JP4374203B2 - Organic coated metal plate with excellent adhesion stability and adhesion method - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、接着性を有する有機被覆金属板及びそれを用いた金属板接着方法に関するものであり、特に、一般に接着時の条件により接合強度にばらつきが出やすい、金属板の接着剤による接合において接着安定性に優れた有機被覆金属板及び金属板接着方法に関する。
【０００２】
【従来の技術】
建材、家電、雑貨、自動車等の分野においては、加工後の金属板に他の性能や意匠性を付与するため、金属板上に接着剤を塗布して、所定目的の部材を積層している。その際、金属板の加工から接着剤の塗布作業及び部材の積層作業は、金属板を使用するユーザー側で行われるのが、一般的である。
【０００３】
ところが、上記作業には、有機溶剤使用による環境汚染への対応、人手不足、設備投資等の問題があるため、このような問題を解決するため、接着剤を予め塗布した金属板が開発されている。
【０００４】
例えば、特開平６−３１６０２８号公報や特開平８−２５８２１８号公報には、ホットメルト接着剤を金属板にプレコートしたものが開示されている。特開平８−２５８２１８号公報に記載の発明においては、特開平６−３１６０２８号公報で問題であった、出荷の際、表裏面が圧着されても接着しない性質である、耐ブロッキング性が改善されている。
【０００５】
【発明が解決しようとする課題】
しかし、特開平８−２５８２１８号公報のような接着剤をプレコートした金属板は、金属板への接着剤塗布時の問題や、耐ブロッキング性のような問題を解決することは可能であるが、接着時に接着部に加わる力のばらつきにより、接着部の接着剤厚さにばらつきが生じやすく、安定した接着力を得にくいという問題があった。そのため、接着剤プレコート金属板による金属板の接合は、信頼性の面からコスト高なカシメやリベット等の機械的接合に代わる方法とはなっていない。
【０００６】
そこで、本発明は、上記課題を解決するものであり、接着部の接着剤厚さのばらつきを無くし、接着安定性に優れた有機被覆金属板及び金属板接着方法を提供することを、その課題としている。
【０００７】
【課題を解決するための手段】
本発明では、金属板にプレコートする接着剤中に、接着時の接着剤厚さを一定に保つことを目的としてスペーサービーズを入れることにより接着力のばらつきを抑えることができることを見出し、かかる知見を基に本発明を完成させたものであって、本発明がその要旨とするところは、以下のとおりである。
【０００８】
（１）接着面に接着層が設けられていない被接着材料と貼り合わされる有機被覆金属板であって、片面又は両面に、接着温度に加熱することにより接着力を発現する樹脂からなる厚さが０．５〜１００μｍの接着層を有し、該接着層中に接着層厚さを調整するためのスペーサービーズを接着層に対する体積比で０．１〜２５％含有し、前記スペーサービーズの平均粒径Ｄｂが、前記接着層の厚さよりも小さいことを特徴とする接着安定性に優れた有機被覆金属板。
（２）接着面に厚さが０．５〜１００μｍの接着層が設けられている被接着材料と貼り合わされる有機被覆金属板であって、片面又は両面に、接着温度に加熱することにより接着力を発現する樹脂からなる厚さが０．５〜１００μｍの接着層を有し、該接着層中に接着層厚さを調整するためのスペーサービーズを接着層に対する体積比で０．１〜２５％含有し、前記スペーサービーズの平均粒径Ｄｂが、両面の接着層の厚さの合計厚さＤａｄよりも小さいことを特徴とする接着安定性に優れた有機被覆金属板。
【０００９】
（３）前記スペーサービーズが、熱硬化性物質、又は、ＪＩＳ−Ｋ−６８６３に規定されたホットメルト接着剤の軟化点試験法によって求めた軟化温度が接着剤の軟化温度より高い熱可塑性物質である上記（１）又は（２）に記載の接着安定性に優れた有機被覆金属板。
【００１１】
（４）前記スペーサービーズが樹脂からなり、そのヤング率Ｙｂが、金属板のヤング率Ｙｍに対して、Ｙｂ≦Ｙｍ／５を満たすことを特徴とする上記（１）〜（３）のいずれかに記載の接着安定性に優れた有機被覆金属板。
【００１２】
（５）片面又は両面に接着温度に加熱することにより接着力を発現する樹脂からなる厚さが０．５〜１００μｍの接着層を有する有機被覆金属板を被接着材料に接着する方法であって、被接着材料の表面には接着層が設けられておらず、前記接着層が接着厚さを調整するためのスペーサービーズを接着層に対する体積比で０．１〜２５％含有し、前記接着層の前記スペーサービーズの平均粒径Ｄｂが、前記接着層の厚さよりも小さことを特徴とする接着安定性に優れた金属板接着方法。
（６）片面又は両面に接着温度に加熱することにより接着力を発現する樹脂からなる厚さが０．５〜１００μｍの接着層を有する有機被覆金属板を被接着材料に接着する方法であって、被接着材料の表面にも厚さが０．５〜１００μｍの接着層が設けられており、前記接着層が接着厚さを調整するためのスペーサービーズを接着層に対する体積比で０．１〜２５％含有し、前記接着層の前記スペーサービーズの平均粒径Ｄｂが、両面の接着層の厚さの合計厚さＤａｄよりも小さいことを特徴とする接着安定性に優れた金属板接着方法。
【００１４】
【発明の実施の形態】
以下、本発明について詳細に説明する。
【００１５】
まず、本発明において接着性塗膜に使用できる樹脂は、通常（室温）では接着力を有せず、加熱により軟化し、接着性を発現するものであるが、熱可塑性でも、空気中の湿気と反応し硬化するタイプや、軟化温度よりさらに加熱することにより架橋、硬化するタイプのように、硬化性のものでも構わない。例えば、エチルセルロース、酢酸ビニル及びその誘導体、ポリエチレン、エチレン酢酸ビニル共重合体、ブチルメタクリル、ポリスチレン及び共重合体、ポイソブチレン、ポリプロピレン、ナイロン、ポリエステル、ポリアクリル、エチレン三元共重合体、フェノキシ、トランスポリイソプレン、ポリスルホン、ポリアリルスルフェン、ポリウレタン、エポキシ、ポリアミド、フェノール、ポリオレフィン等が適した樹脂として挙げられる。
【００１６】
これらの中で、特に通常時(室温時)の非接着性は、ナイロン、ポリアクリル、ポリエチレン、ポリプロピレン、ポリエステル等の結晶性の高い樹脂が優れている。また、本発明では、加工成型に優れていることが望ましく、伸びの良好な樹脂を選択するのがよい。
【００１７】
ナイロン系樹脂を使用する場合には、示差走査熱量測定の融解ピークが５０℃以下に存在すると耐ブロッキング性が劣り、一方、融解ピークが現れる温度が高すぎても接着に必要な加熱温度が高くなってしまって、作業上好ましくないため、５０℃以下に融解ピークが存在せず、５０℃より高く、２００℃以下の温度範囲において融解ピークが存在することが望ましい。なお、融解ピークは、市販の示差走査熱量測定装置（ＤＳＣ）により測定することができる。
【００１８】
なお、その示差走査熱量測定融解ピークの強度が、樹脂を１７０℃から室温放冷により硬化させたものの示差走査熱量測定融解ピークの１０〜１００％となるようにするとよい。１０％未満では、通常時の非接着性が得られない。また、分子量が５０００未満では成形性が劣り、分子量が８００００を超えると耐ブロッキング性が低下するため、分子量が５０００〜８００００のナイロンを使用することが最も望ましい。
【００１９】
また、結晶化率の抑制のため、例えば、ポリエステル、ポリウレタン、ポリアクリル、エポキシ、ポリアミド、フェノール、ポリオレフィン等の非結晶性樹脂をブレンドしても良い。また、エポキシ樹脂、メラミン樹脂、ポリイソシアネート樹脂、フェノール樹脂等を硬化剤として使用することもできる。その際、接着力が失われない程度の硬化剤の量及び焼付け温度を選択すればよい。
【００２０】
接着層に用いる樹脂は、溶剤型、溶融型、水系、紛体等どの形態のものでもよい、さらに接着層に用いる樹脂には、顔料、染料、充填剤、防錆剤等、各種添加剤を添加することもできる。
【００２１】
接着性有機皮膜の膜厚は、０．５μｍより薄いと接着性が失われ、１００μｍより厚いと金属板の成型加工時に有機被覆が剥離する可能性が有るだけでなく、それ以上の厚さを塗布しても、接着力が飽和して不経済であるため、０．５〜１００μｍとする。
【００２２】
本発明では、接着圧の掛かり方によって接着層の厚さがばらつき、接着強度がばらついてしまうことを防ぐために、接着層にスペーサービーズを含有させる。このスペーサービーズの粒径に関しては、その平均粒径が接着層の合計厚さよりも小さくなるようにしておく必要がある。接着層の合計厚さとは、接着される面に接着層が存在しない場合は本発明の金属板の接着剤層の厚さ、被接着面にも接着剤層が存在する場合にはそれぞれの面に設けた接着層の厚さの合計厚さをいうものである。
【００２３】
すなわち、接着層の合計厚さをＤad, スペーサービーズの平均粒径をＤbとするとき、Ｄb ＜Ｄad とする。この理由は、スペーサービーズの平均粒径が接着層の厚さより大きいと、スペーサービーズの粒径に相当する接着厚さ（接着される金属板間の距離）に対して接着剤が相対的に不足するために、被接着面と均一に接着できなくなり、接着強度の不足が生じるためである。
【００２４】
また、スペーサービーズの平均粒径は最大で２００μm以下であることが好ましい。その理由は接着時の厚さはある程度以上厚くなっても接着力が飽和していまい、不経済であるからである。
【００２５】
スペーサービーズは、接着層を接着する温度において、軟化や熱分解せず、スペーサーとしての機能するものであれば、金属粉末やガラス粉末等の無機物から選んでも構わないが、スペーサービーズの硬さが、金属板よりも硬いスペーサービーズを用いると、高い圧力をかけて接着をする際、スペーサービーズにより金属板に疵が入ったり、凹凸が生じてしまったりして、耐食性や機械的性質に悪影響を及ぼすことが懸念されるため、スペーサービーズを樹脂からなるものから選択し、そのヤング率Ｙbが、金属板のヤング率Ｙmに対して、Ｙb≦Ｙm／５を満たすことが好ましい。
【００２６】
そして、スペーサービーズに使用する樹脂は、熱硬化性樹脂であるか、熱可塑性樹脂の場合ＪＩＳ−Ｋ−６８６３に規格されたホットメルト接着剤の軟化点試験方法で求めた軟化温度ＳＴbが、接着層の軟化温度ＳＴadよりも高い樹脂から選択されることが好ましい。ＳＴbがＳＴad以下では、接着時にスペーサービーズが機能を果たさない。
【００２７】
接着性塗膜形成時の焼付温度(最高到達板温)、接着時の焼付温度(最高到達板温)は、共にＳＴb以下であり且つＳＴadより高い温度に設定する。
【００２８】
スペーサービーズへの適用が好ましい樹脂としては、例えば、アクリル樹脂、ポリエステル、ポリウレタン、ポリスチレン、塩化ビニル、フッ素樹脂、シリコン樹脂等が挙げられる。スペーサービーズの含有量は、少なすぎるとスペーサーとしての働きが不十分であり、また多すぎても接着力の低下を引き起こす可能性があるので、接着層に対する体積比で０．１〜２５％とする。
【００２９】
本発明の有機被覆金属板に用いる金属板としては、例えば、冷延鋼板、熱延鋼板、ステンレス鋼板、アルミ板、チタン板、銅板等や、これら金属板上にめっき処理した金属板が挙げられる。この内、鋼板上にめっき処理したの例として、溶融亜鉛めっき鋼板、電気亜鉛めっき鋼板、合金化溶融亜鉛めっき鋼板、アルミめっき鋼板、アルミ−亜鉛合金めっき鋼板、亜鉛−アルミ−マグネシウム合金めっき鋼板、亜鉛−アルミ−マグネシウム−シリコン合金めっき鋼板、亜鉛−マグネシウム合金めっき鋼板、錫めっき鋼板、鉛めっき鋼板、クロムめっき鋼板等の各種めっき鋼板が挙げられる。
【００３０】
これらの金属板をそのままあるいは通常の化成処理を施して使用すればよい。化成処理には、一般に公知の化成処理、例えば、塗布クロメート処理、電解クロメート処理、りん酸亜鉛処理や近年開発されている６価クロムを含まないノンクロメート処理等を使用することができる。また、化成処理前に、アルカリ脱脂等の通常の処理を行うことができる。さらに、化成処理の前にＮｉ表面調整を行うと、塗膜との密着性が向上し、好適である。
【００３１】
また、接着層と金属板との接着性を向上させるために、プライマー処理を施した金属板を使用してもよい。例えば、ナイロン、ポリアクリル、ポリエチレン、ポリプロピレン、ポリエステル、ポリウレタン、エポキシ、ポリアミド、フェノール、ポリオレフィン等が挙げられ、プレコート鋼板のプライマーとして使用しているものを適用することもできる。プライマー中には防錆剤を添加してもよい。なお、プライマー処理は片面でも両面でもよい。
【００３２】
片面に接着層、他方の面には公知のプレコート鋼板と同等な塗膜や潤滑性塗膜を塗布することも可能で、潤滑樹脂を塗布した場合、プレス油を使用しなくてもプレス成型が可能なため、プレス油洗浄の手間が省けるだけでなく、接着面にプレス油が付着する心配が無く、より安定した接着力を提供できる。
【００３３】
有機被覆の金属板表面への塗布方法は、いずれも特に限定されず、一般的に公知の塗装方法、例えば、ロールコート法、ローラーカーテンコート法、カーテンフロー法、エアスプレー法、エアレススプレー法、浸漬法、バーコート法、ドクターブレード法、静電法、刷毛塗り法、Ｔ−ダイ法、ラミネート法等が採用できる。
【００３４】
【実施例】
実施例に基づき、本発明をさらに説明する。
【００３５】
評価に用いた有機被覆金属板の作成方法について述べる。
【００３６】
金属板には塗布型クロメート処理を施した厚さ０．８ｍｍ電気亜鉛めっき鋼板、接着層には平均分子量３００００のナイロン系樹脂からなる熱可塑性ホットメルト接着剤と、水系ウレタン樹脂（三井武田ケミカル株式会社製 タケラックXW-725-B63A）１００重量部に対して硬化剤（三井武田ケミカル株式会社製 タケネートWD-700）を５重量部添加した熱硬化性ホットメルト接着剤を用い、それら接着剤に表１に示したビーズを混和したものを焼付後の膜厚が１０μｍになるように塗布した。ナイロン系接着剤は、表２に示した各焼付温度(最高到達板温度)になるようオーブンで焼付けた後、速やかに水冷し、接着性有機被覆金属板を得た。得られた有機被覆鋼板についてＤＳＣで融解ピークを測定した。融解ピーク強度は、樹脂の融点以上の温度から室温空冷により硬化させたもののピーク強度と比較したときの比率を示した。また、ウレタン系接着剤は55℃で5分間かけて乾燥し、接着性有機被覆金属板を得た。
【００３７】
【表１】
【表２】
以下、物性評価試験方法について述べる。
（剪断強度試験）
２５ｍｍ×１００ｍｍのテストピースの接着剤塗布面同士を２５ｍｍ×１２．５ｍｍの面積だけ重ね、ホットプレスで１分間加熱圧着した。圧着荷重は０.１ＭＰａ、加熱温度は１６０℃とした。その後、引張剪断試験を行い、強度が８０ＭＰａ以上を◎、５０ＭＰａ以上８０ＭＰａ未満を○、２０ＭＰａ以上５０ＭＰａ未満を△、２０ＭＰａ未満を×とした。なお、引張剪断試験は、同種の試験片につき５回ずつ行い、平均強度だけでなく、ばらつきについても確認した。
（圧着時にスペーサービーズによって生じる金属板への疵）
接着後の外観だけでなく、剪断剥離後、接着剤塗布面側にスペーサービーズによる疵、凹凸が生じているかどうかを確認した。接着剤塗布面に、疵、凹凸ともない場合は○、疵、凹凸いずれかがある場合は×とした。
【００４０】
以上の試験結果を表３に示す。
【００４１】
【表３】
実施例１〜５のように、接着層の合計厚さより粒径が小さく、融点が接着剤の融点より高いスペーサービーズを混和したものでは、スペーサービーズ未混和のものと比較して、高く安定した剪断強度が認められた。
【００４３】
その中でも、実施例１、実施例４及び実施例５のように、１％混和したものでは、特に高く安定した剪断強度が認められた。さらに、実施例１や実施例５のように、ヤング率が金属板（亜鉛：１０×１０10 Ｐａ、鉄：２０×１０10 Ｐａ）の１／５より小さい２.６５×１０9 Ｐａのスペーサービーズを混和したものでは、スペーサービーズによる金属板への疵は認められなかった。
【００４４】
比較例２のように、スペーサービーズの融点が接着層の融点より低いスペーサービーズを使った場合は、スペーサービーズを入れた効果は全く認められなかった。比較例３及び比較例４のように、スペーサービーズの粒径が接着層の合計厚さよりも大きいスペーサービーズを混和したものでは、スペーサービーズ未混和のものより接着強度が劣った。実施例４及び比較例４のように、ヤング率が金属板の１／５より大きい１．０８×１０10 Ｐａのスペーサービーズを混和したものでは、スペーサービーズによる金属板への疵が認められた。
【００４５】
【発明の効果】
本発明により、接着剤をプレコートした金属板で、安定した接着力を得ることができるようになったことから、これまで、手間がかかり、コスト高なリベットやカシメ等の機械的接合で接合しなくてならなかった箇所に、接着剤をプレコートした金属板を用いることができるようになったため、金属板ユーザーで金属板を接合する際の手間、コストが大幅に低減される。したがって、本発明は極めて産業上の価値の高い発明であるといえる。[0001]
BACKGROUND OF THE INVENTION
TECHNICAL FIELD The present invention relates to an organic coated metal plate having adhesiveness and a method for bonding a metal plate using the same, and in particular, in bonding of a metal plate with an adhesive, in which bonding strength tends to vary depending on bonding conditions. The present invention relates to an organic coated metal plate excellent in adhesion stability and a metal plate adhesion method.
[0002]
[Prior art]
In fields such as building materials, home appliances, miscellaneous goods, automobiles, etc., in order to give other performance and design to the processed metal plate, an adhesive is applied on the metal plate and a predetermined target member is laminated. . In that case, it is common for the user who uses a metal plate to perform the operation | work of the application | coating of an adhesive agent from the process of a metal plate, and the lamination | stacking operation | work of a member.
[0003]
However, the above work has problems such as response to environmental pollution due to the use of organic solvents, labor shortage, and capital investment. In order to solve such problems, a metal plate pre-coated with an adhesive has been developed. Yes.
[0004]
For example, JP-A-6-316028 and JP-A-8-258218 disclose a hot-melt adhesive precoated on a metal plate. In the invention described in Japanese Patent Application Laid-Open No. 8-258218, the blocking resistance, which is a problem that is a problem in Japanese Patent Application Laid-Open No. 6-316028, does not adhere even when the front and back surfaces are crimped at the time of shipment is improved. ing.
[0005]
[Problems to be solved by the invention]
However, the metal plate pre-coated with the adhesive as in JP-A-8-258218 can solve the problem at the time of applying the adhesive to the metal plate and the problem such as blocking resistance, Due to variations in the force applied to the bonded portion during bonding, there is a problem that the adhesive thickness of the bonded portion tends to vary, making it difficult to obtain a stable adhesive force. For this reason, joining of metal plates with an adhesive pre-coated metal plate is not an alternative to costly mechanical joining such as caulking or rivet from the viewpoint of reliability.
[0006]
Therefore, the present invention is to solve the above-mentioned problems, and to provide an organic coated metal plate and a metal plate bonding method that eliminates variations in the adhesive thickness of the bonded portion and has excellent adhesion stability. It is said.
[0007]
[Means for Solving the Problems]
In the present invention, it was found that the dispersion of the adhesive force can be suppressed by inserting spacer beads in the adhesive pre-coated on the metal plate for the purpose of keeping the adhesive thickness constant at the time of bonding. The present invention has been completed based on the present invention, and the gist of the present invention is as follows.
[0008]
(1) An organic coated metal sheet adhesive layer is bonded to the adherend material is not provided on the adhesive surface, on one or both sides, made of a resin that express adhesion by heating to a bonding temperature thickness There have a bonding layer of 0.5 to 100 [mu] m, containing 0.1 to 25% spacer beads for adjusting the adhesive layer thickness to the adhesive layer in a volume ratio with respect to the adhesive layer, the average of the spacer beads An organic coated metal plate having excellent adhesion stability, wherein the particle diameter Db is smaller than the thickness of the adhesive layer.
(2) An organic-coated metal plate to be bonded to a material to be bonded, which is provided with an adhesive layer having a thickness of 0.5 to 100 μm on the bonding surface, and is bonded to one surface or both surfaces by heating to a bonding temperature. have a bonding layer thickness made of resin is a 0.5~100μm expressing force, the spacer beads for adjusting the adhesive layer thickness to the adhesive layer in a volume ratio with respect to the adhesive layer 0.1 to 25 %, And the spacer beads have an average particle diameter Db smaller than the total thickness Dad of the adhesive layers on both sides.
[0009]
( 3 ) The spacer bead is a thermosetting material or a thermoplastic material having a softening temperature determined by a softening point test method of a hot melt adhesive specified in JIS-K-6863 higher than the softening temperature of the adhesive. An organic coated metal sheet having excellent adhesion stability according to (1) or (2) .
[0011]
( 4 ) Any of the above (1) to (3), wherein the spacer beads are made of a resin, and the Young's modulus Yb satisfies Yb ≦ Ym / 5 with respect to the Young's modulus Ym of the metal plate . An organic coated metal plate having excellent adhesion stability described in 1.
[0012]
(5) A method of adhering an organic coated metal plate having an adhesive layer having a thickness of 0.5 to 100 μm made of a resin that develops an adhesive force by heating to one or both surfaces to an adhesion temperature. The surface of the material to be adhered is not provided with an adhesive layer, and the adhesive layer contains spacer beads for adjusting the adhesive thickness in a volume ratio of 0.1 to 25% with respect to the adhesive layer, and the adhesive layer A metal plate bonding method having excellent bonding stability, wherein the spacer beads have an average particle diameter Db smaller than the thickness of the bonding layer.
(6) A method of adhering an organic coated metal plate having an adhesive layer having a thickness of 0.5 to 100 μm made of a resin that develops an adhesive force by heating to one or both surfaces to an adhesion temperature, to an adherend material. In addition, an adhesive layer having a thickness of 0.5 to 100 μm is also provided on the surface of the material to be adhered, and spacer beads for adjusting the adhesive thickness of the adhesive layer are 0.1 to 0.1 by volume with respect to the adhesive layer. A metal plate bonding method excellent in bonding stability, comprising 25%, wherein an average particle diameter Db of the spacer beads of the bonding layer is smaller than a total thickness Dad of the thicknesses of the bonding layers on both sides.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0015]
First, the resin that can be used for the adhesive coating film in the present invention does not have an adhesive force at normal (room temperature), softens by heating, and exhibits adhesiveness. It may be curable, such as a type that reacts and cures, or a type that crosslinks and cures by heating further than the softening temperature. For example, ethyl cellulose, vinyl acetate and its derivatives, polyethylene, ethylene vinyl acetate copolymer, butyl methacryl, polystyrene and copolymer, poisobutylene, polypropylene, nylon, polyester, polyacryl, ethylene terpolymer, phenoxy, trans Examples of suitable resins include polyisoprene, polysulfone, polyallylsulfene, polyurethane, epoxy, polyamide, phenol and polyolefin.
[0016]
Among these, resins having high crystallinity such as nylon, polyacryl, polyethylene, polypropylene, and polyester are particularly excellent in non-adhesiveness at normal time (at room temperature). In the present invention, it is desirable to be excellent in processing and molding, and it is preferable to select a resin having good elongation.
[0017]
When using a nylon resin, if the melting peak of differential scanning calorimetry is below 50 ° C., the blocking resistance is inferior. On the other hand, even if the temperature at which the melting peak appears is too high, the heating temperature required for adhesion is high. Therefore, it is not preferable from the viewpoint of work. Therefore, it is desirable that a melting peak does not exist at 50 ° C. or lower and a melting peak exists at a temperature range higher than 50 ° C. and 200 ° C. or lower. The melting peak can be measured with a commercially available differential scanning calorimeter (DSC).
[0018]
The intensity of the differential scanning calorimetry melting peak may be 10 to 100% of the differential scanning calorimetry melting peak of the resin cured from 170 ° C. by standing at room temperature. If it is less than 10%, the non-adhesiveness at the normal time cannot be obtained. Further, if the molecular weight is less than 5,000, the moldability is inferior, and if the molecular weight exceeds 80000, the blocking resistance is lowered. Therefore, it is most desirable to use nylon having a molecular weight of 5000 to 80000.
[0019]
In order to suppress the crystallization rate, for example, a non-crystalline resin such as polyester, polyurethane, polyacryl, epoxy, polyamide, phenol, polyolefin may be blended. Moreover, an epoxy resin, a melamine resin, a polyisocyanate resin, a phenol resin, or the like can be used as a curing agent. At that time, the amount of the curing agent and the baking temperature should be selected such that the adhesive strength is not lost.
[0020]
The resin used for the adhesive layer may be in any form such as solvent type, melt type, water-based, powder, etc. In addition, various additives such as pigments, dyes, fillers, rust inhibitors, etc. are added to the resin used for the adhesive layer You can also
[0021]
If the film thickness of the adhesive organic film is less than 0.5 μm, the adhesiveness is lost. If the film thickness is more than 100 μm, the organic coating may peel off during the molding process of the metal plate. Even if it is applied, the adhesive strength is saturated and uneconomical, so the thickness is set to 0.5 to 100 μm.
[0022]
In the present invention, spacer beads are included in the adhesive layer in order to prevent the adhesive layer from varying in thickness depending on how the adhesive pressure is applied and the adhesive strength from being varied. Regarding the particle size of the spacer beads, the average particle size needs to be smaller than the total thickness of the adhesive layer. The total thickness of the adhesive layer is the thickness of the adhesive layer of the metal plate of the present invention when there is no adhesive layer on the surface to be bonded, and each surface when the adhesive layer is also present on the surface to be bonded. This is the total thickness of the adhesive layers provided on the surface.
[0023]
That is, the total thickness of the adhesive layer when D ad, the average particle diameter of spacer beads and D b, and D b <D ad. The reason for this is that when the average particle size of the spacer beads is larger than the thickness of the adhesive layer, the adhesive is relatively insufficient with respect to the adhesive thickness (distance between the metal plates to be bonded) corresponding to the particle size of the spacer beads. For this reason, it becomes impossible to uniformly adhere to the adherend surface, resulting in insufficient adhesive strength.
[0024]
The average particle size of the spacer beads is preferably 200 μm or less at maximum. The reason for this is that even if the thickness at the time of adhesion becomes thicker than a certain level, the adhesive force is saturated, which is uneconomical.
[0025]
The spacer beads may be selected from inorganic materials such as metal powder and glass powder as long as they do not soften or thermally decompose at the temperature at which the adhesive layer is bonded, but function as a spacer. If spacer beads that are harder than the metal plate are used, when the adhesive is applied under high pressure, the metal beads may be wrinkled or uneven by the spacer beads, adversely affecting the corrosion resistance and mechanical properties. Therefore, it is preferable that the spacer beads are selected from those made of resin and the Young's modulus Y b satisfies Y b ≦ Y m / 5 with respect to the Young's modulus Y m of the metal plate.
[0026]
The resin used for the spacer beads is a thermosetting resin, or in the case of a thermoplastic resin, the softening temperature ST b obtained by the softening point test method of the hot melt adhesive standardized in JIS-K-6863 is The resin is preferably selected from resins having a temperature higher than the softening temperature ST ad of the adhesive layer. When ST b is equal to or less than ST ad , the spacer beads do not function during adhesion.
[0027]
The baking temperature (maximum ultimate plate temperature) at the time of forming the adhesive coating film and the baking temperature (maximum ultimate plate temperature) at the time of adhesion are both set to be lower than ST b and higher than ST ad .
[0028]
Examples of the resin that is preferably applied to the spacer beads include acrylic resin, polyester, polyurethane, polystyrene, vinyl chloride, fluororesin, and silicon resin. If the content of the spacer beads is too small, the function as a spacer is insufficient, and if the content is too large, it may cause a decrease in the adhesive strength, so the volume ratio with respect to the adhesive layer is 0.1 to 25% . To do .
[0029]
Examples of the metal plate used in the organic coated metal plate of the present invention include a cold-rolled steel plate, a hot-rolled steel plate, a stainless steel plate, an aluminum plate, a titanium plate, a copper plate, and a metal plate plated on these metal plates. . Among these, as examples of plating treatment on steel plates, hot dip galvanized steel plates, electrogalvanized steel plates, alloyed hot dip galvanized steel plates, aluminum plated steel plates, aluminum-zinc alloy plated steel plates, zinc-aluminum-magnesium alloy plated steel plates, Various plated steel sheets such as zinc-aluminum-magnesium-silicon alloy-plated steel sheet, zinc-magnesium alloy-plated steel sheet, tin-plated steel sheet, lead-plated steel sheet, chrome-plated steel sheet and the like can be mentioned.
[0030]
These metal plates may be used as they are or after being subjected to ordinary chemical conversion treatment. For the chemical conversion treatment, generally known chemical conversion treatments such as coating chromate treatment, electrolytic chromate treatment, zinc phosphate treatment, and recently developed non-chromate treatment containing no hexavalent chromium can be used. Moreover, normal processes, such as alkali degreasing, can be performed before chemical conversion treatment. Furthermore, if the Ni surface is adjusted before the chemical conversion treatment, the adhesion with the coating film is improved, which is preferable.
[0031]
Moreover, in order to improve the adhesiveness between the adhesive layer and the metal plate, a metal plate subjected to primer treatment may be used. For example, nylon, polyacryl, polyethylene, polypropylene, polyester, polyurethane, epoxy, polyamide, phenol, polyolefin and the like can be mentioned, and those used as a primer for a pre-coated steel plate can also be applied. A rust inhibitor may be added to the primer. The primer treatment may be performed on one side or both sides.
[0032]
It is possible to apply an adhesive layer on one side, and a coating film equivalent to a known pre-coated steel plate or a lubricating coating film on the other side. When a lubricating resin is applied, press molding can be performed without using press oil. As a result, it is possible not only to save labor for washing the press oil, but also to provide a more stable adhesive force without fear of the press oil adhering to the adhesive surface.
[0033]
The method for applying the organic coating to the surface of the metal plate is not particularly limited, and generally known coating methods such as a roll coating method, a roller curtain coating method, a curtain flow method, an air spray method, an airless spray method, A dipping method, a bar coating method, a doctor blade method, an electrostatic method, a brush coating method, a T-die method, a laminating method and the like can be employed.
[0034]
【Example】
The invention is further described based on examples.
[0035]
A method for producing an organic coated metal plate used for evaluation will be described.
[0036]
0.8 mm thick electrogalvanized steel sheet with coated chromate treatment on the metal plate, thermoplastic hot melt adhesive made of nylon resin with an average molecular weight of 30000 for the adhesive layer, and aqueous urethane resin (Mitsui Takeda Chemical Co., Ltd.) Takelac XW-725-B63A made by the company) Using 100 parts by weight of a thermosetting hot melt adhesive in which 5 parts by weight of a curing agent (Takenate WD-700 made by Mitsui Takeda Chemical Co., Ltd.) was added. A mixture in which the beads shown in 1 were mixed was applied so that the film thickness after baking was 10 μm. The nylon adhesive was baked in an oven so as to have each baking temperature shown in Table 2 (maximum reached plate temperature), and then quickly cooled with water to obtain an adhesive organic coated metal plate. The melting peak was measured by DSC for the obtained organic coated steel sheet. The melting peak intensity indicates a ratio when compared with the peak intensity of the resin cured by air cooling at room temperature from a temperature equal to or higher than the melting point of the resin. The urethane adhesive was dried at 55 ° C. for 5 minutes to obtain an adhesive organic coated metal plate.
[0037]
[Table 1]
[Table 2]
The physical property evaluation test method will be described below.
(Shear strength test)
The adhesive-coated surfaces of 25 mm × 100 mm test pieces were overlapped with each other by an area of 25 mm × 12.5 mm, and heat-pressed for 1 minute with a hot press. The pressure bonding load was 0.1 MPa, and the heating temperature was 160 ° C. Thereafter, a tensile shear test was performed. The strength was 80 MPa or more, ◎, 50 MPa or more and less than 80 MPa, ○, 20 MPa or more and less than 50 MPa, Δ, and less than 20 MPa as ×. The tensile shear test was performed five times for each test piece of the same type, and not only the average strength but also the variation was confirmed.
(Wrinkles on the metal plate caused by spacer beads during crimping)
In addition to the appearance after bonding, it was confirmed whether or not wrinkles or irregularities due to spacer beads were generated on the adhesive-coated surface side after shear peeling. When there were neither wrinkles nor irregularities on the adhesive application surface, it was marked as “C” when there were either wrinkles or wrinkles.
[0040]
The above test results are shown in Table 3.
[0041]
[Table 3]
As in Examples 1 to 5, a mixture of spacer beads having a particle size smaller than the total thickness of the adhesive layer and a melting point higher than the melting point of the adhesive was higher and more stable than that without spacer beads. Shear strength was observed.
[0043]
Among them, a particularly high and stable shear strength was observed when 1% was mixed as in Example 1, Example 4, and Example 5. Furthermore, like Example 1 and Example 5, the Young's modulus is 2.65 × 10 9 Pa spacer smaller than 1/5 of the metal plate (zinc: 10 × 10 10 Pa, iron: 20 × 10 10 Pa). When the beads were mixed, no wrinkles on the metal plate by the spacer beads were observed.
[0044]
As in Comparative Example 2, when spacer beads having a melting point of the spacer beads lower than the melting point of the adhesive layer were used, the effect of adding the spacer beads was not recognized at all. As in Comparative Example 3 and Comparative Example 4, when the spacer beads were mixed with spacer beads having a particle diameter larger than the total thickness of the adhesive layer, the adhesive strength was inferior to that without spacer beads. As in Example 4 and Comparative Example 4, in the case of mixing 1.08 × 10 10 Pa spacer beads having a Young's modulus larger than 1/5 of the metal plate, wrinkles on the metal plate due to the spacer beads were observed. .
[0045]
【The invention's effect】
According to the present invention, a stable adhesive force can be obtained with a metal plate pre-coated with an adhesive. So far, it takes time and is costly to join by mechanical joining such as rivets and caulking. Since it is possible to use a metal plate pre-coated with an adhesive at a necessary location, labor and cost for joining the metal plate by the metal plate user can be greatly reduced. Therefore, the present invention can be said to be an invention with extremely high industrial value.
Claims (6)
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| JP2003080157A JP4374203B2 (en) | 2002-08-08 | 2003-03-24 | Organic coated metal plate with excellent adhesion stability and adhesion method |
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| JP6605852B2 (en) * | 2015-06-22 | 2019-11-13 | 日鉄建材株式会社 | Design metal plate and manufacturing method thereof |
| JP6651324B2 (en) * | 2015-10-09 | 2020-02-19 | 日鉄日新製鋼株式会社 | Composite and method for producing the same |
| KR20230156169A (en) | 2018-05-31 | 2023-11-13 | 세키스이가가쿠 고교가부시키가이샤 | Spacer particles, adhesive agent and adhesive structural body |
| JP6753992B2 (en) * | 2019-09-17 | 2020-09-09 | 日鉄建材株式会社 | Composition for upper adhesive layer and composition for lower adhesive layer |
| JP7381852B2 (en) * | 2019-10-01 | 2023-11-16 | 日本製鉄株式会社 | Joiner manufacturing method and its manufacturing device, coated metal shape material manufacturing method and its manufacturing device |
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