JP2004275329A - Silicone adhesive composition for dermal pasting material, and dermal pasting material using the same - Google Patents
Silicone adhesive composition for dermal pasting material, and dermal pasting material using the same Download PDFInfo
- Publication number
- JP2004275329A JP2004275329A JP2003069429A JP2003069429A JP2004275329A JP 2004275329 A JP2004275329 A JP 2004275329A JP 2003069429 A JP2003069429 A JP 2003069429A JP 2003069429 A JP2003069429 A JP 2003069429A JP 2004275329 A JP2004275329 A JP 2004275329A
- Authority
- JP
- Japan
- Prior art keywords
- acrylic polymer
- reactive functional
- sensitive adhesive
- functional group
- adhesive composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は皮膚貼付材用シリコーン粘着剤組成物及びこれを用いた皮膚貼付材に関するものである。
【０００２】
【従来の技術】
シリコーン粘着剤は、通気性、低皮膚刺激性から人体貼付用途に使用されている。これらは貼付時の粘着物性を考慮し、過酸化物、白金触媒を用いて架橋させて使用することがあり、また架橋しないで使用されることもある（例えば、特許文献１）。
【０００３】
しかしながら、前記のような方法で架橋させた場合、十分な保持力を発現するが、シリコーン粘着剤が本来有する粘着物性（タック、粘着力）が低下し、人体貼付用粘着剤としての適性が低下することがある。一方、架橋を行わない場合、保持力が不十分となり、剥離後に粘着剤が皮膚面に残存するようになる。
【０００４】
【特許文献１】
特開平３−２００８８５号公報
【０００５】
【発明が解決しようとする課題】
本発明の課題は、シリコーン粘着剤が本来有する粘着物性（皮膚への高い接着性、タック）を維持したまま、保持力を向上させた皮膚貼付材用シリコーン粘着剤組成物及び皮膚貼付材を提供することにある。
【０００６】
【課題を解決するための手段】
本発明者は、前記の課題を解決すべく鋭意研究を重ねた結果、オルガノシロキサン系ポリマーを主成分とするシリコーン粘着剤に少量のアクリル系ポリマーを添加し、アクリル系ポリマーのみを選択的に架橋させることにより、シリコーン粘着剤が本来有する粘着物性を維持しつつ、保持力を向上させることができることを見出し、本発明を完成するに至った。
【０００７】
即ち、本発明は、以下の発明を包含する。
（１）末端に水酸基を有するオルガノシロキサン系ポリマー１００質量部に対して、水酸基以外の反応性官能基を有するアクリル系ポリマーを０．１〜２０質量部、及び前記アクリル系ポリマー中の反応性官能基と反応するが、前記オルガノシロキサン系ポリマー中の水酸基とは反応しない架橋剤を前記アクリル系ポリマー中の反応性官能基に対して０．１〜１当量配合してなる皮膚貼付材用シリコーン粘着剤組成物。
（２）前記アクリル系ポリマー中の水酸基以外の反応性官能基がカルボキシル基である前記（１）に記載のシリコーン粘着剤組成物。
（３）前記架橋剤がアジリジン架橋剤である前記（１）又は（２）に記載のシリコーン粘着剤組成物。
（４）支持体の片面に皮膚貼着用の粘着剤層を積層してなる皮膚貼付材であって、粘着剤層が、前記（１）〜（３）のいずれかに記載のシリコーン粘着剤組成物を架橋することにより形成されたものである皮膚貼付材。
（５）前記（４）に記載の皮膚貼付材における粘着剤層表面の中央域に吸液性パッドを設けてなる救急絆創膏。
【０００８】
【発明の実施の形態】
本発明に用いるオルガノシロキサン系ポリマーとしては、例えば特開平３−２００８８５号公報、特開２００１−１１４２３号公報、特開２００２−２００１６０号公報に記載されたものが挙げられる。
【０００９】
具体的には、一般式（Ｉ）：
【化１】
で示されるオルガノシロキサン系のゴム成分に一般式（ＩＩ）：
【化２】
で示されるシリコーンレジンを配合して脱水縮合することにより得られるオルガノシロキサン系ポリマーが挙げられる。
【００１０】
また、一般式（ＩＩ）以外のシリコーンレジンとして、ケイ素原子に結合した水酸基を分子中に３個以上有する分岐状ポリオルガノシロキサンを単独又は併用することも好ましい。
【００１１】
前記一般式（Ｉ）において、Ｒ１及びＲ２はそれぞれメチル基又はフェニル基であるが、粘着剤層に耐熱性などを付与するためには、メチル基とフェニル基のモル比（メチル基／フェニル基）は、２５／７５〜９８／２、特に８５／１５〜９５／５であることが好ましい。
【００１２】
また、前記式（Ｉ）で示されるオルガノシロキサン系のゴム成分（以下「（１）成分」という。）と、前記式（ＩＩ）で示されるシリコーンレジン又は前記ケイ素原子に結合した水酸基を分子中に３個以上有する分岐状ポリオルガノシロキサン（以下「（２）成分」という。）との部分縮合反応によって得られたシリコーン粘着剤が、ケイ素原子に結合した水酸基を、分子中に０．１〜０．９質量％含有することが好ましい。更に好ましくは、０．２〜０．７質量％である。この範囲では特に粘着特性の経時安定性が優れている。
【００１３】
このようなシリコーン粘着剤として、例えばダウ・コーニング社製３５５；ゼネラル・エレクトリック社製ＰＳＡ５１８、ＰＳＡ５９０、ＰＳＡ５９５、ＰＳＡ６５７４；ＧＥ東芝シリコーン（株）製ＹＲ３３４０、ＸＲ３７−Ｂ６７２２などが市販されており、これらの市販品を用いることができる。
【００１４】
本発明のシリコーン粘着剤組成物には、前記オルガノシロキサン系ポリマー１００質量部に対して、水酸基以外の反応性官能基を有するアクリル系ポリマー０．１〜２０質量部を配合する。前記アクリル系ポリマーの配合量が前記下限未満であると、アクリル系ポリマーによる網目構造の形成が不十分となり、保持力（凝集力）の向上効果が得られず、前記上限を超えると、シリコーン粘着剤が本来有する粘着物性が損なわれる。
【００１５】
前記アクリル系ポリマーの反応性官能基は、使用する架橋剤がアクリル系ポリマーのみを選択的に架橋させることができるように、架橋剤の官能基との関係で適宜選択すればよい。
【００１６】
官能基の組合せとしては、例えば、カルボキシル基とエチレンイミノ基、カルボキシル基と金属キレート、カルボキシル基とアミノ基、アセトアセテート基と金属キレートが挙げられ、これらの一方をアクリル系ポリマーの反応性官能基として、他方を架橋剤の官能基として用いることができる。
【００１７】
前記アクリル系ポリマーの原料単量体の主成分として用いられる（メタ）アクリル酸アルキルエステルとしては、特に制限はないが、通常、エステル基を構成するアルキル基が炭素数１〜１８のアルキル基である各種のアクリル酸アルキルエステル又はメタクリル酸アルキルエステルを使用でき、具体的にはアクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ｎ−ブチル、アクリル酸イソブチル、アクリル酸２−エチルヘキシル、アクリル酸イソオクチル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ｎ−ブチル、メタクリル酸イソブチル、メタクリル酸２−エチルヘキシル、メタクリル酸イソオクチル等を挙げることができる。
【００１８】
本発明において、アクリル系ポリマーを構成する単量体としては、前記（メタ）アクリル酸アルキルエステルを単独で又は２種以上組み合わせて用いてもよい。
【００１９】
アクリル系ポリマーに反応性官能基を導入するための単量体としては、例えば、反応性官能基がカルボキシル基である場合、アクリル酸、メタクリル酸等が挙げられ、反応性官能基がアセトアセテート基である場合、２−（メタ）アクリロイルオキシエチルアセトアセテート等が挙げられる。
【００２０】
更に共重合可能な他の単量体を併用してもよい。共重合可能な他の単量体としては、酢酸ビニル、スチレン、アクリロニトリル、アクリルアミド、ジメチルアクリルアミド、アクリル酸２−ヒドロキシエチル、メタクリル酸グリシジル、アクリル酸４−ヒドロキシブチル、Ｎ−ビニルピロリドン等のアクリル系粘着剤の改質用単量体として知られる各種の単量体をいずれも使用可能である。
【００２１】
これらの単量体の重合は、溶液重合、エマルジヨン重合、塊状重合等の通常の重合方法によって行われる。重合の反応温度は、通常５０〜８５℃、好ましくは６０〜８０℃である。
【００２２】
溶液重合を行う場合には、アセトン、ベンゼン、トルエン、酢酸エチル、ヘキサン、ヘプタン、メタノール、エタノール、イソプロパノール等の溶媒中で、固形分濃度通常０．５〜６０質量％、好ましくは５〜５０質量％で、アゾビスイソブチロニトリル、ベンゾイルペルオキシド等の重合開始剤を用いて行われる。
【００２３】
重合開始剤の配合量（固形分）は、アクリル系ポリマー（固形分）１００質量部に対して、通常０．０５〜１質量部である。
【００２４】
本発明のシリコーン粘着剤組成物は、前記アクリル系ポリマー中の反応性官能基と反応するが、前記オルガノシロキサン系ポリマー中の水酸基とは反応しない架橋剤を含有する。
【００２５】
このような架橋剤は、前述したように、前記アクリル系ポリマーの反応性官能基との関係で適宜選択すればよい。
【００２６】
官能基としてエチレンイミノ基を有する架橋剤としては、アジリジン架橋剤、即ち一分子中に二個以上のエチレンイミノ基を有するアジリジン化合物、例えばＮ，Ｎ′−テトラメチレンビスエチレンイミン、Ｎ，Ｎ′−ペンタメチレンビスエチレンイミン、Ｎ，Ｎ′−ヘキサメチレンビスエチレンイミン、ｐ−フェニレンビスエチレンイミン、ｍ−フェニレンビスエチレンイミン、ｍ−トルイレンビスエチレンイミン、ビフェニル−４，４′−ビスエチレンイミン、３，３′−ジメチルビフェニル−４，４′−ビスエチレンイミン、ジフェニルメタン−４，４′−ビスエチレンイミン等のエチレンイミン化合物；Ｎ，Ｎ′−テトラメチレンビスエチレンアミド、Ｎ，Ｎ′−ヘキサメチレンビスエチレンアミド、ｐ−フェニレンビスエチレンアミド、ｍ−フェニレンビスエチレンアミド、ｍ−トルイレンビスエチレンアミド、ビフェニル−４，４′−ビスエチレンアミド、ジフェニルメタン−４，４′−ビスエチレンアミド等のエチレンアミド化合物；Ｎ，Ｎ′−テトラメチレンビスエチレン尿素、Ｎ，Ｎ′−ヘキサメチレンビスエチレン尿素、ｐ−フェニレンビスエチレン尿素、ｍ−フェニレンビスエチレン尿素、ｍ−トルイレンビスエチレン尿素、１−クロル−ｍ−フェニレンビスエチレン尿素、ビフェニル−４，４′−ビスエチレン尿素、３，３′−ジメチルビフェニル−４，４′−ビスエチレン尿素、３，３′−ジメトキシビフェニル−４，４′−ビスエチレン尿素、ジフェニルメタン−ｐ，ｐ′−ビスエチレン尿素、ｍ−キシリレンビスエチレン尿素、メシチレントリスエチレン尿素等のエチレン尿素化合物；テトラメチレンビスエチレンウレタン、ヘキサメチレンビスエチレンウレタン、１，４−シクロヘキシルエチレンウレタン、２，２′−（ビスｐ−エチレンイミノホルミロキシフェニル）プロパン、１，３−（ビスエチレンイミノホルミロキシメチル）ベンゼン、メシチレントリスエチレンウレタン等のエチレンウレタン化合物；Ｎ，Ｎ′−テトラメチレンビスエチレンチオ尿素、Ｎ，Ｎ′−ヘキサメチレンビスエチレンチオ尿素、ｍ−トルイレンビスエチレンチオ尿素、ビフェニル−４，４′−ビスエチレンチオ尿素、ジフェニルメタン−ｐ，ｐ′−ビスエチレンチオ尿素、ｍ−キシリレンビスエチレンチオ尿素、メシチレントリスエチレン尿素等のエチレンチオ尿素化合物などが挙げられ、これらは一種又は二種以上の混合物を用いることができる。これらの化合物のうち、特に反応速度、粘着物性の観点からＮ，Ｎ′−ヘキサメチレンビスエチレン尿素が好ましい。
【００２７】
前記金属キレート化合物としては、アルミニウム、鉄、銅、亜鉛、スズ、チタン、ニッケル、アンチモン、マグネシウム、バナジウム、クロム、ジルコニウム等の多価金属のアセチルアセトンやアセト酢酸エステル配位化合物等が挙げられる。
【００２８】
前記アミノ基を有する架橋剤としては、ヘキサメチレンジアミン、ポリエチレンイミン、ヘキサメチレンテトラミン、ジエチレントリアミン、トリエチルテトラミン、イソホロンジアミン、アミノ樹脂、メラミン樹脂等が挙げられる。
【００２９】
前記架橋剤の配合量は前記アクリル系ポリマー中の反応性官能基に対して０．１〜１当量、好ましくは０．２〜１当量、更に好ましくは０．３〜１当量である。前記配合量が０．１当量未満では、アクリル系ポリマーによる網目構造の形成が不十分となり、保持力（凝集力）の向上効果が得られず、１当量を超えると、未反応の反応性官能基が残り、皮膚刺激の原因となる。
【００３０】
本発明の粘着剤組成物には、必要に応じて、プロセスオイル、ポリイソブチレン、ポリブテン等の軟化剤；酸化チタン、酸化亜鉛、メタケイ酸アルミニウム、炭酸カルシウム、リン酸カルシウム等の充填剤；デンプン、セルロース誘導体、ポリビニルアルコール等の保水機能付与剤；流動パラフィンなどを配合することができる。
【００３１】
本発明の粘着剤組成物の使用に際しては、トルエン、酢酸エチル、メチルエチルケトン、アセトン等の有機溶剤に溶解したものを支持体又は剥離フィルム等のフィルムに塗布した後、３０〜１７０℃、好ましくは４０〜１５０℃の乾燥温度で乾燥することにより架橋され、その粘着特性が得られる。
【００３２】
本発明の皮膚貼付材又は救急絆創膏に用いる支持体は、前記粘着剤組成物からなる粘着剤層を片面に積層保持するものである。具体的な材質としては、ポリスチレン系の熱可塑性エラストマーフィルムや、ポリエチレン、ポリプロピレン、エチレン／メタクリル酸共重合体、エチレン／メタクリル酸メチルなどのポリオレフィン系フィルム、ポリウレタン系フィルム、ポリエステル系フィルム、各種プラスチック材料からなる織布や不織布、編布、紙、その他これらのフィルム同士の積層体、紙同士の積層体などを用いることができる。
【００３３】
前記支持体の厚みは材質によって任意であるが、通常、フィルムを支持体とする場合には１５〜２５０μｍ、好ましくは３０〜１００μｍ程度とし、織布、不織布、紙などを支持体とする場合には５０〜５００μｍ、好ましくは１００〜３００μｍ程度とする。
【００３４】
本発明の皮膚貼付材及び救急絆創膏は、支持体の片面に特定の組成を有する粘着剤層を積層してなるものである。積層は、前記粘着剤組成物を塗工することにより行うことができ、この塗工は一般の塗工方式に従って直接又は転写塗工方式により行うことができる。
【００３５】
また、本発明に用いる支持体として、透湿性がない材質のフィルムを用いた場合には、皮膚面に長時間貼付すると貼付部位にムレを生じて、その結果、皮膚カブレなどを起こすことがある。従って、このような支持体を用いる場合や透湿性を有する支持体を用いる場合であっても、更に透湿性を付与したい場合には、支持体及び粘着剤層に穿孔処理を施すことが好ましい。穿孔処理を施すには穿孔ロールによる方法や、パンチング、レーザー照射などの方法を用いることができ、孔径は０．２〜２ｍｍ程度とする。
【００３６】
更に、本発明においては、前記のようにして得られる皮膚貼付材の粘着剤層表面の中央域に吸液性パッドを設けて救急絆創膏とすることもできる。吸液性パッドとしては、例えばガーゼや綿布、不織布、脱脂綿と不織布との複合品、脱脂綿と編ネットとの複合品などを用いることができ、創傷部からの滲出液を吸収し、しかも創傷部の保護を行うことができて好ましい。
【００３７】
本発明の皮膚貼付材及び救急絆創膏は、粘着剤層の表面の汚染を防ぐために、使用するまで粘着剤層表面を剥離材にて被覆しておくことが好ましい。この場合、使用する剥離材は紙、ポリオレフィンラミネート紙、ポリエステルフィルムなどにオルガノシロキサン系ポリマーを含有する粘着剤層との離型性を良好とするために剥離材用のフッ素系シリコーンやメチル系シリコーンを塗布したものを用いることが好適である。
【００３８】
【実施例】
以下、実施例及び比較例により本発明を更に具体的に説明するが、これらは本発明の範囲を何ら制限するものではない。以下において、部とは質量部を意味し、％とは質量％を意味する。
【００３９】
（実施例１）
メチルフェニル系シリコーン粘着剤（ＸＲ３７−Ｂ６７２２、ＧＥ東芝シリコーン製）１００部（固形分量）に、酢酸エチルを溶媒、アゾビスイソブチロニトリルを開始剤として０．２５部加えて重合したアクリル酸２−エチルヘキシル、アクリル酸ｎ−ブチル、メタクリル酸共重合体（モノマー組成比（％）：３０：６５：５、固形分５０％）１０部（固形分量）を加え、十分に攪拌した。これにアクリル系ポリマーの架橋剤としてＮ，Ｎ′−ヘキサメチレンビスエチレン尿素５％トルエン溶液を０．０９部（固形分量）（アクリル系ポリマー中の反応性官能基に対して０．２５当量）加え、十分に攪拌した。次に、シリコーン粘着剤用剥離紙（バイナシート７０ＸＴ−０３２ＨＫ−Ｈ、藤森工業製）の上に乾燥後の塗布量が４０ｇ／ｍ２になるようにコートし、１００℃で３分間温風により乾燥した。乾燥後、厚さ２５μｍのポリエチレンテレフタレート（ＰＥＴ）フィルム（ルミラー、東レ製）を貼りあわせ、粘着シートを作成した。
【００４０】
（実施例２）
架橋剤配合量を０．１８部（固形分量）（アクリル系ポリマー中の反応性官能基に対して０．５当量）とした以外は、実施例１と同様の方法にて粘着シートを作成した。
【００４１】
（実施例３）
架橋剤配合量を０．３６部（固形分量）（アクリル系ポリマー中の反応性官能基に対して１．０当量）とした以外は、実施例１と同様の方法にて粘着シートを作成した。
【００４２】
（実施例４）
アクリル系ポリマーの配合量を５部（固形分量）、架橋剤配合量を０．０４５部（アクリル系ポリマー中の反応性官能基に対して０．２５当量）とした以外は、実施例１と同様の方法にて粘着シートを作成した。
【００４３】
（実施例５）
アクリル系ポリマーの配合量を５部（固形分量）、架橋剤配合量を０．０９部（固形分量）（アクリル系ポリマー中の反応性官能基に対して０．５当量）とした以外は実施例１と同様の方法にて粘着シートを作成した。
【００４４】
（実施例６）
アクリル系ポリマーの配合量を１５部（固形分量）、架橋剤配合量を０．１３５部（固形分量）（アクリル系ポリマー中の反応性官能基に対して０．２５当量）とした以外は実施例１と同様の方法にて粘着シートを作成した。
【００４５】
（比較例１）
アクリル系ポリマー及び架橋剤を加えない以外は、実施例１と同様の方法にて粘着シートを作成した。
【００４６】
実施例１〜６及び比較例１の粘着シートについて、被着体をフェノール樹脂板とし、ＪＩＳ Ｚ０２３７に従い粘着力とプローブタックを測定した。また、クリープテスターにより４０℃下での保持力（被着体ＳＵＳ）をおもりの落下時間として測定した。それぞれの配合、測定結果を表１に示す。表１から、未架橋のもの（比較例１）と比較し、いずれも保持力が高くなり（架橋による凝集力の向上に基づく）、粘着力、プローブタックはほぼ維持されていることがわかる。
【００４７】
次に、これらのサンプルを５人のパネラーの前腕内側部に貼付し、３時間経過後に剥離し粘着剤の皮膚への残存状況について確認した。結果を表１にあわせて示す。
【００４８】
アクリル系ポリマーを添加しこれを架橋したものは、いずれの配合もアクリル系ポリマー架橋物の網目構造の形成により粘着剤組成物の凝集性の向上が図られ、皮膚への糊残りが減少し、良好な結果を示した。これは保持力測定の結果からもサポートされると考えられる。
【００４９】
【表１】
【発明の効果】
本発明によれば、シリコーン粘着剤が本来有する粘着物性を維持したまま、保持力を向上させた皮膚貼付材用シリコーン粘着剤組成物及び皮膚貼付材を提供することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
TECHNICAL FIELD The present invention relates to a silicone adhesive composition for a skin patch and a skin patch using the same.
[0002]
[Prior art]
Silicone pressure-sensitive adhesives are used for application to the human body because of their breathability and low skin irritation. In consideration of the adhesive properties at the time of sticking, these may be used by being crosslinked using a peroxide or a platinum catalyst, or may be used without being crosslinked (for example, Patent Document 1).
[0003]
However, when crosslinked by the method described above, sufficient holding power is exhibited, but the adhesive physical properties (tack, adhesive strength) originally possessed by the silicone adhesive are reduced, and the suitability as a pressure sensitive adhesive for human body is reduced. Sometimes. On the other hand, when the crosslinking is not performed, the holding power is insufficient, and the adhesive remains on the skin surface after peeling.
[0004]
[Patent Document 1]
JP-A-3-200885
[Problems to be solved by the invention]
An object of the present invention is to provide a silicone adhesive composition for a skin adhesive and a skin adhesive having an improved holding force while maintaining the inherent adhesive properties (high adhesiveness to the skin and tackiness) inherent in the silicone adhesive. Is to do.
[0006]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, added a small amount of an acrylic polymer to a silicone adhesive containing an organosiloxane polymer as a main component, and selectively crosslinked only the acrylic polymer. By doing so, they have found that it is possible to improve the holding power while maintaining the inherent adhesive properties of the silicone adhesive, and have completed the present invention.
[0007]
That is, the present invention includes the following inventions.
(1) 0.1 to 20 parts by mass of an acrylic polymer having a reactive functional group other than a hydroxyl group, based on 100 parts by mass of an organosiloxane polymer having a hydroxyl group at a terminal, and a reactive functional group in the acrylic polymer Silicone adhesive for skin patch comprising 0.1 to 1 equivalent of a crosslinking agent which reacts with a group but does not react with a hydroxyl group in the organosiloxane polymer with respect to a reactive functional group in the acrylic polymer. Composition.
(2) The silicone pressure-sensitive adhesive composition according to (1), wherein the reactive functional group other than the hydroxyl group in the acrylic polymer is a carboxyl group.
(3) The silicone pressure-sensitive adhesive composition according to (1) or (2), wherein the crosslinking agent is an aziridine crosslinking agent.
(4) A skin adhesive material comprising a support and a skin adhesive layer laminated on one surface of the support, wherein the adhesive layer is the silicone adhesive composition according to any one of (1) to (3) above. A skin patch formed by crosslinking an object.
(5) An emergency bandage which is provided with a liquid-absorbing pad in a central region of the surface of the pressure-sensitive adhesive layer in the skin patch according to (4).
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
Examples of the organosiloxane-based polymer used in the present invention include those described in JP-A-3-200885, JP-A-2001-11423, and JP-A-2002-200160.
[0009]
Specifically, general formula (I):
Embedded image
The organosiloxane rubber component represented by the general formula (II):
Embedded image
And an organosiloxane-based polymer obtained by blending a silicone resin represented by the following formula and subjecting it to dehydration condensation.
[0010]
It is also preferable to use, as the silicone resin other than the general formula (II), a branched polyorganosiloxane having three or more hydroxyl groups bonded to a silicon atom in a molecule, alone or in combination.
[0011]
In the general formula (I), R 1 and R 2 are each a methyl group or a phenyl group. However, in order to impart heat resistance or the like to the pressure-sensitive adhesive layer, the molar ratio between the methyl group and the phenyl group (methyl group / Phenyl group) is preferably 25/75 to 98/2, particularly preferably 85/15 to 95/5.
[0012]
In addition, an organosiloxane rubber component represented by the above formula (I) (hereinafter referred to as “component (1)”) and a silicone resin represented by the above formula (II) or a hydroxyl group bonded to the silicon atom are contained in a molecule. The silicone pressure-sensitive adhesive obtained by a partial condensation reaction with a branched polyorganosiloxane having three or more (hereinafter, referred to as "component (2)") has a hydroxyl group bonded to a silicon atom in a molecule of 0.1 to 0.1%. The content is preferably 0.9% by mass. More preferably, it is 0.2 to 0.7% by mass. In this range, the adhesive property is particularly excellent in stability over time.
[0013]
As such a silicone pressure-sensitive adhesive, for example, 355 manufactured by Dow Corning Co .; PSA518, PSA590, PSA595, PSA6574 manufactured by General Electric; YR3340 and XR37-B6722 manufactured by GE Toshiba Silicone Co., Ltd. are commercially available. Commercial products can be used.
[0014]
In the silicone pressure-sensitive adhesive composition of the present invention, 0.1 to 20 parts by mass of an acrylic polymer having a reactive functional group other than a hydroxyl group is blended with 100 parts by mass of the organosiloxane polymer. When the blending amount of the acrylic polymer is less than the lower limit, formation of a network structure by the acrylic polymer becomes insufficient, and an effect of improving holding power (cohesive force) cannot be obtained. The adhesive properties inherent to the agent are impaired.
[0015]
The reactive functional group of the acrylic polymer may be appropriately selected in relation to the functional group of the crosslinking agent so that the crosslinking agent used can selectively crosslink only the acrylic polymer.
[0016]
Examples of the combination of the functional groups include a carboxyl group and an ethylene imino group, a carboxyl group and a metal chelate, a carboxyl group and an amino group, an acetoacetate group and a metal chelate, and one of them is a reactive functional group of an acrylic polymer. The other can be used as a functional group of a crosslinking agent.
[0017]
The alkyl (meth) acrylate used as the main component of the raw material monomer of the acrylic polymer is not particularly limited, but usually, the alkyl group constituting the ester group is an alkyl group having 1 to 18 carbon atoms. Certain types of alkyl acrylates or alkyl methacrylates can be used, and specifically, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, acrylic acid Examples thereof include isooctyl, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, and isooctyl methacrylate.
[0018]
In the present invention, as the monomer constituting the acrylic polymer, the alkyl (meth) acrylate may be used alone or in combination of two or more.
[0019]
As a monomer for introducing a reactive functional group into the acrylic polymer, for example, when the reactive functional group is a carboxyl group, acrylic acid, methacrylic acid and the like are mentioned, and the reactive functional group is an acetoacetate group. When it is, 2- (meth) acryloyloxyethyl acetoacetate etc. are mentioned.
[0020]
Further, other copolymerizable monomers may be used in combination. Other copolymerizable monomers include acrylics such as vinyl acetate, styrene, acrylonitrile, acrylamide, dimethylacrylamide, 2-hydroxyethyl acrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate, and N-vinylpyrrolidone. Any of various monomers known as monomers for modifying an adhesive can be used.
[0021]
The polymerization of these monomers is carried out by ordinary polymerization methods such as solution polymerization, emulsion polymerization, bulk polymerization and the like. The polymerization reaction temperature is usually 50 to 85 ° C, preferably 60 to 80 ° C.
[0022]
When performing solution polymerization, the solid content is usually 0.5 to 60% by mass, preferably 5 to 50% by mass in a solvent such as acetone, benzene, toluene, ethyl acetate, hexane, heptane, methanol, ethanol and isopropanol. % By using a polymerization initiator such as azobisisobutyronitrile and benzoyl peroxide.
[0023]
The amount (solid content) of the polymerization initiator is usually 0.05 to 1 part by mass based on 100 parts by mass of the acrylic polymer (solid content).
[0024]
The silicone pressure-sensitive adhesive composition of the present invention contains a crosslinking agent that reacts with a reactive functional group in the acrylic polymer but does not react with a hydroxyl group in the organosiloxane polymer.
[0025]
As described above, such a crosslinking agent may be appropriately selected depending on the relationship with the reactive functional group of the acrylic polymer.
[0026]
Examples of the crosslinking agent having an ethyleneimino group as a functional group include an aziridine crosslinking agent, that is, an aziridine compound having two or more ethyleneimino groups in one molecule, such as N, N'-tetramethylenebisethyleneimine, N, N ' -Pentamethylenebisethyleneimine, N, N'-hexamethylenebisethyleneimine, p-phenylenebisethyleneimine, m-phenylenebisethyleneimine, m-toluylenebisethyleneimine, biphenyl-4,4'-bisethyleneimine And ethyleneimine compounds such as 3,3'-dimethylbiphenyl-4,4'-bisethyleneimine and diphenylmethane-4,4'-bisethyleneimine; N, N'-tetramethylenebisethyleneamide, N, N'- Hexamethylenebisethyleneamide, p-phenylenebisethyleneamide N, N'-tetra, ethylene-amide compounds such as m-phenylenebisethyleneamide, m-toluylenebisethyleneamide, biphenyl-4,4'-bisethyleneamide, diphenylmethane-4,4'-bisethyleneamide; Methylene bisethylene urea, N, N'-hexamethylene bisethylene urea, p-phenylene bisethylene urea, m-phenylene bisethylene urea, m-toluylene bisethylene urea, 1-chloro-m-phenylene bisethylene urea, biphenyl -4,4'-bisethylene urea, 3,3'-dimethylbiphenyl-4,4'-bisethylene urea, 3,3'-dimethoxybiphenyl-4,4'-bisethylene urea, diphenylmethane-p, p ' -Bisethylene urea, m-xylylene bisethylene urea, Ethylene urea compounds such as urea; tetramethylene bisethylene urethane, hexamethylene bisethylene urethane, 1,4-cyclohexylethylene urethane, 2,2 '-(bis-p-ethyleneiminoformyloxyphenyl) propane, 1,3- Ethylene urethane compounds such as (bisethyleneiminoformyloxymethyl) benzene and mesitylene lithethyleneethylene urethane; N, N'-tetramethylenebisethylenethiourea, N, N'-hexamethylenebisethylenethiourea, m-toluylenebis Ethylenethiourea compounds such as ethylenethiourea, biphenyl-4,4'-bisethylenethiourea, diphenylmethane-p, p'-bisethylenethiourea, m-xylylenebisethylenethiourea, and mesitylene sthyleneethyleneurea. , These are one Species or a mixture of two or more can be used. Of these compounds, N, N'-hexamethylenebisethylene urea is particularly preferred from the viewpoints of reaction rate and adhesive properties.
[0027]
Examples of the metal chelate compound include acetylacetone and acetoacetate coordination compounds of polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium.
[0028]
Examples of the crosslinking agent having an amino group include hexamethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethyltetramine, isophoronediamine, an amino resin, and a melamine resin.
[0029]
The compounding amount of the crosslinking agent is 0.1 to 1 equivalent, preferably 0.2 to 1 equivalent, more preferably 0.3 to 1 equivalent based on the reactive functional group in the acrylic polymer. If the amount is less than 0.1 equivalent, the formation of the network structure by the acrylic polymer becomes insufficient, and the effect of improving the holding power (cohesive force) cannot be obtained. The radicals remain and cause skin irritation.
[0030]
The pressure-sensitive adhesive composition of the present invention may contain, if necessary, a softener such as process oil, polyisobutylene, or polybutene; a filler such as titanium oxide, zinc oxide, aluminum metasilicate, calcium carbonate, or calcium phosphate; starch, or a cellulose derivative. , A water retention function imparting agent such as polyvinyl alcohol; and liquid paraffin.
[0031]
When using the pressure-sensitive adhesive composition of the present invention, a solution dissolved in an organic solvent such as toluene, ethyl acetate, methyl ethyl ketone, or acetone is applied to a support or a film such as a release film, and then 30 to 170 ° C., preferably 40 to 170 ° C. Crosslinking by drying at a drying temperature of ~ 150 ° C gives its adhesive properties.
[0032]
The support used for the skin patch or the first-aid adhesive plaster of the present invention has an adhesive layer comprising the above-mentioned adhesive composition laminated and held on one surface. Specific materials include polystyrene-based thermoplastic elastomer films, polyolefin-based films such as polyethylene, polypropylene, ethylene / methacrylic acid copolymer, and ethylene / methyl methacrylate, polyurethane-based films, polyester-based films, and various plastic materials. , A nonwoven fabric, a knitted fabric, a paper, a laminate of these films, a laminate of papers, or the like.
[0033]
The thickness of the support is arbitrary depending on the material. Usually, when the film is used as the support, the thickness is 15 to 250 μm, preferably about 30 to 100 μm. Is about 50 to 500 μm, preferably about 100 to 300 μm.
[0034]
The skin patch and the emergency plaster of the present invention are obtained by laminating an adhesive layer having a specific composition on one surface of a support. Lamination can be performed by applying the pressure-sensitive adhesive composition, and this coating can be performed directly or by a transfer coating method according to a general coating method.
[0035]
Further, when a film made of a material having no moisture permeability is used as the support used in the present invention, when the film is applied to the skin surface for a long time, the applied portion may be moistened, and as a result, skin rash may occur. . Therefore, even when such a support is used or when a support having moisture permeability is used, it is preferable to perforate the support and the pressure-sensitive adhesive layer in order to further impart moisture permeability. To perform the perforation treatment, a method using a perforation roll, a method such as punching or laser irradiation can be used, and the hole diameter is about 0.2 to 2 mm.
[0036]
Further, in the present invention, an emergency adhesive plaster can be provided by providing a liquid-absorbent pad in the central region of the surface of the pressure-sensitive adhesive layer of the skin patch obtained as described above. As the absorbent pad, for example, gauze, cotton cloth, nonwoven fabric, a composite product of absorbent cotton and nonwoven fabric, a composite product of absorbent cotton and a knitted net, and the like can be used to absorb exudate from the wound site and furthermore, Is preferred.
[0037]
In order to prevent contamination of the surface of the pressure-sensitive adhesive layer, the surface of the pressure-sensitive adhesive layer is preferably coated with a release material until the surface of the pressure-sensitive adhesive layer is used in the skin adhesive material and the first-aid bandage of the present invention. In this case, the release material used is a fluorine-based silicone or a methyl-based silicone for the release material in order to improve the releasability from the adhesive layer containing the organosiloxane polymer on paper, polyolefin laminated paper, polyester film, or the like. It is preferable to use one coated with.
[0038]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but these do not limit the scope of the present invention at all. In the following, parts mean parts by mass, and% means mass%.
[0039]
(Example 1)
Acrylic acid 2 polymerized by adding 0.25 parts of ethyl acetate as a solvent and azobisisobutyronitrile as an initiator to 100 parts (solid content) of a methylphenyl silicone adhesive (XR37-B6722, manufactured by GE Toshiba Silicone) -10 parts (solid content) of ethylhexyl, n-butyl acrylate, and methacrylic acid copolymer (monomer composition ratio (%): 30: 65: 5, solid content 50%) were added, and the mixture was sufficiently stirred. To this, 0.09 part (solid content) of a 5% toluene solution of N, N'-hexamethylenebisethylene urea as a crosslinking agent for the acrylic polymer (0.25 equivalent based on the reactive functional group in the acrylic polymer) In addition, the mixture was sufficiently stirred. Next, it is coated on a release paper for silicone adhesive (Binasheet 70XT-032HK-H, manufactured by Fujimori Kogyo Co., Ltd.) so that the coating amount after drying is 40 g / m 2, and dried with hot air at 100 ° C. for 3 minutes. did. After drying, a 25 μm-thick polyethylene terephthalate (PET) film (Lumirror, manufactured by Toray Industries, Inc.) was laminated to form an adhesive sheet.
[0040]
(Example 2)
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1, except that the amount of the crosslinking agent was changed to 0.18 part (solid content) (0.5 equivalent to the reactive functional group in the acrylic polymer). .
[0041]
(Example 3)
An adhesive sheet was prepared in the same manner as in Example 1 except that the amount of the crosslinking agent was changed to 0.36 part (solid content) (1.0 equivalent to the reactive functional group in the acrylic polymer). .
[0042]
(Example 4)
Example 1 was repeated except that the blending amount of the acrylic polymer was 5 parts (solid content) and the blending amount of the crosslinking agent was 0.045 parts (0.25 equivalents relative to the reactive functional groups in the acrylic polymer). An adhesive sheet was prepared in the same manner.
[0043]
(Example 5)
Performed except that the blending amount of the acrylic polymer was 5 parts (solid content) and the crosslinking agent was 0.09 parts (solid content) (0.5 equivalent to the reactive functional group in the acrylic polymer). An adhesive sheet was prepared in the same manner as in Example 1.
[0044]
(Example 6)
Performed except that the blending amount of the acrylic polymer was 15 parts (solid content) and the crosslinking agent was 0.135 parts (solid content) (0.25 equivalent to the reactive functional group in the acrylic polymer). An adhesive sheet was prepared in the same manner as in Example 1.
[0045]
(Comparative Example 1)
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1, except that the acrylic polymer and the crosslinking agent were not added.
[0046]
With respect to the pressure-sensitive adhesive sheets of Examples 1 to 6 and Comparative Example 1, the adherend was a phenol resin plate, and the pressure-sensitive adhesive strength and probe tack were measured according to JIS Z0237. Further, the holding force at 40 ° C. (substrate to be adhered SUS) was measured as the falling time of the weight using a creep tester. Table 1 shows the composition and measurement results. From Table 1, it can be seen that, as compared with the uncrosslinked one (Comparative Example 1), the holding power was higher (based on the improvement of the cohesive force due to crosslinking), and the adhesive strength and the probe tack were almost maintained.
[0047]
Next, these samples were affixed to the inner parts of the forearms of five panelists, peeled off after 3 hours, and the state of the adhesive remaining on the skin was confirmed. The results are shown in Table 1.
[0048]
In the case of adding and cross-linking an acrylic polymer, any of the formulations improves the cohesiveness of the pressure-sensitive adhesive composition by forming a network structure of the cross-linked acrylic polymer, reducing adhesive residue on the skin, Good results were shown. This is considered to be supported by the results of the holding force measurement.
[0049]
[Table 1]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the silicone adhesive composition for skin adhesives and the skin adhesives which improved holding power can be provided, maintaining the adhesive physical property which a silicone adhesive has originally.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003069429A JP4363866B2 (en) | 2003-03-14 | 2003-03-14 | Silicone adhesive composition for skin patch and skin patch using the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003069429A JP4363866B2 (en) | 2003-03-14 | 2003-03-14 | Silicone adhesive composition for skin patch and skin patch using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004275329A true JP2004275329A (en) | 2004-10-07 |
| JP4363866B2 JP4363866B2 (en) | 2009-11-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2003069429A Expired - Fee Related JP4363866B2 (en) | 2003-03-14 | 2003-03-14 | Silicone adhesive composition for skin patch and skin patch using the same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006204384A (en) * | 2005-01-25 | 2006-08-10 | Nitto Denko Corp | Adhesive material composition and medical adhesive material using it |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06510279A (en) * | 1991-06-27 | 1994-11-17 | ノーヴェン ファーマシューティカルズ インコーポレイテッド | Drug delivery system and method for varying drug saturation concentration based on solubility parameters |
| JPH0892074A (en) * | 1994-09-28 | 1996-04-09 | Nitto Denko Corp | Plaster |
| JPH08295624A (en) * | 1995-04-26 | 1996-11-12 | Read Chem Kk | Plaster base, its production and patch for external use using the same base |
-
2003
- 2003-03-14 JP JP2003069429A patent/JP4363866B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06510279A (en) * | 1991-06-27 | 1994-11-17 | ノーヴェン ファーマシューティカルズ インコーポレイテッド | Drug delivery system and method for varying drug saturation concentration based on solubility parameters |
| JPH0892074A (en) * | 1994-09-28 | 1996-04-09 | Nitto Denko Corp | Plaster |
| JPH08295624A (en) * | 1995-04-26 | 1996-11-12 | Read Chem Kk | Plaster base, its production and patch for external use using the same base |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006204384A (en) * | 2005-01-25 | 2006-08-10 | Nitto Denko Corp | Adhesive material composition and medical adhesive material using it |
| 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 |
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| Publication number | Publication date |
|---|---|
| JP4363866B2 (en) | 2009-11-11 |
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