付与し，しかも強固な密着性と耐熱性
を有する弗素樹脂被覆物の製造方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a coated material which imparts the characteristics of a fluorine resin as a coating material to stainless steel and has strong adhesion, and more particularly to water repellency, non-adhesiveness and antifouling property of stainless steel. The present invention relates to a method for producing a fluororesin-coated article which imparts properties and has strong adhesion and heat resistance.
【０００２】[0002]
【従来の技術】従来，ステンレスに撥水性，非粘着性，
防汚性を付与した物としては，ステンレス上にポリアミ
ドイミド等のバインダーを弗素樹脂に対して２０％以上
含有する弗素樹脂を被覆したものが一般的である。2. Description of the Related Art Conventionally, water-repellent, non-adhesive,
As an antifouling material, a stainless steel coated with a fluorine resin containing at least 20% of a binder such as polyamideimide with respect to the fluorine resin is generally used.
【０００３】しかしこの場合，弗素樹脂成分が少ないた
め非粘着性が不充分であったり，平板状のステンレスに
被覆を施した後，プレスや曲げ等の加工をしょうとする
と接着力が不充分である，又は被覆が加工時の伸びに追
従できず，裂けたり，ピンホールが発生する。However, in this case, the non-adhesiveness is insufficient due to the small amount of the fluororesin component, or the adhesive force is insufficient when the plate-like stainless steel is coated and then pressed or bent. Yes, or the coating is unable to follow the elongation during processing, causing cracks or pinholes.
【０００４】[0004]
【発明が解決しようとする課題】本願発明は，ステンレ
スに撥水性，非粘着性，防汚性を付与し，しかも強固な
密着性と耐熱性を有する弗素樹脂被覆物の製造方法を提
供しようとするものであり，従来製品に比べてより強固
な密着力により耐久性を向上させると共に，特に通常コ
ーティング後の後加工が困難な弗素樹脂被覆物において
後加工性の付与という課題を解決しようとするものであ
る。DISCLOSURE OF THE INVENTION The present invention is intended to provide a method for producing a fluororesin coating which imparts water repellency, non-adhesiveness, antifouling property to stainless steel, and has strong adhesion and heat resistance. In addition to improving the durability due to stronger adhesion than conventional products, it aims to solve the problem of imparting post-processability especially to fluororesin coatings where post-processing after normal coating is difficult. It is a thing.
【０００５】[0005]
【課題を解決するための手段】本願発明は，弗素樹脂被
覆物の製造方法であり，硫酸と塩化ナトリウムの混合水
溶液を用い，１５℃以下の温度でステンレスを電解エッ
チングし，この上に弗素樹脂の被覆層を設けることを特
徴とするものである。The present invention is a method for producing a fluororesin coating, in which stainless steel is electrolytically etched at a temperature of 15 ° C. or lower using a mixed aqueous solution of sulfuric acid and sodium chloride, and a fluororesin is further formed thereon. The coating layer is provided.
【０００６】なお，上記本願発明の実施に際して少なく
とも下記が含まれる。本願の発明の弗素樹脂被覆物の製
造に於いて，前記のステンレスに平板状のステンレスを
用い，前記の，電解エッチングし，この上に弗素樹脂の
被覆層を設けて後更に，プレス加工，曲げ加工等により
所望の形状に加工することを特徴とする弗素樹脂被覆物
の製造方法。The following are included at the time of carrying out the present invention. In the production of the fluororesin coating of the invention of the present application, flat stainless steel is used as the above-mentioned stainless steel, the above-mentioned electrolytic etching is performed, and a fluororesin coating layer is provided on the stainless steel, and then press working and bending are performed. A method for producing a fluororesin-coated article, which comprises processing the article into a desired shape by processing.
【０００７】[0007]
【作用】本願発明で用いるステンレスとしては，フェラ
イト系，オーステナイト系，マルテンサイト系のいずれ
もが用いられ，特に限定されない。又形状は平板状の
外，箔状，棒状，線状等にも適用でき，特に限定されな
い。As the stainless steel used in the present invention, any of ferrite type, austenite type and martensite type is used, and is not particularly limited. In addition, the shape can be applied to a shape other than a flat plate, a foil, a bar, a line, and the like, and is not particularly limited.
【０００８】本願発明で被覆層として用いる弗素樹脂と
しては，ＰＴＦＥ（ポリテトラフルオロエチレン），Ｐ
ＦＡ（テトラフルオロエチレン〜パーフルオロアルキル
ビニルエーテル共重合体），ＦＥＰ（テトラフルオロエ
チレン〜ヘキサフルオロプロピレン共重合体），ＥＴＦ
Ｅ（テトラフルオロエチレン〜エチレン共重合体），Ｃ
ＴＦＥ（ポリクロロトリフルオロエチレン），ＰＶｄＦ
（ポリ弗化ビニリデン）及びこれらの共重合体を用い
る。The fluorine resin used as the coating layer in the present invention is PTFE (polytetrafluoroethylene), P
FA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene-hexafluoropropylene copolymer), ETF
E (tetrafluoroethylene-ethylene copolymer), C
TFE (polychlorotrifluoroethylene), PVdF
(Polyvinylidene fluoride) and copolymers thereof are used.
【０００９】本願発明で弗素樹脂中に，樹脂被覆表面の
非粘着性が低下し，また平板からプレス加工する時に伸
びに追従できず被覆が裂けたりピンホールが発生するこ
とのない添加量で，混合して用いられる充填剤として
は，色彩や光沢等の外観を向上させるためマイカ，カー
ボン，酸化チタン，酸化鉄，グラファイト等の一般の無
機顔料が用いられ，またステンレスとの密着性を向上さ
せるため，ポリアミドイミド，ポリエーテルスルホン，
ポリフェニレンサルファイド，ポリイミド等の耐熱プラ
スチックが用いられる。これらの充填剤は混合して用い
ても良い。In the present invention, the amount of addition to the fluororesin is such that the non-adhesiveness of the surface of the resin coating is reduced, and when press working from a flat plate, the extension cannot be followed and the coating is torn or pinholes do not occur. As the filler to be mixed and used, general inorganic pigments such as mica, carbon, titanium oxide, iron oxide, and graphite are used to improve appearance such as color and luster, and also improve adhesion to stainless steel. For polyamide imide, polyether sulfone,
Heat-resistant plastics such as polyphenylene sulfide and polyimide are used. These fillers may be used as a mixture.
【００１０】エッチングに使用する液としては，塩化第
二鉄水溶液，塩酸，硫酸，塩化ナトリウム水溶液，弗化
水素水，塩化第二銅水溶液があるが，本願発明では特
に，硫酸と塩化ナトリウムの混合水溶液を用いる。As the liquid used for etching, there are ferric chloride aqueous solution, hydrochloric acid, sulfuric acid, sodium chloride aqueous solution, hydrogen fluoride water and cupric chloride aqueous solution. In the present invention, especially, sulfuric acid and sodium chloride are mixed. Use an aqueous solution.
【００１１】中でも，水に硫酸２％と塩化ナトリウム３
％を混合したエッチング液は，極めて微細な凹凸をステ
ンレス表面に形成する。また上記の混合液に硝酸，グリ
セリン，過酸化水素水，クロム酸，エチルアルコール，
酢酸，カセイカリ，ピクリン酸，アンモニア，硫酸銅，
硫酸鉄，赤血塩，シュウ酸を単独もしくは混合して添加
することによりpH を安定化させるもしくはより微細で
均一な凹凸をステンレス表面に形成することができる。Among them, 2% sulfuric acid and 3 sodium chloride in water
%, The etching solution forms extremely fine irregularities on the stainless steel surface. In addition, nitric acid, glycerin, hydrogen peroxide solution, chromic acid, ethyl alcohol,
Acetic acid, potassium hydroxide, picric acid, ammonia, copper sulfate,
By adding iron sulfate, red blood salt, and oxalic acid individually or as a mixture, the pH can be stabilized or finer and more uniform irregularities can be formed on the stainless steel surface.
【００１２】エッチングは，ステンレスを液中に入れ，
これを陽極として，これと対面して液中に設置する陰極
との間に電圧をかけて行う。充分にステンレス表面に凹
凸を設けるには，２０C / cm2 以上の電気量がステンレ
ス表面において移動するよう電圧とエッチング時間を設
定することが望ましい。Etching is carried out by putting stainless steel in a liquid,
This is performed by applying a voltage between the anode and the cathode, which is placed in the liquid facing the anode. In order to sufficiently provide unevenness on the stainless steel surface, it is desirable to set the voltage and etching time so that an electric quantity of 20 C / cm 2 or more moves on the stainless steel surface.
【００１３】また，エッチングを行う際，液の温度を１
５℃以下にすることにより，エッチングで形成される凹
凸がさらに微細かつ均一なものとなる。When etching is performed, the temperature of the liquid is set to 1
By setting the temperature to 5 ° C. or less, the unevenness formed by etching becomes finer and more uniform.
【００１４】本願発明でステンレスをエッチングする時
には，まず基材をメチルエチルケトン，アセトン等の有
機溶媒又は１０％水酸化ナトリウム水溶液等のアルカリ
水溶液で洗浄し，表面に付着したごみや油分を充分に取
り除いておき，均一にエッチングされる様にする。When etching stainless steel according to the present invention, first, the base material is washed with an organic solvent such as methyl ethyl ketone or acetone or an alkaline aqueous solution such as a 10% sodium hydroxide aqueous solution to sufficiently remove dust and oil adhering to the surface. So that it is etched uniformly.
【００１５】また，より微細で均一な凹凸をステンレス
表面に形成する方法として，エッチング前にステンレス
の鋭敏化熱処理を行うか，又はスコッチブライト等の研
磨剤でブラッシングする、もしくはブラストを行うこと
によりステンレス表面に存在する不動態層を実質的に取
り去る方法がある。これらは単独で行っても良いし，併
用しても良い。As a method of forming finer and more uniform unevenness on the stainless steel surface, the stainless steel is sensitized by heat treatment before etching, brushed with an abrasive such as Scotchbright, or blasted. There is a method of substantially removing the passivation layer existing on the surface. These may be performed alone or in combination.
【００１６】このうち鋭敏化熱処理は，オーステナイト
系の場合400 ℃〜850 ℃で１Ｈ程度の熱処理，フェライ
ト系の場合850 ℃以上の温度から冷却を行うことで，こ
れによりステンレスの結晶粒界にクロム炭化物が析出す
る。このため粒界近傍でクロムが欠乏して耐食性が低下
し，硝酸等で洗浄することにより粒界が脱落して表面に
凹凸が形成される。さらに上記に示した液ならびに方法
でエッチングを行うことにより粒界に沿って腐食され複
雑かつ微細な凹凸が形成される。しかしこのままでは凹
部では粒界に沿ってクラックが入りやすくステンレスが
応力腐食割れを起こしやすくなる。そこでステンレスを
1000 ℃〜1100 ℃で数十分間熱処理（これを溶体化処理
という）し，粒界に析出したクロム炭化物を再固溶させ
て，材質をもとのステンレスに戻す。これにより粒界腐
食により得られた凹凸とエッチングにより得られる凹凸
が合わさってより複雑かつ微細な凹凸が形成され，後に
弗素樹脂層を設けた場合に充分な投錨効果がえられる。Among them, the sensitization heat treatment is a heat treatment at 400 ° C. to 850 ° C. for about 1 H in the case of austenite, and a cooling from a temperature of 850 ° C. or higher in the case of ferrite, so that the crystal grain boundaries of stainless are chromium. Carbide precipitates. Therefore, chromium is deficient in the vicinity of the grain boundaries and the corrosion resistance is reduced, and washing with nitric acid or the like causes the grain boundaries to fall off, forming irregularities on the surface. Further, by performing etching with the above-described liquid and method, complicated and fine irregularities are formed by being corroded along grain boundaries. However, in this state, cracks easily occur along the grain boundaries in the concave portions, so that stainless steel easily causes stress corrosion cracking. So stainless steel
Heat treatment is performed at 1000 ℃ ~ 1100 ℃ for several tens of minutes (this is called solution heat treatment), the chromium carbide precipitated at the grain boundaries is re-dissolved, and the material is returned to the original stainless steel. As a result, the irregularities obtained by grain boundary corrosion and the irregularities obtained by etching are combined to form more complicated and fine irregularities, and a sufficient anchoring effect can be obtained when a fluorine resin layer is provided later.
【００１７】本願発明でステンレス表面を削り取るため
に使用するバフとしては，特に限定されないが住友３Ｍ
社製のスコッチブライトの様に，繊維が硬く，研磨剤を
ふくむものが望ましい。またブラストの場合も特にブラ
スト剤は限定されないが，例えば＃100 程度のガラスビ
ーズを１kg ／cm2 の圧力程度で基材に吹き付けること
により表面の不動態層が部分的に除去されるとともに表
面が粗面化される。The buff used to scrape off the stainless steel surface in the present invention is not particularly limited, but Sumitomo 3M
It is desirable that the fiber is hard and contains an abrasive, such as Scotch Bright manufactured by the company. Also in the case of blasting, the blasting agent is not particularly limited, but for example, by spraying glass beads of about # 100 onto the substrate at a pressure of about 1 kg / cm 2 , the passivation layer on the surface is partially removed and the surface is removed. To be roughened.
【００１８】本願発明でエッチング前の浸漬に用いる酸
性水溶液としては，塩酸，硫酸，りん酸，弗化水素水，
クロム酸，又はこれらの混合物を用いると均一かつすば
やく表面層を溶解させることができるが，これらに限定
はされない。また塩化第二鉄水溶液を用いる場合は４２
ボーメ濃度の液を用いるのがよい。As the acidic aqueous solution used for the immersion before etching in the present invention, hydrochloric acid, sulfuric acid, phosphoric acid, hydrogen fluoride water,
The use of chromic acid or a mixture thereof can dissolve the surface layer uniformly and quickly, but is not limited thereto. When using a ferric chloride aqueous solution, 42
It is better to use a solution with a Baume concentration.
【００１９】このようにして表面の光沢がなくなるまで
ステンレス表面を溶解させることによりステンレス表面
に存在する不動態層を完全に除去し，後にエッチングを
行った際に均一でむらのないエッチング面が得られ弗素
樹脂をコーティングしても，局部的に接着力が弱くなっ
たりすることがない。また，この不動態層の除去は前述
のバフによる研磨又はブラストの後に行うことにより速
度が早くなる。By thus dissolving the stainless steel surface until the surface becomes glossless, the passivation layer existing on the stainless steel surface is completely removed, and a uniform and even etching surface is obtained when etching is performed later. Even if it is coated with a fluororesin, the adhesive strength does not weaken locally. The speed of the removal of the passivation layer is increased by performing the removal or polishing after the buffing or blasting.
【００２０】[0020]
【実施例】以下に本願発明の実施例を述べる。 （実施例）素材として表１に示す種類の板厚0 .4 m m
のステンレス平板を用いた。これに表１に示した前処理
を行った後，表１に示したエッチング液でエッチングし
た。そして１０％硝酸に浸漬して表面に不動態層を形
成，乾燥させた。こうして得られたエッチング板に表２
に示す配合の樹脂をコーティング手段を変えてコートし
乾燥・焼成した。Embodiments of the present invention will be described below. (Example) Thickness of the type shown in Table 1 as material 0.4 mm
The stainless steel flat plate of was used. After performing the pretreatment shown in Table 1 on this, it etched with the etching liquid shown in Table 1. Then, it was immersed in 10% nitric acid to form a passivation layer on the surface and dried. The etching plate thus obtained is shown in Table 2.
The resin having the composition shown in (1) was coated by changing the coating means and dried and baked.
【００２１】このようにして得られたコーティング板を
プレス成形によって釜形状に加工し，以下の項目を評価
した。結果を表２に示す。The coated plate thus obtained was processed into a pot shape by press molding, and the following items were evaluated. Table 2 shows the results.
【００２２】（剥離強度）市販のＦＥＰシートを塗膜面
に熱融着したのち１c m の巾で１８０°方向に剥離し，
その時の引き剥がし力を剥離強度（単位：K g / c m ）
とする。(Peeling Strength) A commercially available FEP sheet was heat-sealed on the surface of the coating film, and then peeled in a direction of 180 ° with a width of 1 cm.
The peeling force at that time is the peeling strength (unit: K g / cm).
And
【００２３】（碁盤目試験）コーティング面にJIS K 54
00-1990 ,8 .5 .2 に規定された碁盤目１００ますを作
成し，この面にセロテープ（ニチバン（株））を充分に
密着させ，ただちに引き剥がす。新しいセロテープでこ
の引き剥がしを４０回行い１００ます中何ますが残存し
ているかを評価する。(Cross-cut test) JIS K 54 on the coated surface
Make a square grid 100 stipulated in 00-1990, 8.5.2, make a cellotape (Nichiban Co., Ltd.) sufficiently adhere to this surface, and immediately peel it off. This peeling is performed 40 times with a new cellophane tape, and 100 of the 100 pieces are evaluated to evaluate how much remains.
【００２４】（対水接触角）協和界面科学（株）製接触
角計を用い，液滴法によって純水に対する対水接触角を
求める。(Contact angle to water) Using a contact angle meter manufactured by Kyowa Interface Science Co., Ltd., the contact angle to water with respect to pure water is determined by the droplet method.
【００２５】（ピンホール度）釜に2 .5 ％塩化ナトリ
ウム水溶液を入れ，釜をマイナス，液中に電極を入れ，
これをプラスとし10 V で５秒間通電した時ピンホール
部分により流れる電流(m A )を単位面積当たりに換算し
て求める。［m A / c m 2 ］(Pinhole degree) Put 2.5% sodium chloride aqueous solution into the pot, put the pot into the minus, put the electrode in the liquid,
Taking this as a positive value, calculate the current (mA) flowing through the pinhole when it is energized for 5 seconds at 10 V per unit area. [M A / cm 2 ]
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【表２】 [Table 2]
【００２８】表２に示されるように本願発明によるもの
は，剥離強度，碁盤目試験，対水接触角，ピンホール度
いずれも優れている。As shown in Table 2, the one according to the present invention is excellent in all of the peel strength, the grid test, the contact angle with water, and the pinhole degree.
【００２９】[0029]
【発明の効果】以上の様に，本願発明によると，ステン
レスに弗素樹脂被覆材料の優れた特性である撥水性，非
粘着性，防汚性を付与し，しかも強固な密着性と耐熱性
を有する弗素樹脂被覆物が得られる，特に，従来製品に
比べてより強固な密着力により耐久性を向上させると共
に通常コーティング後の後加工が困難な弗素樹脂被覆物
において後加工性を付与する。As described above, according to the present invention, it is possible to impart the water-repellent property, the non-adhesive property, and the antifouling property, which are the excellent characteristics of the fluororesin coating material, to the stainless steel, and to provide the strong adhesion and the heat resistance. A fluororesin coating having the above can be obtained. Particularly, the adhesion is stronger than that of the conventional product to improve the durability and the post-processing is imparted to the fluororesin coating which is usually difficult to be post-processed after coating.
Claims (1)
い，１５℃以下の温度でステンレスを電解エッチング
し，この上に弗素樹脂の被覆層を設けることを特徴とす
る弗素樹脂被覆物の製造方法。1. A method for producing a fluororesin coating, which comprises electrolytically etching stainless steel at a temperature of 15 ° C. or lower using a mixed aqueous solution of sulfuric acid and sodium chloride, and forming a fluororesin coating layer thereon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35401795A JP2681025B2 (en) | 1991-11-15 | 1995-12-31 | Method for producing fluororesin coating |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3-354107 | 1991-11-15 | ||
| JP35410791 | 1991-11-15 | ||
| JP35401795A JP2681025B2 (en) | 1991-11-15 | 1995-12-31 | Method for producing fluororesin coating |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4339430A Division JP2585936B2 (en) | 1991-11-15 | 1992-11-06 | Method for producing fluororesin coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08252886A true JPH08252886A (en) | 1996-10-01 |
| JP2681025B2 JP2681025B2 (en) | 1997-11-19 |
Family
ID=26579966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35401795A Expired - Fee Related JP2681025B2 (en) | 1991-11-15 | 1995-12-31 | Method for producing fluororesin coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2681025B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005241635A (en) * | 2004-01-30 | 2005-09-08 | Jfe Steel Kk | Corrosion solution for appearance of prior austenite grain boundaries in steel materials and method of appearance of prior austenite grain boundaries in steel materials |
| JP2005350734A (en) * | 2004-06-10 | 2005-12-22 | Nippon Steel & Sumikin Stainless Steel Corp | Method for producing ferritic stainless steel strip with good paint adhesion |
| WO2006030999A1 (en) * | 2004-09-16 | 2006-03-23 | Bukwang Technology Co., Ltd. | Electroless plating method and plating film obtained by the electroless plating method |
| KR101465561B1 (en) * | 2013-08-27 | 2014-11-27 | 인하대학교 산학협력단 | Processing method for superhydrophobic stainless steel substrate surface and stainless steel substrate having the superhydrophobic surface prepared with the same |
| WO2019231125A1 (en) | 2018-05-28 | 2019-12-05 | Samsung Electronics Co., Ltd. | Composite of stainless steel and resin, method for manufacturing the same |
| KR20200065418A (en) * | 2018-11-30 | 2020-06-09 | 주식회사 포스코 | Method for improving the surface of stainless steel |
-
1995
- 1995-12-31 JP JP35401795A patent/JP2681025B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005241635A (en) * | 2004-01-30 | 2005-09-08 | Jfe Steel Kk | Corrosion solution for appearance of prior austenite grain boundaries in steel materials and method of appearance of prior austenite grain boundaries in steel materials |
| JP2005350734A (en) * | 2004-06-10 | 2005-12-22 | Nippon Steel & Sumikin Stainless Steel Corp | Method for producing ferritic stainless steel strip with good paint adhesion |
| WO2006030999A1 (en) * | 2004-09-16 | 2006-03-23 | Bukwang Technology Co., Ltd. | Electroless plating method and plating film obtained by the electroless plating method |
| KR101465561B1 (en) * | 2013-08-27 | 2014-11-27 | 인하대학교 산학협력단 | Processing method for superhydrophobic stainless steel substrate surface and stainless steel substrate having the superhydrophobic surface prepared with the same |
| WO2019231125A1 (en) | 2018-05-28 | 2019-12-05 | Samsung Electronics Co., Ltd. | Composite of stainless steel and resin, method for manufacturing the same |
| KR20200065418A (en) * | 2018-11-30 | 2020-06-09 | 주식회사 포스코 | Method for improving the surface of stainless steel |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2681025B2 (en) | 1997-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2585936B2 (en) | Method for producing fluororesin coating | |
| JP3404286B2 (en) | Metal surface treatment method, and metal member having a surface obtained by the surface treatment method | |
| KR910000077B1 (en) | Method of manufacturing poly (arylene sulfide) printed circuit board | |
| JP5131683B2 (en) | Plating jig used for plating of resin moldings | |
| JP2009538968A5 (en) | ||
| JP2681025B2 (en) | Method for producing fluororesin coating | |
| Wharton et al. | Non-chromate conversion coating treatments for electrodeposited zinc-nickel alloys | |
| JPH05245848A (en) | Release film of mold and method for forming the same | |
| JP4668063B2 (en) | Resin-coated aluminum plate and method for producing the same | |
| JP2681024B2 (en) | Method for producing fluororesin coating | |
| KR910001900B1 (en) | Aluminum material coated with fluorine resin | |
| Tsai et al. | Adhesion of natural rubber compounds to plasma-polymerized acetylene films | |
| JP2001316872A (en) | Method for functionalizing surface on electroconductive metal | |
| JP3941649B2 (en) | Aluminum substrate and surface treatment method thereof | |
| JP2002030499A (en) | Method for producing aluminum base material for cooker | |
| CN115055351A (en) | A kind of preparation method of superhydrophobic film layer on the surface of electrogalvanized zinc | |
| JPH0523643A (en) | Method for forming fluorinated resin film and article providing fluorinated resin film by the same method | |
| JP2544974B2 (en) | Surface treatment method for stainless steel with excellent paint adhesion | |
| JPS6142797B2 (en) | ||
| JP3804549B2 (en) | Manufacturing method of gasket | |
| JP2003213494A (en) | String for musical instrument and method of manufacturing the same | |
| JP2001038288A (en) | Painted stainless steel sheet excellent in non-adhesiveness and coating film adhesion, and method for producing the same | |
| JP3673889B2 (en) | Super water-repellent composite plating film, base material provided with super water-repellent composite plating film, and method for producing the same | |
| JP3442532B2 (en) | Manufacturing method for endoscope parts | |
| JPS5873186A (en) | Mandrel and electroforming using same or method of producing printed circuit |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |