JP6343909B2 - 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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- JP6343909B2 JP6343909B2 JP2013238658A JP2013238658A JP6343909B2 JP 6343909 B2 JP6343909 B2 JP 6343909B2 JP 2013238658 A JP2013238658 A JP 2013238658A JP 2013238658 A JP2013238658 A JP 2013238658A JP 6343909 B2 JP6343909 B2 JP 6343909B2
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- acrylate
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- 239000010408 film Substances 0.000 claims description 145
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- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 43
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 41
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- 150000004291 polyenes Chemical class 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
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- 229920000098 polyolefin Polymers 0.000 description 1
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- IZCABQCSROGIGG-UHFFFAOYSA-M potassium;2-methylprop-2-ene-1-sulfonate Chemical compound [K+].CC(=C)CS([O-])(=O)=O IZCABQCSROGIGG-UHFFFAOYSA-M 0.000 description 1
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- JNLTYWDDGFTRSX-UHFFFAOYSA-N prop-1-ene-1,1-diol Chemical group CC=C(O)O JNLTYWDDGFTRSX-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Surface Treatment Of Optical Elements (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Liquid Crystal (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polarising Elements (AREA)
- Laminated Bodies (AREA)
Description
これらは、活性エネルギー線で重合し得る樹脂とα,β−不飽和二重結合基を有する単量体のみを含有し、単量体が溶媒の機能をかねていることから塗膜形成時に溶剤が揮発しないという利点があるからである。そして、この活性エネルギー線重合性を有する樹脂として、低分子量のポリエステル系樹脂、ポリウレタン系樹脂、ポリエポキシ系樹脂、ポリアクリル系樹脂等の分子末端にα,β−不飽和二重結合基を有するオリゴマーやα,β−不飽和二重結合基を有する単量体等が利用されている。
また、表示装置には、液晶層を背面から照らして発光させる バックライト方式が普及し、液晶層の下面側にエッジライト型、直下型等のバックライトユニットが装備されている。かかるエッジライト型のバックライトユニットは、基本的には光源としての線状のランプと、ランプに端部が沿うように配置される方形板状の導光板と、導光板の表面側に配設される光拡散シートと、光拡散シートの表面側に配設されるプリズムシートを備えている。最近では、光源に令陰極管(COFL)から色再現性や省電力に優れた発光ダイオード(LED)が使用されるようになってきたため、より耐熱性や寸法安定性の要求が高まってきている。
このようなフィルムは、表層に傷つき防止、指紋付着防止、帯電防止、あるいは易接着化のため、コート剤を介して、コート層を設けたり、接着剤を介して被着体に貼着して光学素子用積層体として表示装置に使用されている。表示装置に用いられるコート剤や接着剤は、まず透明性や耐熱性に優れることが要求されるので、ポリアクリル系樹脂を主剤とする溶剤含有の2液の熱硬化型接着剤や活性エネルギー線重合性接着剤が一般に使用されている。
しかしながら、従来の活性エネルギー線重合性樹脂組成物の重合物には、光学用途に用いるには透明性が劣ることや、各層を構成する材料の寸法変化特性が異なるため、温度や湿度の変化に伴う寸法変化によるソリ(カールともいう)が生じやすかったり、屈折率を自由に選べないこと、また、高屈折率を有するものは接着性が十分でないといった問題点が指摘されている。
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個以上の窒素原子含有の環構造を有する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、分子内にヘテロ原子を含有しない環構造を有するα,β−不飽和二重結合基含有化合物(C)(ただし、オリゴマー(A)に該当するものを除く)とを、必須成分とする樹脂組成物に関する。
また、ヘキサヒドロ無水フタル酸の誘導体((3−メチル−ヘキサヒドロ無水フタル酸、4−メチル−ヘキサヒドロ無水フタル酸)、テトラヒドロ無水フタル酸の誘導体(1,2,3,6−テトラヒドロ無水フタル酸、3−メチル−1,2,3,6−テトラヒドロ無水フタル酸、4−メチル−1,2,3,6−テトラヒドロ無水フタル酸、メチルブテニル−1,2,3,6−テトラヒドロ無水フタル酸等)等の水素添化した無水フタル酸誘導体も脂環族ジカルボン酸無水物として利用できる。
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。
なお、酸価(AV)、水酸基価(OHV)、及び数平均分子量(Mn)の測定方法は後述する。
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個以上の窒素原子含有の環構造を有する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個の窒素原子と少なくとも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)の窒素原子は塩基性が高いため、後述の基材(G)表面の極性基と、酸塩基相互作用や双極子相互作用等の相互作用があるため、本発明の樹脂組成物を後述の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、密着性の向上に大きな効果をもたらし、更には、窒素原子含有のヘテロ環由来のため、塗膜のガラス転移点(Tg)が向上することで、高凝集力を発現し、耐熱性や耐水性等の耐性の良好なコーティング剤層、あるいは接着剤層を形成することが可能となるものである。このような分子内に1個以上の窒素原子含有の環構造を有するα,β−不飽和二重結合基含有化合物(B)としては、環構造に窒素原子だけが1個以上含有している化合物(b1)、環構造に窒素原子と酸素原子との双方を含有している化合物(b2)、および環構造に窒素原子と硫黄原子との双方を含有している化合物(b3)とが挙げられる。
化合物(B)としては、その構造中に1個以上の窒素原子を有するものであれば、特に制限はなく使用でき、α,β−不飽和二重結合基としては、アクリロイル基(bI)、メタクリロイル基(bII)、エテニル基(bIII)、アリル基(bIV)、メタリル基(bV)等が挙げられ、特に制限はない。
bV)>メタクリロイル基(bII)>アクリロイル基(bI)である。
更に、化合物(B)の分子内に1個以上の窒素原子含有の環構造は、5員環以上が好ましい。3、4員環であると、熱や活性エネルギー線によって、開環反応を引き起こす可能性が高いので好ましくない。
本発明において、分子内にヘテロ原子を含有しない環構造を有するα,β−不飽和二重結合基含有化合物(C)としては、上述の化合物(B)やそれ以外のヘテロ環を含まず、シクロアルカン環、シクロアルケン環および/またはベンゼン環のいずれか一つ以上の環構造を有するα,β−不飽和二重結合基含有化合物であることが、耐熱性や耐水性等の耐久性の面から好ましい。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(C)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使用した際には、後述の各種基材(G)との密着性を更に向上させるため、シクロアルカン環、シクロアルケン環および/またはベンゼン環に加え、更に水酸基を有する、分子内にヘテロ原子を含有しない環構造を有し、かつ水酸基を有するα,β−不飽和二重結合基含有化合物(c1)を使用することがよりできる。また、シクロアルカン環、シクロアルケン環および/またはベンゼン環だけで、更に水酸基を有しない、分子内にヘテロ原子を含有しない環構造を有し、かつ水酸基も有しないα,β−不飽和二重結合基含有化合物(c2)は、後述の水酸基含有のα,β−不飽和二重結合基含有化合物(d1)と弊用することで、後述の各種基材(G)との密着性を向上することが可能となる。(c1)および(c2)の選択は、使用目的に応じて選択すればよい。
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等が挙げられる。
オリゴマー(A)が100重量部に対して、化合物(B)と化合物(C)が、それぞれ1重量部以上であると、十分な凝集力が得られ易く耐熱性や耐湿熱性の向上効果が期待できる。
一方、オリゴマー(A)が100重量部に対して、化合物(B)と化合物(C)が、それぞれ500重量部以下であると、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、基材(G)に対する密着性や接着性が向上するので好ましい。
さらに、オリゴマー(A)100重量部に対して、化合物(B)と化合物(C)が、それぞれ10〜300重量部の範囲であると、凝集力、耐熱性、耐湿熱性、接着性および密着性の点で極めて好適である。
本発明の樹脂組成物は、前記、オリゴマー(A)、化合物(B)、及び化合物(C)以外に、分子構造中にα,β−不飽和二重結合基を有するその他の化合物(D)を含有することができる(ただし、オリゴマー(A)に該当するものを除く)。
その他のα,β−不飽和二重結合基含有化合物(D)とは分子構造中にα,β−不飽和二重結合基有する化合物である。化合物(D)としては、粘度が0.5〜2000mPa・sのものが好ましく、1〜1000mPa・sのものが好ましい。このような化合物(D)を用いることによって、オリゴマー(A)、化合物(B)や化合物(C)に起因する樹脂組成物の高粘度化を抑制し、薄膜塗工性を改良しつつ、活性エネルギー線重合性を維持するとともに、後述のコート剤や接着剤の接着力や粘度、あるいは加工性を維持することができる。
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;
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、キサントンフルオレノン、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−チオキサントン、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(アデカ社製)、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、上述の各成分を、当技術分野で周知の方法に従って均一に混合することによって調製することができる。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様々な用途に使用することができる。本発明の一実施形態において、上記樹脂組成物は、好ましくは、コート剤又は接着剤の用途で使用される。
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、必要に応じて、粘度を調整するために、有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。また、溶剤を使用することなく、樹脂組成物を加熱して粘度を低下させることもできる。
樹脂組成物は、重合硬化物のTgが上記のようになるように、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個以上の窒素原子含有の環構造を有するα,β−不飽和二重結合基含有化合物(B)、子内にヘテロ原子を含有しない環構造を有するα,β−不飽和二重結合基含有化合物(C)、(A)、(B)、および(C)以外のその他の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)、活性エネルギー線重合開始剤(E)及びシラン化合物(F)から、適宜化合物を選択してなるものである。(A)、(B)、及び(C)を必須成分とし、いずれの化合物を用いることができる。特に、(B)は、分子内に酸素原子や硫黄原子を含まず、1個以上の窒素原子含有の環構造を有し、エテニル基を有する化合物が好適であり、(C)では、ヘテロ原子を含有しないシクロアルカン環、シクロアルケン環および/またはベンゼン環のいずれか一つ以上の環構造を有するα,β−不飽和二重結合基含有化合物が好適であり、更に水酸基を有する化合物がより好適である。(D)では、水酸基を含有するα,β−不飽和二重結合基含有化合物が好適である。
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。
本発明の一実施形態において、樹脂組成物を活性エネルギー線重合性コート剤(以下、コート剤と称す)として使用され、樹脂組成物は基材(G)の片面や両面を覆うコート層を形成する。このような実施形態において、上記基材(G)は、木材、金属板、プラスチック板、フィルム状基材、ガラス板、紙加工品等であってよく、これらを特に制限なく使用することができる。
本発明における光学用積層体の具体例として、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)、加飾フィルム(タッチパネル用充填シートを意味する)、及び導光フィルム(導光板ともいう)等が挙げられ、光学フィルム(I)と称する。本発明の樹脂組成物を接着剤として使用して、上記光学素子用積層体を、さらに、液晶表示装置、PDPモジュール、タッチパネルモジュール、及び有機ELモジュール等のガラス板に貼着させてもよい。また、別の形態として、本発明の樹脂組成物を接着剤として使用して、上記光学素子用積層体を、上記各種光学フィルム(I)に貼着させてもよい。
(I)第1の透明フィルム(H)(第1の保護フィルム)の一方の主面に、接着剤として本発明の樹脂組成物を塗工し、第1の重合性接着層(2’)を形成する。
第2の透明フィルム(H)(第2の保護フィルム)の一方の主面に、接着剤として本発明の樹脂組成物を塗工し、第2の重合性接着層を形成する。
次いで、ポリビニルアルコール系偏光子の各面に、第1の重合性接着層と、第2の重合性接着層とを、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の重合性接着層及び第2の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。
[配合例1〜37]
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個以上の窒素原子含有の環構造を有する含有化合物(B)、分子内にヘテロ原子を含有しない環構造を有するα,β−不飽和二重結合基含有化合物(C)および、(A)、(B)、および(C)以外のその他の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)、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溶液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、数平均分子量(Mn)と重量平均分子量(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。
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。
[実施例1〜38][比較例1〜7]
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 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「ZF−14」(厚み100μm)を用い、保護フィルム(2)として、三菱レイヨン社製 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、活性エネルギー線重合性接着層との間に上記の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。「△」評価以上の場合、実際の使用時に特に問題ない。
(評価基準)
◎: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。「△」評価以上の場合、実際の使用時に特に問題ない。
ゲル分率(%)={1−(重量1−重量2)/重量1)}×100
(評価基準)
○: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。「△」評価以上の場合、実際の使用時に特に問題ない。
(評価基準)
◎:0mm
○:1mm以下
△:1〜3mm
×:3mm以上
上記偏光板小片を80℃−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。「△」評価以上の場合、実際の使用時に特に問題ない。
(評価基準)
○: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。
各実施例と比較例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。「△」評価以上の場合、実際の使用時に特に問題ない。
(評価基準)
◎: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。
各実施例と比較例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。「△」評価以上の場合、実際の使用時に特に問題ない。
(評価基準)
◎: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、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。「△」評価以上の場合、実際の使用時に特に問題ない。
(評価基準)
◎:0マス
○:1〜10マス
△:11〜30マス
×:31マス以上
各実施例と比較例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。「△」評価以上の場合、実際の使用時に特に問題ない。
(評価基準)
○: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53〜56、61〜85、93では、密着性、及び耐熱性とも優れ、特に問題無い。また、実施例51、52、57〜60、86〜92、94、95では、密着性、および耐熱性のレベルが低いが、使用することが可能である。これに対して比較例11〜17では、特に密着性、あるいは耐熱性に劣ることがわかる。
Claims (14)
- 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、環構造に酸素原子を含有しないが1個以上の窒素原子含有の環構造を有する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、
分子内にヘテロ原子を含有しない環構造を有するα,β−不飽和二重結合基含有化合物(C)(ただし、オリゴマー(A)に該当するものを除く)とを、必須成分とする光学素子用樹脂組成物。 - オリゴマー(A)100重量部に対して、分子内に1個以上の窒素原子含有の環構造を有するα,β−不飽和二重結合基含有化合物(B)1〜500重量部と、分子内にヘテロ原子を含有しない環構造を有するα,β−不飽和二重結合基含有化合物(C)1〜500重量部とを含有してなる請求項1記載の光学素子用樹脂組成物。
- α,β−不飽和二重結合基含有化合物(B)のα,β−不飽和二重結合基が、エテニル基であることを特徴とする請求項1または2に記載の光学素子用樹脂組成物。
- 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1〜3いずれか1項に記載の光学素子用樹脂組成物。
- 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1〜4いずれか1項に記載の光学素子用樹脂組成物。
- 更に、α,β−不飽和二重結合基含有化合物(B)および(C)以外の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1〜5いずれか1項に記載の光学素子用樹脂組成物。
- 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1〜6いずれか1項に記載の光学素子用樹脂組成物。
- 請求項1〜7いずれか1項に記載の光学素子用樹脂組成物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光学素子用活性エネルギー線重合性コート剤。
- 請求項1〜7いずれか1項に記載の光学素子用樹脂組成物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光学素子用活性エネルギー線重合性接着剤。
- 請求項8記載の光学素子用活性エネルギー線重合性コート剤及び/又は請求項9記載の光学素子用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10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請求項11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12記載の積層体。
- 請求項10〜13いずれか1項に記載の積層体を用いて得られる光学素子。
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