JP2004175863A - Adhesive transfer sheet and laminate - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、通信機器、自動車部品、建材、電気製品等の積層体およびその製造方法に用いる接着剤転写シートに関する。
【０００２】
【従来の技術】
従来、物品と他物品とを接着させる方法として、基体シート上に接着剤層を形成した接着剤転写シートを作成し、接着剤転写シートから物品に接着剤層を転写形成した後、その接着剤層上に他物品を接着させる方法があった。
【０００３】
この方法は、物品上に均一な膜厚で接着剤層を形成でき、残留溶媒による物品表面の汚染、変質がないという特長があった。そして、その接着剤の材質としては、熱可塑性樹脂、熱硬化性樹脂および電離放射線照射により瞬時に硬化する電離放射線硬化型樹脂が使用されていた。
【０００４】
【発明が解決しようとする課題】
しかし、熱可塑性樹脂を使用した場合は、高温下で接着剤が可塑状態になり、接着強度が低下する性質があるため、高温環境下で使用される製品へは適用できなかった。また、熱可塑性樹脂自体の接着強度が、もともと低いという問題もあった。一方、熱硬化性樹脂を使用した場合は、高温下で長時間かけて硬化する必要があり、耐熱性が低い樹脂でできた物品と他物品とを接着させる場合には、物品または他物品が熱で変形する問題があった。
【０００５】
また、電離放射線照射により瞬時に硬化する電離放射線硬化型樹脂を使用した場合は、積層後に電離放射線を照射せざるを得ず、物品および他物品のいずれかを電離放射線が透過できる材質にしなければならなかった。また、積層させた状態で電離放射線を照射する際には、積層体がかさばるため、大きな照射装置が必要であり、取り扱いにくい問題もあった。
【０００６】
【課題を解決するための手段】
上記課題を解決するために、本発明者は、基体シート上に電離放射線硬化型接着剤層が形成された接着剤転写シートであって、該電離放射線接着剤層が電離放射線照射後であっても物品と他物品とを仮接着させることが可能であり、かつ仮接着時から一定時間経過後の物品と他物品との接着強度が、仮接着時の物品と他物品との接着強度より高いことを特徴とする接着剤転写シートを発明した。
【０００７】
すなわち、本発明の接着剤転写シートは、電離放射線硬化型接着剤層を、物品表面上に転写形成するための接着剤転写シートである。そして、本発明に係る積層体の製造方法によって得られた電離放射線硬化型接着剤層付き物品は、接着性を有しない他物品と接着可能となる。
【０００８】
また、本発明の接着剤転写シートは、電離放射線硬化型接着剤層が粘着性を有したものであってもよい。粘着性を有すれば、物品と他物品とが接触しやすくなり、仮接着させやすくなるからである。
【０００９】
また、本発明の接着剤転写シートは、電離放射線硬化型接着剤層の粘着性が仮接着時からの時間経過とともに低下する接着剤転写シートであってもよい。反応が完結し、電離放射線硬化型接着剤層が強固な三次元網目構造をもった層に固化すれば、粘着性を有しなくなる場合が多いからである。
【００１０】
また、本発明の接着剤転写シートは、前記電離放射線硬化型接着剤層の主成分が、光カチオン性重合接着剤である接着剤転写シートであってもよい。主成分とは、前記電離放射線硬化型接着剤層中の重量含有率が５０％以上のものをいう。光カチオン性重合接着剤を用いるのは、添加剤等のブレンド比率により、所望の可使時間を設定することが比較的容易なためである。
【００１１】
また、本発明の接着剤転写シートは、電離放射線硬化型接着層に電離放射線を照射した後も、物品と他物品とを仮接着できる性能を有しており、その仮接着できる時間（以下、可使時間という。）が電離放射線の照射時から５分間以上ある接着剤転写シートであってもよい。
【００１２】
可使時間を５分間以上としたのは、接着剤転写シートから物品上に電離放射線硬化型接着剤層を転写させ、物品と他物品とを仮接着させるのに、５分間以上時間がかかることがあり、照射後５分間未満で反応が完結する電離放射線硬化型接着層であると仮接着できなくなる場合があるためである。
【００１３】
可使時間内では、物品と他物品とは仮接着させるだけであるため、位置ずれ、シワ等が入る等の不具合があった場合、不良部分をはがし、再度、仮接着し直すこともできる。
【００１４】
また、本発明者は、基体シート上に電離放射線硬化型接着剤層が形成された接着剤転写シートに、接着剤転写シートの状態で電離放射線を照射した後、接着剤転写シートの電離放射線硬化型接着剤層と物品とが接するように積層し、基体シートを剥離することにより物品上に電離放射線硬化型接着剤層を形成した後、該電離放射線硬化型接着剤層と他物品とを仮接着することを特徴とする積層体の製造方法を発明した。
【００１５】
また、本発明者は、基体シート上に電離放射線硬化型接着剤層が形成された接着剤転写シートを、接着剤転写シートの電離放射線硬化型接着剤層と物品とが接するように積層し、基体シート上から電離放射線を照射した後、基体シートを剥離することにより物品上に電離放射線硬化型接着剤層を形成した後、該電離放射線硬化型接着剤層と他物品とを仮接着することを特徴とする積層体の製造方法を発明した。
【００１６】
また、本発明者は、基体シート上に電離放射線硬化型接着剤層が形成された接着剤転写シートを、接着剤転写シートの電離放射線硬化型接着剤層と物品とが接するように積層した後、基体シートを剥離することにより物品上に電離放射線硬化型接着剤層を形成した後、該電離放射線硬化型接着剤層に電離放射線を照射し、電離放射線硬化型接着剤層と他物品とを仮接着する積層体の製造方法を発明した。
【００１７】
上記いずれの積層体の製造方法の発明も、電離放射線硬化型接着剤層に電離放射線を照射してから仮接着することを特徴としている。したがって、従来技術のように、電離放射線硬化型接着剤層に電離放射線を照射しないで、物品と他物品とを接着させるということはない。
【００１８】
なお、ここでいう物品または他物品は、有体物であれば、その材質・大きさ・形状、模様、色彩に関わらず、全て含むものとする。
【００１９】
ここでいう電離放射線の照射とは、従来の電離放射線硬化型接着剤層で瞬時に硬化するような強度（例えば、電離放射線が紫外線の場合、０．１〜５０Ｊ／ｃｍ２程度の強度）の電離放射線を照射することをいう。
【００２０】
ここでいう仮接着とは、電離放射線を照射することにより、電離放射線硬化型接着剤層の反応が開始されてはいるが、まだ、その反応が完結していない状態で、物品と他物品とを積層することをいう。
【００２１】
ここでいう接着強度とは、ＪＩＳ―Ｋ―５４００、８．５準拠の碁盤目試験の接着力，ＪＩＳ−Ｋ−５４００、８．７準拠の付着強さ試験による接着力，ＡＳＴＭ―Ｄ―９０３準拠の１８０°剥離試験による接着力など、一般規格に準拠した方法によって測定した接着力をいう。いずれの規格に準拠した試験方法を選定するかは、物品または他物品の材質・大きさ・形状によってかわり、試験者が適宜選択する。
【００２２】
ここでいう粘着性を有するとは、ＪＩＳ―Ｚ―０２３７に準拠されているボールタック（Ｊ．Ｄｏｗ法）試験において、標準条件（２３℃、６５ＲＨ％、助走距離１００ｍｍ、電離放射線硬化型接着剤層滑走距離１００ｍｍ、傾斜角度３０°）下で得られる粘着力が０．４Ｎ／ｃｍ以上の場合をいう。
【００２３】
ここでいう一定時間とは、仮接着時から電離放射線硬化型接着剤層の反応が完結するまでのいずれかの時間をいい、材質や放置する際の条件（温度、湿度等）によって左右され、一概には言えない。
【００２４】
ただし、常温で半年以上かかるような場合には、生産性が低下するし、逆に数分で完結してしまう場合は、従来の電離放射線硬化型接着剤層品と変わりがなく取り扱いにくい。したがって、生産性と取り扱い性を考慮すれば、１時間から１週間までが好ましい。
【００２５】
仮接着時から一定時間経過し、やがて電離放射線硬化型接着剤層の反応が完結した時には、接着強度は、仮接着時より高いレベルで安定化する（図４）。反応が完結すれば、電離放射線硬化型接着剤層は強固な３次元網目構造をもった層になるため、耐薬品性、耐熱性等の耐久性がすぐれた積層体が得られる。
【００２６】
【発明の実施の形態】
以下、図面を参照しながら、本発明の接着剤転写シート等を説明する。本発明の接着剤転写シートＡは，基体シート１上に電離放射線硬化型接着剤層３が形成された接着剤転写シートである。
【００２７】
接着剤転写シートＡの基体シート１の材質は、樹脂や紙など特に限定されないが、電離放射線を透過するものが好ましい。例えば、電離放射線が紫外線である場合は、ポリエチレンテレフタレートフィルム、ポリプロピレンフィルム、ポリエチレンフィルム等の紫外線を透過する透明なプラスチックシートなどが好ましい。基体シート１の厚みは、作業性のよい６μｍ〜３００μｍが好ましい。
【００２８】
上記材質にすることにより、基体シート１を剥がしてから電離放射線を照射する場合は勿論のこと、基体シート１を積層した状態をもって電離放射線を照射する場合でも、反応が開始される。
【００２９】
また、接着剤転写シートＡは、基体シート１と電離放射線硬化型接着剤層３の間に離型層２を配置してもよい。離型層２は、基体シート１から電離放射線硬化型接着剤層３をよりスムーズに剥離させるための層であり、剥離時には基体シート１側に残る層である（図２参照）。離型層２の材質は、アクリル系樹脂、メラミン系樹脂、シリコーン系樹脂、ポリエステル系樹脂、ポリプロピレン系樹脂、ポリエチレン系樹脂、ポリスチレン系樹脂、フッ素系樹脂、ビニロン系樹脂、アセテート系樹脂、ポリアミド系樹脂を挙げることができ、電離放射線硬化型接着剤層３との離型性に応じて、適宜、好ましい材料を選択する。
【００３０】
離型層２の膜厚は０．５μｍ〜５０μｍが好ましい。膜厚が０．５μｍより薄いと、十分な離型性が得られないという問題があり、５０μｍより厚いと、印刷後に乾燥し難いという問題があるためである。離型層２の形成方法は、グラビア印刷、オフセット印刷、スクリーン印刷などの方法でも、塗装、ディッピング、リバースコーターなどの方法でもよい。
【００３１】
電離放射線硬化型接着剤層３は、イオン重合性接着剤やラジカル重合性接着剤等からなる。しかし、電離放射線を照射しても瞬時には反応せず、一定時間仮接着することが可能な状態を保持し、その後も経時的に反応が進行していくという、本発明の求める特性の材料としては、光カチオン性重合接着剤を主成分とするものの方が好ましい。反応の進行を添加剤等でコントロールしやすいためである
【００３２】
光カチオン型重合性接着剤は、エポキシ基を持つ樹脂またはエポキシ基を持つ化合物、水酸基を持つ化合物、光カチオン重合触媒等よりなる。エポキシ基を持つ樹脂としては、ビスフェノールＡ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、グリジルエーテル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、脂環型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂がある。
【００３３】
エポキシ基を持つ化合物としては、エポキシ基を有するモノマーまたはオリゴマーまたはこれらを他の共重合部分とともに共重合させた樹脂がある。水酸基を持つ化合物としては、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール等がある。光カチオン重合触媒としては、芳香族ジアゾニウム塩、芳香族ハロニウム塩、芳香族スルホニウム塩等の塩類や有機金属錯体などの、光照射により酸を発生する触媒がある。
【００３４】
エポキシ基を持つ樹脂またはエポキシ基を持つ化合物と、水酸基を持つ化合物との混合割合は、１００：０．１〜１００：１０が好ましく、エポキシ基をもつ樹脂またはエポキシ基を持つ化合物と、光カチオン重合触媒との混合割合は、１００：０．０１〜１００：１が好ましい。
【００３５】
光カチオン型重合性接着剤と混合させる材料としては、電離放射線照射後、光カチオン型重合性接着剤の反応に関与できるものが好ましい。例えば、アクリル系、ゴム系等の粘着剤、接着剤がある。
【００３６】
なお、電離放射線硬化型接着剤層３をラジカル重合性接着剤とする場合には、光開始剤としてベンゾフェノン、ベンゾインベンジル、トリクロロアセトフェノンなど、増感剤としてチオキンサントン、アントラセン、クマリン誘導体などを添加しておくとよい。また、電離放射線硬化型接着剤層３は、前記イオン重合性接着剤やラジカル重合性接着剤等を不織布等のシートに含浸させたものであってもよい。
【００３７】
電離放射線硬化型接着剤層３の膜厚は、０．５μｍ〜３００μｍが好ましい。膜厚が０．５μｍより薄いと、十分な密着が得られないという問題があり、３００μｍより厚いと、印刷後に乾燥し難いという問題があるためである。ただし、電離放射線硬化型接着剤層３が不織布等のシートに含浸させたものであれば、乾燥がしやすいため５ｍｍまで可能である。
【００３８】
電離放射線硬化型接着剤層３の形成方法は、グラビア印刷、オフセット印刷、スクリーン印刷、各種コーティング方法（グラビアコーター、マイクロコーター、バーコーター、リップコーター、リバースコーター等）、ディッピング、スプレー塗装等である。ただし、電離放射線硬化型接着剤層３が不織布等のシートに含浸させたものであれば、ドライラミネートや熱ラミネートなどの方法もある。
【００３９】
電離放射線硬化型接着剤層３は、透明または半透明で電離放射線の透過を阻害する物質を含まないのが好ましい。電離放射線硬化型接着剤層３の内部の反応を阻害する可能性があるためである。ただし、電離放射線硬化型接着剤層３にデザイン的に隠蔽がほしい場合や着色がしたい場合もあり、その場合は染料、顔料等を電離放射線硬化型接着剤層３の反応を阻害しない材料・割合を考慮して入れてもよい。
【００４０】
接着剤転写シートＡから物品Ｂに電離放射線硬化型接着剤層３を転写する方法は、特に限定されないが、アップダウン転写法、ロール転写法、熱ラミネート法、ドライラミネート法などがある。
【００４１】
しかし、物品Ｂが三次元形状を有するものであり、その表面形状に沿って接着剤転写シートＡを物品Ｂに転写する場合には、接着剤転写シートＡを三次元形状にすることができる加工方法を選択する必要がある。
【００４２】
接着剤転写シートＡを三次元形状に加工する方法としては、真空成形法、真空圧空成形法、プラグアシスト成形法、真空プレス法、金型プレス法、成形同時転写法およびこれらの改良方法等がある。
【００４３】
これらの方法は、接着剤転写シートＡを軟化点程度に加熱して軟化させることが可能であり、軟化した状態で加圧することにより三次元形状に加工できる。とくに、この中でより好ましい方法は、真空プレス方式、真空圧空成形法およびこれらの改良方法である。
【００４４】
真空圧空成形の改良方法としては、接着剤転写シートＡを平滑に載置し、接着剤転写シートＡに隔てられた上下空間を最初１気圧以下の減圧状態に保ったまま、バルブの開閉により瞬時に上方のみ１気圧以上に加圧する方法が好ましい。そのようにすれば、最初から接着剤転写シートＡが気圧差で伸びたりすることがなく、下方の空間には空気がないため、窪んだ物品の上から接着剤転写シートＡを積層する場合でも、接着剤転写シートＡと物品との間に空気溜りができることがないからである。
【００４５】
本発明の接着剤転写シートＡを三次元形状に加工する工程と、電離放射線硬化型接着剤層３に電離放射線を照射する工程とを組み合わせる方法としては、▲１▼平滑な状態の接着剤転写シートＡの電離放射線硬化型接着剤層３に電離放射線を照射した後に、接着剤転写シートＡを所望の三次元形状に加工し、その後物品Ｂ上に積層させる方法、▲２▼平滑な状態の接着剤転写シートＡの電離放射線硬化型接着剤層３に電離放射線を照射した後に、接着剤転写シートＡを所望の三次元形状に加工すると同時に物品Ｂ上に積層させる方法、▲３▼接着剤転写シートＡを所望の三次元形状に加工した後、電離放射線を照射し、その後物品Ｂ上に積層させる方法、▲４▼接着剤転写シートＡを所望の三次元形状に加工した後、物品Ｂ上に積層し、その後電離放射線を照射する方法がある。
【００４６】
この中で最も好ましい方法は、▲２▼の平滑な状態の接着剤転写シートＡの電離放射線硬化型接着剤層３に電離放射線を照射した後に、接着剤転写シートＡを所望の三次元形状に加工すると同時に物品Ｂ上に積層させる方法である。平滑な状態の接着剤転写シートＡに電離放射線を照射するため、均一に電離放射線照射ができるという長所や、所望の形状に加工すると同時に積層するため、工程短縮ができる長所、及び所望の形状に加工した接着剤転写シートＡを一時保管する必要がないという長所などを、全て兼ね備えているからである。
【００４７】
また、本発明の物品Ｂと他物品Ｃとを仮接着した後、加温しても良い。その理由は、本発明の接着剤転写シートＡの電離放射線硬化型接着剤層３に電離放射線を照射すれば、反応が開始されるので、常温放置しても経時的に反応は進むが、仮接着した後は反応をなるべく早く完結させた方が良いためである。つまり、仮接着した後は、より早く接着強度を安定化させ強固な三次元網目構造にすることにより、不意に、物品Ｂと他物品Ｃとの間に剥離する負荷がかかったとしても、剥がれないようにするためである。
【００４８】
反応は加温する温度が高いほど加速されるが、物品Ｂと他物品Ｃとがプラスチック等である場合には、８０℃以上に加温すると変形してしまう場合があるため、４０〜６０℃で加温するのが好ましい。
【００４９】
【実施例】
（実施例１）基体シート１として２５μｍのポリエチレンテレフタレートフィルムを用い、その表面にメラミン系樹脂からなるグラビアインキを用い、１μｍの全面ベタの離型層２を形成した。次に、その離型層２上に下記比率からなり、１００μｍの電離放射線硬化型接着剤層３を形成し、可使時間が４時間の接着剤転写シートＡを得た。。
【００５０】
＜電離放射線硬化型接着剤層組成＞
ビスフェノールＡ型エポキシ樹脂 １００部
ポリエーテルポリオール ３部
芳香族ジアゾニウム塩 ０．３部
【００５１】
この接着剤転写シートＡの電離放射線硬化型接着剤層３側から、１５Ｊ／ｃｍ２の紫外線を照射した。その１５分後、真空プレス法でもって、用意した木目模様パネル（物品Ｂ）の裏面の三次元形状に沿わせながら、木目模様パネルの裏面に電離放射線硬化型接着剤層３を転写形成した。得られた電離放射線硬化型接着剤層付き木目模様パネルを、電離放射線硬化型接着剤層３を介して自動車内装ボディ（他物品Ｃ）に仮接着させた。
【００５２】
この電離放射線硬化型接着剤層付き木目模様パネルと、自動車内装ボディとが仮接着された時の接着強度を、５箇所測定したところ、すべて０．１２〜０．２５Ｎ／ｃｍの範囲であった。
【００５３】
この電離放射線硬化型接着剤層付き木目模様パネルと、自動車内装ボディとが仮接着された木目模様自動車内装ボディ（積層体Ｄ）を、５０℃で１２時間加温した後、再度、接着強度を５箇所測定したところ、すべて４〜５Ｎ／ｃｍになり、接着性能に優れた木目模様自動車内装ボディとなった。
【００５４】
（実施例２）基体シート１として２５μｍのポリエチレンテレフタレートフィルムを用い、その表面にメラミン系樹脂からなるグラビアインキを用い、１μｍの全面ベタの離型層２を形成した。次に、その離型層２上に下記比率からなる５０μｍの電離放射線硬化型接着剤層３を形成し、可使時間が２時間の接着剤転写シートＡを得た。
【００５５】
＜電離放射線硬化型接着剤層組成＞
フェノールノボラック型エポキシ樹脂 １００部
ポリエステルポリオール ３部
芳香族ハロニウム塩 ０．５部
【００５６】
この接着剤転写シートＡを真空成形法でもって三次元形状に沿わせた後、接着剤転写シートＡを射出成形金型内にセットして、アクリロニトリルブタジエンスチレン樹脂を充填し、成形同時転写法により、電離放射線硬化型接着剤層付き成形品（物品Ｂ）を得た。
【００５７】
このようにして得られた電離放射線硬化型接着剤層付き成形品の電離放射線硬化型接着剤層３に、０．８Ｊ／ｃｍ２の紫外線を照射した。その３０分後、用意したメタリック調加飾シート（他物品Ｃ）を、真空プレス法でもって、電離放射線硬化型接着剤層付き成形品の三次元形状に沿って加工すると同時に仮接着させた。
【００５８】
この電離放射線硬化型接着剤層付き成形品と、メタリック調加飾シートとが仮接着された時のメタリック調成形品（積層体Ｄ）の接着強度を、５箇所測定したところ、すべて０．２２〜０．３５Ｎ／ｃｍの範囲であった。このメタリック調成形品を３日間４０℃で放置し、再度、５箇所測定したところ、すべて５〜８Ｎ／ｃｍになり、接着性能に優れたメタリック調成形品となった。
【００５９】
【発明の効果】
本発明は、接着剤転写シートの接着剤層を、電離放射線を照射した後でも仮接着可能な電離放射線硬化型接着剤層とすることを特徴としている。電離放射線硬化型接着剤層が硬化して強固な三次元網目構造となっているため、耐熱性が高く、高温下で可塑状態になりにくい。また、電離放射線で硬化させるので、物品が熱で変形するという問題が発生しにくい。また、積層体の状態ではなく。接着剤転写シートまたは物品の状態で電離放射線を照射しても、積層体を製造できる。
【００６０】
したがって、高温下で接着強度が低下することもなく、耐熱性が低い樹脂でできた物品と他物品でも接着させることができ、接着強度も高く維持できるという効果がある。また、物品および他物品の両方とも、電離放射線を透過させる材質に限定しなくてもよいという効果がある。また、接着剤転写シートまたは物品の状態で電離放射線を照射できるので、かさばることは少なく、小さな電離放射線照射装置でも使用可能であり、取り扱いやすいという効果がある。
【００６１】
【図面の簡単な説明】
【図１】本発明に係る接着剤転写シートの一実施例を示す断面図である。
【図２】本発明に係る接着剤転写シートと物品とを積層し、接着剤転写シートの基体シートを剥離したときの一実施例を示す断面図である。
【図３】本発明に係る積層体の一実施例を示す断面図である。
【図４】本発明に係る接着剤転写シートの電離放射線硬化型接着剤層の反応の進行を示す説明図である。
【符号の説明】
Ａ 接着剤転写シート
Ｂ 物品
Ｃ 他物品
Ｄ 積層体
１ 基体シート
２ 離型層
３ 電離放射線硬化型接着剤層[0001]
TECHNICAL FIELD OF THE INVENTION
TECHNICAL FIELD The present invention relates to a laminate of communication equipment, automobile parts, building materials, electric products, and the like, and an adhesive transfer sheet used in a method for producing the laminate.
[0002]
[Prior art]
Conventionally, as a method of bonding an article and another article, an adhesive transfer sheet having an adhesive layer formed on a base sheet is prepared, and the adhesive layer is transferred from the adhesive transfer sheet to the article, and then the adhesive is transferred. There was a method of bonding other articles on the layer.
[0003]
This method has an advantage that an adhesive layer can be formed on an article with a uniform thickness, and there is no contamination or deterioration of the article surface due to a residual solvent. As a material of the adhesive, a thermoplastic resin, a thermosetting resin, and an ionizing radiation-curable resin that is instantaneously cured by irradiation with ionizing radiation have been used.
[0004]
[Problems to be solved by the invention]
However, when a thermoplastic resin is used, the adhesive is in a plastic state at a high temperature and has a property of lowering the adhesive strength, so that it cannot be applied to a product used in a high temperature environment. There is also a problem that the adhesive strength of the thermoplastic resin itself is originally low. On the other hand, when a thermosetting resin is used, it is necessary to cure over a long period of time at a high temperature, and when bonding an article made of a resin with low heat resistance to another article, the article or other article is hardened. There was a problem of deformation by heat.
[0005]
In addition, when using an ionizing radiation-curable resin that cures instantaneously upon irradiation with ionizing radiation, the ionizing radiation must be applied after lamination, and either the article or any other article must be made of a material that can transmit the ionizing radiation. did not become. In addition, when irradiating with ionizing radiation in a stacked state, a large irradiation device is required because the laminate is bulky, and there is a problem that it is difficult to handle.
[0006]
[Means for Solving the Problems]
In order to solve the above problems, the present inventor has provided an adhesive transfer sheet having an ionizing radiation-curable adhesive layer formed on a base sheet, wherein the ionizing radiation adhesive layer has been irradiated with ionizing radiation. It is also possible to temporarily bond the article and the other article, and the adhesive strength between the article and the other article after a certain period of time from the temporary bonding is higher than the bonding strength between the article and the other article during the temporary bonding. An adhesive transfer sheet characterized by the above is invented.
[0007]
That is, the adhesive transfer sheet of the present invention is an adhesive transfer sheet for transfer-forming an ionizing radiation-curable adhesive layer on the surface of an article. The article with the ionizing radiation-curable adhesive layer obtained by the method for producing a laminate according to the present invention can be bonded to other articles having no adhesiveness.
[0008]
Further, the adhesive transfer sheet of the present invention may be one in which the ionizing radiation-curable adhesive layer has tackiness. This is because if the article has adhesiveness, the article and another article can easily come into contact with each other and can easily be temporarily bonded.
[0009]
Further, the adhesive transfer sheet of the present invention may be an adhesive transfer sheet in which the tackiness of the ionizing radiation-curable adhesive layer decreases with time from the time of temporary bonding. This is because if the reaction is completed and the ionizing radiation-curable adhesive layer is solidified into a layer having a strong three-dimensional network structure, the adhesiveness is often lost.
[0010]
Further, the adhesive transfer sheet of the present invention may be an adhesive transfer sheet in which the main component of the ionizing radiation-curable adhesive layer is a photo-cationic polymerization adhesive. The main component means a component having a weight content of 50% or more in the ionizing radiation-curable adhesive layer. The reason for using the photo-cationic polymerization adhesive is that it is relatively easy to set a desired pot life according to the blend ratio of additives and the like.
[0011]
Further, the adhesive transfer sheet of the present invention has a performance of temporarily adhering an article and another article even after irradiating the ionizing radiation-curable adhesive layer with ionizing radiation. The adhesive transfer sheet may have a pot life of 5 minutes or more from the time of irradiation with ionizing radiation.
[0012]
The pot life is set to 5 minutes or more because it takes 5 minutes or more to transfer the ionizing radiation-curable adhesive layer from the adhesive transfer sheet onto the article and temporarily bond the article to another article. This is because if the ionizing radiation-curable adhesive layer completes the reaction in less than 5 minutes after irradiation, temporary adhesion may not be possible.
[0013]
During the pot life, the article and the other article are only temporarily bonded, so that if there is a problem such as displacement, wrinkles, or the like, the defective portion can be removed and temporarily bonded again.
[0014]
Further, the present inventors irradiate the adhesive transfer sheet having the ionizing radiation-curable adhesive layer formed on the base sheet with ionizing radiation in the state of the adhesive transfer sheet, and then cure the ionizing radiation of the adhesive transfer sheet. After laminating the mold adhesive layer and the article so as to be in contact with each other, and peeling the base sheet to form an ionizing radiation-curable adhesive layer on the article, the ionizing radiation-curable adhesive layer and another article are temporarily bonded. We have invented a method of manufacturing a laminate characterized by bonding.
[0015]
Further, the present inventor laminates an adhesive transfer sheet having an ionizing radiation-curable adhesive layer formed on a base sheet, so that the ionizing radiation-curable adhesive layer of the adhesive transfer sheet and the article are in contact with each other, After irradiating the substrate sheet with ionizing radiation, peeling the substrate sheet to form an ionizing radiation-curable adhesive layer on the article, and then temporarily bonding the ionizing radiation-curable adhesive layer to another article. And a method for manufacturing a laminate characterized by the following.
[0016]
Further, the present inventor, after laminating an adhesive transfer sheet having an ionizing radiation-curable adhesive layer formed on a base sheet, so that the ionizing radiation-curable adhesive layer of the adhesive transfer sheet and the article are in contact with each other. After forming the ionizing radiation-curable adhesive layer on the article by peeling the base sheet, irradiating the ionizing radiation-curable adhesive layer with ionizing radiation, the ionizing radiation-curable adhesive layer and other articles A method of manufacturing a laminate to be temporarily bonded was invented.
[0017]
The invention of any of the above-mentioned methods for producing a laminate is characterized in that the ionizing radiation-curable adhesive layer is irradiated with ionizing radiation and then temporarily bonded. Therefore, unlike the related art, the article is not bonded to another article without irradiating the ionizing radiation-curable adhesive layer with the ionizing radiation.
[0018]
It should be noted that the articles or other articles referred to here are all tangible, regardless of their material, size, shape, pattern, and color.
[0019]
Irradiation with ionizing radiation as used herein means that the ionizing radiation hardens instantaneously with a conventional ionizing radiation-curable adhesive layer (for example, when ionizing radiation is ultraviolet light, the intensity is about 0.1 to 50 J / cm 2 ). Irradiation with ionizing radiation.
[0020]
The term “temporary adhesion” here means that the irradiation of the ionizing radiation-curable adhesive layer is started by irradiating ionizing radiation, but the reaction between the article and another article is not completed yet. Means stacking.
[0021]
Here, the adhesive strength means the adhesive strength in a grid test in accordance with JIS-K-5400, 8.5, the adhesive strength in an adhesive strength test in accordance with JIS-K-5400, 8.7, or ASTM-D-903. It refers to an adhesive force measured by a method based on general standards, such as an adhesive force obtained by a compliant 180 ° peel test. Which standard is used for selecting a test method depends on the material, size, and shape of the article or other articles, and is appropriately selected by the tester.
[0022]
The term "having tackiness" as used herein means that, in a ball tack (J. Dow method) test conforming to JIS-Z-0237, standard conditions (23 ° C., 65 RH%, run distance 100 mm, ionizing radiation curable adhesive) This means that the adhesive strength obtained under a layer sliding distance of 100 mm and an inclination angle of 30 ° is 0.4 N / cm or more.
[0023]
Here, the certain time refers to any time from the time of temporary bonding to the time when the reaction of the ionizing radiation-curable adhesive layer is completed, and is affected by the material and the conditions when left (temperature, humidity, etc.) I can't say it.
[0024]
However, when it takes more than six months at room temperature, the productivity is reduced, and when it is completed in a few minutes, it is difficult to handle without any difference from the conventional ionizing radiation-curable adhesive layer product. Therefore, in consideration of productivity and handleability, the time is preferably from one hour to one week.
[0025]
When a certain period of time has passed since the temporary bonding and the reaction of the ionizing radiation-curable adhesive layer is eventually completed, the bonding strength is stabilized at a higher level than at the time of the temporary bonding (FIG. 4). When the reaction is completed, the ionizing radiation-curable adhesive layer becomes a layer having a strong three-dimensional network structure, so that a laminate having excellent durability such as chemical resistance and heat resistance can be obtained.
[0026]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the adhesive transfer sheet and the like of the present invention will be described with reference to the drawings. The adhesive transfer sheet A of the present invention is an adhesive transfer sheet in which an ionizing radiation-curable adhesive layer 3 is formed on a base sheet 1.
[0027]
The material of the base sheet 1 of the adhesive transfer sheet A is not particularly limited, such as resin and paper, but is preferably a material that transmits ionizing radiation. For example, when the ionizing radiation is ultraviolet light, a transparent plastic sheet that transmits ultraviolet light such as a polyethylene terephthalate film, a polypropylene film, and a polyethylene film is preferable. The thickness of the base sheet 1 is preferably 6 μm to 300 μm with good workability.
[0028]
By using the above-mentioned material, the reaction is started not only when the substrate sheet 1 is peeled off and the ionizing radiation is irradiated in a state where the substrate sheets 1 are stacked but also when the substrate sheet 1 is laminated.
[0029]
In the adhesive transfer sheet A, a release layer 2 may be disposed between the base sheet 1 and the ionizing radiation-curable adhesive layer 3. The release layer 2 is a layer for more smoothly releasing the ionizing radiation-curable adhesive layer 3 from the base sheet 1 and is a layer remaining on the base sheet 1 side at the time of release (see FIG. 2). The material of the release layer 2 is an acrylic resin, a melamine resin, a silicone resin, a polyester resin, a polypropylene resin, a polyethylene resin, a polystyrene resin, a fluorine resin, a vinylon resin, an acetate resin, or a polyamide resin. Resins can be mentioned, and a preferable material is appropriately selected according to the releasability from the ionizing radiation-curable adhesive layer 3.
[0030]
The thickness of the release layer 2 is preferably 0.5 μm to 50 μm. If the thickness is less than 0.5 μm, there is a problem that sufficient releasability cannot be obtained. If the thickness is more than 50 μm, there is a problem that drying after printing is difficult. The method for forming the release layer 2 may be a method such as gravure printing, offset printing, screen printing, or a method such as painting, dipping, or a reverse coater.
[0031]
The ionizing radiation-curable adhesive layer 3 is made of an ion-polymerizable adhesive, a radical-polymerizable adhesive, or the like. However, even when irradiated with ionizing radiation, it does not react instantaneously, maintains a state in which temporary bonding can be performed for a certain period of time, and the reaction proceeds with time thereafter, a material having the characteristics required by the present invention. It is more preferable that the main component be a photo-cationic polymerization adhesive. This is because the progress of the reaction can be easily controlled with additives and the like.
The photocationic polymerizable adhesive comprises a resin having an epoxy group or a compound having an epoxy group, a compound having a hydroxyl group, a photocationic polymerization catalyst, and the like. Examples of the resin having an epoxy group include bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, glycidyl ether type epoxy resin, glycidylamine type epoxy resin, alicyclic type epoxy resin, and bisphenol F type epoxy resin. There is.
[0033]
Examples of the compound having an epoxy group include a monomer or oligomer having an epoxy group or a resin obtained by copolymerizing these with another copolymerized portion. Examples of the compound having a hydroxyl group include polyether polyol, polyester polyol, and polycarbonate polyol. Examples of the photocationic polymerization catalyst include a catalyst that generates an acid upon irradiation with light, such as a salt such as an aromatic diazonium salt, an aromatic halonium salt, or an aromatic sulfonium salt, or an organic metal complex.
[0034]
The mixing ratio of the resin having an epoxy group or the compound having an epoxy group to the compound having a hydroxyl group is preferably 100: 0.1 to 100: 10. The mixing ratio with the polymerization catalyst is preferably from 100: 0.01 to 100: 1.
[0035]
As the material to be mixed with the photocationic polymerizable adhesive, those capable of participating in the reaction of the photocationic polymerizable adhesive after irradiation with ionizing radiation are preferable. For example, there are acrylic and rubber-based adhesives and adhesives.
[0036]
When the ionizing radiation-curable adhesive layer 3 is a radical polymerizable adhesive, benzophenone, benzoinbenzyl, trichloroacetophenone and the like are added as a photoinitiator, and thioquinsanthone, anthracene, a coumarin derivative and the like are added as a sensitizer. It is good to keep. Further, the ionizing radiation-curable adhesive layer 3 may be formed by impregnating a sheet such as a nonwoven fabric with the ion-polymerizable adhesive or the radical-polymerizable adhesive.
[0037]
The thickness of the ionizing radiation-curable adhesive layer 3 is preferably 0.5 μm to 300 μm. If the thickness is less than 0.5 μm, there is a problem that sufficient adhesion cannot be obtained. If the thickness is more than 300 μm, there is a problem that it is difficult to dry after printing. However, as long as the ionizing radiation-curable adhesive layer 3 is impregnated in a sheet such as a nonwoven fabric, the sheet can be dried easily and can be up to 5 mm.
[0038]
The method of forming the ionizing radiation-curable adhesive layer 3 includes gravure printing, offset printing, screen printing, various coating methods (gravure coater, micro coater, bar coater, lip coater, reverse coater, etc.), dipping, spray coating, and the like. . However, as long as the ionizing radiation-curable adhesive layer 3 is obtained by impregnating a sheet such as a nonwoven fabric, a method such as dry lamination or heat lamination is also available.
[0039]
The ionizing radiation-curable adhesive layer 3 is preferably transparent or translucent and does not contain a substance that inhibits the transmission of ionizing radiation. This is because a reaction inside the ionizing radiation-curable adhesive layer 3 may be inhibited. However, there may be cases where the ionizing radiation-curable adhesive layer 3 is desired to be concealed or colored in such a case. In such a case, a dye or a pigment is used to prevent the reaction of the ionizing radiation-curable adhesive layer 3 from being inhibited. May be taken into account.
[0040]
The method of transferring the ionizing radiation-curable adhesive layer 3 from the adhesive transfer sheet A to the article B is not particularly limited, but includes an up-down transfer method, a roll transfer method, a heat lamination method, a dry lamination method, and the like.
[0041]
However, when the article B has a three-dimensional shape and the adhesive transfer sheet A is transferred to the article B along the surface shape, a process capable of forming the adhesive transfer sheet A into a three-dimensional shape. You need to choose a method.
[0042]
Examples of the method of processing the adhesive transfer sheet A into a three-dimensional shape include a vacuum forming method, a vacuum pressure forming method, a plug assist forming method, a vacuum press method, a mold pressing method, a molding simultaneous transfer method, and a method for improving these methods. is there.
[0043]
In these methods, the adhesive transfer sheet A can be softened by heating to about the softening point, and can be processed into a three-dimensional shape by applying pressure in the softened state. In particular, a more preferable method among them is a vacuum press method, a vacuum pressure forming method, and an improved method thereof.
[0044]
As an improved method of vacuum pressure forming, the adhesive transfer sheet A is placed smoothly, and while the upper and lower spaces separated by the adhesive transfer sheet A are initially kept at a reduced pressure of 1 atm or less, the valve is opened and closed instantaneously. It is preferable to pressurize only the upper part to 1 atm or more. In this case, since the adhesive transfer sheet A does not expand due to the pressure difference from the beginning, and there is no air in the space below, even when the adhesive transfer sheet A is laminated from above the depressed article. This is because there is no air trap between the adhesive transfer sheet A and the article.
[0045]
The method of combining the step of processing the adhesive transfer sheet A of the present invention into a three-dimensional shape and the step of irradiating the ionizing radiation-curable adhesive layer 3 with ionizing radiation includes: (1) adhesive transfer in a smooth state After irradiating the ionizing radiation-curable adhesive layer 3 of the sheet A with ionizing radiation, the adhesive transfer sheet A is processed into a desired three-dimensional shape, and then laminated on the article B. A method of irradiating the ionizing radiation-curable adhesive layer 3 of the adhesive transfer sheet A with ionizing radiation, processing the adhesive transfer sheet A into a desired three-dimensional shape, and simultaneously laminating the adhesive transfer sheet A on the article B; After processing the transfer sheet A into a desired three-dimensional shape, irradiating it with ionizing radiation and then laminating it on the article B. {circle around (4)} After processing the adhesive transfer sheet A into the desired three-dimensional shape, the article B Laminated on top of that A method of irradiating ionizing radiation.
[0046]
Among these, the most preferable method is to irradiate the ionizing radiation-curable adhesive layer 3 of the adhesive transfer sheet A in the smooth state of (2) with ionizing radiation, and then to form the adhesive transfer sheet A into a desired three-dimensional shape. This is a method of laminating on the article B at the same time as processing. In order to irradiate the adhesive transfer sheet A in a smooth state with the ionizing radiation, it is possible to uniformly irradiate the ionizing radiation, and to form the laminate into a desired shape at the same time as laminating the laminate, so that the process can be shortened. This is because it has all the advantages that there is no need to temporarily store the processed adhesive transfer sheet A.
[0047]
Further, after the article B of the present invention and the other article C are temporarily bonded, heating may be performed. The reason is that when the ionizing radiation-curable adhesive layer 3 of the adhesive transfer sheet A of the present invention is irradiated with ionizing radiation, the reaction starts, and the reaction proceeds with time even at room temperature. This is because it is better to complete the reaction as soon as possible after bonding. In other words, after the temporary bonding, the bonding strength is stabilized more quickly to form a strong three-dimensional network structure, so that even if a load for separating between the article B and the other article C is unexpectedly applied, the separation is performed. This is to prevent it.
[0048]
The reaction is accelerated as the heating temperature is higher. However, when the article B and the other article C are made of plastic or the like, the article may be deformed when heated to 80 ° C. or more. It is preferable to heat the mixture.
[0049]
【Example】
Example 1 A 25 μm polyethylene terephthalate film was used as a base sheet 1, and a 1 μm solid release layer 2 was formed on the entire surface using gravure ink made of a melamine resin. Next, an ionizing radiation-curable adhesive layer 3 having the following ratio and a thickness of 100 μm was formed on the release layer 2, and an adhesive transfer sheet A having a pot life of 4 hours was obtained. .
[0050]
<Ionizing radiation-curable adhesive layer composition>
Bisphenol A type epoxy resin 100 parts Polyether polyol 3 parts Aromatic diazonium salt 0.3 part
The adhesive transfer sheet A was irradiated with 15 J / cm 2 ultraviolet rays from the ionizing radiation-curable adhesive layer 3 side. Fifteen minutes later, the ionizing radiation-curable adhesive layer 3 was transferred and formed on the back surface of the wood-grain pattern panel by a vacuum press method while conforming to the three-dimensional shape of the back surface of the prepared wood-grain pattern panel (article B). The obtained grained panel with an ionizing radiation-curable adhesive layer was temporarily bonded to an automobile interior body (other article C) via the ionizing radiation-curable adhesive layer 3.
[0052]
The adhesive strength when the woodgrain pattern panel with the ionizing radiation-curable adhesive layer and the automobile interior body were temporarily bonded was measured at five places, and all were in the range of 0.12 to 0.25 N / cm. .
[0053]
The woodgrained automobile interior body (laminate D) in which the ionizing radiation-curable adhesive-coated adhesive-grained adhesive layer was temporarily bonded to the car interior body was heated at 50 ° C. for 12 hours, and then the bonding strength was again increased. When measured at five places, the results were all 4 to 5 N / cm, and a wood grain car interior body with excellent adhesion performance was obtained.
[0054]
Example 2 A 25 μm polyethylene terephthalate film was used as the base sheet 1, and a 1 μm solid release layer 2 was formed on the entire surface using gravure ink made of a melamine resin. Next, a 50 μm ionizing radiation-curable adhesive layer 3 having the following ratio was formed on the release layer 2, and an adhesive transfer sheet A having a pot life of 2 hours was obtained.
[0055]
<Ionizing radiation-curable adhesive layer composition>
Phenol novolak type epoxy resin 100 parts Polyester polyol 3 parts Aromatic halonium salt 0.5 part
After the adhesive transfer sheet A is made to conform to a three-dimensional shape by a vacuum molding method, the adhesive transfer sheet A is set in an injection mold, filled with acrylonitrile butadiene styrene resin, and formed by a simultaneous molding transfer method. Thus, a molded article (article B) having an ionizing radiation-curable adhesive layer was obtained.
[0057]
The ionizing radiation-curable adhesive layer 3 of the molded article with the ionizing radiation-curable adhesive layer thus obtained was irradiated with 0.8 J / cm 2 of ultraviolet light. Thirty minutes later, the prepared metallic decorative sheet (other article C) was processed by a vacuum press method along the three-dimensional shape of the molded article with the ionizing radiation-curable adhesive layer, and was simultaneously temporarily bonded.
[0058]
The adhesive strength of the metallic-tone molded article (laminate D) when the molded article with the ionizing radiation-curable adhesive layer and the metallic decorative sheet were temporarily bonded was measured at five places. ０．３0.35 N / cm. The metallic molded article was left at 40 ° C. for 3 days, and measured again at 5 points. The results were all 5 to 8 N / cm, and the metallic molded article was excellent in adhesive performance.
[0059]
【The invention's effect】
The present invention is characterized in that the adhesive layer of the adhesive transfer sheet is an ionizing radiation-curable adhesive layer that can be temporarily bonded even after irradiation with ionizing radiation. Since the ionizing radiation-curable adhesive layer is cured to form a strong three-dimensional network structure, it has high heat resistance and is unlikely to be in a plastic state at high temperatures. In addition, since the article is cured by ionizing radiation, the problem that the article is deformed by heat hardly occurs. Also, not the state of the laminate. Even when ionizing radiation is irradiated in the state of the adhesive transfer sheet or the article, the laminate can be manufactured.
[0060]
Therefore, there is an effect that an article made of a resin having low heat resistance can be adhered to another article without lowering the adhesive strength at a high temperature, and the adhesive strength can be kept high. In addition, there is an effect that both the article and the other article need not be limited to a material that transmits ionizing radiation. In addition, since ionizing radiation can be irradiated in the state of the adhesive transfer sheet or the article, it is less bulky and can be used even with a small ionizing radiation irradiating apparatus, and has an effect of being easy to handle.
[0061]
[Brief description of the drawings]
FIG. 1 is a sectional view showing one embodiment of an adhesive transfer sheet according to the present invention.
FIG. 2 is a cross-sectional view showing one embodiment when an adhesive transfer sheet according to the present invention and an article are laminated, and a base sheet of the adhesive transfer sheet is peeled off.
FIG. 3 is a cross-sectional view showing one embodiment of a laminate according to the present invention.
FIG. 4 is an explanatory diagram showing the progress of the reaction of the ionizing radiation-curable adhesive layer of the adhesive transfer sheet according to the present invention.
[Explanation of symbols]
A adhesive transfer sheet B article C other article D laminate 1 base sheet 2 release layer 3 ionizing radiation-curable adhesive layer
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2002341876A JP4472246B2 (en) | 2002-11-26 | 2002-11-26 | Adhesive transfer sheet and method for producing laminate using the same |
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| JP2002341876A JP4472246B2 (en) | 2002-11-26 | 2002-11-26 | Adhesive transfer sheet and method for producing laminate using the same |
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| JP2004175863A true JP2004175863A (en) | 2004-06-24 |
| JP4472246B2 JP4472246B2 (en) | 2010-06-02 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010221441A (en) * | 2009-03-19 | 2010-10-07 | Panasonic Electric Works Co Ltd | Transparent substrate/glass plate composite film, method of manufacturing same, flexible organic electroluminescence light, and flexible solar cell |
| JP2012212176A (en) * | 2005-04-04 | 2012-11-01 | Essilor Internatl Co Generale & D'optique | Process for transferring coatings onto surface of lens substrate with most precise optical quality |
| JP2015196289A (en) * | 2014-03-31 | 2015-11-09 | リンテック株式会社 | Method of producing laminated molding |
| GB2600917A (en) * | 2020-10-28 | 2022-05-18 | Mclaren Automotive Ltd | Perform assembly |
-
2002
- 2002-11-26 JP JP2002341876A patent/JP4472246B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012212176A (en) * | 2005-04-04 | 2012-11-01 | Essilor Internatl Co Generale & D'optique | Process for transferring coatings onto surface of lens substrate with most precise optical quality |
| JP2010221441A (en) * | 2009-03-19 | 2010-10-07 | Panasonic Electric Works Co Ltd | Transparent substrate/glass plate composite film, method of manufacturing same, flexible organic electroluminescence light, and flexible solar cell |
| JP2015196289A (en) * | 2014-03-31 | 2015-11-09 | リンテック株式会社 | Method of producing laminated molding |
| GB2600917A (en) * | 2020-10-28 | 2022-05-18 | Mclaren Automotive Ltd | Perform assembly |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4472246B2 (en) | 2010-06-02 |
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