JP4669196B2 - Bonding medium, bonding structure and precoat material excellent in peel strength - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、接合媒体、接合構造体及びプレコート材に関するものであり、特に高い剥離強度を示す接合媒体、接合構造体及びプレコート材に関する。
【０００２】
【従来の技術】
接合媒体中に粒子等の充填剤を混和する例としては、接着剤の例がある。その目的としては、山口章三郎 監修「接着」(1981年6月、朝倉書店発行、P.43)では、１）粘度を高くする、また粘性を変える、２）固形分を高くして固化収縮を小さくして空隙充填性をよくする、３）硬化接着剤の熱膨張係数を低下させて、膨張係数の異なる比着体の接着をする、４）熱伝導性をよくする、５）接着層を厚くする、又は一定厚さにするためにビーズを入れる、６）電気伝導性をあたえる、７）着色する、８）硬度のアップ、また見掛け耐熱性の向上、９）コストダウン、が記載されている。このように、固化後の接着そのものの機械的強度については、より硬くすることを目的として充填剤を混和するというのが一般的であるが、接着剤の硬度を上げるためには、充填剤として混和される粒子と接着剤との密着性が高いことが前提とされる。
【０００３】
【非特許文献１】
山口章三郎 監修「接着」(1981年6月、朝倉書店発行、P.43, P.84)
【非特許文献２】
芝崎一郎著「接着百科(上)」(1975年3月、高分子刊行会発行、P.60)
【０００４】
【発明が解決しようとする課題】
接着剤による接合を代表とする接合媒体層を介しての接合は、機械的接合と違い、接合面全体による接合であるため、面全体で力を受けるような破壊には強く、高い剪断強度を有する接合が可能である。しかし、剥離のように応力が局部的に集中しやすいような破壊には弱く、接着剤による接合の短所として知られており、山口章三郎 監修「接着」(1981年6月、朝倉書店発行、P.84)や芝崎一郎著「接着百科(上)」(1975年3月、高分子刊行会発行、P.60)にも欠点、短所として記載されている。本発明は、これら課題を解決するものであり、より高い剥離強度が得られる接合媒体及び接合構造体等を提供することをその課題としている。
【０００５】
【課題を解決するための手段】
本発明では、接合媒体に接合媒体中の密着性を発現する成分を含有する密着性が低い粒子を混和すると、接合構造体剥離時に、接合媒体中の密着性を発現する成分と混和した粒子が離れて、混和した粒子の周りに空隙を生じ、接合媒体層の変形に対する自由度が高くなることで、粒子を混和していないものよりも高い剥離強度が得られることを見出し、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通りである。
(１) 少なくともアクリル樹脂又はその共重合体（エラストマーを除く）からなる粒子と密着性を発現する成分としてポリアミド系ホットメルト接着剤を含有する接合媒体であって、前記密着性を発現する成分単味で構造体を接合した際の剥離強度の90%以上の力が前記接合媒体にかかった場合に、前記粒子の視野投影長さの30%以上が前記密着性を発現する成分から剥離した粒子を少なくとも有することを特徴とする剥離強度に優れた接合媒体。
(２) 前記剥離した粒子が全体の50%以上である(１)に記載の剥離強度に優れた接合媒体。
(３) 前記粒子が、短軸:長軸=4:6〜5:5のアスペクト比の球状粒子である(１)又は（２）の何れかに記載の剥離強度に優れた接合媒体。
(４) 前記粒子の含有量が、5体積%〜25体積%であることを特徴とする(１)〜(３)の何れかに記載の剥離強度に優れた接合媒体。
(５) 前記粒子の粒径が0.1μm〜100μmであることを特徴とする(１)〜(４)の何れかに記載の剥離強度に優れた接合媒体。
(６) 少なくとも(１)〜(５)の何れかに記載の接合媒体を配して構造体と構造体を接合してなることを特徴とする剥離強度に優れた接合構造体。
(７) (１)〜(５)の何れかに記載の接合媒体を母材表面の少なくとも一部に被覆してなるプレコート材料。
(８) 前記母材が金属板であることを特徴とする(７)記載のプレコート材料。
(９) (７)又は(８)に記載のプレコート材料と被着材が接合してなる接合構造体。
【０００６】
【発明の実施の形態】
以下、本発明について詳細に説明する。
【０００７】
本発明は接合媒体に特徴があり、接合媒体中に粒子を含み、その粒子が接合媒体中の密着性を発現する成分との密着性が低いことを特徴としている。そうすることで、その接合媒体を用いて接合した接合構造体を剥離する等、接合媒体層を変形させようとする力が働いたときに、接合媒体層中の密着性を発現する成分と接合媒体中に混和した粒子が、接合媒体層が破断する前に剥離して接合媒体層中の密着性を発現する成分と粒子の間に空隙を生じることで、接合媒体層に変形の自由度や柔軟性を与える。そのため、剥離の方向に力がかかった際にその応力が一ヶ所に集中せず、高い剥離強度を得ることができる。
【０００８】
接合媒体中の密着性を発現する成分と粒子とが剥離し空隙を生じることは、接合媒体層の凝集破壊によって剥離する構造体を接合剥離した場合、剥離面を顕微鏡や走査型電子顕微鏡で観察することによって確認できる。接合媒体層に柔軟性を持たせるためには、剥離面の法線方向から走査型電子顕微鏡等で観察して、粒子を平面的に円として見たとき、図１の剥離部のように粒子と密着性を発現する成分との間に空隙を生じている部分が粒子の周囲の長さにして30%以上ある粒子を少なくとも含まなくてはならない。粒子と接合媒体の密着性を発現する成分との密着性が高く、視野投影長さの30%以上が剥離する粒子を含まない場合は、一般的な充填材の効果として知られる接合媒体の硬度を高くする効果の方が強く出る可能性が高く、接合媒体層に十分な柔軟性を与えられない可能性がある。また、剥離面の法線方向から走査型電子顕微鏡等で観察して、50%以上の粒子が前記のような剥離をすることが望ましい。前記のような剥離をし、周りに空隙を生じる粒子が50%に満たない場合も、接合媒体の硬度を高くする効果の方が強く出る可能性が高く、接合媒体層に十分な柔軟性を与えられない可能性がある。
【０００９】
また、空隙は接合媒体層を変形させるような力が働く前から存在していても構わない。
【００１０】
ここでは、接合媒体の定義のため、接合媒体の状態を確認しやすい系として、密着性を発現する成分単身で構造体を接合、剥離をした際、凝集破壊により剥離する系で本発明の接合媒体について説明したが、実際は、接合媒体と構造体の界面破壊により剥離する系でも、密着性を発現する成分との密着性が低い粒子を密着性を発現する成分に混和することによる剥離強度の向上は認められる。
【００１１】
接合媒体中に混和する粒子の形状は特定されないが、接合構造体の剥離等、接合媒体層変形時に応力が接合媒体層に分散してかかるようにするため、アスペクト比4:6〜5:5程度の球状であるものが望ましい。ここでアスペクト比は最長軸とその最長軸の中心で垂直に交わる軸の最短軸との比である。
【００１２】
接合媒体中に混和する粒子の割合は、体積割合で5%〜25%程度が望ましい。5%以下では十分な効果を発揮できない可能性があり、25%以上では接着剤の強度を下げてしまう可能性がある。
【００１３】
接合媒体中に混和する粒子の粒径は、0.1μm〜100μmであることが望ましく、さらに接合時に必要とする接合媒体層の厚さよりも小さいことが望ましいが、接合媒体に混和する粒子の粒径を接合時に希望する接合媒体層の厚さにあわせれば、粒子が接合時の接合媒体層の厚さを一定に保つスペーサーとしての役割を果すことも可能で、それにより、さらに安定した接合強度が得やすくなる。
【００１４】
粒子の材質は、アクリルまたは、その共重合体（エラストマーを除く）である。
【００１６】
また、これらの粒子は単独で用いでも構わないが、2種類以上を混合しても構わない。
【００１７】
一方、密着性を発現する成分は、ポリアミド系ホットメルト接着剤である。
【００１８】
構造体を接合媒体で接合する際の接合媒体の使用方法としては、接合したい箇所に接合媒体を塗布、その後接合媒体が硬化する前に接合するといった一般的な方法でももちろん使用できるが、接合媒体が常温では接着力を有せず、加熱することにより接着力を発現するポリアミド系ホットメルト接着剤を使用することから、事前に接着剤の塗布だけを行い、接合したいときに接合したい部分を重ね合わせ、加熱圧着することで接合できる接合部材を作ることもできる。例えば、塗装鋼板製造ライン、フィルムコーティングライン等の塗装ラインで平板状の母材に接着剤の塗布、乾燥を行い、その接着剤を被覆してなるプレコート材料を加工成型した後、加熱圧着することで接合するといった方法も考えられる。
【００２０】
ポリアミド系樹脂を使用する場合には、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のポリアミド樹脂を使用することが望ましい。
【００２３】
プレコートする接着剤は、溶剤型、溶融型、水系、紛体等、どの形態のものでもよい。
【００２４】
上記接合媒体と接合される構造体は特に限定されるものではなく、金属、ガラス、セラミック、プラスチック、ゴム、紙、布、皮革等の各種材料が挙げられる。
【００２５】
金属の例では、金属板として、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が挙げられる。
【００２６】
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く、化成処理として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、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表面調整を行うこともできる。
【００２７】
また、接着剤と構造体との接着性を向上させるために、構造体に対してプライマー処理を施してもよい。たとえば、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、プレコート金属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。
【００２８】
構造体にとしての金属板に接着剤をプレコートする場合、接着剤の塗布は金属板の両面でも片面でもよく、片面に接着剤、他方の面には公知のプレコート金属板と同等な塗膜や潤滑性塗膜を塗布することも可能である。接着剤をプレコートした金属板は、接着剤を塗布した後、プレス等の加工成型を加えた後に加熱圧着する使用形態が多いが、接着剤をプレコートした面の裏面に潤滑性の塗膜を塗布した場合、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。
【００２９】
構造体に接着剤を塗布する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、刷毛塗り法、浸漬法、バーコート法、静電法、T-ダイ法、ラミネート法等が採用できる。
【００３０】
【実施例】
以下、接合媒体によって接合した接合構造体の作成方法、剥離試験方法及び評価結果について述べる。
【００３１】
(実施例１〜５)
接合媒体としてポリアミド系ホットメルト接着剤(ヘンケルジャパン株式会社製マクロメルト6212)に、樹脂ビーズ(大日精化学工業株式会社製ラブコロール030(10MD)クリアー)を体積割合にして2.5%〜50%混和したものを用い、厚さ0.6mmクロメート処理亜鉛めっき鋼板に厚さ10μmになるようにバーコート法により塗装し、熱風乾燥炉で最高到達板温が180℃になるように乾燥した。ここで用いた樹脂ビーズは、アクリルコポリマーからなるアスペクト比4:6より真球状に近い粒径約10μmの粒子で、ポリアミド系ホットメルト接着剤との密着性が低いものである。それを25mm×200mmになるよう切断し、その板を端から50mmのところで接着剤を塗布していない面側へ90°折り曲げ、接着剤塗布面同士を重ね合わせ、180℃でホットプレスにより1分間圧着し、T字型の接合構造体を作成した。
【００３２】
(実施例6)
接合媒体として実施例1〜5で用いたポリアミド系ホットメルト接着剤に実施例1〜5で用いた樹脂ビーズを平均粒径約5μmの無定形状態に冷凍粉砕したものを体積割合にして10%混和したもの用い、厚さ0.6mmクロメート処理亜鉛めっき鋼板に厚さ10μmになるようにバーコート法により塗装し、熱風乾燥炉で最高到達板温が180℃になるように乾燥した。それを25mm×200mmになるよう切断し、その板を端から50mmのところで接着剤を塗布していない面側へ90°折り曲げ、接着剤塗布面同士を重ね合わせ、180℃でホットプレスにより1分間圧着し、T字型の接合構造体を作成した。
【００３３】
(比較例1)
接合媒体として実施例1〜5で用いたポリアミド系ホットメルト接着剤を用い、厚さ0.6mmクロメート処理亜鉛めっき鋼板に厚さ10μmになるようにバーコート法により塗装し、熱風乾燥炉で最高到達板温が180℃になるように乾燥した。それを25mm×200mmになるよう切断し、その板を端から50mmのところで接着剤を塗布していない面側へ90°折り曲げ、接着剤塗布面同士を重ね合わせ、180℃でホットプレスにより1分間圧着し、T字型の接合構造体を作成した。
【００３４】
(比較例2)
接合媒体として実施例1〜5で用いたポリアミド系ホットメルト接着剤に実施例1〜5で用いた樹脂ビーズにシランカップリング処理を施し、接着剤との密着性を高めたものを混和したものを用い、厚さ0.6mmクロメート処理亜鉛めっき鋼板に厚さ10μｍになるようにバーコート法により塗装し、熱風乾燥炉で最高到達板温が180℃になるように乾燥した。それを25mm×200mmになるよう切断し、その板を端から50mmのところで接着剤を塗布していない面側へ90°折り曲げ、接着剤塗布面同士を重ね合わせ、180℃でホットプレスにより1分間圧着し、T字型の接合構造体を作成した。
【００３５】
これら接合構造体に対し、ホットプレス24時間後、JIS K 6854-3に規格された剥離試験を行った。
【００３６】
【表１】
以上の試験結果を表1に示した。ここでの試験結果はいずれのサンプルについても5回ずつ試験を行った結果の平均値であり、剥離強度が4kN/m以上のものは◎、2kN/m以上4kN/m未満のものは○、1kN/m以上2kN/m未満のものは△、1kN/m未満のものは×とした。
【００３８】
実施例1〜6のように接合媒体の密着成分と密着性が低い粒子を2.5体積%〜50体積%混和するにすると、接着剤中に粒子を混和していない比較例と比較して剥離強度が向上した。また、これら剥離試験後の試験片を剥離面の法線方向から走査型電子顕微鏡で観察したところ、50%以上の粒子が視野投影長さの30%以上が剥離して空隙を生じていた。
【００３９】
しかし、実施例1のように粒子の少ないものや、実施例5のように粒子が多すぎるものでは、粒子を入れた効果がやや低かった。実施例6のように球状粒子を冷凍粉砕し、砕片状にしたものを混和した場合、粒子の混和量は最も高い剥離強度の向上が認められた実施例3と同じであるにも関わらず、形状の違いにより粒子を入れた効果はやや低かった。
【００４０】
比較例2のように、実施例1〜5に用いた粒子に対しシランカップリング処理を施し、接合媒体の密着成分との密着性を高めたものを混和した場合、粒子の混和量、形状が最も高い剥離強度の向上が認められた実施例3と同じであるにも関わらず、剥離強度の向上は認められなかった。また、剥離試験後の試験片を剥離面の法線方向から走査型電子顕微鏡で観察したところ、視野投影長さの30%以上が剥離して空隙を生じていた粒子は20%以下であった。
【００４１】
【発明の効果】
これまで、接合媒体による接合は、剥離強度が弱いことが欠点とされてきたが、本発明により、高位に安定した剥離強度を有する接合構造体、また、それを作成するための接合媒体、接着剤、接着剤プレコート材が得られるようになった。
これにより、これまで信頼性の問題から、カシメやリベット等、手間とコストのかかる機械的接合をしていた接合構造体でも、安価で容易な接合媒体による接合ができるようになった。したがって、本発明は、産業上極めて重要な発明である。
【図面の簡単な説明】
【図１】構造体を本発明の接合媒体で接合し、それが接合媒体の凝集破壊によって剥離した場合、剥離面の法線方向から顕微鏡や走査型電子顕微鏡で観察したときの粒子と密着性を発現する成分とが剥離している状態を説明するための図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a bonding medium, a bonding structure, and a precoat material, and particularly to a bonding medium, a bonding structure, and a precoat material that exhibit high peel strength.
[0002]
[Prior art]
As an example of mixing a filler such as particles in the bonding medium, there is an example of an adhesive. The purpose is “Adhesion” supervised by Shozaburo Yamaguchi (June 1981, published by Asakura Shoten, P.43) 1) Increase viscosity and change viscosity 2) Increase solid content and solidify shrinkage 3) Reduce the thermal expansion coefficient of the cured adhesive to adhere specific adhesives with different expansion coefficients, 4) Improve thermal conductivity, 5) Adhesive layer 6) Provide electrical conductivity, 7) Color, 8) Increase hardness, increase apparent heat resistance, 9) Reduce cost ing. Thus, the mechanical strength of the adhesive itself after solidification is generally mixed with a filler for the purpose of making it harder, but in order to increase the hardness of the adhesive, as a filler It is assumed that the adhesion between the particles to be mixed and the adhesive is high.
[0003]
[Non-Patent Document 1]
Supervised by Shozaburo Yamaguchi "Adhesion" (June 1981, published by Asakura Shoten, P.43, P.84)
[Non-Patent Document 2]
Ichiro Shibazaki “Adhesion Encyclopedia (above)” (published in March 1975, published by Kobunshi Shuppankai, p. 60)
[0004]
[Problems to be solved by the invention]
Unlike mechanical bonding, bonding via a bonding medium layer typified by bonding with an adhesive is bonding with the entire bonding surface. Can be joined. However, it is vulnerable to fractures where stress is likely to concentrate locally, such as peeling, and is known as a disadvantage of bonding with adhesives, and is supervised by Shozaburo Yamaguchi (June 1981, published by Asakura Shoten, P.84) and Ichiro Shibazaki's “Adhesion Encyclopedia (above)” (published in March 1975, published by Kobunshi Shuppankai, P.60) are also described as disadvantages and disadvantages. This invention solves these subjects, and makes it the subject to provide the joining medium, joining structure, etc. from which higher peeling strength is obtained.
[0005]
[Means for Solving the Problems]
In the present invention, when particles having low adhesion containing a component that expresses adhesion in the bonding medium are mixed in the bonding medium, the particles mixed with the component that expresses adhesion in the bonding medium when the bonded structure is peeled off. Based on this finding, it was found that voids are created around the mixed particles and the bonding medium layer has a higher degree of freedom in deformation, so that a higher peel strength can be obtained than when the particles are not mixed. The present invention has been completed and the gist of the present invention is as follows.
(1) A joining medium containing a polyamide-based hot-melt adhesive as a component that exhibits adhesion with particles composed of at least an acrylic resin or a copolymer thereof (excluding an elastomer). When a force of 90% or more of the peel strength when the structure is bonded with the taste is applied to the bonding medium, 30% or more of the projected field length of the particles is peeled off from the component exhibiting the adhesion A bonding medium having excellent peel strength, characterized by comprising at least
(2) The bonding medium having excellent peel strength according to (1), wherein the peeled particles are 50% or more of the whole.
(3) The bonding medium having excellent peel strength according to any one of (1) and (2), wherein the particles are spherical particles having an aspect ratio of minor axis: major axis = 4: 6 to 5: 5.
(4) The bonding medium having excellent peel strength according to any one of (1) to (3), wherein the content of the particles is 5% by volume to 25% by volume.
(5) The bonding medium having excellent peel strength according to any one of (1) to (4), wherein a particle diameter of the particles is 0.1 μm to 100 μm.
(6) A bonded structure excellent in peel strength, comprising at least the bonding medium according to any one of (1) to (5) and bonding the structure and the structure.
(7) A precoat material obtained by coating at least a part of the surface of a base material with the joining medium according to any one of (1) to (5).
(8) The precoat material according to (7), wherein the base material is a metal plate.
(9) A joined structure obtained by joining the precoat material according to (7) or (8) and an adherend.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0007]
The present invention is characterized by a bonding medium, characterized in that the bonding medium contains particles, and the particles have low adhesion to a component that develops adhesion in the bonding medium. By doing so, when a force is applied to deform the bonding medium layer, such as peeling the bonded structure bonded using the bonding medium, bonding with the component that exhibits adhesion in the bonding medium layer The particles mixed in the medium are separated before the bonding medium layer breaks, and a gap is formed between the component that expresses adhesion in the bonding medium layer and the particles, so that the degree of freedom of deformation in the bonding medium layer is increased. Give flexibility. Therefore, when a force is applied in the peeling direction, the stress is not concentrated in one place, and a high peeling strength can be obtained.
[0008]
The separation of the component that expresses adhesion in the bonding medium and the particles and the formation of voids means that when the structure that peels due to cohesive failure of the bonding medium layer is bonded and peeled, the peeled surface is observed with a microscope or scanning electron microscope You can confirm by doing. In order to give flexibility to the bonding medium layer, when observed with a scanning electron microscope or the like from the normal direction of the separation surface and viewing the particles as a circle in a plane, the particles are as in the separation portion of FIG. At least a particle having a gap between the particle and the component exhibiting adhesiveness, which is 30% or more in length around the particle, must be included. When the adhesion between the particles and the component that expresses the adhesion of the bonding medium is high, and the particles do not contain particles that peel off more than 30% of the projected field length, the hardness of the bonding medium known as a general filler effect There is a high possibility that the effect of increasing the strength will be strong, and there is a possibility that sufficient flexibility cannot be given to the bonding medium layer. Further, it is desirable that 50% or more of the particles peel as described above when observed with a scanning electron microscope or the like from the normal direction of the peeled surface. Even when less than 50% of the particles that peel as described above and create voids around them, the effect of increasing the hardness of the bonding medium is likely to be stronger, and the bonding medium layer has sufficient flexibility. It may not be given.
[0009]
The void may exist before a force that deforms the bonding medium layer is applied.
[0010]
Here, because of the definition of the bonding medium, the bonding according to the present invention is a system in which the state of the bonding medium is easy to confirm, and a structure that peels by cohesive failure when the structure is bonded and peeled by a single component that exhibits adhesion. Although the medium has been described, in reality, even in a system that peels due to interfacial fracture between the bonding medium and the structure, the peel strength obtained by mixing particles having low adhesion with the component that exhibits adhesion into the component that exhibits adhesion. An improvement is observed.
[0011]
The shape of particles mixed in the bonding medium is not specified, but the aspect ratio is 4: 6 to 5: 5 in order to apply stress to the bonding medium layer when the bonding medium layer is deformed, such as peeling of the bonding structure. It is desirable to have a spherical shape. Here, the aspect ratio is the ratio between the longest axis and the shortest axis perpendicular to the center of the longest axis.
[0012]
The proportion of particles mixed in the joining medium is preferably about 5% to 25% by volume. If it is 5% or less, there is a possibility that a sufficient effect cannot be exhibited, and if it is 25% or more, the strength of the adhesive may be lowered.
[0013]
The particle size of the particles mixed in the bonding medium is preferably 0.1 μm to 100 μm, and more preferably smaller than the thickness of the bonding medium layer required at the time of bonding. By adjusting the thickness of the bonding medium layer desired at the time of bonding, the particles can also serve as a spacer to keep the thickness of the bonding medium layer at the time of bonding constant, thereby further stabilizing the bonding strength. It becomes easy to obtain.
[0014]
The material of the particles is acrylic or a copolymer thereof (excluding an elastomer) .
[0016]
These particles may be used alone or in combination of two or more.
[0017]
Meanwhile, component expressing adhesion is Polyamide based hot melt adhesive.
[0018]
As a method of using the bonding medium when bonding the structure with the bonding medium, it is possible to use a general method in which the bonding medium is applied to a portion to be bonded and then bonded before the bonding medium is cured. There does not have a bond strength at normal temperature, from the use of polyamide-based hot melt adhesive which express adhesion by heating, is performed only prior to the adhesive application, overlapped portion to be joined when you want to joint The joining member which can be joined by combining and thermocompression bonding can also be made. For example, painting the steel sheet production line, the adhesive on a flat base material by coating line such as a film coating line coating and drying, the After the adhesive precoat material formed by coating the processed molding, thermocompression bonding It is also conceivable to join them.
[0020]
When using a polyamide-based resin, the intensity of the differential scanning calorimetry melting peak should be 10 to 100% of the differential scanning calorimetry melting peak of the resin cured from 170 ° C. by room temperature cooling. Good. If it is less than 10%, non-adhesiveness during normal operation cannot be obtained. Further, if the molecular weight is less than 5000, the moldability is inferior, and if the molecular weight exceeds 80000, the blocking resistance is lowered. Therefore, it is desirable to use a polyamide resin having a molecular weight of 5000 to 80000.
[0023]
The adhesive to be precoated may be in any form such as a solvent type, a melt type, an aqueous type, and a powder .
[0024]
The structure to be joined to the joining medium is not particularly limited, and examples thereof include various materials such as metal, glass, ceramic, plastic, rubber, paper, cloth, and leather.
[0025]
In the metal example, examples of the metal plate 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. Of these, examples of plating treatment on steel sheets include hot dip galvanized steel sheets, electrogalvanized steel sheets, galvannealed steel sheets, aluminum plated steel sheets, aluminum-zinc alloy plated steel sheets, zinc-aluminum-magnesium alloy plated steel sheets, 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.
[0026]
These metal plates may be used as they are or after being subjected to ordinary chemical conversion treatment. As chemical conversion treatment, generally known chemical conversion treatments such as coating chromate treatment, electrolytic chromate treatment, zinc phosphate treatment and the like have been developed in recent years. Non-chromate treatment that does not contain hexavalent chromium can be used. Moreover, normal processes, such as alkali degreasing, can be performed before chemical conversion treatment. Furthermore, the Ni surface can be adjusted before the chemical conversion treatment.
[0027]
Moreover, in order to improve the adhesiveness between the adhesive and the structure, the structure may be subjected to a primer treatment. 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 metal plate can also be applied. A rust inhibitor may be added to the primer.
[0028]
When pre-coating an adhesive on a metal plate as a structure, the adhesive may be applied on both sides or one side of the metal plate, with an adhesive on one side and a coating film equivalent to a known pre-coated metal plate on the other side. It is also possible to apply a lubricating coating. Metal plates pre-coated with adhesives are often used for thermocompression bonding after applying adhesives, and after processing such as pressing, but apply a lubricating coating on the back side of the pre-coated surface. In this case, since press molding is possible without using press oil, not only is it unnecessary to wash the press oil, but there is no fear of the press oil adhering to the adhesive surface, and a more stable adhesive force can be provided.
[0029]
The application method for applying the adhesive to the structure 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 brush A coating method, a dipping method, a bar coating method, an electrostatic method, a T-die method, a laminating method, etc. can be employed.
[0030]
【Example】
Hereinafter, a method for producing a bonded structure bonded by a bonding medium, a peeling test method, and an evaluation result will be described.
[0031]
(Examples 1-5)
A polyamide-based hot-melt adhesive as a bonding medium (Henkel Japan Ltd. Macromelt 6212), the resin beads (large Nissei Chemical Industry Co., Ltd. Rabuko b Lumpur 030 (10MD) Clear) to the volume rate of 2.5% to 50 The mixture was coated on a 0.6 mm thick galvanized steel sheet with a thickness of 10 μm by a bar coating method and dried in a hot air drying furnace so that the maximum plate temperature reached 180 ° C. The resin beads used here are particles made of an acrylic copolymer and having a particle size of about 10 μm, which is nearly spherical with an aspect ratio of 4: 6, and have low adhesion to a polyamide-based hot melt adhesive. Cut it to 25mm x 200mm, fold the plate 90 ° to the side where the adhesive is not applied at 50mm from the edge, overlap the adhesive coated surfaces, and hot press at 180 ° C for 1 minute Crimped to create a T-shaped joint structure.
[0032]
(Example 6)
10% as a volume ratio of the resin beads used in Examples 1 to 5 frozen and ground to an amorphous state with an average particle size of about 5 μm in the polyamide hot melt adhesive used in Examples 1 to 5 as the joining medium Using the mixture, it was coated on a 0.6 mm thick galvanized steel plate with a thickness of 10 μm by a bar coating method and dried in a hot air drying furnace so that the maximum plate temperature reached 180 ° C. Cut it to 25mm x 200mm, fold the plate 90 ° to the side where the adhesive is not applied at 50mm from the edge, overlap the adhesive coated surfaces, and hot press at 180 ° C for 1 minute Crimped to create a T-shaped joint structure.
[0033]
(Comparative Example 1)
Using the polyamide-based hot melt adhesive used in Examples 1 to 5 as the joining medium, it was coated on a 0.6mm thick chromed galvanized steel sheet by a bar coating method to a thickness of 10μm, and reached the maximum in a hot air drying furnace It dried so that plate | board temperature might be 180 degreeC. Cut it to 25mm x 200mm, fold the plate 90 ° to the side where the adhesive is not applied at 50mm from the edge, overlap the adhesive coated surfaces, and hot press at 180 ° C for 1 minute Crimped to create a T-shaped joint structure.
[0034]
(Comparative Example 2)
A polyamide hot melt adhesive used in Examples 1 to 5 as a bonding medium is subjected to silane coupling treatment on the resin beads used in Examples 1 to 5 and mixed with an adhesive having improved adhesion to the adhesive. Was applied to a 0.6 mm thick galvanized steel sheet with a thickness of 10 μm by a bar coating method and dried in a hot air drying furnace so that the maximum plate temperature reached 180 ° C. Cut it to 25mm x 200mm, fold the plate 90 ° to the side where the adhesive is not applied at 50mm from the edge, overlap the adhesive coated surfaces, and hot press at 180 ° C for 1 minute Crimped to create a T-shaped joint structure.
[0035]
A peel test standardized in JIS K 6854-3 was performed on these bonded structures after 24 hours of hot pressing.
[0036]
[Table 1]
The test results are shown in Table 1. The test result here is the average value of the results of the test conducted 5 times for each sample, ◎ if the peel strength is 4 kN / m or more, ◎, 2 kN / m or more and less than 4 kN / m ○ Those with a value of 1 kN / m or more and less than 2 kN / m were marked with Δ, and those with a value of less than 1 kN / m were marked with ×.
[0038]
When the particles having low adhesion with the adhesion component of the bonding medium as in Examples 1 to 6 are mixed in an amount of 2.5% by volume to 50% by volume, the peel strength compared to the comparative example in which the particles are not mixed in the adhesive. Improved. Further, when the test pieces after the peeling test were observed with a scanning electron microscope from the normal direction of the peeling surface, 50% or more of the particles were peeled off by 30% or more of the field projection length, resulting in voids.
[0039]
However, when the number of particles was small as in Example 1 and the number of particles was too large as in Example 5, the effect of adding particles was slightly low. When spherical particles were frozen and pulverized as in Example 6 and mixed into crushed pieces, the amount of particles mixed was the same as in Example 3 where the highest improvement in peel strength was observed, The effect of adding particles due to the difference in shape was slightly low.
[0040]
As in Comparative Example 2, when the particles used in Examples 1 to 5 were subjected to silane coupling treatment and mixed with those having improved adhesion to the adhesion component of the bonding medium, the amount of particles mixed and the shape was Despite being the same as Example 3 where the highest improvement in peel strength was observed, no improvement in peel strength was observed. Further, when the test piece after the peeling test was observed with a scanning electron microscope from the normal direction of the peeling surface, particles that were peeled off by 30% or more of the projected field length were 20% or less .
[0041]
【The invention's effect】
Until now, it has been considered that bonding with a bonding medium has a low peel strength. However, according to the present invention, a bonding structure having a high and stable peeling strength, a bonding medium for producing the bonding structure, and adhesion Agents and adhesive precoat materials can be obtained.
As a result, due to the problem of reliability, it has become possible to perform bonding with an inexpensive and easy bonding medium even with a bonded structure that has been mechanically bonded with labor and cost, such as caulking and rivets. Therefore, the present invention is a very important invention in the industry.
[Brief description of the drawings]
FIG. 1 shows a structure and a bonding medium that are bonded with the bonding medium of the present invention, and when the structure is peeled off due to cohesive failure of the bonding medium, particles and adhesion when observed with a microscope or scanning electron microscope from the normal direction of the peeled surface. It is a figure for demonstrating the state which has peeled from the component which expresses.
Claims (9)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20150115839A (en) * | 2013-01-29 | 2015-10-14 | 에보니크 데구사 게엠베하 | Adhesion promoter compositions and primer compositions for metal-plastic hybrid components |
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| JPS6084718A (en) * | 1983-10-14 | 1985-05-14 | 日立化成工業株式会社 | Conductive anisotropic adhesive sheet |
| JPH10130616A (en) * | 1996-10-31 | 1998-05-19 | Sumitomo Bakelite Co Ltd | Adhesive for semiconductor |
| JP2002226824A (en) * | 2000-11-28 | 2002-08-14 | Hitachi Chem Co Ltd | Adhesive composition, adhesive film and semiconductor device |
| JP2002309221A (en) * | 2001-04-11 | 2002-10-23 | Shigeru Koshibe | High purity adhesive for semiconductor |
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| JPS5366947A (en) * | 1976-11-18 | 1978-06-14 | Minnesota Mining & Mfg | Hot melt adhesives |
| JPS6084718A (en) * | 1983-10-14 | 1985-05-14 | 日立化成工業株式会社 | Conductive anisotropic adhesive sheet |
| JPH10130616A (en) * | 1996-10-31 | 1998-05-19 | Sumitomo Bakelite Co Ltd | Adhesive for semiconductor |
| JP2002226824A (en) * | 2000-11-28 | 2002-08-14 | Hitachi Chem Co Ltd | Adhesive composition, adhesive film and semiconductor device |
| JP2002309221A (en) * | 2001-04-11 | 2002-10-23 | Shigeru Koshibe | High purity adhesive for semiconductor |
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| KR20150115839A (en) * | 2013-01-29 | 2015-10-14 | 에보니크 데구사 게엠베하 | Adhesion promoter compositions and primer compositions for metal-plastic hybrid components |
| KR101873092B1 (en) * | 2013-01-29 | 2018-06-29 | 에보니크 데구사 게엠베하 | Adhesion promoter compositions and primer compositions for metal-plastic hybrid components |
| US10273390B2 (en) | 2013-01-29 | 2019-04-30 | Evonik Degussa Gmbh | Adhesion promoter compositions and primer compositions for metal-plastic hybrid components |
| US11078390B2 (en) | 2013-01-29 | 2021-08-03 | Evonik Operations Gmbh | Adhesion promoter compositions and primer compositions for metal-plastic hybrid components |
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