JP2016156004A - 活性エネルギー線重合性樹脂組成物および積層体 - Google Patents
活性エネルギー線重合性樹脂組成物および積層体 Download PDFInfo
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- JP2016156004A JP2016156004A JP2016020473A JP2016020473A JP2016156004A JP 2016156004 A JP2016156004 A JP 2016156004A JP 2016020473 A JP2016020473 A JP 2016020473A JP 2016020473 A JP2016020473 A JP 2016020473A JP 2016156004 A JP2016156004 A JP 2016156004A
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- acrylate
- acrylic acid
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Abstract
Description
このような薄膜を工業的に設けるには、活性エネルギー線重合性樹脂組成物をフィルム等に塗工する際、小径グラビアコーターを用いることが好ましい。小径グラビアコーターは、より細かい凹版を用いることによって薄膜を形成できる。しかし、フィルム等への活性エネルギー線重合性樹脂組成物の濡れ性が悪い場合、0.1〜3μmのような薄膜の活性エネルギー線重合性樹脂組成物層を形成しようとすると、塗工した際にハジキによる塗膜欠陥や平滑性が不十分であるという問題があった。なお、通常活性エネルギー線重合性樹脂組成物は薄膜であるほどハジキが発生しやすく、3μm以上ではハジキが発生しない場合でも0.1〜3μmのような薄膜ではハジキが発生することがある。一般的に、フィルムの表面にコロナ処理やプラズマ処理を施すことによって、フィルムの表面自由エネルギーを高くし、濡れ性を向上させることはできる。しかし、コロナ処理やプラズマ処理は均一に放電することが困難であり部分的にコロナ処理やプラズマ処理されない部分や処理の弱い部分が発生する。その結果、ハジキが生じることがある。つまり、コロナ処理やプラズマ処理だけでは、まだ不十分であり、活性エネルギー線重合性樹脂組成物の濡れ性を上げることが求められている。
このような課題に対し、一般的な濡れ剤の添加により、表面張力を下げ濡れ性を向上させることは可能ではある。濡れ剤としてはシリコーン系やアクリル樹脂系、ポリエステル系、ポリエーテル系、脂肪酸エステル系などが知られているが、一般的な濡れ剤は、活性エネルギー線重合性樹脂組成物との相溶性が悪いことが多く、活性エネルギー線重合性樹脂組成物が白濁して透明性が損なわれてしまうことがあった。さらに、活性エネルギー線重合性樹脂組成物をフィルムに塗工した場合、濡れ剤は活性剤の機能があるため、活性エネルギー線重合性樹脂組成物とフィルムの界面に移行し、硬化後、密着阻害を引き起こすことが問題であった。
分子量が500未満のα,β−不飽和二重結合基含有化合物(A)(以下、「化合物(A)」ともいう)について説明する。化合物(A)は、樹脂組成物の主成分であり、分子量が500未満であることにより、実質的に有機溶媒が含有しなくても樹脂組成物の低粘度化が可能になり、塗工時の塗膜平滑性等の薄膜塗工適性に優れた作用を及ぼす。化合物(A)は、さらに好ましくは分子量300未満であり、より薄膜塗工をし易くなる。
例えば、(メタ)アクリル酸2−ヒドロキシエチル、(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、シクロヘキサンジメタノールモノ(メタ)アクリル酸エステル、(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、2−(アクリロイルオキシ)エチル6−ヒドロキシヘキサノネート等の前記水酸基含有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−カプロラクトンラクトンの開環付加により末端に水酸基を有する(メタ)アクリル酸エステルや、前記水酸基含有α,β−エチレン性不飽和二重結合基含有化合物に対してエチレンオキサイド、プロピレンオキサイド、ブチレンオキサイドなどのアルキレンオキサイドを繰り返し付加したアルキレンオキサイド付加(メタ)アクリル酸エステル等の水酸基含有の脂肪族(メタ)アクリル酸エステル;
化合物(a1−1)は、基材との密着性の面より、(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、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炭素数2〜18であるα,β−エチレン性不飽和二重結合基含有化合物がより好ましい。
化合物(a1−2)は、例えば、(メタ)アクリル酸1,2−シクロヘキサンジメタノール、(メタ)アクリル酸1,3−シクロヘキサンジメタノール、(メタ)アクリル酸1,4−シクロヘキサンジメタノール、(メタ)アクリル酸2−ヒドロキシ−3−フェノキシメチル、(メタ)アクリル酸2−ヒドロキシ−3−フェノキシエチル、(メタ)アクリル酸2−ヒドロキシ−3−フェノキシプロピル、(メタ)アクリル酸2−ヒドロキシ−3−フェノキシブチル、(メタ)アクリル酸2−ヒドロキシ−3−フェノキシデシル、(メタ)アクリル酸2−ヒドロキシ−3−フェノキシオクタデシル、(メタ)アクリル酸モノヒドロキシエチルフタレート、(メタ)アクリル酸2−(4−ベンゾイル−3−ヒドロキシフェノキシ)エチル等の水酸基とヘテロ環以外の環状構造を有する(メタ)アクリル酸エステル;
例えば、ビニルスルホン酸アンモニウム、ビニルスルホン酸ナトリウム、ビニルスルホン酸カリウム、ナトリウムビニルアルキルスルホサクシネート等の金属塩やアンモニウム塩;
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;
例えば、(メタ)アリルクロロシラン、(メタ)アリルトリメトキシシラン、(メタ)アリルトリエトキシシラン、(メタ)アリルアミノトリメチルシラン、ジエトキシエチルビニルシラン、トリクロロビニルシラン、トリメトキシビニルシラン、トリエトキシビニルシラン、トリプロポキシビニルシラン、ビニルトリス(2−メトキシエトキシ)シラン等のアルコキシシリル基含有α,β−不飽和二重結合基含有化合物類;
例えば、ビニルスルホン酸アンモニウム、ビニルスルホン酸ナトリウム、ビニルスルホン酸カリウム、ナトリウムビニルアルキルスルホサクシネート等の金属塩やアンモニウム塩類;
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;
例えば、(メタ)アクリロニトリル、α−クロロアクリロニトリル、クロトンニトリル、マレインニトリル、フマロニトリル、メサコンニトリル、シトラコンニトリル、イタコンニトリル、2−プロペンニトリル、(メタ)アクリル酸2−シアノエチルなどのニトリル基含有α,β−不飽和二重結合基含有化合物;
例えば、グリシジルシンナマート、アリルグリシジルエーテル、1,3−ブタジエンモノオキシラン等のグリシジル基含有ビニルエステル;
例えば、アレン、1,2−ブタジエン、1,3−ブタジエン、2−メチル−1,3−ブタジエン、2−クロロ−1,3−ブタジエンなどのジエン;
例えば、cis−コハク酸ジアリル、2−メチリデンコハク酸ジアリル、(E)−ブタ−2−エン酸ビニル、(Z)−オクタデカ−9−エン酸ビニル、(9Z,12Z,15Z)−オクタデカ−9,12,15−トリエン酸ビニル等の多官能の不飽和結合を含有するα,β−不飽和二重結合基含有化合物;
化合物(a1):10〜80質量%、化合物(a2):0〜20質量%、化合物(a3):20〜90質量%が好ましく、化合物(a1):20〜75質量%、化合物(a2):0〜10質量%、化合物(a3):25〜80質量%がより好ましい。
α,β−不飽和二重結合基含有アクリル系共重合体(B)(以下「化合物(B)」という)は、濡れ剤として機能する。一般的に濡れ剤は、親水部および疎水部を有する構造であり、界面活性機能を有する。その構造により、樹脂組成物と基材、または空気との界面に配向し、樹脂組成物の表面張力を下げ、濡れ性を向上させて、塗膜の平滑性向上やハジキ、凹凸、ピンホール、ユズハダ等の塗膜欠陥を防止できる。
公知の濡れ剤でも、樹脂組成物と基材の濡れ性を上げ、塗膜の平滑性を向上させることは可能である。しかし、濡れ剤は樹脂組成物と基材の界面に配向するため、接着阻害が生じ、大幅な接着力の低下を招くことがある。
SP値=(ΔH/V)1/2
炭素数4〜14のアルキル基含有(メタ)アクリル酸エステルは炭素数4以上になり濡れ剤としての機能が向上する。また、炭素数14以下になると化合物(A)との相溶性が向上し、塗膜外観(樹脂層外観)がより向上する。
メトキシエチレン(メタ)アクリレート、メトキシジエチレングリコール(メタ)アクリレート、エトキシエチレン(メタ)アクリレート、エトキシジエチレングリコール(メタ)アクリレート、ブトキシエチレン(メタ)アクリレート、ブトキシジエチレングリコール(メタ)アクリレート等のアルコキシポリエチレングリコール(メタ)アクリレート;、
メトキシプロピレン(メタ)アクリレート、メトキシジプロピレングリコール(メタ)アクリレート、エトキシプロピレン(メタ)アクリレート、エトキシジプロピレングリコール(メタ)アクリレート、ブトキシプロピレン(メタ)アクリレート、ブトキジプロピレングリコール(メタ)アクリレート等のアルコキシポリプロピレングリコール(メタ)アクリレート;
メトキシテトラメチレン(メタ)アクリレート、メトキシジテトラメチレングリコール(メタ)アクリレート、エトキシテトラメチレン(メタ)アクリレート、エトキシジテトラメチレングリコール(メタ)アクリレート、ブトキシテトラメチレン(メタ)アクリレート、ブトキシジテトラメチレングリコール(メタ)アクリレート等のアルコキシポリテトラメチレンエチレングリコール(メタ)アクリレート;
フェノキシエチレン(メタ)アクリレート、フェノキシジエチレングリコール(メタ)アクリレート等のフェノキシポリエチレングリコール(メタ)アクリレート類;ノニルフェノキシポリエチレングリコール(メタ)アクリレート等のアルキルフェノキシポリエチレングリコール(メタ)アクリレート類等の1個の(メタ)アクリレート基を有する化合物;
(1)α,β−不飽和二重結合基を有せず、水酸基、カルボキシル基およびエポキシ基からなる群から選択される1種以上の官能基を有するアクリル系共重合体(b1)を得た後、水酸基、カルボキシル基およびエポキシ基からなる群から選択される1種以上の官能基と反応可能な官能基およびα,β−不飽和二重結合基を有する化合物(b2)を反応する方法。
(2)1個および2個以上のα,β−不飽和二重結合基を有する化合物をリビング重合させることで、α,β−不飽和二重結合基の一部を残留させる方法。リビング重合と言ってもらわないとわかりません。
(3)α,β−不飽和二重結合基を有しないアクリル系共重合体を得た後、α,β−不飽和二重結合基を有する化合物をグラフト反応させる方法。
これらの中でも、上記方法(1)は、二重結合等量の制御が容易で好ましい。
さらに化合物(b2)のα,β−不飽和二重結合基を保護するため、ハイドロキノン、メトキシハイドロキノン等の重合禁止剤を用いることもできる。
含有量が0.001質量%より少ないと、濡れ性が向上せず表面平滑性や塗膜欠陥が改善されない恐れがある。含有量が2質量%より多いと、硬化後の膜が白濁したり基材密着性が低下する恐れがある。
本発明の樹脂組成物は、任意成分としオリゴマーを含むことができる。オリゴマーは、重量平均分子量が500〜100000であるポリエステル系オリゴマー(d1)、ポリウレタン系オリゴマー(d2)およびポリエポキシ系オリゴマー(d3)からなる群から選択される1種以上の化合物が好ましい。オリゴマー(d1〜d3)の配合により、樹脂組成物をコート剤や接着剤として使用した時に、が向上し、硬化収縮性を抑制できる。また樹脂層の耐熱性又は耐湿熱性を向上させることが容易となる。
高分子量ポリアミドポリオールの市販品は、富士化成工業社製のTPAE617等が挙げられる。
高分子量ポリカーボネートポリオールの市販品は、例えば、パーストープ社製のオキシマーN112、旭化成ケミカルズ社製のPCDLシリーズ、クラレ社製のクラレポリオールPMHCシリーズ、クラレポリオールCシリーズ等が挙げられる。
その他、ポリカプロラクトンジオール、ポリ(β−メチル−γ−バレロラクトン)ジオール、ポリバレロラクトンジオール等のラクトン類を開環重合して得られるポリエステルポリオール等も、上記高分子量ポリオールに含まれる。
単官能ポリイソシアネートは、例えば、メチルイソシアネート、エチルイソシアネート、プロピルイソシアネート、ブチルイソシアネート、オクチルイソシアネート、デシルイソシアネート、オクタデシルイソシアネート、ステアリルイソシアネート、シクロヘキシルイソシアネート、フェニルイソシアネート、ベンジルイソシアネート、p−クロロフェニルイソシアネート、p−ニトロフェニルイソシアネート、2−クロロエチルイソシアネート、2,4−ジクロロフェニルイソシアネート、3−クロロ−4−メチルフェニルイソシアネート、トリクロロアセチルイソシアネート、クロロスルホニルイソシアネート、(R)−(+)−α−メチルベンジルイソシアネート、(S)−(−)−α−メチルベンジルイソシアネート、(R)−(−)−1−(1−ナフチル)エチルイソシアネート、(R)−(+)−1−フェニルエチルイソシアネート、(S)−(−)−1−フェニルエチルイソシアネート、p−トルエンスルホニルイソシアネート等が挙げられる。
本発明の樹脂組成物は、必要に応じて、活性エネルギー線重合開始剤(E)を含んでもよい。活性エネルギー線重合開始剤(E)を使用することによって、重合反応を促進できる。本発明において活性エネルギーは、紫外線が好ましい。活性エネルギー線重合開始剤(E)は、ラジカル重合開始剤(e1)およびカチオン重合開始剤(e2)が好ましい。
活性エネルギー線重合開始剤(E)の反応性を高めるため活性エネルギー線の増感剤を併用できる。増感剤は、例えば、ベンゾフェノン誘導体、カルコン誘導体、ジベンザルアセトン等の不飽和ケトン誘導体、ベンジル、カンファーキノン等の1,2−ジケトン誘導体、ベンゾイン誘導体、フルオレン誘導体、ナフトキノン誘導体、アントラキノン誘導体、キサンテン誘導体、チオキサンテン誘導体、キサントン誘導体、チオキサントン誘導体、クマリン誘導体、ケトクマリン誘導体、シアニン誘導体、メロシアニン誘導体、オキソノ−ル誘導体等のポリメチン色素、アクリジン誘導体、アジン誘導体、チアジン誘導体、オキサジン誘導体、インドリン誘導体、アズレン誘導体、アズレニウム誘導体、スクアリリウム誘導体、ポルフィリン誘導体、テトラフェニルポルフィリン誘導体、トリアリールメタン誘導体、テトラベンゾポルフィリン誘導体、テトラピラジノポルフィラジン誘導体、フタロシアニン誘導体、テトラアザポルフィラジン誘導体、テトラキノキサリロポルフィラジン誘導体、ナフタロシアニン誘導体、サブフタロシアニン誘導体、ピリリウム誘導体、チオピリリウム誘導体、テトラフィリン誘導体、アヌレン誘導体、スピロピラン誘導体、スピロオキサジン誘導体、チオスピロピラン誘導体、金属アレーン錯体、有機ルテニウム錯体等が挙げられる。、その他さらに具体例には大河原信ら編、「色素ハンドブック」(1986年、講談社)、大河原信ら編、「機能性色素の化学」(1981年、シーエムシー)、池森忠三朗ら編、「特殊機能材料」(1986年、シーエムシー)に記載された色素や増感剤も挙げられる。色素は、紫外から近赤外域にかけての光に対して吸収を示す化合物が増感剤として使用できる。増感剤は単独または2種類以上を併用できる。
本発明の樹脂組成物は、任意成分としてカチオン重合性化合物(F)を含んでもよい。カチオン重合性化合物(F)を含むことで、樹脂組成物をコーティング剤や接着剤として使用した時に、活性エネルギー線照射による異種重合硬化が可能なるため、硬化物が相分離構造を形成できる。これにより塗膜(樹脂層)の弾性と応力緩和性やクリープ特性を制御しやすいため、適度な弾性や可撓性維持と硬化収縮抑制をより向上させることができる。また、硬化収縮が大きいことに起因する硬化塗膜の外観不良を改善できる。さらに樹脂層の耐熱性又は耐湿熱性を向上できる。
カチオン重合性化合物(F)は、単独または2種類以上を併用できる。
本発明の樹脂組成物は、好ましくは、コート剤又は接着剤の用途で使用される。代表的に、樹脂組成物は、常法にしたがい適当な方法で、基材の片面、または両面に塗工され、次いで活性エネルギー線照射により重合硬化することで、樹脂層を形成する。したがって、本発明の一実施形態は、後述の基材(G)と、該基材(G)の少なくとも一方の面に設けられた樹脂層とを有する積層体である。本実施形態において、樹脂層の膜厚は、積層体の用途に応じて設定される。
本発明の積層体では、基材(G)として、フィルム状基材を使用することが好ましい。フィルム状基材の具体例として、セロハン、各種プラスチックフィルム、及び紙等が挙げられる。なかでも、透明な各種プラスチックフィルムの使用が好ましい。また、フィルム状基材としては、フィルムが透明であれば、単層構造であってもよいし、複数の基材を積層してなる多層構造を有するものであってもよく、いずれの構造を有するフィルムであっても好適に使用することができる。本発明の積層体を構成する場合、透明なフィルムの少なくとも一方の面に本発明の樹脂組成物からなる樹脂層を形成することが好ましい。
プリズムシートとは、ディスプレイに使用され、正面方向の輝度を向上させるために、液晶パネルのバックライトの導光板上面に設置されるシートで、前方への集光効果を持たせ、正面輝度を向上させるレンズシートと呼ばれる光学フィルム(I)である。
上記、プリズムシートは、一般的に、ポリエステル系樹脂のベースフィルムの上に、アクリル系樹脂のプリズム部(レンズ部)が微細に積層された構造を有し、照度分布,輝度分布,出射角度特性などを考慮して正面輝度の向上のために2枚のプリズムシートを光学軸が互いに異なるように積層(ほぼ直交)して使用される。この際、プリズムピッチ,プリズム深さ,プリズムの材質、光学軸角度により、正面輝度が変化するため、接着剤等で積層固定されて使用されて、これをさらに導光板等の他の光学フィルムに積層されて光学素子用積層体として使用される。
[合成例1]
冷却管、撹拌装置、温度計、窒素導入管を備えた4つ口フラスコに、メチルアクリレート90部、グリシジルメタクリレート10部、酢酸エチル100部を仕込み、窒素雰囲気下で撹拌しながら80℃まで昇温した。次いで、アゾビスイソブチロニトリル1部を添加して重合反応を行った。アゾビスイソブチロニトリルの添加量と添加時刻は、80℃まで昇温した後、1部添加して2時間保持し、エポキシ基を有するアクリル系共重合体(b1)を含む溶液を得た。
引き続き、上記溶液にハイドロキノンを0.03部、ジメチルベンジルアミンを0.8部、アクリル酸を5部添加し、80℃で1.5時間加熱撹拌し、二重結合当量1540、重量平均分子量24000、固形分51%の化合物(B)を得た。
合成例1の(メタ)アクリル酸エステル、重合開始剤、触媒、重合禁止剤を表1に示す化合物、仕込み量に変え、化合物(B)を得た。表1に示した各材料の略号を以下に記す。
冷却管、撹拌装置、温度計、窒素導入管を備えた4つ口フラスコに、2−エチルヘキシルアクリレート80部、グリシジルメタクリレート20部、酢酸エチル100部を仕込み、窒素雰囲気下で撹拌しながら80℃まで昇温した。次いで、アゾビスイソブチロニトリル1部、nードデシルメルカプタン0.1部を添加して重合反応を行った。アゾビスイソブチロニトリルの添加量と添加時刻は、80℃まで昇温した後、1部添加して2時間保持しエポキシ基を有するアクリル系共重合体(b1)を含む溶液を得た。
引き続き、上記溶液にハイドロキノンを0.03部、ジメチルベンジルアミンを0.8部、アクリル酸を5部添加し、80℃で1.5時間加熱撹拌し、二重結合当量1672、重量平均分子量5000、固形分53%の化合物(B)を得た。
合成例19の(メタ)アクリル酸エステル、重合開始剤、触媒、連鎖移動剤、重合禁止剤を表1に示す化合物、仕込み量に変え、化合物(B)を得た。表1に示した各材料の略号を以下に記す。
<疎水性(メタ)アクリル酸エステル>
MA:メチルアクリレート
BA:ブチルメタクリレート
2EHA:2−エチルヘキシルアクリレート
TM−0701:シリコーン基含有メタアクリル酸エステル(JNC社製、商品名:サイラプレーン(登録商標)TM−0701)
ビスコート3F:2,2,2−トリフルオロエチルアクリレート(大阪有機化学工業社製、商品名:ビスコート3F)
<親水性(メタ)アクリル酸エステル>
2HEMA:2−ヒドロキシエチルメタクリレート
AA:アクリル酸
GMA:グリシジルメタクリレート
ライトエステルBC:ブトキシジエチレングリコールメタクリレート(共栄社化学社製、商品名:ライトエステルBC)
<重合開始剤>
AIBN:アゾビスイソブチロニトリル
<化合物(b2)>
GMA:グリシジルメタクリレート
MOI:2−イソシアナートエチルメタクリレート(昭和電工社製 商品名:カレンズMOI)
AA:アクリル酸
<触媒>
DMBA:ジメチルベンジルアミン
<重合禁止剤>
HQ:ハイドロキノン
二重結合当量は、二重結合1molあたりのアクリル系共重合体の質量として以下の式で算出した。
溶剤を除く全仕込み量(g)/{化合物(b2)の量(mol)/化合物(b2)1分子あたりのα,β−不飽和二重結合基の数}
重量平均分子量の測定は、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」を用いた試料をテトラヒドロフランに溶解して、テトラヒドロフランを展開溶剤として流速を0.6ml/min、カラム温度を40℃の条件にて測定した。標準物質として重量平均分子量既知の単分散分子量のポリスチレンを使用した検量線を作成し、化合物(B)の重量平均分子量を検量線法によって決定した。
<オリゴマー(d3)>
撹拌機、蒸留管、ガス導入管、温度計を備えた5口セパラブルフラスコに、JER1010(三菱化学社製エポキシ樹脂、重量平均分子量5500、エポキシ当量3000〜5000(g/eq))200部、メチルイソブチルケトン200部を窒素雰囲気下で約100℃で3時間攪拌し、エポキシ樹脂を溶解した。次にアクリル酸30部、ジメチルエタノールアミン3部、ハイドロキノン0.2部を加え100℃で5時間攪拌した。得られた化合物を真空乾燥機で10torr、50℃の条件で48時間乾燥し、メチルイソブチルケトンおよび過剰のアクリル酸、ジメチルエタノールアミンを除去し、重量平分子量5700のエポキシ系オリゴマーを得た。
合成例22のJER1010をJER4250(三菱化学社製エポキシ樹脂、重量平均分子量60000、エポキシ当量7500〜8900(g/eq))に変更した以外は同様に反応させ、重量平均分子量60000のエポキシ系オリゴマーを得た。
酸素濃度が10%以下に置換された遮光された容量300mLのガラス瓶に、4−ヒドロキシブチルアクリレート68.9部、イソボルニルアクリレート(大阪有機化学工業社製 商品名IBXA)30部、UV−7000B(α,β−不飽和二重結合基含有ポリウレタン系オリゴマー、日本合成化学工業社製 商品名:紫光UV−7000B)10部、合成例1で得られたα,β−不飽和二重結合基含有アクリル系共重合体(B)溶液0.2部、イルガキュア184(BASF社製)1部を加え、十分に攪拌と脱泡を行い、粘度25mPa・s、表面張力32.0mN/mの活性エネルギー線重合性樹脂組成物を得た。
表2に示した活性エネルギー線重合性樹脂組成物を使用して積層体Aを作成した。基材としてポリアクリル系の透明フィルムであるプリズムシート(日本特殊光学樹脂社製プリズムシート:商品名「LPV90−1.0」、材質:ポリ(メチルメタクリレート)、厚さ:2mm)を2枚用意した。第1のプリズムシートの背面(プリズムを有しない面)に、300W・分/m2の放電量でコロナ処理を行った後、表2に記載された実施例および比較例に示す組成物を、ワイヤーバーコーターを用いて塗工後の膜厚が1μmとなるように塗工し、塗工面の平滑性を目視評価し表3に示した。次に第2のプリズムシートの正面(プリズム面)を、第1のプリズムシートの光学軸と第2のプリズムシートの光学軸とが直交するように積層し、第1のプリズムシート/樹脂層/第2のプリズムシートからなる積層体を得た。 次に、第1のプリズムシートの正面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を用いて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の紫外線を第2のプリズムシートの背面側から照射して、固定化したプリズムシートの積層体Aを製造した。
活性エネルギー線重合性樹脂組成物を塗工した第1のプリズムシートを15cm四方に切り出し、15cm四方中のハジキの個数を数え、以下に示す基準で評価した。
○:ハジキなし (良好)
○:1〜2個 (使用可)
×:3個以上 (不良)
剥離強度は、JIS K6854−4 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、得られた積層体A(固定化したプリズムシートの積層体)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、固定化したプリズムシートの積層体Aと金属板との測定用の積層体を得た。測定用の積層体には、2枚のプリズムシートの間に予め切り込みを設けておき、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、剥離強度とした。この剥離強度を下記4段階で評価した。。
(評価基準)
◎:剥離力が5.0(N/25mm)以上、剥離不可またはプリズムシート破壊。(極めて良好)
○:剥離力が1.0(N/25mm)以上5.0(N/25mm)未満。(良好)
△:剥離力が0.5(N/25mm)以上1.0(N/25mm)未満。(使用可)
×:剥離力が0.5(N/25mm)未満。(不良)
ダンベル社製のスーパーストレートカッター(100mm×100mm)を用い、上記例で作製した固定化したプリズムシートの積層体Aを第2のプリズムシートの背面側から打ち抜いた。打ち抜いた積層体Aについて、打ち抜きによって生じたプリズムシートと樹脂層との距離を定規で測定し、その距離の平均値について、以下の3段階で評価した。
(評価基準)
○:0mm、浮き、剥がれ無し(良好)
△:0〜0.5mm(使用可)
×:0.5mmを越える(不良)
上記固定化したプリズムシートの積層体を、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、上記固定化したプリズムシートの積層体の端部の剥がれの有無を目視にて、以下の4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。(極めて良好)
○:80℃−dry条件下で剥がれが全く無し。(良好)
△:80℃−dry条件下で0.5mm未満の剥がれあり。(使用可)
×:80℃−dry条件下で0.5mm以上の剥がれあり。(不良)
表2に示した活性エネルギー線重合性樹脂組成物を使用し、以下の積層体Bを作成した。
透明フィルムとして、ポリアセチルセルロース系フィルム(富士フィルム社製、商品名「フジタック:80μm」、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)を用いた。透明フィルム表面を300W・分/m2の放電量でコロナ処理を行った後、表3に記載された実施例および比較例に示す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塗工後の膜厚が2μmとなるように塗工し、樹脂層を形成した。透明フィルムがブリキ板に接するように、この積層体B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の紫外線を樹脂層側から照射して積層体Bを作製した。
積層体を15cm四方に切り出し、15cm四方中のハジキの個数を数え、以下に示す基準で評価した。
○:ハジキなし (良好)
○:1〜2個 (使用可)
×:3個以上 (不良)
積層体の透明性をHACH社製の濁度計(2100P TURBIDMETER)を用いて以下の基準で評価した。○以上が実用レベルである。
◎:0〜10NTU未満 (良好)
○:10NTU以上〜30NTU未満 (使用可)
△:30NTU以上 (不良)
《密着力》
JIS K5600ー5−6:1999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。
(評価基準)
◎:0マス(極めて良好)
○:1〜10マス(良好)
△:11〜30マス(使用可)
×:31マス以上(不良)
積層体を、50mm×40mmの大きさに裁断し、60℃−90%RH及び85℃−85%RHの環境下にそれぞれ1000時間暴露した。暴露後の積層体について、端部における樹脂層の剥がれた距離を定規で測定し、その距離の平均値について、以下の4段階で評価をした。
(評価基準)
◎:85℃−85%RHの条件下で剥がれ無し。(極めて良好)
○:60℃−90%RHの条件下で剥がれ無し。(良好)
△:60℃−90%RHの条件下で0.5mm未満の剥がれあり。(使用可)
×:60℃−90%RHの条件下で0.5mm以上の剥がれあり。(不良)
化合物(A)、化合物(B)、オリゴマー(d1〜d3)および開始剤を、表2に示す比率に変えた以外は、実施例1と同様にして、活性エネルギー線重合性樹脂組成物を得た。表2に示した各材料の略号を以下に記す。
4HBA:4−ヒドロキシブチルアクリレート
DCPA:ジメチロール-トリシクロデカンジアクリレート(共栄社科学社製 商品名ライトアクリレートDCP−A)
<オリゴマー(d1)>
EBECRYL812:α,β−不飽和二重結合基含有ポリエステル系オリゴマー(ダイセル・オルネックス社製 重量平均分子量800)
EBECRYL884:α,β−不飽和二重結合基含有ポリエステル系オリゴマー(ダイセル・オルネックス社製 重量平均分子量3000)
EBECRYL525:α,β−不飽和二重結合基含有ポリエステル系オリゴマー(ダイセル・オルネックス社製 重量平均分子量40000、トリプロピレングリコールジアクリレート40%含有)
<オリゴマー(d2)>
EBECRYL5129:α,β−不飽和二重結合基含有ポリウレタン系オリゴマー(ダイセル・オルネックス社製 重量平均分子量800)
UV−7000B:α,β−不飽和二重結合基含有ポリウレタン系オリゴマー(日本合成化学工業社製 商品名:紫光UV−7000B 重量平均分子量3500)
UN−5500:α,β−不飽和二重結合基含有ポリウレタン系オリゴマー(根上工業社製 商品名:アートレジンUN−5500 重量平均分子量50000)
<オリゴマー(d3)>
EBECRYL3702:α,β−不飽和二重結合基含有ポリエポキシ系オリゴマー(ダイセル・オルネックス社製 重量平均分子量500)
活性エネルギー線重合性樹脂組成物を25℃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た。
協和界面科学社製全自動表面張力計CBVP−Zを用い、Wilhelmy法により環境温度25℃で白金プレートを使用し測定した。
Claims (9)
- 分子量500未満であるα,β−不飽和二重結合基含有化合物(A)と、重量平均分子量が2000〜100000であるα,β−不飽和二重結合基含有アクリル系共重合体(B)とを含有する活性エネルギー線重合性樹脂組成物であって、活性エネルギー線重合性組成物中、α,β−不飽和二重結合基含有アクリル系共重合体(B)の含有率が、0.001〜2質量%である、活性エネルギー線重合性樹脂組成物。
- α,β−不飽和二重結合基含有アクリル系共重合体(B)の二重結合当量が、500〜30000g/molである、請求項1記載の活性エネルギー線重合性樹脂組成物。
- α,β−不飽和二重結合基含有アクリル系共重合体(B)が、炭素数4〜14のアルキル基含有(メタ)アクリル酸エステル、シリコーン基含有(メタ)アクリル酸エステルおよびフッ素含有(メタ)アクリル酸エステルからなる群から選択される1種以上の化合物と、水酸基含有(メタ)アクリル酸エステル、カルボキシル基含有(メタ)アクリル酸エステルおよびオキシアルキレン基含有(メタ)アクリル酸エステルからなる群から選択される1種以上の化合物との共重合体である、請求項1または2記載の活性エネルギー線重合性樹脂組成物。
- α,β−不飽和二重結合基含有アクリル系共重合体(B)が、水酸基、カルボキシル基およびエポキシ基からなる群から選択される1種以上の官能基を有するアクリル系共重合体(b1)と、水酸基、カルボキシル基およびエポキシ基からなる群から選択される1種以上の官能基と、反応可能な官能基およびα,β−不飽和二重結合基を有する化合物(b2)と、の反応生成物である、請求項1〜3いずれか1項に記載の活性エネルギー線重合性樹脂組成物。
- 活性エネルギー線重合性樹脂組成物の表面張力が、α,β−不飽和二重結合基含有化合物(A)の表面張力よりも1〜15mN/m低い、請求項1〜4いずれか1項に記載の活性エネルギー線重合性樹脂組成物。
- さらに、重量平均分子量が500〜100000であるポリエステル系オリゴマー(d1)、重量平均分子量が500〜100000であるポリウレタン系オリゴマー(d2)および重量平均分子量が500〜100000であるポリエポキシ系オリゴマー(d3)からなる群から選択される1種以上の化合物を含む、請求項1〜5いずれか1項に記載の活性エネルギー線重合性樹脂組成物。
- 基材(G)と、請求項1〜6いずれか1項に記載の活性エネルギー線重合性樹脂組成物からなる樹脂層とを備えた、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7記載の積層体。
- 透明フィルム(H)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およびポリイミド系フィルムからなる群から選択される少なくとも1種である、請求項8記載の積層体。
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CN113950507A (zh) * | 2019-07-08 | 2022-01-18 | Dic株式会社 | 树脂组合物、预浸体、层叠板、多层印刷配线板及半导体封装 |
CN116218282A (zh) * | 2021-12-06 | 2023-06-06 | 精工爱普生株式会社 | 放射线固化型喷墨组合物及喷墨记录装置 |
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