JP4610818B2 - Adhesive tape - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、様々な用途に用いられる粘着テープにおいて、使用目的に応じた粘着力を有する粘着剤層を二層以上の積層粘着剤層によって形成している粘着テープに関するものである。より詳細には、本発明は、粘着力の異なる粘着剤層を積層することによって、所望の粘着特性を有する積層粘着剤層を形成せしめた粘着テープに関するものである。
【０００２】
【従来の技術】
従来、粘着テープは、粘着剤層の持つ接着機能に加えて、テープ基材の持つ物理的、化学的性質や外観などの機能を活用して、材料の固定、接合、結束等の手段として様々な用途に使用されている。これらの粘着テープに用いられる粘着剤には、目的とする粘着特性を得るために、エラストマーの分子量を操作したり、硬化剤の量を調整したり、粘着付与樹脂やオイルの量を加減して粘着力が調整されているものが使用されている。
【０００３】
また、用途にあった粘着特性（糊質）を得るために、たとえば、アクリル系粘着剤の場合には、モノマー組成の選択や併用する粘着付与樹脂の選択等による粘着特性の調整が主として行われており、ゴム系の場合には、エラストマーの種類や粘着付与樹脂の選択等による粘着特性の調整が行われている。特に、養生工程が必要な分野で使用される粘着テープの場合は、養生工程での加熱条件下で、粘着剤層の粘着特性に変化が生じても、養生工程終了後に粘着テープを引き剥がすことができるように、粘着剤層の粘着特性を調整することが必要である。
【０００４】
【発明が解決しようとする課題】
しかし、前記のような粘着特性の調整操作では、強粘着、低粘着、再剥離などの単一の機能を満たす調整は可能であるが、養生テープのように、貼着対象面に貼り付ける際には貼り付け位置の修正などの接着作業が容易に行えるような特性（低タック又は低粘着性）を備え、しかも、養生テープとしての役割が求められる期間中はしっかり接着した状態を保持でき（強粘着性）、養生工程の終了後に剥がす時には簡単に剥離することができる特性（再剥離性）を備えることが求められる。更に多機能の粘着テープの場合は、粘着テープに難燃性や導電性機能を粘着剤に付与するために、難燃性フィラーや導電性粒子を大量に粘着剤中に配合しなければならず、単層構造の粘着剤層では、粘着剤層の粘着力を低下させることとなり、所望の粘着特性を得ることが困難であるという問題もあった。
【０００５】
このような養生用の粘着テープにおける問題を解決する手段として、粘着剤層中に硬化剤を封じ込めたマイクロカプセルを配合したり、アダクト反応させた硬化剤を使用したりすることなども行われていたが、架橋度のコントロールのみで制御できる粘着特性の程度は限られており、前記のような養生用の多機能粘着テープに求められる粘着特性を満足させることはできない。
本発明は、多様な需要に簡単に対応できる粘着特性を備えた粘着剤層を有する粘着テープに関する発明を提供することを目的とするものである。
【０００６】
【課題を解決するための手段】
本発明は、粘着付与樹脂の含有量が異なる粘着剤エラストマーからなる二種以上の粘着剤層を二層以上積層して粘着剤層を形成し、各粘着剤層相互間において粘着付与樹脂が移動し、その結果外側粘着剤層の粘着力が変化する現象を利用することにより、積層粘着剤層における被着体に対面する外側粘着剤層の粘着特性（粘着力）をその内側に配置されている粘着剤層によって制御している形式の粘着テープに関する発明であり、以下の各発明を包含する。
【０００７】
（１） 基材面に、共にアクリル系、天然ゴム系及び合成ゴム系から選ばれる同一種類の粘着剤エラストマーを含有する内側粘着剤層と外側粘着剤層とを隣接して積層した積層粘着剤層を有しており、該内外側粘着剤層間には、前記外側粘着剤層における粘着付与樹脂の含有割合が、前記内側粘着剤層における粘着付与樹脂の配合割合よりも低くすることによって双方の粘着力に差が設けられていることを特徴とする両面又は片面粘着テープ
【００１０】
（２） 前記外側粘着剤層が、粘着剤エラストマーを含有する複数の粘着剤層を隣接して積層した積層粘着剤層であることを特徴とする（１）に記載の両面又は片面粘着テープ。
【００１５】
（３） 前記両面又は片面粘着テープは、粗面や凹凸面等貼着しにくい個所に用いられる永久接着用の粘着テープであることを特徴とする（１）又は（２）に記載の両面又は片面粘着テープ。
【００１６】
【発明の実施の形態】
以下、本発明を図面で説明すると、図１は本発明による粘着剤層が二層である片面粘着テープの断面図、図２は粘着剤層が三層である両面粘着テープの断面図、及び図３は粘着剤層が四層の両面粘着テープの断面図である。図４は従来の粘着剤層が単層である片面粘着テープの断面図である。
図中、１は基材であり、２は内側粘着剤層、３は外側粘着剤層、４は通常の単層粘着剤層である。
【００１７】
本発明の両面又は片面粘着テープにおいて、その粘着剤層に使用される粘着剤は、粘着付与樹脂を含んだアクリル系粘着剤及びゴム系粘着剤から選ばれる少なくとも一種であり、必要に応じて各粘着剤ともオイル、充填剤、老化防止剤等を加えてもよい。また、目的に応じて、難燃性フィラー、導電性粒子等を加えることができる。
【００１８】
本発明で用いられるアクリル系粘着剤は、アルキル基の炭素数が２〜１５の(メタ)アクリル酸エステルを主成分とし、必要に応じてこれらと共重合可能な(メタ)アクリル酸、イタコン酸、マレイン酸、酢酸ビニル、アクリロニトリル等のモノマーを単独又は２種類以上を併用した公知のアクリル系粘着剤であり、特に限定されるものではない。
【００１９】
上記アクリル系粘着剤は、使用に際して、イソシアネート化合物、酸無水物、アミン化合物、エポキシ化合物、金属キレート類、アジリジン化合物等の架橋剤を用いて架橋して用いることもあるが、これらの架橋剤は使用する官能基含有モノマーの種類に適応するように選択される。
【００２０】
ゴム系粘着剤のエラストマー成分としては、特に限定されるものではないが、例えば、天然ゴム、合成イソプレンゴム、スチレンイソプレンゴム、ブチルゴム、ブタジエンゴム、クロロプレンゴム、スチレン・イソプレンブロックコポリマー等が挙げられ、これらを単独又は２種類以上を併用してもよい。
【００２１】
上記エラストマー成分は、アクリル系粘着剤の場合と同様、過酸化物、反応性フェノール樹脂、硫黄、チウラム類等の硫黄化合物、マレイミド等の加硫剤で加硫して用いてもよい。架橋或いは加硫して用いた方が、再剥離用途や耐熱クリープ性が要求される用途に対しては好ましいが、多用すると粘着付与樹脂の内側粘着剤と外側粘着剤層間の移動の妨げとなる場合がある。
【００２２】
本発明の両面又は片面粘着テープの粘着剤層に用いられる粘着付与樹脂は、各層を構成するアクリル系共重合体又はゴム系エラストマー１００質量部に対して０〜３００質量部の範囲で含まれるように用いられる。粘着付与樹脂としては、例えば、ロジン、ロジンエステル等のロジン系樹脂、テルペン樹脂、芳香族変性テルペン樹脂、水添テルペン樹脂、テルペンフェノール等のテルペン系樹脂、脂肪族系石油樹脂、芳香族系石油樹脂、共重合系石油樹脂、脂環属系石油樹脂、クマロン・インデン樹脂、ピュア・モノマー系樹脂等の重合系樹脂、フェノール系樹脂、キシレン樹脂等の縮合系樹脂など、特に限定されるものではなく、これらのうち１種又は２種以上を組み合わせて使用することができる。
【００２３】
また、各粘着剤層は、同じ種類の粘着剤系で粘着付与樹脂の量を変えたものに限らず、別の種類の粘着剤系を用いても構わない。例えば、内側粘着剤層がアクリル系粘着剤で外側粘着剤層がゴム系粘着剤の構成や、内側粘着剤層が天然ゴム/ＳＢＲ＝８０/２０のエラストマー比率であるのに対して、外側粘着剤層のエラストマーが天然ゴム/ＳＢＲ＝５０/５０の比率である場合等が含まれる。
【００２４】
上記内側粘着剤層と外側粘着剤層の厚さ(塗布質量)は特に限定されるものではないが、外側粘着剤層が薄く内側粘着剤層が厚いと、内側粘着剤層の粘着特性を強く反映するし、逆に、外側粘着剤層が厚く内側粘着剤層が薄いと、内側粘着剤層の粘着付与樹脂の外側粘着剤層への層間移動による影響力が低下する。一般的には、外側粘着剤層の厚さは、２〜１００μｍが好ましく、更に好ましくは５〜５０μｍであり、内側粘着剤層の厚さは、１０〜２００μｍ程度であり、好ましくは３０〜６０μｍである。
【００２５】
本発明の両面又は片面粘着テープの当初の粘着特性は、外側粘着剤層の配合処方に左右され、一般にアクリル系共重合体やゴム系エラストマーに対する外側粘着剤層の粘着付与樹脂の添加比率が大きい場合には、粘着力は高いが低いタック(初期接着性)を示す。逆に外側粘着剤層の粘着付与樹脂の比率が低い場合には、粘着力は比較的低いが高いタックを示し、被着体への初期接着性が好ましい場合が多い。このため、マスキングテープなど貼り付け位置の修正等の作業が必要な際には、外側粘着剤層の粘着付与樹脂の比率を内側粘着剤層の粘着付与樹脂の比率より高くし、初期接着性を低くして、粗面、凹凸面、カーペット等貼着しにくいものを固定する両面テープ等に用いる場合には、外側粘着剤層の粘着付与樹脂の比率を低くして、タック(初期接着性)を高く設定することができる。
【００２６】
また、アクリル系共重合体やゴム系エラストマーに対する内側粘着剤層の粘着付与樹脂の添加比率を、外側粘着剤層の粘着付与樹脂の添加比率より高くすると、加熱処理や経時変化による粘着付与樹脂の外側粘着剤層への移動により粘着力の上昇が大きくなり、各種両面粘着テープなどの永久接着用途に適する糊質に変化する。逆の添加比率の場合、例えばマスキング工程などの加熱処理や経時変化により粘着付与樹脂が内側粘着剤層へ移動し、実質的な粘着特性を示す外側粘着剤層の粘着力が低下して、容易に剥離できるようになる。
【００２７】
また、粘着付与樹脂の他、難燃性フィラーや導電性粒子を粘着剤に混合する際には、内側粘着剤に多量に混合し、外側粘着剤に少量混合するか或いは混合せずに塗布すると、高い難燃性や導電性と高い粘着力を併せ持つ粘着テープを作ることができる。この場合、内側粘着剤の塗布量を多くして、外側粘着剤の塗布量を少なくすると、難燃性や導電性を更に高めることができ、内側粘着剤層と外側粘着剤層の粘着付与樹脂量の比率を調整することにより、粘着特性の制御をも同時に行うことができる。
【００２８】
本発明の片面又は両面粘着テープに使用する基材としては、ポリエステル、ポリイミド、ポリプロピレン、ポリエチレン等のフィルム又はこれらの発泡体、スフ、綿、ガラス、ポリエステル、ポリエチレン、ポリプロピレン等のクロス基材、クレープ紙、和紙、クラフト紙等の紙基材、アルミニウム、銅、鉛、ステンレス等の金属箔、レーヨン、ポリエステル、ポリアミド等の不織布基材等の公知の基材であり、これらの単独又は複合体を用いることができる。この基材の厚さは特に限定されるものではないが、薄すぎるとその用途に適した強度を付与することが困難となる可能性があり、厚すぎるとテープとしての柔軟性が失われるため、各基材とも通常２〜３００μｍ程度であるが、好ましくは１０〜１８０μｍ程度が一般的である。
【００２９】
本発明の片面又は両面粘着テープに用いるゴム系粘着剤の作製方法は、特に限定されるものではないが、例えば、適度の可塑度に素練りした天然ゴムや合成ゴム、又は必要に応じて無機充填剤等を混練した混合物をトルエンなどの溶剤に溶解して粘着付与樹脂を加え、必要に応じて加硫剤、無機充填剤、難燃性フィラー、導電性粒子、老化防止剤、軟化剤等を加えて攪拌し、これらを溶解、分散して作製する。
【００３０】
本発明に用いるアクリル系粘着剤は、前記モノマーとＡＩＢＮ等の重合開始剤を酢酸エチル等の溶剤に溶解し、窒素雰囲気下、適温で数時間反応させて得られる公知のアクリル系粘着剤に粘着付与樹脂を加え、必要に応じて架橋剤、無機充填剤、難燃性フィラー、導電性粒子、老化防止剤、軟化剤等を加え攪拌して作製する。
【００３１】
本発明の片面粘着テープの作製方法としては、いかなる方法が採用されても構わないが、例えば、上記方法で作製したゴム系又はアクリル系粘着剤をロールコーターやリバースコーター等で、前記の基材に所定量塗布、乾燥して内側粘着剤塗工済みテープを作製し、この内側粘着剤塗工面の上から同様の方法で外側粘着剤を塗布、乾燥して巻き取るのみで目的の粘着テープを得ることができる。また、必要に応じて、内側粘着剤を塗工する前に背面離型処理を行ったり、内側粘着剤が塗布される面に易接着処理を行うと、巻戻し性や耐糊残性が改善される。
【００３２】
本発明の両面テープの製造方法も、特に限定されるものではないが、例えば、片面テープと同様な方法で内側粘着剤と外側粘着剤を塗布、乾燥した後、外側粘着剤面に両面離型処理を施したセパレーターを貼り合せて一旦巻き取り、粘着剤が塗工されていない基材面に、同様の方法で内側粘着剤と外側粘着剤を塗布乾燥して、巻き取ることにより作製できる。また、図２の粘着剤層が三層である両面粘着テープは、例えば、ディップコーター等で不織布や布等に内側粘着剤を含浸・乾燥させた後、両面離型処理を施したセパレーターを貼り合わせて一旦巻き取り、次に、セパレーターを剥がしながら、外側粘着剤層をディッピングすることにより両側に塗工して、両面処理を行ったセパレーターを貼り合わせて巻き取ることにより得ることができる。
【００３３】
【作用】
本発明は、粘着付与樹脂を異なる比率で配合した粘着剤からなる二種の粘着剤を二層以上に形成してなる粘着テープであり、各層間の粘着付与樹脂の移動特性を利用することにより、所望の粘着特性に制御できる粘着テープを提供するものである。この方法で作製した粘着テープは、被着体への貼り付け作業時と貼着後や剥離の際とで、異なる粘着特性を得ることができる。従って、貼着しにくい形状の個所に用いるマスキングテープ等、強粘着を要求されながら再剥離する用途や、粗面や凹凸面等貼り付け作業が困難な個所に用いられる両面テープ等、タック(初期接着性)と経時後の強い接着強度の両立が求められる粘着テープ等に有用である。
【００３４】
【実施例】
以下、本発明を実施例で更に具体的に説明するが、本発明はこれら実施例になんら限定されるものではない。尚、実施例中において表現する「部」は質量部を示すものである。
【００３５】
実施例１
ＳＢＲ［ＪＳＲ（株）製、１０１３Ｎ］３５部とウォーレス可塑度を３０に調整した素練り天然ゴム６５部をトルエンに溶解し、粘着付与樹脂［日本ゼオン（株）製、クイントンＵ−１８５］５０部とＮ−β(アミノエチル)γ-アミノプロピルトリメトキシシラン２部、水酸化マグネシウム［共和化学工業（株）製、キスマ５Ａ］１５０部を加えて攪拌することによりゴム系粘着剤を得た。
【００３６】
実施例２
ＳＢＲ［ＪＳＲ（株）製、１０１３Ｎ］３５部とウォーレス可塑度を３０に調整した素練り天然ゴム６５部をトルエンに溶解し、粘着付与樹脂［日本ゼオン製、クイントンＵ−１８５］１２０部とＮ−β(アミノエチル)γ-アミノプロピルトリメトキシシラン２部、水酸化マグネシウム［共和化学工業（株）製、キスマ５Ａ］１５０部を加えて攪拌することによりゴム系粘着剤を得た。
【００３７】
参考例３
実施例１の粘着剤を予め片面に易接着処理が施された３８μｍのＰＥＴフィルムに、内側粘着剤として４０μｍの厚さとなるように塗布、乾燥を行い、次に、実施例２の粘着剤を内側粘着剤が既に塗布されている面に、厚さが２０μｍになるように塗布、乾燥して巻き取ることにより目的の粘着テープを得た。
【００３８】
実施例４
実施例２の粘着剤を予め片面に易接着処理が施された３８μｍのＰＥＴフィルムに、内側粘着剤として４０μｍの厚さとなるように塗布、乾燥を行い、次に、実施例１の粘着剤を内側粘着剤が既に塗布されている面に、厚さが２０μｍになるように塗布、乾燥して巻き取ることにより目的の粘着テープを得た。
【００３９】
実施例５
アクリル酸ｎ−ブチル５５部、アクリル酸２−エチルヘキシル４０部、アクリル酸５部、重合開始剤としてベンゾイルパーオキサイド１部を酢酸エチルに溶解し、窒素雰囲気下、６５℃で６時間反応させてアクリル系粘着剤を得た。
【００４０】
実施例６
実施例５で得られたアクリル系粘着剤に、粘着付与樹脂［ヤスハラケミカル（株）製、ＹＳポリスター ２１００］を１００部添加し、溶解、攪拌することにより粘着付与樹脂入りのアクリル系粘着剤を得た。
【００４１】
参考例７
実施例５の粘着剤を予め片面に易接着処理が施された３８μｍのＰＥＴフィルムに、内側粘着剤として４０μｍの厚さとなるように塗布、乾燥を行い、次に、実施例６の粘着剤を内側粘着剤が既に塗布されている面に、厚さが２０μｍになるように塗布、乾燥してセパレーターを貼合せた後、巻き取ることにより目的の粘着テープを得た。
【００４２】
実施例８
実施例６の粘着剤を予め片面に易接着処理が施された３８μｍのＰＥＴフィルムに、内側粘着剤として４０μｍの厚さとなるように塗布、乾燥を行い、次に、実施例５の粘着剤を内側粘着剤が既に塗布されている面に、厚さが２０μｍになるように塗布、乾燥して巻き取ることにより目的の粘着テープを得た。
【００４３】
実施例９
実施例５で得られたアクリル系粘着剤に、粘着付与樹脂〔ヤスハラケミカル(株）製ＹＳポリスター２１００〕を５部添加し、溶解、撹拌することにより粘着付与樹脂を少量混合したアクリル系粘着剤を得た。
【００４４】
参考例１０
実施例９の粘着剤を予め片面に易接着処理が施された３８μｍのＰＥＴフイルムに、内側粘着剤として４０μｍの厚さとなるように塗布、乾燥を行い、次に、実施例６の粘着剤を内側粘着剤が既に塗布されている面に、厚さが２０μｍになるように塗布、乾燥してセパレーターを貼合せた後、巻き取ることにより目的の粘着テープを得た。
【００４５】
実施例１１
実施例６の粘着剤を予め片面に易接着処理が施された３８μｍのＰＥＴフイルムに、内側粘着剤として４０μｍの厚さとなるように塗布、乾燥を行い、次に、実施例９の粘着剤を内側粘着剤が既に塗布されている面に、厚さが２０μｍになるように塗布、乾燥して巻き取ることにより目的の粘着テープを得た。
【００４６】
比較例１
実施例１のゴム系粘着剤を、予め片面に易接着処理が施された３８μｍのＰＥＴフィルムに、６０μｍの厚さとなるように塗布、乾燥を行い、巻き取ることにより片面粘着テープを得た。
【００４７】
比較例２
実施例５のアクリル系粘着剤を、予め片面に易接着処理が施された３８μｍのＰＥＴフィルムに、６０μｍの厚さとなるように塗布、乾燥を行い、セパレーターを貼合せた後、巻き取ることにより片面粘着テープを得た。
【００４８】
【試験方法】
１）粘着力：ＪＩＳ Ｃ-２１０７-1999
２）加熱後粘着力：ＪＩＳ Ｃ-２１０７-1999（１２０℃×２Ｈ）
３）タック：ＪＩＳ Ｚ-０２３７-2000（角度２０°）
表１に本実施例３、４、７、８、１０、１１及び比較例１〜２の粘着特性の試験結果を示す。
【００４９】
【表１】
【００５０】
【発明の効果】
以上のように、本発明の粘着テープは、内側粘着剤層と外側粘着剤層の両層間で粘着付与樹脂の移動が起こる特性を有しており、被着体への貼り付け作業時と貼着状態や剥離時とで粘着層が異なる糊質に変化して粘着力に変化が生じていることが分る。このように、使用条件下で粘着剤層の粘着特性が変化することを利用できることから、貼着しにくい形状の個所に用いるマスキングテープ等のように、強粘着性を要求されながら、なおかつ、最終的に再剥離しなければならないような用途に使用されるテープや、粗面や凹凸面のような貼り付け作業が困難な個所に用いられる両面テープ等のように、タック(初期接着性)と強い接着強度の両立が求められる両面粘着テープ等として極めて有用である。
【図面の簡単な説明】
【図１】粘着剤層が二層である本発明の片面粘着テープの断面図。
【図２】粘着剤層が三層である本発明の片面粘着テープの断面図。
【図３】粘着剤層が四層である本発明の両面粘着テープの断面図。
【図４】粘着剤層が単層である通常の粘着テープの断面図
【符号の説明】
１：基材、２：内側粘着剤層、３：外側粘着剤層、４：粘着剤層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a pressure-sensitive adhesive tape in which two or more laminated pressure-sensitive adhesive layers form a pressure-sensitive adhesive layer having an adhesive force according to the purpose of use in pressure-sensitive adhesive tapes used for various applications. More specifically, the present invention relates to an adhesive tape in which a laminated adhesive layer having desired adhesive properties is formed by laminating adhesive layers having different adhesive strengths.
[0002]
[Prior art]
In the past, adhesive tapes have various adhesive, bonding, binding, and other means by utilizing the physical and chemical properties and appearance of the tape base material in addition to the adhesive function of the adhesive layer. It is used for various purposes. The pressure-sensitive adhesive used in these pressure-sensitive adhesive tapes can be obtained by manipulating the molecular weight of the elastomer, adjusting the amount of curing agent, or adjusting the amount of tackifying resin or oil to obtain the desired pressure-sensitive adhesive properties. The one whose adhesive strength is adjusted is used.
[0003]
In order to obtain the adhesive properties (paste) suitable for the application, for example, in the case of acrylic adhesives, the adjustment of the adhesive properties is mainly performed by selecting the monomer composition or selecting the tackifying resin to be used together. In the case of rubber-based materials, the adhesion characteristics are adjusted by selecting the type of elastomer or tackifying resin. In particular, in the case of pressure-sensitive adhesive tapes used in fields that require a curing process, the adhesive tape should be peeled off after the curing process is completed, even if the adhesive properties of the pressure-sensitive adhesive layer change under the heating conditions in the curing process. It is necessary to adjust the adhesive properties of the adhesive layer so that the
[0004]
[Problems to be solved by the invention]
However, in the adjustment operation of the adhesive property as described above, adjustment satisfying a single function such as strong adhesion, low adhesion, and re-peeling is possible, but when pasting on the surface to be adhered like a curing tape Has a characteristic (low tack or low tack) that can easily perform bonding work such as correction of the pasting position, and can maintain a tightly bonded state during a period when a role as a curing tape is required ( It is required to have a property (removability) that can be easily peeled when peeled after the end of the curing process. Furthermore, in the case of multi-functional pressure-sensitive adhesive tapes, a large amount of flame-retardant filler or conductive particles must be blended in the pressure-sensitive adhesive in order to give the pressure-sensitive adhesive a flame retardant or conductive function. In the pressure-sensitive adhesive layer having a single-layer structure, the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer is lowered, and it is difficult to obtain desired pressure-sensitive adhesive properties.
[0005]
As means for solving such problems in adhesive tapes for curing, it is also practiced to mix microcapsules containing a curing agent in the adhesive layer or to use an adduct-reacting curing agent. However, the degree of the adhesive property that can be controlled only by controlling the degree of crosslinking is limited, and the adhesive property required for the multifunctional adhesive tape for curing as described above cannot be satisfied.
An object of this invention is to provide the invention regarding the adhesive tape which has an adhesive layer provided with the adhesive characteristic which can respond easily to various demands.
[0006]
[Means for Solving the Problems]
The present invention forms a pressure-sensitive adhesive layer by laminating two or more pressure-sensitive adhesive layers composed of pressure-sensitive adhesive elastomers having different contents of the pressure-sensitive adhesive resin, and the pressure-sensitive adhesive resin moves between the pressure-sensitive adhesive layers. As a result, by utilizing the phenomenon that the adhesive force of the outer adhesive layer changes, the adhesive property (adhesive force) of the outer adhesive layer facing the adherend in the laminated adhesive layer is arranged inside The present invention relates to an adhesive tape of the type controlled by the adhesive layer, and includes the following inventions.
[0007]
(1) A laminated pressure-sensitive adhesive in which an inner pressure-sensitive adhesive layer and an outer pressure-sensitive adhesive layer containing the same type of pressure-sensitive adhesive elastomer selected from acrylic, natural rubber and synthetic rubber are laminated on the base material surface. The content ratio of the tackifying resin in the outer pressure-sensitive adhesive layer is lower than the blending ratio of the tackifying resin in the inner pressure-sensitive adhesive layer. Double-sided or single-sided adhesive tape characterized by having a difference in adhesive strength
(2) The double-sided or single-sided pressure-sensitive adhesive tape according to (1), wherein the outer pressure-sensitive adhesive layer is a laminated pressure-sensitive adhesive layer in which a plurality of pressure-sensitive adhesive layers containing a pressure-sensitive adhesive elastomer are laminated adjacently .
[0015]
(3) The double-sided or single-sided adhesive tape according to (1 ) or (2), wherein the double-sided or single-sided adhesive tape is a pressure-sensitive adhesive tape for permanent adhesion used in places that are difficult to stick, such as rough surfaces and uneven surfaces. Single-sided adhesive tape.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described with reference to the drawings. FIG. 1 is a sectional view of a single-sided adhesive tape having two adhesive layers according to the present invention, FIG. 2 is a sectional view of a double-sided adhesive tape having three adhesive layers, and FIG. 3 is a sectional view of a double-sided pressure-sensitive adhesive tape having four pressure-sensitive adhesive layers. FIG. 4 is a cross-sectional view of a single-sided pressure-sensitive adhesive tape in which the conventional pressure-sensitive adhesive layer is a single layer.
In the figure, 1 is a substrate, 2 is an inner pressure-sensitive adhesive layer, 3 is an outer pressure-sensitive adhesive layer, and 4 is a normal single-layer pressure-sensitive adhesive layer.
[0017]
In the double-sided or single-sided pressure-sensitive adhesive tape of the present invention, the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer is at least one selected from an acrylic pressure-sensitive adhesive and a rubber-based pressure-sensitive adhesive containing a tackifying resin, and each of them as necessary. Oils, fillers, anti-aging agents, etc. may be added to the adhesive. Moreover, a flame-retardant filler, electroconductive particle, etc. can be added according to the objective.
[0018]
The acrylic pressure-sensitive adhesive used in the present invention is mainly composed of (meth) acrylic acid ester having an alkyl group having 2 to 15 carbon atoms, and (meth) acrylic acid or itaconic acid copolymerizable with these as required. , A known acrylic pressure-sensitive adhesive in which monomers such as maleic acid, vinyl acetate, and acrylonitrile are used alone or in combination of two or more thereof, and is not particularly limited.
[0019]
The acrylic pressure-sensitive adhesive may be used after being cross-linked using a cross-linking agent such as an isocyanate compound, an acid anhydride, an amine compound, an epoxy compound, a metal chelate, or an aziridine compound. It is selected to suit the type of functional group-containing monomer used.
[0020]
The elastomer component of the rubber-based pressure-sensitive adhesive is not particularly limited, and examples thereof include natural rubber, synthetic isoprene rubber, styrene isoprene rubber, butyl rubber, butadiene rubber, chloroprene rubber, and styrene / isoprene block copolymer. You may use these individually or in combination of 2 or more types.
[0021]
As in the case of the acrylic pressure-sensitive adhesive, the elastomer component may be used after being vulcanized with a peroxide, a reactive phenol resin, a sulfur compound such as sulfur or thiuram, or a vulcanizing agent such as maleimide. Cross-linking or vulcanization is preferred for re-peeling applications and applications that require heat-resistant creep resistance, but if used frequently, it will hinder movement between the inner and outer adhesive layers of the tackifying resin. There is a case.
[0022]
The tackifier resin used in the pressure-sensitive adhesive layer of the double-sided or single-sided pressure-sensitive adhesive tape of the present invention is included in the range of 0 to 300 parts by mass with respect to 100 parts by mass of the acrylic copolymer or rubber-based elastomer constituting each layer. Used for. Examples of tackifier resins include rosin resins such as rosin and rosin ester, terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene resins such as terpene phenol, aliphatic petroleum resins, and aromatic petroleum. Resin, copolymerized petroleum resin, alicyclic petroleum resin, coumarone / indene resin, polymer resin such as pure monomer resin, condensation resin such as phenol resin, xylene resin, etc. None of these can be used alone or in combination of two or more.
[0023]
In addition, each pressure-sensitive adhesive layer is not limited to the same type of pressure-sensitive adhesive system and the amount of the tackifying resin is changed, and another type of pressure-sensitive adhesive system may be used. For example, the inner pressure-sensitive adhesive layer has an acrylic pressure-sensitive adhesive and the outer pressure-sensitive adhesive layer has a rubber-based pressure-sensitive adhesive composition, or the inner pressure-sensitive adhesive layer has an elastomer ratio of natural rubber / SBR = 80/20. The case where the elastomer of the agent layer has a ratio of natural rubber / SBR = 50/50 is included.
[0024]
The thickness (coating mass) of the inner pressure-sensitive adhesive layer and the outer pressure-sensitive adhesive layer is not particularly limited, but if the outer pressure-sensitive adhesive layer is thin and the inner pressure-sensitive adhesive layer is thick, the pressure-sensitive adhesive properties of the inner pressure-sensitive adhesive layer are strengthened. In contrast, if the outer pressure-sensitive adhesive layer is thick and the inner pressure-sensitive adhesive layer is thin, the influence of the inner pressure-sensitive adhesive layer due to the interlayer transfer of the tackifying resin to the outer pressure-sensitive adhesive layer is reduced. In general, the thickness of the outer pressure-sensitive adhesive layer is preferably 2 to 100 μm, more preferably 5 to 50 μm, and the thickness of the inner pressure-sensitive adhesive layer is about 10 to 200 μm, preferably 30 to 60 μm. It is.
[0025]
The initial adhesive properties of the double-sided or single-sided adhesive tape of the present invention depend on the formulation of the outer adhesive layer, and generally the addition ratio of the tackifying resin in the outer adhesive layer to the acrylic copolymer or rubber elastomer is large. In some cases, the tack is high but low tack (initial adhesion). Conversely, when the ratio of the tackifying resin in the outer pressure-sensitive adhesive layer is low, the tackiness is relatively low but shows a high tack, and the initial adhesion to the adherend is often preferred. For this reason, when work such as masking tape correction such as affixing position is required, the ratio of the tackifying resin in the outer pressure-sensitive adhesive layer is made higher than the ratio of the tackifying resin in the inner pressure-sensitive adhesive layer to improve the initial adhesiveness. When used for double-sided tapes that fix low-rough surfaces, uneven surfaces, carpets, etc. that are difficult to stick, reduce the ratio of tackifying resin in the outer pressure-sensitive adhesive layer, tack (initial adhesiveness) Can be set high.
[0026]
Moreover, if the addition ratio of the tackifying resin of the inner pressure-sensitive adhesive layer to the acrylic copolymer or rubber-based elastomer is higher than the addition ratio of the tackifying resin of the outer pressure-sensitive adhesive layer, Due to the movement to the outer pressure-sensitive adhesive layer, the increase in the adhesive force increases, and the paste changes to a paste suitable for permanent adhesive applications such as various double-sided pressure-sensitive adhesive tapes. In the case of the reverse addition ratio, for example, the tackifying resin moves to the inner pressure-sensitive adhesive layer due to a heat treatment such as a masking process or a change with time, and the pressure-sensitive adhesive force of the outer pressure-sensitive adhesive layer showing substantial adhesive properties is reduced, which is easy. Can be peeled off.
[0027]
In addition to tackifying resins, when mixing flame retardant fillers and conductive particles into the adhesive, mix a large amount with the inner pressure-sensitive adhesive and apply a small amount to the outer pressure-sensitive adhesive or without mixing. It is possible to make an adhesive tape having both high flame retardancy and conductivity and high adhesive strength. In this case, if the coating amount of the inner pressure-sensitive adhesive is increased and the coating amount of the outer pressure-sensitive adhesive is decreased, the flame retardancy and conductivity can be further increased, and the tackifier resin of the inner pressure-sensitive adhesive layer and the outer pressure-sensitive adhesive layer. By adjusting the ratio of the amounts, it is possible to simultaneously control the adhesive property.
[0028]
As a base material used for the single-sided or double-sided pressure-sensitive adhesive tape of the present invention, a film such as polyester, polyimide, polypropylene, polyethylene or the like, a foam, a cloth base material such as suf, cotton, glass, polyester, polyethylene, polypropylene, crepe Paper, Japanese paper, kraft paper and other paper base materials, aluminum, copper, lead, stainless steel and other metal foils, rayon, polyester, polyamide and other non-woven base materials, such as single or composite Can be used. The thickness of the base material is not particularly limited, but if it is too thin, it may be difficult to give strength suitable for the application, and if it is too thick, the flexibility as a tape is lost. Each substrate is usually about 2 to 300 μm, preferably about 10 to 180 μm.
[0029]
The production method of the rubber-based pressure-sensitive adhesive used for the single-sided or double-sided pressure-sensitive adhesive tape of the present invention is not particularly limited. For example, natural rubber or synthetic rubber kneaded to an appropriate plasticity, or inorganic if necessary Dissolve the mixture kneaded with a filler in a solvent such as toluene and add a tackifying resin. If necessary, vulcanizing agents, inorganic fillers, flame retardant fillers, conductive particles, anti-aging agents, softening agents, etc. Are added and stirred to dissolve and disperse them.
[0030]
The acrylic pressure-sensitive adhesive used in the present invention is a pressure-sensitive adhesive to a known acrylic pressure-sensitive adhesive obtained by dissolving the above monomer and a polymerization initiator such as AIBN in a solvent such as ethyl acetate and reacting at a suitable temperature for several hours in a nitrogen atmosphere. An imparting resin is added, and a cross-linking agent, an inorganic filler, a flame retardant filler, conductive particles, an anti-aging agent, a softening agent and the like are added and stirred as necessary.
[0031]
As a method for producing the single-sided pressure-sensitive adhesive tape of the present invention, any method may be adopted. For example, the base material described above may be prepared by using a roll coater, a reverse coater or the like with a rubber-based or acrylic pressure-sensitive adhesive prepared by the above method. Apply a predetermined amount to the tape and dry it to produce an inner adhesive-coated tape, then apply the outer adhesive on the inner adhesive-coated surface in the same way, dry it and wind it up. Obtainable. In addition, if necessary, if you perform backside mold release treatment before applying the inner adhesive, or if you perform easy adhesion treatment on the surface to which the inner adhesive is applied, the unwinding property and adhesive residue resistance will improve. Is done.
[0032]
The method for producing the double-sided tape of the present invention is not particularly limited. For example, after the inner pressure-sensitive adhesive and the outer pressure-sensitive adhesive are applied and dried in the same manner as the single-sided tape, the double-sided mold release is performed on the outer pressure-sensitive adhesive surface. It can be produced by laminating a separator having been treated and winding it once, applying and drying the inner pressure-sensitive adhesive and the outer pressure-sensitive adhesive on the substrate surface on which the pressure-sensitive adhesive is not coated, and winding it. In addition, the double-sided pressure-sensitive adhesive tape having three pressure-sensitive adhesive layers shown in FIG. 2 is obtained by, for example, impregnating and drying the inner pressure-sensitive adhesive on a nonwoven fabric or cloth with a dip coater or the like, and then attaching a separator subjected to double-sided mold release treatment. The separator can be obtained by winding up once, then applying the both sides by dipping the outer pressure-sensitive adhesive layer while peeling off the separator, and laminating and winding up the separator that has been subjected to double-side treatment.
[0033]
[Action]
The present invention is a pressure-sensitive adhesive tape formed by forming two or more types of pressure-sensitive adhesives composed of pressure-sensitive adhesives blended at different ratios into two or more layers, and by utilizing the transfer characteristics of the pressure-sensitive adhesive resin between the respective layers. The present invention provides an adhesive tape that can be controlled to have desired adhesive properties. The pressure-sensitive adhesive tape produced by this method can obtain different pressure-sensitive adhesive properties at the time of application to the adherend and after or after peeling. Therefore, tack (such as masking tape used in places that are difficult to stick, etc.) such as masking tape that requires strong adhesion and re-peeling, and double-sided tape used in places where pasting work such as rough or uneven surfaces is difficult. This is useful for pressure-sensitive adhesive tapes and the like that are required to satisfy both adhesiveness) and strong adhesive strength after aging.
[0034]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples at all. In addition, “parts” expressed in the examples indicate mass parts.
[0035]
Example 1
35 parts of SBR [manufactured by JSR Corporation, 1013N] and 65 parts of kneaded natural rubber whose Wallace plasticity is adjusted to 30 are dissolved in toluene, and tackifying resin [manufactured by Nippon Zeon Co., Ltd., Quinton U-185] 50 Part, N-β (aminoethyl) γ-
[0036]
Example 2
35 parts of SBR [manufactured by JSR Co., Ltd., 1013N] and 65 parts of kneaded natural rubber whose Wallace plasticity is adjusted to 30 are dissolved in toluene, 120 parts of tackifier resin [manufactured by Nippon Zeon, Quinton U-185] and N A rubber-based pressure-sensitive adhesive was obtained by adding 2 parts of -β (aminoethyl) γ-aminopropyltrimethoxysilane and 150 parts of magnesium hydroxide [manufactured by Kyowa Chemical Industry Co., Ltd., Kisuma 5A] and stirring.
[0037]
Reference example 3
The pressure-sensitive adhesive of Example 1 was applied to a 38 μm PET film that had been subjected to easy adhesion treatment on one side in advance so as to have a thickness of 40 μm as an inner pressure-sensitive adhesive, and then the pressure-sensitive adhesive of Example 2 was applied. The target pressure-sensitive adhesive tape was obtained by coating the surface on which the inner pressure-sensitive adhesive had already been applied so as to have a thickness of 20 μm, drying and winding up.
[0038]
Example 4
The pressure-sensitive adhesive of Example 2 was applied to a 38 μm PET film that had been subjected to easy adhesion treatment on one side in advance so as to have a thickness of 40 μm as an inner pressure-sensitive adhesive, and then the pressure-sensitive adhesive of Example 1 was applied. The target pressure-sensitive adhesive tape was obtained by coating the surface on which the inner pressure-sensitive adhesive had already been applied so as to have a thickness of 20 μm, drying and winding up.
[0039]
Example 5
55 parts of n-butyl acrylate, 40 parts of 2-ethylhexyl acrylate, 5 parts of acrylic acid and 1 part of benzoyl peroxide as a polymerization initiator are dissolved in ethyl acetate and reacted at 65 ° C. for 6 hours in a nitrogen atmosphere. A system adhesive was obtained.
[0040]
Example 6
To the acrylic pressure-sensitive adhesive obtained in Example 5, 100 parts of a tackifier resin [YShara Chemical Co., Ltd., YS Polyster 2100] was added and dissolved and stirred to obtain an acrylic pressure-sensitive adhesive containing a tackifier resin. It was.
[0041]
Reference Example 7
The pressure-sensitive adhesive of Example 5 was applied to a 38 μm PET film that had been subjected to easy adhesion treatment on one side in advance so as to have a thickness of 40 μm as an inner pressure-sensitive adhesive, and then the pressure-sensitive adhesive of Example 6 was applied. The surface of the surface on which the inner pressure-sensitive adhesive had already been applied was applied and dried so as to have a thickness of 20 μm, and a separator was bonded thereto, followed by winding to obtain the desired pressure-sensitive adhesive tape.
[0042]
Example 8
The pressure-sensitive adhesive of Example 6 was applied to a 38 μm PET film that had been subjected to easy adhesion treatment on one side in advance so as to have a thickness of 40 μm as an inner pressure-sensitive adhesive, and then the pressure-sensitive adhesive of Example 5 was applied. The target pressure-sensitive adhesive tape was obtained by coating the surface on which the inner pressure-sensitive adhesive had already been applied so as to have a thickness of 20 μm, drying and winding up.
[0043]
Example 9
To the acrylic pressure-sensitive adhesive obtained in Example 5, 5 parts of tackifier resin [YShara Chemical Co., Ltd. YS Polyster 2100] was added, dissolved, and stirred to obtain a mixture of a small amount of the tackifier resin. Obtained.
[0044]
Reference Example 10
The pressure-sensitive adhesive of Example 9 was applied to a 38 μm PET film that had been subjected to easy adhesion treatment on one side in advance so as to have a thickness of 40 μm as an inner pressure-sensitive adhesive, and then the pressure-sensitive adhesive of Example 6 was applied. The surface of the surface on which the inner pressure-sensitive adhesive had already been applied was applied and dried so as to have a thickness of 20 μm, and a separator was bonded thereto, followed by winding to obtain the desired pressure-sensitive adhesive tape.
[0045]
Example 11
The pressure-sensitive adhesive of Example 6 was applied and dried to a 38 μm PET film that had been subjected to easy adhesion treatment on one side in advance so as to have a thickness of 40 μm as an inner pressure-sensitive adhesive. Next, the pressure-sensitive adhesive of Example 9 was applied. The target pressure-sensitive adhesive tape was obtained by coating the surface on which the inner pressure-sensitive adhesive had already been applied so as to have a thickness of 20 μm, drying and winding up.
[0046]
Comparative Example 1
The rubber-based pressure-sensitive adhesive of Example 1 was applied to a 38 μm PET film that had been subjected to easy adhesion treatment on one side in advance, dried to a thickness of 60 μm, and wound to obtain a single-sided pressure-sensitive adhesive tape.
[0047]
Comparative Example 2
By applying and drying the acrylic pressure-sensitive adhesive of Example 5 on a 38 μm PET film that has been subjected to easy adhesion treatment on one side in advance to a thickness of 60 μm, pasting a separator, and then winding up A single-sided adhesive tape was obtained.
[0048]
【Test method】
1) Adhesive strength: JIS C- 2107-1999
2) Adhesive strength after heating: JIS C- 2107-1999 (120 ° C x 2H)
3) Tack: JIS Z- 0237-2000 (Angle 20 °)
Table 1 shows the test results of the adhesive properties of Examples 3, 4, 7, 8, 10, 11 and Comparative Examples 1-2.
[0049]
[Table 1]
[0050]
【The invention's effect】
As described above, the pressure-sensitive adhesive tape of the present invention has a characteristic that the tackifying resin moves between both the inner pressure-sensitive adhesive layer and the outer pressure-sensitive adhesive layer. It can be seen that the adhesive layer changes to a different paste depending on the wearing state and at the time of peeling, resulting in a change in adhesive force. Thus, since it can be used that the adhesive properties of the pressure-sensitive adhesive layer change under use conditions, it is required to have strong adhesiveness, such as a masking tape used in a place where the shape is difficult to stick, and the final. Tack (initial adhesiveness), such as tape used for applications that must be re-peeled and double-sided tape used in places where pasting work is difficult such as rough or uneven surfaces It is extremely useful as a double-sided pressure-sensitive adhesive tape or the like that requires both strong adhesive strength.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a single-sided pressure-sensitive adhesive tape of the present invention having two pressure-sensitive adhesive layers.
FIG. 2 is a cross-sectional view of the single-sided pressure-sensitive adhesive tape of the present invention having three pressure-sensitive adhesive layers.
FIG. 3 is a cross-sectional view of the double-sided pressure-sensitive adhesive tape of the present invention having four pressure-sensitive adhesive layers.
FIG. 4 is a cross-sectional view of a normal pressure-sensitive adhesive tape having a single pressure-sensitive adhesive layer.
1: base material, 2: inner pressure-sensitive adhesive layer, 3: outer pressure-sensitive adhesive layer, 4: pressure-sensitive adhesive layer
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001296011A JP4610818B2 (en) | 2001-09-27 | 2001-09-27 | Adhesive tape |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001296011A JP4610818B2 (en) | 2001-09-27 | 2001-09-27 | Adhesive tape |
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| Publication Number | Publication Date |
|---|---|
| JP2003096415A JP2003096415A (en) | 2003-04-03 |
| JP4610818B2 true JP4610818B2 (en) | 2011-01-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001296011A Expired - Fee Related JP4610818B2 (en) | 2001-09-27 | 2001-09-27 | Adhesive tape |
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| Country | Link |
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| JP (1) | JP4610818B2 (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005220677A (en) * | 2004-02-09 | 2005-08-18 | Public Works Research Institute | Method for preventing corrosion of concrete and/or mortar structure |
| JP2005274667A (en) * | 2004-03-23 | 2005-10-06 | Matsushita Electric Ind Co Ltd | Touch panel and input device using the same |
| JP2007118592A (en) * | 2005-09-29 | 2007-05-17 | Kokuyo S&T Co Ltd | Pressure sensitive adhesive for bookbinding and bookbinding method for using the same |
| JP2007119758A (en) * | 2005-09-29 | 2007-05-17 | Kokuyo S&T Co Ltd | Method of pasting, pressure-sensitive adhesive for pasting and adhesive product having pressure sensitive adhesive layer |
| JP5108452B2 (en) * | 2007-03-29 | 2012-12-26 | コクヨＳ＆Ｔ株式会社 | Bulletin board |
| WO2008126509A1 (en) * | 2007-03-29 | 2008-10-23 | Kokuyo S & T Co., Ltd. | Tack board |
| JP2011213751A (en) * | 2010-03-31 | 2011-10-27 | Nitto Denko Corp | Method for producing self-adhesive tape |
| JP2011213753A (en) * | 2010-03-31 | 2011-10-27 | Nitto Denko Corp | Self-adhesive tape |
| JP2011213752A (en) * | 2010-03-31 | 2011-10-27 | Nitto Denko Corp | Adhesive tape |
| JP2011241313A (en) * | 2010-05-19 | 2011-12-01 | Nitto Denko Corp | Adhesive tape |
| JP2011241355A (en) * | 2010-05-21 | 2011-12-01 | Nitto Denko Corp | Adhesive tape |
| JP2012144668A (en) * | 2011-01-14 | 2012-08-02 | Nitto Denko Corp | Adhesive tape |
| WO2014097903A1 (en) * | 2012-12-21 | 2014-06-26 | 日東電工株式会社 | Adhesive tape |
| TWI506108B (en) * | 2013-03-04 | 2015-11-01 | Rohm & Haas | Multilayer pressure sensitive adhesive |
| AR094694A1 (en) * | 2013-03-04 | 2015-08-19 | Rohm & Haas | SENSITIVE ADHESIVE TO MULTIPLE LAYER PRESSURE |
| JP5684341B2 (en) | 2013-08-01 | 2015-03-11 | 株式会社トンボ鉛筆 | Pressure sensitive transfer adhesive tape |
| JP2017066211A (en) * | 2015-09-28 | 2017-04-06 | リンテック株式会社 | Manufacturing method of adhesive sheet and adhesive sheet |
| WO2017122671A1 (en) * | 2016-01-14 | 2017-07-20 | リンテック株式会社 | Adhesive sheet |
| JP6905320B2 (en) * | 2016-09-27 | 2021-07-21 | デクセリアルズ株式会社 | Adhesive film winding body, manufacturing method of adhesive film winding body |
| JP2021095511A (en) | 2019-12-18 | 2021-06-24 | スリーエム イノベイティブ プロパティズ カンパニー | Adhesive sheet, panel product, sheet product and cable product |
| WO2023054483A1 (en) * | 2021-09-29 | 2023-04-06 | 日東電工株式会社 | Adhesive tape and method for manufacturing adhesive tape |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57111835U (en) * | 1980-12-27 | 1982-07-10 | ||
| JPS60233178A (en) * | 1984-05-04 | 1985-11-19 | Daimatsu Kagaku Kogyo Kk | Sticker base |
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- 2001-09-27 JP JP2001296011A patent/JP4610818B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57111835U (en) * | 1980-12-27 | 1982-07-10 | ||
| JPS60233178A (en) * | 1984-05-04 | 1985-11-19 | Daimatsu Kagaku Kogyo Kk | Sticker base |
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| JP2003096415A (en) | 2003-04-03 |
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