JP4057174B2 - Adhesive composition and method for producing adhesive product - Google Patents

Description

などで示される鎖状、環状のものや、これらのユニットを２個以上有する
【００２６】
【化２】

などで示されるものが挙げられる。
【００２７】
またこれら（Ｂ）成分の使用にあたっては、（Ａ）成分や（Ｃ）成分、（Ｅ）成分との相溶性、あるいは系中における分散安定性がよいものが好ましい。
特に系全体の粘度が低い場合には、（Ｂ）成分として上記各成分との相溶性の低いものを使用すると、相分離が起こり硬化不良を引き起こすことがある。また、分散性助剤として、微粉末シリカ等の粒径の小さいフィラーを配合してもよい。
（Ａ）成分および（Ｅ）成分との相溶性、あるいは分散安定性が比較的良好なものとして具体的に示すと、
【００２８】
【化３】

などが挙げられる。
【００２９】
また、本発明における（Ｂ）成分の使用量としては、（Ａ）成分のアルケニル基の総量に対して、（Ｂ）成分のケイ素原子結合水素原子が０．８〜５．０当量となるように使用することが好ましい。上記（Ａ）成分のアルケニル基総量に対して（Ｂ）成分のケイ素原子結合水素原子が０．８に満たない場合、架橋が不十分となる。また、５．０を越える場合には、硬化後に残留するケイ素原子結合水素原子の影響により物性が大きく変化することが問題となる。特にこの影響を抑制したい場合には１．０〜２．０当量となるように（Ｂ）成分を用いることが好ましい。
【００３０】
本発明の（Ｃ）成分である可塑剤は、本粘着剤組成物から得られる粘着剤の粘着特性を向上させるために必須となる成分である。この（Ｃ）成分としては、前記目的を達することができれば、特に限定はないが、１）（Ａ）成分との相溶性が良好であること、２）硬化条件下において揮発分が少ないことが好ましい。すなわち（Ｃ）成分としては、極性の低い炭化水素系化合物であること、炭素数６以上の化合物であることが好ましく、炭素数８以上の化合物がさらに好ましい。（Ｃ）成分の具体例としては、Ｃ６〜Ｃ３０、好ましくはＣ８〜Ｃ１８の炭化水素系プロセスオイルなどが挙げられるが、これらに限定されるものではない。（Ｃ）成分の配合量は、（Ａ）成分１００重量部に対して１〜２００重量部、好ましくは５〜１５０重量部、さらに好ましくは１０重量部〜１００重量部用いることが好ましい。配合量が２００重量部を越えるとゲル分率の高い粘着剤を得ることが困難になり、１部より少ないと粘着性が得られない。
【００３１】
本発明の（Ｄ）成分であるヒドロシリル化触媒については、特に制限はなく、任意のものが使用できる。具体的に例示すれば、塩化白金酸、白金の単体、アルミナ、シリカ、カ−ボンブラック等の担体に固体白金を担持させたもの；白金ービニルシロキサン錯体｛例えば、Ｐｔ_n（ＶｉＭｅ₂ＳｉＯＳｉＭｅ₂Ｖｉ）ｎ、Ｐｔ〔（ＭｅＶｉＳｉＯ）₄〕_m｝；白金ーホスフィン錯体｛例えば、Ｐｔ（ＰＰｈ₃）₄、Ｐｔ（ＰＢｕ₃）₄｝；白金ーホスファイト錯体｛例えば、Ｐｔ〔Ｐ（ＯＰｈ）₃〕₄、Ｐｔ〔Ｐ（ＯＢｕ）₃〕₄（式中、Ｍｅはメチル基、Ｂｕはブチル基、Ｖｉはビニル基、Ｐｈはフェニル基を表し、ｎ、ｍは整数を表）｝、Ｐｔ（ａｃａｃ）₂、また、Ａｓｈｂｙらの米国特許第３１５９６０１及び３１５９６６２号明細書中に記載された白金−炭化水素複合体、並びにＬａｍｏｒｅａｕｘらの米国特許第３２２０９７２号明細書中に記載された白金アルコラ−ト触媒も挙げられる。
【００３２】
また、白金化合物以外の触媒の例としては、ＲｈＣｌ（ＰＰｈ₃）₃、ＲｈＣｌ₃、Ｒｈ／Ａl₂Ｏ₃、ＲｕＣｌ₃、ＩｒＣｌ₃、ＦｅＣｌ₃、ＡｌＣｌ₃、ＰｄＣｌ₂・２Ｈ₂Ｏ、ＮｉＣｌ₂、ＴｉＣｌ₄、等が挙げられる。これらの触媒は単独で使用してもよく、２種以上併用しても構わない。触媒活性の点から塩化白金酸、白金−オレフィン錯体、白金−ビニルシロキサン錯体、Ｐｔ（ａｃａｃ）₂等が好ましい。触媒量としては特に制限はないが、（Ａ）成分中のアルケニル基１ｍｏｌに対して１０^-1〜１０^-8ｍｏｌの範囲で用いるのが好ましく、１０^-2〜１０^-6ｍｏｌの範囲で用いるのがさらに好ましい。また、ヒドロシリル化触媒は、一般に高価で腐食性であり、また、水素ガスを大量に発生して硬化物が発泡してしまう場合があるので１０^-1モル以上用いない方がよい。
【００３３】
本発明においては、貴金属触媒を用いたアルケニル基に対するＳｉ−Ｈ基の付加反応によって硬化性組成物が硬化するので、硬化速度が非常に速く、ライン生産を行う上で好都合である。
【００３４】
本発明の（Ｅ）成分である粘着付与樹脂には特に限定はなく、通常、粘着付与剤として使用されるものを使用できる。具体例としては、フェノール樹脂、変性フェノール樹脂、シクロペンタジエン−フェノール樹脂、キシレン樹脂、クマロン樹脂、石油樹脂、テルペン樹脂、テルペンフェノール樹脂、ロジンエステル樹脂などが挙げられる。これらの中では、テルペン系樹脂、石油樹脂が特に相溶性がよく、粘着特性が良好であるので好ましい。これらは単独で用いてもよく、２種以上を併用してもよい。
【００３５】
粘着付与樹脂の使用量は、（Ａ）成分１００重量部に対して１０〜３００重量部、さらに好ましくは３０〜１５０重量部が挙げられるが、これに限定されるものではない。該量が１０部未満または３００部より多くなるとタックが不足したり、粘着力が不足したりする傾向にある。
【００３６】
また、本発明の硬化性組成物には保存安定性を改良する目的で、保存安定性改良剤を使用することができる。この保存安定性改良剤としては、本発明の（Ｂ）成分の保存安定剤として知られている通常の安定剤であり、所期の目的を達成するものであればよく、特に限定されるものではない。具体的には、脂肪族不飽和結合を含有する化合物、有機リン化合物、有機硫黄化合物、窒素含有化合物、スズ系化合物、有機過酸化物等を好適に用いることができる。さらに具体的には、２−ベンゾチアゾリルサルファイド、ベンゾチアゾ−ル、チアゾ−ル、ジメチルアセチレンダイカルボキシレ−ト、ジエチルアセチレンダイカルボキシレ−ト、ＢＨＴ、ブチルヒドロキシアニソ−ル、ビタミンＥ、２−（４−モルフォジニルジチオ）ベンゾチアゾ−ル、３−メチル−１−ブテン−３−オ−ル、アセチレン性不飽和基含有オルガノシロキサン、アセチレンアルコ−ル、３−メチル−１−ブチル−３−オ−ル、ジアリルフマレ−ト、ジアリルマレエ−ト、ジエチルフマレ−ト、ジエチルマレエ−ト、ジメチルマレエ−ト、２−ペンテンニトリル、２，３−ジクロロプロペン等が挙げられるが、これらに限定されるわけではない。
また、本発明の粘着剤組成物には、さらに必要に応じて、各種支持体（プラスチックフィルム、金属ホイル、紙など）に対する接着性を向上させるための含窒素シラン化合物、酸化防止剤、紫外線吸収剤、顔料、界面活性剤等を適宜添加することができる。これらの使用にあたっては、ヒドロシリル化反応に対する影響を考慮しなければならない。前記含窒素シラン化合物の具体例としては、Ｈ₂ＮＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃、Ｈ₂ＮＣＨ₂ＣＨ₂ＮＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃、Ｈ₂ＮＣＨ₂ＣＨ₂ＮＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＣＨ₃）（ＯＣＨ₃）₂、（Ｃ₂Ｈ₅Ｏ）₃ＳｉＣＨ₂ＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＮＨＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣ₂Ｈ₅）₃などのアミノ基および／またはイミノ基含有アルコキシシラン、前記アミノ基および／またはイミノ基含有アルコキシシランと
【００３７】
【化４】

のようなエポキシシラン化合物との反応生成物、前記アミノ基および／またはイミノ基含有アルコキシシランとＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃）₃、ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₂ＯＣＨ₃）₃のようなメタクリルオキシシラン化合物との反応生成物などが挙げられる。前記含窒素シラン化合物の使用量は、（Ａ）成分と（Ｂ）成分の合計量１００重量部に対して０．０１〜１０重量部が好ましく、０．１〜５重量部がさらに好ましい。前記充填剤の具体例としては、シリカ微粉末、炭酸カルシウム、クレー、タルク、酸化チタン、亜鉛華、ケイソウ土、硫酸バリウム、カーボンブラックなどが挙げられる。これらの充填剤の中では、特にシリカ微粉末、とりわけ粒子径が５０〜７０ｎｍ（ＢＥＴ比表面積が５０〜３８０ｍ²／ｇ）程度の微粉末シリカが好ましく、その中でも表面処理を施した疎水性シリカが、強度を好ましい方向に改善する働きが大きいので特に好ましい。
【００３８】
次に、本発明の粘着製品の製造方法を製造プロセスの例を挙げて説明する。
ただし、本発明は支持体に粘着剤組成物を塗布し熱硬化させるものであればよく、以下の例に限定されるものでない。
【００３９】
支持体上にコーターで前記粘着剤組成物を塗布し、これを加熱硬化させて粘着製品を得る。支持体としては、合成樹脂製または変成天然物製のフィルム、紙、あらゆる種類の布、金属箔などを用いることができる。支持体の具体例としては、ポリエチレン、ポリプロピレン、ポリイミド、ポリカーボネート、ポリ塩化ビニル、ポリエステル、ポリウレタン、セロハン、含浸紙、コート紙、上質紙、クラフト紙、布、アセテート布、不織布、ガラス布、金属箔が挙げられるが、これらに限定されるわけではない。これらはそれぞれ単独で用いてもよいし、少なくとも２種以上を積層して用いてもよい。熱硬化させる方法は特に限定されないが、その温度は、使用する重合体、及び添加される化合物等の種類により異なるが、通常４０℃〜１８０℃の範囲内が好ましく、７０℃〜１４０℃の範囲内がより好ましい。硬化時間は、使用する重合体、及び添加される化合物、反応温度等により異なるが、通常０．１分〜２４時間、好ましくは１分〜１０時間、さらに好ましくは１分〜１時間の範囲内である。
【００４０】
本発明においては、（Ａ）成分として飽和炭化水素系重合体を用いていることから、得られる粘着剤は優れた耐熱性、耐候性、耐水性、耐薬品性、電気絶縁性を有し、その適用範囲は広く幅広い用途に応用でき得る。さらに（Ａ）成分としてイソブチレン系重合体を用いれば、前記特性に加え、低透湿性、低吸湿性、低気体透過性に優れた粘着剤を得ることができる。本発明の粘着製品は、包装用粘着テープ、事務用粘着テープ、塗装マスキング用テープ、電気絶縁用粘着テープ、結束用粘着テープ、保護用粘着テープ、識別・装飾用粘着テープおよびシート、医療用粘着テープ、両面粘着テープ、電磁波障害対策フィルムおよびテープ、再剥離フィルムおよびテープ、化粧板フィルム、半導体チップ搬送用テープ、マーキングフィルム、深絞り加工用保護フィルム、ガラス飛散防止フィルム、発泡粘着テープ、防水・止水テープ、防食用粘着テープ、表面保護用粘着テープ、ダイシング用粘着テープ、バックグラインド用粘着テープ、印刷用粘着シート、粘着ラベル等の粘着製品に好適な材料となる。
【００４１】
【実施例】
以下の実施例に基づき本発明をさらに詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。
（実施例１）
次に実施例を挙げて、本発明をより一層明らかにするが、実施例により本発明は何ら限定されるものではない。
（Ａ）成分としては、特開平８−１３４２２０に記載されている方法により合成した下記の構造を示す化合物（分析値は表１に示す）を使用した。
【００４２】
【表１】

【００４３】
【化５】

（Ａ）成分１００重量部に対し、（Ｃ）成分として炭化水素系プロセスオイル（出光石油化学製 ＰＷ−３８０）を５０重量部、酸化防止剤としてＭＡＲＫＡＯ−５０（アデカアーガス化学（株））を１重量部加えて、手混ぜ混練した。この際、酸化防止剤を溶解させるため７０℃程度に加温した。該配合物を室温に戻した後、（Ａ）成分１００重量部に対して。（Ｅ）成分として、石油樹脂系粘着付与樹脂（荒川化学工業（株）製、商品名：アルコンＰ−１００）７５重量部を５０重量％トルエン溶液にして加え、ついで、この混合物に下記に構造を示す（Ｂ）成分
【００４４】
【化６】

を（Ａ）成分１００重量部に対し３重量部混合した。更に、（Ｄ）成分としてビス（１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン）白金錯体触媒（１７．９×１０^-5ｍｍｏｌ／μｌ、キシレン溶液）を白金が（Ａ）成分のアルケニル基量のモル数に対して５×１０^-4当量となる量、及び保存安定性改良剤としてジメチルマレエートを白金に対し３モル当量秤量し、均一混合した。このようにして得られた粘着剤組成物を、乾燥後の厚さが約５０μｍとなるように厚さ５０μｍのコロナ処理を施したポリエチレンテレフタレートフィルム（東レ（株）製）に塗布し、室温で１時間乾燥させた後、１２０℃で１０分間加熱硬化させ、粘着テープを作製した。このように得られた粘着テープの粘着力をステンレス鋼板に貼り付けた粘着テープの手剥がしにより評価し、タックを手触りにて評価し、結果を表２に示した。手剥がしによる粘着力は、粘着力の強いものを○、少し粘着力が弱いものを△、粘着力がほとんどないものを×というように評価した。手触りによるタックの評価は、指を軽く粘着テープに押しあてた後、粘着テープが指についたまま持ち上がったものを○、一部が持ち上がったものを△、全く持ち上がらなかったものを×とした。さらに、粘着特性（粘着力、タック、保持力）をＪＩＳ Ｚ−０２３７に準じ、以下の方法にしたがって測定し、結果を表３に示した。
（１）粘着力
得られた粘着テープを幅２５ｍｍに切断し、粘着テープの粘着面をステンレス鋼板（ＳＵＳ＃３０４）に貼着、３０分放置した後、引張試験機にて２３℃、６５％ＲＨ条件下、剥離速度３００ｍｍ／ｍｉｎで１８０度引き剥がし粘着力を測定した。ただし、ＳＵＳ板の表面は２４０番耐水研磨紙にて研磨したものを使用した。
（２）タック
傾斜角３０度の斜面に、得られた粘着テープをセットし、２３℃、６５％ＲＨ条件下、助走距離１０ｃｍでステンレス鋼製ボールを転がし、粘着面１０ｃｍ以内のところで停止する最大のボール番号を測定した。
（３）保持力
得られた粘着テープをの粘着面のうち縦２５ｍｍ、横２５ｍｍの部分をステンレス鋼板（ＳＵＳ＃３０４）に貼着し、１００℃の雰囲気下、１ｋｇの荷重をかけ、粘着テープがずれた距離を測定した。
また、屋外にて１週間放置後のサンプルの外観の変化についてを観察を行って耐候評価を行い、結果を表３に示した。さらに、ステンレス鋼板に貼り付けた粘着テープを水に浸し、３日間放置した後、その粘着力の強さを手剥がしすることで耐水評価を行った。この結果を表３に示した。耐候評価については、外観変化がないものを○、一部変化が見られるものを△、変色の見られるものを×とした。耐水評価については、手剥がしで、粘着力の変化がないものを○、やや剥がれやすくなったものを△、すぐに剥がれたものを×とした。
（実施例２）
実施例１における（Ｅ）成分を石油樹脂系粘着付与樹脂アルコンＭ−１００（荒川化学工業（株）製）に変え、それ以外はすべて実施例１と同様に行った。結果を表２、３に示す。
（実施例３）
実施例１における（Ｅ）成分を石油樹脂系粘着付与樹脂リガライトＲ−１２５（理化ハーキュレス（株）製）に変え、それ以外はすべて実施例１と同様に行った。結果を表２、３に示す。
（実施例４）
実施例１における（Ｅ）成分をテルペン系粘着付与樹脂クリアロンＰ−１０５（安原油脂（株）製）に変え、それ以外はすべて実施例１と同様に行った。
結果を表２、３に示す。
（比較例１）
実施例１における（Ｃ）成分である可塑剤を添加せず、実施例１における（Ｅ）成分をテルペン系粘着付与樹脂クリアロンＰ−１０５（安原油脂（株）製）に変えて粘着テープを作成し、タックを手触りにて、粘着力をステンレス鋼板に貼り付けた粘着テープの手剥がしにより評価した。結果を表２に示す。
（比較例２）
実施例１における（Ｃ）成分である可塑剤を添加せず、実施例１における（Ｅ）成分を石油樹脂系粘着付与樹脂リガライトＲ−１２５（理化ハーキュレス（株）製）に変えて粘着テープを作成し、タックを手触りにて、粘着力をステンレス鋼板に貼り付けた粘着テープの手剥がしにより評価した。結果を表２に示す。
【００４５】
【表２】

【００４６】
【表３】

表より、本発明における粘着剤組成物はタック、粘着力のバランスに優れることが明らかである。また、耐候性、耐水性とも良好であるという結果が得られた。
【００４７】
【発明の効果】
本発明により、耐候、耐水等に優れ、粘着特性が改良された粘着剤組成物を提供することができる。さらに、この組成物を用いた粘着製品の製造方法も提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a pressure-sensitive adhesive composition and a method for producing a pressure-sensitive adhesive product using the same. More specifically, the main component is a saturated hydrocarbon polymer having at least one hydrosilylation-reactive alkenyl group in the molecule, a compound having at least two hydrosilyl groups in the molecule, a hydrosilylation catalyst, and a plasticizer. The present invention relates to an addition-type curable pressure-sensitive adhesive composition and a method for producing a pressure-sensitive adhesive product using the same.
[0002]
[Prior art]
The pressure-sensitive adhesive is also called a pressure-sensitive adhesive, and has a property of easily adhering to the surface of an object with a pressure small enough to be pressed with a fingertip. Such an adhesive is used for adhesive products, such as a cellophane tape, a masking tape, a vinyl tape for electrical insulation, an adhesive sheet, and an adhesive label, for example. In particular, a pressure-sensitive adhesive tape having a support made of polyvinyl chloride is widely used because it has various excellent characteristics such as being inexpensive and having excellent water resistance and electrical characteristics.
[0003]
As the pressure-sensitive adhesive used in the pressure-sensitive adhesive tape, those mainly composed of natural rubber, synthetic rubber and the like and those mainly composed of an acrylate copolymer are mainly used. However, these pressure-sensitive adhesive compositions are generally easily deteriorated by heat, light, etc., and when a pressure-sensitive adhesive product using the pressure-sensitive adhesive composition is used outdoors, the weather resistance is insufficient, so that end peeling or the like is likely to occur. As a result, the function as an adhesive product cannot be exhibited sufficiently. In order to solve this problem, a saturated hydrocarbon polymer having a hydroxyl group bonded to a silicon atom or a hydrolyzable group and having at least one silicon-containing group that can be crosslinked by forming a siloxane bond, and an adhesive A pressure-sensitive adhesive composition containing an imparting resin has been developed, but since this pressure-sensitive adhesive composition is cured by a condensation reaction of a functional silyl group, the curing speed may not be sufficient depending on the application. If it is slow, there is a problem that it is inconvenient for line production (Japanese Patent Laid-Open No. 1-170681). In order to solve this problem, a compound having at least one alkenyl group in the molecule, a compound having at least two hydrosilyl groups in the molecule, and a fast-curing addition-type pressure-sensitive adhesive mainly comprising a hydrosilylation catalyst Although a composition has been developed (Japanese Patent Laid-Open No. 4-145188), particularly when a saturated hydrocarbon polymer is used as a compound having at least one alkenyl group in the molecule, in some cases, tack and adhesive strength may be reduced. There was sometimes room for improvement.
[0004]
[Problems to be solved by the invention]
The present invention improves the adhesive properties of an adhesive composition using a saturated hydrocarbon polymer among the adhesive compositions disclosed in JP-A-4-145188, and contains at least one hydrosilyl group in the molecule. Saturated hydrocarbon polymer having an alkenyl group capable of oxidization reaction, compound having at least two hydrosilyl groups in the molecule, hydrosilylation catalyst, tackiness and adhesion by adding hydrocarbon plasticizer to tackifying resin An improved pressure-sensitive adhesive composition excellent in heat resistance, weather resistance, water resistance, and the like, and a method for producing a pressure-sensitive adhesive product are provided.
[0005]
[Means for Solving the Problems]
The present inventors add a plasticizer and a pressure-sensitive adhesive to a curable material comprising a saturated hydrocarbon polymer having an alkenyl group capable of hydrosilylation reaction, a curing agent having a hydrosilyl group, and a hydrosilylation catalyst. Thus, it was found that a pressure-sensitive adhesive composition having excellent heat resistance, weather resistance, water resistance and the like and having improved adhesive properties can be obtained. That is, the present invention
(1) (A) Saturated hydrocarbon polymer having in the molecule at least one alkenyl group capable of hydrosilylation reaction
(B) Compound having at least two hydrosilyl groups in the molecule
(C) Plasticizer
(D) Hydrosilylation catalyst
(E) Tackifying resin
It is related with the adhesive composition which consists of.
[0006]
The present invention also provides:
(2) The pressure-sensitive adhesive composition according to (1), wherein an alkenyl group capable of hydrosilylation in the polymer of component (A) is present at the molecular end.
[0007]
The present invention also provides:
(3) The pressure-sensitive adhesive composition according to (1) or (2), wherein the saturated hydrocarbon polymer of component (A) is an isobutylene polymer.
[0008]
The present invention also provides:
(4) The pressure-sensitive adhesive composition according to (1) to (3), wherein the total amount of repeating units derived from isobutylene in the polymer of component (A) is 50% by weight or more.
[0009]
The present invention also provides:
(5) The compound having at least two hydrosilyl groups in the molecule of component (B) is a polyorganohydrogensiloxane having an average of more than two silicon-bonded hydrogen atoms in one molecule (1) It relates to the pressure-sensitive adhesive composition of (4).
[0010]
The present invention also provides:
(6) The pressure-sensitive adhesive composition according to (1) to (5), wherein the plasticizer of component (C) is a hydrocarbon process oil.
[0011]
The present invention also provides:
(7) It is related with the adhesive composition of (1)-(6) whose tackifying resin of (E) component is a terpene type tackifying resin and / or a petroleum resin type tackifying resin.
[0012]
The present invention also provides:
(8) It is related with the adhesive composition of (1)-(7) whose tackifying resin of (E) component is an alicyclic petroleum resin type tackifying resin.
[0013]
The present invention also provides:
(9) It is related with the manufacturing method of the adhesive product hardened after apply | coating an adhesive composition to a support body, and this adhesive composition is the following component;
(A) Saturated hydrocarbon polymer having in the molecule at least one alkenyl group capable of hydrosilylation reaction
(B) Compound having at least two hydrosilyl groups in the molecule
(C) Plasticizer
(D) Hydrosilylation catalyst
(E) Tackifying resin
It is related with the manufacturing method of the adhesion product characterized by becoming an essential component.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The component (A) used in the present invention is a saturated hydrocarbon polymer having more than one alkenyl group capable of hydrosilylation reaction in the molecule. Here, the saturated hydrocarbon polymer means a polymer having no carbon-carbon unsaturated bond other than an aromatic ring in the main chain, and the repeating unit constituting the main chain is composed of a hydrocarbon group. The polymer is shown. In addition, the main chain in the present invention refers to a portion in the polymer excluding an alkenyl group capable of hydrosilylation reaction.
[0015]
Further, the alkenyl group of the present invention is not particularly limited as long as it is a group containing a carbon-carbon double bond that is active for hydrosilylation reaction. Alkenyl groups include vinyl, allyl, methylvinyl, propenyl, butenyl, pentenyl, hexenyl and other aliphatic unsaturated hydrocarbon groups, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl. And cyclic unsaturated hydrocarbon groups such as methacrylic groups. The component (A) in the present invention preferably has an alkenyl group capable of hydrosilylation at the polymer end. When the alkenyl group is present at the polymer end, the effective network chain amount of the finally formed cured product is increased, and thus a pressure-sensitive adhesive exhibiting high adhesive properties is easily obtained.
[0016]
The polymer constituting the skeleton of the saturated hydrocarbon polymer of the component (A) is (1) polymerized using a olefin compound having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene and isobutylene as a main monomer. (2) It can be obtained by a method such as homopolymerizing a diene compound such as butadiene or isoprene, or copolymerizing the olefin compound and the diene compound and then hydrogenating. It is an isobutylene polymer, a hydrogenated polybutadiene polymer, or a hydrogenated polyisoprene polymer from the viewpoints of easy introduction of functional groups, easy control of molecular weight, and increased number of terminal functional groups. Is desirable.
[0017]
In the isobutylene polymer, all of the monomer units may be formed from isobutylene units, and the monomer units copolymerizable with isobutylene are preferably 50% (weight%, in the isobutylene polymer). The same shall apply hereinafter), more preferably 30% or less, and particularly preferably 20% or less.
[0018]
Examples of such monomer components include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, allyl silanes, and the like. Specific examples of such copolymer components include 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, Vinyl cyclohexane, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methyl styrene, dimethyl styrene, pt-butoxy styrene, p-hexenyloxy styrene, p-allyloxy styrene, p-hydroxy styrene , Β-pinene, indene, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane Allyldimethylmethoxysilane, Examples include allyltrimethylsilane, diallyldimethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropylmethyldimethoxysilane.
[0019]
The hydrogenated polybutadiene polymer and other saturated hydrocarbon polymers also contain other monomer units in addition to the main monomer unit as in the case of the isobutylene polymer. You may let them.
[0020]
Further, the saturated hydrocarbon polymer used as the component (A) in the present invention includes butadiene, isoprene, 1,13-tetradecadiene, 1,9-decadiene, 1, as long as the object of the present invention is achieved. A monomer unit such as a polyene compound such as 7-octadiene and 1,5-hexadiene that may leave a double bond after polymerization may be contained in a small amount, preferably in the range of 10% or less.
[0021]
The number average molecular weight (GPC method, in terms of polystyrene) of the saturated hydrocarbon polymer, preferably isobutylene polymer, hydrogenated polyisoprene or hydrogenated polybutadiene polymer, is determined by its ease of handling, rubber elasticity after curing. It is preferable that it is about 2000-50000 from a point.
[0022]
As the method for producing the component (A) of the present invention, a compound having an unsaturated group is reacted with a polymer having a functional group such as a hydroxyl group as disclosed in JP-A-3-152164 and JP-A-7-304909. And a method of introducing an unsaturated group into the polymer. In addition, to introduce an unsaturated group into a polymer having a halogen atom, a method of performing a Friedel-Crafts reaction with alkenylphenyl ether, a method of performing a substitution reaction with allyltrimethylsilane in the presence of a Lewis acid, various phenols and Friedel For example, a method in which the above alkenyl group introduction method is used in combination with the introduction of a hydroxyl group by carrying out a kraft reaction. Furthermore, a method of introducing an unsaturated group at the time of polymerization of a monomer as disclosed in US Pat. No. 4,316,973, Japanese Patent Laid-Open No. 63-105005, and Japanese Patent Laid-Open No. 4-288309 is also possible.
[0023]
The curing agent which is the component (B) of the present invention is not limited as long as it contains more than two silicon-bonded hydrogen atoms in the molecule. Here, when two hydrogen atoms are bonded to the same silicon atom, it is calculated as two silicon-bonded hydrogen atoms.
[0024]
As the component (B), polyorganohydrogensiloxane is mentioned as one of preferable ones. The polyorganohydrogensiloxane as used herein refers to a siloxane compound having a hydrocarbon group or a hydrogen atom on a silicon atom. Specifically, the structure is as follows:
[0025]
[Chemical 1]

It has chain or ring shape shown by etc., and has 2 or more of these units
[0026]
[Chemical 2]

And the like.
[0027]
In using these components (B), those having good compatibility with the components (A), (C), and (E) or good dispersion stability in the system are preferred.
In particular, when the viscosity of the entire system is low, if a component (B) having low compatibility with each of the above components is used, phase separation may occur and poor curing may occur. Moreover, you may mix | blend a filler with small particle diameters, such as a fine powder silica, as a dispersibility adjuvant.
Specifically, the compatibility with the component (A) and the component (E) or the dispersion stability is shown as being relatively good.
[0028]
[Chemical 3]

Etc.
[0029]
The amount of the component (B) used in the present invention is such that the silicon atom-bonded hydrogen atom of the component (B) is 0.8 to 5.0 equivalents relative to the total amount of the alkenyl groups of the component (A). It is preferable to use for. When the silicon atom-bonded hydrogen atom of the component (B) is less than 0.8 with respect to the total amount of the alkenyl group of the component (A), crosslinking is insufficient. On the other hand, when it exceeds 5.0, there is a problem that the physical properties are largely changed by the influence of silicon-bonded hydrogen atoms remaining after curing. In particular, when it is desired to suppress this influence, it is preferable to use the component (B) so as to be 1.0 to 2.0 equivalents.
[0030]
The plasticizer which is (C) component of this invention is an essential component in order to improve the adhesive characteristic of the adhesive obtained from this adhesive composition. The component (C) is not particularly limited as long as the object can be achieved, but 1) the compatibility with the component (A) is good, and 2) the volatile content is low under curing conditions. preferable. That is, the component (C) is preferably a hydrocarbon compound having a low polarity, a compound having 6 or more carbon atoms, and more preferably a compound having 8 or more carbon atoms. Specific examples of the component (C) include C6-C30, preferably C8-C18 hydrocarbon process oils, but are not limited thereto. Component (C) is used in an amount of 1 to 200 parts by weight, preferably 5 to 150 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of component (A). When the blending amount exceeds 200 parts by weight, it is difficult to obtain a pressure-sensitive adhesive having a high gel fraction, and when it is less than 1 part, tackiness cannot be obtained.
[0031]
There is no restriction | limiting in particular about the hydrosilylation catalyst which is (D) component of this invention, Arbitrary things can be used. Specifically, solid platinum supported on a carrier such as chloroplatinic acid, platinum alone, alumina, silica, carbon black, etc .; platinum-vinylsiloxane complex {for example, Pt _n (ViMe ₂ SiOSiMe ₂ Vi) n, Pt [(MeViSiO) _Four ] _m }; Platinum-phosphine complex {eg, Pt (PPh _Three ) _Four , Pt (PBu _Three ) _Four }; Platinum-phosphite complex {eg, Pt [P (OPh) _Three ] _Four , Pt [P (OBu) _Three ] _Four (Wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent an integer)}, Pt (acac) ₂ Also included are the platinum-hydrocarbon complexes described in Ashby et al., US Pat. Nos. 3,159,601 and 3,159,622, and the platinum alcohol catalysts described in Lamoreaux et al., US Pat. No. 3,220,972. It is done.
[0032]
Examples of catalysts other than platinum compounds include RhCl (PPh _Three ) _Three , RhCl _Three , Rh / Al ₂ O _Three , RuCl _Three , IrCl _Three , FeCl _Three AlCl _Three , PdCl ₂ ・ 2H ₂ O, NiCl ₂ TiCl _Four , Etc. These catalysts may be used alone or in combination of two or more. From the point of catalytic activity, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex, Pt (acac) ₂ Etc. are preferred. Although there is no restriction | limiting in particular as a catalyst amount, It is 10 with respect to 1 mol of alkenyl groups in (A) component. ^-1 -10 ^-8 It is preferably used in the range of mol. ^-2 -10 ^-6 More preferably, it is used in the range of mol. In addition, the hydrosilylation catalyst is generally expensive and corrosive, and since a large amount of hydrogen gas is generated and the cured product may foam, 10 ^-1 It is better not to use more than moles.
[0033]
In the present invention, the curable composition is cured by the addition reaction of the Si—H group to the alkenyl group using a noble metal catalyst. Therefore, the curing rate is very fast, which is convenient for line production.
[0034]
There is no limitation in particular in the tackifying resin which is (E) component of this invention, What is normally used as a tackifier can be used. Specific examples include phenol resin, modified phenol resin, cyclopentadiene-phenol resin, xylene resin, coumarone resin, petroleum resin, terpene resin, terpene phenol resin, rosin ester resin, and the like. Among these, terpene resins and petroleum resins are particularly preferable because they have good compatibility and good adhesive properties. These may be used alone or in combination of two or more.
[0035]
Although the usage-amount of tackifying resin is 10-300 weight part with respect to 100 weight part of (A) component, More preferably, 30-150 weight part is mentioned, However It is not limited to this. When the amount is less than 10 parts or more than 300 parts, the tack tends to be insufficient or the adhesive strength tends to be insufficient.
[0036]
In the curable composition of the present invention, a storage stability improving agent can be used for the purpose of improving storage stability. The storage stability improver is a normal stabilizer known as a storage stabilizer for the component (B) of the present invention, and may be any one that can achieve the intended purpose, and is particularly limited. is not. Specifically, a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, an organic peroxide, or the like can be preferably used. More specifically, 2-benzothiazolyl sulfide, benzothiazol, thiazole, dimethylacetylene dicarboxylate, diethylacetylene dicarboxylate, BHT, butylhydroxyanisole, vitamin E, 2 -(4-morphodinyldithio) benzothiazol, 3-methyl-1-butene-3-ol, acetylenically unsaturated group-containing organosiloxane, acetylene alcohol, 3-methyl-1-butyl-3 -All, diallyl fumarate, diallyl maleate, diethyl fumarate, diethyl maleate, dimethyl maleate, 2-pentenenitrile, 2,3-dichloropropene and the like, but are not limited thereto. .
In addition, the pressure-sensitive adhesive composition of the present invention further includes a nitrogen-containing silane compound, an antioxidant, an ultraviolet ray absorbing agent for improving adhesion to various supports (plastic film, metal foil, paper, etc.) as necessary. Agents, pigments, surfactants, and the like can be added as appropriate. In their use, the impact on the hydrosilylation reaction must be considered. Specific examples of the nitrogen-containing silane compound include H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH _Three ) _Three , H ₂ NCH ₂ CH ₂ NCH ₂ CH ₂ CH ₂ Si (OCH _Three ) _Three , H ₂ NCH ₂ CH ₂ NCH ₂ CH ₂ CH ₂ Si (CH _Three ) (OCH _Three ) ₂ , (C ₂ H _Five O) _Three SiCH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OC ₂ H _Five ) _Three An amino group and / or imino group-containing alkoxysilane, and the amino group and / or imino group-containing alkoxysilane
[0037]
[Formula 4]

A reaction product with an epoxy silane compound such as amino group and / or imino group-containing alkoxysilane and CH ₂ = C (CH _Three ) COOCH ₂ CH ₂ CH ₂ Si (OCH _Three ) _Three , CH ₂ = C (CH _Three ) COOCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₂ OCH _Three ) _Three Reaction products with methacryloxysilane compounds such as The amount of the nitrogen-containing silane compound used is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). Specific examples of the filler include silica fine powder, calcium carbonate, clay, talc, titanium oxide, zinc white, diatomaceous earth, barium sulfate, and carbon black. Among these fillers, especially silica fine powder, especially the particle diameter is 50 to 70 nm (BET specific surface area is 50 to 380 m). ² / G) of finely divided silica is preferable, and among these, hydrophobic silica subjected to surface treatment is particularly preferable because it has a large effect of improving the strength in a preferable direction.
[0038]
Next, the manufacturing method of the pressure-sensitive adhesive product of the present invention will be described with an example of the manufacturing process.
However, the present invention is not limited to the following examples as long as the pressure-sensitive adhesive composition is applied to the support and thermally cured.
[0039]
The pressure-sensitive adhesive composition is applied onto a support with a coater, and this is heat-cured to obtain a pressure-sensitive adhesive product. As the support, a film made of synthetic resin or a modified natural product, paper, all kinds of cloth, metal foil, and the like can be used. Specific examples of the support include polyethylene, polypropylene, polyimide, polycarbonate, polyvinyl chloride, polyester, polyurethane, cellophane, impregnated paper, coated paper, fine paper, craft paper, cloth, acetate cloth, non-woven cloth, glass cloth, metal foil However, it is not necessarily limited to these. These may be used singly or may be used by laminating at least two kinds. The method of thermosetting is not particularly limited, but the temperature varies depending on the type of polymer to be used and the compound to be added, but is usually preferably within a range of 40 ° C to 180 ° C, and a range of 70 ° C to 140 ° C. The inside is more preferable. The curing time varies depending on the polymer to be used, the compound to be added, the reaction temperature, etc., but is usually in the range of 0.1 minute to 24 hours, preferably 1 minute to 10 hours, more preferably 1 minute to 1 hour. It is.
[0040]
In the present invention, since a saturated hydrocarbon polymer is used as the component (A), the resulting adhesive has excellent heat resistance, weather resistance, water resistance, chemical resistance, and electrical insulation, Its application range is wide and can be applied to a wide range of applications. Furthermore, when an isobutylene polymer is used as the component (A), in addition to the above properties, an adhesive having excellent low moisture permeability, low moisture absorption, and low gas permeability can be obtained. The pressure-sensitive adhesive product of the present invention includes a packaging pressure-sensitive adhesive tape, office pressure-sensitive adhesive tape, paint masking tape, electrical insulating pressure-sensitive adhesive tape, bundling pressure-sensitive adhesive tape, protective pressure-sensitive adhesive tape, identification / decorative pressure-sensitive adhesive tape and sheet, and medical pressure-sensitive adhesive. Tape, double-sided adhesive tape, electromagnetic interference prevention film and tape, re-peeling film and tape, decorative board film, semiconductor chip transport tape, marking film, deep drawing protective film, glass scattering prevention film, foam adhesive tape, waterproof / It is a material suitable for adhesive products such as water-stopping tape, anticorrosive adhesive tape, surface protective adhesive tape, dicing adhesive tape, back grind adhesive tape, printing adhesive sheet, and adhesive label.
[0041]
【Example】
The present invention will be described in more detail based on the following examples, but the present invention is not limited only to these examples.
Example 1
EXAMPLES Next, although an Example is given and this invention is clarified further, this invention is not limited at all by an Example.
As the component (A), a compound having the following structure (analytical values shown in Table 1) synthesized by the method described in JP-A-8-134220 was used.
[0042]
[Table 1]

[0043]
[Chemical formula 5]

(A) 100 parts by weight of component, 50 parts by weight of hydrocarbon process oil (PW-380 made by Idemitsu Petrochemical Co., Ltd.) as component (C), and MARKAO-50 (Adeka Argas Chemical Co., Ltd.) as an antioxidant 1 part by weight was added and kneaded by hand. At this time, the solution was heated to about 70 ° C. in order to dissolve the antioxidant. After returning the blend to room temperature, 100 parts by weight of component (A). As component (E), 75 parts by weight of petroleum resin-based tackifier resin (Arakawa Chemical Industries, trade name: Alcon P-100) was added as a 50% by weight toluene solution, and then the following structure was added to this mixture. (B) component which shows
[0044]
[Chemical 6]

Was mixed with 3 parts by weight per 100 parts by weight of component (A). Furthermore, as component (D), bis (1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex catalyst (17.9 × 10 ^-Five mmol / μl, xylene solution) is 5 × 10 5 with respect to the number of moles of the alkenyl group of component (A). ^-Four Equivalent amount, and dimethyl maleate as a storage stability improver was weighed in 3 molar equivalents with respect to platinum and mixed uniformly. The pressure-sensitive adhesive composition thus obtained was applied to a polyethylene terephthalate film (manufactured by Toray Industries, Inc.) subjected to corona treatment having a thickness of 50 μm so that the thickness after drying was about 50 μm, and at room temperature. After drying for 1 hour, it was heat-cured at 120 ° C. for 10 minutes to produce an adhesive tape. The adhesive strength of the pressure-sensitive adhesive tape thus obtained was evaluated by peeling off the pressure-sensitive adhesive tape affixed to the stainless steel plate, the tack was evaluated by touch, and the results are shown in Table 2. The adhesive strength by hand peeling was evaluated as ◯ when the adhesive strength was strong, Δ when the adhesive strength was slightly weak, and × when the adhesive strength was almost zero. The evaluation of tack by touch was evaluated as “◯” when a finger was lightly pressed against an adhesive tape and then lifted while the adhesive tape was attached to the finger, “Δ” when a part was lifted, and “X” when it was not lifted at all. Furthermore, the adhesive properties (adhesive strength, tack, holding power) were measured according to the following method according to JIS Z-0237, and the results are shown in Table 3.
(1) Adhesive strength
The obtained adhesive tape was cut to a width of 25 mm, and the adhesive surface of the adhesive tape was attached to a stainless steel plate (SUS # 304), left for 30 minutes, and then peeled off at 23 ° C. and 65% RH using a tensile tester. The adhesive strength was measured by peeling 180 degrees at a speed of 300 mm / min. However, the surface of the SUS plate was polished with No. 240 water-resistant abrasive paper.
(2) Tack
Set the obtained adhesive tape on a slope with an inclination angle of 30 degrees, roll a stainless steel ball at 23 ° C and 65% RH with a run-up distance of 10 cm, and set the maximum ball number to stop within 10 cm of the adhesive surface. It was measured.
(3) Holding power
Of the adhesive surface of the obtained adhesive tape, a 25 mm long and 25 mm wide part was attached to a stainless steel plate (SUS # 304), and a 1 kg load was applied in an atmosphere of 100 ° C. It was measured.
Moreover, the weather resistance evaluation was performed by observing the change in the appearance of the sample after being left outdoors for 1 week, and the results are shown in Table 3. Furthermore, the adhesive tape affixed to the stainless steel plate was immersed in water and allowed to stand for 3 days, and then the water resistance was evaluated by manually peeling off the strength of the adhesive force. The results are shown in Table 3. For the weather resistance evaluation, the case where there was no change in appearance was indicated by ◯, the case where a partial change was observed was indicated by Δ, and the case where discoloration was observed was indicated by ×. For the water resistance evaluation, the case of peeling off by hand and having no change in adhesive strength was evaluated as “◯”, the case of being easily peeled off as “Δ”, and the case of immediately peeling off as “X”.
(Example 2)
The component (E) in Example 1 was changed to petroleum resin-based tackifying resin Alcon M-100 (manufactured by Arakawa Chemical Industries, Ltd.), and everything else was carried out in the same manner as in Example 1. The results are shown in Tables 2 and 3.
(Example 3)
The component (E) in Example 1 was changed to petroleum resin-based tackifying resin Rigalite R-125 (manufactured by Rika Hercules Co., Ltd.), and everything else was carried out in the same manner as in Example 1. The results are shown in Tables 2 and 3.
Example 4
The component (E) in Example 1 was changed to the terpene-based tackifying resin Clearon P-105 (manufactured by Anne Crude Oil Co., Ltd.), and everything else was carried out in the same manner as in Example 1.
The results are shown in Tables 2 and 3.
(Comparative Example 1)
Without adding the plasticizer which is the component (C) in Example 1, the component (E) in Example 1 was changed to the terpene-based tackifying resin Clearon P-105 (manufactured by Yasu Crude Oil Co., Ltd.) to create an adhesive tape The tack was touched and the adhesive strength was evaluated by peeling off the adhesive tape attached to the stainless steel plate. The results are shown in Table 2.
(Comparative Example 2)
The plasticizer which is the component (C) in Example 1 was not added, and the component (E) in Example 1 was changed to petroleum resin-based tackifying resin Rigalite R-125 (manufactured by Rika Hercules Co., Ltd.), and an adhesive tape was used. It was prepared, and the tack was touched and the adhesive strength was evaluated by peeling off the adhesive tape attached to the stainless steel plate. The results are shown in Table 2.
[0045]
[Table 2]

[0046]
[Table 3]

From the table, it is clear that the pressure-sensitive adhesive composition of the present invention has an excellent balance between tack and adhesive strength. Moreover, the result that both weather resistance and water resistance were favorable was obtained.
[0047]
【The invention's effect】
ADVANTAGE OF THE INVENTION By this invention, it is excellent in a weather resistance, water resistance, etc., and can provide the adhesive composition with which the adhesive characteristic was improved. Furthermore, the manufacturing method of the adhesive product using this composition can also be provided.

Claims (8)

A pressure-sensitive adhesive composition comprising the following components (A) to (E) as essential components.
(A) Saturated hydrocarbon polymer having at least one hydrosilylation capable alkenyl group in the molecule (B) Compound having at least two hydrosilyl groups in the molecule (C) Hydrocarbon process as a plasticizer Oil (D) Hydrosilylation catalyst (E) Tackifying resin The pressure-sensitive adhesive composition according to claim 1, wherein an alkenyl group capable of hydrosilylation reaction in the polymer of component (A) is present at the molecular end. The pressure-sensitive adhesive composition according to claim 1 or 2 , wherein the saturated hydrocarbon polymer of component (A) is an isobutylene polymer. The pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein the total amount of repeating units derived from isobutylene in the polymer of component (A) is 50% by weight or more. Compounds having at least two hydrosilyl groups in the molecule of component (B), it polyorganohydrogensiloxane der having a silicon-bonded hydrogen atoms exceeds 2, on average in one molecule, the respective formulas It is shown by either , The adhesive composition of any one of Claims 1-4 .

The pressure-sensitive adhesive composition according to any one of claims 1 to 5, wherein the tackifying resin of component (E) is a terpene-based tackifying resin and / or a petroleum resin-based tackifying resin. The pressure-sensitive adhesive composition according to any one of claims 1 to 6, wherein the (E) component tackifying resin is an alicyclic petroleum resin-based tackifying resin. A method for producing a pressure-sensitive adhesive product which is cured after applying a pressure-sensitive adhesive composition to a support, wherein the pressure-sensitive adhesive composition comprises the following components:
(A) Saturated hydrocarbon polymer having at least one hydrosilylation capable alkenyl group in the molecule (B) Compound having at least two hydrosilyl groups in the molecule (C) Hydrocarbon process as a plasticizer An oil (D) hydrosilylation catalyst (E) a tackifying resin as an essential component.