JP2004182936A - Pressure sensitive adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pressure sensitive adhesive composition with slight degradation of a near-infrared ray-absorptive pigment due to ultraviolet rays and suitable for forming an adhesive layer or the like to laminate a laminar material for forming a plasma display, etc. <P>SOLUTION: The pressure sensitive adhesive composition comprises a pressure sensitive adhesive polymer(A), a near-infrared ray-absorptive pigment(B), an ultraviolet ray absorber(C) and/or a hindered amine-base light stabilizer(D), and preferably further comprises an antioxidant(E). In the above pressure sensitive adhesive composition, the above pressure sensitive adhesive polymer(A) has (1) a glass transition temperature of -80 to -20°C and/or (2) a weight-averaged molecular weight of ≥250,000. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００３４】
（式中、αは、同一若しくは異なって、ＳＲ^１、ＯＲ^２、ＮＨＲ^３又はハロゲン原子を表し、ＮＨＲ^３を必須とする。Ｒ^１、Ｒ^２及びＲ^３は、同一若しくは異なって、置換基を有してもよいフェニル基、炭素数１〜２０のアルキル基又は炭素数７〜２０のアラルキル基を表す。βは、同一若しくは異なって、ＳＲ^１、ＯＲ^２又はハロゲン原子を表し、ＳＲ^１又はＯＲ^２を必須とする。ただし、α及びβのうち少なくとも１つは、ハロゲン原子又はＯＲ^２を必須とする。Ｍは、無金属、金属、金属酸化物又は金属ハロゲン化物を表す。）で表される化合物であることが好ましい。これにより本発明の作用効果をより充分に発揮させることができる。
【００３５】
上記一般式（１）において、炭素数１〜２０のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、１，２−ジメチルプロピル基、ｎ−ヘキシル基、１，３−ジメチルブチル基、１−イソプロピルプロピル基、１，２−ジメチルブチル基、ｎ−ヘプチル基、１，４−ジメチルペンチル基、２−メチル−１−イソプロピルプロピル基、１−エチル−３−メチルブチル基、ｎ−オクチル基、２−エチルヘキシル基等の直鎖又は分岐状のアルキル基；シクロヘキシル基等の環状アルキル基等が挙げられる。炭素数７〜２０のアラルキル基としては、例えば、ベンジル基、フェネチル基等が挙げられる。ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、フッ素原子であることが好ましい。
【００３６】
上記Ｒ^１、Ｒ^２及びＲ^３におけるフェニル基、炭素数１〜２０のアルキル基又は炭素数７〜２０のアラルキル基は、置換基を１個又は２個以上有してもよい。このような置換基としては、例えば、ハロゲン原子、アシル基、アルキル基、アルコキシ基、ハロゲン化アルコキシ基、ニトロ基、アミノ基、アルキルアミノ基、アルキルカルボニルアミノ基、アリールアミノ基、アリールカルボニルアミノ基、カルボニル基、アルコキシカルボニル基等が挙げられる。
【００３７】
上記一般式（１）中のＭにおいて、無金属とは、金属以外の原子、例えば、２個の水素原子であることを意味する。具体的には、フタロシアニン構造の中央部分に存在する、置換基を有してもよい相対する２つの窒素原子に水素原子が結合している構造となる。金属としては、例えば、鉄、マグネシウム、ニッケル、コバルト、銅、パラジウム、亜鉛、バナジウム、チタン、インジウム、錫等が挙げられる。金属酸化物としては、例えば、チタニル、バナジル等が挙げられる。金属ハロゲン化物としては、例えば、塩化アルミニウム、塩化インジウム、塩化ゲルマニウム、塩化錫、塩化珪素等が挙げられる。Ｍとしては、金属、金属酸化物又は金属ハロゲン化物であることが好ましく、具体的には、ニッケル、コバルト、銅、亜鉛、鉄、バナジル、ジクロロ錫等が挙げられる。より好ましくは、亜鉛、コバルト、バナジル、ジクロロ錫である。
【００３８】
上記一般式（１）で表される化合物の好ましい形態としては、８個のβのうち４〜８個が、同一若しくは異なって、ＳＲ^１又はＯＲ^２を表すことである。より好ましくは、８個のβがすべて、同一若しくは異なって、ＳＲ^１又はＯＲ^２を表すことである。このような近赤外線吸収色素としては、例えば、ＺｎＰｃ（ＰｈＳ）_８（ＰｈＮＨ）_３Ｆ_５、ＺｎＰｃ（ＰｈＳ）_８（ＰｈＮＨ）_４Ｆ_４、ＺｎＰｃ（ＰｈＳ）_８ ＰｈＮＨ）_５Ｆ_３、ＺｎＰｃ（ＰｈＳ）_８（ＰｈＣＨ_２ＮＨ）_４Ｆ_４、ＺｎＰｃ（ＰｈＳ）_８（ＰｈＣＨ_２ＮＨ）_５Ｆ_３、ＺｎＰｃ（ＰｈＳ）_８（ＰｈＣＨ_２ＮＨ）_６Ｆ_２、ＣｕＰｃ（ＰｈＳ）_８（ＰｈＮＨ）_７Ｆ、ＣｕＰｃ（ＰｈＳ）_８（ＰｈＮＨ）_６Ｆ_２、ＣｕＰｃ（ＰｈＳ）_８（ＰｈＮＨ）_５Ｆ_３、ＶＯＰｃ（ＰｈＯ）_８（ＰｈＣＨ_２ＮＨ）_５Ｆ_３、ＶＯＰｃ（ＰｈＯ）_８（ＰｈＣＨ_２ＮＨ）_６Ｆ_２、ＶＯＰｃ（ＰｈＯ）_８（ＰｈＣＨ_２ＮＨ）_８、ＶＯＰｃ（ＰｈＳ）_８（ＰｈＣＨ_２ＮＨ）_８、ＶＯＰｃ（２，５−Ｃｌ_２ＰｈＯ）_８｛２，６−（ＣＨ_３）_２ＰｈＯ｝_４｛Ｐｈ（ＣＨ_３）ＣＨＮＨ｝_３Ｆ、ＶＯＰｃ（２，５−Ｃｌ_２ＰｈＯ）_８｛２，６−（ＣＨ_３）_２ＰｈＯ｝_４｛Ｐｈ（ＣＨ_２ＮＨ）_４、ＣｕＰｃ（２，５−Ｃｌ_２ＰｈＯ）_８｛２，６−（ＣＨ_３）_２ＰｈＯ｝_４｛Ｐｈ（ＣＨ_２ＮＨ）_４、ＣｕＰｃ（ＰｈＳ）_８｛２，６−（ＣＨ_３）_２ＰｈＯ｝_４（ＰｈＣＨ_２ＮＨ）_４、ＶＯＰｃ（４−ＣＮＰｈＯ）_８｛２，６−Ｂｒ_２−４−（ＣＨ_３）ＰｈＯ｝_４｛Ｐｈ（ＣＨ_３）ＣＨＮＨ｝_４、ＺｎＰｃ（２，６−Ｃｌ_２ＰｈＯ）_８｛２，６−Ｂｒ_２−４−（ＣＨ_３）ＰｈＯ｝_４｛Ｐｈ（ＣＨ_３）ＣＨＮＨ｝_３Ｆの略称で表されるフタロシアニン化合物等が挙げられる。またこれらの化合物の中でも８個のαのうち４個が、同一若しくは異なってＯＲ^２又はハロゲン原子を表す化合物で、例えば、ＺｎＰｃ（ＰｈＳ）_８（ＰｈＮＨ）_３Ｆ_５、ＺｎＰｃ（ＰｈＳ）_８（ＰｈＮＨ）_４Ｆ_４、ＺｎＰｃ（ＰｈＳ）_８（ＰｈＣＨ_２ＮＨ）_４Ｆ_４、ＶＯＰｃ（２，５−Ｃｌ_２ＰｈＯ）_８｛２，６−（ＣＨ_３）_２ＰｈＯ｝_４｛Ｐｈ（ＣＨ_３）ＣＨＮＨ｝_３Ｆ、ＶＯＰｃ（２，５−Ｃｌ_２ＰｈＯ）_８｛２，６−（ＣＨ_３）_２ＰｈＯ｝_４｛Ｐｈ（ＣＨ_２ＮＨ）_４、ＣｕＰｃ（２，５−Ｃｌ_２ＰｈＯ）_８｛２，６−（ＣＨ_３）_２ＰｈＯ｝_４｛Ｐｈ（ＣＨ_２ＮＨ）_４、ＣｕＰｃ（ＰｈＳ）_８｛２，６−（ＣＨ_３）_２ＰｈＯ｝_４（ＰｈＣＨ_２ＮＨ）_４、ＶＯＰｃ（４−ＣＮＰｈＯ）_８｛２，６−Ｂｒ_２−４−（ＣＨ_３）ＰｈＯ｝_４｛Ｐｈ（ＣＨ_３）ＣＨＮＨ｝_４、ＺｎＰｃ（２，６−Ｃｌ_２ＰｈＯ）_８｛２，６−Ｂｒ_２−４−（ＣＨ_３）ＰｈＯ｝_４｛Ｐｈ（ＣＨ_３）ＣＨＮＨ｝_３Ｆの略称で一般的に表される化合物等が挙げられる。上記化合物の略号において、Ｐｃはフタロシアニン核を表し、Ｐｃの後には、β位に置換する８個の置換基を表し、その後にα位に置換する８個の置換基を表す。また、上記Ｐｈはフェニル基を表す。更に具体的には、上記略号は、中心金属：Ｐｃ：β位の８個の置換基：α位の８個の置換基を表す。例えば、ＺｎＰｃ（ＰｈＳ）_８（ＰｈＮＨ）_３Ｆ_５で説明すると、Ｚｎ Ｐｃ （ＰｈＳ） _８ （ＰｈＮＨ） _３ Ｆ _５ の下線部が上の説明に該当する。
【００３９】
上記近赤外線吸収色素（Ｂ）の使用量としては、感圧接着性重合体（Ａ）１００重量部に対して、０．００５重量部以上とすることが好ましい。０．０００５重量部未満であると、感圧接着剤組成物から形成される塗膜や接着層が充分な近赤外線吸収性能を発揮しないおそれがある。より好ましくは、０．０２５重量部以上であり、更に好ましくは、０．０５重量部以上である。また、２０重量部以下とすることが好ましい。２０重量部を超えると、塗膜の物性が低下するおそれがある。より好ましくは、１０重量部以下であり、更に好ましくは、５重量部以下である。また、塗膜の厚さにより適宜設定することが好ましく、例えば、厚さ１０μｍでは、０．５重量部以上とすることが好ましく、また、２０重量部以下とすることが好ましく、１．０重量部以上とすることがより好ましく、また、１０重量部以下とすることがより好ましい。厚さ３ｍｍの塗膜とする場合には、０．００２重量部以上とすることが好ましく、また、０．０６重量部以下とすることが好ましく、０．００５重量部以上とすることがより好ましく、また、０．０３重量部以下とすることがより好ましい。厚さ１０ｍｍでは、０．０００５重量部以上とすることが好ましく、また、０．０２重量部以下とすることが好ましく、０．００１０重量部以上とすることが好ましく、また、０．０１重量部以下とすることがより好ましい。更に、塗膜の単位面積あたりに含有される重量としては、例えば、０．０１ｇ／ｍ^２以上とすることが好ましい。０．０１ｇ／ｍ^２未満であると、近赤外線吸収色素の作用が充分に発揮されないおそれがある。より好ましくは、０．０５ｇ／ｍ^２以上であり、更に好ましくは、０．１ｇ／ｍ^２以上である。また、２．５ｇ／ｍ^２以下とすることが好ましい。２．５ｇ／ｍ^２を超えると、塗膜の製造コストが高くなるおそれがある。より好ましくは、１．０ｇ／ｍ^２以下であり、更に好ましくは、０．５ｇ／ｍ^２以下である。
【００４０】
本発明における紫外線吸収剤（Ｃ）としては、上述したように添加型及び／又は反応型のものを用いることができ、サリチル酸系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤、シアノアクリレート系紫外線吸収剤、ベンゾエート系紫外線吸収剤が好適である。これらの中でも、反応型の紫外線吸収剤としては、上述した紫外線吸収性単量体が好適である。
上記サリチル酸系紫外線吸収剤としては、フェニルサリシレート、ｐ−ｔｅｒｔ−ブチルフェニルサリシレート、ｐ−オクチルフェニルサリシレートが好適である。また、フェニルサリシレートの市販品として、ＳＡＰ（商品名、岩城製薬社製）、ザロール（商品名、Ｄｏｗ Ｃｈｅｍ．社製）、ザロール−Ｐ（商品名、八代製薬社製）が、ｐ−ｔｅｒｔ−ブチルフェニルサリシレートの市販品として、ＴＢＳ（商品名、Ｄｏｗ Ｃｈｅｍ．社製）、ＴＢＳ（商品名、八代製薬社製）、バイオソーブ−９０（商品名、共同薬品社製）、ブチルザロール（商品名、岩城製薬社製）が、ｐ−オクチルフェニルサリシレートの市販品として、ＯＰＳ（商品名、イーストマン・ケミカル社製）、ＯＰＳ（商品名、八代製薬社製）が挙げられる。
【００４１】
上記ベンゾフェノン系紫外線吸収剤としては、２，４−ジヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン、２−ヒドロキシ−４−オクトキシベンゾフェノン、２−ヒドロキシ−４−ドデシルオキシベンゾフェノン、２，２′−ジヒドロキシ−４−メトキシベンゾフェノン、２，２′−ジヒドロキシ−４−ジメトキシベンゾフェノン、２，２′−ジヒドロキシ−４，４′−ジメトキシベンゾフェノン、２−ヒドロキシ−４−メトキシ−５−スルホベンゾフェノン、ビス（２−メトキシ−４−ヒドロキシ−５−ベンゾイルフェニル）メタンが好適である。また、２，４−ジヒドロキシベンゾフェノンの市販品として、ＡＳＬ−２３（商品名、湘南化学社製）、シーソーブ−１００（商品名、白石カルシウム社製）、ジスライザーＯ（商品名、三協化成社製）、スミソーブ−１００（商品名、住友化学社製）、ＤＨＢＰ（商品名、イーストマン・ケミカル社製）、バイオソーブ−１００（商品名、共同薬品社製）、Ｕｖｉｎｕｌ−４００（商品名、ＢＡＳＦ社製）が、２−ヒドロキシ−４−メトキシベンゾフェノンの市販品としては、ＡＳＬ−２３（商品名、湘南化学社製）、Ｃｙａｓｏｒｂ ＵＶ−９（商品名、Ｃｙｔｅｃ社製）、ジスライザーＭ（商品名、三協化成社製）、スミソーブ−１００（商品名、住友化学社製）、シーソーブ−１０１（商品名、白石カルシウム社製）、バイオソーブ−１１０（商品名、共同薬品社製）、Ｕｖｉｎｕｌ−Ｍ−４０（商品名、ＢＡＳＦ社製）、オーソレックス４３６０（商品名、メルク・ジャパン社製）が、２−ヒドロキシ−４−オクトキシベンゾフェノンの市販品としては、Ｃｙａｓｏｒｂ ＵＶ−５３１（商品名、Ｃｙｔｅｃ社製）、シーソーブ−１０２（商品名、白石カルシウム社製）、ジスライザーＥ（商品名、三協化成社製）、スミソーブ−１３０（商品名、住友化学社製）、シーソーブ−１３０（商品名、白石カルシウム社製）、バイオソーブ−１３０（商品名、共同薬品社製）、Ａｄｖａｓｔａｂ−４６、アデカスタブ１４１３（商品名、旭電化工業社製）、２−ヒドロキシ−４−ドデシルオキシベンゾフェノンの市販品としては、ＤＯＰＢ（商品名、イーストマン・ケミカル社製）、ＡＭ−３２０（商品名）が、２，２′−ジヒドロキシ−４−ジメトキシベンゾフェノンの市販品としては、Ｃｙａｓｏｒｂ ＵＶ−２４（商品名、Ｃｙｔｅｃ社製）が挙げられる。２，２′−ジヒドロキシ−４，４′−メトキシベンゾフェノンの市販品としては、ＡＳＬ−４０（商品名、湘南化学社製）、Ｕｖｉｎｕｌ−Ｄ−４９（商品名、ＢＡＳＦ社製）が、２−ヒドロキシ−４−メトキシ−５−スルホベンゾフェノンの市販品としては、Ｕｖｉｎｕｌ−ＭＳ−４０（商品名、ＢＡＳＦ社製）、ビス（２−メトキシ−４−ヒドロキシ−５−ベンゾイルフェニル）メタンの市販品としては、アデカスタブＬＡ−５１（商品名、旭電化工業社製）が挙げられる。
【００４２】
上記ベンゾトリアゾール系紫外線吸収剤としては、２−（２′−ヒドロキシ−５′−メチルフェニル）ベンゾトリアゾール、２−（２′−ヒドロキシ−５′−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾール、２−（２′−ヒドロキシ−３′，５′−ジ−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾール、２−（２′−ヒドロキシ−３′−ｔｅｒｔ−ブチル−５′−メチルフェニル）−５−クロロベンゾトリアゾール、２−（２′−ヒドロキシ−３′，５′−ジ−ｔｅｒｔ−ブチルフェニル）−５−クロロベンゾトリアゾール、２−（２′−ヒドロキシ−３′，５′−ジ−ｔｅｒｔ−アミルフェニル）ベンゾトリアゾール、２−（２′−ヒドロキシ−４′−オクトキシフェニル）ベンゾトリアゾール、２−（２′−ヒドロキシ−３′−（３″，４″，５″，６″−テトラヒドロフタルイミドメチル）−５′−メチルフェニル）ベンゾトリアゾール、２，２−メチレンビス［４−（１，１，３，３−テトラメチルブチル）−６−（２Ｈ−ベンゾトリアゾール−２−イル）フェノール］、２（２′−ヒドロキシ−５′−メタアクリロキシフェニル）−２Ｈ−ベンゾトリアゾール、２，２′−メチレンビス［４−（１，１，３，３−テトラメチルブチル）−６−〔（２Ｈ−ベンゾトリアゾール−２−イル）フェノール〕］、２（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾールが好適である。また、２−（２′−ヒドロキシ−５′−メチルフェニル）ベンゾトリアゾールの市販品として、ＪＦ−７７（商品名、城北化学社製）、Ｔｉｎｕｖｉｎ−Ｐ（商品名、チバ・スペシャルティ・ケミカルズ社製）、シーソーブ−７０１（商品名、白石カルシウム社製）、スミソーブ−２００（商品名、住友化学社製）、バイオソーブ−５２０（商品名、共同薬品社製）、アデカスタブＬＡ−３２（商品名、旭電化工業社製）が、２−（２′−ヒドロキシ−５′−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾールの市販品として、Ｔｉｎｕｖｉｎ−ＰＳ（商品名、チバ・スペシャルティ・ケミカルズ社製）が、２−（２′−ヒドロキシ−３′，５′−ジ−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾールの市販品として、Ｔｉｎｕｖｉｎ−３２０（商品名、チバ・スペシャルティ・ケミカルズ社製）、バイオソーブ−５８２（商品名、共同薬品社製）、ＪＦ−８６（商品名、城北化学社製）が、２−（２′−ヒドロキシ−３′−ｔｅｒｔ−ブチル−５′−メチルフェニル）−５−クロロベンゾトリアゾールの市販品として、Ｔｉｎｕｖｉｎ−３２６（商品名、チバ・スペシャルティ・ケミカルズ社製）、シーソーブ−７０３（商品名、白石カルシウム社製）、バイオソーブ−５５０（商品名、共同薬品社製）、スミソーブ−３００（商品名、住友化学社製）、ＪＦ−７９（商品名、城北化学社製）、アデカスタブＬＡ−３６（商品名、旭電化工業社製）が、２−（２′−ヒドロキシ−３′，５′−ジ−ｔｅｒｔ−ブチルフェニル）−５−クロロベンゾトリアゾールの市販品として、Ｔｉｎｕｖｉｎ−３２７（商品名、チバ・スペシャルティ・ケミカルズ社製）、シーソーブ−７０２（商品名、白石カルシウム社製）、バイオソーブ−５８０（商品名、共同薬品社製）、ＪＦ−７８（商品名、城北化学社製）、アデカスタブＬＡ−３４（商品名、旭電化工業社製）が、２−（２′−ヒドロキシ−３′，５′−ジ−ｔｅｒｔ−アミルフェニル）ベンゾトリアゾールの市販品として、Ｔｉｎｕｖｉｎ−３２８（商品名、チバ・スペシャルティ・ケミカルズ社製）、バイオソーブ−５９１（商品名、共同薬品社製）、スミソーブ−３５０（商品名、住友化学社製）、ＪＦ−８０（商品名、城北化学社製）が、２−（２′−ヒドロキシ−３′−（３″，４″，５″，６″−テトラヒドロフタルイミドメチル）−５′−メチルフェニル）ベンゾトリアゾールの市販品として、バイオソーブ−５９０（商品名、共同薬品社製）、スミソーブ−２５０（商品名、住友化学社製）、シーソーブ−７０６（商品名、白石カルシウム社製）が、２，２′−メチレンビス［４−（１，１，３，３−テトラメチルブチル）−６−〔（２Ｈ−ベンゾトリアゾール−２−イル）フェノール〕］の市販品として、アデカスタブＬＡ−３１（商品名、旭電化工業社製）が、２（２′−ヒドロキシ−５′−メタアクリロキシフェニル）−２Ｈ−ベンゾトリアゾールの市販品として、ＲＵＶＡ−９３（商品名、大塚化学社製）が挙げられる。
【００４３】
上記シアノアクリレート系紫外線吸収剤としては、２−エチルヘキシル−２−シアノ−３，３′−ジフェニルアクリレート、エチル−２−シアノ−３，３′−ジフェニルアクリレートが好適である。２−エチルヘキシル−２−シアノ−３，３′−ジフェニルアクリレートの市販品として、Ｕｎｉｎｏｌ ３０３９，Ｎ５３９Ｔ（商品名、ＢＡＳＦ社製）、バイオソーブ−９３０（商品名、共同薬品社製）が、エチル−２−シアノ−３，３′−ジフェニルアクリレートの市販品として、Ｕｎｉｎｏｌ ３０３５（商品名、ＢＡＳＦ社製）、バイオソーブ−９１０（商品名、共同薬品社製）が挙げられる。
上記ベンゾエート系紫外線吸収剤としては、Ｔｉｎｕｖｉｎ−１２０（商品名、チバ・スペシャルティ・ケミカルズ社製）、ｓｕｍｉｓｏｒｂ ４００（商品名、住友化学社製）が好適である。
【００４４】
上記紫外線吸収剤（Ｃ）の使用量としては、感圧接着性重合体（Ａ）１００重量部に対して、添加型の紫外線吸収剤及び反応型の紫外線吸収剤の合計を０．１重量部以上とすることが好ましく、また、１００重量部以下とすることが好ましい。０．１重量部未満であると、近赤外線吸収色素の劣化が大きくなるおそれがある。１００重量部を超えると、粘着性に乏しくなるおそれがある。より好ましくは、１重量部以上であり、更に好ましくは、３重量以上である。また、より好ましくは、５０重量部以下であり、更に好ましくは、２０重量以下である。なお、上記紫外線吸収剤（Ｃ）の使用量は、添加型及び反応型のものを含む量である。
【００４５】
上記ヒンダードアミン系光安定剤（Ｄ）としては、上述したように添加型及び／又は反応型のものを用いることができる。このような光安定剤として、ヒンダードフェノール骨格を有さないヒンダードアミン系光安定剤（ｄ−１）とヒンダードフェノール骨格を有するヒンダードアミン系光安定剤（ｄ−２）との２種類が挙げられ、これらは効果が異なるものである。なお、本発明においては、これらを併用してもよい。ヒンダードフェノール骨格を有するヒンダードアミン系光安定剤（ｄ−２）は、典型的な酸化防止剤の一種であり、紫外線によって発生したラジカル種をトラップし、劣化を防ぐ効果がある。従って、ヒンダードフェノール骨格を有するヒンダードアミン系光安定剤（ｄ−２）を併用することで、紫外線による劣化抑制にも効果があることから好ましい。すなわち本発明における好ましい形態としては、紫外線吸収剤（Ｃ）と、ヒンダードフェノール骨格を有するヒンダードアミン系光安定剤（ｄ−２）を必須とするヒンダードアミン系光安定剤（Ｄ）とを併用することである。
【００４６】
上記ヒンダードフェノール骨格を有さないヒンダードアミン系光安定剤（ｄ−１）としては、Ｓａｎｏｌ ＬＳ−７７０（商品名、三共社製）、アデカスタブＬＡ−７７（商品名、旭電化工業社製）、スミソーブ−５７７（商品名、住友化学社製）、バイオソーブ−０４（商品名、共同薬品社製）、Ｃｈｉｍａｓｓｏｒｂ９４４ＬＤ（商品名、チバ・スペシャリティ・ケミカルズ社製）、Ｔｉｎｕｖｉｎ−６２２ＬＤ（商品名チバ・スペシャリティ・ケミカルズ社製）、バイオソーブ−０３（商品名、共同薬品社製）、アデカスタブＬＡ−５７、アデカスタブＬＡ−６２、アデカスタブＬＡ−６７、アデカスタブＬＡ−６３、アデカスタブＬＡ−６８、アデカスタブＬＡ−８２、アデカスタブＬＡ−８７、アデカスタブＬＡ−５２（いずれも商品名、旭電化工業社製）、Ｇｏｏｄｒｉｔｅ ＵＶ−３０３４（商品名、Ｇｏｏｄｒｉｃｈ社製）が挙げられる。
上記ヒンダードフェノール骨格を有するヒンダードアミン系光安定剤（ｄ−２）としては、ＴＩＮＵＶＩＮ１４４（商品名、チバ・スペシャリティ・ケミカルズ社製）が好適である。
【００４７】
上記ヒンダードアミン系光安定剤（Ｄ）の添加量としては、ヒンダードフェノール骨格を有さないヒンダードアミン系光安定剤（ｄ−１）であれば、感圧接着性重合体（Ａ）１００重量部に対して、０．１重量部以上とすることが好ましく、また、１０重量部以下とすることが好ましい。０．１重量部未満であると、近赤外線吸収色素の劣化が大きいおそれがあり、１０重量部を超えると、粘着性に乏しくなるおそれがある。より好ましくは、０．３重量部以上であり、更に好ましくは、０．５重量部以上である。また、より好ましくは、５重量部以下であり、更に好ましくは、２重量部以下である。また、ヒンダードフェノール骨格を有するヒンダードアミン系光安定剤（ｄ−２）であれば、感圧接着性重合体（Ａ）１００重量部に対して、０．１重量部以上とすることが好ましく、また、５０重量部以下とすることが好ましい。この範囲より少なくても多くても、近赤外線吸収色素の劣化を充分に抑制することができなくなるおそれがある。より好ましくは、０．３重量部以上であり、更に好ましくは、０．５重量部以上である。また、より好ましくは、２０重量部以下であり、更に好ましくは、１０重量部以下である。
【００４８】
上記酸化防止剤（Ｅ）としては、ラジカル連鎖禁止剤（１次酸化防止剤）、過酸化物分解剤（２次酸化防止剤）を用いることができる。
ラジカル連鎖禁止剤（１次酸化防止剤）としては、フェノール系酸化防止剤、アミン系酸化防止剤挙げられる。フェノール系酸化防止剤としては、２，６−ジ−ｔ−ブチル−ｐ−クレゾール、ブチル化ヒドロキシアニソール（ＢＨＡ）、２，６−ジ−ｔ−ブチル−４−エチルフェノール、ステアリル−β−｛３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル｝プロピオネート等のモノフェノール系酸化防止剤；２，２′−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、２，２′−メチレンビス（４−エチル−６−ｔ−ブチルフェノール）、４，４′−チオビス（３−メチル−６−ｔ−ブチルフェノール）、４，４′−ブチリデンビス（３−メチル−６−ｔ−ブチルフェノール）、３，９−ビス〔１，１−ジメチル−２−〔β−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ〕エチル〕２，４，８，１０−テトラオキサスピロ〔５，５〕ウンデカン等のビスフェノール系酸化防止剤；１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタン、テトラキス−〔メチレン−３−（３′，５′−ジ−ｔ−ブチル−４′−ヒドロキシフェニル）プロピオネート〕メタン、ビス〔３，３′−ビス−（４′−ヒドロキシ−３′−ｔ−ブチルフェニル）ブチリックアシッド〕グリコールエステル、１，３，５−トリス（３′，５′−ジ−ｔ−ブチル−４′−ヒドロキシベンジル）−ｓｅｃ−トリアジン−２，４，６−（１Ｈ，３Ｈ，５Ｈ）トリオン、トコフェロール（類）等の高分子型フェノール系酸化防止剤が好適である。
【００４９】
上記過酸化物分解剤としては、硫黄系酸化防止剤、リン系酸化防止剤が挙げられる。硫黄系酸化防止剤としては、ジラウリル３，３′−チオジプロピオネート、ジミリスチル３，３′−チオジプロピオネート、ジステアリル３，３′−チオジプロピオネートが好適である。リン系酸化防止剤としては、トリフェニルホスファイト、ジフェニルイソデシルホスファイト、フェニルジイソデシルホスファイト、４，４′−ブチリデン−ビス（３−メチル−６−ｔ−ブチルフェニル ジトリデシル）ホスファイト、サイクリックネオペンタンテトライルビス（オクタデシルホスファイト）、トリス（ノニルフェニル）ホスファイト、トリス（モノ及び／又はジノニルフェニル）ホスファイト、ジイソデシルペンタエリスリトールジフォスファイト、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン＝１０−オキサイド、１０−（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド、１０−デシロキシ−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト、サイクリックネオペンタンテトライルビス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト、サイクリックネオペンタンテトライルビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ホスファイト、２，２−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）オクチルホスファイトが好適である。
これらの中でも、感圧接着性重合体（Ａ）との混和性がよく、着色等が少ないヒンダードフェノール系が好ましい。
【００５０】
上記酸化防止剤（Ｅ）の添加量としては、感圧接着性重合体（Ａ）１００重量部に対して、０．１重量部以上とすることが好ましい。より好ましくは、１重量部以上であり、更に好ましくは、３重量部以上である。また、１００重量部以下とすることが好ましい。より好ましくは、５０重量部以下であり、更に好ましくは、２０重量部以下である。酸化防止剤（Ｅ）の添加量が少なすぎると、近赤外線吸収色素が劣化しやすくなり、多すぎると、粘着性が乏しくなったり、析出して塗膜の透明性がなくなるおそれがある。
【００５１】
本発明において、紫外線吸収剤（Ｃ）とヒンダードアミン系光安定剤（Ｄ）とを併用する場合には、これらの配合比としては、ヒンダードフェノール骨格を有さないヒンダードアミン系光安定剤（ｄ−１）を用いる場合には、紫外線吸収剤（Ｃ）１００重量部に対して、０．１重量部以上とすることが好ましい。より好ましくは、１重量部以上であり、更に好ましくは、５重量部以上である。また、１００重量部以下とすることが好ましく、より好ましくは、５０重量部以下であり、更に好ましくは、３０重量部以下である。また、ヒンダードフェノール骨格を有するヒンダードアミン系光安定剤（ｄ−２）を用いる場合には、紫外線吸収剤（Ｃ）１００重量部に対して、０．１重量部以上とすることが好ましい。より好ましくは、１重量部以上であり、更に好ましくは、５重量部以上である。また、１００重量部以下とすることが好ましい。より好ましくは、５０重量部以下であり、更に好ましくは、３０重量部以下である。
【００５２】
本発明の感圧接着剤組成物から形成される塗膜やフィルムは、架橋、未架橋のいずれでも使用可能である。
本発明の感圧接着剤組成物は、それが用いられる用途や架橋剤の種類によって様々な硬化条件で硬化させることができるものであり、常温硬化型、加熱硬化型、紫外線又は電子線硬化型等として用いることができる。また、架橋剤の使用量や、添加及び分散方法等は特に限定されず、例えば、感圧接着性重合体（Ａ）が１分子内に水酸基を複数有するポリオールとなる場合では、ポリオールに通常用いられる使用量や、添加及び分散方法とすればよい。
【００５３】
上記架橋剤としては、感圧接着性重合体（Ａ）がポリオールにより構成される場合では、（ブロック）ポリイソシアネート化合物、アミノプラスト樹脂が好適である。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。
【００５４】
上記（ブロック）ポリイソシアネート化合物とは、ポリイソシアネート化合物及び／又はブロックポリイソシアネート化合物を意味する。
上記ポリイソシアネート化合物としては、イソシアネート基を分子内に少なくとも２つ有する化合物であればよく、トリレンジイソシアネート、キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、１，６−ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、４，４′−メチレンビス（シクロヘキシルイソシアネート）、リジンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、１，３−（イソシアナートメチル）シクロヘキサン、１，５−ナフタレンジイソシアネート、トリフェニルメタントリイソシアネート等のポリイソシアネート；これらのポリイソシアネートのアダクト体、ビュレット体、イソシアヌレート体等のポリイソシアネートの誘導体（変性物）等が挙げられる。
【００５５】
上記ブロックポリイソシアネート化合物とは、感圧接着剤組成物を加熱乾燥するときに架橋させ、かつ、常温での貯蔵安定性を向上させるために、通常、ポリイソシアネート化合物のイソシアネート基をブロック化剤でブロックしたものである。
上記ブロック化剤としては、ε−カプロラクタム、フェノール、クレゾール、オキシム、アルコール等の化合物等が挙げられる。
上記（ブロック）ポリイソシアネート化合物の市販品としては、例えば、スミジュールＮ３２００、スミジュールＮ３３００、スミジュールＢＬ３１７５、デスモジュールＮ３４００、デスモジュールＮ３６００、デスモジュールＶＰＬＳ２１０２（商品名、住友バイエルウレタン社製）、デュラネートＥ−４０２−９０Ｔ（商品名、旭化成工業社製）等が挙げられる。また、感圧接着剤組成物から形成される塗膜の黄変を防止するために、芳香環に直接結合したイソシアネート基を有しない無黄変性ポリイソシアネート化合物が好ましい。
【００５６】
上記（ブロック）ポリイソシアネート化合物の使用量としては感圧接着剤組成物中の水酸基１モルに対して、（ブロック）ポリイソシアネート化合物におけるイソシアネート基が０．０１モル以上であることが好ましく、また、５モル以下が好ましい。０．０１モル未満であると、感圧接着剤組成物中に末反応の水酸基が多く残存するので、得られる感圧接着剤組成物を用いて形成される塗膜の耐候性が低下することがある。５モルを超えると、未反応のイソシアネート基が塗膜中に多く残存し、これが塗膜硬化時に空気中の水分と反応して、塗膜が発泡や白化を起こすことがある。より好ましくは、０．１モル以上であり、更に好ましくは、０．５モル以上である。また、より好ましくは、２モル以下であり、更に好ましくは、１．２モル以下である。
【００５７】
上記アミノプラスト樹脂は、メラミンやグアナミン等のアミノ基を有する化合物とホルムアルデヒドとの付加縮合物であり、アミノ樹脂とも呼ばれているものである。
上記アミノプラスト樹脂としては、ジメチロールメラミン、トリメチロールメラミン、テトラメチロールメラミン、ペンタメチロールメラミン、ヘキサメチロールメラミン、完全アルキル型メチル化メラミン、完全アルキル型ブチル化メラミン、完全アルキル型イソブチル化メラミン、完全アルキル型混合エーテル化メラミン、メチロール基型メチル化メラミン、イミノ基型メチル化メラミン、メチロール基型混合エーテル化メラミン、イミノ基型混合エーテル化メラミン等のメラミン樹脂；ブチル化ベンゾグアナミン、メチル／エチル混合アルキル化ベンゾグアナミン、メチル／ブチル混合アルキル化ベンゾグアナミン、ブチル化グリコールウリル等のグアナミン樹脂等が挙げられる。
【００５８】
上記アミノプラスト樹脂の市販品としては、サイメル１１２８、サイメル３０３、マイコート５０６、サイメル２３２、サイメル２３５、サイメル７７１、サイメル３２５、サイメル２７２、サイメル２５４、サイメル１１７０（いずれも商品名、三井サイテック社製）等が挙げられる。
【００５９】
上記アミノプラスト樹脂の使用量としては、感圧接着性重合体（Ａ）１００重量部に対するアミノプラスト樹脂の固形分質量が０．１重量部以上となるように配合することが好ましく、より好ましくは、０．５重量部以上である。また、１０重量部以下となるように配合することが好ましい。より好ましくは、５重量部以下である。アミノプラスト樹脂が多すぎると粘着性がなくなるおそれがあり、少なすぎると架橋が進まず凝集力が乏しくなるおそれがある。
【００６０】
本発明の感圧接着剤組成物における架橋システムとしては、上述したＯＨ／イソシアネート以外に、酸／エポキシ、酸／金属キレート、酸／オキサゾリン、酸／アミンが好適である。本発明の感圧接着剤組成物には、本発明の効果を損なわない範囲で、上記ポリイソシアネート化合物以外の架橋剤、エポキシ化合物、アジリジン化合物、オキサゾリン化合物、メラミン化合物、金属キレート化合物、カルボジイミド化合物、グリシジルアミン化合物、アミン化合物等を含有させることもできる。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。
【００６１】
本発明の感圧接着剤組成物は、必要に応じて、感圧接着性重合体（Ａ）と、架橋剤との架橋反応を促進させるための硬化触媒を１種又は２種以上含んでもよい。このような硬化触媒としては特に限定されるものではないが、例えば、上記（ブロック）ポリイソシアネート化合物を用いる場合には、ジブチル錫ジラウレート、第３級アミン等の触媒を使用することが好ましく、上記アミノプラスト樹脂を使用する場合には、酸性又は塩基性の硬化触媒を使用することが好ましい。
【００６２】
本発明の感圧接着剤組成物には、上述した以外の配合物として、溶剤や添加剤等を１種又は２種以上含んでいてもよい。このような溶剤としては、上述したのと同様の有機溶剤等が挙げられ、また、添加剤としては、フィルムやコーティング膜等を形成する樹脂組成物に一般に使用される従来公知の添加剤等を用いることができ、例えば、レベリング剤；コロイド状シリカ、アルミナゾル等の無機微粒子、消泡剤、タレ性防止剤、シランカップリング剤、チタン白、複合酸化物顔料、カーボンブラック、有機顔料、顔料中間体等の顔料；顔料分散剤；粘性改質剤；紫外線安定剤；金属不活性化剤；過酸化物分解剤；充填剤；補強剤；可塑剤；潤滑剤；防食剤；防錆剤；有機及び無機系紫外線吸収剤、無機系熱線吸収剤；有機・無機防炎剤；静電防止剤；粘着付与剤；結晶核剤等が挙げられる。
【００６３】
上記粘着付与剤は、粘着性の改質剤であり、粘着力を調節する（向上させる）ことができることになる。粘着付与剤としては、例えば、（重合）ロジン系、（重合）ロジンエステル系、テルペン系、テルペンフェノール系、クマロン系、クマロンインデン系、スチレン樹脂系、キシレン樹脂系、フェノール樹脂系、石油樹脂系等のものが挙げられる。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。このような粘着付与剤を含有させる場合、その含有量は、所望する粘着性能が得られるように適宜設定すればよく、特に限定されるものではない。結晶核剤としては、リン酸２，２′−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）ナトリウム、リン酸ビス（４−ｔ−ブチルフェニル）ナトリウム、ビス（ｐ−メチルベンジリデン）ソルビトール、アルキル置換ジベンジリデンソルビトール、ビス（ｐ−エチルベンジリデン）ソルビトールが挙げられる。結晶核剤の添加量としては、感圧接着性重合体（Ａ）１００重量部に対して、０．０１〜５重量部が好ましい。より好ましくは、０．１〜２重量部である。少なすぎると、充分な効果が得らないおそれがある。
【００６４】
本発明の感圧接着剤組成物はまた、ヒンダードアミン系光安定剤（Ｄ）以外の光安定剤を含んでいてもよい。このような光安定剤としては、ニッケルビス（オクチルフェニル）サルファイド、〔２，２′−チオビス｛４−ｔｅｒｔ−オクチルフェノラート｝〕−ｎ−ブチルアミンニッケル、ニッケルコンプレックス−３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル−リン酸モノエチレート、ニッケル−ジブチルジチオカーバメートが挙げられる。ニッケルビス（オクチルフェニル）サルファイドの市販品として、ＡＭ−１０１（商品名、フェロケミカル社製）、ＡＭ−１０５（商品名、フェロケミカル社製）が、〔２，２′−チオビス｛４−ｔｅｒｔ−オクチルフェノラート｝〕−ｎ−ブチルアミンニッケルの市販品として、Ｃｙａｓｏｒｂ ＵＶ−１０８４（商品名、Ｃｙｔｅｃ社製）が、ニッケルコンプレックス−３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル−リン酸モノエチレートの市販品として、Ｉｒｇａｓｏｒｂ−２００２（商品名、チバ・スペシャルティ・ケミカルズ社製）が、ニッケル−ジブチルジチオカーバメートの市販品として、ＮＢＣ（商品名、ＩＣＩ社製、大内新興化学社製）が好適である。
【００６５】
本発明の感圧接着剤組成物から形成される塗膜やフィルムの使用形態としては、例えば、感圧接着剤組成物から形成される塗膜やフィルムを接着層として、透明基材上に設けた積層体や２枚の透明基材で挟んだ積層体等が挙げられる。
上記透明基材としては、ポリカーボネート樹脂、アクリル系樹脂、ポリエチレン樹脂、ポリエステル系樹脂、ポリプロピレン樹脂、ポリスチレン樹脂、ポリ塩化ビニル樹脂、ポリビニルアルコール樹脂、ポリエチレンテレフタレート樹脂、トリアセチルセルロース樹脂等の有機系基材；ガラス等の無機系基材が好適である。
【００６６】
上記接着層の形成方法としては、感圧接着剤組成物を透明基材上に塗布することにより行うことができる。感圧接着剤組成物を基材に塗布する方法としては、特に限定されるものではなく、従来公知の方法を採用すればよい。例えば、基材に直接塗布してもよいし、剥離ライナー（離型紙、離型フィルム）へあらかじめ塗布し、乾燥後に基材に転写してもよい。また、感圧接着剤組成物は、基材の片面に塗布されていてもよいし、両面に塗布されていてもよい。また、本発明の感圧接着剤組成物から形成されるフィルムや塗膜は粘着性を有するものであるから、該感圧接着剤組成物を基材に塗布して接着層を形成した後、更に他の基材を用いて積層体を形成する場合や、感圧接着剤組成物をフィルム化して用いる場合には、該接着層表面又はフィルム表面を剥離紙でラミネートし、使用時に剥離紙を剥がして用いることが好ましい。
【００６７】
上記接着層の形成方法において、感圧接着剤組成物を透明基材上に塗布する方法としては、塗布する感圧接着剤組成物の形態等により適宜選択すればよく、▲１▼感圧接着剤組成物を有機溶剤に溶解した均一な溶液として各種フィルムやシート（基材）表面に塗工する溶剤型塗工法、▲２▼感圧接着剤組成物を水中に分散させたエマルションとして各種基材表面に塗工するエマルション型塗工法、▲３▼感圧接着剤組成物を高温下で溶融混合し基材表面に塗工するホットメルト型塗工法、▲４▼無溶剤型塗工法であるカレンダ型塗工法が挙げられる。▲１▼溶剤型塗工法又は▲２▼エマルション型塗工法においては、感圧接着剤組成物に上述した有機溶剤を適宜混合させて塗布することができ、塗工方法としては、各種コータを用いて塗布する方法、浸漬、吹き付け、刷毛塗り、静電塗装等の方法が挙げられる。各種コータとしては、アークグラビアコータ、オフセットグラビアコータ、パンフィードグラビアコータ、ダイフィードグラビアコータ等のグラビアコータ；トップフィードリバースコータ、ボトムフィードリバースコータ等のリバースコータ；コンマダイレクトコータ、コンマリバースコータ、Ｕコンマコータ等のコンマコータ；エアナイフコータ、ナイフコータ、ファウンテンダイコータ、リップコータ、マイヤバーコータ、カーテンフローコータ、ロールコータ、スピンコータ、ブレードコータ、バーコータ、ダイコータ、スプレーコータ等が挙げられる。また、感圧接着剤組成物を硬化させる方法としては、構成成分の種類等により適宜設定すればよく、例えば、加熱する方法、紫外線や電子線を照射する方法等が挙げられる。
【００６８】
上記接着層の厚さとしては、使用用途等により適宜設定すればよく特に限定されるものではない。例えば、乾燥時の厚さを５μｍ以上とすることが好ましく、また、２００μｍ以下となるようにすることが好ましい。より好ましくは、１５μｍ以上であり、また、１００μｍ以下である。更に好ましくは、５０μｍ以下である。接着層が薄いと接着性が悪く、浮いたり、剥がれたりして好ましくない。また、厚いと接着剤がはみだしたりして好ましくない。
【００６９】
上記積層体においては、近赤外線吸収層の光入射側に、紫外線吸収層を設けることが好ましい。これにより、近赤外線吸収性色素の劣化をより効果的に抑制することができる。このような積層体の積層構造としては特に限定されず、例えば、（１）光入射側から紫外線吸収層、接着層、基材の順に積層された形態、（２）光入射側から紫外線吸収層、基材、接着層の順に積層された形態等が挙げられる。また、耐擦り傷性及び耐汚染性を向上させるために、積層体表面にシリコン系や有機系のハードコート層、光触媒機能層等の表面保護層を更に設けてもよく、必要により基材と積層体との間や積層体の各層間にプライマー層を設けてもよい。このような紫外線吸収層や表面保護層、プライマー層の組成や厚さとしては、特に限定されるものではない。
【００７０】
本発明の感圧接着剤組成物から形成される塗膜は、近赤外線吸収性能の劣化が少ないこと、及び、粘着性を有することを特長としており、塗膜が持つ物性として、耐光性試験後の近赤外線吸収性色素の近赤外線吸収性能の低下が少ない、すなわち吸収能残存率が高いことが挙げられ、以下の近赤外線吸収色素の劣化性評価におけるＵＶ照射９６時間後のフィルムの最大吸収波長（近赤外線吸収色素の最大吸収波長：７８０〜１２００ｎｍ）の吸光度が、初期値を１００としたときに５％以上であることが好ましい。より好ましくは、５０％以上であり、更に好ましくは、８５％以上であり、最も好ましくは、９５％以上である。なお、ＵＶ照射後の吸光度は、初期値を１００としたときの相対値である。
【００７１】
（近赤外線吸収色素の劣化性評価）
ＵＶ照射後の近赤外線吸収色素の最大吸収波長の吸光度を追跡する。
感圧接着剤組成物を離型フィルム（シリコン処理したＰＥＴフィルム）へ、乾燥後の厚みが２５μとなるようにアプリケーターにて塗布して粘着層を形成する。これを１００℃で２分間乾燥した。上記粘着層を５０μ厚又は１００μ厚ＰＥＴフィルムでラミネートする（粘着層はこちらに転着する）。感圧接着剤組成物の離型フィルムを剥がし、５０μＰＥＴでラミネートする。
分光光度計（島津製作所社製、商品名「ＵＶ−３１００」）を用い、上記フィルムの最大吸収波長（近赤外線吸収色素の最大吸収波長：７８０〜１２００ｎｍ）の吸光度を測定する。上記フィルムに、紫外線オートフェードメーター（スガ試験機社製、商品名「ＦＡＬ−ＡＵ−Ｂ」）にてＵＶ照射する。ＵＶ照射４８時間ごとに、分光光度計（島津製作所社製、商品名「ＵＶ−３１００」）を用い、フィルムの最大吸収波長（近赤外線吸収色素の最大吸収波長：７８０〜１２００ｎｍ）の吸光度を測定する。初期値を１００としたときの吸光度の相対値を記録する。１００％に近いほど色素の劣化がなく良好である。
【００７２】
本発明の感圧接着剤組成物から形成される塗膜やフィルム、該塗膜やフィルムを接着層として含む積層体は、透明性を高くすることが好ましく、例えば、ヘイズ（曇価）を３．０％以下とすることが好ましい。より好ましくは、２．０％以下であり、更に好ましくは、１．０％以下である。
【００７３】
本発明の感圧接着剤組成物は、粘着用途全般に広く用いることができるものであるが、中でも、プラズマディスプレイ等の電子機器における接着層を形成する材料として好適に適用されるものである。
このような感圧接着剤組成物が接着層として機能するとともに近赤外線吸収層として機能する場合には、プラズマディスプレイ等の層構造を少なくして近赤外線等が画面から放射されることを抑制することができることとなる。
【００７４】
【実施例】
以下に実施例を挙げて本発明を更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。なお、特に断りのない限り、「部」は、「重量部」を意味するものとする。
【００７５】
合成例１（モノマー滴下重合法）
２−エチルへキシルアクリレート（２ＥＨＡ）３５８．２ｇ、シクロヘキシルメタクリレート（ＣＨＭＡ）２４０ｇ、２−ヒドロキシエチルアクリレート（ＨＥＡ）１．８ｇを量り、よく混ぜた（この混合物を、単量体混合物（Ａ１）とする）。単量体混合物（Ａ１）の４０％と酢酸エチル１９６．４ｇとを温度計、攪拌機、不活性ガス導入管、還流冷却器及び滴下ロートを備えたフラスコに量った。また、単量体混合物（Ａ１）の６０％、酢酸エチル１６ｇ及び重合開始剤ナイパーＢＭＴＫ４０（商品名、日本油脂社製）０．７２ｇを滴下ロートへ入れ、よく混ぜた（この混合物を、単量体混合物（Ｂ１）とする）。窒素ガス２０ｍＬ／分を適量流しながら、フラスコの内温を８５℃まで上昇させた。重合開始剤ナイパーＢＭＴＫ４０（商品名、日本油脂社製）０．９６ｇをフラスコへ投入し、反応を開始した。重合開始剤の投入から１５分後に、単量体混合物（Ｂ１）を９０分かけて、均等にフラスコへ添加しながら反応を進めた。単量体混合物（Ｂ１）の添加終了直後に酢酸エチル５０ｇを添加した。８０℃で熟成反応を９０分行った。重合開始剤ＡＢＮ−Ｅ（商品名、日本ヒドラジン工業社製）１．８ｇと酢酸エチル３９ｇの混合溶液を３０分ごとに５回に分けて添加した（残存モノマー反応用）。８０℃で熟成反応を９０分間行い、トルエン５７５ｇを添加し、反応を終了し、感圧接着性ポリマー（Ａ−１）を得た。
【００７６】
合成例２（モノマー一括重合法）
２ＥＨＡ２０９．１ｇ、ＣＨＭＡ６０ｇ、ＨＥＡ０．９ｇ、ＲＵＶＡ−９３（商品名、大塚化学社製）３０ｇ、酢酸エチル２４５ｇを、温度計、攪拌機、不活性ガス導入管、還流冷却器及び滴下ロートを備えたフラスコに量った。窒素ガス２０ｍＬ／分を適量流しながら、フラスコの内温を８５℃まで上昇させた。重合開始剤ナイパーＢＭＴＫ４０（商品名、日本油脂社製）０．６ｇをフラスコへ投入し、反応を開始した。９０分間反応させた。重合開始剤ナイパーＢＭＴＫ４０（商品名、日本油脂社製）０．３ｇと酢酸エチル１５ｇの混合溶液を１時間ごとに２回に分けて添加した（残存モノマー反応用）。８０℃で熟成反応を１５０分間行い、トルエン１５５ｇを添加し、反応を終了し、感圧接着ポリマー（Ａ−２）を得た。
【００７７】
合成例３〜５（モノマー一括重合法）
単量体組成を表１に示すようにした以外は、合成例２と同様にして感圧接着ポリマー（Ａ−３）、感圧接着ポリマー（Ａ−４）及び感圧接着ポリマー（Ａ−５）を得た。
【００７８】
合成例６（モノマー滴下重合法）
ブチルアクリレート（ＢＡ）１２０ｇ、２ＥＨＡ４５６ｇ、ステアリルアクリレート（ＳＴＡ）６ｇ及びＨＥＡ１８ｇを量り、よく混ぜた（この混合物を、単量体混合物（Ａ２）とする）。単量体混合物（Ａ２）の４０％と酢酸エチル２９３．３ｇとを、温度計、攪拌機、不活性ガス導入管、還流冷却器及び滴下ロートを備えたフラスコに量った。単量体混合物（Ａ２）６０％、酢酸エチル１０ｇ、トルエン６０ｇ及び重合開始剤ナイパーＢＭＴＫ４０（商品名、日本油脂社製）０．３６ｇを滴下ロートへ入れ、よく混ぜた（この混合物を、単量体混合物（Ｂ２）とする）。窒素ガス２０ｍＬ／分を適量流しながら、フラスコの内温を８５℃まで上昇させた。重合開始剤ナイパーＢＭＴＫ４０（商品名、日本油脂社製）０．４８ｇをフラスコへ投入し、反応を開始した。重合開始剤の投入から１０分後に、単量体混合物（Ｂ２）を６０分かけて、均等にフラスコへ添加しながら反応を進めた。単量体混合物（Ｂ２）の添加終了直後に酢酸エチル６ｇ、トルエン５２．４ｇを添加した。８６℃で熟成反応を９０分行った。重合開始剤ナイパーＢＭＴＫ４０（商品名、日本油脂社製）０．６ｇとトルエン３０ｇの混合溶液を１時間ごとに２回に分けて添加した（残存モノマー反応用）。８６℃で熟成反応を９０分間行い、酢酸エチル３１８．５ｇ、トルエン４２３．４ｇを添加し、反応を終了した。最後に、架橋促進剤ジラウリン酸ジ−ｎ−ブチルスズ０．１５ｇ、酢酸３ｇ及びトルエン２５ｇの混合溶液を添加し、よく混ぜて感圧接着ポリマー（Ａ−６）を得た。
【００７９】
合成例７（モノマー滴下重合法）
ＢＡ２７５．５ｇ、２ＥＨＡ１３６．８ｇ、アクリル酸（ＡＡ）３６ｇ、酢酸ビニル（ＶＡＣ）１４９．９ｇ及びＨＥＡ１．８ｇを量り、よく混ぜた（この混合物を、単量体混合物（Ａ３）とする）。単量体混合物（Ａ３）の３３％、酢酸エチル３１２．９ｇ及びトルエン３．３ｇを、温度計、攪拌機、不活性ガス導入管、還流冷却器及び滴下ロートを備えたフラスコに量った。単量体混合物（Ａ３）の６７％、酢酸エチル１３９．９ｇ及び重合開始剤ＡＢＮ−Ｅ（商品名、日本ヒドラジン工業社製）０．７９ｇを滴下ロートへ入れ、よく混ぜた（この混合物を、単量体混合物（Ｂ３）とする）。窒素ガス２０ｍＬ／分を適量流しながら、フラスコの内温を８２℃まで上昇させた。重合開始剤ナイパーＢＭＴＫ４０（商品名、日本油脂社製）０．７９ｇをフラスコへ投入し、反応を開始した。重合開始剤の投入から１５分後に、単量体混合物（Ｂ３）を９０分かけて、均等にフラスコへ添加しながら反応を進めた。単量体混合物（Ｂ３）の添加終了直後にトルエン１５１．２ｇを添加した。８０℃で熟成反応を９０分行った。トルエン１８２．９を添加した。引き続き、重合開始剤ＡＢＮ−Ｒ（商品名、日本ヒドラジン工業社製）１．８ｇとトルエン２３．４ｇとの混合溶液を３０分ごとに５回に分けて添加した（残存モノマー反応用）。８０℃で熟成反応を９０分間行い、トルエン１６４．４ｇを添加し、反応を終了し、感圧接着ポリマー（Ａ−７）を得た。
【００８０】
【表１】

【００８１】
表１について、以下に説明する。ＢＡとは、ブチルアクリレートであり、２ＥＨＡとは、２−エチルへキシルアクリレートであり、ＣＨＭＡとは、シクロヘキシルメタクリレートであり、ＨＥＡとは、２−ヒドロキシエチルアクリレートであり、ＲＵＶＡとは、ＲＵＶＡ−９３（商品名、大塚化学社製）であり、ＶＡＣとは、酢酸ビニルであり、ＡＡとは、アクリル酸であり、ＳＴＡとは、ステアリルアクリレートである。
Ｔｇは、各ホモポリマーのＴｇから計算した計算値である。各ホモポリマーのＴｇは次の値を使用した。ＢＡ：−５５℃、２ＥＨＡ：−７０℃、ＣＨＭＡ：６６℃、ＨＥＡ：−１５℃、ＲＵＶＡ：１００℃、ＶＡＣ：２５℃、ＡＡ：１０６℃、ＳＴＡ：−７０℃
水酸基価及び酸価は、重合体固形分１ｇあたりの値である。
【００８２】
実施例１
感圧接着ポリマー（Ａ−１）溶液（不揮発分（ＮＶ）４０．６％）２２．９３ｇに、近赤外線吸収色素ＩＲ−１２（日本触媒社製、商品名「イーエクスカラー」）０．２ｇ、紫外線吸収剤ＴＩＮＵＶＩＮ２３４（商品名、チバ・スペシャリティ・ケミカルズ社製）０．４９ｇ及びトルエンを入れた。トルエンは、２ｇ（理論不揮発分が３９％になる量）を入れた。ペイントシェーカーで、均一な溶液になるまで混合攪拌して樹脂溶液を作製した。ＩＲ−１２の最大吸収波長λｍａｘは８８５ｎｍ（トルエン溶液）であった。
【００８３】
上記樹脂溶液を離型フィルム（シリコン処理したＰＥＴフィルム）へ、乾燥後の厚みが２５μとなるようにアプリケーターにて塗布して粘着層を形成した。これを１００℃で２分間乾燥した。上記粘着層を５０μ厚又は１００μ厚ＰＥＴフィルムでラミネートした（粘着層はこちらに転着する）。この粘着試料について下記の方法により、粘着性及び外観の評価並びに近赤外吸収色素の劣化性評価を行った。結果を表２に示す。
【００８４】
実施例２〜１０及び比較例１
樹脂溶液の組成を表２〜４に示した配合比率としたこと以外は、実施例１と同様の操作を行った。結果を表２〜４に示す。
【００８５】
実施例１１〜２５
樹脂溶液の組成を表２〜３に示した配合比率としたこと以外は、実施例１と同様の操作を行った。次いで、樹脂溶液１００部に対して、イソシアネート架橋剤コロネートＬ−５５Ｅ（商品名、日本ポリウレタン社製）１．０部を配合し、よく混ぜた。この場合の粘着試料は、室温で１週間以上養生してから評価試験に使用した。結果を表２〜３に示す。
【００８６】
（粘着性の評価）
上記のように調製した粘着試料から、離型フィルムを剥がし、指で触って確かめた。べたべたするものを、粘着性あり（○）。全くべたべたしないものを、粘着性なし（×）とした。
【００８７】
（外観の評価）
上記のように調製した粘着試料を目視で観察した。透明性のあるものを良好（○）とし、透明性のないもの（白濁するもの、斑点等の異物の発生するもの）を不良（×）とした。
【００８８】
（近赤外線吸収色素の劣化性評価）
ＵＶ照射後の近赤外線吸収色素の最大吸収波長の吸光度を追跡した。
粘着試料の離型フィルムを剥がし、５０μＰＥＴでラミネートした。分光光度計（島津製作所社製、商品名「ＵＶ−３１００」）を用い、上記フィルムの最大吸収波長（近赤外線吸収色素の最大吸収波長：７８０〜１２００ｎｍ）の吸光度を測定した。
上記フィルムに、紫外線オートフェードメーター（スガ試験機社製、商品名「ＦＡＬ−ＡＵ−Ｂ」）にてＵＶ照射した。ＵＶ照射４８時間ごとに、分光光度計（島津製作所社製、商品名「ＵＶ−３１００」）を用い、フィルムの最大吸収波長（近赤外線吸収色素の最大吸収波長：７８０〜１２００ｎｍ）の吸光度を測定した。初期値を１００としたときの吸光度の相対値を記録した。１００％に近いほど色素の劣化がなく良好である。
【００８９】
【表２】

【００９０】
【表３】

【００９１】
【表４】

【００９２】
表２〜４について、以下に説明する。近赤外吸収色素Ｂにおいて、ＩＲ１２とは、日本触媒社製の近赤外線吸収色素（商品名、エクスカラー）である。紫外線吸収剤Ｃにおいて、ＴＩＮＵＶＩＮ２３４及びＴＩＮＵＶＩＮ３８４（いずれも商品名）とは、チバ・スペシャリティ・ケミカルズ社製の紫外線吸収剤である。ヒンダードアミン系光安定剤ｄ−１及びヒンダードアミン系光安定剤ｄ−２において、ＴＩＮＵＶＩＮ７６５及びＴＩＮＵＶＩＮ１４４（いずれも商品名）とは、チバ・スペシャリティ・ケミカルズ社製の光安定剤である。酸化防止剤Ｅにおいて、ＢＨＴ（商品名）とは、住友化学社製のヒンダードフェノール系酸化防止剤である。
【００９３】
【発明の効果】
本発明の感圧接着剤組成物は、上述の構成からなるので、紫外線による近赤外線吸収色素の劣化が少なく、プラズマディスプレイ等を形成する層状の材料を貼り合わせる接着層等を形成に好適なものである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a pressure-sensitive adhesive composition. More specifically, the present invention relates to a pressure-sensitive adhesive composition suitable for an adhesive layer to which a layered material for forming a plasma display or the like is attached.
[0002]
[Prior art]
A pressure-sensitive adhesive composition is a composition containing an adhesive that is tacky at room temperature and adheres to an adherend only by applying pressure, and is widely used in, for example, electric and electronic parts and other fields. Have been. Among such applications of the pressure-sensitive adhesive composition, many layered materials are formed from the pressure-sensitive adhesive composition for a plasma display (PDP) used for a large thin television, a thin display, and the like. It will be integrated by the adhesive layer.
[0003]
By the way, in a plasma display, for example, a film or a coating film having a property of absorbing near infrared rays as heat rays is used, and has an important function. That is, in a plasma display or the like, near infrared rays are radiated from a screen, and this acts on peripheral electronic devices such as a remote control device that uses near infrared rays to cause a malfunction. In a plasma display, near infrared rays emitted from a screen are blocked by forming a near infrared ray absorbing layer that absorbs near infrared rays and transmits visible light rays. Usually, it is formed of a near infrared absorbing resin composition. In the manufacture of such a plasma display, it is desired to reduce the weight of the plasma display or to simplify the manufacturing process to reduce the manufacturing cost.
[0004]
As a conventional pressure-sensitive adhesive, a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive polymer having a hydroxyl group and a crosslinking accelerator, and a pressure-sensitive adhesive composition also containing a volatile acid is disclosed (for example, see Patent Document 1). .). Also, a sheet for forming a surface protective film for a display having a surface protective layer containing at least an ultraviolet absorber, an adhesive layer and a separator on a peelable substrate in this order (for example, see Patent Document 2), a heat ray shielding. A heat ray shielding pressure-sensitive adhesive containing an acrylic copolymer obtained by dispersing and polymerizing conductive fine particles (for example, see Patent Document 3) is disclosed. However, since these pressure-sensitive adhesive compositions are not set so as to be applicable to plasma displays, they can be suitably applied to materials for forming an adhesive layer in electronic devices such as plasma displays. In addition, there is room for contrivance to make the adhesive layer have the function of a near-infrared absorbing layer so that the layer structure of the plasma display etc. can be reduced and the weight can be reduced and the manufacturing process can be simplified. was there.
[0005]
Further, an optical filter (for example, see Patent Document 4) including a pressure-sensitive adhesive layer or an adhesive layer containing a dye having a maximum absorption wavelength at 570 to 600 nm, or a colored pressure-sensitive adhesive composition (for example, see Patent Document 5). , A laser light-absorbing heat-sensitive adhesive (for example, see Patent Document 6), and a near-infrared absorbing material (for example, see Patent Document 7). However, there is still room for contrivance so that these can be suitably applied to a material for forming an adhesive layer in an electronic device such as a plasma display. Further, when these are applied to form an adhesive layer in an electronic device such as a plasma display, there is a problem that the pigment is deteriorated and the near-infrared absorbing ability cannot be maintained.
[0006]
[Patent Document 1]
JP-A-2002-241732 (pages 1 and 2)
[Patent Document 2]
JP-A-9-166983 (pages 1 and 2)
[Patent Document 3]
JP-A-10-8010 (pages 1 and 2)
[Patent Document 4]
JP 2001-228323 A (pages 1 and 2)
[Patent Document 5]
JP-A-3-79687 (page 1)
[Patent Document 6]
JP-A-9-95657 (pages 1 and 2)
[Patent Document 7]
JP-A-9-169849 (pages 1 and 2)
[0007]
[Problems to be solved by the invention]
The present invention has been made in view of the above-mentioned circumstances, and a pressure-sensitive adhesive suitable for forming an adhesive layer or the like in which a near-infrared absorbing dye due to ultraviolet light is less deteriorated and a layered material for forming a plasma display or the like is bonded. It is intended to provide a composition.
[0008]
[Means for Solving the Problems]
The present inventors have conducted various studies on the pressure-sensitive adhesive composition, and found that the pressure-sensitive adhesive composition containing a pressure-sensitive adhesive polymer contains a near-infrared absorbing dye to form a layered layer for forming a plasma display or the like. It has been noted that the formation of an adhesive layer or the like for bonding the above materials makes it possible to reduce the layer structure of a plasma display or the like, to reduce the weight and to simplify the manufacturing process. In an electronic device such as a plasma display, a near-infrared absorbing dye is deteriorated by ultraviolet light accompanying plasma emission or the like, and is easily deteriorated in a pressure-sensitive adhesive polymer, and the near-infrared absorbing ability is reduced. When an ultraviolet absorber and / or a hindered amine light stabilizer is used, deterioration due to ultraviolet rays is suppressed to improve the durability of the near-infrared absorbing dye, which is almost the same as when applied to an adhesive layer in electronic equipment such as a plasma display. The inventors have found that the infrared absorbing ability can be sufficiently maintained, and have come to think that the above problem can be solved successfully. When an adhesive layer in a plasma display or the like is formed from the pressure-sensitive adhesive composition of the present invention, it also functions as a near-infrared absorbing layer. Can be reduced. In such a pressure-sensitive adhesive composition, in order to sufficiently enhance the function as a pressure-sensitive adhesive, an antioxidant is used, or the glass transition temperature or the weight average molecular weight of the pressure-sensitive adhesive polymer is specified. In consideration of the compatibility and cost of the pressure-sensitive adhesive polymer with the ultraviolet absorber and / or the hindered amine light stabilizer, the reactive type and the addition type are used as the ultraviolet absorber and / or the hindered amine light stabilizer. It has been found that the use and combination of the present invention can more fully exert the effects of the present invention, and have reached the present invention.
[0009]
That is, the present invention provides a pressure-sensitive adhesive comprising a pressure-sensitive adhesive polymer (A), a near-infrared absorbing dye (B), an ultraviolet absorber (C) and / or a hindered amine light stabilizer (D). Agent composition.
Hereinafter, the present invention will be described in detail.
[0010]
In the pressure-sensitive adhesive composition of the present invention, an ultraviolet absorber (C) and / or a hindered amine light stabilizer (D) are essential together with the pressure-sensitive adhesive polymer (A) and the near-infrared absorbing dye (B). Although it is contained as a component, a preferred form is a form in which an ultraviolet absorber (C) and a hindered amine light stabilizer (D) are used in combination. In this case, the effect of suppressing the deterioration of the near-infrared absorbing dye (B) by the ultraviolet rays is remarkably improved. One or more of these essential components can be used. Further, the composition preferably further contains an antioxidant (E), and it is preferable to use the ultraviolet absorber (C), the hindered amine light stabilizer (D), and the antioxidant (E) in combination. Thereby, the function and effect of the present invention can be more sufficiently exhibited.
[0011]
In the present invention, as the ultraviolet absorber (C) and / or the hindered amine light stabilizer (D), an addition type and / or a reaction type can be used, and a reaction type is preferably used. More preferably, a reactive type ultraviolet absorber (C) is used. When the reactive ultraviolet absorber (C) and / or the hindered amine light stabilizer (D) are used, the reactive ultraviolet absorber (C) and / or the reactive ultraviolet absorber (C) in the production of the pressure-sensitive adhesive polymer (A). By using the hindered amine light stabilizer (D), the reaction type ultraviolet absorber (C) and / or the hindered amine light stabilizer (D) is incorporated into the pressure-sensitive adhesive polymer (A), that is, It is preferable to use a pressure-sensitive adhesive polymer (A) obtained by reacting an ultraviolet absorber (C) and / or a hindered amine light stabilizer (D). In this case, too, the ultraviolet absorber (C ) And / or a hindered amine light stabilizer (D). When only the addition type ultraviolet absorber (C) and / or the hindered amine light stabilizer (D) is used, if the compatibility with the pressure-sensitive adhesive polymer (A) is poor, or if the addition amount is large, the coating film may be formed. In some cases, crystallization (precipitation) occurs in the adhesive layer and the transparency is lost. Further, spots may be formed on the coating film or the adhesive layer or the film may become cloudy.
Further, together with the pressure-sensitive adhesive polymer (A) obtained by the reaction of the ultraviolet absorber (C) and / or the hindered amine light stabilizer (D), the addition type ultraviolet absorber (C) and / or the hindered amine light stabilizer are used. It is preferable to use the agent (D) in combination. In this case, the compatibility between the pressure-sensitive adhesive polymer (A) and the ultraviolet absorber (C) and / or the hindered amine light stabilizer (D) can be improved, and the reaction type ultraviolet absorber can be improved. This is advantageous in cost as compared with the case where only the agent (C) and / or the hindered amine light stabilizer (D) is used.
[0012]
The pressure-sensitive adhesive polymer (A) in the present invention may be any polymer having adhesiveness or tackiness to an adherend under pressure, and for example, a tacky polymer having a hydroxyl group is suitable. . Examples of such a polymer include modified polymers such as a fluoropolymer, a (meth) acrylic polymer, a polyester polymer, a polyether polymer, an alkyd polymer, a silicone polymer, and a polyester-modified acrylic polymer. A polymer and a polymer obtained by polymerizing a monomer having an ethylenically unsaturated bond are preferred. Rubber-based polymers such as natural rubber, styrene-isoprene-styrene (SIS) block copolymer, styrene-butadiene-styrene (SBS) block copolymer, and synthetic rubber can also be used. Among these, a (meth) acrylic polymer is preferable from the viewpoint of easy adjustment of weather resistance and adhesive strength. More preferably, it is an acrylic polymer.
[0013]
The pressure-sensitive adhesive polymer (A) can be obtained by polymerizing a monomer component containing one or more monomers. The monomer contained in the monomer component and the ratio thereof may be appropriately selected depending on the physical properties desired for the pressure-sensitive adhesive polymer (A). For example, if the polymer is a (meth) acrylic polymer, Those having a (meth) acrylic acid ester having an alkyl group having 4 to 12 carbon atoms in the side chain as a main component are preferred.
Examples of the (meth) acrylate having an alkyl group having 4 to 12 carbon atoms in the side chain include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t- Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, Examples include decyl (meth) acrylate, dodecyl (meth) acrylate, amyl (meth) acrylate, n-lauryl (meth) acrylate, benzyl (meth) acrylate, and isobornyl (meth) acrylate.
[0014]
The monomer component contains a monomer (other monomer) other than the above (meth) acrylic acid ester in order to adjust the Tg and the polarity of the obtained pressure-sensitive adhesive polymer (A). Is also good. The following monomers are suitable as other monomers.
Vinyl esters such as vinyl acetate and vinyl butyrate; unsaturated monomers containing fluorine atoms such as trifluoroethyl (meth) acrylate and tetrafluoropropyl (meth) acrylate; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether; γ-methacrylic Unsaturated monomers containing a silicon atom such as roxypropyltrimethoxysilane; unsaturated monomers containing an epoxy group such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate; ethylene glycol diacrylate, neopentyl glycol Polyfunctional unsaturated monomers such as diacrylate and polypropylene glycol diacrylate.
[0015]
Aromatic unsaturated monomers such as styrene, α-methylstyrene and vinyl toluene; hydrocarbon-based unsaturated monomers such as butadiene and isoprene; halogen-containing unsaturated monomers such as chloroprene and vinyl chloride; N'-dimethylaminoethyl (meth) acrylate, (meth) acrylamide, N-isopropylacrylamide, N-butoxymethylacrylamide, N-phenylmaleimide, N-cyclohexylmaleimide, N-vinylpyridine, N-vinylimidazole, N-vinyl Unsaturated monomers containing a nitrogen atom such as pyrrolidone, N-dimethylacrylamide and isopropenyloxazoline; unsaturated cyanide compounds such as (meth) acrylonitrile;
[0016]
In the above-mentioned monomer component, a monomer having a functional group such as a hydroxyl group or a carboxyl group can also be used for adjusting Tg or polarity or as a crosslinking point (crosslinkable monomer). The following monomers are suitable as such monomers.
2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate, methyl α- (hydroxymethyl) acrylate, α- (hydroxymethyl) acryl Monomers having hydroxyl groups such as mono (meth) acrylate of polyester diol obtained from ethyl acrylate, phthalic acid and propylene glycol; (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, carboxyl group-terminated caprolactone Unsaturated monomers containing an acidic functional group such as (meth) acrylate;
[0017]
When a reactive ultraviolet absorber (C) and / or a hindered amine light stabilizer (D) are used as the monomer forming the pressure-sensitive adhesive polymer (A), the following monomers are preferable. is there.
2- [2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(meth) acryloyloxypropylphenyl] -2H-benzotriazole, Reactive benzotriazole-type UV-absorbing monomers such as commercially available RUVA-93 (trade name, manufactured by Otsuka Chemical Co., Ltd.) (disclosed in JP-A-8-151415); 2-hydroxy-4-methacryloxybenzophenone; Reactive benzophenone type ultraviolet absorbing monomers such as 2-hydroxy-4- (2-hydroxy-3-methacryloyloxy) propoxybenzophenone; reactive triazine type ultraviolet absorbing monomers; 4- (meth) acryloyloxy- 2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1 2,2,6,6-pentamethylpiperidine, commercially available ADK STAB LA-82 and LA-87 (both are trade names, manufactured by Asahi Denka Kogyo KK), and commercially available FA-711MM and FA-712HM (both are trade names, Reactive ultraviolet light-stable monomers such as Hitachi Chemical Co., Ltd. (disclosed in JP-A-1-261409 and the like) are preferred.
[0018]
As the polymerization method for polymerizing the monomer component, a conventionally known polymerization method such as a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, and a bulk polymerization method can be employed, but from the viewpoint of simplicity in production, It is preferred to employ a solution polymerization method. Solvents that can be used when employing the solution polymerization method are substantially inert to the pressure-sensitive adhesive polymer (A) and dissolve or disperse the pressure-sensitive adhesive polymer (A). Aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl amyl ketone can be used. Alcohol solvents such as methanol, ethanol, n-propyl alcohol, and isopropyl alcohol; ethylene glycol monomethyl ether (methyl cellosolve); ethylene glycol monoethyl ether (ethyl cellosolve); ethylene glycol monobutyl ether (butyl cellosolve); propylene glycol monomethyl ether; Alkyre Glycol monoalkyl ether solvent; tetrahydrofuran, N, N-dimethylformamide, dimethylacetamide, dioxane, or an organic solvent other such solvents such as chloroform, water is preferred. These may be used alone or in combination of two or more. In the case where the pressure-sensitive adhesive composition contains a polyisocyanate compound described below, a solvent having an activity toward isocyanate groups such as an alcohol-based solvent, an alkylene glycol monoalkyl ether-based solvent or water may not be preferable. Many.
[0019]
The amount of the solvent used is preferably such that the proportion of the solvent in the pressure-sensitive adhesive composition is 95% by mass or less. More preferably, the content is 10% by mass or more. More preferably, it is 15% by mass or more and 90% by mass or less.
[0020]
When polymerizing the above monomer components, a polymerization initiator can be used. As the polymerization initiator, an ordinary radical polymerization initiator can be used, and an azo-based initiator such as 2,2'-azobis (2-methylbutyronitrile) and 2,2'-azobisisobutyronitrile can be used. A compound such as t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, di-t-butyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane; Oxide initiators and the like can be mentioned. The amount of the polymerization initiator to be used is preferably 0.05 to 20% by mass, more preferably 0.1 to 15% by mass, based on 100% by mass of the total mass of the monomer components.
[0021]
When polymerizing the above monomer component, a chain transfer agent or a polymerization regulator may be used, if necessary, for the purpose of controlling the molecular weight. For example, alkyl mercaptans such as n-butyl mercaptan, n-hexyl mercaptan, dodecyl mercaptan; other mercaptans such as thioglycolic acid, mercaptopropionic acid, thioglycerol, 2-mercaptoethanol; α-methylstyrene dimer, disulfide, isopropyl Alcohol, dioxane, carbon tetrachloride, chloroform and the like. These may be used alone or in combination of two or more. The amount of these used is preferably 0.01 to 10% by mass relative to 100% by mass of the total mass of the monomer components.
[0022]
The reaction temperature at the time of polymerizing the above monomer component is preferably room temperature to 200 ° C, more preferably 40 to 140 ° C. The reaction time may be appropriately set according to the reaction temperature, the composition of the monomer component to be used, the type of the polymerization initiator, and the like so that the polymerization reaction is completed.
[0023]
The pressure-sensitive adhesive polymer (A) according to the present invention preferably has a glass transition temperature of -80 to -20 ° C. It is preferable to appropriately set the composition of the monomer component and the like. When the glass transition temperature is lower than -80 ° C, the high-temperature cohesive strength tends to decrease. When the glass transition temperature exceeds -20 ° C, pressure-sensitive adhesiveness may not be exhibited at room temperature. May not be expressed. The glass transition temperature Tg is easily calculated by the following equation based on the glass transition temperature Tg (K) of each homopolymer described in “POLYMERHANDBOOK Third Edition” (issued by John Wiley & Sons, Inc.). Can be sought. It can also be determined by DSC (differential scanning calorimeter) or DTA (differential thermal analyzer).
[0024]
1 / Tg (K) = W₁ / Tg₁ + W₂ / Tg₂ + ... + Wn / Tgn
In the formula, Wn is the mass fraction of each monomer, Tgn is the Tg (K) of the homopolymer of each monomer, and is described in Polymer Handbook (3rd Ed., J. Brandrup and E). .H. Immergut, WILEY INTERSCIENCE), and the like, may be used.
[0025]
The pressure-sensitive adhesive polymer (A) preferably has a weight average molecular weight (Mw) of 250,000 or more. In addition, it is preferable that it is 2,000,000 or less. When it is less than 250,000, for example, it is difficult to exhibit a holding force (cohesive force) even when cross-linked, and further, the removability is reduced, and it may be difficult to balance various physical properties. If it exceeds 2,000,000, the polymerization stability may be deteriorated. More preferably, it is 400,000 or more, and 1.5 million or less. The weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC).
[0026]
The pressure-sensitive adhesive polymer (A) preferably has an acid value or a hydroxyl value set in a specific range. The solid content of the pressure-sensitive adhesive polymer (A) preferably has an acid value of 30 mgKOH / g or less. More preferably, it is 15 mgKOH / g or less. More preferably, it is 8 mgKOH / g or less. If the acid value is too high, the near-infrared absorbing dye may deteriorate or react with the reactive ultraviolet absorber (C) or the hindered amine light stabilizer (D) to lose the tackiness. The hydroxyl value of the pressure-sensitive adhesive polymer (A) is preferably 10 mgKOH / g or less. More preferably, it is 5 mgKOH / g or less. More preferably, it is 2.5 mgKOH / g or less. If the hydroxyl value is too high, the near-infrared absorbing dye may be deteriorated.
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated, and is measured according to the method described in JIS-K-0070. Or it may be calculated as a theoretical value from the charged composition. The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of a sample, and is measured by the method described in JIS-K-0070 or calculated from the charged composition. it can.
[0027]
The compounding amount of the pressure-sensitive adhesive polymer (A) is preferably 3% by mass or more, and 99.9% by mass or less based on 100% by mass of the pressure-sensitive adhesive composition. Is preferred. If the amount is less than 3% by mass, there is a possibility that problems such as insufficient adhesion and poor coatability may occur. If the amount is more than 99.9% by mass, the coatability is poor, the viscosity is high and the handleability is high. However, there is a possibility that problems such as poor dyeing, difficulty in mixing the pigment, and insufficient pot life may be caused. More preferably, it is 10% by mass or more, and 90% by mass or less, further preferably, 20% by mass or more, and 85% by mass or less.
[0028]
As the near infrared absorbing dye (B) in the present invention, a dye having a maximum absorption wavelength at 780 to 1200 nm is suitable. Two or more kinds having different near-infrared absorption characteristics may be used in combination. In this case, the near-infrared absorption effect may be improved. In addition, near-infrared absorptivity is used in the same meaning as heat ray absorptivity.
[0029]
A preferred form of the near infrared absorbing dye (B) is a dye having solubility in an organic solvent, that is, a near infrared absorbing dye soluble in an organic solvent. When the dye is soluble in the organic solvent, it can be easily dissolved in the pressure-sensitive adhesive polymer (A), so that the preparation of the coating agent becomes easy. On the other hand, if the dye has poor solubility, it becomes difficult to mix the dye with the pressure-sensitive adhesive polymer (A), and thus it becomes difficult to prepare a coating agent. As the solubility in an organic solvent, it is preferable to use a near-infrared absorbing dye having a solubility of 0.01% by mass or more based on 100% by mass of the organic solvent. Organic solvents soluble in organic solvents include aromatic solvents such as toluene and xylene; alcohol solvents such as iso-propyl alcohol, n-butyl alcohol, propylene glycol methyl ether and dipropylene glycol methyl ether; butyl acetate, ethyl acetate And ester solvents such as cellosolve acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; and one or more kinds of dimethyl formamide.
[0030]
As the type of the near-infrared absorbing dye, phthalocyanine dye, naphthalocyanine dye, anthraquinone dye, naphthoquinone dye, cyanine dye, aminium dye, immonium dye, polymethine dye, aromatic dithiol dye, Examples include aromatic diol-based dyes, and specific products include the "EEX Color" series manufactured by Nippon Shokubai Co., Ltd., the "Epolite" series manufactured by Eporin, USA, and the "KAYASORB" series manufactured by Nippon Kayaku Co., Ltd. However, among these, it is preferable to use a phthalocyanine dye because of its excellent near-infrared absorption performance and organic solvent solubility.
[0031]
In the present specification, the phthalocyanine-based is phthalocyanine, a phthalocyanine complex, or a phthalocyanine and a phthalocyanine complex, in which one or more substituents of OR, SR, NHR, or NRR ′ are provided on the benzene ring of the phthalocyanine skeleton by one. It has the above. Here, R and R 'are the same or different and each represent a phenyl group which may have a substituent, an alkyl group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms. Preferably, one of the substituents is phthalocyanine substituted with NHR.
[0032]
In the present invention, the near-infrared absorbing dye (B) is represented by the following general formula (1);
[0033]
Embedded image

[0034]
(Where α is the same or different, and¹, OR², NHR³Or a halogen atom, NHR³Is required. R¹, R²And R³Represents the same or different and may be a phenyl group which may have a substituent, an alkyl group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. β is the same or different and SR¹, OR²Or a halogen atom, SR¹Or OR²Is required. However, at least one of α and β is a halogen atom or OR²Is required. M represents a non-metal, a metal, a metal oxide or a metal halide. ) Is preferable. Thereby, the function and effect of the present invention can be more sufficiently exhibited.
[0035]
In the general formula (1), examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , N-pentyl group, isopentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl Linear or branched alkyl groups such as a group, 1,4-dimethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group; cyclohexyl And a cyclic alkyl group such as a group. Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenethyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
[0036]
R above¹, R²And R³The phenyl group, the alkyl group having 1 to 20 carbon atoms or the aralkyl group having 7 to 20 carbon atoms in may have one or more substituents. Examples of such a substituent include a halogen atom, an acyl group, an alkyl group, an alkoxy group, a halogenated alkoxy group, a nitro group, an amino group, an alkylamino group, an alkylcarbonylamino group, an arylamino group, and an arylcarbonylamino group. , A carbonyl group and an alkoxycarbonyl group.
[0037]
In M in the general formula (1), “metal-free” means an atom other than a metal, for example, two hydrogen atoms. Specifically, a structure in which a hydrogen atom is bonded to two opposing nitrogen atoms which may have a substituent and are present in the central portion of the phthalocyanine structure. Examples of the metal include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, tin and the like. Examples of the metal oxide include titanyl and vanadyl. Examples of the metal halide include aluminum chloride, indium chloride, germanium chloride, tin chloride, and silicon chloride. M is preferably a metal, a metal oxide or a metal halide, and specific examples include nickel, cobalt, copper, zinc, iron, vanadyl, and dichlorotin. More preferred are zinc, cobalt, vanadyl and dichlorotin.
[0038]
In a preferred embodiment of the compound represented by the general formula (1), 4 to 8 of the 8 βs are the same or different,¹Or OR²It is to express. More preferably, all eight βs are the same or different,¹Or OR²It is to express. Such near-infrared absorbing dyes include, for example, ZnPc (PhS)₈(PhNH)₃F₅, ZnPc (PhS)₈(PhNH)₄F₄, ZnPc (PhS)₈  PhNH)₅F₃, ZnPc (PhS)₈(PhCH₂NH)₄F₄, ZnPc (PhS)₈(PhCH₂NH)₅F₃, ZnPc (PhS)₈(PhCH₂NH)₆F₂, CuPc (PhS)₈(PhNH)₇F, CuPc (PhS)₈(PhNH)₆F₂, CuPc (PhS)₈(PhNH)₅F₃, VOPc (PhO)₈(PhCH₂NH)₅F₃, VOPc (PhO)₈(PhCH₂NH)₆F₂, VOPc (PhO)₈(PhCH₂NH)₈, VOPc (PhS)₈(PhCH₂NH)₈, VOPc (2,5-Cl₂PhO)₈｛2,6- (CH₃)₂PhO｝₄｛Ph (CH₃) CHNH｝₃F, VOPc (2,5-Cl₂PhO)₈｛2,6- (CH₃)₂PhO｝₄｛Ph (CH₂NH)₄, CuPc (2,5-Cl₂PhO)₈｛2,6- (CH₃)₂PhO｝₄｛Ph (CH₂NH)₄, CuPc (PhS)₈｛2,6- (CH₃)₂PhO｝₄(PhCH₂NH)₄, VOPc (4-CNPhO)₈｛2,6-Br₂-4- (CH₃) PhO｝₄｛Ph (CH₃) CHNH｝₄, ZnPc (2,6-Cl₂PhO)₈｛2,6-Br₂-4- (CH₃) PhO｝₄｛Ph (CH₃) CHNH｝₃And a phthalocyanine compound represented by the abbreviation F. Among these compounds, four of the eight αs are the same or different and OR²Or a compound representing a halogen atom, for example, ZnPc (PhS)₈(PhNH)₃F₅, ZnPc (PhS)₈(PhNH)₄F₄, ZnPc (PhS)₈(PhCH₂NH)₄F₄, VOPc (2,5-Cl₂PhO)₈｛2,6- (CH₃)₂PhO｝₄｛Ph (CH₃) CHNH｝₃F, VOPc (2,5-Cl₂PhO)₈｛2,6- (CH₃)₂PhO｝₄｛Ph (CH₂NH)₄, CuPc (2,5-Cl₂PhO)₈｛2,6- (CH₃)₂PhO｝₄｛Ph (CH₂NH)₄, CuPc (PhS)₈｛2,6- (CH₃)₂PhO｝₄(PhCH₂NH)₄, VOPc (4-CNPhO)₈｛2,6-Br₂-4- (CH₃) PhO｝₄｛Ph (CH₃) CHNH｝₄, ZnPc (2,6-Cl₂PhO)₈｛2,6-Br₂-4- (CH₃) PhO｝₄｛Ph (CH₃) CHNH｝₃Examples include compounds generally represented by the abbreviation F. In the abbreviations of the above compounds, Pc represents a phthalocyanine nucleus, and after Pc, eight substituents substituted at the β-position, followed by eight substituents substituted at the α-position. The above Ph represents a phenyl group. More specifically, the above-mentioned abbreviations represent central metal: Pc: eight substituents at the β-position: eight substituents at the α-position. For example, ZnPc (PhS)₈(PhNH)₃F₅To explain,Zn  Pc  (PhS) ₈   (PhNH) ₃ F ₅ The underlined part corresponds to the above description.
[0039]
The amount of the near-infrared absorbing dye (B) used is preferably 0.005 parts by weight or more based on 100 parts by weight of the pressure-sensitive adhesive polymer (A). If the amount is less than 0.0005 parts by weight, the coating film or the adhesive layer formed from the pressure-sensitive adhesive composition may not exhibit sufficient near-infrared absorption performance. More preferably, it is at least 0.025 parts by weight, even more preferably at least 0.05 parts by weight. Further, the content is preferably 20 parts by weight or less. If it exceeds 20 parts by weight, physical properties of the coating film may be reduced. More preferably, it is 10 parts by weight or less, and still more preferably 5 parts by weight or less. Further, it is preferable to appropriately set the thickness according to the thickness of the coating film. For example, when the thickness is 10 μm, it is preferably 0.5 parts by weight or more, and preferably 20 parts by weight or less, and more preferably 1.0 part by weight. Parts by weight or more, and more preferably 10 parts by weight or less. In the case of a coating film having a thickness of 3 mm, it is preferably at least 0.002 parts by weight, more preferably at most 0.06 parts by weight, more preferably at least 0.005 parts by weight. It is more preferable that the content be 0.03 parts by weight or less. For a thickness of 10 mm, it is preferably at least 0.0005 parts by weight, more preferably at most 0.02 parts by weight, preferably at least 0.0010 parts by weight, and also 0.01 parts by weight. It is more preferable to set the following. Further, the weight contained per unit area of the coating film is, for example, 0.01 g / m²It is preferable to make the above. 0.01 g / m²If it is less than 3, the effect of the near-infrared absorbing dye may not be sufficiently exhibited. More preferably, 0.05 g / m²And more preferably 0.1 g / m²That is all. In addition, 2.5 g / m²It is preferable to set the following. 2.5g / m²If it exceeds 300, the production cost of the coating film may increase. More preferably, 1.0 g / m²Or less, more preferably 0.5 g / m²It is as follows.
[0040]
As the ultraviolet absorber (C) in the present invention, an addition type and / or a reaction type can be used as described above, and a salicylic acid-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, Preferred are cyanoacrylate-based ultraviolet absorbers and benzoate-based ultraviolet absorbers. Among these, the above-mentioned UV-absorbing monomer is suitable as the reactive UV absorber.
As the salicylic acid-based ultraviolet absorber, phenyl salicylate, p-tert-butylphenyl salicylate, and p-octylphenyl salicylate are preferable. Further, as commercial products of phenyl salicylate, SAP (trade name, manufactured by Iwaki Pharmaceutical Co., Ltd.), Zallol (trade name, manufactured by Dow Chem.), Zallol-P (trade name, manufactured by Yatsushiro Pharmaceutical Co., Ltd.) include p-tert- As commercial products of butylphenyl salicylate, TBS (trade name, manufactured by Dow Chem.), TBS (trade name, manufactured by Yatsushiro Pharmaceutical Co.), Biosorb-90 (trade name, manufactured by Kyodo Yakuhin), butyl zallol (trade name, Iwaki) OPS (trade name, manufactured by Eastman Chemical Co., Ltd.) and OPS (trade name, manufactured by Yatsushiro Pharmaceutical Co., Ltd.) are commercially available products of p-octylphenyl salicylate.
[0041]
Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, and 2,2′-. Dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2 -Methoxy-4-hydroxy-5-benzoylphenyl) methane is preferred. In addition, as commercial products of 2,4-dihydroxybenzophenone, ASL-23 (trade name, manufactured by Shonan Chemical Co., Ltd.), Seesorb-100 (trade name, manufactured by Shiraishi Calcium Co., Ltd.), Distilizer O (trade name, manufactured by Sankyo Chemical Co. ), Sumisorb-100 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), DHBP (trade name, manufactured by Eastman Chemical Co., Ltd.), Biosorb-100 (trade name, manufactured by Kyodo Yakuhin), Uvinul-400 (trade name, BASF Corporation) Commercially available products of 2-hydroxy-4-methoxybenzophenone, ASL-23 (trade name, manufactured by Shonan Chemical Co., Ltd.), Cyasorb UV-9 (trade name, manufactured by Cytec), Disizer M (trade name, Sumisorb-100 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), Seesorb-101 (trade name, manufactured by Shiraishi Calcium Co., Ltd.), Biosorb 110 (trade name, manufactured by Kyodo Yakuhin Co., Ltd.), Uvinul-M-40 (trade name, manufactured by BASF), Ortholex 4360 (trade name, manufactured by Merck Japan Co., Ltd.) are 2-hydroxy-4-octoxybenzophenone. Commercially available products include Cyasorb UV-531 (trade name, manufactured by Cytec), Seesorb-102 (trade name, manufactured by Shiraishi Calcium Co.), Zyslyzer E (trade name, manufactured by Sankyo Chemical Co., Ltd.), and Sumisorb-130 (trade name) , Sumitomo Chemical Co., Ltd.), Seesorb-130 (trade name, manufactured by Shiraishi Calcium Co.), Biosorb-130 (trade name, manufactured by Kyodo Yakuhin), Advastab-46, Adekastab 1413 (trade name, manufactured by Asahi Denka Kogyo), As a commercially available product of 2-hydroxy-4-dodecyloxybenzophenone, DOPB (trade name, Eastman Chemical Company) ), AM-320 (trade name), as commercially available products of 2,2'-dihydroxy-4-dimethoxybenzophenone, Cyasorb UV-24 (trade name, manufactured by Cytec Co., Ltd.). As commercial products of 2,2'-dihydroxy-4,4'-methoxybenzophenone, ASL-40 (trade name, manufactured by Shonan Chemical Co., Ltd.) and Uvinul-D-49 (trade name, manufactured by BASF) are commercially available. Examples of commercially available products of hydroxy-4-methoxy-5-sulfobenzophenone include Uvinul-MS-40 (trade name, manufactured by BASF) and bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane. Is ADK STAB LA-51 (trade name, manufactured by Asahi Denka Kogyo KK).
[0042]
Examples of the benzotriazole-based ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, and 2- (2 '-Hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (2'-hydroxy-3 '-(3 " 4 ", 5", 6 "-tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H- Benzotriazol-2-yl) phenol], 2 (2'-hydroxy-5'-methacryloxyphenyl) -2H-benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetra Methylbutyl) -6-[(2H-benzotriazol-2-yl) phenol]], 2 (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole is preferred. As commercial products of 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, JF-77 (trade name, manufactured by Johoku Chemical Co., Ltd.) and Tinuvin-P (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) ), Seesorb-701 (trade name, manufactured by Shiraishi Calcium Co., Ltd.), Sumisorb-200 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), Biosorb-520 (trade name, manufactured by Kyodo Yakuhin Co., Ltd.), ADK STAB LA-32 (trade name, Asahi As a commercial product of 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, Tinuvin-PS (trade name, manufactured by Ciba Specialty Chemicals) is 2- ( As a commercial product of 2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, Tinuvin-320 Trade name, Ciba Specialty Chemicals Co., Ltd.), Biosorb-582 (trade name, manufactured by Kyodo Yakuhin), JF-86 (trade name, manufactured by Johoku Chemical Co., Ltd.) were replaced by 2- (2'-hydroxy-3'- As commercial products of tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, Tinuvin-326 (trade name, manufactured by Ciba Specialty Chemicals), Seesorb-703 (trade name, manufactured by Shiraishi Calcium Co.), Biosorb-550 (trade name, manufactured by Kyodo Yakuhin), Sumisorb-300 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), JF-79 (trade name, manufactured by Johoku Chemical Co., Ltd.), ADK STAB LA-36 (trade name, Asahi Denka Kogyo Co., Ltd.) As a commercial product of 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole. uvin-327 (trade name, manufactured by Ciba Specialty Chemicals), Seesorb-702 (trade name, manufactured by Shiraishi Calcium), Biosorb-580 (trade name, manufactured by Kyodo Yakuhin), JF-78 (trade name, Johoku) Adekastab LA-34 (trade name, manufactured by Asahi Denka Kogyo KK) is a commercial product of 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole, which is Tinuvin. -328 (trade name, manufactured by Ciba Specialty Chemicals), Biosorb-591 (trade name, manufactured by Kyodo Yakuhin), Sumisorb-350 (trade name, manufactured by Sumitomo Chemical), JF-80 (trade name, Johoku Chemical) 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) ben As commercial products of zotriazole, Biosorb-590 (trade name, manufactured by Kyodo Yakuhin), Sumisorb-250 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), Seesorb-706 (trade name, manufactured by Shiraishi Calcium Co., Ltd.), 2,2 As a commercial product of '-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzotriazol-2-yl) phenol]], ADK STAB LA-31 (trade name, Asahi) As a commercial product of 2 (2'-hydroxy-5'-methacryloxyphenyl) -2H-benzotriazole, RUVA-93 (trade name, manufactured by Otsuka Chemical Co., Ltd.) may be mentioned.
[0043]
As the cyanoacrylate-based ultraviolet absorber, 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-diphenyl acrylate are suitable. As commercially available products of 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, Unisol 3039, N539T (trade name, manufactured by BASF) and Biosorb-930 (trade name, manufactured by Kyodo Yakuhin) are ethyl-2. Commercial products of -cyano-3,3'-diphenyl acrylate include Uninol 3035 (trade name, manufactured by BASF) and Biosorb-910 (trade name, manufactured by Kyodo Yakuhin).
As the benzoate-based ultraviolet absorber, Tinuvin-120 (trade name, manufactured by Ciba Specialty Chemicals) and sumisorb 400 (trade name, manufactured by Sumitomo Chemical Co., Ltd.) are preferable.
[0044]
The amount of the ultraviolet absorber (C) used is 0.1 parts by weight of the total of the addition type ultraviolet absorber and the reaction type ultraviolet absorber with respect to 100 parts by weight of the pressure-sensitive adhesive polymer (A). It is preferable that the amount is not less than 100 parts by weight. If the amount is less than 0.1 part by weight, the deterioration of the near-infrared absorbing dye may be increased. If it exceeds 100 parts by weight, the adhesiveness may be poor. More preferably, it is at least 1 part by weight, even more preferably at least 3 parts by weight. Further, it is more preferably 50 parts by weight or less, and still more preferably 20 parts by weight or less. The amount of the ultraviolet absorbent (C) used is an amount including the addition type and the reaction type.
[0045]
As the hindered amine light stabilizer (D), an addition type and / or a reaction type can be used as described above. Examples of such light stabilizers include a hindered amine light stabilizer (d-1) having no hindered phenol skeleton and a hindered amine light stabilizer (d-2) having a hindered phenol skeleton. , These have different effects. In the present invention, these may be used in combination. The hindered amine light stabilizer (d-2) having a hindered phenol skeleton is one of typical antioxidants, and has an effect of trapping radical species generated by ultraviolet rays and preventing deterioration. Therefore, it is preferable to use a hindered amine-based light stabilizer (d-2) having a hindered phenol skeleton because it is effective in suppressing deterioration due to ultraviolet rays. That is, in a preferred embodiment of the present invention, a combination of an ultraviolet absorber (C) and a hindered amine light stabilizer (D) having a hindered amine light stabilizer (d-2) having a hindered phenol skeleton is essential. It is.
[0046]
Examples of the hindered amine light stabilizer (d-1) having no hindered phenol skeleton include Sanol LS-770 (trade name, manufactured by Sankyo), ADK STAB LA-77 (trade name, manufactured by Asahi Denka Kogyo KK), Sumisorb-577 (trade name, manufactured by Sumitomo Chemical), Biosorb-04 (trade name, manufactured by Kyodo Yakuhin), Chimassorb 944LD (trade name, manufactured by Ciba Specialty Chemicals), Tinuvin-622LD (trade name: Ciba Specialty) Chemicals), Biosorb-03 (trade name, manufactured by Kyodo Yakuhin), ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63, ADK STAB LA-68, ADK STAB LA-82, ADK STAB LA -87, ADK STAB LA-52 (all Product name, manufactured by Asahi Denka Co., Ltd.), Goodrite UV-3034 (trade name, manufactured by Goodrich Co., Ltd.) and the like.
As the hindered amine light stabilizer (d-2) having a hindered phenol skeleton, TINUVIN 144 (trade name, manufactured by Ciba Specialty Chemicals) is preferable.
[0047]
The amount of the hindered amine light stabilizer (D) to be added is 100 parts by weight of the pressure-sensitive adhesive polymer (A) if the hindered amine light stabilizer (d-1) does not have a hindered phenol skeleton. On the other hand, it is preferably at least 0.1 part by weight, and more preferably at most 10 parts by weight. If the amount is less than 0.1 part by weight, the near-infrared absorbing dye may be greatly deteriorated. If the amount exceeds 10 parts by weight, the adhesiveness may be poor. More preferably, it is at least 0.3 part by weight, even more preferably at least 0.5 part by weight. Further, the amount is more preferably 5 parts by weight or less, and still more preferably 2 parts by weight or less. Further, in the case of a hindered amine light stabilizer (d-2) having a hindered phenol skeleton, the amount is preferably 0.1 part by weight or more based on 100 parts by weight of the pressure-sensitive adhesive polymer (A). Further, the content is preferably not more than 50 parts by weight. If the amount is less or more than this range, the deterioration of the near-infrared absorbing dye may not be sufficiently suppressed. More preferably, it is at least 0.3 part by weight, even more preferably at least 0.5 part by weight. Further, the amount is more preferably 20 parts by weight or less, and further preferably 10 parts by weight or less.
[0048]
As the antioxidant (E), a radical chain inhibitor (primary antioxidant) and a peroxide decomposer (secondary antioxidant) can be used.
Radical chain inhibitors (primary antioxidants) include phenolic antioxidants and amine antioxidants. Examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole (BHA), 2,6-di-t-butyl-4-ethylphenol, and stearyl-β- ｛. Monophenolic antioxidants such as 3,5-di-t-butyl-4-hydroxyphenyl} propionate; 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis ( 4-ethyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 3,9 -Bis [1,1-dimethyl-2- [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-te Bisphenol antioxidants such as traoxaspiro [5,5] undecane; 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, tetrakis- [methylene-3- ( 3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3'-bis- (4'-hydroxy-3'-tert-butylphenyl) butyric acid] glycol Ester, 1,3,5-tris (3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) -sec-triazine-2,4,6- (1H, 3H, 5H) trione, tocopherol ( ) And the like.
[0049]
Examples of the peroxide decomposer include a sulfur-based antioxidant and a phosphorus-based antioxidant. As the sulfur-based antioxidant, dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and distearyl 3,3'-thiodipropionate are preferred. Examples of phosphorus antioxidants include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, 4,4'-butylidene-bis (3-methyl-6-t-butylphenyl ditridecyl) phosphite, and cyclic Neopentanetetraylbis (octadecylphosphite), tris (nonylphenyl) phosphite, tris (mono and / or dinonylphenyl) phosphite, diisodecylpentaerythritol diphosphite, 9,10-dihydro-9-oxa-10 -Phosphaphenanthrene = 10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-oxide Desiloxy-9,10 Dihydro-9-oxa-10-phosphaphenanthrene, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,4-di-t-butylphenyl) phosphite, Cyclic neopentanetetraylbis (2,6-di-t-butyl-4-methylphenyl) phosphite and 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite are preferred. .
Among them, hindered phenols which have good miscibility with the pressure-sensitive adhesive polymer (A) and little coloration are preferred.
[0050]
The amount of the antioxidant (E) to be added is preferably 0.1 part by weight or more based on 100 parts by weight of the pressure-sensitive adhesive polymer (A). More preferably, it is at least 1 part by weight, even more preferably at least 3 parts by weight. Further, it is preferable that the content be 100 parts by weight or less. More preferably, it is 50 parts by weight or less, and further preferably, it is 20 parts by weight or less. If the amount of the antioxidant (E) is too small, the near-infrared absorbing dye tends to deteriorate. If the amount is too large, the adhesiveness may be poor, or the coating may be lost due to precipitation.
[0051]
In the present invention, when the ultraviolet absorber (C) and the hindered amine light stabilizer (D) are used in combination, the compounding ratio of the hindered amine light stabilizer having no hindered phenol skeleton (d- When 1) is used, the amount is preferably 0.1 part by weight or more based on 100 parts by weight of the ultraviolet absorbent (C). More preferably, it is at least 1 part by weight, even more preferably at least 5 parts by weight. Further, it is preferably not more than 100 parts by weight, more preferably not more than 50 parts by weight, and still more preferably not more than 30 parts by weight. When a hindered amine light stabilizer (d-2) having a hindered phenol skeleton is used, the amount is preferably 0.1 parts by weight or more based on 100 parts by weight of the ultraviolet absorber (C). More preferably, it is at least 1 part by weight, even more preferably at least 5 parts by weight. Further, it is preferable that the content be 100 parts by weight or less. More preferably, it is 50 parts by weight or less, and still more preferably 30 parts by weight or less.
[0052]
The coating film or film formed from the pressure-sensitive adhesive composition of the present invention can be used in either crosslinked or uncrosslinked form.
The pressure-sensitive adhesive composition of the present invention can be cured under various curing conditions depending on the use and the type of the cross-linking agent in which the composition is used, and is a room-temperature curing type, a heat curing type, an ultraviolet ray or an electron beam curing type. Etc. can be used. The amount of the crosslinking agent, the method of addition and dispersion, and the like are not particularly limited. For example, when the pressure-sensitive adhesive polymer (A) is a polyol having a plurality of hydroxyl groups in one molecule, it is usually used as a polyol. The amount used and the method of addition and dispersion may be used.
[0053]
When the pressure-sensitive adhesive polymer (A) is composed of a polyol, a (block) polyisocyanate compound and an aminoplast resin are suitable as the crosslinking agent. These may be used alone or in combination of two or more.
[0054]
The (block) polyisocyanate compound means a polyisocyanate compound and / or a blocked polyisocyanate compound.
The polyisocyanate compound may be any compound having at least two isocyanate groups in the molecule, such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, and 4,4'- Polyisocyanates such as methylene bis (cyclohexyl isocyanate), lysine diisocyanate, trimethylhexamethylene diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, 1,5-naphthalenediisocyanate, triphenylmethane triisocyanate; adducts of these polyisocyanates; Derivatives (modified products) of polyisocyanates such as burettes and isocyanurates are listed.
[0055]
The above-mentioned blocked polyisocyanate compound is cross-linked when the pressure-sensitive adhesive composition is dried by heating, and in order to improve storage stability at room temperature, the isocyanate group of the polyisocyanate compound is usually blocked with a blocking agent. It's a block.
Examples of the blocking agent include compounds such as ε-caprolactam, phenol, cresol, oxime, and alcohol.
Commercially available (block) polyisocyanate compounds include, for example, Sumidur N3200, Sumidur N3300, Sumidur BL3175, Desmodur N3400, Desmodur N3600, Desmodur VPLS2102 (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.), Duranate E-402-90T (trade name, manufactured by Asahi Kasei Corporation) and the like. Further, in order to prevent yellowing of a coating film formed from the pressure-sensitive adhesive composition, a non-yellowing-modified polyisocyanate compound having no isocyanate group directly bonded to an aromatic ring is preferable.
[0056]
The amount of the (block) polyisocyanate compound used is preferably 0.01 mol or more of the isocyanate group in the (block) polyisocyanate compound per 1 mol of the hydroxyl group in the pressure-sensitive adhesive composition. 5 mol or less is preferable. If the amount is less than 0.01 mol, a large number of unreacted hydroxyl groups remain in the pressure-sensitive adhesive composition, so that the weather resistance of a coating film formed using the obtained pressure-sensitive adhesive composition is reduced. There is. If it exceeds 5 moles, a large amount of unreacted isocyanate groups remain in the coating film, which reacts with moisture in the air when the coating film is cured, and may cause foaming or whitening of the coating film. More preferably, it is at least 0.1 mol, even more preferably at least 0.5 mol. Further, it is more preferably at most 2 mol, still more preferably at most 1.2 mol.
[0057]
The aminoplast resin is an addition condensation product of a compound having an amino group such as melamine and guanamine and formaldehyde, and is also called an amino resin.
Examples of the aminoplast resin include dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, fully alkylated methylated melamine, fully alkylated butylated melamine, fully alkylated isobutylated melamine, and completely alkylated melamine. Resins such as melamine type mixed etherified melamine, methylol group type methylated melamine, imino group type methylated melamine, methylol group type mixed etherified melamine, imino group type mixed etherified melamine, etc .; Butylated benzoguanamine, methyl / ethyl mixed alkylation Examples thereof include guanamine resins such as benzoguanamine, methyl / butyl mixed alkylated benzoguanamine, and butylated glycoluril.
[0058]
Commercially available aminoplast resins include Cymel 1128, Cymel 303, Mycoat 506, Cymel 232, Cymel 235, Cymel 771, Cymel 325, Cymel 272, Cymel 254, Cymel 1170 (all trade names, manufactured by Mitsui Cytec Co., Ltd.). ) And the like.
[0059]
The amount of the aminoplast resin used is preferably such that the solid content of the aminoplast resin is at least 0.1 part by weight based on 100 parts by weight of the pressure-sensitive adhesive polymer (A), and more preferably. , 0.5 parts by weight or more. Further, it is preferable that the content is blended so as to be 10 parts by weight or less. More preferably, the amount is 5 parts by weight or less. If the amount of the aminoplast resin is too large, the tackiness may be lost. If the amount is too small, crosslinking may not proceed and the cohesive strength may be poor.
[0060]
As the crosslinking system in the pressure-sensitive adhesive composition of the present invention, in addition to the above-mentioned OH / isocyanate, acid / epoxy, acid / metal chelate, acid / oxazoline, and acid / amine are suitable. In the pressure-sensitive adhesive composition of the present invention, a crosslinking agent other than the polyisocyanate compound, an epoxy compound, an aziridine compound, an oxazoline compound, a melamine compound, a metal chelate compound, a carbodiimide compound, as long as the effects of the present invention are not impaired. A glycidylamine compound, an amine compound and the like can be contained. These may be used alone or in combination of two or more.
[0061]
The pressure-sensitive adhesive composition of the present invention may contain one or more curing catalysts for accelerating the crosslinking reaction between the pressure-sensitive adhesive polymer (A) and the crosslinking agent, if necessary. . Although such a curing catalyst is not particularly limited, for example, when the (block) polyisocyanate compound is used, it is preferable to use a catalyst such as dibutyltin dilaurate and a tertiary amine. When an aminoplast resin is used, it is preferable to use an acidic or basic curing catalyst.
[0062]
The pressure-sensitive adhesive composition of the present invention may contain one or more solvents, additives, and the like as a compound other than those described above. Examples of such a solvent include the same organic solvents as described above, and examples of the additive include conventionally known additives and the like generally used in a resin composition forming a film or a coating film. For example, a leveling agent; inorganic fine particles such as colloidal silica and alumina sol, an antifoaming agent, an anti-sagging agent, a silane coupling agent, titanium white, a composite oxide pigment, carbon black, an organic pigment, and a pigment intermediate Pigments such as pigments; Pigment dispersants; Viscosity modifiers; UV stabilizers; Metal deactivators; Peroxide decomposers; Fillers; Reinforcers; Plasticizers; And inorganic UV absorbers, inorganic heat ray absorbers; organic / inorganic flame retardants; antistatic agents; tackifiers; crystal nucleating agents and the like.
[0063]
The tackifier is a tackifier, and can adjust (improve) the adhesive strength. Examples of the tackifier include (polymerized) rosin type, (polymerized) rosin ester type, terpene type, terpene phenol type, coumarone type, coumarone indene type, styrene resin type, xylene resin type, phenol resin type, petroleum resin And the like. These may be used alone or in combination of two or more. When such a tackifier is contained, the content thereof is not particularly limited, and may be appropriately set so as to obtain desired adhesive performance. Examples of the crystal nucleating agent include sodium 2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate, sodium bis (4-t-butylphenyl) phosphate, bis (p-methylbenzylidene) sorbitol, Examples include alkyl-substituted dibenzylidene sorbitol and bis (p-ethylbenzylidene) sorbitol. The addition amount of the crystal nucleating agent is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the pressure-sensitive adhesive polymer (A). More preferably, it is 0.1 to 2 parts by weight. If the amount is too small, a sufficient effect may not be obtained.
[0064]
The pressure-sensitive adhesive composition of the present invention may also contain a light stabilizer other than the hindered amine light stabilizer (D). Such light stabilizers include nickel bis (octylphenyl) sulfide, [2,2'-thiobis {4-tert-octylphenolate}]-n-butylamine nickel, nickel complex-3,5-di-tert. -Butyl-4-hydroxybenzyl-phosphate monoethylate, nickel-dibutyldithiocarbamate. As commercial products of nickel bis (octylphenyl) sulfide, AM-101 (trade name, manufactured by Ferrochemical Co.) and AM-105 (trade name, manufactured by Ferrochemical Co.) are [2,2'-thiobis @ 4-tert]. -Octylphenolate}]-n-butylamine nickel is commercially available as Cyasorb UV-1084 (trade name, manufactured by Cytec). Nickel complex-3,5-di-tert-butyl-4-hydroxybenzyl-phosphate Irgasorb-2002 (trade name, manufactured by Ciba Specialty Chemicals) as a commercial product of monoethylate, and NBC (trade name, manufactured by ICI, Ouchi Shinko Chemical) as a commercial product of nickel-dibutyl dithiocarbamate. It is suitable.
[0065]
As a use form of the coating film or film formed from the pressure-sensitive adhesive composition of the present invention, for example, a coating film or film formed from the pressure-sensitive adhesive composition is provided as an adhesive layer on a transparent substrate. And a laminate sandwiched between two transparent substrates.
Examples of the transparent base material include organic base materials such as polycarbonate resin, acrylic resin, polyethylene resin, polyester resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyvinyl alcohol resin, polyethylene terephthalate resin, and triacetyl cellulose resin. An inorganic base material such as glass is suitable.
[0066]
The adhesive layer can be formed by applying the pressure-sensitive adhesive composition on a transparent substrate. The method for applying the pressure-sensitive adhesive composition to the substrate is not particularly limited, and a conventionally known method may be employed. For example, it may be applied directly to the substrate, or may be previously applied to a release liner (release paper, release film), dried and then transferred to the substrate. Further, the pressure-sensitive adhesive composition may be applied to one side of the substrate, or may be applied to both sides. Further, since the film or coating formed from the pressure-sensitive adhesive composition of the present invention has tackiness, after forming the adhesive layer by applying the pressure-sensitive adhesive composition to a substrate, When a laminate is formed using another base material or when the pressure-sensitive adhesive composition is used in the form of a film, the surface of the adhesive layer or the film surface is laminated with release paper, and the release paper is used at the time of use. It is preferable to use it after peeling it off.
[0067]
In the method for forming the adhesive layer, the method of applying the pressure-sensitive adhesive composition on the transparent substrate may be appropriately selected depending on the form of the pressure-sensitive adhesive composition to be applied, and the like. Solvent-based coating method in which the adhesive composition is applied as a uniform solution in an organic solvent to the surface of various films or sheets (substrate); (2) Various types of emulsions in which the pressure-sensitive adhesive composition is dispersed in water Emulsion type coating method for coating on the surface of material, (3) Hot melt type coating method for melting and mixing the pressure sensitive adhesive composition at high temperature and coating on the substrate surface, (4) Solventless type coating method A calendar type coating method may be used. (1) In the solvent-type coating method or (2) the emulsion-type coating method, the above-mentioned organic solvent can be appropriately mixed and applied to the pressure-sensitive adhesive composition. As the coating method, various coaters are used. And immersion, spraying, brush coating, electrostatic coating and the like. Examples of various coaters include gravure coaters such as arc gravure coater, offset gravure coater, pan feed gravure coater, and die feed gravure coater; reverse coaters such as top feed reverse coater and bottom feed reverse coater; comma direct coater, comma reverse coater, U Comma coaters such as comma coaters; air knife coaters, knife coaters, fountain die coaters, lip coaters, myrbar coaters, curtain flow coaters, roll coaters, spin coaters, blade coaters, bar coaters, die coaters, spray coaters and the like. The method of curing the pressure-sensitive adhesive composition may be appropriately set according to the type of the constituent components and the like, and examples thereof include a heating method and a method of irradiating an ultraviolet ray or an electron beam.
[0068]
The thickness of the adhesive layer is not particularly limited as long as it is appropriately set according to the intended use. For example, the thickness when dried is preferably 5 μm or more, and more preferably 200 μm or less. More preferably, it is 15 μm or more and 100 μm or less. More preferably, it is 50 μm or less. If the adhesive layer is thin, the adhesiveness is poor, and it is not preferable because it floats or peels off. On the other hand, if the thickness is too large, the adhesive is undesirably protruding.
[0069]
In the laminate, it is preferable to provide an ultraviolet absorbing layer on the light incident side of the near infrared absorbing layer. Thereby, the deterioration of the near-infrared absorbing dye can be more effectively suppressed. The laminated structure of such a laminate is not particularly limited. For example, (1) a form in which an ultraviolet absorbing layer, an adhesive layer, and a substrate are laminated in this order from the light incident side, and (2) an ultraviolet absorbing layer from the light incident side , A substrate, and an adhesive layer in this order. Further, in order to improve abrasion resistance and stain resistance, a surface protective layer such as a silicon-based or organic hard coat layer, a photocatalytic function layer, etc. may be further provided on the surface of the laminate. A primer layer may be provided between the body and each layer of the laminate. The composition and thickness of such an ultraviolet absorbing layer, surface protective layer, and primer layer are not particularly limited.
[0070]
The coating film formed from the pressure-sensitive adhesive composition of the present invention is characterized in that the deterioration of near-infrared absorption performance is small, and that it has tackiness. The decrease in near-infrared absorbing performance of the near-infrared absorbing dye of the present invention is small, that is, the absorption ability retention rate is high, and the maximum absorption wavelength of the film after 96 hours of UV irradiation in the following evaluation of deterioration of the near-infrared absorbing dye The absorbance at (the maximum absorption wavelength of the near-infrared absorbing dye: 780 to 1200 nm) is preferably 5% or more when the initial value is 100. It is more preferably at least 50%, further preferably at least 85%, and most preferably at least 95%. The absorbance after UV irradiation is a relative value when the initial value is set to 100.
[0071]
(Evaluation of deterioration of near infrared absorbing dye)
The absorbance at the maximum absorption wavelength of the near infrared absorbing dye after UV irradiation is tracked.
The pressure-sensitive adhesive composition is applied to a release film (a silicon-treated PET film) using an applicator so that the thickness after drying becomes 25 μm, thereby forming an adhesive layer. This was dried at 100 ° C. for 2 minutes. The above adhesive layer is laminated with a 50 μ or 100 μ thick PET film (the adhesive layer is transferred here). The release film of the pressure-sensitive adhesive composition is peeled off and laminated with 50 μPET.
Using a spectrophotometer (manufactured by Shimadzu Corporation, trade name "UV-3100"), the absorbance at the maximum absorption wavelength of the film (the maximum absorption wavelength of the near infrared absorbing dye: 780 to 1200 nm) is measured. The film is irradiated with UV using an ultraviolet auto-fade meter (trade name “FAL-AU-B” manufactured by Suga Test Instruments Co., Ltd.). Every 48 hours of UV irradiation, the absorbance at the maximum absorption wavelength of the film (the maximum absorption wavelength of the near infrared absorbing dye: 780 to 1200 nm) is measured using a spectrophotometer (manufactured by Shimadzu Corporation, trade name "UV-3100"). I do. The relative value of the absorbance when the initial value is set to 100 is recorded. The closer to 100%, the better, without deterioration of the dye.
[0072]
It is preferable that the coating film or film formed from the pressure-sensitive adhesive composition of the present invention and the laminate including the coating film or film as an adhesive layer have high transparency. 0.0% or less. More preferably, it is 2.0% or less, and still more preferably, it is 1.0% or less.
[0073]
The pressure-sensitive adhesive composition of the present invention can be widely used for general pressure-sensitive adhesive applications, and among them, it is suitably applied as a material for forming an adhesive layer in electronic equipment such as a plasma display.
When such a pressure-sensitive adhesive composition functions as an adhesive layer and also functions as a near-infrared absorbing layer, the layer structure of a plasma display or the like is reduced to suppress emission of near-infrared rays or the like from a screen. You can do it.
[0074]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “parts” means “parts by weight”.
[0075]
Synthesis Example 1 (Monomer drop polymerization method)
358.2 g of 2-ethylhexyl acrylate (2EHA), 240 g of cyclohexyl methacrylate (CHMA), and 1.8 g of 2-hydroxyethyl acrylate (HEA) were weighed and mixed well (the mixture was mixed with the monomer mixture (A1)). Do). 40% of the monomer mixture (A1) and 196.4 g of ethyl acetate were weighed into a flask equipped with a thermometer, a stirrer, an inert gas inlet tube, a reflux condenser, and a dropping funnel. Also, 60% of the monomer mixture (A1), 16 g of ethyl acetate, and 0.72 g of a polymerization initiator nipper BMTK40 (trade name, manufactured by NOF CORPORATION) were placed in a dropping funnel and mixed well (this mixture was mixed in a single amount. Body mixture (B1)). The internal temperature of the flask was raised to 85 ° C. while flowing an appropriate amount of nitrogen gas at 20 mL / min. 0.96 g of a polymerization initiator Niper BMTK40 (trade name, manufactured by NOF Corporation) was charged into the flask, and the reaction was started. Fifteen minutes after the addition of the polymerization initiator, the reaction was allowed to proceed while uniformly adding the monomer mixture (B1) to the flask over 90 minutes. Immediately after the addition of the monomer mixture (B1) was completed, 50 g of ethyl acetate was added. The aging reaction was performed at 80 ° C. for 90 minutes. A mixed solution of 1.8 g of a polymerization initiator ABN-E (trade name, manufactured by Nippon Hydrazine Industry Co., Ltd.) and 39 g of ethyl acetate was added in five batches every 30 minutes (for residual monomer reaction). An aging reaction was performed at 80 ° C. for 90 minutes, 575 g of toluene was added, and the reaction was terminated to obtain a pressure-sensitive adhesive polymer (A-1).
[0076]
Synthesis Example 2 (Monomer batch polymerization method)
209.1 g of 2EHA, 60 g of CHMA, 0.9 g of HEA, 30 g of RUVA-93 (trade name, manufactured by Otsuka Chemical Co., Ltd.), and 245 g of ethyl acetate were charged with a thermometer, a stirrer, an inert gas inlet tube, a reflux condenser, and a dropping funnel. Weighed. The internal temperature of the flask was raised to 85 ° C. while flowing an appropriate amount of nitrogen gas at 20 mL / min. 0.6 g of a polymerization initiator Niper BMTK40 (trade name, manufactured by NOF Corporation) was charged into the flask, and the reaction was started. The reaction was performed for 90 minutes. A mixed solution of 0.3 g of a polymerization initiator Niper BMTK40 (trade name, manufactured by NOF CORPORATION) and 15 g of ethyl acetate was added in two portions every hour (for reacting the remaining monomer). An aging reaction was performed at 80 ° C. for 150 minutes, 155 g of toluene was added, and the reaction was terminated to obtain a pressure-sensitive adhesive polymer (A-2).
[0077]
Synthesis Examples 3 to 5 (monomer batch polymerization method)
A pressure-sensitive adhesive polymer (A-3), a pressure-sensitive adhesive polymer (A-4) and a pressure-sensitive adhesive polymer (A-5) were prepared in the same manner as in Synthesis Example 2 except that the monomer composition was changed as shown in Table 1. ) Got.
[0078]
Synthesis Example 6 (Monomer drop polymerization method)
120 g of butyl acrylate (BA), 456 g of 2EHA, 6 g of stearyl acrylate (STA) and 18 g of HEA were weighed and mixed well (this mixture is referred to as a monomer mixture (A2)). 40% of the monomer mixture (A2) and 293.3 g of ethyl acetate were weighed into a flask equipped with a thermometer, a stirrer, an inert gas inlet tube, a reflux condenser, and a dropping funnel. 60% of the monomer mixture (A2), 10 g of ethyl acetate, 60 g of toluene, and 0.36 g of a polymerization initiator nipper BMTK40 (trade name, manufactured by NOF CORPORATION) were placed in a dropping funnel, and mixed well (this mixture was mixed in a single amount). Body mixture (B2)). The internal temperature of the flask was raised to 85 ° C. while flowing an appropriate amount of nitrogen gas at 20 mL / min. 0.48 g of a polymerization initiator nipper BMTK40 (trade name, manufactured by NOF Corporation) was charged into the flask, and the reaction was started. Ten minutes after the addition of the polymerization initiator, the reaction was allowed to proceed while uniformly adding the monomer mixture (B2) to the flask over 60 minutes. Immediately after the addition of the monomer mixture (B2) was completed, 6 g of ethyl acetate and 52.4 g of toluene were added. The aging reaction was performed at 86 ° C. for 90 minutes. A mixed solution of 0.6 g of a polymerization initiator Niper BMTK40 (trade name, manufactured by NOF CORPORATION) and 30 g of toluene was added in two portions every hour (for residual monomer reaction). An aging reaction was performed at 86 ° C. for 90 minutes, and 318.5 g of ethyl acetate and 423.4 g of toluene were added to terminate the reaction. Finally, a mixed solution of 0.15 g of a crosslinking accelerator di-n-butyltin dilaurate, 3 g of acetic acid and 25 g of toluene was added and mixed well to obtain a pressure-sensitive adhesive polymer (A-6).
[0079]
Synthesis Example 7 (Monomer drop polymerization method)
275.5 g of BA, 136.8 g of 2EHA, 36 g of acrylic acid (AA), 149.9 g of vinyl acetate (VAC) and 1.8 g of HEA were weighed and mixed well (this mixture is referred to as a monomer mixture (A3)). 33% of the monomer mixture (A3), 312.9 g of ethyl acetate and 3.3 g of toluene were weighed into a flask equipped with a thermometer, a stirrer, an inert gas inlet tube, a reflux condenser and a dropping funnel. 67% of the monomer mixture (A3), 139.9 g of ethyl acetate, and 0.79 g of a polymerization initiator ABN-E (trade name, manufactured by Nippon Hydrazine Industry Co., Ltd.) were put into a dropping funnel, and mixed well (this mixture was mixed with Monomer mixture (B3)). The internal temperature of the flask was raised to 82 ° C. while flowing an appropriate amount of nitrogen gas at 20 mL / min. 0.79 g of a polymerization initiator nipper BMTK40 (trade name, manufactured by NOF Corporation) was charged into the flask, and the reaction was started. Fifteen minutes after the addition of the polymerization initiator, the reaction was allowed to proceed while uniformly adding the monomer mixture (B3) to the flask over 90 minutes. Immediately after the addition of the monomer mixture (B3) was completed, 151.2 g of toluene was added. The aging reaction was performed at 80 ° C. for 90 minutes. Toluene 182.9 was added. Subsequently, a mixed solution of 1.8 g of a polymerization initiator ABN-R (trade name, manufactured by Nippon Hydrazine Industry Co., Ltd.) and 23.4 g of toluene was added in five portions every 30 minutes (for the reaction of residual monomer). An aging reaction was performed at 80 ° C. for 90 minutes, 164.4 g of toluene was added, and the reaction was terminated to obtain a pressure-sensitive adhesive polymer (A-7).
[0080]
[Table 1]

[0081]
Table 1 is described below. BA is butyl acrylate, 2EHA is 2-ethylhexyl acrylate, CHMA is cyclohexyl methacrylate, HEA is 2-hydroxyethyl acrylate, and RUVA is RUVA-93. (Trade name, manufactured by Otsuka Chemical Co., Ltd.), VAC is vinyl acetate, AA is acrylic acid, and STA is stearyl acrylate.
Tg is a calculated value calculated from Tg of each homopolymer. The following values were used for Tg of each homopolymer. BA: -55 ° C, 2EHA: -70 ° C, CHMA: 66 ° C, HEA: -15 ° C, RUVA: 100 ° C, VAC: 25 ° C, AA: 106 ° C, STA: -70 ° C
The hydroxyl value and the acid value are values per 1 g of the solid content of the polymer.
[0082]
Example 1
To 22.93 g of the pressure-sensitive adhesive polymer (A-1) solution (nonvolatile content (NV) 40.6%), 0.2 g of a near-infrared absorbing dye IR-12 (trade name “EEX Color” manufactured by Nippon Shokubai Co., Ltd.) 0.49 g of UV absorber TINUVIN234 (trade name, manufactured by Ciba Specialty Chemicals) and toluene. Toluene was charged in an amount of 2 g (an amount at which the theoretical nonvolatile content became 39%). Using a paint shaker, a resin solution was prepared by mixing and stirring until a uniform solution was obtained. The maximum absorption wavelength λmax of IR-12 was 885 nm (toluene solution).
[0083]
The above resin solution was applied to a release film (a PET film subjected to silicon treatment) with an applicator so that the thickness after drying was 25 μm to form an adhesive layer. This was dried at 100 ° C. for 2 minutes. The above adhesive layer was laminated with a 50 μ or 100 μ thick PET film (the adhesive layer is transferred here). This adhesive sample was evaluated for the adhesiveness and appearance and the deterioration of the near infrared absorbing dye by the following methods. Table 2 shows the results.
[0084]
Examples 2 to 10 and Comparative Example 1
The same operation as in Example 1 was performed except that the composition of the resin solution was set to the mixing ratio shown in Tables 2 to 4. The results are shown in Tables 2 to 4.
[0085]
Examples 11 to 25
The same operation as in Example 1 was performed except that the composition of the resin solution was set to the compounding ratio shown in Tables 2 and 3. Next, 1.0 part of an isocyanate crosslinking agent Coronate L-55E (trade name, manufactured by Nippon Polyurethane Co., Ltd.) was mixed with 100 parts of the resin solution and mixed well. The adhesive sample in this case was cured at room temperature for at least one week before being used in the evaluation test. The results are shown in Tables 2 and 3.
[0086]
(Evaluation of tackiness)
The release film was peeled off from the adhesive sample prepared as described above, and confirmed by touching with a finger. Sticky, sticky (O). Those that were not sticky at all were rated as non-adhesive (x).
[0087]
(Appearance evaluation)
The adhesive sample prepared as described above was visually observed. A sample having transparency was evaluated as good (O), and a sample having no transparency (white turbidity, a sample having foreign matters such as spots) was evaluated as poor (x).
[0088]
(Evaluation of deterioration of near infrared absorbing dye)
The absorbance at the maximum absorption wavelength of the near infrared absorbing dye after UV irradiation was tracked.
The release film of the adhesive sample was peeled off and laminated with 50 μPET. Using a spectrophotometer (manufactured by Shimadzu Corporation, trade name “UV-3100”), the absorbance at the maximum absorption wavelength (the maximum absorption wavelength of the near-infrared absorbing dye: 780 to 1200 nm) of the film was measured.
The film was irradiated with UV using an ultraviolet auto-fade meter (trade name “FAL-AU-B” manufactured by Suga Test Instruments Co., Ltd.). Every 48 hours of UV irradiation, the absorbance at the maximum absorption wavelength of the film (the maximum absorption wavelength of the near-infrared absorbing dye: 780 to 1200 nm) was measured using a spectrophotometer (trade name “UV-3100” manufactured by Shimadzu Corporation). did. The relative value of the absorbance when the initial value was set to 100 was recorded. The closer to 100%, the better, without deterioration of the dye.
[0089]
[Table 2]

[0090]
[Table 3]

[0091]
[Table 4]

[0092]
Tables 2 to 4 are described below. In the near infrared absorbing dye B, IR12 is a near infrared absorbing dye (trade name, Excolor) manufactured by Nippon Shokubai Co., Ltd. In the ultraviolet absorber C, TINUVIN 234 and TINUVIN 384 (both trade names) are ultraviolet absorbers manufactured by Ciba Specialty Chemicals. In the hindered amine light stabilizer d-1 and the hindered amine light stabilizer d-2, TINUVIN 765 and TINUVIN 144 (both trade names) are light stabilizers manufactured by Ciba Specialty Chemicals. In the antioxidant E, BHT (trade name) is a hindered phenolic antioxidant manufactured by Sumitomo Chemical Co., Ltd.
[0093]
【The invention's effect】
Since the pressure-sensitive adhesive composition of the present invention has the above-described configuration, the near-infrared absorbing dye is less deteriorated by ultraviolet rays, and is suitable for forming an adhesive layer or the like for bonding a layered material for forming a plasma display or the like. It is.

Claims (4)

A pressure-sensitive adhesive comprising a pressure-sensitive adhesive polymer (A), a near-infrared absorbing dye (B), an ultraviolet absorber (C) and / or a hindered amine light stabilizer (D). Composition. The pressure-sensitive adhesive composition according to claim 1, further comprising an antioxidant (E). 3. The pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive polymer (A) has a glass transition temperature of −80 to −20 ° C. 4. 4. The pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive polymer (A) has a weight average molecular weight of 250,000 or more.