JPS637877A - Surface treatment of stainless steel excellent in close adhesiveness of paint - Google Patents
Surface treatment of stainless steel excellent in close adhesiveness of paintInfo
- Publication number
- JPS637877A JPS637877A JP15210886A JP15210886A JPS637877A JP S637877 A JPS637877 A JP S637877A JP 15210886 A JP15210886 A JP 15210886A JP 15210886 A JP15210886 A JP 15210886A JP S637877 A JPS637877 A JP S637877A
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- film
- paint
- silane coupling
- coupling agent
- 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
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 29
- 239000010935 stainless steel Substances 0.000 title claims abstract description 29
- 239000003973 paint Substances 0.000 title claims abstract description 24
- 238000004381 surface treatment Methods 0.000 title claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 14
- -1 alkyl silicate Chemical compound 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 32
- 239000000377 silicon dioxide Substances 0.000 abstract description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000137 annealing Methods 0.000 abstract description 3
- 238000010422 painting Methods 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 2
- 238000004070 electrodeposition Methods 0.000 abstract description 2
- 229910052682 stishovite Inorganic materials 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-N hydrofluoric acid Substances F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明はステンレス鋼の塗装に当たって塗料の密着性を
向上せしめるためにステンレス鋼表面にアルキルシリケ
ート処理によるシリカ(SiO2)皮膜を形成させた上
にシランカップリング剤の皮膜を形成させる表面処理方
法に関するものである。Detailed Description of the Invention (Industrial Application Field) The present invention involves forming a silica (SiO2) film on the surface of stainless steel by alkyl silicate treatment in order to improve the adhesion of the paint when painting stainless steel. The present invention relates to a surface treatment method for forming a film of a silane coupling agent.
(従来の技術)
ステンレス鋼は本来無塗装で使用されるものであるが、
最近、自動車、建材、耐久消費材などでは、多様化を求
めてカラー化とともに耐食性のよク一層の向上をはかる
ため、ステンレス鋼にショットプラストや研磨を施し、
または硝フッ酸や塩化第二鉄などの腐食液によシ粗面を
形成させ塗料の密着性のよい表面にする方法がとられて
いる。(Conventional technology) Stainless steel is originally used unpainted, but
Recently, in order to diversify products such as automobiles, building materials, and durable consumer goods, stainless steel has been shot-plast or polished in order to provide color and further improve corrosion resistance.
Alternatively, a method is used in which a corrosive solution such as nitric-hydrofluoric acid or ferric chloride is used to form a rough surface to provide a surface with good paint adhesion.
また、さらに特公昭60−58819号の発明のように
塩化ナトリウム溶液中で電解処理して間口よシ奥の方が
広い孔食を発生せしめて、塗料の密着性のよい表面を形
成する方法が提案されている。一般には金属の塗装下地
処理としてクロム酸塩、リン酸塩およびシリケート系薬
剤を用いる化成処理が知られているが、ステンレス鋼へ
の適用に当タっては不働態皮膜を除去するための活性化
処理が前もって必要となる。Further, as in the invention of Japanese Patent Publication No. 60-58819, there is a method of electrolytically treating in a sodium chloride solution to generate pitting corrosion that is wider at the front than at the back, thereby forming a surface with good paint adhesion. Proposed. Generally, chemical conversion treatment using chromate, phosphate, and silicate chemicals is known as a base treatment for metal painting, but when applied to stainless steel, active treatment to remove the passive film is used. oxidation treatment is required in advance.
(発明が解決しようとする問題点)
ステンレス鋼の耐食性を保持しているのは表面の不働態
皮膜であシ、また光輝焼鈍仕上材には特有の酸化皮膜(
BA皮膜)が形成されて耐食性向上に役立っている。こ
れらの皮膜は腐食性物質に対して抵抗を示すと同時に塗
料や化成処理剤に対しても密着性を阻害する因子となる
ので、前述のように皮膜除去の処理を行っているのが現
状である。しかしながら塗膜はある程度の水や空気を通
し、さらに紫外線によシ劣化するので、素地の耐食性が
良好であることが望まれる。したがって、素地のステン
レス鋼の耐食性を損なわないために、不働態皮膜やBA
皮膜を除去せずに、そのままの表面に密着性のよい塗装
をすることが耐久性保持の上から必要となる。(Problems to be solved by the invention) The corrosion resistance of stainless steel is maintained by the passive film on the surface, and the bright annealed finish material has a unique oxide film (
BA film) is formed, which helps improve corrosion resistance. These films exhibit resistance to corrosive substances, and at the same time are a factor that inhibits adhesion to paints and chemical conversion agents, so the current practice is to remove the films as described above. be. However, since the coating film allows a certain amount of water and air to pass through and is further deteriorated by ultraviolet rays, it is desirable that the base material has good corrosion resistance. Therefore, in order not to impair the corrosion resistance of the base stainless steel, a passive film or BA
To maintain durability, it is necessary to apply a coating with good adhesion to the surface without removing the film.
本発明は塗料の密着性に劣るステンレス鋼の表面皮膜に
良好な塗装を施すという問題点を解決するためになされ
たものである。The present invention was made in order to solve the problem of applying a good coating to the surface film of stainless steel, which has poor paint adhesion.
(問題点を解決するための手段)
本発明の要旨はアルキルシリケートをステンレス鋼表面
に塗布して乾燥後、分子中に2個以上の異なった反応基
をもつ有機ケイ素単量体のシランカップリング剤を含有
するアルコール溶液を塗布して乾燥させることを特徴と
する塗料密着性にすぐれたステンレス鋼の表面処理方法
である。即ち本発明は、ステンレス鋼の表面皮膜を除去
して粗面にすることなしに密着性の良好な塗装を施すた
めにまず、表面皮膜に親和性のある有機ケイ素化合物で
あるアルキルシリケートを塗布して乾燥し、シリカ(
Sin2)皮膜を形成させて表面を改質するが、とのシ
リカ皮膜だけでは塗料の密着性に劣るので、本発明はさ
らにシリカ皮膜と塗料の両者に親和性のある皮膜を形成
させるものである。(Means for Solving the Problems) The gist of the present invention is to apply an alkyl silicate to a stainless steel surface, dry it, and then conduct silane coupling of an organosilicon monomer having two or more different reactive groups in the molecule. This is a method for surface treatment of stainless steel with excellent paint adhesion, which is characterized by applying an alcohol solution containing a chemical agent and drying it. That is, in the present invention, in order to apply a coating with good adhesion without removing the surface film of stainless steel and making the surface rough, first, an alkyl silicate, which is an organosilicon compound that has an affinity for the surface film, is applied. and dry, coat with silica (
Sin 2) The surface is modified by forming a film, but since a silica film alone has poor adhesion to the paint, the present invention further forms a film that has an affinity for both the silica film and the paint. .
(作用) まず第一段階のシリカ皮膜形成の方法について述べる。(effect) First, the method for forming the silica film in the first step will be described.
従来から知られているように、アルキルシリケートとし
て代表的なエチルシリケートは加水分解によってシリカ
とエチルアルコールニ分離して金属などの表面に耐熱性
や耐食性にすぐれた密着性のよいシリカ皮膜を形成する
。この薬剤としては通常はシリカの収率をよくするため
に,Si0240%のエチルシリケート4oが使用され
てぃる〇本覧明では薄く均一に形成させる必要から、こ
れを加水分解加工したものをアルコール(エチルアルコ
ールまたはインプロビルアルコール)テ稀釈して滴下ロ
ール絞シで光輝焼鈍仕上のステンレス鋼板に塗布し、乾
燥した。以上の処理によってステンレス鋼の表面は極め
て薄いシリヵ皮膜で均一に被覆される。本発明における
アルキルシリヶート処理液には一般にエチルシリケート
が用いられるが、その他のメチルシリケートやプロビル
シリケートも使用可能である。ただし、アルキル基が長
鎖になるほど加水分解反応性が低下するので、本発明で
は処理皮膜は均一で薄い方がよいので、上述の条件が最
適である。As has long been known, ethyl silicate, a typical alkyl silicate, separates into silica and ethyl alcohol through hydrolysis, forming a highly adhesive silica film with excellent heat resistance and corrosion resistance on metal surfaces. . Ethyl silicate 4O with 40% Si02 is usually used as this agent to improve the yield of silica.In this paper, it is necessary to form it thinly and uniformly, so a hydrolyzed product of alcohol is used. It was diluted (ethyl alcohol or Improvil alcohol) and applied to a bright annealed stainless steel plate using a dropping roll squeegee and dried. Through the above treatment, the surface of the stainless steel is uniformly coated with an extremely thin silica film. Ethyl silicate is generally used as the alkyl silicate treatment solution in the present invention, but other methyl silicate and probyl silicate can also be used. However, since the hydrolytic reactivity decreases as the alkyl group becomes longer, it is better for the treated film to be uniform and thin in the present invention, so the above-mentioned conditions are optimal.
次いで第二段階では、シランカップリング剤を用いて塗
料の密着性にすぐれた表面の形成を行う。Next, in the second step, a silane coupling agent is used to form a surface with excellent paint adhesion.
シランカッフリング剤は無機質材料と化学結合する反応
基(メトキシ基,エトキシ基,シラノール基など)と、
有機質材料と化学結合する反応基(ビニル基,エポキシ
基,メタアクリル基.アミン基など)の2種の異なる反
応基をもつ有機ケイ素単量体であシ、トリメチルメトキ
シシラン,ビニルトリエトキシシラン,N一β(アミノ
エチル)γ−アミノプロピルトリメトキシシラン,γ−
アミノプロビルトリエトキシシラン,γ−メタアクリロ
キシプロビルトリメトキシシラン,γ−グリシドキシプ
ロビルトリメトキシシランなどが市販されている。これ
らは従来から接着性向上のための処理剤として広く利用
されておシ、この関係の公知技術には特公昭55−41
711号,%公昭55−4 1 7 1 2号,特公昭
55−41713号,特公昭60−22067号などが
ある。これらの発明における処理液はシランカップリン
グ剤の水溶液またはアルコール水溶液に水溶性のTi,
Zr, Moなどの化合物を添加して性能向上をはか
ったものである。これらの処理対象となるものは鉄,非
鉄金属,メッキ鋼板,化成処理鋼板などであるが、ステ
ンレス鋼とくに光輝焼鈍仕上のBA皮膜で被覆されたス
テンレス銅帯に対しては水溶液や水分散液はぬれ性に問
題があるので,本発明者らはその適用条件確立のため検
討を行った。以下その結果について述べる。Silane cuffling agents have reactive groups (methoxy groups, ethoxy groups, silanol groups, etc.) that chemically bond with inorganic materials.
Organosilicon monomers with two different reactive groups (vinyl group, epoxy group, methacrylic group, amine group, etc.) that chemically bond with organic materials, trimethylmethoxysilane, vinyltriethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, γ-
Aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and the like are commercially available. These have been widely used as processing agents for improving adhesion, and known techniques related to this include Japanese Patent Publication No. 55-41.
711, % Publication No. 55-4 17 1 2, Special Publication No. 55-41713, Special Publication No. 60-22067, etc. The treatment liquid in these inventions is an aqueous solution of a silane coupling agent or an aqueous alcohol solution containing water-soluble Ti,
Compounds such as Zr and Mo are added to improve performance. The objects to be treated include iron, non-ferrous metals, plated steel sheets, and chemically treated steel sheets, but aqueous solutions and aqueous dispersions are not suitable for stainless steel, especially stainless steel copper strips coated with bright annealed BA coating. Since there is a problem with wettability, the present inventors conducted studies to establish the applicable conditions. The results will be described below.
供試材にはO、4 mm厚さのSUS 4 3 0ステ
ンレス冷延鋼板の光輝焼鈍仕上材を用い、これにエチル
シリケート薬剤をイソプロビルアルコールで稀釈シて滴
下ロール絞シで塗布し、乾燥して表面にシリ力皮膜を形
成させた。この処理をしたものと、光輝焼鈍仕上のまま
の無処理のものの両者に対し、シランカップリング剤で
あるN−β(アミノエチル)γ−アミノプロピルトリメ
トキシシラン80g/l’のイソプロビルアルコール溶
液とその水溶液をそれぞれ滴下ロール絞シで塗布して、
100〜120℃で乾燥した。以上の処理材について、
エチルシリケート処理のままのものと、無処理の光輝焼
鈍のままのものとともに塗装を施し、塗膜の密着性試験
に供した。塗装にはアクリル系カチオン塗料を用いて電
着塗装(26℃, 120V, 2min) を行い
、180℃で25分焼付して20〜23μの膜厚を得た
。The test material used was a 4 mm thick SUS 430 cold-rolled stainless steel plate with a bright annealing finish. Ethyl silicate was diluted with isopropyl alcohol, applied with a dropping roller, and dried. A silicate film was formed on the surface. A solution of 80 g/l' of N-β (aminoethyl) γ-aminopropyltrimethoxysilane in isopropyl alcohol, which is a silane coupling agent, for both the treated product and the untreated product with bright annealing finish. and its aqueous solution were applied using a dripping roll squeezer,
It was dried at 100-120°C. Regarding the above treated materials,
Both the ethyl silicate-treated specimen and the untreated bright annealed specimen were coated and subjected to a coating film adhesion test. Electrodeposition coating (26°C, 120V, 2min) was performed using an acrylic cationic paint, and baking was performed at 180°C for 25 minutes to obtain a film thickness of 20 to 23μ.
これを40℃温水に2 4 0 hr浸漬後、2 mm
ゴバン目試験で塗膜の密着性を評価した。この場合
、塗膜の剥離なしを01わずかでも剥離したものを×と
して、試験結果を第1表に示した。After immersing this in 40℃ hot water for 240 hours, the thickness of 2 mm
The adhesion of the coating film was evaluated using a goblin test. In this case, the test results are shown in Table 1, with 0 indicating no peeling of the coating film and 0 indicating poor coating peeling.
第 1 表
第1表に見られるように、光輝焼鈍のままのものやエチ
ルシリケート処理のみのものでは塗料の密着性が劣シ、
シランカップリング剤の処理を施す場合も水溶液では付
着が困難であシ、アルコール溶液が最適であることが分
かる。シランカップリング剤の無機質材料と結合する反
応基はステンレス鋼表面皮膜(BA皮膜や不働態皮膜)
ではなく、シリカ皮膜と結合し、その結果、有機質材料
と結合する反応基が最外表面に形成されて塗料と結合す
ることになる。Table 1 As shown in Table 1, paints that are brightly annealed or treated only with ethyl silicate have poor adhesion to the paint.
It can be seen that when treating with a silane coupling agent, it is difficult to adhere with an aqueous solution, and an alcohol solution is most suitable. The reactive group that binds to the inorganic material of the silane coupling agent is a stainless steel surface film (BA film or passive film).
Instead, it bonds with the silica film, and as a result, reactive groups that bond with organic materials are formed on the outermost surface and bond with the paint.
本発明でのシランカップリング剤処理液には先述のもの
がすべて使用可能であシ、それぞれに稀釈可能溶媒とし
て各種アルコール,アセトン,トルエン,エーテルなど
が使用できるが、作業性,安全性,経済性の面からエチ
ルアルコールまたはイソプロビルアルコールが最適であ
る。シランヵップリング剤の濃度としては0.5〜2
0 0 g/ノが適当である。すなわち、塗料密着性に
効果のあるのは0.5g/l 以上であるが、この形
成された皮膜が厚くなると塗装した際の塗膜の色調が不
均一となるので、上限を2 0 0 g/4とした。All of the above-mentioned solvents can be used as the silane coupling agent treatment liquid in the present invention, and various alcohols, acetone, toluene, ether, etc. can be used as dilutable solvents for each, but they are not suitable for workability, safety, economy, etc. Ethyl alcohol or isopropyl alcohol is most suitable from the viewpoint of stability. The concentration of silane coupling agent is 0.5-2
0 0 g/no is suitable. In other words, 0.5 g/l or more is effective for paint adhesion, but if the formed film becomes thick, the color tone of the paint film will become uneven when applied, so the upper limit should be set at 200 g/l. /4.
本発明における表面処理液の塗布は従来の方法でよいが
、塗装の下地としてはできるだけ薄く均一にする方がよ
いのでロール絞シで仕上げるのがもっともよい。塗布後
の乾燥も通常の方法でよく、60〜300℃で行えばよ
い。次に実施例により本発明の効゛果を具体的に示す。In the present invention, the surface treatment liquid may be applied by any conventional method, but it is best to use a roll squeegee to finish the coating, as it is better to make it as thin and uniform as possible as a base for coating. Drying after coating may also be carried out by a normal method, and may be carried out at 60 to 300°C. Next, the effects of the present invention will be specifically illustrated by examples.
(実施例)
0. 4 mm厚さのSOS 4 3 0ステンレス冷
延鋼板の光輝焼鈍仕上材にエチルシリケート薬剤をイン
グロビルアルコールで稀釈したものを滴下ロール絞シで
塗布し、乾燥して表面にシリカ皮膜を形成させた。つい
でシランカップリング剤処理液にはN−β(アミノエチ
ル)γ−アミノプロピルトリメトキシシランのイソプロ
ビルアルコールi液o.t,0.8, 0.5, 1,
10, 50, 100, 200g/1濃度のもの
、およびγ−アミノプロビルトリエトキシシランのエチ
ルアルコール溶液0.1, 0.3, 0.5, 1,
10,50,100, 200g/ノ濃度のものを用
意し、この処理液をそれぞれ滴下ロール絞りで塗布し、
100〜120℃で乾燥した◎これらにアクリル系カチ
オン塗料を用いて電着塗装(26℃, 120V, 2
min)を行い、180℃で25分焼付した。これを4
0℃温水に2 4 0 hr浸漬後、2伽ゴバン目試験
で塗膜の密着性を評価した。試験結果を第2表に示す。(Example) 0. An ethyl silicate agent diluted with Inglobil alcohol was applied to a bright annealed SOS 430 cold rolled stainless steel plate with a thickness of 4 mm using a dropping roll and dried to form a silica film on the surface. . Next, in the silane coupling agent treatment solution, isopropyl alcohol i solution o. t, 0.8, 0.5, 1,
10, 50, 100, 200g/1 concentration, and ethyl alcohol solution of γ-aminoprobyltriethoxysilane 0.1, 0.3, 0.5, 1,
Prepare treatment liquids with concentrations of 10, 50, 100, and 200 g/no, and apply each treatment liquid using a dripping roll squeezer.
◎These were dried at 100-120°C and then electrodeposited using acrylic cationic paint (26°C, 120V, 2
min) and baked at 180°C for 25 minutes. This is 4
After immersion in 0° C. hot water for 240 hr, the adhesion of the coating film was evaluated by a two-way cross test. The test results are shown in Table 2.
なお、塗料密着性の評価において、塗膜の剥離なしを○
、わずかでも剥離したものを×とした。以上の結果、塗
料の密着性に効果のあるシランカップリング剤の濃度は
0.5g/λ以上であることが判る。In addition, in evaluating paint adhesion, no peeling of the paint film is rated as ○.
, If even a slight amount of peeling occurred, it was rated as ×. The above results show that the concentration of the silane coupling agent that is effective in improving the adhesion of the paint is 0.5 g/λ or more.
第 2 表
(発明の効果)
塗料の密着性に劣るステンレス鋼の光輝焼鈍仕上材に本
発明の処理を施すことにょシ、耐食性のより一層の向上
をはかったカラーステンレス製品を作ることが可能とな
シ、ステンレス鋼の利用分野が拡大される。また、本発
明の処理液はケイ素化合物であるので、クロム酸とは異
なシ、無公害であシ、作業性から見ても有利である。Table 2 (Effects of the Invention) By applying the treatment of the present invention to bright annealed stainless steel materials that have poor paint adhesion, it is possible to produce colored stainless steel products with further improved corrosion resistance. Furthermore, the fields of use of stainless steel will be expanded. Furthermore, since the treatment liquid of the present invention is a silicon compound, it is different from chromic acid and is non-polluting, which is advantageous in terms of workability.
Claims (1)
後、分子中に2個以上の異なった反応基をもつ有機ケイ
素単量体のシランカップリング剤を含有するアルコール
溶液を塗布して乾燥させることを特徴とする塗料密着性
にすぐれたステンレス鋼の表面処理方法。It is characterized by applying an alkyl silicate to the stainless steel surface and drying it, then applying an alcohol solution containing a silane coupling agent of an organosilicon monomer having two or more different reactive groups in the molecule and drying it. A method of surface treatment of stainless steel with excellent paint adhesion.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15210886A JPS637877A (en) | 1986-06-28 | 1986-06-28 | Surface treatment of stainless steel excellent in close adhesiveness of paint |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15210886A JPS637877A (en) | 1986-06-28 | 1986-06-28 | Surface treatment of stainless steel excellent in close adhesiveness of paint |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS637877A true JPS637877A (en) | 1988-01-13 |
Family
ID=15533228
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP15210886A Pending JPS637877A (en) | 1986-06-28 | 1986-06-28 | Surface treatment of stainless steel excellent in close adhesiveness of paint |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS637877A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02305993A (en) * | 1989-05-17 | 1990-12-19 | Takasago Tekko Kk | Surface treatment of metallic material with superior adhesion of coating |
US5326594A (en) * | 1992-12-02 | 1994-07-05 | Armco Inc. | Metal pretreated with an inorganic/organic composite coating with enhanced paint adhesion |
JPH0899061A (en) * | 1994-09-30 | 1996-04-16 | Tonen Corp | Formation of silicon oxide-based ceramic film |
WO2008111535A1 (en) * | 2007-03-09 | 2008-09-18 | Kazufumi Ogawa | Insulating fine-particle film, process for producing the same, and capacitor employing insulating fine-particle film |
-
1986
- 1986-06-28 JP JP15210886A patent/JPS637877A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02305993A (en) * | 1989-05-17 | 1990-12-19 | Takasago Tekko Kk | Surface treatment of metallic material with superior adhesion of coating |
US5326594A (en) * | 1992-12-02 | 1994-07-05 | Armco Inc. | Metal pretreated with an inorganic/organic composite coating with enhanced paint adhesion |
US5478655A (en) * | 1992-12-02 | 1995-12-26 | Armco Inc. | Metal pretreated with an inorganic/organic composite coating with enhanced paint adhesion |
JPH0899061A (en) * | 1994-09-30 | 1996-04-16 | Tonen Corp | Formation of silicon oxide-based ceramic film |
WO2008111535A1 (en) * | 2007-03-09 | 2008-09-18 | Kazufumi Ogawa | Insulating fine-particle film, process for producing the same, and capacitor employing insulating fine-particle film |
JP2008226545A (en) * | 2007-03-09 | 2008-09-25 | Kagawa Univ | Insulating particulate film, its manufacturing method, and capacitor using insulating particulate film |
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