JP5417652B1 - 樹脂組成物、活性エネルギー線重合性接着剤、及び積層体 - Google Patents
樹脂組成物、活性エネルギー線重合性接着剤、及び積層体 Download PDFInfo
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- JP5417652B1 JP5417652B1 JP2013080718A JP2013080718A JP5417652B1 JP 5417652 B1 JP5417652 B1 JP 5417652B1 JP 2013080718 A JP2013080718 A JP 2013080718A JP 2013080718 A JP2013080718 A JP 2013080718A JP 5417652 B1 JP5417652 B1 JP 5417652B1
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- 238000007639 printing Methods 0.000 description 1
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- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- MHWRYTCHHJGQFQ-UHFFFAOYSA-N prop-2-enoic acid hydrate Chemical compound O.OC(=O)C=C MHWRYTCHHJGQFQ-UHFFFAOYSA-N 0.000 description 1
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- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- GHJOIQFPDMIKHT-UHFFFAOYSA-N propane-1,2,3-triol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCC(O)CO GHJOIQFPDMIKHT-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
優れた耐熱性等を有する新規な活性エネルギー線重合性樹脂組成物であって、各種光学フィルムの貼り合わせにおいて、概活性エネルギー線重合性樹脂組成物を使用した活性エネルギー線重合性接着剤、及び/または活性エネルギー線重合性コート剤を使用する事によって、各種光学フィルムの種類を問わず、簡便かつ強固に接着や密着ができ、低露光量での重合硬化性に優れ、有機溶剤を実質的に含まない光学素子用積層体を提供することを目的とする。
【解決手段】
分子内に、少なくともα,β−不飽和二重結合基を1個以上有するオリゴマー(A)と、
分子内に1個以上のカルボキシル基を有するα,β−不飽和二重結合含有化合物(B)と、及びカルボジイミド化合物(C)とを、必須成分とする樹脂組成物に、光重合開始剤を含有した活性エネルギー線重合性接着剤、及び/または活性エネルギー線重合性コート剤。
【選択図】なし
Description
しかしながら、この組成物は床材被膜用とであり、床材に反りが生じる事は少ないが、樹脂組成物の重合収縮が大きいため、コートフィルムとしてはカールが大きく、低カール性と密着性等のコート性能を両立するものではなかった。また、本文献には、2〜5μmの薄膜のコート層を作製する場合、120℃以上にて乾燥させると、活性エネルギー線重合性組成物中に含有されている活性エネルギー線重合開始剤が乾燥時の熱により揮発し、活性エネルギー線により重合硬化させる場合、反応が不十分となるためコート性が劣るものであった。
すなわち、本発明は、分子内に、少なくともα,β−不飽和二重結合基を1個以上有するオリゴマー(A)と、分子内に1個以上のカルボキシル基を有するα,β−不飽和二重結合基含有化合物(B)(ただし、オリゴマー(A)に該当するものを除く)と、及びカルボジイミド化合物(C)とを必須成分とすることを特徴とする活性エネルギー線重合性樹脂組成物に関する。
比較的低分子量のポリオール類としては、より具体的には、例えば、エチレングリコール、プロピレングリコール、ジプロピレングリコール、ジエチレングリコール、トリエチレングリコール、ブチレングリコール、3−メチル−1,5−ペンタンジオール、2,4−ジエチル−1,5−ペンタンジオール、2−メチル−1,8−オクタンジオール、3,3'−ジメチロールヘプタン、2−ブチル−2−エチル−1,3−プロパンジオール、ポリオキシエチレングリコール(付加モル数10以下)、ポリオキシプロピレングリコール(付加モル数10以下)、プロパンジオール、1,3−ブタンジオール、1,4−ブタンジオール、1,5−ペンタンジオール、1,6−ヘキサンジオール、1,9−ノナンジオール、ネオペンチルグリコール、オクタンジオール、ブチルエチルペンタンジオール、2−エチル−1,3−ヘキサンジオール、シクロヘキサンジオール、シクロヘキサンジメタノール,トリシクロデカンジメタノール、シクロペンタジエンジメタノール、ダイマージオール等の脂肪族又は脂環式ジオール類;
1,3−ビス(2−ヒドロキシエトキシ)ベンゼン、1,2−ビス(2−ヒドロキシエトキシ)ベンゼン、1,4−ビス(2−ヒドロキシエトキシ)ベンゼン、4,4'−メチレンジフェノール、4,4'−(2−ノルボルニリデン)ジフェノール、4,4'−ジヒドロキシビフェノール、o−,m−及びp−ジヒドロキシベンゼン、4,4'−イソプロピリデンフェノール、ビスフェノールにアルキレンオキサイドを付加させた付加型ビスフェノール等の芳香族ジオール類等を挙げることができる。
付加型ビスフェノールの原料ビスフェノールとしては、ビスフェノールA、ビスフェノールF等が挙げられ、原料アルキレンオキサイドとしては、エチレンオキサイド、プロピレンオキサイド等が挙げられる。
クラレ社製のUE−3600(Mn=20,000,Tg=75℃,水酸基価=4,酸価=1)、UE−3690(Mn=14,000,Tg=91℃,水酸基価=8,酸価=1)〔以上、ユニチカ社製〕、P1010(Mn=1,000,水酸基価=112,酸価<0.5,線形液状タイプ)、P2010(Mn=2,000,水酸基価=56,酸価<0.5,線形液状タイプ)、P4010(Mn=4,000,水酸基価=28,酸価<0.5,線形液状タイプ)、P5010(Mn=5,000,水酸基価=22,酸価<0.5,線形液状タイプ)、P6010(Mn=6,000,水酸基価=19,酸価<0.5,線形液状タイプ)、P4050(Mn=4,000,水酸基価=28,酸価<0.5,線形液状タイプ)、P6010(Mn=6,000,水酸基価=19,酸価<0.5,線形液状タイプ)、N4010(Mn=4,000,水酸基価=28,酸価<0.5,線形液状タイプ)、PNOA4014(Mn=4,000,水酸基価=28,酸価<0.5,線形液状タイプ)、P2011(Mn=2,000,水酸基価=56,酸価<0.5,線形液状タイプ)、及び、P4011(Mn=4,000,水酸基価=28,酸価<0.5,線形液状タイプ);
協和発酵ケミカル社製のキョーワポール2000BA(Mn=2,000,水酸基価=58,酸価<0.5,線形液状タイプ)、及び、キョーワポール5000PA(Mn=5,000,水酸基価=22,酸価<0.5,線形液状タイプ)等が挙げられる。
クラレ社製のPMHC−1050(Mn=1,000,水酸基価=112,酸価<0.5,線形液状タイプ)、PMHC−2050(Mn=2,000,水酸基価=56,酸価<0.5,線形液状タイプ)、C−1090(Mn=1,000,水酸基価=112,酸価<0.5,線形液状タイプ)、C−2090(Mn=2,000,水酸基価=56,酸価<0.5,線形液状タイプ)、C−3090(Mn=3,000,水酸基価=37,酸価<0.5,線形液状タイプ)、C−4090(Mn=4,000,水酸基価=28,酸価<0.5,線形液状タイプ)、C−5090(Mn=5,000,水酸基価=22,酸価<0.5,線形液状タイプ)、C−1065N(Mn=1,000,水酸基価=112,酸価<0.5,線形液状タイプ)、C−2065N(Mn=2,000,水酸基価=56,酸価<0.5,線形液状タイプ)、C−1015N(Mn=1,000,水酸基価=112,酸価<0.5,線形液状タイプ)、及び、C−2015N(Mn=2,000,水酸基価=56,酸価<0.5,線形液状タイプ)等が挙げられる。
三井化学ポリウレタン社製のタケラックE158(水酸基価=20,酸価<3)、タケラックE551T(水酸基価=30,酸価<3)、及び、タケラックA2789(水酸基価=10,酸価<2)等が挙げられる。
イソホロンジアミン、ジシクロヘキシルメタン−4,4’−ジアミン等の脂環式ポリアミン;
フェニレンジアミン、キシリレンジアミン、2,4−トリレンジアミン、2,6−トリレンジアミン、ジエチルトルエンジアミン,3,3’−ジクロロ−4,4’−ジアミノジフェニルメタン、4,4’−ビス−(sec−ブチル)ジフェニルメタン等の芳香族ジアミン;
1,1,3,3−テトラメチルジシラザン、ヘキサメチルジシラザン、1,3−ジビニル−1,1,3,3−テトラメチルジシラザン、N,N'−ビス(トリメチルシリル)−N−フェニルウレア等の2官能のシリルアミノ基を保有するシリルアミン類;1,1,3,3,5,5−ヘキサメチルシクロトリシラザン、1,1,3,3,5,5,7,7−オクタメチルシクロテトラシラザン等の3官能以上の環状シリルアミノ基を保有するシリルアミン;
オリゴマー(A)のMwが300未満の場合は、活性エネルギー線重合性接着剤の接着フィルムを各種基材(G)等に貼着した後、活性エネルギー線重合性接着剤層の凝集破壊が起こりやすくなる場合がある。
本発明において、分子内に1個以上のカルボキシル基を有するα,β−不飽和二重結合基含有化合物(B)(以下化合物(B)と称す。)は、分子内に少なくとも1個のカルボキシル基と少なくとも1個のα,β−不飽和二重結合基を含有する化合物である。ただし、オリゴマー(A)に該当するものは含まれない。化合物(B)のカルボキシル基は後述のカルボジイミド化合物(C)中の反応性基と、酸塩基反応や付加反応等の相互作用があるため、化合物(B)とカルボジイミド化合物(C)とが混成し、複数のα,β−不飽和二重結合基を有する化合物としての機能するため、重合硬化塗膜の架橋密度の向上に大きな効果をもたらすものである。
化合物(B)としては、その構造中にカルボキシル基を有するものであれば、特に制限はなく、より具体的には、例えば、(メタ)アクリル酸〔アクリル酸とメタクリル酸を併せて「(メタ)アクリル酸」と表記する。以下同様。〕、(メタ)アクリル酸2−カルボキシエチル、(メタ)アクリル酸2−カルボキシプロピル、(メタ)アクリル酸3−カルボキシプロピル、(メタ)アクリル酸4−カルボキシブチル、(メタ)アクリル酸ダイマー、マレイン酸、フマル酸、モノメチルマレイン酸、モノメチルフマル酸、アコニチン酸、ソルビン酸、ケイ皮酸、α−クロロソルビン酸、グルタコン酸、シトラコン酸、メサコン酸、イタコン酸、チグリン酸、アンゲリカ酸、セネシオ酸、クロトン酸、イソククロトン酸、ムコブロム酸、ムコクロル酸、ソルビン酸、ムコン酸、アコニット酸、ペニシル酸、ゲラン酸、シトロネル酸、4−アクリルアミドブタン酸、6−アクリルアミドヘキサン酸、2−(メタ)アクリロイルオキシエチルサクシネート、あるいはモノ(メタ)アクリル酸ω−カルボキシポリカプロラクトンエステル等のラクトン環の開環付加により末端にカルボキシル基を有するポリラクトン系(メタ)アクリル酸エステル、あるいはエチレンオキサイドやプロピレンオキサイド等のアルキレンオキサイドの繰り返し付加した末端にカルボキシル基を有するアルキレンオキサイド付加系コハク酸と(メタ)アクリル酸のエステル等のカルボキシル基含有の脂肪族系のα,β−不飽和二重結合基含有カルボン酸類やその酸無水物類;
本発明において、カルボジイミド化合物(C)は、反応基としてカルボジイミド結合基、すなわち、−N=C=N−を分子内に1個以上有する化合物であり、中でもカルボジイミド結合基を分子内に1〜4個有する化合物が好ましい。また、カルボジイミド結合基が、アミノ基、ニトロ基、シリル基、カルボニル基、アミド基、あるいはエステル基等のその他結合基と結合してもよい。
本発明におけるカルボジイミド化合物(C)を得る方法の一つとして、有機溶媒中で触媒の存在下に、上記した少なくとも1個以上のイソシアネート基を有する化合物を100〜200℃で脱二酸化炭素する反応方法がある。100℃以下では反応に長時間要し、200℃以上では副反応が起こりやすい。かかる反応は、窒素雰囲気下で行うことが好ましい。
カルボジイミド結合基を形成する反応に用いられる触媒としては、ホスホレン、ホスホレンオキサイド類が上げられる。具体的には、1−エチル−3−メチル−3ホスホレンオキサイド、1−フェニル−3−メチル−3−ホスホレンオキサイド、1−フェニル−3−メチル−2−ホスホレンオキサイド等を使用することができる。
カルボジイミド結合基を形成する反応に用いられる有機溶媒としては、沸点が高く、また原料である少なくとも1個以上のイソシアネート基を有する化合物、及び生成するカルボジイミド化合物(C)と反応するような活性水素を持たないことが必要である。
より具体的に、例えば、トルエン、キシレン、ジエチルベンゼン等の芳香族炭化水素類;
ジエチレングリコールジアセテート、ジプロピレングリコールジブチレート、ヘキシレングリコールジアセテート、グリコールジアセテート、メチルグリコールアセテート、エチルグリコールアセテート、ブチルグリコールアセテート、エチルジグリコールアセテート、ブチルジグリコールアセテート等のグリコールエーテルエステル類;
エチルブチルケトン、アセトフェノン、プロピオフェノン、ジイソブチルケトン、シクロヘキサノン等のケトン類;
酢酸アルミ、プロピオン酸プロピル、酪酸エチル等の脂肪族エステル類等がある。
カルボジイミド結合基の生成は、2260cm-1のイソシアネ−ト基の吸収ピ−クの消失、及びカルボジイミド結合基の吸収ピ−クの生成によって確認することができる。
比率が2/8よりも(C)が多くなると、樹脂組成物の粘度が上がるため、塗工性に問題が生じるため好ましくない。一方、比率が8/2よりも(C)が少なくなると、樹脂組成物を活性エネルギー線重合性コート剤、あるいは活性エネルギー線重合性接着剤として用いた場合には、基材(G)に対する密着性や接着性が低下するので好ましくない。
本発明の樹脂組成物には、分子内にカルボキシル基を有しないα,β−不飽和二重結合基含有化合物(D)(ただし、オリゴマー(A)に該当するものを除く)を含有することができる。その際、α,β−不飽和二重結合基を有し、カルボキシル基を有しなければ、特に制限することはなく、より具体的には、例えば、(メタ)アクリル酸2−ヒドロキシエチル〔アクリル酸2−ヒドロキシエチルとメタクリル酸2−ヒドロキシエチルとを併せて「(メタ)アクリル酸2−ヒドロキシエチル」と表記する。以下同様。〕、(メタ)アクリル酸1−ヒドロキシプロピル、(メタ)アクリル酸2−ヒドロキシプロピル、(メタ)アクリル酸3−ヒドロキシプロピル、(メタ)アクリル酸1−ヒドロキシブチル、(メタ)アクリル酸2−ヒドロキシブチル、(メタ)アクリル酸3−ヒドロキシブチル、(メタ)アクリル酸4−ヒドロキシブチル、(メタ)アクリル酸6−ヒドロキシヘキシル、(メタ)アクリル酸8−ヒドロキシオクチル、(メタ)アクリル酸10−ヒドロキシデシル、(メタ)アクリル酸12−ヒドロキシラウリル、(メタ)アクリル酸エチル−α−(ヒドロキシメチル)、単官能(メタ)アクリル酸グリセロール、あるいは(メタ)アクリル酸グリシジルラウリン酸エステル、(メタ)アクリル酸グリシジルオレイン酸エステル、(メタ)アクリル酸グリシジルステアリン酸エステル等の脂肪酸エステル系(メタ)アクリル酸エステル、あるいはラクトン環の開環付加により末端に水酸基を有するポリラクトン系(メタ)アクリル酸エステル、あるいはエチレンオキサイドやプロピレンオキサイド等のアルキレンオキサイドの繰り返し付加した末端に水酸基を有するアルキレンオキサイド付加系(メタ)アクリル酸エステル、(メタ)アクリル酸2−ヒドロキシエチルホスフェート等の水酸基含有の脂肪族(メタ)アクリル酸エステル類;
2−(2'−ヒドロキシ−5'−(メタ)アクリロイルオキシプロピルフェニル)−5−クロロ−2H−ベンゾトリアゾール、2−(2'−ヒドロキシ−3'−tert−ブチル−5'−(メタ)アクリロイルオキシエチルフェニル)−2H−ベンゾトリアゾール、2−(2'−ヒドロキシ−3'−tert−ブチル−5'−(メタ)アクリロイルオキシエチルフェニル)−5−クロロ−2 H−ベンゾトリアゾール等の水酸基含有ベンゾトリアゾール系(メタ)アクリル酸エステル類;
等のアルコキシシリル基含有(メタ)アクリル酸エステル類;
2−メチル−2−プロペニルスルホン酸アンモニウム、2−メチル−2−プロペニルスルホン酸ナトリウム、2−メチル−2−プロペニルスルホン酸カリウム等の2−メチル−2−プロペニルスルホン酸の金属塩やアンモニウム塩類;
4−ビニル安息香酸メチルポリ(エチレンオキサイド)、4−ビニル安息香酸エチルポリ(エチレンオキサイド)、4−イソプロペニル安息香酸メチルポリ(プロピレンオキサイド)、4−イソプロペニル安息香酸エチルポリ(プロピレンオキサイド)などのポリアルキレンオキサイド部位を有するビニル安息香酸エステル系またはイソプロペニル安息香酸エステル系単量体類;
スチレンスルホン酸ナトリウム、スチレンスルホン酸カリウム、スチレンスルホン酸リチウム、スチレンスルホン酸マグネシウム、スチレンスルホン酸亜鉛、スチレンスルホン酸鉄等のスチレンスルホン酸の金属塩類;
ビニルオキシベンゼンスルホン酸アンモニウム、ビニルオキシベンゼンスルホン酸ナトリウム、ビニルオキシベンゼンスルホン酸カリウム等のアルケニル基含有ビニルオキシベンゼンスルホン酸の金属塩やアンモニウム塩類;
2−メチル−2−プロペニルオキシベンゼンスルホン酸アンモニウム、2−メチル−2−プロペニルオキシベンゼンスルホン酸ナトリウム、2−メチル−2−プロペニルオキシベンゼンスルホン酸カリウム等の2−メチル−2−プロペニルオキシベンゼンスルホン酸の金属塩やアンモニウム塩類;
本発明に使用される活性エネルギー線重合開始剤(E)は、公知のものから任意に選択し使用できるが、その具体例としては、例えば、2,2−ジメトキシ−2−フェニルアセトフェノン、アセトフェノン、ベンゾフェノン、キサントフルオレノン、ベンズアルデヒド、アントラキノン、3−メチルアセトフェノン、4−クロロベンゾフェノン、4,4‘−ジアミノベンゾフェノン、ベンゾインプロピルエーテル、ベンゾインエチルエーテル、ベンジルジメチルケタール、1−(4−イソプロピルフェニル)−2−ヒドロキシ-2−メチルプロパン-1−オン、2−ヒドロキシ−2−メチル−1−フェニルプロパン−1−オン、4−オキサントン、カンファーキノン、2−メチル−1−[4−(メチルチオ)フェニル]−2−モルホリノプロパン−1−オン等が挙げられる。市販品としては、例えば、イルガキュアー184,907,651,1700,1800,819,369,261、DAROCUR-TPO(BASF社製 2,4,6-トリメチルベンゾイル-ジフェニル−フォスフィンオキサイド)、ダロキュア-1173(メルク社製)、エザキュアーKIP150、TZT(日本シイベルヘグナー社製)、カヤキュアBMS、カヤキュアDMBI(日本化薬社製)等が挙げられる。
また、分子内に少なくとも1個の(メタ)アクリロイル基を有する光重合開始剤も用いることができる。これらの活性エネルギー線重合開始剤(E)は単独または2種類以上の混合物として使用することができる。
本発明の樹脂組成物には、シラン化合物(F)を含有することが好ましい。シラン化合物(F)としては、公知のシラン化合物を用いることができ、後述の基材(G)との密着性が向上するものであれば特に限定されない。例えば、アルキル系アルコキシシラン、アリール系アルコキシシラン、ビニル系アルコキシシラン、アミノ系アルコキシシラン、エポキシ系アルコキシシラン、ハロゲン系アルコキシシラン、(メタ)アクリロイル系アルコキシシラン、メルカプト系アルコキシシラン、カチオン系アルコキシシラン、イソシアネート系アルコキシシラン等のアルコキシル基を有するアルコキシシラン類、及び/または、珪素原子に水素原子が直接結合して反応性を有する有機シラン類等が挙げられる。より具体的に、例えば、テトラメトキシシラン、テトラエトキシシラン、テトライソプロポキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリイソプロポキシシラン、メチルトリアセトキシシラン、メチルトリス( メトキシエトキシ) シラン、メチルトリス( メトキシプロポキシ)シラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリイソプロポキシシラン、プロピルトリメトキシシラン、プロピルトリエトキシシラン、プロピルトリイソプロポキシシラン、ブチルトリメトキシシラン、ブチルトリエトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、オクチルトリメトキシシラン、オクチルトリエトキシシラン、デシルトリメトキシシラン、デシルトリエトキシシラン、シクロヘキシルトリメトキシシラン、シクロヘキシルトリエトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジメチルジイソプロポキシシラン、ジメチルジアセトキシシラン、ジメチルビス(メトキシエトキシ)シラン、ジメチルビス(メトキシプロポキシ)シラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、ジエチルジイソプロポキシシラン、ジエチルジアセトキシシラン、メチルエチルジメトキシシラン、メチルエチルジエトキシシラン、メチルエチルジイソプロポキシシラン、メチルエチルジアセトキシシラン、メチルプロピルジメトキシシラン、メチルプロピルジエトキシシラン、メチルプロピルジイソプロポキシシラン、メチルプロピルジアセトキシシラン、等のアルキル系アルコキシシラン類;
本発明における樹脂組成物は、更に酸化防止剤を含んでも良い。酸化防止剤を含むことによって、活性エネルギー線重合後の重合塗膜層の経時での着色を抑制することができる。
酸化防止剤としては、例えば、アデカスタブAO‐50、アデカスタブAO‐80(ADEKA社製)、などのフェノール系酸化防止剤や、IRGANOX‐PS‐800FD(BASF社製)、などのイオウ系酸化防止剤、TINUBIN622LD、TINUBIN144、TINUBIN765(3種ともBASF社製)等のヒンダードアミン系の光安定剤等の市販品が挙げられるが、これらに限定されるものではない。
酸化防止剤の配合割合は、樹脂組成物100重量部に対して、0.01〜20重量部であり、0.01〜10重量部であることが好ましい。0.01重量部より少ないと、活性エネルギー線により早期に消費されてしまうため、重合率が下がり、逆に20重量部より多くなると、重合率は上がるが、重合塗膜の分子量が低下し、樹脂組成物を活性エネルギー線重合性コート剤、あるいは活性エネルギー線重合性接着剤として使用した場合には、重合架橋塗膜の凝集力の低下させるため、耐久性を低下させる。
本発明の樹脂組成物は、液状、ペースト状及びフィルム状のいずれの形態でも使用することができる。
なお、本発明における樹脂組成物は、実質的に有機溶剤を含まないことが好ましいが、機溶剤を含有することも可能である。 例えば、メタノール、エタノール、イソプロピルアルコール、アセトン、メチルエチルケトン、メチルイソブチルケトン、酢酸メチル、酢酸エチル、酢酸ブチル、シクロヘキサン、トルエン、キシレンその他の炭化水素系溶媒等の有機溶媒や、水をさらに添加して、樹脂組成物の粘度を調整することもできるし、樹脂組成物を加熱して粘度を低下させることもできる。
また、樹脂組成物層の膜厚が使用用途によって、6〜300μmの場合には、粘度は1500〜100,000mPa・sであることが重要であり、好ましくは3,000〜50,000mPa・sであることがより好ましい。
樹脂組成物の粘度は、オリゴマー(A)の粘度で殆ど決定されるため、オリゴマー(A)の粘度を1〜100,000mPa・sの範囲で管理することにより、樹脂組成物の粘度も管理が可能である。
常法にしたがって適当な方法で基材(G)の片面、または両面に樹脂組成物を塗工して、基材(G)上に樹脂組成物の積層構造(樹脂組成物層ともいう)を形成することができる。樹脂組成物層の要求膜厚が使用用途によって、0.1〜6μmの場合には、樹脂組成物層の厚さは、0.1〜6μmの薄膜塗工であることが好ましく、0.1μm〜3μmであることがより好ましい。0.1μm未満では、樹脂組成物を活性エネルギー線重合性コート剤、あるいは活性エネルギー線重合性接着剤として用いた場合には、十分な密着性や接着力が得られないことがあり、6μmを超えても密着性や接着力等の特性はそれ以上向上しない場合が多い。
本発明の樹脂組成物は、さらに活性エネルギー線重合性コート剤(以下コート剤と称す)や活性エネルギー線重合性接着剤(以下接着剤と称す)として好適である。
基材(G)としては、樹脂組成物をコート剤として基材(G)一層の片面や両面に使用した場合には、木材、金属板、プラスチック板、フィルム状基材、ガラス板、紙加工品等、特に制限無く使用できる。一方、二つ以上の基材(G)を貼り合わせる接着剤として使用する場合には、活性エネルギー線を照射して重合させるために、活性エネルギー線を透過し易い基材を使用する必要があり、特に透明フィルム(H)や透明ガラス板を使用する事が好ましい。片方を活性エネルギー線が透過し難い基材、例えば、木材、金属板、プラスチック板、紙加工品等を使用した場合でも、もう片方を透明フィルム(H)や透明ガラス板を使用し、透明フィルム(H)や透明ガラス板側から照射し、重合硬化を行えば使用は可能である。
本発明の樹脂組成物の活性エネルギー線による重合反応を使用する場合は、即ち、前記した基材(G)のうち、フィルム状基材である透明フィルム(H)と該透明フィルム(H)の少なくとも一方の面に位置する樹脂組成物層とを具備する積層体の形成に使用されることが好ましい。
樹脂組成物を活性エネルギー線重合性コート剤として使用した場合には、フィルム状基材である透明フィルム(H)の片面にコート剤を塗工することによって、積層体を得ることができる。この際、コート層は、易接着化のためのプライマー層としても使用される。
コート剤や接着剤の活性エネルギー線重合反応は、コート剤や接着剤の塗工時、あるいは積層する際、さらには積層した後に活性エネルギー線を照射して進行するが、積層した後に活性エネルギー線を照射して重合反応を進めることが好ましい。
本発明の透明フィルム(H)は、ディスプレイやタッチパネル等の情報通信機器等の光学フィルム(I)に使用する事ができる。
ここで、光学素子用積層体について一般的な説明をする。
コート剤や接着剤は、光学素子用積層体を形成するために用いられる。
光学用積層体の基本的積層構成は、樹脂組成物を活性エネルギー線重合性コート剤として使用した場合には、透明フィルム/コート層、あるいはコート層/透明フィルム/コート層のようなシート状の光学コート積層体である。
なお、光学フィルム(I)である偏光板フィルムの偏光子の両側に透明フィルム(H)を設ける場合、その表裏で同じポリマー材料からなる透明フィルム(H)を用いてもよく、異なるポリマー材料等からなる透明フィルム(H)を用いても良い。
本発明における光学用積層体としては、上記の各種透明フィルム(H)のうち、主に光学用途にて用いられる光学フィルム(I)が好適に使用される。光学フィルム(I)としては、上記透明フィルム(H)に特殊な処理を施されたものであり、光学的機能(光透過、光拡散、集光、屈折、散乱、HAZE等の諸機能)を有するものが光学フィルムと称されている。これらの光学フィルムは単独で、または数種の光学フィルムをコート剤や接着剤で多層に積層されて光学素子用積層体として使用される。例えば、ハードコートフィルム、帯電防止コートフィルム、防眩コートフィルム、偏光フィルム、位相差フィルム、楕円偏光フィルム、反射防止フィルム、光拡散フィルム、輝度向上フィルム、プリズムフィルム(プリズムシートともいう)、導光フィルム(導光板ともいう)等が挙げられる。
(I)第1の透明フィルム(H)である保護フィルムの一方の面に、活性エネルギー線重合性接着剤を塗工し、第1の重合性接着層(2’)を形成し、
透明フィルム(H)である第2の保護フィルムの一方の面に、活性エネルギー線重合性接着剤を塗工し、第2の活性エネルギー線重合性接着層を形成し、
次いで、ポリビニルアルコール系偏光子の各面に、第1の活性エネルギー線重合性接着層及び第2の活性エネルギー線重合性接着層を、同時に/または順番に重ね合わせた後、活性エネルギー線を照射し、第1の活性エネルギー線重合性接着層及び第2の活性エネルギー線重合性接着層を重合硬化することによって製造する方法。
酸素濃度が10%以下に置換された遮光された300mlのマヨネーズ瓶に、分子内に、少なくともα,β−不飽和二重結合基を1個以上有するオリゴマー(A)、分子内に1個以上のカルボキシル基を有するα,β−不飽和二重結合含有化合物(B)、カルボジイミド化合物(C)、分子内にカルボキシル基を有しないα,β−不飽和二重結合含有化合物(D)(ただし、オリゴマー(A)に該当するものを除く)、活性エネルギー線重合開始剤(E)及びシラン化合物(F)を表1に示す比率で仕込み、にて十分に攪拌を行い、十分に脱泡を行った後、配合例に示す樹脂組成物を得た。
各配合例で得られた樹脂組成物の液体外観を目視にて評価した。
各配合例で得られた樹脂組成物を23℃の雰囲気下でE型粘度計(東機産業社製 TV−22)にて、約1.2mlを測定用試料とし、回転速度0.5〜100rpm、1分間回転の条件で測定し、溶液粘度(mPa・s)とした。
数平均分子量(Mn)と重量平均分子量(Mw)の測定は、昭和電工社製GPC(ゲルパーミエーションクロマトグラフィー)「ShodexGPC System−21」を用いた。GPCは溶媒に溶解した物質をその分子サイズの差によって分離定量する液体クロマトグラフィーであり、溶媒としてはテトロヒドロフラン、重量平均分子量(Mn)の決定はポリスチレン換算で行った。
共栓三角フラスコ中に試料、約1gを精密に量り採り、トルエン/エタノール(容量比:トルエン/エタノール=2/1)混合液100mlを加えて溶解する。更にアセチル化剤(無水酢酸25gをピリジンで溶解し、容量100mlとした溶液)を正確に5ml加え、約1時間攪拌した。これに、フェノールフタレイン試液を指示薬として加え、30秒間持続する。その後、溶液が淡紅色を呈するまで0.1Nアルコール性水酸化カリウム溶液で滴定する。
水酸基価は次式により求めた。水酸基価は樹脂の乾燥状態の数値とした(単位:mgKOH/g)。
水酸基価(mgKOH/g)=[{(b−a)×F×28.25}/S]/(不揮発分濃度/100)+D
ただし、S:試料の採取量(g)
a:0.1Nアルコール性水酸化カリウム溶液の消費量(ml)
b:空実験の0.1Nアルコール性水酸化カリウム溶液の消費量(ml)
F:0.1Nアルコール性水酸化カリウム溶液の力価
D:酸価(mgKOH/g)
共栓三角フラスコ中に試料化合物(B)を、約1gを精密に量り採り、トルエン/エタノール(容積比:トルエン/エタノール=2/1)混合液100mlを加えて溶解した。これに、フェノールフタレイン試液を指示薬として加え、30秒間保持した後、溶液が淡紅色を呈するまで0.1Nアルコール性水酸化カリウム溶液で滴定した。
乾燥状態の樹脂の値として、酸価(mgKOH/g)を次式により求めた。
酸価(mgKOH/g)={(5.611×a×F)/S}/(不揮発分濃度/100)
ただし、S:試料の採取量(g)
a:0.1Nアルコール性水酸化カリウム溶液の消費量(ml)
F:0.1Nアルコール性水酸化カリウム溶液の力価
ロボットDSC(示差走査熱量計、セイコーインスツルメンツ社製「RDC220」)に「SSC5200ディスクステーション」(セイコーインスツルメンツ社製)を接続して、測定に使用した。
表1の樹脂組成物を、剥離処理されたポリエステルフィルムに塗工し、活性エネルギー線を照射し、重合硬化させたものを約10mgかきとり、試料としてアルミニウムパンに入れ、秤量して示差走査熱量計にセットし、試料を入れない同タイプのアルミニウムパンをリファレンスとして、100℃の温度で5分間加熱した後、液体窒素を用いて−120℃まで急冷処理した。その後10℃/分で昇温し、昇温中に得られたDSCチャートからガラス転移温度(Tg、単位:℃)を決定した。
表1及び2に示した樹脂組成物を活性エネルギー線重合性接着剤として使用して、以下の積層体を作成した。
透明フィルム(H)である保護フィルム(1)として、日本ゼオン社製の紫外線吸収剤を含有しないポリノルボルネン系フィルム:商品名「Z−14:100μm」を用い、保護フィルム(2)として、三菱レイヨン社製の紫外線吸収剤を含有しないポリアクリル系フィルム:商品名「HDB−002」(厚み50μm)を使用し、それぞれその表面に300W・min/m2 の放電量でコロナ処理を行い、表面処理後1時間以内に、配合例1に示す活性エネルギー線重合性接着剤をワイヤーバーコーターを用いて膜厚4μmとなるように塗工し、活性エネルギー線重合性接着層を形成し、前記活性エネルギー線重合性接着層との間にポリビニルアルコール系偏光子を挟み、保護フィルム(1)/接着層/PVA系偏光子/接着層/保護フィルム(2)からなる積層体を得た。
保護フィルム(1)がブリキ板に接するように、この積層体の四方をセロハンテープで固定し、ブリキ板に固定した。
活性エネルギー線照射装置(東芝社製 高圧水銀灯)で最大照度300mW/cm2、積算光量300mJ/cm2の紫外線を保護フィルム(2)側から照射して、偏光板を作製した。
接着力は、JIS K6 854−4 接着剤−剥離接着強さ試験方法−第4部:浮動ローラー法に準拠して測定した。
即ち、得られた偏光板を、25mm×150mmのサイズにカッターを用いて裁断して測定用サンプルとした。サンプルを両面粘着テープ(トーヨーケム社製DF8712S)を使用して、ラミネータを用いて金属板上に貼り付けて、偏光板と金属板との測定用の積層体を得た。測定用の積層体の偏光板には、保護フィルムと偏光子の間に予め剥離のキッカケを設けておき、この測定用の積層体を23℃、相対湿度50%の条件下で、300mm/分の速度で引き剥がし、剥離力とした。この際、ポリビニルアルコール系偏光子と保護フィルム(1)、及びポリビニルアルコール系偏光子と保護フィルム(2)との双方の剥離力を測定した。この剥離力を接着力として4段階で評価した。
◎:剥離不可、あるいは偏光板破壊
○:剥離力が2.0(N/25mm)以上〜5.0(N/25mm)未満。
△:剥離力が1.0(N/25mm)以上〜2.0(N/25mm)未満。
×:剥離力が1.0(N/25mm)未満。
コロナ処理を施していない日本ゼオン社製のポリノルボルネン系フィルム(商品名「ゼオノア ZF−14:100μm」に、活性エネルギー線重合性接着剤を、ワイヤーバーコーターを用いて膜厚20〜25μmとなるように塗工し、活性エネルギー線重合性接着層を形成した。さらに活性エネルギー線重合性接着層の上にコロナ処理を施していないゼオノア ZF−14を重ね、3層からなる積層体を得た後、活性エネルギー線照射装置(東芝社製 高圧水銀灯)で最大照度300mW/cm2、積算光量300mJ/cm2の活性エネルギー線を照射し活性エネルギー線重合性接着層を重合硬化させた。3層からなる積層体のゼオノア ZF−14を剥離し接着剤層を得た。
接着剤層の重量を測定した後(重量1)を金属メッシュと金属メッシュの間に挟み接着剤層同士が重ならないようにし、メチルエチルケトン(MEK)中で3時間還流した。さらに80℃−30分乾燥し、接着剤層の重量を測定した(重量2)。下記式よりゲル分率を求め、3段階評価した。
ゲル分率(%)={1−(重量1−重量2)/重量1)}×100
○:ゲル分率が90%以上
△:ゲル分率が80%以上〜90%未満
×:ゲル分率が80%未満
ダンベル社製の100mm×100mmの刃を用い、作製した偏光板を保護フィルム(1)側から打ち抜いた。
打ち抜いた偏光板の、周辺の剥離距離を定規で測定し、以下の4段階で評価した。
◎:0mm
○:1mm以下
△:1〜3mm
×:3mm以上
上記偏光板小片を60℃−dryと60℃−90RH%の恒温恒湿機中に放置し、60時間後の延伸方向の縮み量を測定し、元の長さ(100mm)に対する縮み量の割合を収縮率とし求め、以下の3段階で評価をした。
なお、「dry」とは、湿度調整機能付のオーブンで、温度のみコントロールし、湿度のコントロールを行わなかった場合の試験条件である。
○:収縮率が0.2%以下
△:収縮率が0.2%より大きくて0.4%以下
×:収縮率が0.4%を超える。
各実施例1〜16、比較例1〜4で得られた偏光板を、50mm×40mmの大きさに裁断し、80℃−dry、及び100℃−dryの条件下で、それぞれ1000時間暴露した。暴露後偏光板の端部の剥がれの有無を目視にて、以下の3段階で評価をした。
◎:100℃dryの条件下でも剥がれが全く無し。
○:80℃−dry条件下で剥がれが全く無し。
△:80℃−dry条件下で1mm未満の剥がれあり。
×:80℃−dry条件下で1mm以上の剥がれあり。
各実施例1〜16、比較例1〜4で得られた偏光板を、50mm×40mmの大きさに裁断し、60℃−90%RHの条件下、及び85℃−85%RHの条件下で1000時間暴露した。暴露後偏光板の端部の剥がれの有無を目視にて、以下の3段階で評価をした。
◎:85℃−85%RHの条件下でも剥がれが全く無し。
○:60℃−90%RHの条件下で剥がれが全く無し。
△:60℃−90%RHの条件下で1mm未満の剥がれあり。
×:60℃−90%RHの条件下で1mm以上の剥がれあり。
ZF−14:日本ゼオン社製ポリノルボルネン系フィルム、HBD−002:三菱レイヨン社製アクリル系フィルム。
表1及び2に示した樹脂組成物を活性エネルギー線重合性コート剤として使用して、以下の積層体を作成した。
光学フィルムとして、富士フィルム社製の紫外線吸収剤含有ポリトリアセチルセルロース系フィルム:商品名「フジタック:80μm」を用いた。光学フィルム表面を300W・min/m2の放電量でコロナ処理を行い、表面処理後1時間以内に、配合例1に示す樹脂組成物を活性エネルギー線重合性コート剤として、ワイヤーバーコーターを用いて膜厚4μmとなるように塗工し、活性エネルギー線重合性コート剤層を形成した。
光学フィルムがブリキ板に接するように、この積層体の四方をセロハンテープで、ブリキ板に固定した。
UV照射装置(東芝社製 高圧水銀灯)内を乾燥窒素で置換後、波長365nmの最大照度300mW/cm2、積算光量300mJ/cm2の紫外線を活性エネルギー線重合性コート剤層側から照射して、活性エネルギー線重合性コート剤層を有する積層体を作製した。
JIS K5400に従い碁盤目剥離試験を実施した。100マス中の剥離したマス数を4段階評価した。
◎:0マス
○:1〜10マス
△:11〜30マス
×:31マス以上
実施例21〜39、比較例5〜8で得られた積層体を、50mm×40mmの大きさに裁断し、80℃−dryの条件下で1000時間暴露した。暴露後積層体の端部の剥がれの有無を目視にて、以下の3段階で評価をした。
○:剥がれが全く無し
△:1mm未満の剥がれあり
×:1mm以上の剥がれあり
また、本発明の樹脂組成物を活性エネルギー線重合性コート剤として用いた場合は、表3と同様の傾向であり、表4に示す様に実施例21〜39では、密着力、及び耐熱性とも優れ、特に問題無い。これに対して比較例5〜8では、特に密着力、あるいは耐熱性に劣ることがわかる。
Claims (24)
- 分子内に、少なくともα,β−不飽和二重結合基を1個以上有するオリゴマー(A)と、
分子内に1個以上のカルボキシル基を有するα,β−不飽和二重結合基含有化合物(B)(ただし、オリゴマー(A)に該当するものを除く)と、
カルボジイミド化合物(C)とを含有する樹脂組成物からなることを特徴とする活性エネルギー線重合性コート剤。 - 更に、分子内にカルボキシル基を有しないα,β−不飽和二重結合基含有化合物(D)(ただし、オリゴマー(A)に該当するものを除く)を含有することを特徴とする請求項1記載の活性エネルギー線重合性コート剤。
- 更に、樹脂組成物100重量部に対して、活性エネルギー線重合開始剤(E)を0.01〜20重量部を含有してなる請求項1又は2記載の活性エネルギー線重合性コート剤。
- 更に、シラン化合物(F)を含有することを特徴とする請求項1〜3いずれか記載の活性エネルギー線重合性コート剤。
- 分子内に、少なくともα,β−不飽和二重結合基を1個以上有するオリゴマー(A)と、
分子内に1個以上のカルボキシル基を有するα,β−不飽和二重結合基含有化合物(B)(ただし、オリゴマー(A)に該当するものを除く)と、
カルボジイミド化合物(C)とを含有する樹脂組成物からなることを特徴とする活性エネルギー線重合性接着剤。 - 更に、分子内にカルボキシル基を有しないα,β−不飽和二重結合基含有化合物(D)(ただし、オリゴマー(A)に該当するものを除く)を含有することを特徴とする請求項5記載の活性エネルギー線重合性コート剤。
- 更に、樹脂組成物100重量部に対して、活性エネルギー線重合開始剤(E)を0.01〜20重量部を含有してなる請求項5又は6記載の活性エネルギー線重合性接着剤。
- 更に、シラン化合物(F)を含有することを特徴とする請求項5〜7いずれか記載の活性エネルギー線重合性接着剤。
- 分子内に、少なくともα,β−不飽和二重結合基を1個以上有するオリゴマー(A)と、
分子内に1個以上のカルボキシル基を有するα,β−不飽和二重結合基含有化合物(B)(ただし、オリゴマー(A)に該当するものを除く)と、
カルボジイミド化合物(C)とを、
必須成分とする樹脂組成物。 - 樹脂組成物100重量部中、オリゴマー(A)1〜99.8重量部と、分子内に1個以上のカルボキシル基を有するα,β−不飽和二重結合基含有化合物(B)0.1〜49.5重量部と、カルボジイミド化合物(C)0.1〜49.5重量部とを含有してなる請求項9記載の樹脂組成物。
- オリゴマー(A)が、ポリエステル系オリゴマー(a−1)、ポリウレタン系オリゴマー(a−2)、ポリエポキシ系オリゴマー(a−3)及びポリアクリル系オリゴマー(a−4)よりなる群から選ばれた少なくとも1種類以上のオリゴマーであることを特徴とする請求項9又は10記載の樹脂組成物。
- オリゴマー(A)の重量平均分子量が300〜30,000であることを特徴とする請求項9〜11いずれかに記載の樹脂組成物。
- 分子内に1個以上のカルボキシル基を有するα,β−不飽和二重結合基含有化合物(B)の酸価が、100〜1,000mgKOH/gであることを特徴とする請求項9〜12いずれかに記載の樹脂組成物。
- カルボジイミド化合物(C)が、カルボジイミド結合基を分子内に1個以上含有する化合物であることを特徴とする請求項9〜13いずれかに記載の樹脂組成物。
- 更に、分子内にカルボキシル基を有しないα,β−不飽和二重結合基含有化合物(D)(ただし、オリゴマー(A)に該当するものを除く)を含有することを特徴とする請求項9〜14いずれかに記載の樹脂組成物。
- 更に、樹脂組成物100重量部に対して、活性エネルギー線重合開始剤(E)を0.01〜20重量部を含有してなる請求項9〜15いずれかに記載の樹脂組成物。
- 更に、シラン化合物(F)を含有することを特徴とする請求項9〜16いずれかに記載の樹脂組成物。
- 請求項9〜17いずれかに記載の樹脂組成物からなる活性エネルギー線重合性コート剤。
- 請求項9〜17いずれかに記載の樹脂組成物からなる活性エネルギー線重合性接着剤。
- 請求項1〜4いずれか記載の活性エネルギー線重合性コート剤、請求項18記載の活性エネルギー線重合性コート剤、請求項5〜9いずれか記載の活性エネルギー線重合性接着剤または請求項19の活性エネルギー線重合性接着剤からなる層を、基材(G)の片面、又は両面に積層してなることを特徴とする積層体。
- 基材(G)が透明フィルム(H)であることを特徴とする請求項20記載の積層体。
- 透明フィルム(H)が光学フィルム(I)であることを特徴とする21記載の積層体。
- 光学フィルム(I)が、ポリアセチルセルロース系フィルム,ポリノルボルネン系フィルム,ポリプロピレン系フィルム,ポリアクリル系フィルム,ポリカーボネート系フィルム,ポリエステル系フィルム,ポリビニルアルコール系フィルムまたはポリイミド系フィルムであることを特徴とする請求項22記載の積層体。
- 請求項20〜23いずれかに記載の積層体を用いて得られる光学素子用積層体。
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