JPH0760899A - Fluoroplastic film laminated steel panel - Google Patents
Fluoroplastic film laminated steel panelInfo
- Publication number
- JPH0760899A JPH0760899A JP23084693A JP23084693A JPH0760899A JP H0760899 A JPH0760899 A JP H0760899A JP 23084693 A JP23084693 A JP 23084693A JP 23084693 A JP23084693 A JP 23084693A JP H0760899 A JPH0760899 A JP H0760899A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- film
- laminated
- laminated steel
- polyester resin
- 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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Links
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- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、製造が容易で、耐変色
性、密着性に優れたフッ素樹脂フィルムラミネ−ト鋼板
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluororesin film laminated steel sheet which is easy to manufacture and has excellent discoloration resistance and adhesion.
【０００２】[0002]
【従来技術】ガステ−ブルのような厨房品は、ステンレ
ス鋼板を加工したままのものであったが、意匠性に乏し
く、また、汚れが付着し易いので、近年着色化と耐汚染
性の向上が検討され、その一環として、ガステ−ブルの
天板部材にフッ素樹脂のプレコ−ト鋼板が使用されてい
る。この鋼板はフッ素樹脂塗膜を鋼板に設けたもので、
フッ素樹脂の耐汚染性、耐薬品性および非粘着性を利用
して油汚れや食品のこびり付きが生じないようにすると
ともに、付着しても拭き取り易くしている。この着色化
と耐汚染性の向上は、近年、ガステ−ブルの周辺、シス
テムキッチン全体にも及んでいる。2. Description of the Related Art Kitchen products such as gas tables were produced by processing a stainless steel plate as they are, but they are poor in design and stains are likely to adhere to the kitchen products. Has been studied, and as a part thereof, a fluororesin pre-coated steel sheet is used for the top member of the gas table. This steel plate has a fluororesin coating on the steel plate,
The stain resistance, chemical resistance and non-adhesiveness of the fluororesin are used to prevent oil stains and food stickiness, and to make it easier to wipe off even if they adhere. In recent years, the coloring and the improvement of the stain resistance have spread to the periphery of the gas table and the entire system kitchen.
【０００３】しかしながら、プレコ−ト鋼板の製造に使
用するフッ素樹脂は、ベ−ス樹脂が黄色系色調を有する
ポリエ−テルサルフォン樹脂であるため、任意の色に着
色することが難しく、顔料も分散しにくいため、色調は
黒色系に限られていた。また、塗膜密着性も劣るため、
部材にプレス加工した場合、コ−ナ−部に塗膜剥離が発
生し易いものであった。However, since the base resin of the fluororesin used for producing the precoated steel sheet is a polyether sulfone resin having a yellowish color tone, it is difficult to color it in any color, and the pigment is dispersed. Since it is difficult to do so, the color tone was limited to black. Also, since the coating film adhesion is poor,
When the member was pressed, coating film peeling was likely to occur at the corners.
【０００４】そこで、このような問題のない鋼板とし
て、エチレン−テトラフルオロエチレン共重合体フィル
ムを積層したラミネ−ト鋼板を使用する方法が提案され
ている。エチレン−テトラフルオロエチレン共重合体
（以下ＥＴＦＥという）は耐汚染性、耐薬品性および非
粘着性を有する樹脂であり、押し出し成形加工法で容易
にフィルム化できるので、鋼板に熱融着によりラミネ−
トすることができる。このラミネ−ト鋼板の製造は鋼板
をＥＴＦＥの融点である２６０℃より３０〜５０℃高い
２９０〜３１０℃に加熱して、フィルムを熱融着により
ラミネ−トした後、鋼板をラミネ−ト時と同じ温度に再
加熱する方法で行われている。Therefore, as a steel sheet having no such problem, a method of using a laminated steel sheet laminated with an ethylene-tetrafluoroethylene copolymer film has been proposed. Ethylene-tetrafluoroethylene copolymer (hereinafter referred to as ETFE) is a resin having stain resistance, chemical resistance and non-adhesiveness, and can be easily formed into a film by an extrusion molding method. −
You can This laminated steel sheet is manufactured by heating the steel sheet to 290 to 310 ° C., which is 30 to 50 ° C. higher than the melting point of ETFE, which is 260 ° C., and laminating the film by heat fusion, and then laminating the steel sheet. It is done by the method of reheating to the same temperature as.
【０００５】しかし、熱融着法での製造は、ラミネ−ト
温度が高く、また、高温で再加熱しなければならないた
め、製造上制約が多く、生産性も低いものであった。ま
た、製造したラミネ−ト鋼板は長期間使用すると、耐水
接着性、耐湿接着性が劣るものであった。これは鋼板に
フィルムを熱融着させる際、ＥＴＦＥフィルムの濡れ性
が不十分であるため、十分接着せず、ＥＴＦＥと鋼板と
の間に水が浸透し易いためと考えられる。However, since the production by the heat fusion method has a high laminate temperature and must be reheated at a high temperature, there are many production restrictions and the productivity is low. Further, the produced laminated steel sheet was inferior in water resistance and moisture resistance after long-term use. It is considered that this is because when the film is heat-sealed to the steel sheet, the wettability of the ETFE film is insufficient, so that the ETFE film does not adhere sufficiently and water easily penetrates between the ETFE and the steel sheet.
【０００６】[0006]
【発明が解決しようとする課題】そこで、本発明では、
製造が容易で、耐水、耐湿接着性に優れたＥＴＦＥフィ
ルムラミネ−ト鋼板を提供するものである。Therefore, according to the present invention,
The present invention provides an ETFE film laminated steel sheet which is easy to manufacture and has excellent water resistance and moisture resistant adhesion.
【０００７】[0007]
【課題を解決するための手段】本発明は、鋼板表面に着
色樹脂層を設けた後、芳香族ポリエステル樹脂成分を含
む接着剤を介して透明エチレン−テトラフルオロエチレ
ン共重合体フィルムを積層した。According to the present invention, a colored resin layer is provided on the surface of a steel sheet, and then a transparent ethylene-tetrafluoroethylene copolymer film is laminated via an adhesive containing an aromatic polyester resin component.
【０００８】[0008]
【作用】着色樹脂層は、透明ＥＴＦＥフィルムで被覆し
てあるので、付着物拭き取りの際こすっても変色せず、
まだら模様にならない。また、ＥＴＦＥは、非粘着性に
優れているので、表面は極めて不活性で、接着剤として
一般に使用されているエポキシ系樹脂、アクリル系樹脂
では耐水性、耐湿性を付与することは困難であるが、芳
香族ポリエステル樹脂成分を含むものはそれらを付与で
きる。Since the colored resin layer is covered with the transparent ETFE film, it does not discolor even when it is rubbed when wiping off the adhering substance.
It does not look mottled. Since ETFE is excellent in non-adhesiveness, its surface is extremely inactive, and it is difficult to impart water resistance and moisture resistance to epoxy resins and acrylic resins generally used as adhesives. However, those containing an aromatic polyester resin component can provide them.
【０００９】着色樹脂層は、鋼板に直接設けてもよく、
密着性を高めたい場合にはまずプライマ−層を設けて、
その上に設けてもよい。前者の場合、樹脂は鋼板および
接着剤の芳香族ポリエステル樹脂成分との接着性から、
ポリエステル系樹脂、エポキシ系樹脂、フェノキシ系樹
脂が適し、樹脂中には着色顔料とともに、必要に応じて
体質顔料、紫外線吸収剤、酸化防止剤、防錆顔料などを
添加してもよい。The colored resin layer may be directly provided on the steel plate,
If you want to improve the adhesion, first provide a primer layer,
You may provide on it. In the former case, the resin is adhesive from the steel sheet and the aromatic polyester resin component of the adhesive,
A polyester resin, an epoxy resin, or a phenoxy resin is suitable, and an extender pigment, an ultraviolet absorber, an antioxidant, a rust preventive pigment, etc. may be added to the resin, if necessary, together with a color pigment.
【００１０】一方、後者の場合は、プライマ−層で鋼板
との接着性を確保できるので、樹脂としては前記樹脂以
外にアクリル系樹脂も使用できる。プライマ−層は鋼板
との接着性を良好にするため、着色顔料を添加せず、防
錆顔料を添加する程度に止めることが好ましい。樹脂と
してはポリエステル系樹脂、エポキシ系樹脂、フェノキ
シ系樹脂が適している。On the other hand, in the latter case, since the primer layer can secure the adhesiveness to the steel sheet, an acrylic resin can be used as the resin in addition to the above resins. In order to improve the adhesion of the primer layer to the steel sheet, it is preferable to add no color pigment and stop the addition of a rust preventive pigment. Suitable resins are polyester resins, epoxy resins, and phenoxy resins.
【００１１】接着剤層成分の芳香族ポリエステル樹脂と
は、芳香族多価カルボン酸化合物または芳香族多価ヒド
ロキシ化合物を必須成分として得られるもので、芳香族
多価カルボン酸化合物としては、例えば、テレフタル
酸、イソフタル酸、オルソフタル酸、２,６−ナフタレ
ンジカルボン酸、ビフェニルジカルボン酸、トリメリッ
ト酸などが挙げられ、また、芳香族多価ヒドロキシ化合
物としては、ジヒドロキシナフタレン、ビスフェノ−ル
Ａなどが挙げられる。なお、芳香族ポリエステル樹脂は
イソシアネ−トによりウレタン変性したものでもよい。The aromatic polyester resin as the adhesive layer component is obtained by using an aromatic polyvalent carboxylic acid compound or an aromatic polyvalent hydroxy compound as an essential component. Examples of the aromatic polyvalent carboxylic acid compound include: Examples thereof include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimellitic acid, and the like, and aromatic polyvalent hydroxy compounds include dihydroxynaphthalene and bisphenol A. To be The aromatic polyester resin may be urethane-modified with isocyanate.
【００１２】共重合成分としては、脂肪族多価カルボン
酸化合物、脂肪族多価ヒドロキシ化合物が使用できる。
前者のものとしては、例えば、アジピン酸、スベリン
酸、アゼライン酸、セバシン酸、ドデカンジオン酸、
１,４−シクロヘキサンジカルボン酸などが挙げられ、
後者のものとしては、エチレングリコ−ル、プロピレン
グリコ−ル、１,４−ブタンジオ−ル、１,５−ペンタン
ジオ−ル、１,６−ヘキサンジオ−ル、ネオペンチルグ
リコ−ル、ジエチレングリコ−ル、トリエチレングリコ
−ル、ポリエチレングリコ−ル、ポリテトラメチレング
リコ−ル、１,４−シクロヘキサンジメタノ−ル、トリ
メチロ−ルプロパン、ペンタエルスリト−ルなどが挙げ
られる。As the copolymerization component, an aliphatic polycarboxylic acid compound or an aliphatic polyhydroxy compound can be used.
Examples of the former include, for example, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid,
1,4-cyclohexanedicarboxylic acid and the like,
Examples of the latter include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, Examples thereof include triethylene glycol, polyethylene glycol, polytetramethylene glycol, 1,4-cyclohexane dimethanol, trimethylol propane and pentaerythritol.
【００１３】接着剤は、芳香族ポリエステル樹脂含有量
を通常１５重量％以上、好ましくは２５重量％以上に
し、硬化剤として、例えば、（ポリ）イソシアネ−ト、
エポキシ樹脂、酸無水物、フェノ−ル樹脂、ポリウレタ
ン樹脂などを混合したものでもよい。接着剤には、必要
に応じて、脂肪族ポリエステル樹脂、エポキシ樹脂、ポ
リアミド樹脂、アクリル樹脂などを添加してもよく、ま
た、防錆顔料、着色顔料、体質顔料などを添加してもよ
い。The adhesive has an aromatic polyester resin content of usually 15% by weight or more, preferably 25% by weight or more, and a curing agent such as (poly) isocyanate,
It may be a mixture of epoxy resin, acid anhydride, phenol resin, polyurethane resin and the like. If necessary, an aliphatic polyester resin, an epoxy resin, a polyamide resin, an acrylic resin, or the like may be added to the adhesive, or a rust preventive pigment, a coloring pigment, an extender pigment, or the like may be added.
【００１４】本発明のラミネ−ト鋼板は、鋼板に着色樹
脂塗料を塗装して焼き付けすることによりまず着色樹脂
層を形成し、次に、接着剤を塗装して加熱により接着剤
層を形成した後、接着剤層が接着性を有している間にＥ
ＴＦＥフィルムをラミネ−トロ−ルでラミネ−トするこ
とにより製造できる。最初の着色樹脂層の形成にあたっ
ては、形成前に脱脂処理、化成処理などの前処理を通常
施すが、これは鋼板の表面性状により省略することも可
能である。鋼板には特に限定はなく、例えば、冷延鋼
板、亜鉛めっき鋼板、アルミニウムめっき鋼板、複合め
っき鋼板、ステンレス鋼板などでよい。In the laminated steel sheet of the present invention, a colored resin coating is applied to the steel sheet and baked to form a colored resin layer first, and then an adhesive is applied to form an adhesive layer by heating. After that, while the adhesive layer has adhesiveness, E
It can be produced by laminating a TFE film with a laminer roll. In forming the first colored resin layer, a pretreatment such as a degreasing treatment or a chemical conversion treatment is usually performed before the formation, but this may be omitted depending on the surface properties of the steel sheet. The steel plate is not particularly limited, and may be, for example, a cold rolled steel plate, a galvanized steel plate, an aluminum plated steel plate, a composite plated steel plate, a stainless steel plate, or the like.
【００１５】接着剤層を形成した後のラミネ−トは、熱
風オ−ブンなどで鋼板温度が１２０〜２５０℃、好まし
くは１８０〜２３０℃に加熱して、ＥＴＦＥフィルムを
ラミネ−トする。ＥＴＦＥフィルムは押し出し成形加工
法によりフィルムにしたもので、エチレンモノマ−の組
成比は特に限定されないが、４０〜６０mol％が好まし
い。フィルムは透明なものを使用するが、必ずしも無色
透明である必要はなく、半透明でもよく、紫外線吸収剤
などの添加剤の添加も可能である。フィルムの厚さは１
０μｍ以上あれば十分な耐汚染性、耐薬品性および非粘
着性が得られる。また、フィルムは接着剤層側にコロナ
放電処理を施しておくと、接着性が大きくなる。After the adhesive layer has been formed, the ETFE film is laminated by heating the steel sheet to a temperature of 120 to 250 ° C., preferably 180 to 230 ° C. with a hot air oven or the like. The ETFE film is formed by an extrusion molding method, and the composition ratio of ethylene monomer is not particularly limited, but 40 to 60 mol% is preferable. Although a transparent film is used, it is not necessarily required to be colorless and transparent, and may be semitransparent, and an additive such as an ultraviolet absorber can be added. The film thickness is 1
If it is 0 μm or more, sufficient stain resistance, chemical resistance and non-adhesiveness can be obtained. Further, when the film is subjected to corona discharge treatment on the adhesive layer side, the adhesiveness is increased.
【００１６】[0016]
実施例１ 溶融亜鉛めっき鋼板（目付量片面４５ｇ／ｍ2、板厚０.
５ｍｍ）に塗布型クロメ−ト処理を施して、フェノキシ
樹脂系プライマ−塗料を乾燥厚さで５μｍになるように
塗布し、焼き付け乾燥後、プライマ−層の上に白色ポリ
エステル樹脂系塗料を乾燥厚さで１３μｍになるように
塗布して焼き付け乾燥した。次に、ポリエステル樹脂系
接着剤［酸化合物：テレフタル酸/イソフタル酸/セバチ
ン酸/アジピン酸＝５３/１８/２５/４（mol％）とヒド
ロキシ化合物：ネオペンチルグリコ−ル/エチレングリ
コ−ル＝５１/４９（mol％）からなる芳香族ポリエステ
ル樹脂、溶剤（トルエン/ＭＥＫ＝９/１、重量比）］を
乾燥厚さで１０μｍになるように塗布して、最高到達鋼
板温度が２１０℃になるように焼き付け、直ちにシリコ
−ンゴム製のラミネ−トロ−ルを用いて透明ＥＴＦＥフ
ィルム［旭硝子（株）製、１５μｍ厚さ、接着側面にコ
ロナ放電処理材］をラミネ−トした。Example 1 Hot-dip galvanized steel sheet (weight per unit surface: 45 g / m 2 , plate thickness:
(5 mm) is coated with chromate, and a phenoxy resin-based primer coating is applied to a dry thickness of 5 μm. After baking and drying, a white polyester resin-based coating is dried to a dry thickness on the primer layer. Then, the coating was applied so as to have a thickness of 13 μm, followed by baking and drying. Next, a polyester resin adhesive [acid compound: terephthalic acid / isophthalic acid / sebacic acid / adipic acid = 53/18/25/4 (mol%) and hydroxy compound: neopentyl glycol / ethylene glycol = Aromatic polyester resin consisting of 51/49 (mol%), solvent (toluene / MEK = 9/1, weight ratio)] is applied to a dry thickness of 10 μm, and the maximum steel plate temperature reaches 210 ° C. It was baked so that it was immediately laminated with a transparent ETFE film [manufactured by Asahi Glass Co., Ltd., 15 μm thick, corona discharge treated material on the adhesive side surface] using a silicone rubber laminating roll.
【００１７】得られたラミネ−ト鋼板とヘアトニック、
ヘアリキッド、マジックインキ（黒）、コ−ヒ−、紅
茶、マヨネ−ズ、ケチャップ、醤油、ソ−ス、わさび、
からしなどの汚染因子を室温下で１週間接触させた後、
エタノ−ルで拭き取った結果、いずれも汚染因子には全
く汚染されなかった。The obtained laminated steel sheet and hair tonic,
Hair liquid, magic ink (black), coffee, tea, mayonnaise, ketchup, soy sauce, sauce, wasabi,
After contacting pollutants such as mustard at room temperature for 1 week,
As a result of wiping with ethanol, none of them was contaminated with the contaminating factor.
【００１８】次に、ラミネ−ト鋼板にゴバン目の切り込
みをカッタ−ナイフで施し、エリクセン試験（６ｍｍ押
し出し）を行った結果、フィルム剥離は認められなかっ
た。また、ラミネ−ト鋼板を沸騰水に２時間浸漬した
後、同様のエリクセン試験を行ってもフィルム剥離は認
められなかった。さらに、エリクセン試験後２００℃の
雰囲気中に２０日間放置する耐熱性試験を行ったが、フ
ィルムの剥離、縮み、変退色は認められなかった。Next, as a result of performing an Erichsen test (extrusion of 6 mm) by making a cut with a cutter knife on the laminated steel sheet, no film peeling was observed. Further, even after the laminated steel sheet was immersed in boiling water for 2 hours and the same Erichsen test was conducted, no film peeling was observed. Furthermore, after the Erichsen test, a heat resistance test was conducted by leaving it in an atmosphere of 200 ° C. for 20 days, but no peeling, shrinkage or discoloration of the film was observed.
【００１９】実施例２ 電気亜鉛めっき鋼板（目付量片面２０ｇ／ｍ2、板厚０.
４ｍｍ）に塗布型クロメ−ト処理を施して、黒色エポキ
シ樹脂系塗料を乾燥厚さで８μｍになるように塗布、焼
き付け乾燥した後、ポリエステル樹脂系接着剤［酸化合
物：テレフタル酸/イソフタル酸/アジピン酸＝２５/２
５/５０（mol％）とヒドロキシ化合物：ネオペンチルグ
リコ−ル/エチレングリコ−ル＝５１/４９（mol％）か
らなる芳香族ポリエステル樹脂、溶剤（トルエン/ＭＥ
Ｋ＝８/２、重量比）］を乾燥厚さで１０μｍになるよ
うに塗布して、最高到達鋼板温度が２１０℃になるよう
に焼き付け、直ちにシリコ−ンゴム製のラミネ−トロ−
ルを用いて透明ＥＴＦＥフィルム［旭硝子（株）製、１
２μｍ厚さ、接着側面にコロナ放電処理材］をラミネ−
トした。Example 2 Electrogalvanized steel sheet (weight per unit surface: 20 g / m 2 , plate thickness: 0.
4 mm) is coated with chromate, and a black epoxy resin coating is applied to a dry thickness of 8 μm, baked and dried, and then a polyester resin adhesive [acid compound: terephthalic acid / isophthalic acid / Adipic acid = 25/2
Aromatic polyester resin consisting of 5/50 (mol%) and hydroxy compound: neopentyl glycol / ethylene glycol = 51/49 (mol%), solvent (toluene / ME)
K = 8/2, weight ratio)] to a dry thickness of 10 μm and baked so that the maximum temperature of the steel plate reached 210 ° C., immediately followed by laminator made of silicone rubber.
Transparent ETFE film [1 by Asahi Glass Co., Ltd.
2 μm thick, corona discharge treated material on the adhesive side]
I got it.
【００２０】得られたラミネ−ト鋼板と実施例１で使用
した種々の汚染因子を実施例１と同様の条件で接触させ
たが、いずれの汚染因子にも全く汚染されなかった。ま
た、ラミネ−ト鋼板に実施例１のようなエリクセン試
験、２時間沸騰水浸漬試験、耐熱性試験を行ったが、い
ずれの試験とも結果は実施例１と同様であった。The obtained laminated steel sheet was contacted with the various pollutants used in Example 1 under the same conditions as in Example 1, but none was polluted at all. Further, the Laminated steel sheet was subjected to the Erichsen test, the two-hour boiling water immersion test, and the heat resistance test as in Example 1, and the results were the same as those in Example 1.
【００２１】実施例３ ステンレス鋼板（ＳＵＳ４３０、板厚０.４５ｍｍ）に
リン酸塩処理、塗布型クロメ−ト処理を順次施して、黄
色フェノキシ樹脂系塗料を乾燥厚さで９μｍになるよう
に塗布、焼き付け乾燥した後、その上にポリエステル樹
脂系接着剤［酸化合物：テレフタル酸/イソフタル酸＝
５０/５０（mol％）とヒドロキシ化合物：ネオペンチル
グリコ−ル/１,６−ヘキサンジオ−ル＝５０/５０（mol
％）からなる芳香族ポリエステル樹脂、溶剤（トルエン
/ＭＥＫ＝８/２、重量比）］を乾燥厚さで８μｍになる
ように塗布して、最高到達鋼板温度が２１０℃になるよ
うに焼き付け、直ちにシリコ−ンゴム製のラミネ−トロ
−ルを用いて透明ＥＴＦＥフィルム［旭硝子（株）製、
２０μｍ厚さ、接着側面にコロナ放電処理材］をラミネ
−トした。Example 3 A stainless steel plate (SUS430, plate thickness 0.45 mm) was sequentially subjected to a phosphate treatment and a coating type chromate treatment, and a yellow phenoxy resin-based paint was applied so that the dry thickness was 9 μm. After baking and drying, a polyester resin adhesive [acid compound: terephthalic acid / isophthalic acid =
50/50 (mol%) and hydroxy compound: neopentyl glycol / 1,6-hexanediol = 50/50 (mol
%) Aromatic polyester resin, solvent (toluene
/ MEK = 8/2, weight ratio)] to a dry thickness of 8 μm, and bake it so that the maximum steel plate temperature reaches 210 ° C, and immediately apply a laminer roll made of silicone rubber. Use a transparent ETFE film [Asahi Glass Co., Ltd.,
20 μm thick, and a corona discharge treated material] was laminated on the adhered side surface.
【００２２】得られたラミネ−ト鋼板と実施例１で使用
した種々の汚染因子を実施例１と同様の条件で接触させ
たが、いずれの汚染因子にも全く汚染されなかった。ま
た、ラミネ−ト鋼板に実施例１のようなエリクセン試
験、２時間沸騰水浸漬試験、耐熱性試験を行ったが、い
ずれの試験とも結果は実施例１と同様であった。The obtained laminated steel sheet was contacted with the various pollutants used in Example 1 under the same conditions as in Example 1, but none was polluted at all. Further, the Laminated steel sheet was subjected to the Erichsen test, the two-hour boiling water immersion test, and the heat resistance test as in Example 1, and the results were the same as those in Example 1.
【００２３】実施例４ ステンレス鋼板（ＳＵＳ４３０、板厚０.４５ｍｍ）に
リン酸塩処理、塗布型クロメ−ト処理を順次施して、フ
ェノキシ樹脂系プライマ−塗料を乾燥厚さで４μｍにな
るように塗布、焼き付け乾燥した後、赤色ポリエステル
樹脂系塗料を乾燥厚さで１４μｍになるように塗布、焼
き付けした。その後ポリエステル樹脂系接着剤［酸化合
物：テレフタル酸/イソフタル酸＝５０/５０（mol％）
とヒドロキシ化合物：ネオペンチルグリコ−ル/１,６−
ヘキサンジオ−ル＝５０/５０（mol％）からなる芳香族
ポリエステル樹脂、溶剤（トルエン/ＭＥＫ＝８/２、重
量比）、硬化剤：ポリイソシアネ−ト（ポリエステル樹
脂１００重量部に対して１０phr添加）］を乾燥厚さで
８μｍに塗布して、最高到達鋼板温度が２００℃になる
ように焼き付け、直ちにシリコ−ンゴム製のラミネ−ト
ロ−ルを用いて透明ＥＴＦＥフィルム［旭硝子（株）
製、２０μｍ厚さ、接着側面にコロナ放電処理材］をラ
ミネ−トした。Example 4 A stainless steel plate (SUS430, plate thickness 0.45 mm) was sequentially subjected to a phosphate treatment and a coating chromate treatment so that the phenoxy resin-based primer coating composition had a dry thickness of 4 μm. After coating, baking and drying, the red polyester resin-based paint was applied and baked so that the dry thickness was 14 μm. Then polyester resin adhesive [acid compound: terephthalic acid / isophthalic acid = 50/50 (mol%)
And hydroxy compounds: neopentyl glycol / 1,6-
Hexanediol = 50/50 (mol%) aromatic polyester resin, solvent (toluene / MEK = 8/2, weight ratio), curing agent: polyisocyanate (10 phr added to 100 parts by weight of polyester resin) ] To a dry thickness of 8 μm, baked so that the maximum temperature of the steel plate reached 200 ° C., and immediately, using a laminer roll made of silicone rubber, a transparent ETFE film [Asahi Glass Co., Ltd.]
Manufactured, and having a thickness of 20 μm and a corona discharge treated material on the adhered side surface.
【００２４】得られたラミネ−ト鋼板と実施例１で使用
した種々の汚染因子を実施例１と同様の条件で接触させ
たが、いずれの汚染因子にも全く汚染されなかった。ま
た、ラミネ−ト鋼板に実施例１のようなエリクセン試
験、２時間沸騰水浸漬試験、耐熱性試験を行ったが、い
ずれの試験とも結果は実施例１と同様であった。The obtained laminated steel sheet was contacted with the various pollutants used in Example 1 under the same conditions as in Example 1, but none was polluted at all. Further, the Laminated steel sheet was subjected to the Erichsen test, the two-hour boiling water immersion test, and the heat resistance test as in Example 1, and the results were the same as those in Example 1.
【００２５】実施例５ 実施例４において、プライマ−を乾燥塗膜厚４μｍのポ
リエステル樹脂系のものに、また、赤色ポリエステル樹
脂系塗料を乾燥塗膜厚１２μｍの褐色のものにした。さ
らに、ポリエステル樹脂系接着剤をジイソシアネ−ト変
性ポリエステル樹脂系接着剤［酸化合物：テレフタル酸
/イソフタル酸/セバチン酸/アジピン酸＝５３/１８/２
５/４（mol％）とヒドロキシ化合物：ネオペンチルグリ
コ−ル/エチレングリコ−ル＝５１/４９（mol％）から
なる芳香族ポリエステル樹脂をヘキサメチレンジイソシ
アネ−ト１００mol％で変性、溶剤（シクロヘキサノン/
トルエン/ＭＥＫ＝６/３/１、重量比）］にして、６μ
ｍ塗布後最高到達鋼板温度を１８０℃で焼き付けた。ま
た、フィルムとしては厚さ１２μｍのものを使用した。Example 5 In Example 4, the primer was a polyester resin-based paint having a dry coating film thickness of 4 μm, and the red polyester resin-based coating was a brown coating film having a dry coating film thickness of 12 μm. Furthermore, the polyester resin adhesive is a diisocyanate-modified polyester resin adhesive [acid compound: terephthalic acid
/ Isophthalic acid / Sebacic acid / Adipic acid = 53/18/2
Aromatic polyester resin composed of 5/4 (mol%) and a hydroxy compound: neopentyl glycol / ethylene glycol = 51/49 (mol%) is modified with 100 mol% of hexamethylene diisocyanate, a solvent ( Cyclohexanone /
Toluene / MEK = 6/3/1, weight ratio)]
After the coating, the highest reached steel plate temperature was baked at 180 ° C. A film having a thickness of 12 μm was used.
【００２６】得られたラミネ−ト鋼板と実施例１で使用
した種々の汚染因子を実施例１と同様の条件で接触させ
たが、いずれの汚染因子にも全く汚染されなかった。ま
た、ラミネ−ト鋼板に実施例１のようなエリクセン試
験、２時間沸騰水浸漬試験、耐熱性試験を行ったが、い
ずれの試験とも結果は実施例１と同様であった。The obtained laminated steel sheet was contacted with the various pollutants used in Example 1 under the same conditions as in Example 1, but none of them was polluted at all. Further, the Laminated steel sheet was subjected to the Erichsen test, the two-hour boiling water immersion test, and the heat resistance test as in Example 1, and the results were the same as those in Example 1.
【００２７】[0027]
比較例１ 実施例１において、ポリエステル樹脂系接着剤の代わり
にアクリル樹脂系接着剤を乾燥厚さで５μｍ塗布し、最
高到達鋼板板温２３０℃で焼き付けした。得られたラミ
ネ−ト鋼板はエリクセン試験、２時間沸騰水浸漬試験で
フィルムの剥離が認められた。Comparative Example 1 In Example 1, an acrylic resin adhesive was applied in a dry thickness of 5 μm in place of the polyester resin adhesive, and baked at a maximum steel plate temperature of 230 ° C. In the obtained Laminated steel sheet, peeling of the film was observed in the Erichsen test and the boiling water immersion test for 2 hours.
【００２８】比較例２ 実施例４において、接着剤として、脂肪族ポリエステル
樹脂系接着剤［酸化合物：セバチン酸/アジピン酸＝５
３/４７（mol％）とヒドロキシ化合物：ネオペンチルグ
リコ−ル/エチレングリコ−ル＝５０/５０（mol％）か
らなる脂肪族ポリエステル樹脂、溶剤（トルエン/ＭＥ
Ｋ＝８/２、重量比）］を使用し、５μｍ塗布後板温を
１８０℃で焼き付けた。また、フィルムとしては白色の
ものを使用した。得られたラミネ−ト鋼板はエリクセン
試験、２時間沸騰水浸漬試験および耐熱性試験でフィル
ムの剥離や縮みなどの異常が認められた。Comparative Example 2 In Example 4, as an adhesive, an aliphatic polyester resin adhesive [acid compound: sebacic acid / adipic acid = 5
Aliphatic polyester resin consisting of 3/47 (mol%) and hydroxy compound: neopentyl glycol / ethylene glycol = 50/50 (mol%), solvent (toluene / ME
K = 8/2, weight ratio)] was used and the plate temperature was baked at 180 ° C. after application of 5 μm. A white film was used as the film. The obtained Laminated steel sheet was found to have abnormalities such as peeling and shrinkage of the film in the Erichsen test, the 2-hour boiling water immersion test and the heat resistance test.
【００２９】[0029]
【発明の効果】以上のように、本発明のラミネ−ト鋼板
は、ＥＴＦＥフィルムを接着剤を用いてラミネ−トして
いるので、高温でラミネ−ト、さらに高温で再加熱しな
くとも、優れた耐水および耐湿接着性を付与でき、従来
の熱融着法より製造が簡単で、生産性も高い。As described above, in the laminated steel sheet of the present invention, since the ETFE film is laminated using the adhesive, it is possible to laminate it at a high temperature and to reheat it at a higher temperature. It can provide excellent water and moisture resistant adhesion, is easier to manufacture than conventional heat fusion methods, and has high productivity.
フロントページの続き (72)発明者 輿石 謙二 千葉県市川市高谷新町７番地の１ 日新製 鋼株式会社鉄鋼研究所塗覆装研究部内Front page continued (72) Inventor Kenji Koshiishi 1 at 7 Takamachi Shinmachi, Ichikawa City, Chiba Nisshin Steel Co., Ltd.
Claims (3)
エチレン共重合体フィルムを積層したラミネ−ト鋼板に
おいて、鋼板表面に着色樹脂層を設けた後、芳香族ポリ
エステル樹脂成分を含む接着剤を介して透明エチレン−
テトラフルオロエチレン共重合体フィルムを積層したこ
とを特徴とするフッ素樹脂フィルムラミネ−ト鋼板。1. A laminated steel sheet having an ethylene-tetrafluoroethylene copolymer film laminated on the surface of a steel sheet, wherein a colored resin layer is provided on the surface of the steel sheet and then transparent through an adhesive containing an aromatic polyester resin component. Ethylene
A fluororesin film-laminated steel sheet, which is obtained by laminating tetrafluoroethylene copolymer films.
とを特徴とする請求項１に記載のフッ素樹脂フィルムラ
ミネ−ト鋼板。2. The fluororesin film laminated steel sheet according to claim 1, wherein the colored resin layer comprises a primer layer.
り層の２層からなることを特徴とする請求項１に記載の
フッ素樹脂フィルムラミネ−ト鋼板。3. The fluororesin film laminated steel sheet according to claim 1, wherein the colored resin layer comprises two layers of a primer layer and a colored intermediate coating layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23084693A JP3069473B2 (en) | 1993-08-24 | 1993-08-24 | Fluororesin film laminated steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23084693A JP3069473B2 (en) | 1993-08-24 | 1993-08-24 | Fluororesin film laminated steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0760899A true JPH0760899A (en) | 1995-03-07 |
| JP3069473B2 JP3069473B2 (en) | 2000-07-24 |
Family
ID=16914209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23084693A Expired - Fee Related JP3069473B2 (en) | 1993-08-24 | 1993-08-24 | Fluororesin film laminated steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3069473B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6087727A (en) * | 1995-12-01 | 2000-07-11 | Mitsubishi Denki Kabushiki Kaisha | Misfet semiconductor device having different vertical levels |
-
1993
- 1993-08-24 JP JP23084693A patent/JP3069473B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6087727A (en) * | 1995-12-01 | 2000-07-11 | Mitsubishi Denki Kabushiki Kaisha | Misfet semiconductor device having different vertical levels |
| US6281051B1 (en) | 1995-12-01 | 2001-08-28 | Mitsubishi Denki Kabushiki Kaisha | Semiconductor device and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3069473B2 (en) | 2000-07-24 |
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