JP2017082166A - 感圧式接着剤及び感圧式接着フィルム - Google Patents
感圧式接着剤及び感圧式接着フィルム Download PDFInfo
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- JP2017082166A JP2017082166A JP2015214492A JP2015214492A JP2017082166A JP 2017082166 A JP2017082166 A JP 2017082166A JP 2015214492 A JP2015214492 A JP 2015214492A JP 2015214492 A JP2015214492 A JP 2015214492A JP 2017082166 A JP2017082166 A JP 2017082166A
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- Prior art keywords
- meth
- group
- vinyl
- copolymer
- sensitive adhesive
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- 150000001875 compounds Chemical class 0.000 claims abstract description 197
- 229920001577 copolymer Polymers 0.000 claims abstract description 175
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 54
- 239000000178 monomer Substances 0.000 claims abstract description 40
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 125000003277 amino group Chemical group 0.000 claims abstract description 24
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 claims abstract description 23
- 125000001841 imino group Chemical group [H]N=* 0.000 claims abstract description 19
- 125000001424 substituent group Chemical group 0.000 claims abstract description 12
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- 239000010408 film Substances 0.000 claims description 157
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- 125000000623 heterocyclic group Chemical group 0.000 claims description 31
- 229910000077 silane Inorganic materials 0.000 claims description 27
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 33
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 10
- 150000002513 isocyanates Chemical class 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 9
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- 238000006845 Michael addition reaction Methods 0.000 description 7
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- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 125000005442 diisocyanate group Chemical group 0.000 description 7
- AZDCYKCDXXPQIK-UHFFFAOYSA-N ethenoxymethylbenzene Chemical compound C=COCC1=CC=CC=C1 AZDCYKCDXXPQIK-UHFFFAOYSA-N 0.000 description 7
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- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 6
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
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Abstract
Description
また、表示装置として利用するだけではなく、その表面にタッチパネルの機能を設けて、入力装置として利用されることもある。タッチパネルにも、保護フィルム、反射防止フィルムやITO蒸着樹脂フィルムなどが使用されている。
このようなフィルムは、感圧式接着剤を介して被着体等の基材に貼着して表示装置に使用されている。表示装置に用いられる感圧式接着剤は、まず透明性に優れることが要求されるので、アクリル系樹脂を主剤とする感圧式接着剤が一般に使用されている。
しかし、貼着後の積層体は、一般に、接着性向上のために高温下で一定時間保管した後に検査されるので、その間に剥離強度が高くなって偏光フィルムを剥ぎ取り難くなるばかりでなく、偏光フィルムの再剥離性(リワーク性と称することもある)が低下して剥がした後、ガラス面に糊残りや曇り等の汚染が生じる場合があった。
そこで感圧式接着剤の分子量や感圧式接着剤の架橋度を調整し、接着力を高くすることによって、偏光フィルムの寸法変化に抗して、過酷な環境下でも発泡、浮き、剥がれが生じないようにする試みがなされた。
例えば、感圧式接着光学フィルム用の感圧式接着剤として、α,β−不飽和二重結合基含有化合物を共重合した樹脂に可塑剤などの低分子量体を添加することで、感圧式接着層を適度に軟らかくして応力緩和性を付与する感圧式接着剤が開示されている(例えば特許文献1参照)。
また、電子顕微鏡でなければ確認できない10μm以下の気泡が、中央部に1m2あたり10個程度発生してしまう。
さらに、19インチ以上の表示装置では、見やすさの観点から光源の輝度を高く設定しなければならない。特許文献1に記載される感圧式接着剤を積層して用いてなる光学用の感圧式接着フィルム(光学用接着フィルムとも称す)は、19インチ未満の表示装置では白抜けは問題視されなかった。しかし、架橋剤による架橋収縮や不十分な接着性の影響で、19インチ以上で使用される高輝度の光源を用いた表示装置では白抜けが目立ってしまうという問題も生じた。
さらには、透明性や樹脂、溶剤への溶解性(相溶性)、並びに耐湿熱性を併せ持つ感圧式接着剤が望まれていた。
すなわち、本発明の実施態様は、共重合体を構成する単量体単位として、水酸基を有するα,β−不飽和二重結合基含有化合物(a1)単位と、カルボニル基を有し、水酸基を有しないα,β−不飽和二重結合基含有化合物(a2)単位とを含有する、重量平均分子量200,000〜2,000,000の共重合体(A1)、および共重合体を構成する単量体単位として、アミノ基、イミノ基、ヒドラジノ基および活性水素を有する含窒素ヘテロ環基からなる群より選ばれる1種以上の置換基を有するα,β−不飽和二重結合基含有化合物(a3)単位を含有する、重量平均分子量10,000〜100,000の共重合体(A2)を含有することを特徴とする感圧式接着剤に関する。
また、「(メタ)アクリル」、「(メタ)アクリロイル」、「(メタ)アクリル酸」、「(メタ)アクリレート」、「(メタ)アクリロイルオキシ」、及び「(メタ)アリル」と表記した場合には、特に説明がない限り、それぞれ、「アクリルまたはメタクリル」、「アクリロイルまたはメタクリロイル」、「アクリル酸またはメタクリル酸」、「アクリレートまたはメタクリレート」、「アクリロイルオキシまたはメタクリロイルオキシ」、及び「アリルまたはメタリル」を表すものとする。
本発明の接着剤は、共重合体を構成する単量体単位として、水酸基を有するα,β−不飽和二重結合基含有化合物(a1)単位と、カルボニル基を有し、水酸基を有しないα,β−不飽和二重結合基含有化合物(a2)単位とを含有する、重量平均分子量200,000〜2,000,000の共重合体(A1)を含有することが特徴である。共重合体(A1)は、少なくとも化合物(a1)と、化合物(a2)とを含む単量体の共重合であり、これら単量体を共重合することにより得ることができる。
化合物(a1)は、その構造中に、水酸基と、α,β−不飽和二重結合基とを有する化合物であり、水酸基とα,β−不飽和二重結合基とを有し、環状構造を有しない化合物(a1−1)と、水酸基とα,β−不飽和二重結合基とを有し、環状構造を有する化合物(a1−2)に類別することができる。
化合物(a1−1)としては、基材との密着性を向上させる観点より、(メタ)アクリル酸2−ヒドロキシエチル、(メタ)アクリル酸2−ヒドロキシプロピル、(メタ)アクリル酸4−ヒドロキシブチル等の炭素数2〜18の脂肪酸エステル系(メタ)アクリル酸エステルや、ε−カプロラクトン1〜2mol付加(メタ)アクリル酸2−ヒドロキシエチル等の水酸基含有α,β−エチレン性不飽和二重結合基含有化合物に対してε−カプロラクトンを開環付加することにより得られる炭素数2〜18の末端に水酸基を有する(メタ)アクリル酸エステル、ヒドロキシエチルビニルエーテル等の水酸基含有の脂肪族ビニルエーテル、N−ヒドロキシエチルアクリルアミド等の水酸基含有の(メタ)アクリルアミドといった炭素数2〜18であるα,β−不飽和二重結合基含有化合物が好ましい。
さらに、後述のシラン化合物(B)、または反応性化合物(C)を配合した場合には、シラン化合物(B)に含まれるシロキシ基との縮合反応に伴う架橋反応や反応性化合物(C)に含まれる反応性官能基との架橋反応が進行し、塗工塗膜の凝集力向上が望めるため、光学部材に使用した光学積層体を製造する場合は、耐熱性、耐湿熱性、及び耐水性等が優れるだけで無く、十分な加工性を付与することが容易となる。
次に、共重合体(A1)を構成する単量体単位である、カルボニル基を有し、水酸基を有しないα,β−不飽和二重結合基含有化合物(a2)について説明する。
カルボニル基を有し、水酸基を有しないα,β−不飽和二重結合基含有化合物(a2)は、置換基としてカルボニル基を有するα,β−不飽和二重結合基含有化合物である。ただし、化合物(a2)は、水酸基を有しない。また、α,β−不飽和二重結合基含有化合物の内、(メタ)アクリロイル基等に代表される炭素−炭素二重結合に直接結合した炭素−酸素二重結合は、前記「カルボニル基」には包含されないものとする。
カルボニル基を有し、水酸基を有しない(a2)としては、カルボニル基がアシル基由来のカルボニル基含有化合物(a2−1)、カルボニル基がエステル基由来のカルボニル基含有化合物(a2−2)、カルボニル基がカルボキシル基由来のカルボニル基含有化合物(a2−3)に類別できる。ただし、カルボキシル基として、酸無水物基(−C(=O)OC(=O)−)も含まれる。具体例として、以下の化合物が挙げられる。
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化合物類;
アミノ基、イミノ基、ヒドラジノ基、活性水素を有する含窒素ヘテロ環基からなる群より選ばれる1種以上の置換基とカルボニル基の反応性は、(反応性高)ホルミル基≧アシル基(ホルミル基を除く)>カルボキシル基>エステル基(反応性低)の順番であり、これらの反応性の差はアミノ基、イミノ基、ヒドラジノ基、活性水素を有する含窒素ヘテロ環基からなる群より選ばれる1種以上の置換基が求核剤として作用するため、カルボニル炭素が正電荷に帯電する度合いで決定される。
このように、カルボニル基を有するα,β−不飽和二重結合基含有化合物(a2)を、共重合体を構成する単量体単位として使用した共重合体(A1)を配合した感圧式接着剤は、耐熱性や耐湿熱性等の耐久性を著しく向上させることが可能となる。
化合物(a1)および化合物(a2)を、それぞれ0.1重量%以上含有すると、後述の共重合体(A2)との架橋反応が起こり易く、架橋樹脂のガラス転移温度(Tg)向上に繋がり、凝集力の向上が期待できる。また、後述のシラン化合物(B)や反応性化合物(C)を、さらに配合して感圧式接着剤として使用した場合には、共重合体(A1)に含まれる水酸基と、シラン化合物(B)に含まれるシロキシ基との縮合反応や反応性化合物(C)に含まれる反応性官能基との架橋反応が進行し、架橋樹脂の凝集力を制御することが可能となる。
また、化合物(a1)および化合物(a2)が、それぞれ30重量%以下であると、架橋樹脂のTgが適度に制御され、十分な粘着性(タックとも称す)を確保できるため、接着力の向上に繋げることが可能となる。
次に共重合体(A2)について説明する。
共重合体(A2)は、共重合体を構成する単量体単位として、アミノ基、イミノ基、ヒドラジノ基および活性水素を有する含窒素ヘテロ環基からなる群より選ばれる1種以上の置換基を有するα,β−不飽和二重結合基含有化合物(a3)単位を含有する、重量平均分子量10,000〜100,000の共重合体である。ただし、化合物(a3)は、化合物(a1)および化合物(a2)を除くものである。
活性水素を有する含窒素飽和ヘテロ環基を含有するα,β−不飽和二重結合基含有化合物類としては、アゼチジノ基を有するビニル化合物類、ピロリジル基を有するビニル化合物類、ピペリジル基を有するビニル化合物類、ピペラジル基を有するビニル化合物類等が挙げられる。
活性水素を有する含窒素不飽和ヘテロ環基を含有するビニル化合物類としては、ピローリル基を有するアルケニル基含有化合物類、イミダゾリル基を有するα,β−不飽和二重結合基含有化合物類、インダゾリル基を有するビニル化合物類、ベンゾイミダゾリル基を有するビニル化合物類、ピラゾリル基を有するアルケニル基含有化合物類等が挙げられる。
化合物(a3)を0.1重量%以上含有すると、、架橋樹脂のTg向上に繋がり、凝集力の向上が期待できる。また、化合物(a3)が30重量%以下であると、架橋樹脂のTgが適度に制御され、十分な粘着性(タックとも称す)を確保できるため、接着力の向上に繋げることが可能となる。
化合物(a4)を構成単量体の一部として使用することにより、共重合体(A1)または共重合体(A2)を構成する単量体単位である化合物(a1)、化合物(a2)または化合物(a3)との共重合反応の効率化を図ることが容易となることがある。また、共重合体(A1)または共重合体(A2)それぞれを容易に低粘度化できるとともに、塗工時の作業性を向上させることが容易となることがある。
さらに、共重合体(A1)または共重合体(A2)の重量平均分子量(Mw)を適度に制御可能としたり、塗工物のガラス転移温度(以下、Tgと称す)を制御させて粘着性(タックとも称す)を向上したり、塗膜の凝集力を向上させて、耐熱性や耐水性等の耐性の良好な接着層を形成することが可能となることがある。
化合物(a4)のなかでも、単独重合体(ホモポリマーとも称す)のTgが、−80〜0℃であり、炭素数2〜20のアルキル基を有するα,β−不飽和二重結合基含有化合物(a4−1)を共重合反応の単量体単位として使用することが好ましい。化合物(a4−1)を共重合反応の単量体単位として使用することにより、共重合体(A1)または共重合体(A2)のタックが向上し、また共重合体(A1)と共重合体(A2)との相溶性を適度に制御することができるため、感圧式接着剤としてより好適に使用することが可能となる。
しかも、共重合体(A1)中の水酸基が、ミクロスケールで接着剤全体に均一に分布しているので、共重合体(A1)中のカルボニル基と、共重合体(A2)中の、アミノ基、イミノ基、ヒドラジノ基または活性水素を有する含窒素ヘテロ環基とのマイケル付加反応を促進する触媒的な効果を付与するだけでなく、共重合体(A2)との相溶性の制御が可能となり、後述の基材(G)に塗工した際に、塗膜の透明性を維持し易く、また濡れ性も向上する。
更に、共重合体(A1)のMwが、共重合体(A2)のMwよりも大きいことが好ましい。共重合体(A2)のMwが、共重合体(A1)よりも小さいと、共重合体(A1)中への共重合体(A2)の侵入が容易となるため好ましい。
なお、上記重量平均分子量及び数平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)法により測定したポリスチレン換算の値である。GPCの測定法の詳細は、実施例に記載する。
共重合体(A1)のTgは、−80〜0℃の範囲が好ましく、共重合体(A2)のTgは、0〜100℃の範囲が好ましい。共重合体(A1)及び共重合体(A2)のTgが、上記の範囲内であると、本願の感圧式接着剤を使用した接着層は、効果的にIPN構造を形成しやすくなり、耐熱性や耐湿熱性等の耐久性を向上することが可能となる。
<FOX式>1/Tg=W1/Tg1+W2/Tg2+…+Wi/Tgi+…+Wn/Tgn
〔上記FOX式は、n種のα,β−不飽和二重結合基含有化合物からなる重合体を構成する各化合物の単独重合体のガラス転移温度をTgi(K)とし、各化合物の質量分率を、Wiとしており、(W1+W2+…+Wi+…Wn=1)である。〕
次に、シラン化合物(B)について説明する。本発明の感圧式接着剤の一実施形態において、感圧式接着剤は、上記成分に加えて、シラン化合物(B)を併用することで、シラン化合物同士の自己縮合反応や基材(G)表面の極性基との間で化学結合や物理吸着等の相互作用が進行し、感圧式接着剤の接着力を向上させることができる。特に、ガラスや金属箔、金属蒸着フィルム、金属板、または無機フィラー含有のフィルム等の無機材料表面に対し、相互作用が高いため、接着強度を向上させることが容易となる。
次に、共重合体(A1)中の水酸基と反応し得る官能基を有する反応性化合物(C)について説明する。
本発明の感圧式接着剤の一実施形態において、感圧式接着剤は、上記必須成分に加えて、共重合体(A1)中の水酸基と反応し得る官能基を分子内に有する反応性化合物(C)を含んでもよい。
反応性化合物(C)は、共重合体(A1)中の水酸基と反応し、本願の感圧式接着剤を用いた接着層に形成されたIPN構造を固定化するだけでなく、感圧式接着剤の架橋分子量を向上させ、凝集力をさらに向上させる役割を持つ。また、反応性化合物(C)は、後述する基材(G)表面との化学結合や物理吸着等の相互作用を向上させる効果が期待できる。例えば、コロナ放電処理等の物理処理、酸などで改質された化学処理のなされた基材に対しては、反応性化合物(C)中の反応性官能基を基材と化学反応させることで、共重合体(A1)と基材との間に物理的、または化学的な結合形成に伴う強固な相互作用を発現させることも可能となる。
錫系化合物としては、例えば、ジブチル錫ジクロライド、ジブチル錫オキサイド、ジブチル錫ジブロマイド、ジブチル錫ジマレエート、ジブチル錫ジラウレート(別名:DBTDL)、ジブチル錫ジアセテート、ジブチル錫スルファイド、トリブチル錫スルファイド、トリブチル錫オキサイド、トリブチル錫アセテート、トリエチル錫エトキサイド、トリブチル錫エトキサイド、ジオクチル錫オキサイド、トリブチル錫クロライド、トリブチル錫トリクロロアセテート、2−エチルヘキサン酸錫等が挙げられる。
非錫系化合物としては、例えば、ジブチルチタニウムジクロライド、テトラブチルチタネート、ブトキシチタニウムトリクロライドなどのチタン系、オレイン酸鉛、2−エチルヘキサン酸鉛、安息香酸鉛、ナフテン酸鉛などの鉛系、2−エチルヘキサン酸鉄、鉄2,4−ペンタジオネートなどの鉄系、安息香酸酸コバルト、2−エチルヘキサン酸コバルトなどのコバルト系、ナフテン酸亜鉛、2−エチルヘキサン酸亜鉛などの亜鉛系、ナフテン酸ジルコニウムなどが挙げられる。
カルボジイミド化触媒としては、1−フェニル−2−ホスホレン−1−オキシド、3−メチル−2−ホスホレン−1−オキシド、1−エチル−3−メチル−2−ホスホレン−1−オキシド、1−エチル−2−ホスホレン−1−オキシド、あるいはこれらの3−ホスホレン異性体等のホスホレンオキシドを利用することができる。
本発明の感圧式接着剤の一実施形態において、本発明による効果を損なわない範囲であれば、感圧式接着剤には、上記必須成分に加えて、その他の成分(P)を適宜配合することも可能である。
その他の成分(P)としては、例えば、重合硬化収縮率低減、熱膨張率低減、寸法安定性向上、弾性率向上、粘度調整、熱伝導率向上、強度向上、靭性向上、及び着色向上等の観点から、有機又は無機の充填剤を配合することができる。このような充填剤は、ポリマー、セラミックス、金属、金属酸化物、金属塩、及び染顔料等の材料から構成されるものであってよい。また、その形状については、特に限定されず、例えば、粒子状及び繊維状等であってよい。なお、上記ポリマー系の材料を配合する場合には、柔軟性付与剤、可塑剤、難燃化剤、保存安定剤、酸化防止剤、紫外線吸収剤、チクソトロピー付与剤、分散安定剤、流動性付与剤、タッキファイヤー、帯電防止剤及び消泡剤等の、独立した充填剤としてではなく、ポリマーブレンド又はポリマーアロイとして、感圧式接着剤中に、溶解、半溶解又はミクロ分散させることも可能である。
次に感圧式接着剤について説明する。「感圧式接着剤」とは、慣用的には粘着剤とも称し、接着剤の固化によらず、粘稠な性質を有し、常温で短時間、圧力を加えるだけで接着する接着剤のことを意味する。
本発明の感圧式接着剤は、上で述べた共重合体(A1)および共重合体(A2)を含む事が特徴であり、必要に応じて、シラン化合物(B)、反応性化合物(C)、その他の成分(P)を適宜配合したものである。
したがって、塗膜形成の観点から、感圧式接着剤の粘度は、25℃にてB型粘度計で測定した際の粘度が、500〜8,000mPa・sの範囲であることが好ましく、1,000〜5,000mPa・sの範囲であることがより好ましい。粘度が8,000mPa・s以下の場合、塗工によって基材(G)上に0.5〜300μmの薄膜を容易に形成することができ、透過率等の光学的特性を高めることも容易である。一方、粘度が500mPa・s以上の場合、感圧式接着剤から形成する樹脂層の膜厚を制御することが容易である。本実施形態において、接着剤層の膜厚、粘度、あるいは不揮発分濃度は、積層体の用途に応じて設定される。
次に感圧式接着フィルムについて、説明する。
本発明の感圧式接着フィルムは、後述の基材(G)上に上記の感圧式接着剤からなる接着層が形成されたものである。感圧式接着フィルムの製造方法として、例えば、表面を剥離処理したシート状基材(剥離ライナーとも称す)の剥離処理面に感圧式接着剤を塗工、乾燥し、基材(G)を貼り合わせて作成する方法、または基材(G)に感圧式接着剤を直接塗工、乾燥し、接着層の表面に剥離ライナーの剥離処理面を貼り合わせて作成する方法が挙げられる。
例えば、偏光フィルムは偏光板とも呼ばれ、ポリビニルアルコール系偏光子の片面又は両面に、ポリノルボルネン系フィルムであるポリシクロオレフィ系フィルム、ポリアクリル酸エステル系樹脂のフィルム、ポリカーボネート系フィルム、またはポリエステル系フィルム等のフィルムを積層した多層構造フィルムである。偏光フィルムの場合、高温雰囲気及び高温高湿雰囲気に放置されたときにも、接着層は応力緩和性が良好であるため偏光フィルムの反りに起因する光漏れを抑制できる。
(合成例1)
重合槽、攪拌機、温度計、還流冷却器、滴下装置、窒素導入管を備えた重合反応装置の反応槽及び滴下装置に、下記単量体、重合開始剤及び有機溶剤をそれぞれ下記の比率で仕込んだ。
アクリル酸n−ブチル(a4−1) 46部
アクリル酸2−ヒドロキシエチル(a1−1) 1部
N−(1,1−ジメチル−3−オキソブチル)アクリルアミド(a2−1) 6部
アセトン(有機溶剤) 33部
V−65(重合開始剤) 0.05部
[滴下装置]
アクリル酸n−ブチル(a4−1) 46部
アクリル酸2−ヒドロキシエチル(a1−1) 1部
アセトン(有機溶剤) 33部
V−65(重合開始剤) 0.05部
表1に記載した材料を、化合物(a2)は全て重合槽に仕込み、化合物(a1)、化合物(a4)、有機溶剤及び重合開始剤は、重合槽と滴下装置にそれぞれ半量ずつ仕込むように変更した以外は、合成例1と同様の方法で、それぞれ共重合体(A1)を合成した。得られた共重合体溶液の溶液外観、不揮発分濃度(NV)、溶液粘度(Vis)、共重合体の重量平均分子量(Mw)及びガラス転移温度(Tg)を、後述の方法に従って求め、結果を表1に示した。尚、表1に記載された単量体として使用した化合物は、重合槽への仕込み量と滴下装置への仕込み量との合計値(部)を表す。
(合成例51)
重合槽、攪拌機、温度計、還流冷却器、滴下装置、窒素導入管を備えた重合反応装置の反応槽及び滴下装置に、下記単量体、重合開始剤及び有機溶剤をそれぞれ下記の比率で仕込んだ。
酢酸エチル(有機溶剤) 105部
V−65(重合開始剤) 1部
[滴下装置]
アクリル酸n−ブチル(a4−1) 38部
アクリル酸メチル(a4−2) 40部
メタクリル酸メチル(a4−2) 20部
アクリル酸N−メチルアミノエチル(a3) 2部
酢酸エチル(有機溶剤) 45部
V−65(重合開始剤) 1部
表2に記載した材料を、化合物(a3)、化合物(a4)、化合物(a1)は全て滴下装置に仕込み、重合開始剤は、重合槽と滴下装置に半量ずつ仕込み、また有機溶剤は、重合槽/滴下装置=7/3(重量比率)の割合で仕込むように変更した以外は、合成例51と同様の方法で、それぞれ共重合体を合成した。得られた共重合体溶液の溶液外観、不揮発分濃度(NV)、溶液粘度(Vis)、共重合体の重量平均分子量(Mw)及びガラス転移温度(Tg)を、後述の方法に従って求め、結果を表2に示した。尚、表2に記載された単量体として使用した化合物は、重合槽への仕込み量と滴下装置への仕込み量との合計値(部)を表す。
各合成例で得られた共重合体の溶液外観を目視にて観察した。無色透明であれば良好である。
各合成例で得られた共重合体の溶液、約1gを金属容器に秤量し、150℃オーブン中にて20分間乾燥して、残分を秤量して残率計算をし、不揮発分濃度(固形分)とした(単位:%)。
各合成例で得られた共重合体溶液を25℃でB型粘度計(東機産業社製 TV−22)にて、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)を用いた。数平均分子量(Mn)と重量平均分子量(Mw)の決定は、標準物質であるポリスチレンの換算値とした。
装置名: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」
カラム:東ソー社製GMHXL:4本、東ソー社製HXL-H:1本を直列に連結した。
移動相溶媒 : テトラヒドロフラン(THF)
流量 : 1.0ml/分
カラム温度 : 40℃
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。
試料約10mgを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分間保持した後、液体窒素を用いて−120℃まで急冷した。その後、昇温速度10℃/分で昇温し、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。
・化合物(a1−1)
2HEA:アクリル酸2−ヒドロキシエチル、4HBA:アクリル酸4−ヒドロキシブチル、4HBMA:メタクリル酸4−ヒドロキシブチル、HEVE:ヒドロキシエチルビニルエーテル、NHAA:N−ヒドロキシエチルアクリルアミド
・化合物(a1−2)
HPPA:アクリル酸2−ヒドロキシ−3−フェノキシプロピル
・化合物(a2−1)
DAAM:N−(1,1−ジメチル−3−オキソブチル)アクリルアミド、AAEM:メタクリル酸2−オキソブタノイルエチル、MCEA:アクリル酸(メトキシカルボニル)エチル、AVPC:アセトプロピオン酸ビニル、AAVE:2−アセトアセトキシエチルビニルエーテル
・化合物(a2−2)
PAV:プロピオン酸ビニル
・化合物(a2−3)
CEA:アクリル酸2−カルボキシエチル
・化合物(a4−1)
BA:アクリル酸n−ブチル、2EHA:アクリル酸2−エチルヘキシル、LMA:メタクリル酸ラウリル
・化合物(a3)
NMEA:アクリル酸N−メチルアミノエチル、HDA:アクリル酸ヒドラジド、TMPMA:メタクリル酸テトラメチルピペリジニル、VIM:2−ビニルイミダゾール、ARAM:アリルアミン
・化合物(a4−2)
MA:アクリル酸メチル、MMA:メタクリル酸メチル、PHEA:アクリル酸フェノキシエチル、AA:アクリル酸
・重合開始剤
V65:2,2’−アゾビス(2,4−ジメチルバレロニトリル) [和光純薬工業社製「V65」]、PBO:t−ブチルパーオキシ−2−エチルヘキサノエート [日油社製「パーブチルO」]
・有機溶剤
Ace:アセトン、MEK:メチルエチルケトン、MeAc:酢酸メチル、EAc:酢酸エチル
なお、表1及び表2中の有機溶剤の欄で、「EAc/EAc」という表記は、「共重合体重合時の有機溶剤/希釈溶剤」ということを表し、共重合体重合時の有機溶剤はEAcを使用し、希釈溶剤はEAcを使用したことを意味する。
(実施例1〜90、比較例1〜10)
各合成例で得られた共重合体(A1)と共重合体(A2)を、表3に記載した重量比(部)に従い、併せて合計100部となるように配合し、必要に応じて、シラン化合物(B)、反応性化合物(C)、その他の成分(P)を、表3に挙げた重量比(部)で配合し、酢酸エチルを加えて不揮発分濃度30%となるように調製して感圧式接着剤を得た。得られた感圧式接着剤を、各基材に塗工、乾燥、及び貼り合わせを施し、感圧式接着フィルムを作成し、以下の方法で評価した。それぞれの結果を表3に示す。
各感圧式接着剤について、粘度変化と溶液層の分離や沈殿物の発生等の外観変化を3段階で評価した。尚、感圧式接着剤の粘度は、感圧式接着剤を調製直後、5、25及び40℃において1ヶ月間保存した後について、B型粘度計(東京計器社製)を用い、25℃、12rpm、1分間回転の条件で測定し、粘度変化と溶液層の分離や沈殿物の発生等の外観変化を3段階で評価した。「○」または「△」評価の場合、実際の使用時に支障はない。
○:溶液層の分離や沈殿物の発生もなく、1ヶ月までの粘度上昇率が50%未満。良好。
△:溶液層の分離や沈殿物の発生もなく、1ヶ月までの粘度上昇率が50%以上100%未満。使用可。
×:1ヶ月以内にゲル化するか、または粘度上昇率が100%以上、あるいは溶液層の分離や沈殿物の発生が認められた。不良。
ここで、粘度上昇率は、下記の方法で算出した。
粘度上昇率(%)=100×{(1ヶ月間保存後の粘度)−(調製直後の粘度)}/(調製直後の粘度)
各感圧式接着剤を、基材として厚さ38μmの剥離処理されたポリエチレンテレフタレートフィルム(セラピールMF:東レフィルム加工社製)(以下、「剥離ライナー」という。)上に、乾燥後の厚さが25μmになるように塗工し、100℃で2分間熱風乾燥することで接着層を形成した。次いで、上記塗工面に100μm厚のポリエチレンテレフタレートフィルム(PETフィルム)を貼り合せて、接着フィルムを作製した。そして剥離フィルムを剥がした後の接着層表面(塗工面)の状態を目視にて観察し、3段階で評価した。「○」または「△」評価の場合、実際の使用時に支障ない。
○:平滑な塗工面が得られた。良好。
△:塗工面の端部に若干のハジキや発泡が認められる。実用上使用可。
×:塗工面にハジキ、発泡やスジ引きが認められた。不良。
上記《塗工性の評価》と同じ方法により作成した各接着フィルムを、幅25mmに裁断し、剥離ライナーを剥がし、露出した接着層を厚さ100μmの無アルカリガラス板に23℃、相対湿度50%の環境下で、ラミネータを用いて貼着した。続いて、50℃、5気圧の条件のオートクレーブ内に20分間保持して測定試料を得た。前記測定試料を、23℃で1日間放置した後に、23℃、相対湿度50%の環境下で、引張試験機(オリエンテック社製「テンシロン」)を用いて、剥離速度300mm/分、剥離角度180度の条件で剥離強度を測定した(貼合せ1日後の剥離強度測定)。また、前記測定試料を、23℃で14日間放置した後に、同様の方法で剥離強度を測定した(貼合せ14日後の剥離強度測定)。この剥離強度を接着力として3段階で評価した。「○」または「△」評価の場合、実際の使用時に支障ない。
○:剥離強度が8.0(N/25mm)以上12.0(N/25mm)未満。良好。
△:剥離強度が5.0(N/25mm)以上8.0(N/25mm)未満、あるいは剥離力が12.0(N/25mm)以上15.0(N/25mm)未満。実用可。
×:剥離強度が5.0(N/25mm)未満、あるいは15.0(N/25mm)以上。不良。
感圧式接着剤を、上記剥離ライナー上に、乾燥後の厚さが25μmになるように塗工し、100℃で2分間熱風乾燥することで接着層を形成した。次いで、別途用意した剥離ライナーを接着層に貼り合せて、接着層が剥離ライナーで挟持された試料を作製した。次に、両方の剥離ライナーを取り除き、接着層の外観を目視判定するとともに、ヘーズを「NDH−300A(日本電色工業社製)」で測定した。「○」または「△」評価の場合、実際の使用時に支障ない。
○:曇り等が観察されず、かつヘーズ:0.5未満。良好。
△:曇り等は観察されないが、ヘーズ:0.5以上2未満、実用上支障無く使用できる。
×:曇りが観察される、またはヘーズ:2以上。不良。
上記接着フィルムを、幅100mm×長さ100mmに裁断し、これを30枚重ね、40℃−60Kg/cm2の条件で1時間プレスした際の接着フィルム端部からの接着層のはみ出しの様子を以下のように3段階で評価した。「○」または「△」評価の場合、実際の使用時に支障ない。
○:接着層のはみ出しが観測されない。良好。
△:0.3mm未満の接着層のはみ出しが観測されるが、実用上使用可能。
×:0.3mm以上の接着層のはみ出しが観測される。不良。
接着フィルムを、幅100mm×長さ100mmに裁断し、剥離ライナーを剥離して、ポリカーボネート(PC)板に貼り合わせて固定し、50℃雰囲気下で0.5MPaの圧力をかけ20分間オートクレーブ内に保持して「ポリエステルフィルム/接着層/PC板」なる構成の層構造を有する試験片(積層体)を作製した。上記試験片を用いて、80℃のオーブン中で24時間熱処理(耐熱性試験)を行った。この耐熱性試験後、試験片の接着界面(接着層とPC板との界面)を目視にて観察し、3段階で評価した。「○」または「△」評価の場合、実際の使用時に支障ない。
○:気泡や浮きが全く認められず、良好。
△:細かい気泡や浮きが若干端部に認められるが、実用上使用可能。
×:全面的に気泡や浮きが認められた。不良。
感圧式接着剤を、基材として厚さ38μmの剥離処理されたポリエチレンテレフタレートフィルム(セラピールMF:東レフィルム加工株式会社製)(以下、「剥離ライナー」という。)上に、乾燥後の厚さが25μmになるように塗工し、100℃で2分間熱風乾燥することで接着層を形成した。
次いで、この接着層に、光学フィルム(I)として、ポリビニルアルコール(PVA)系偏光フィルムの両面をトリアセチルセルロース系フィルム(以下、「TACフィルム」という)で挟んだ積層構造の偏光フィルム(HLC2−5618:SANRITZ製)の片面を貼り合せ、次いで、温度35℃相対湿度55%の条件で1週間熟成させて「剥離ライナー/接着層/TACフィルム/PVA/TACフィルム」という構成の光学用接着フィルム(偏光フィルム接着シートとも称す)を得た。
上記の偏光フィルム接着シートの吸収軸の軸方向が、長辺に対して45°の角度になるように、80mm×150mmに裁断した。次に、剥離ライナーを剥がし、露出した接着層を厚さ0.4mmの無アルカリガラス板の両面に、それぞれの吸収軸の軸方向が直交するように配置して、50℃雰囲気下で5Kg/cm2の圧力を加え、20分間オートクレーブ内に保持して貼り合せた後、80℃の雰囲気中に500時間放置した後に25℃に戻し、四隅もしくは周辺端部からの光漏れ現象の有無を目視で観察し、光漏れ性として3段階で評価した。「○」または「△」評価の場合、実際の使用時に支障ない。
○:光漏れが認められない。良好。
△:光漏れがやや目立つが、実用上使用可能。
×:光漏れが極めて顕著である。不良。
上記の偏光フィルム接着シートを25mm×150mmの大きさに裁断し、剥離ライナーを剥がし、厚さ1.1mmのフロートガラス板にラミネータを用いて貼り付け、50℃で5気圧の条件のオートクレーブ内に20分保持させて、偏光フィルム接着シートとガラス板との積層体を得た。
この積層体の偏光フィルムを180度方向に300mm/分の速度で引き剥がし、剥離後のガラス表面の曇りを目視で観察し、3段階で評価した。「○」または「△」評価の場合、実際の使用時に支障ない。
○:曇りがなく、実用上全く問題がない。非常に良好。
△:若干曇りが認められるが、実用上問題ない。良好。
×:全面的に感圧式接着剤の転着が認められ、実用不可である。
上記の偏光フィルム接着シートの剥離ライナーを剥がし、露出した接着層を厚さ0.4mmの無アルカリガラス板の片面に、50℃雰囲気下で5Kg/cm2の圧力を加え、20分間オートクレーブ内に保持して貼り合せた後、80℃の雰囲気中に500時間放置した(耐熱性試験)。また、同様にして、60℃−相対湿度90%の恒温恒湿槽に500時間放置した(耐湿熱性試験)。
放置後、25℃に戻し、偏光フィルム接着シートの浮き・剥がれ、発泡、クラックの発生状態を目視で観察し、3段階で評価した。「○」または「△」評価の場合、実際の使用時に支障ない。
発泡とは、感圧式接着層とガラスとの界面(周辺端部以外)に比較的大きな気泡が発生している状態である。
浮き・剥がれとは、偏光フィルム接着シートがガラスから浮き上がり、剥がれてしまっている状態である。
クラックとは、偏光フィルム接着シートの周辺端部に、直径1mm以下の細かい気泡がスジ状に連なるように発生している状態である。
それぞれの評価基準は以下の通りである。
○:発泡、浮き・剥がれやクラックが全く発生せず。良好。
△:0.5mm以下の発泡、浮き、剥がれ、クラックのいずれかの軽微な発生が認められるが、実用上使用可能。
×:全面的に発泡、浮き、剥がれ、クラック等、顕著な発生が認められる。実用上使用不可。
・共重合体(A1)
表1記載の各合成例で得られた共重合体(合成例1〜31)
・共重合体(A2)
表2記載の各合成例で得られた共重合体(合成例51〜70)
・化合物(B)
MAS:3−アミノプロピルトリメトキシシラン 、HTS:ヘキシルトリメトキシシラン、EPS:3−グリシドキシプロピルトリメトキシシラン、EAS:ジエチルアミノトリメチルシラン
・化合物(C)
TDI/TMP:トリレンジイソシネートのトリメチロールプロパンアダクト体、XDI/TMP:キシリレンジイソシネートのトリメチロールプロパンアダクト体、V05:カルボジイミド [日清紡ケミカル株式会社製「カルボジライトV−05」]、HBAP:2,2’−ビスヒドロキシメチルブタノールトリス[3−(1−アジリジニル)プロピオネート]、ALAA:アルミニウムトリス(アセチルアセトネート)、TGXA:N,N,N’,N’−テトラグリシジル−m−キシリレンジアミン
・その他の成分(P)
AO50:フェノール系酸化防止剤 [アデカ社製「アデカスタブ AO−50」]
また、実施例2、3、18,19,20〜23、27、28においては、各評価の「△」評価(実用可能レベル)が13項目中4〜13個であり、「×」評価(不良レベル)が一つもないため、実用上支障なく使用することが可能である。
これに対して、比較例1〜10では、溶液経時安定性、塗工性、剥離強度、光学特性、加工性、耐発泡剥がれ性、光漏れ性、リワーク性、耐熱性、及び耐湿熱性のいずれかが極端に劣ることがわかる。
Claims (10)
- 共重合体を構成する単量体単位として、水酸基を有するα,β−不飽和二重結合基含有化合物(a1)単位と、カルボニル基を有し、水酸基を有しないα,β−不飽和二重結合基含有化合物(a2)単位とを含有する、重量平均分子量200,000〜2,000,000の共重合体(A1)、および
共重合体を構成する単量体単位として、アミノ基、イミノ基、ヒドラジノ基および活性水素を有する含窒素ヘテロ環基からなる群より選ばれる1種以上の置換基を有するα,β−不飽和二重結合基含有化合物(a3)単位を含有する、重量平均分子量10,000〜100,000の共重合体(A2)を含有することを特徴とする感圧式接着剤。 - 共重合体(A1)を構成する全単量体単位中、
化合物(a1)単位を0.1〜30重量%、
化合物(a2)単位を0.1〜30重量%、
含有することを特徴とする請求項1記載の感圧式接着剤。 - 共重合体(A2)を構成する全単量体単位中、
化合物(a3)単位を0.1〜30重量%、
含有することを特徴とする請求項1または2記載の感圧式接着剤。 - 共重合体(A1)と共重合体(A2)との重量比が、共重合体(A1)/共重合体(A2)=0.9/0.1〜0.5/0.5の範囲内であることを特徴とする請求項1〜3のいずれかに記載の感圧式接着剤。
- 共重合体(A1)と共重合体(A2)との合計100重量部に対して、さらにシラン化合物(B)を0.01〜10重量部含有することを特徴とする請求項1〜4いずれか記載の感圧式接着剤。
- さらに、共重合体(A1)中の水酸基と反応し得る官能基を有する反応性化合物(C)を含有することを特徴とする請求項1〜5いずれか記載の感圧式接着剤。
- 請求項1〜6いずれか記載の感圧式接着剤から形成された接着層が、基材(G)の少なくとも一方の面に積層された感圧式接着フィルム。
- 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7記載の感圧式接着フィルム。
- 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請求項8記載の感圧式接着フィルム。
- 基材(G)と、請求項1〜6いずれか記載の感圧式接着剤から形成された接着層と、ガラスとが、順次積層された積層体。
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