JPH04190878A - Precoating method - Google Patents
Precoating methodInfo
- Publication number
- JPH04190878A JPH04190878A JP31587790A JP31587790A JPH04190878A JP H04190878 A JPH04190878 A JP H04190878A JP 31587790 A JP31587790 A JP 31587790A JP 31587790 A JP31587790 A JP 31587790A JP H04190878 A JPH04190878 A JP H04190878A
- Authority
- JP
- Japan
- Prior art keywords
- group
- aluminum
- coating
- chromate
- functional group
- 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
- 238000000034 method Methods 0.000 title description 14
- 238000000576 coating method Methods 0.000 claims abstract description 32
- 125000000524 functional group Chemical group 0.000 claims abstract description 28
- -1 silyl compound Chemical class 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 8
- 239000003973 paint Substances 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 11
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract description 24
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 229910019142 PO4 Inorganic materials 0.000 abstract description 4
- 229910001092 metal group alloy Inorganic materials 0.000 abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 4
- 239000010452 phosphate Substances 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000007613 environmental effect Effects 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
- 239000008397 galvanized steel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、塗膜密着性と耐久性に優れたプレコート板を
生産するためのプレコート方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a precoating method for producing a precoated board with excellent coating film adhesion and durability.
本発明のプレコート方法は特に接着によりパネルを接合
してなる自動車車体用のプレコート板の製造に有用であ
る。The precoating method of the present invention is particularly useful for producing precoated plates for automobile bodies, which are formed by bonding panels together by adhesive.
（従来の技術）
一般にプレコート方法は亜鉛めっき鋼板、−冷延鋼板、
アルミニウム板等の金属板に予め塗料を塗装するもので
あり、これにより生産されるプレコート板は任意の形状
に成形加工され最終の用途に供されるものである。この
様なプレコート板は従来例えば冷蔵庫、洗濯機、電気ス
トーブなどの家電製品、自動販売機や事務機器等の什器
類などにおもに用いられてきた。この様なプレコート方
式にあっては、金属板を先に成形加工して所望の形状に
した後に塗装を行うポストコート方式に比べて、塗装工
程が合理化されること、品質が均一になること、塗料の
消費量が節約されること等の他に、特に大型構造物であ
る自動車車体等においては、塗装ブース、焼付はオーブ
ン等に費やされる草大なエネルギーの節約も見込まれ、
省エネルギー、環境保全といった面でも大きなメリット
となる。(Prior art) Generally, pre-coating methods are used to coat galvanized steel sheets, - cold rolled steel sheets,
A metal plate such as an aluminum plate is coated with a paint in advance, and the pre-coated plate produced by this process is formed into an arbitrary shape and used for the final use. Such pre-coated boards have conventionally been used mainly for home appliances such as refrigerators, washing machines, and electric stoves, and fixtures such as vending machines and office equipment. In this pre-coating method, compared to the post-coating method in which the metal plate is first formed into the desired shape and then painted, the painting process is streamlined and the quality is uniform. In addition to reducing paint consumption, it is also expected to save a huge amount of energy that would otherwise be consumed in paint booths, baking ovens, etc., especially for large structures such as automobile bodies.
It also has great benefits in terms of energy saving and environmental protection.
プレコート板に要求される性能としては、塗膜形成後に
成形加工されるため、その塗膜が折り曲げ、絞り加工等
に耐えられる十分な伸張性と金属面に対する密着性を保
持することがあげられる。As the pre-coated board is molded after the coating is formed, the coating must have sufficient extensibility to withstand bending, drawing, etc., as well as adhesion to metal surfaces.
一方、近年の環境保全、省エネルギー等の社会的要求に
対しての自動車の取り組みとして、燃費の改善、車両重
量の軽減などが行われており、その材料としてアルミニ
ウムの多量採用の傾向がみられる。アルミニウムが自動
車車体に採用されるには、冷延鋼板や亜鉛めっき鋼板と
比較するといくつかの解決すべき課題がある。たとえば
、鉄と接触すると電食が起こることからその隙間を絶縁
すべきこと、スポット溶接に大電流を要することなどの
対処すべき課題が出現する。これらの課題を解決する手
法としてプレコートしたアルミニウム板を用い、接着剤
により他の部材と接合するという車の製造法は大きなメ
リットを有する。On the other hand, in recent years automobile efforts have been made to improve fuel efficiency and reduce vehicle weight in response to social demands such as environmental protection and energy conservation, and there is a tendency to use a large amount of aluminum as a material for this purpose. In order for aluminum to be used in automobile bodies, there are several issues that need to be resolved compared to cold-rolled steel sheets and galvanized steel sheets. For example, there are issues that need to be addressed, such as the need to insulate the gap because electrical corrosion occurs when it comes into contact with iron, and the large current required for spot welding. To solve these problems, a car manufacturing method that uses pre-coated aluminum plates and connects them to other parts with adhesives has great advantages.
従来よりアルミニウム板等にプレコート１１するにあた
っては化成処理を行うのが通常であり、−船釣にはクロ
メート処理が採用され、クロム酸クロメート１、リン酸
クロメートが目的に応じて使い分けられる。しかしなが
ら、化成処理を介したアルミニウムと塗膜との密着は、
成形加工による化成処理被膜の伸長が期待できないこと
から、全表面積に占める密着している部分の割合が城し
られ塗膜の密着性が低下することになり、接合する部位
に大きな剥離強度が要求される自動車車体用には従来の
方法によるプレコート板の適用は困難であった。Conventionally, when precoating 11 on aluminum plates, etc., it has been usual to perform a chemical conversion treatment, and - for boat fishing, chromate treatment is adopted, and chromate chromate 1 and chromate phosphate 1 are used depending on the purpose. However, the adhesion between aluminum and paint film through chemical conversion treatment is
Since the chemical conversion coating cannot be expected to elongate due to molding, the proportion of the adhering area to the total surface area is limited and the adhesion of the coating decreases, requiring a high peel strength at the bonded area. It has been difficult to apply precoated plates by conventional methods to automobile bodies.
さらに従来のクロメート処理の欠点としては熱に弱いこ
とがあり、クロメート処理後の乾燥は通常６０°Ｃ以下
の温度で行われる。そのため、後工程で塗膜の焼付は等
の熱処理が必要な自動車車体に対しては、クロメート皮
膜の耐食性が低下するために塗膜の耐久性が不十分とな
る。Furthermore, a drawback of conventional chromate treatment is that it is sensitive to heat, and drying after chromate treatment is usually carried out at a temperature of 60° C. or lower. Therefore, for automobile bodies that require heat treatment such as baking of the paint film in a subsequent process, the corrosion resistance of the chromate film decreases, resulting in insufficient durability of the paint film.
かかる問題に対応する技術としては、以下の様な技術が
開示されている。例えば、水溶性有機高分子化合物を含
有させたクロメート処理液で金属表面を処理する方法（
特開昭６０−２６６７２号公報）がある。この場合、か
かる水溶性有機高分子化合物は多量のクロム酸、重クロ
ム酸の存在下では凝集現象を起こすことが知られており
、クロム酸や重クロム酸の高濃度な処理液を補給できな
い等、液管理の面で困難を伴う。さらに、別の技術とし
てクロメート処理後に塗布する塗料中にクロム酸ストロ
ンチウム等を配合し、耐食性等を向上させる技術（特開
平２−３６３８４号公報）があるが処理の対象となる金
属板はアルミニウム亜鉛合金めっき鋼板のみであり、ア
ルミニウム板等に対し塗膜密着性、耐久性とも十分なプ
レコートを提供する方法ではない。The following techniques have been disclosed as techniques to address this problem. For example, a method of treating metal surfaces with a chromate treatment solution containing a water-soluble organic polymer compound (
JP-A-60-26672). In this case, such water-soluble organic polymer compounds are known to cause agglomeration in the presence of large amounts of chromic acid or dichromic acid, making it impossible to replenish processing solutions with high concentrations of chromic acid or dichromic acid. , it is difficult in terms of liquid management. Furthermore, there is another technique (Japanese Unexamined Patent Publication No. 2-36384) in which strontium chromate is added to the paint applied after chromate treatment to improve corrosion resistance, but the metal plate to be treated is aluminum zinc. This method only applies to alloy-plated steel sheets, and is not a method that provides a precoat with sufficient adhesion and durability to aluminum sheets, etc.
（発明が解決しようとする課題）
本発明は上記の問題を解決し、塗膜の密着性に優れ、か
つ耐久性も格段に向上したプレコート板を住産するだめ
のプレコート方法を提供すること、特にアルミニウム、
アルミニウム合金へのプレコート方法を提供することを
目的とする。(Problems to be Solved by the Invention) The present invention solves the above problems and provides a pre-coating method for producing a pre-coated board with excellent coating film adhesion and significantly improved durability. Especially aluminum,
The purpose of the present invention is to provide a method for precoating aluminum alloys.
（課題を解決するための手段）
本発明者らは、上記目的を達成すべく鋭意研究を行った
結果、クロム酸クロメート処理やリン酸クロメート処理
による化成処理を施した金属または金属合金表面に、有
機官能基を有するシリル化合物を被覆量で１０〜５００
ｍｇ／ｍ”塗布、乾燥することにより付着させてプレコ
ート塗装を行うことを特徴とするプレコート方法が著し
い効果をもたらすことを見出し本発明を完成させた。(Means for Solving the Problems) As a result of intensive research to achieve the above object, the present inventors found that the surface of a metal or metal alloy that has been subjected to chemical conversion treatment by chromate chromate treatment or chromate phosphate treatment, The coating amount of silyl compound having an organic functional group is 10 to 500.
The present invention was completed based on the discovery that a pre-coating method, which is characterized in that a pre-coating method is carried out by coating and drying the coating material, brings about remarkable effects.
以下本発明の詳細な説明する。The present invention will be explained in detail below.
本発明のプレコート方法においては、金属または金属合
金に化成処理であるクロム酸クロメート処理、リン酸ク
ロメート処理を施した後、有機官能基を有するシリル化
合物を表面に１０〜５００ｍｇ／ｍ２被覆させてプレコ
ート用塗料を塗布する。かかる有機官能基を有するシリ
ル化合物としては、下記構造式で表される化合物を用い
ることができる。In the precoating method of the present invention, the metal or metal alloy is subjected to chemical conversion treatment such as chromate chromate treatment or chromate phosphoric acid treatment, and then the surface is coated with 10 to 500 mg/m2 of a silyl compound having an organic functional group and precoated. Apply paint. As the silyl compound having such an organic functional group, a compound represented by the following structural formula can be used.
但し Ｘは有機官能基
Ｙ１〜３はシラノール基または加水分解性反応基
この有機官能基としては、ビニル基、メタクリロイル基
、メタクリロキシプロピル基などの不飽和基を有する官
能基、グリシドキシプロビル基、（３，４エポキシシク
ロへキシル）エチル基などのエポキシ基を有する官能基
、アミノプロピル基、Ｎ−フェニルアミノプロピル基、
Ｎ−（アミノエチル）アミノプロピル基などのアミノ基
を有する官能基、その他の官能基としてメルカプトプロ
ピル基、クロロプロピル基などが挙げられるが、これに
限定されるものではない。さらに、加水分解性反応基と
しては、ハロゲン原子、メトキシ基、呈トキシ基、その
他のアルコキシ基などが挙げられる。However, X is an organic functional group Y1-3 are a silanol group or a hydrolyzable reactive group This organic functional group includes a functional group having an unsaturated group such as a vinyl group, a methacryloyl group, a methacryloxypropyl group, and a glycidoxypropyl group. group, a functional group having an epoxy group such as (3,4 epoxycyclohexyl)ethyl group, aminopropyl group, N-phenylaminopropyl group,
Functional groups having an amino group such as N-(aminoethyl)aminopropyl group, and other functional groups include, but are not limited to, mercaptopropyl group and chloropropyl group. Furthermore, examples of the hydrolyzable reactive group include a halogen atom, a methoxy group, a toxoxy group, and other alkoxy groups.
さらに、本発明における有機官能基を有するシリル化合
物としては、上記構造式で表される化合物と他のシリル
化物との縮合反応によって得られる化合物を用いること
ができる。ここで他のシリル化物とはケイ酸、水ガラス
などのケイ酸塩、さらにはトリメチルクロロシラン、ヘ
キサメチルジシロキサンなどのトリメチルシリル化剤な
どをいうが、上記構造式で表される化合物と縮合反応し
得るシリル化物であれば本発明で用いることができる。Further, as the silyl compound having an organic functional group in the present invention, a compound obtained by a condensation reaction between a compound represented by the above structural formula and another silylated product can be used. Here, other silylated substances include silicates such as silicic acid and water glass, and trimethylsilylating agents such as trimethylchlorosilane and hexamethyldisiloxane, which do not undergo a condensation reaction with the compound represented by the above structural formula. Any silylated product obtained can be used in the present invention.
なお、かかる縮合反応によって生成する化合物の分子量
や分子構造等については特に制限されない。また、かか
る有機官能基を有するシリル化物は直接あるいは有機溶
剤等で希釈して被処理材に被覆でき、被覆方法としては
浸漬、スプレー、ハケ塗り等より幅広く選択可能である
。Note that there are no particular limitations on the molecular weight, molecular structure, etc. of the compound produced by this condensation reaction. Furthermore, the silylated product having such an organic functional group can be coated on the material to be treated either directly or diluted with an organic solvent, and the coating method can be selected from a wide range of methods such as dipping, spraying, and brushing.
本発明において対象とする金属または金属合金としては
、アルミニウム、アルミニウム合金が用いられる。具体
的には、自動車車体用等に供される圧延アルミニウム板
やアルミニウム合金板等である。また、プレコート塗料
はアルキドメラミン系、ポリエステル系、アクリル系、
ウレタン系、エポキシフェノール系等通常用いられるも
のであればいずれでもよい。Aluminum and aluminum alloys are used as the metal or metal alloy targeted in the present invention. Specifically, these include rolled aluminum plates and aluminum alloy plates used for automobile bodies and the like. In addition, pre-coat paints include alkyd melamine, polyester, acrylic,
Any commonly used material such as urethane type or epoxyphenol type may be used.
（作用）
本発明においては、アルミニウム板等をプレコートする
にあたり、クロム酸クロメートやリン酸クロメートなど
の化成処理を施した後、表面に有機官能基を有するシリ
ル化物または他のシリル化物を被覆し、その上にプレコ
ート塗膜を塗布する。(Function) In the present invention, when precoating an aluminum plate or the like, after applying a chemical conversion treatment such as chromate chromate or chromate phosphate, the surface is coated with a silylated substance having an organic functional group or other silylated substance, A precoat film is applied thereon.
かかる有機官能基を有するシリル化合物中の水酸基や加
水分解性反応基はアルミニウムあるいはクロメート皮膜
との間に強い結合力を生じ、一方、有機官能基はプレヨ
ー１−１膜との間に強い結合力を生じる。そのため塗膜
の密着力を向上させる。The hydroxyl group or hydrolyzable reactive group in the silyl compound having such an organic functional group creates a strong bond with the aluminum or chromate film, while the organic functional group creates a strong bond with the Pleyo 1-1 film. occurs. Therefore, it improves the adhesion of the paint film.
さらに、かかる有機官能基を有するシリル化合物にはク
ロメート皮膜の封孔作用および加熱の際のクロメート皮
膜の保護作用が有る。従って、クロメート皮膜の耐食性
が良好となり塗膜の耐久性を向上させる。Furthermore, the silyl compound having such an organic functional group has a pore-sealing effect on the chromate film and a protective effect on the chromate film during heating. Therefore, the corrosion resistance of the chromate film becomes good and the durability of the coating film is improved.
（実施例）
以下、本発明を実施例および比較例によって具体的に説
明する。(Examples) Hereinafter, the present invention will be specifically explained using Examples and Comparative Examples.
１〜４、 ７１〜３
被処理材は２００ Ｘ２００ Ｘｏ、８皿アルミニウム
合金板（５０５２合金）を用い、表面処理はアルクロム
７１３（日本パーカライジング製、クロム酸−クロム酸
塩系処理液）を５５゛ｃで２分間スプレーし、約４５°
Ｃで乾燥させＣｒ量にして約５０ｍｇ／ｍ２を付着させ
た。つぎに、構造式が式（１）で表される有機官能基を
有するシリル化合物であるＴ−グリシドキシプロビルメ
トキシシランの１０重量％エーテル溶液に被処理板を浸
漬、引き上げた後、約５０°Ｃで乾燥させた。第１表に
示す被覆量（乾燥状態）になる様に浸漬、乾燥を繰り返
した。次いで、プレコート塗料（オイルフリーポリエス
テル塗料二関西ペイント社製、製品番号３３１−１５０
０）をアプリケータで２５μｍ （乾燥膜厚）になるよ
うに塗布し、電気オープンで２２０°Ｃ２分間焼付は硬
化させ、プレコート板を作成した。1-4, 71-3 The material to be treated was a 200 x 200 Spray for 2 minutes at c, approx. 45°
After drying with C, a Cr amount of approximately 50 mg/m2 was deposited. Next, the plate to be treated is immersed in a 10% by weight ether solution of T-glycidoxypropylmethoxysilane, which is a silyl compound having an organic functional group represented by formula (1), and then pulled up. Dry at 50°C. Dipping and drying were repeated until the coating amount (dry state) shown in Table 1 was achieved. Next, a pre-coat paint (oil-free polyester paint 2 manufactured by Kansai Paint Co., Ltd., product number 331-150) was applied.
0) was applied with an applicator to a thickness of 25 μm (dry film thickness) and cured by baking at 220° C. for 2 minutes with an electric open circuit to create a pre-coated board.
Ｘ ５〜７、 六１４〜７
構造式が弐（１）で表される有機官能基を有するシリル
化物としてＴＴ（メタクリロキシプロピル）トリメトキ
シシラン、Ｎ−β（アミノエチル）Ｔ−アミノプロピル
トリメトキシシラン、Ｔ−メルカプトプロピルトリメト
キシシラン、エチルトリエトキシシランのなかから１種
を用い、各々を実施例１の場合と同様に第１表に示す被
覆量（乾燥状態）になる様に被処理板に付着させた。そ
の後、実施例１と同様にしてプレコート塗料を塗布しプ
レコート板を作成した。X 5-7, 614-7 Silylated products having an organic functional group whose structural formula is represented by 2 (1) include TT (methacryloxypropyl)trimethoxysilane, N-β (aminoethyl)T-aminopropyltri Using one type of methoxysilane, T-mercaptopropyltrimethoxysilane, and ethyltriethoxysilane, each was treated in the same way as in Example 1 so that the coating amount (dry state) shown in Table 1 was obtained. attached to the board. Thereafter, a precoat paint was applied in the same manner as in Example 1 to create a precoat board.
８〜９、 六１８
有機官能基を有するシリル化物は以下のように合成した
。三ツロフラスコにジオキサン５０ｍ ｌを入れ、ヘキ
サメチルジシロキサン６．４８ｇおよび１１．５Ｎ −
ＨＣ１を８．７２ｍｆｆ１注入し１時間撹拌し、撹拌を
続けながら水ガラス３号の２０．９ｇと蒸留水１００＋
＋＋４２の？容液を滴下した。次いで、構造式が弐（１
）で表される有機官能基を有するシリル化合物としてｒ
−（メタクリロキシプロピル）トリメトキシシラン２．
８ｇを加える５時間線合反応を行った。8-9, 618 A silylated product having an organic functional group was synthesized as follows. Put 50ml of dioxane into a Mitsuro flask, add 6.48g of hexamethyldisiloxane and 11.5N-
Inject 8.72mff1 of HC1, stir for 1 hour, and while stirring, add 20.9g of water glass No. 3 and distilled water 100+.
++42? The solution was added dropwise. Next, the structural formula is 2 (1
) as a silyl compound having an organic functional group represented by r
-(methacryloxypropyl)trimethoxysilane2.
Linearization reaction was carried out for 5 hours by adding 8 g.
下層粘性物をデカンテーションやエバポレーション等の
操作で分離、精製して有機官能基を有するシリル化物Ｎ
）を得た。なお、この化合物の数平均分子量は１７００
であった。この有機官能基を有するシリル化物（１）の
１０重量％メチルイソブチルケトン溶液を調製した後、
第１表に示す被覆量（乾燥状態）になる様に他は実施例
１と同様にして付着させ、プレコート板を作成した。The viscous substance in the lower layer is separated and purified by operations such as decantation and evaporation to obtain silylated product N having organic functional groups.
) was obtained. The number average molecular weight of this compound is 1700
Met. After preparing a 10% by weight solution of silylated product (1) having this organic functional group in methyl isobutyl ketone,
A pre-coated plate was prepared in the same manner as in Example 1 except that the coating amount (dry state) shown in Table 1 was achieved.
１０〜１１、 六 ９
構造式が式（１）で表される有機官能基を有するシリル
化物としてＴ−グリシドキシプロピルトリメトキシシラ
ンを用い実施例８と同様の方法で縮合反応を行い有機官
能基を有するシリル化物（ＩＩ）を得た。（数平均分子
量は１０００） この化合物の１０重量％エーテル溶液
を調整し、表１に示す被覆量（乾燥状態）になる様に他
は実施例１と同様にして付着させ、プレコート板を作成
した。10-11, 6 9 A condensation reaction was carried out in the same manner as in Example 8 using T-glycidoxypropyltrimethoxysilane as a silylated product having an organic functional group whose structural formula is represented by formula (1). A silylated compound (II) having the group was obtained. (The number average molecular weight is 1000) A 10% by weight ether solution of this compound was prepared and deposited in the same manner as in Example 1 so that the coating amount (dry state) shown in Table 1 was obtained, thereby creating a pre-coated board. .
上記実施例１〜１１および比較例１〜９で作製したプレ
コート板につき、以下に示す方法で性能評価を行い得た
結果を第１表に併記する。The performance of the precoated plates produced in Examples 1 to 11 and Comparative Examples 1 to 9 was evaluated using the method described below, and the results are also listed in Table 1.
鼓伍亙史
（プレコート板の耐食性）
実施例および比較例で作成したプレコート板を電気オー
ブン中１７５°Ｃで３０分間加熱した。各仮にクロスカ
ットを塗膜から下地に至るまでカッターで切込み塩水噴
霧試験機（ＪＩＳ Ｋ−５４００７，８）に１０００時
間投入した後、クロス力・ント部の錆の有無および塗膜
のふくれ幅を評価した。History of the Precoated Board (Corrosion Resistance of Precoated Boards) The precoated boards prepared in Examples and Comparative Examples were heated in an electric oven at 175°C for 30 minutes. After cutting each temporary cross cut with a cutter from the paint film to the base and placing it in a salt spray tester (JIS K-54007, 8) for 1000 hours, the cross force, the presence of rust on the tip part, and the blistering width of the paint film were measured. evaluated.
（塗膜密着性）
実施例および比較例で作成したプレコート板を第１図お
よび第２図に示すドアヘム部を模擬した形状（ｆ、 ＝
１５０口、ｄ−３０胴、ｆｆ１ｚ’＝１２５賦、４２３
＝８０ｍｍ、 ｈ ＝３０ｍｍ）にプレス成形し、×
印の部位より切り出して密着性評価用テストピース２５
Ｘ８０ｍｍとした。このテストピース２枚を接着剤（住
友スリーエム製 ５Ｗ２２１４）を介して貼り合わせた
。なお接着層のラップ長は１２．５ｍｍ、厚さは０、１
５ｍｍとし、焼付けは１７０°Ｃで３０分行った。次い
で、インストロンを用いて引っ張り速度５ｍｍ／ｍｉｎ
で剪断強度を測定した。(Coating film adhesion) The pre-coated plates prepared in Examples and Comparative Examples were shaped to simulate the door hem part shown in Figures 1 and 2 (f, =
150 units, d-30 body, ff1z'=125 units, 423
= 80 mm, h = 30 mm), ×
Test piece 25 for adhesion evaluation cut out from the marked area
It was set to x80mm. These two test pieces were bonded together with an adhesive (5W2214 manufactured by Sumitomo 3M). The wrap length of the adhesive layer is 12.5 mm, and the thickness is 0 and 1.
5 mm, and baking was performed at 170°C for 30 minutes. Next, using an Instron, the pulling speed was 5 mm/min.
The shear strength was measured.
（発明の効果）
以上説明してきたように、本発明においては、アルミニ
ウムまたはアルミニウム合金に化成処理を施した後、有
機官能基を有するシリル化合物または他のシリル化物と
の縮合体を規定膜厚で付着させた後、プレコート用塗料
を塗布する構成としたことにより、第１表からプレコー
ト板の耐食性は有機官能基を有するシリル化合物が被覆
されると良好になり、プレコート板の塗膜密着性はかか
るシリル化合物の被覆量によって変化し、良好な密着性
を得るには被覆量１０〜５００ｍｇ／ｍ２の範囲がよく
比較例１〜３．５〜９のものにあっては密着性が十分で
なく、また、有機官能基を含有しないシリル化合物を用
いたもの（比較例４）にあっては密着性が十分でないこ
とが明らかである。一方、実施例にあっては耐食性、塗
膜密着性ともに満足しているものであった。(Effects of the Invention) As explained above, in the present invention, after chemical conversion treatment is applied to aluminum or an aluminum alloy, a condensate with a silyl compound having an organic functional group or another silylated product is applied to a specified film thickness. By adopting a structure in which the pre-coating paint is applied after the adhesion, as shown in Table 1, the corrosion resistance of the pre-coated plate becomes better when coated with a silyl compound having an organic functional group, and the coating film adhesion of the pre-coated plate improves. It varies depending on the coating amount of the silyl compound, and in order to obtain good adhesion, the coating amount is preferably in the range of 10 to 500 mg/m2, and in Comparative Examples 1 to 3.5 to 9, the adhesion is not sufficient. Furthermore, it is clear that the adhesiveness is not sufficient in the case of using a silyl compound containing no organic functional group (Comparative Example 4). On the other hand, in Examples, both corrosion resistance and coating adhesion were satisfactory.
第１図はドアヘム部の模擬成形品の平面図、第２図は第
１図に示す成形品の断面図である。FIG. 1 is a plan view of a simulated molded product of a door hem portion, and FIG. 2 is a sectional view of the molded product shown in FIG. 1.
Claims (1)
施した後、有機官能基を有するシリル化合物または他の
シリル化合物との縮合体を被覆量１０〜５００ｍｇ／ｍ
＾２の範囲で付着させてプレコート用塗料を塗布するこ
とを特徴とするプレコート方法。1. After chemical conversion treatment is applied to aluminum or aluminum alloy, a silyl compound having an organic functional group or a condensate with another silyl compound is applied in a coating amount of 10 to 500 mg/m
A pre-coating method characterized by applying a pre-coating paint by adhering it within a range of ^2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31587790A JPH04190878A (en) | 1990-11-22 | 1990-11-22 | Precoating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31587790A JPH04190878A (en) | 1990-11-22 | 1990-11-22 | Precoating method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04190878A true JPH04190878A (en) | 1992-07-09 |
Family
ID=18070678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31587790A Pending JPH04190878A (en) | 1990-11-22 | 1990-11-22 | Precoating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04190878A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5578347A (en) * | 1994-05-24 | 1996-11-26 | E. I. Du Pont De Nemours And Company | Process for applying a finish to a metal substrate |
| JP2004523353A (en) * | 2001-03-08 | 2004-08-05 | マクダーミド・インコーポレーテツド | Corrosion prevention of aluminum using mercapto-substituted silane |
-
1990
- 1990-11-22 JP JP31587790A patent/JPH04190878A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5578347A (en) * | 1994-05-24 | 1996-11-26 | E. I. Du Pont De Nemours And Company | Process for applying a finish to a metal substrate |
| JP2004523353A (en) * | 2001-03-08 | 2004-08-05 | マクダーミド・インコーポレーテツド | Corrosion prevention of aluminum using mercapto-substituted silane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5759629A (en) | Method of preventing corrosion of metal sheet using vinyl silanes | |
| CA2304240C (en) | Improved methods and compositions for preventing corrosion of metal substrates | |
| US6132808A (en) | Method of treating metals using amino silanes and multi-silyl-functional silanes in admixture | |
| JP4138253B2 (en) | Method for treating metals using a mixture of ureido silane and polysilyl functional silane | |
| JP5550210B2 (en) | Method of manufacturing a repair coating on a coated metal surface | |
| KR100740068B1 (en) | Conductive organic coatings | |
| JP2006519308A (en) | Method for coating a metal surface with a polymer-rich composition | |
| WO2001005520A2 (en) | Protective treatment of metal surfaces with aqueous mixture of vinyl silane and bis-silyl aminosilane | |
| ZA200302865B (en) | Method for pretreating and subsequently coating metallic surfaces with a paint-tpe coating prior to forming and use of substrates coated in this way. | |
| CN111304641A (en) | Hot-dip aluminum-zinc plate chromium-free passivation solution and preparation method of hot-dip aluminum-zinc fingerprint-resistant plate | |
| JP2003105562A (en) | Surface treated steel sheet having excellent white rust resistance | |
| JPH04190878A (en) | Precoating method | |
| JPH1095933A (en) | Coating composition and metal material coated with the same | |
| JPS6335712B2 (en) | ||
| JPS60199074A (en) | Surface treatment composition and process thereof | |
| JP2003253464A (en) | Nonchromium treatment for nonchromic chemical conversion treated steel sheet | |
| JP3389191B2 (en) | Painted steel plate using non-chromium compound rust preventive pigment for coating film | |
| JP3124266B2 (en) | Painted steel plate with excellent coating film adhesion and corrosion resistance of the processed part and low environmental load | |
| JP3090207B1 (en) | Painted steel sheet with excellent corrosion resistance and low environmental load | |
| JP2001199003A (en) | Organic composite coated steel panel excellent in solvent resistance | |
| JPH03281782A (en) | Surface treated steel material and its production | |
| JP2000154349A (en) | Coating composition and metal material coated with the same | |
| JPH05301070A (en) | Organic coated rust preventing steel sheet | |
| AU724978C (en) | Method and compositions for preventing corrosion of metal substrates | |
| ZA200302864B (en) | Method for pretreating and/or coating metallic surfaces with a paint-like coating prior to forming and use of substrates coated in this way. |