JPH0938572A - Surface treated metal plate excellent in stain-proofing and manufacture thereof - Google Patents
Surface treated metal plate excellent in stain-proofing and manufacture thereofInfo
- Publication number
- JPH0938572A JPH0938572A JP19871295A JP19871295A JPH0938572A JP H0938572 A JPH0938572 A JP H0938572A JP 19871295 A JP19871295 A JP 19871295A JP 19871295 A JP19871295 A JP 19871295A JP H0938572 A JPH0938572 A JP H0938572A
- Authority
- JP
- Japan
- Prior art keywords
- metal plate
- treated metal
- film
- resin
- stain resistance
- 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.)
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- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐汚染性に優れた
表面処理金属板及びその製造方法に関し、詳細には、表
面に耐汚染性皮膜を有する表面処理金属板及びその製造
方法に関し、特には、建材パネル、レンジフードカバー
や、家電製品、自動車等のシャーシパネルの如く、室内
室外を問わず汚染環境に曝されて使用される表面処理金
属板及びその製造方法に関する技術分野に属するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-treated metal sheet having excellent stain resistance and a method for manufacturing the same, and more particularly, to a surface-treated metal sheet having a stain-resistant film on the surface and a method for manufacturing the same. Is a technical field relating to a surface-treated metal plate used in a contaminated environment regardless of indoor or outdoor, such as a chassis panel of a building material panel, a range hood cover, a home appliance, an automobile, etc., and a manufacturing method thereof. is there.
【０００２】[0002]
【従来の技術】鋼板及びアルミニウム板に代表されるよ
うな金属板は、使用される環境における耐食性、耐熱
性、耐薬品性や、加工性等の様々な機能を付与するた
め、種々の無機化合物及び／又は有機化合物を用いた化
成処理や塗装処理等の様々な表面処理が施される。その
付与する機能の一つとして耐汚染性がある。即ち、金属
板表面が汚染されると美観が損なわれるのは勿論のこ
と、汚染された部分にて腐食が発生するという問題があ
り、その対策として耐汚染性の付与が行われる。2. Description of the Related Art Metal plates such as steel plates and aluminum plates are provided with various inorganic compounds in order to impart various functions such as corrosion resistance, heat resistance, chemical resistance, and workability in an environment in which they are used. And / or various surface treatments such as chemical conversion treatment and coating treatment using an organic compound. One of the functions imparted is stain resistance. That is, when the surface of the metal plate is contaminated, not only the appearance is impaired, but also the corrosion occurs in the contaminated portion. As a countermeasure, contamination resistance is imparted.
【０００３】汚染には二種類あり、その一つは煤煙や油
分のような有機物によるもの、もう一つは砂塵や金属粉
のような無機物によるものである。この有機物による汚
染の防止方法としては、材料表面に極力有機物が付着し
ないように、材料の表面エネルギーを低下させる方法が
採られてきた。一方、無機物による汚染の防止方法とし
ては、この汚染原因は硬い砂塵や金属粉が材料表面に押
し込まれることにあることから、材料表面の硬度を高く
（硬く）するという方法が採られてきた。There are two types of pollution, one of which is caused by organic substances such as soot and oil, and the other is caused by inorganic substances such as dust and metal powder. As a method of preventing the contamination by the organic substance, a method has been adopted in which the surface energy of the material is reduced so that the organic substance does not adhere to the material surface as much as possible. On the other hand, as a method of preventing contamination by inorganic substances, a method of increasing the hardness (hardness) of the material surface has been adopted because the cause of the contamination is that hard dust or metal powder is pushed into the material surface.
【０００４】このような耐汚染性を向上させる方法とし
て、これまで、様々な金属板の表面処理方法が提案され
ている。その詳細を以下説明する。 特許1161079 号、特許1549730 号、特開昭58-17747
5 号、特開平3-52976号、特開平3-224950号、特開平4-1
1671 号、特開平5-177766号公報では、フッ素樹脂及び
フッ素系界面活性剤を添加した樹脂を塗装した後、焼き
付けることにより、金属板表面に皮膜を形成させる方法
（以降、従来法Ａという）が提案されている。 特許1101649 号、特開昭53-77234号、特開昭59-194
838 号、特開昭60-112865 号公報、特許1101649 号、特
開平2-103216号、特開平3-258374号、特開平3-261551
号、特開平4-284239号、特開平5-193017号、特開平5-28
5450号、特開平6-47340 号、特開平6-47341 号公報で
は、放射線、電子線、及び／又は、紫外線で樹脂を硬化
させることにより、金属板表面に皮膜を形成させる方法
（以降、従来法Ｂという）が提案されている。 特開昭54-127428 号、特開平4-135841号、特開平4-
146132号、特開平4-146133号、特開平4-146136号、特開
平4-146127号、特開平5-38782 号、特開平5-185555号、
特開平5-318654号、特開平6-23319 号、特開平6-8369号
公報では、フッ素樹脂、ポリエチレン樹脂、PVC 樹脂等
のフイルムを金属板表面に接着させる方法（以降、従来
法Ｃという）が提案されている。[0004] As a method of improving such stain resistance, various surface treatment methods for metal plates have been proposed. The details will be described below. Patent No. 1161079, Patent No. 1549730, JP-A-58-17747
No. 5, JP-A-3-52976, JP-A-3-224950, JP-A-4-1
No. 1671 and JP-A-5-177766 discloses a method of forming a film on the surface of a metal plate by coating a resin to which a fluororesin and a fluorosurfactant are added and then baking the resin (hereinafter referred to as conventional method A). Has been proposed. Patent No. 1101649, JP-A-53-77234, JP-A-59-194
838, JP 60-112865, JP 1101649, JP 2-103216, JP 3-258374, JP 3-261551
No., JP-A-4-284239, JP-A-5-93017, JP-A-5-28
No. 5,450, JP-A-6-47340 and JP-A-6-47341 disclose a method of forming a film on the surface of a metal plate by curing a resin with radiation, an electron beam, and / or ultraviolet rays (hereinafter, a conventional method). Law B) has been proposed. JP-A-54-127428, JP-A-4-35841, JP-A-4-
146132, JP-A-4-146133, JP-A-4-146136, JP-A-4-146127, JP-A-5-38782, JP-A-5-185555,
JP-A-5-318654, JP-A-6-23319, and JP-A-6-8369 disclose a method of adhering a film such as a fluororesin, a polyethylene resin, or a PVC resin to a metal plate surface (hereinafter referred to as conventional method C). Has been proposed.
【０００５】[0005]
【発明が解決しようとする課題】ところが、これら従来
法においては次のような問題点がある。即ち、従来法Ａ
においては、フッ素樹脂が高価であるためにコストが高
くつくこと、200 ℃以上の高温で焼き付けるために金属
板に歪みが生じ易いこと、皮膜が柔らかいために砂塵や
金属粉のような硬質な無機物の表面への押し込みには弱
いこと等の問題点がある。従来法Ｂにおいては、放射
線、電子線、及び／又は、紫外線で硬化する樹脂を用い
る必要があるが、その樹脂が高価であるためにコストが
高くつくこと、放射線、電子線、及び／又は、紫外線の
発生に大量の電気を使用するために生産コストが高くつ
くこと、形成される皮膜と金属板との密着性が不充分で
あること等の問題点がある。従来法Ｃにおいては、樹脂
フイルムを金属板表面に接着させるために、生産コスト
が高くつくこと、生産性が低いこと等の問題点がある。However, these conventional methods have the following problems. That is, conventional method A
, The cost is high because the fluororesin is expensive, the metal plate is easily distorted because it is baked at a high temperature of 200 ° C or higher, and the film is soft, so hard inorganic substances such as dust and metal powder There is a problem that it is weak in pushing into the surface. In the conventional method B, it is necessary to use a resin that is cured by radiation, electron beams, and / or ultraviolet rays, but the cost is high because the resin is expensive, radiation, electron beams, and / or Since a large amount of electricity is used to generate ultraviolet rays, there are problems such as high production costs and insufficient adhesion between the formed film and the metal plate. In the conventional method C, since the resin film is adhered to the surface of the metal plate, there are problems that the production cost is high and the productivity is low.
【０００６】本発明はこの様な事情に着目してなされた
ものであって、その目的は、前記従来法の有する問題点
を解消し、耐汚染性及び皮膜の密着性に優れ、しかも低
コスト且つ高生産性で製造して得ることが可能な表面処
理金属板及びその製造方法を提供しようとするものであ
る。The present invention has been made in view of such circumstances, and its purpose is to solve the problems of the above-mentioned conventional method, to provide excellent stain resistance and film adhesion, and to reduce the cost. Further, the present invention aims to provide a surface-treated metal plate which can be produced and obtained with high productivity and a method for producing the same.
【０００７】[0007]
【課題を解決するための手段】上記の目的を達成するた
めに、本発明に係る表面処理金属板及びその製造方法
は、請求項１〜４記載の表面処理金属板の製造方法、請
求項５〜８記載の表面処理金属板としており、それは次
のような構成としたものである。即ち、請求項１記載の
表面処理金属板の製造方法は、金属板の表面に下記化学
式(1) で示される化合物及び／又は化学式(2) で示され
る化合物を有するシリコーン樹脂を塗布し、乾燥するこ
とにより皮膜を形成することを特徴とする耐汚染性に優
れた表面処理金属板の製造方法である（第１発明）。 R2Si(OR1)3 ------ 化学式(1) R2R3Si(OR1)2 ------ 化学式(2) 但し、上記化学式において、R1はメチル基又はエチル
基、R2はアルキル基又はそのハロゲン化物誘導体、R3は
アルキル基又はそのハロゲン化物誘導体である。In order to achieve the above object, a surface-treated metal sheet and a method for producing the same according to the present invention are the method for producing a surface-treated metal sheet according to any one of claims 1 to 4, and claim 5. ~ 8 surface-treated metal plate, which has the following configuration. That is, the method for producing a surface-treated metal plate according to claim 1 is to apply a silicone resin having a compound represented by the following chemical formula (1) and / or a compound represented by the chemical formula (2) to the surface of the metal plate and dry it. This is a method for producing a surface-treated metal sheet having excellent stain resistance, which is characterized by forming a coating film (first invention). R 2 Si (OR 1 ) 3 ------ Chemical formula (1) R 2 R 3 Si (OR 1 ) 2 ------ Chemical formula (2) However, in the above chemical formula, R 1 is a methyl group or An ethyl group, R 2 is an alkyl group or a halide derivative thereof, and R 3 is an alkyl group or a halide derivative thereof.
【０００８】請求項２記載の表面処理金属板の製造方法
は、前記乾燥する際の乾燥温度が室温〜150 ℃である請
求項１記載の耐汚染性に優れた表面処理金属板の製造方
法である（第２発明）。請求項３記載の表面処理金属板
の製造方法は、前記シリコーン樹脂を塗布する前に下地
処理として金属板の表面にクロメート処理又は有機樹脂
被覆処理を施す請求項１又は２記載の耐汚染性に優れた
表面処理金属板の製造方法である（第３発明）。請求項
４記載の表面処理金属板の製造方法は、前記有機樹脂被
覆処理における有機樹脂がエポキシ系樹脂、ポリアクリ
ル系樹脂、ポリウレタン系樹脂の１種又は２種以上から
なる請求項３記載の耐汚染性に優れた表面処理金属板の
製造方法である（第４発明）。The method for producing a surface-treated metal sheet according to claim 2 is the method for producing a surface-treated metal sheet excellent in stain resistance according to claim 1, wherein the drying temperature at the time of drying is room temperature to 150 ° C. There is (the second invention). The method for producing a surface-treated metal plate according to claim 3, wherein the surface of the metal plate is subjected to a chromate treatment or an organic resin coating treatment as a base treatment before applying the silicone resin. It is an excellent method for producing a surface-treated metal plate (third invention). The method for producing a surface-treated metal sheet according to claim 4, wherein the organic resin in the organic resin coating treatment is one or more of an epoxy resin, a polyacrylic resin, and a polyurethane resin. This is a method for producing a surface-treated metal plate having excellent stain resistance (fourth invention).
【０００９】請求項５記載の表面処理金属板は、前記請
求項１、２、３又は４に記載の製造方法によって得られ
る耐汚染性に優れた表面処理金属板である（第５発
明）。請求項６記載の表面処理金属板は、金属板表面
に、シラノール結合を有する分子構造からなるシリコー
ン樹脂皮膜を有することを特徴とする耐汚染性に優れた
表面処理金属板である（第６発明）。請求項７記載の表
面処理金属板は、前記シリコーン樹脂皮膜と金属板との
間にクロメート皮膜を有する請求項６記載の耐汚染性に
優れた表面処理金属板である（第７発明）。請求項８記
載の表面処理金属板は、前記シリコーン樹脂皮膜と金属
板との間にエポキシ系樹脂、ポリアクリル系樹脂、ポリ
ウレタン系樹脂の１種又は２種以上からなる有機樹脂皮
膜を有する請求項６記載の耐汚染性に優れた表面処理金
属板である（第８発明）。A surface-treated metal plate according to a fifth aspect is a surface-treated metal plate excellent in stain resistance obtained by the manufacturing method according to the first, second, third or fourth aspect (fifth invention). The surface-treated metal plate according to claim 6 is a surface-treated metal plate having excellent stain resistance, which has a silicone resin film having a molecular structure having a silanol bond on the surface of the metal plate (sixth invention). ). The surface-treated metal plate according to claim 7 is the surface-treated metal plate having excellent stain resistance according to claim 6, which has a chromate film between the silicone resin film and the metal plate (seventh invention). The surface-treated metal plate according to claim 8, wherein an organic resin film made of one or more of an epoxy resin, a polyacrylic resin, and a polyurethane resin is provided between the silicone resin film and the metal plate. The surface-treated metal plate according to item 6, which has excellent stain resistance (eighth invention).
【００１０】[0010]
【発明の実施の形態】本発明は例えば次のようにして実
施する。先ず、下記化学式(1) で示される化合物及び／
又は化学式(2) で示される化合物を有するシリコーン樹
脂を準備する。 R2Si(OR1)3 ------ 化学式(1) R2R3Si(OR1)2 ------ 化学式(2) 但し、上記化学式において、R1はメチル基又はエチル
基、R2はアルキル基又はそのハロゲン化物誘導体、R3は
アルキル基又はそのハロゲン化物誘導体である。次に、
金属板の表面に上記シリコーン樹脂を塗布した後、これ
を所定の乾燥温度、例えば80℃にして乾燥させることに
より、皮膜を形成させる。これにより、金属板の表面に
皮膜が形成された表面処理金属板が得られる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is implemented, for example, as follows. First, a compound represented by the following chemical formula (1) and /
Alternatively, a silicone resin having a compound represented by the chemical formula (2) is prepared. R 2 Si (OR 1 ) 3 ------ Chemical formula (1) R 2 R 3 Si (OR 1 ) 2 ------ Chemical formula (2) However, in the above chemical formula, R 1 is a methyl group or An ethyl group, R 2 is an alkyl group or a halide derivative thereof, and R 3 is an alkyl group or a halide derivative thereof. next,
After coating the silicone resin on the surface of the metal plate, the silicone resin is dried at a predetermined drying temperature, for example, 80 ° C. to form a film. Thereby, a surface-treated metal plate having a film formed on the surface of the metal plate is obtained.
【００１１】このようにして形成された皮膜は耐汚染性
及び耐食性並びに密着性に優れているため、かかる皮膜
を有する表面処理金属板は耐汚染性及び耐食性に優れ、
又、皮膜と金属板との密着性に優れている。Since the film thus formed has excellent stain resistance, corrosion resistance and adhesion, the surface-treated metal sheet having such a film has excellent stain resistance and corrosion resistance,
Also, the adhesion between the film and the metal plate is excellent.
【００１２】この詳細を以下説明する。前記シリコーン
樹脂の塗布後の乾燥の過程において（により）、このシ
リコーン樹脂〔即ち、R2Si(OR1)3及び／又はR2R3Si(O
R1)2を有する〕は下記に示す反応式（但しR2R3Si(OR1)2
の場合は省略する。即ちR2Si(OR1)3＝R2(OR1)1Si-O-R1
の場合のみを示す。）にて反応し、架橋が進み、皮膜と
なる。 R2(OR1)2Si-O-R1 ＋ H2O ＝ R2(OR1)2Si-OH ＋ R1-OH --- 式 R2(OR1)2Si-OH ＋ HO-SiR2(OR1)2 ＝ R2(OR1)2-Si-O-Si-R2(OR1)2 ＋ H2O --- 式The details will be described below. In the course of drying after applying the silicone resin, the silicone resin [ie R 2 Si (OR 1 ) 3 and / or R 2 R 3 Si (O 2
R 1 ) 2 ] is represented by the following reaction formula (provided that R 2 R 3 Si (OR 1 ) 2
Omitted in case of. That is, R 2 Si (OR 1 ) 3 = R 2 (OR 1 ) 1 Si-OR 1
Only the case is shown. ), The crosslinking proceeds to form a film. R 2 (OR 1 ) 2 Si-OR 1 + H 2 O = R 2 (OR 1 ) 2 Si-OH + R 1 -OH --- Formula R 2 (OR 1 ) 2 Si-OH + HO-SiR 2 (OR 1 ) 2 = R 2 (OR 1 ) 2 -Si-O-Si-R 2 (OR 1 ) 2 + H 2 O --- formula
【００１３】即ち、式にてシリコーン樹脂と水とが反
応し、脱メタノール（もしくは脱エタノール）反応が生
じ、シリコーン樹脂はヒドロキシル化（-OH ）される。
その後、式にて、前記ヒドロキシル化されたシリコー
ン樹脂のヒドロキシル基間で脱水縮合が生じ、シラノー
ル結合（-Si-O-Si- ）が生じる。以降、この、式の
反応が次々と生じ、上記シリコーン樹脂の構造中の-OR1
の部分でシラノール結合化していき皮膜となる。That is, in the formula, the silicone resin and water react to cause a demethanol (or deethanol) reaction, and the silicone resin is hydroxylated (-OH).
Then, in the formula, dehydration condensation occurs between the hydroxyl groups of the hydroxylated silicone resin, and a silanol bond (-Si-O-Si-) is generated. Thereafter, the reactions of this formula occur one after another, and -OR 1 in the structure of the above silicone resin is
The silanol bond is formed at the part of and becomes a film.
【００１４】ここで、シラノール結合は強固な結合であ
り、又、Siは硬い物質であるため、上記反応により形成
される皮膜は硬い皮膜となる。従って、砂塵や金属粉の
ような硬質な無機物の表面への押し込みに起因する汚染
を防ぐことが可能となり、かかる無機物に対する耐汚染
性を向上させることが可能となる。Since the silanol bond is a strong bond and Si is a hard substance, the film formed by the above reaction is a hard film. Therefore, it is possible to prevent contamination caused by pushing hard inorganic substances such as dust and metal powder into the surface, and it is possible to improve the contamination resistance to such inorganic substances.
【００１５】また、上記、式にて皮膜が形成される
ときに、アルキル基又はそのハロゲン化物誘導体である
R2、アルキル基又はそのハロゲン化物誘導体であるR
3は、下記化学構造式に示すように皮膜最表面に密に
並んだ構造となるため、皮膜表面の表面エネルギーが極
端に低下する。従って、水ばかりでなく煤煙や油分も付
着し難い表面となり、かかる有機物に対する耐汚染性を
向上させることが可能となる。 When a film is formed by the above formula, it is an alkyl group or a halide derivative thereof.
R 2 , R which is an alkyl group or a halide derivative thereof
As shown in the following chemical structural formula, 3 has a structure in which it is closely arranged on the outermost surface of the film, so that the surface energy of the film surface is extremely reduced. Therefore, not only water but also soot and oil will be hard to adhere to the surface, and it becomes possible to improve the stain resistance to such organic substances.
【００１６】更に、上記式にて生じるヒドロキシル化
されたシリコーン樹脂の一部のヒドロキシル基が金属表
面のヒドロキシル基との間で脱水縮合を生じ、 -Si-O-M
e(金属) の結合を生じるため、皮膜と金属表面との間で
優れた密着性を有する。Further, a part of the hydroxyl groups of the hydroxylated silicone resin produced in the above formula causes dehydration condensation with the hydroxyl groups on the metal surface, and -Si-OM
Because of the bonding of e (metal), it has excellent adhesion between the film and the metal surface.
【００１７】従って、上記のようにして形成される皮膜
は耐汚染性及び耐食性並びに密着性に優れているので、
かかる皮膜を有する表面処理金属板は耐汚染性及び耐食
性に優れ、又、皮膜と金属板との密着性に優れている。
本発明によれば、このように優れた特性を有する表面処
理金属板が得られる。Therefore, the film formed as described above is excellent in stain resistance, corrosion resistance and adhesion,
The surface-treated metal plate having such a coating has excellent stain resistance and corrosion resistance, and also has excellent adhesion between the coating and the metal plate.
According to the present invention, a surface-treated metal plate having such excellent characteristics can be obtained.
【００１８】又、本発明は、R2Si(OR1)3及び／又はR2R3
Si(OR1)2を有するシリコーン樹脂の塗布、乾燥という簡
単な工程により表面処理金属板の製造ができること、及
び、このシリコーン樹脂は従来法Ａに係るフッ素樹脂や
従来法Ｂに係る放射線等で硬化する特殊な樹脂と異な
り、一般的なものであって比較的低コストであることか
ら、従来法Ａ、Ｂ及びＣに比較して、低コスト且つ高生
産性で表面処理金属板を得ることができる。又、後述の
如く乾燥温度は室温等でよいので、従来法Ａの如き高温
焼き付けによる金属板の歪みが生じない利点がある。The present invention also provides R 2 Si (OR 1 ) 3 and / or R 2 R 3
A surface-treated metal plate can be produced by a simple process of coating and drying a silicone resin having Si (OR 1 ) 2 , and this silicone resin can be treated with fluororesin according to conventional method A or radiation according to conventional method B. Unlike a special resin that cures, it is a general one and is relatively low cost, so it is possible to obtain a surface-treated metal plate at low cost and high productivity as compared with the conventional methods A, B and C. You can Further, since the drying temperature may be room temperature or the like as described later, there is an advantage that distortion of the metal plate due to high temperature baking unlike the conventional method A does not occur.
【００１９】ところで、上記式の反応に関与する水は
空気中の水分を吸湿することにより付与されるため、
式の反応は室温で充分に進行する。また、式での脱メ
タノール反応（もしくは脱エタノール反応）により生じ
る R1-OH：メタノール（もしくはエタノール）の沸点は
64.7℃（78.3℃）であり、水の沸点は100 ℃であるた
め、これらの物質を皮膜中から除去するのには乾燥温
度：100 ℃にすれば充分であり、又、これらの物質は室
温でもある程度の時間で揮発し充分に除去可能である。
更に、乾燥温度を室温以下にしても皮膜形成は充分に可
能であるが、わざわざ室温以下の乾燥条件にすることは
無意味であり、冷却操作を要する他、生産性の低下を招
く。一方、乾燥温度を150 ℃以上に高くすると、上記
、式で生じる R1-OH、H2O(水) が急激に蒸発するた
め、シラノール結合により形成された皮膜の収縮が急激
に生じ、それにより皮膜にひび割れが入り易くなる。以
上の点から、乾燥温度は室温〜150 ℃にすることが望ま
しい（第２発明）。By the way, since the water involved in the reaction of the above formula is given by absorbing moisture in the air,
The reaction of the formula proceeds well at room temperature. Also, the boiling point of R 1 -OH: methanol (or ethanol) generated by the demethanol reaction (or deethanol reaction) in the formula is
Since it is 64.7 ° C (78.3 ° C) and the boiling point of water is 100 ° C, a drying temperature of 100 ° C is sufficient to remove these substances from the film. However, it volatilizes in a certain amount of time and can be sufficiently removed.
Further, even if the drying temperature is lower than room temperature, a film can be sufficiently formed, but it is meaningless to set the drying condition at room temperature or lower, and a cooling operation is required and productivity is lowered. On the other hand, when the drying temperature is increased to 150 ° C or higher, R 1 -OH and H 2 O (water) generated in the above formula evaporate rapidly, and the shrinkage of the film formed by the silanol bond occurs rapidly, which As a result, the film is likely to crack. From the above points, it is desirable that the drying temperature is room temperature to 150 ° C. (second invention).
【００２０】前記シリコーン樹脂を塗布する前に下地処
理として金属板の表面にクロメート処理又は有機樹脂被
覆処理を施すことが望ましい（第３発明）。そうする
と、クロメート処理の場合はクロメート皮膜が形成さ
れ、この皮膜は表面に金属板表面よりも多くのヒドロキ
シル基を有するため、より多くの -Si-O-Me(金属) 即ち
-Si-O-Cr（クロメート皮膜) 結合を生じ、その結果、金
属表面（クロメート皮膜）とその上層の皮膜（耐汚染性
等を発揮する皮膜）との密着性がより向上し、又、耐食
性も向上する。一方、有機樹脂被覆処理の場合は有機樹
脂皮膜が形成され、この皮膜が上記クロメート皮膜の場
合と同様の作用効果を奏し、密着性がより向上し、又、
耐食性も向上する。但し、この場合、-Si-O-Cr結合では
なく、-Si-O-C(有機樹脂皮膜) 結合を生じる。Before applying the silicone resin, it is desirable to perform chromate treatment or organic resin coating treatment on the surface of the metal plate as a base treatment (third invention). Then, in the case of chromate treatment, a chromate film is formed, and since this film has more hydroxyl groups on the surface than the surface of the metal plate, more -Si-O-Me (metal), that is,
-Si-O-Cr (chromate film) bond is generated, and as a result, the adhesion between the metal surface (chromate film) and the film above it (a film that exhibits stain resistance) is further improved, and corrosion resistance is also improved. Also improves. On the other hand, in the case of the organic resin coating treatment, an organic resin film is formed, and this film has the same function and effect as in the case of the chromate film, and the adhesion is further improved.
Corrosion resistance is also improved. However, in this case, not a -Si-O-Cr bond but a -Si-OC (organic resin film) bond is generated.
【００２１】前記有機樹脂被覆処理における有機樹脂
は、エポキシ系樹脂、ポリアクリル系樹脂、ポリウレタ
ン系樹脂の１種又は２種以上からなることが望ましい
（第４発明）。この場合、より多くの-Si-O-C 結合が生
じ、ひいては、密着性がより確実に向上する。The organic resin in the organic resin coating treatment is preferably made of one or more of epoxy resins, polyacrylic resins, and polyurethane resins (fourth invention). In this case, more —Si—OC bonds are generated, and thus the adhesion is more surely improved.
【００２２】以上のような方法により得られる表面処理
金属板は、金属板表面に、シラノール結合を有する分子
構造からなるシリコーン樹脂皮膜を有している。そし
て、この皮膜は、前述の如く、シラノール結合が強固な
結合であることと、Siが硬い物質であることに起因して
硬く、そのため、砂塵や金属粉のような硬質な無機物に
対する耐汚染性に優れている。又、皮膜表面の表面エネ
ルギーが低いことに起因して有機物に対する耐汚染性に
優れており、更に、-Si-O-Me結合等に起因して密着性に
優れている。The surface-treated metal plate obtained by the above method has a silicone resin film having a molecular structure having a silanol bond on the surface of the metal plate. And, as described above, this film is hard because the silanol bond is a strong bond and Si is a hard substance, and therefore, the stain resistance to hard inorganic substances such as dust and metal powder is high. Is excellent. Further, it has excellent stain resistance to organic substances due to the low surface energy of the film surface, and further has excellent adhesion due to —Si—O—Me bonds and the like.
【００２３】従って、金属板表面に、シラノール結合を
有する分子構造からなるシリコーン樹脂皮膜を有するよ
うにした表面処理金属板は、砂塵や金属粉のような硬質
な無機物に対する耐汚染性、及び、有機物に対する耐汚
染性に優れ、又、その耐汚染性皮膜の密着性が優れて耐
久性に優れている（第６発明）。Therefore, the surface-treated metal plate having a silicone resin film having a molecular structure having a silanol bond on the surface of the metal plate has a stain resistance to hard inorganic substances such as dust and metal powder, and an organic substance. The stain resistant coating is excellent in adhesion, and the stain resistant film has excellent adhesion and durability (sixth invention).
【００２４】かかる表面処理金属板において、シリコー
ン樹脂皮膜と金属板との間にクロメート皮膜を有するよ
うにすることは、前記第３発明の場合の説明からわかる
如く、耐汚染性皮膜の密着性をより向上させる点で好ま
しい（第７発明）。In such a surface-treated metal plate, it is necessary to provide a chromate film between the silicone resin film and the metal plate so that the adhesion of the stain resistant film can be improved, as can be seen from the description of the third invention. It is preferable in terms of further improvement (seventh invention).
【００２５】又、シリコーン樹脂皮膜と金属板との間に
エポキシ系樹脂、ポリアクリル系樹脂、ポリウレタン系
樹脂の１種又は２種以上からなる有機樹脂皮膜を有する
ようにすることは、前記第４発明の場合の説明からわか
る如く、耐汚染性皮膜の密着性をより向上させる点で好
ましい（第８発明）。In addition, it is necessary to have an organic resin film made of one or more of epoxy resin, polyacrylic resin and polyurethane resin between the silicone resin film and the metal plate. As can be seen from the description of the invention, it is preferable in that the adhesion of the stain resistant coating is further improved (eighth invention).
【００２６】尚、本発明においてシリコーン樹脂はR2Si
(OR1)3及び／又はR2R3Si(OR1)2を有するシリコーン樹脂
であり、必ずR2Si(OR1)3、R2R3Si(OR1)2の１種又は２種
を含むものであるが、その他に必要に応じて有機系もし
くは無機系の架橋促進剤、架橋剤、脱水剤、着色剤等を
含むことができる。又、R2Si(OR1)3及び／又はR2R3Si(O
R1)2の量や、R2Si(OR1)3量とR2R3Si(OR1)2量との比率に
ついては特には限定されるものではない。In the present invention, the silicone resin is R 2 Si.
(OR 1) 3 and / or R 2 R 3 Si is a silicone resin having a (OR 1) 2, always R 2 Si (OR 1) 3 , R 2 R 3 Si (OR 1) 2 of one or In addition to the seeds, an organic or inorganic crosslinking accelerator, a crosslinking agent, a dehydrating agent, a coloring agent and the like may be contained as necessary. In addition, R 2 Si (OR 1 ) 3 and / or R 2 R 3 Si (O
R 1) 2 of the amount and, R 2 Si (OR 1) 3 amount and the R 2 R 3 Si (OR 1 ) for the ratio between the 2 amounts do not particularly limited.
【００２７】本発明に係る金属板の種類は特には限定さ
れるものではなく、鋼板、アルミニウム板、銅板、亜鉛
板及びその他の金属板を使用することができ、又、それ
らの大きさについても限定されるものではない。The type of the metal plate according to the present invention is not particularly limited, and a steel plate, an aluminum plate, a copper plate, a zinc plate and other metal plates can be used, and the size thereof is also used. It is not limited.
【００２８】[0028]
（実施例１）アルミニウム合金板（材質：5000系合金、
厚さ：0.3 mm）について脱脂し、水洗した後、充分に乾
燥させた。しかる後、このアルミニウム合金板表面にR2
Si(OR1)3及びR2R3Si(OR1)2を有するシリコーン樹脂（信
越化学工業株式会社製）を乾燥後の膜厚が10μm となる
ように塗布した後、室温で10分間乾燥して皮膜を形成
し、表面処理金属板を得た。(Example 1) Aluminum alloy plate (material: 5000 series alloy,
The thickness: 0.3 mm) was degreased, washed with water, and then thoroughly dried. After that, R 2 is applied to the surface of this aluminum alloy plate.
A silicone resin containing Si (OR 1 ) 3 and R 2 R 3 Si (OR 1 ) 2 (manufactured by Shin-Etsu Chemical Co., Ltd.) was applied so that the film thickness after drying would be 10 μm, and then dried at room temperature for 10 minutes. Then, a film was formed to obtain a surface-treated metal plate.
【００２９】（実施例２）塗布後の乾燥条件を前記室温
で10分間の条件に代えて100 ℃で１分間の条件とし、こ
の点を除き、実施例１と同様の方法により表面処理金属
板を得た。Example 2 A surface-treated metal sheet was prepared by the same method as in Example 1 except that the drying condition after coating was changed to the condition of room temperature for 10 minutes instead of 100 ° C. for 1 minute. Got
【００３０】（実施例３）前記シリコーン樹脂の塗布前
にアルミニウム合金板にCr量が20mg/m2 となるようにク
ロメート処理を施した。この点を除き、実施例１と同様
の方法により表面処理金属板を得た。(Example 3) Prior to the application of the silicone resin, an aluminum alloy plate was subjected to a chromate treatment so that the Cr content was 20 mg / m 2 . A surface-treated metal plate was obtained in the same manner as in Example 1 except for this point.
【００３１】（実施例４）前記シリコーン樹脂の塗布前
にアルミニウム合金板にポリエポキシ系樹脂の被覆処理
を乾燥後の膜厚が３μm となるように施した。この点を
除き、実施例１と同様の方法により表面処理金属板を得
た。(Example 4) Prior to coating the silicone resin, an aluminum alloy plate was coated with a polyepoxy resin so that the film thickness after drying would be 3 μm. A surface-treated metal plate was obtained in the same manner as in Example 1 except for this point.
【００３２】（実施例５）前記シリコーン樹脂の塗布前
にアルミニウム合金板にポリアクリル系樹脂の被覆処理
を乾燥後の膜厚が３μm となるように施した。この点を
除き、実施例１と同様の方法により表面処理金属板を得
た。(Example 5) Prior to coating the silicone resin, an aluminum alloy plate was coated with a polyacrylic resin so that the film thickness after drying would be 3 μm. A surface-treated metal plate was obtained in the same manner as in Example 1 except for this point.
【００３３】（実施例６）前記シリコーン樹脂の塗布前
にアルミニウム合金板にポリウレタン系樹脂の被覆処理
を乾燥後の膜厚が３μm となるように施した。この点を
除き、実施例１と同様の方法により表面処理金属板を得
た。(Example 6) Before applying the silicone resin, the aluminum alloy plate was coated with a polyurethane resin so that the film thickness after drying was 3 μm. A surface-treated metal plate was obtained in the same manner as in Example 1 except for this point.
【００３４】（実施例７）シリコーン樹脂塗布後の乾燥
条件を実施例３での室温で10分間の条件に代えて200 ℃
で１分間の条件とし、この点を除き、実施例３と同様の
方法により表面処理金属板を得た。(Example 7) The drying conditions after coating the silicone resin were changed to the conditions of Example 3 at room temperature for 10 minutes, but at 200 ° C.
The surface-treated metal plate was obtained in the same manner as in Example 3 except that the conditions were 1 minute.
【００３５】（比較例１）アルミニウム合金板（材質：
5000系合金、厚さ：0.3 mm）について脱脂し、水洗した
後、充分に乾燥させた。次に、このアルミニウム合金板
にCr量が20mg/m2となるようにクロメート処理を施し
た。次に、その表面に合成樹脂プライマーを乾燥後の膜
厚が５μm となるように塗布した後、220 ℃で１分間乾
燥してプライマー皮膜を形成した。しかる後、フッ素樹
脂塗料を乾燥後の膜厚が10μm となるように塗布した
後、230 ℃で１分間乾燥して皮膜を形成し、表面処理金
属板を得た。(Comparative Example 1) Aluminum alloy plate (material:
5000 series alloy, thickness: 0.3 mm) was degreased, washed with water, and then thoroughly dried. Next, the aluminum alloy plate was subjected to a chromate treatment so that the Cr content was 20 mg / m 2 . Next, a synthetic resin primer was applied on the surface so that the film thickness after drying was 5 μm, and then dried at 220 ° C. for 1 minute to form a primer film. After that, a fluororesin coating material was applied so that the film thickness after drying was 10 μm, and then dried at 230 ° C. for 1 minute to form a film, and a surface-treated metal plate was obtained.
【００３６】（比較例２）前記フッ素樹脂塗料に代えて
ポリエステル系樹脂塗料を用い、この点を除き、比較例
１と同様の方法により表面処理金属板を得た。Comparative Example 2 A surface-treated metal plate was obtained in the same manner as in Comparative Example 1 except that the polyester resin paint was used instead of the fluororesin paint.
【００３７】（比較例３）前記比較例１と同様の脱脂、
水洗、乾燥、そしてクロメート処理が施されたアルミニ
ウム合金板にアクリレート系紫外線硬化型塗料を乾燥後
の膜厚が10μm となるように塗布した後、紫外線を５秒
間照射して皮膜を形成し、表面処理金属板を得た。Comparative Example 3 The same degreasing as in Comparative Example 1,
Acrylic UV-curable paint was applied to an aluminum alloy plate that had been washed with water, dried, and chromated to a film thickness of 10 μm after drying, and then irradiated with UV light for 5 seconds to form a film, and then the surface A treated metal plate was obtained.
【００３８】（評価試験）上記実施例１〜７、比較例１
〜３に係る表面処理金属板について、下記の如き各種評
価試験を行った。(Evaluation Test) Examples 1 to 7 and Comparative Example 1 above
The following various evaluation tests were performed on the surface-treated metal sheets according to 3 to 3.
【００３９】(1) 有機物に対する耐汚染性の評価試験 油はじき性評価試験 水平放置：表面処理金属板の表面に鉱物油（粘度：８cS
t)を滴下し、この金属板を水平に放置した状態で、鉱物
油のはじき性を評価した。評価結果は、水玉状に集まる
場合を○、若干水玉状に集まる場合を△、拡がる場合を
×で示した。垂直放置：表面処理金属板の表面に鉱物油
（粘度：８cSt)を滴下し、この金属板を垂直に放置した
状態で、鉱物油の流れ落ち性を評価した。評価結果は、
流れ落ちる場合を○、垂れる場合を×で示した。 マジック不描性評価試験 表面処理金属板の表面を黒色油性マジックで線引きし、
マジックのはじき具合で評価した。評価結果は、完全に
はじくものを○、少しはじくものを△、はじかないもの
を×で示した。 耐マジック汚染性評価試験 ａ．水拭き試験：表面処理金属板の表面を黒色油性マジ
ックで線引きし、15分間放置した後、水にひたしたガー
ゼにて上記線引き部分を10回拭き取った。そしてマジッ
クの残存状況にて評価した。評価結果は、完全に取れ痕
跡の残らないものを○、取れて痕跡が僅かに残るものを
△、取れないものを×で示した。 ｂ．ベンジン拭き試験：上記水にひたしたガーゼに代え
てベンジンにひたしたガーゼを用い、上記と同様の方法
により同様の評価を行った。(1) Evaluation test of stain resistance to organic matter Oil repellency evaluation test Horizontal standing: Surface treatment Mineral oil (viscosity: 8 cS
t) was dropped and the repellency of the mineral oil was evaluated while the metal plate was left horizontally. The evaluation results are shown by ◯ when gathering in the form of polka dots, Δ when slightly gathering in the form of polka dots, and x when spreading. Vertical standing: Mineral oil (viscosity: 8 cSt) was dropped on the surface of the surface-treated metal plate, and the runoff property of the mineral oil was evaluated in a state where the metal plate was left standing vertically. The evaluation result is
The case of runoff is indicated by ◯, and the case of sagging is indicated by x. Magic non-drawability evaluation test The surface of the surface-treated metal plate was drawn with black oil-based magic,
It was evaluated according to the repellency of Magic. The evaluation results are shown by ○ for completely repelling, Δ for slightly repelling, and × for non-repelling. Magic stain resistance evaluation test a. Water wiping test: The surface of the surface-treated metal plate was drawn with a black oil-based marker, left for 15 minutes, and then the drawn part was wiped off 10 times with gauze soaked in water. And it was evaluated by the remaining condition of Magic. The results of the evaluation are indicated by を when no trace was completely removed, Δ when the trace was slightly removed after removal, and × when the trace was not removed. b. Benzine wiping test: The same evaluation was carried out by the same method as above, using gauze dipped in benzine in place of the gauze dipped in water.
【００４０】(2) 表面硬度の評価試験（無機物に対する
耐汚染性の評価試験の一種） JIS 規格のK5400 の鉛筆引掻き試験方法により、表面鉛
筆硬度を測定し、表面処理金属板の表面硬度を評価し
た。(2) Surface hardness evaluation test (a type of evaluation test for stain resistance to inorganic substances) The surface hardness of the surface-treated metal plate is evaluated by measuring the surface pencil hardness by the JIS standard K5400 pencil scratch test method. did.
【００４１】(3) 表面処理皮膜の密着性の評価試験 表面処理金属板の表面に刃物でクロスカットを入れ、そ
の部分にセロハンテープをはった後、一気に引き剥がす
こと（クロスカットテープ剥離試験）により、表面処理
皮膜の密着性を評価した。評価結果は、剥離の無いもの
を○、若干剥離部分が認められるものを△、完全に剥離
するものを×で示した。(3) Evaluation test of adhesion of surface-treated film A cross-cut is put on the surface of a surface-treated metal plate with a knife, cellophane tape is applied to that portion, and then peeled off at once (cross-cut tape peeling test ), The adhesiveness of the surface treatment film was evaluated. The evaluation results are indicated by を for no peeling, Δ for slight peeling, and × for completely peeling.
【００４２】(4) 耐食性の評価試験 JIS Z2371 の塩水噴霧試験（連続噴霧1000時間）、JIS
H8681 のCASS試験（連続噴霧 200時間）を行った。評価
結果は、レイティングナンバーにて示した。(4) Corrosion resistance evaluation test JIS Z2371 salt water spray test (continuous spraying 1000 hours), JIS
A CASS test of H8681 (200 hours continuous spraying) was performed. The evaluation results are shown by rating numbers.
【００４３】[0043]
【表１】 [Table 1]
【００４４】（評価試験結果）上記評価試験結果をまと
めて表１に示す。表１からわかる如く、実施例１〜６に
係る表面処理金属板は、油はじき性、マジック不描性及
び耐マジック汚染性が良好（○）であり、有機物に対す
る耐汚染性に優れており、又、鉛筆引掻き試験での鉛筆
硬度が７Ｈであって皮膜表面硬度が高く、無機物に対す
る耐汚染性にも優れている。又、密着性及び耐食性も良
好である。中でも、実施例３、４〜６の場合は、実施例
１、２よりも密着性及び耐食性に優れていた。(Evaluation Test Results) The above evaluation test results are summarized in Table 1. As can be seen from Table 1, the surface-treated metal sheets according to Examples 1 to 6 have good oil repellency, magic non-drawability and magic stain resistance (○), and have excellent stain resistance to organic substances, Further, the pencil hardness in a pencil scratching test is 7H, the coating surface hardness is high, and the stain resistance to inorganic substances is also excellent. Also, the adhesion and corrosion resistance are good. Among them, in Examples 3 and 4 to 6, the adhesiveness and the corrosion resistance were superior to those in Examples 1 and 2.
【００４５】実施例７に係る表面処理金属板は、シリコ
ーン樹脂塗布後の乾燥温度が高い(200℃）ことに起因し
て皮膜に微小なクラックが多数発生し、そのため、密着
性が低く（△）、又、耐食性も若干低いが、有機物及び
無機物に対する耐汚染性は実施例１〜６の場合と同様に
優れている。In the surface-treated metal plate according to Example 7, a large number of minute cracks were generated in the coating film due to the high drying temperature (200 ° C.) after coating the silicone resin, resulting in low adhesion (Δ). ) Moreover, although the corrosion resistance is slightly low, the stain resistance to organic substances and inorganic substances is excellent as in the case of Examples 1 to 6.
【００４６】比較例１に係る表面処理金属板は、有機物
に対する耐汚染性は良好（○）であるが、鉛筆引掻き試
験での鉛筆硬度が２Ｈであって皮膜表面硬度が低く、無
機物に対する耐汚染性が不充分である。比較例２に係る
表面処理金属板は、油がはじかず（×）、マジックがは
じき難く（△）、又、マジックが水拭き試験で取れず
（×）、有機物に対する耐汚染性が不充分である。又、
鉛筆硬度が３Ｈであって皮膜表面硬度が低く、無機物に
対する耐汚染性が不充分である。比較例３に係る表面処
理金属板は、有機物に対する耐汚染性が不充分（△）で
あり、又、密着性が悪い（×）。The surface-treated metal sheet according to Comparative Example 1 has a good stain resistance to organic substances (◯), but has a pencil hardness of 2H in a pencil scratching test and has a low coating surface hardness, and has a stain resistance to inorganic substances. The sex is insufficient. In the surface-treated metal plate according to Comparative Example 2, oil was not repelled (x), the magic was not easily repelled (△), and the magic could not be removed by a water wiping test (x), and the stain resistance to organic substances was insufficient. is there. or,
The pencil hardness is 3H, the film surface hardness is low, and the stain resistance to inorganic substances is insufficient. The surface-treated metal plate according to Comparative Example 3 has insufficient stain resistance to organic substances (Δ) and poor adhesion (×).
【００４７】[0047]
【発明の効果】本発明によれば、有機物及び無機物に対
する耐汚染性、耐食性及び皮膜の密着性に優れた表面処
理金属板が得られ、しかも、かかる優れた特性を有する
表面処理金属板を低コスト且つ高生産性で得ることがで
きるようになる。According to the present invention, it is possible to obtain a surface-treated metal plate having excellent stain resistance, corrosion resistance, and film adhesion to organic and inorganic substances, and to reduce the surface-treated metal plate having such excellent characteristics. It can be obtained at high cost and high productivity.
Claims (8)
る化合物及び／又は化学式(2) で示される化合物を有す
るシリコーン樹脂を塗布し、乾燥することにより皮膜を
形成することを特徴とする耐汚染性に優れた表面処理金
属板の製造方法。 R2Si(OR1)3 ------ 化学式(1) R2R3Si(OR1)2 ------ 化学式(2) 但し、上記化学式において、R1はメチル基又はエチル
基、R2はアルキル基又はそのハロゲン化物誘導体、R3は
アルキル基又はそのハロゲン化物誘導体である。1. A coating is formed by applying a silicone resin having a compound represented by the following chemical formula (1) and / or a compound represented by the following chemical formula (2) on the surface of a metal plate and drying it. A method for producing a surface-treated metal sheet having excellent stain resistance. R 2 Si (OR 1 ) 3 ------ Chemical formula (1) R 2 R 3 Si (OR 1 ) 2 ------ Chemical formula (2) However, in the above chemical formula, R 1 is a methyl group or An ethyl group, R 2 is an alkyl group or a halide derivative thereof, and R 3 is an alkyl group or a halide derivative thereof.
℃である請求項１記載の耐汚染性に優れた表面処理金属
板の製造方法。2. The drying temperature for the drying is room temperature to 150.
The method for producing a surface-treated metal sheet having excellent stain resistance according to claim 1, which is at a temperature of 0 ° C.
処理として金属板の表面にクロメート処理又は有機樹脂
被覆処理を施す請求項１又は２記載の耐汚染性に優れた
表面処理金属板の製造方法。3. The method for producing a surface-treated metal plate excellent in stain resistance according to claim 1, wherein the surface of the metal plate is subjected to a chromate treatment or an organic resin coating treatment as a base treatment before applying the silicone resin. .
がエポキシ系樹脂、ポリアクリル系樹脂、ポリウレタン
系樹脂の１種又は２種以上からなる請求項３記載の耐汚
染性に優れた表面処理金属板の製造方法。4. The surface-treated metal plate excellent in stain resistance according to claim 3, wherein the organic resin in the organic resin coating treatment is one or more of epoxy resin, polyacrylic resin and polyurethane resin. Manufacturing method.
造方法によって得られる耐汚染性に優れた表面処理金属
板。5. A surface-treated metal sheet having excellent contamination resistance, obtained by the production method according to claim 1, 2, 3, or 4.
分子構造からなるシリコーン樹脂皮膜を有することを特
徴とする耐汚染性に優れた表面処理金属板。6. A surface-treated metal plate having excellent stain resistance, which has a silicone resin film having a molecular structure having a silanol bond on the surface of the metal plate.
にクロメート皮膜を有する請求項６記載の耐汚染性に優
れた表面処理金属板。7. The surface-treated metal plate having excellent stain resistance according to claim 6, which has a chromate film between the silicone resin film and the metal plate.
にエポキシ系樹脂、ポリアクリル系樹脂、ポリウレタン
系樹脂の１種又は２種以上からなる有機樹脂皮膜を有す
る請求項６記載の耐汚染性に優れた表面処理金属板。8. The stain resistance according to claim 6, wherein an organic resin film made of one or more of an epoxy resin, a polyacrylic resin, and a polyurethane resin is provided between the silicone resin film and the metal plate. Excellent surface treated metal plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19871295A JPH0938572A (en) | 1995-08-03 | 1995-08-03 | Surface treated metal plate excellent in stain-proofing and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19871295A JPH0938572A (en) | 1995-08-03 | 1995-08-03 | Surface treated metal plate excellent in stain-proofing and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0938572A true JPH0938572A (en) | 1997-02-10 |
Family
ID=16395764
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19871295A Pending JPH0938572A (en) | 1995-08-03 | 1995-08-03 | Surface treated metal plate excellent in stain-proofing and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0938572A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008221201A (en) * | 2007-02-16 | 2008-09-25 | Fujifilm Corp | Hydrophilic member and its manufacturing method |
-
1995
- 1995-08-03 JP JP19871295A patent/JPH0938572A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008221201A (en) * | 2007-02-16 | 2008-09-25 | Fujifilm Corp | Hydrophilic member and its manufacturing method |
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