JP6264000B2 - 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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- JP6264000B2 JP6264000B2 JP2013252461A JP2013252461A JP6264000B2 JP 6264000 B2 JP6264000 B2 JP 6264000B2 JP 2013252461 A JP2013252461 A JP 2013252461A JP 2013252461 A JP2013252461 A JP 2013252461A JP 6264000 B2 JP6264000 B2 JP 6264000B2
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- XMRZNNGTCUALQE-UHFFFAOYSA-N tert-butyl 3-(4-ethenylphenoxy)propanoate Chemical compound CC(C)(C)OC(=O)CCOC1=CC=C(C=C)C=C1 XMRZNNGTCUALQE-UHFFFAOYSA-N 0.000 description 1
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- YQPZJBVEKZISEF-UHFFFAOYSA-N tetracont-1-ene Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC=C YQPZJBVEKZISEF-UHFFFAOYSA-N 0.000 description 1
- NPWJBNPQTPEEGC-UHFFFAOYSA-N tetradecyl 4-ethenylbenzoate Chemical compound C(CCCCCCCCCCCCC)OC(C1=CC=C(C=C1)C=C)=O NPWJBNPQTPEEGC-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 1
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- SWZDQOUHBYYPJD-UHFFFAOYSA-N tridodecylamine Chemical compound CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC SWZDQOUHBYYPJD-UHFFFAOYSA-N 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- NELVVTIEGZVCKM-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;sulfate Chemical compound [O-]S([O-])(=O)=O.C[N+](C)(C)CCCNC(=O)C=C.C[N+](C)(C)CCCNC(=O)C=C NELVVTIEGZVCKM-UHFFFAOYSA-N 0.000 description 1
- VUWVDNLZJXLQPT-UHFFFAOYSA-N tripropoxy(propyl)silane Chemical compound CCCO[Si](CCC)(OCCC)OCCC VUWVDNLZJXLQPT-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- CIBGZAYGXFGOFK-UHFFFAOYSA-L zinc;2-phenylethenesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C=CC1=CC=CC=C1.[O-]S(=O)(=O)C=CC1=CC=CC=C1 CIBGZAYGXFGOFK-UHFFFAOYSA-L 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
- Laminated Bodies (AREA)
- Polymerisation Methods In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (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。
分子内にカルボニル基を有しないα,β−不飽和二重結合基含有化合物(B)(ただし、ここでいうカルボニル基は、α,β−不飽和二重結合基に直接結合しているカルボニル基を除く。また、1級及び/または2級アミノ基を有するα,β−不飽和二重結合基含有化合物除く。)と、
アミン系化合物(C)と、を必須成分とする活性エネルギー線重合性樹脂組成物に関する。
化合物(A)を0.5〜30重量%、
化合物(B)を40〜99重量%
化合物(C)を0.5〜30重量%
含有することを特徴とする上記活性エネルギー線重合性樹脂組成物に関する。
<活性エネルギー線重合性樹脂組成物>
本発明の活性エネルギー線重合性樹脂組成物は、分子内に、少なくとも分子内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(A)(ただし、ここでいうカルボニル基は、α,β−不飽和二重結合基に直接結合しているカルボニル基を除く。)と、分子内にカルボニル基を有しないα,β−不飽和二重結合基含有化合物(B)(ただし、ここでいうカルボニル基は、α,β−不飽和二重結合基に直接結合しているカルボニル基を除く。また、1級及び/または2級アミノ基を除く。)と、アミン系化合物(C)と、を必須成分とを、必須成分とすることが特徴である。
(A)成分:
本発明の樹脂組成物において、分子内に、少なくとも分子内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(A)(以下、化合物(A)に含有されるカルボニル基は、α,β−不飽和二重結合基に直接結合しているカルボニル基を除く。より具体的には、ケト基、アルデヒド基、オキシカルボニル基、オキシカルボニルオキシ基、あるいはアシル基(ただし、エステル基中のアシル基は除く。)が挙げられる。化合物(A)のカルボニル基は成型品のガラス転移点(Tg)が向上させるため、高凝集力を発現し、耐熱性や耐水性等の耐性の良好成型品を形成することが可能となるものである。
なお、本願では、「(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、「アクリロイル及び/又はメタクリロイル」、「アクリル酸及び/又はメタクリル酸」、「アクリレート及び/又はメタクリレート」、「アクリロイルオキシ及び/又はメタクリロイルオキシ」、及び「アリル及び/又はメタリル」を表すものとする。
本発明の化合物(A)は、後述の分子内にカルボニル基を有しないα,β−不飽和二重結合基含有化合物(B)との共重合反応性と共重合反応後における塗膜の凝集力向上の点をを考慮すると、化合物(A)に含有されるα,β−不飽和二重結合基が、アクリロイル基、またはメタクリロイル基であることが好ましい。さらに、後述の基材(G)に対する密着性や接着性の向上を可能にすることができる。
化合物(A)のうち、工業的に、アクリル酸(メトキシカルボニル)メチル、N−(2−オキソブタノイルエチル)(メタ)アクリルアミド、アクリル酸2−オキソブタノイルエチル、メタクリル酸2−オキソブタノイルエチル、アセト酢酸ビニルが特に好ましく使用される。
本発明の樹脂組成物において、分子内にカルボニル基を有しないα,β−不飽和二重結合基含有化合物(B)(以下、化合物(B)は、α,β−不飽和二重結合基に直接結合しているカルボニル基を除く場合で有り、さらに、分子中に1級及び/または2級アミノ基を有しない、α,β−不飽和二重結合基含有化合物である。すなわち、上記成分(B)は、上述の化合物(A)を含まず、さらに、後述の分子中に1級及び/または2級アミノ基を有するα,β−不飽和二重結合基含有化合物(c3)を含まないα,β−不飽和二重結合基含有化合物である。
特に、1個以上のα,β−不飽和二重結合基を含有する化合物であれば、特に制限はなく、使用できるが、その構造中に1個以上の水酸基を含有するα,β−エチレン性不飽和二重結合基含有化合物(b1)を含有することが好ましい。化合物(b1)には、水酸基を有し、環状構造を有しない化合物(b1−1)と、水酸基を有し、環状構造を有する化合物(b1−2)に分けられるが、いずれも水酸基を有することによって、後述の基材(G)との密着性向上に大きな効果を示す。
更に、耐熱性、あるいは耐湿熱性等の耐久性向上の点で、分子内に水酸基を有せず、かつ、1個以上の環状構造を有するα,β−エチレン性不飽和二重結合基含化合物(b2)を含有することが好ましい。また、(b1),(b2)以外のα,β−エチレン性不飽和二重結合基含有化合物(b3)も含有することができる。
上記樹脂組成物に上記成分(B)を含有することによって、上記化合物(A)と化合物(B)との共重合反応の効率化及び高感度化を図ることが容易である。また、上記樹脂組成物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。特に限定するものではないが、成分(B)として使用可能な化合物としては、以下が挙げられる。
化合物(Bb1−1)としては、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特に好ましい。
化合物(b1−2)としては、その構造中に水酸基と環状構造の双方を有するものであれば特に制限はなく、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等が挙げられる。
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類;
化合物(b1)が1重量部より少ないと、後述の基材(G)との密着性が低下する。化合物(b1)が45重量部より多いと、耐水性が劣るため好ましくない。化合物(b2)が1重量部より少ないと、塗膜の耐熱性や耐湿熱性が低下する。化合物(b2)が45重量部より多いと、塗膜の柔軟性が失われ、脆くなったりするため好ましくない。
本発明の樹脂組成物において、アミン系化合物(C)は、活性水素を有する1級、及び/または2級アミノ基を有する場合で有り、活性水素を有しない3級アミノ基、及びアミド基を含まず、それらとは区別される、反応性化合物である。
特に、1個以上の1級、及び/または2級アミノ基を有する化合物であれば、特に制限はなく、使用できるが、その構造中に2個以上のアミノ基を含有するアミン系化合物を含有することが好ましい。
アミン系化合物(C)には、1個の1級、または2級アミノ基を有する化合物と2個以上有する化合物に分けられるが、いずれも1級、及び/または2級アミノ基を有することによって、後述の基材(G)との密着性向上に大きな効果を示す。
更に、耐熱性、あるいは耐湿熱性等の耐久性向上の点で、分子内にα,β−不飽和二重結合基を有する化合物を含有することができる。従って、アミン系化合物(C)としては、1個の1級、または2級アミノ基を有し、α,β−不飽和二重結合基を有しない化合物(c1)(以下、化合物(c1)と標記する。)、2個以上の1級、または2級アミノ基を有し、α,β−不飽和二重結合基を有しない化合物(c2)(以下、化合物(c2)と標記する。)、及び1個以上の1級、または2級アミノ基を有し、かつ、α,β−不飽和二重結合基を有する化合物(c3)(以下、化合物(c3)と標記する。)に分類することができ、1個以上の1級、または2級アミノ基を有し、かつ、α,β−不飽和二重結合基を有する化合物(c3)を含有することが好ましい。また、(c1),(c2)も含有することができる。
上記樹脂組成物に上記アミン系化合物(C)を含有することによって、上記化合物(A)との相互作用によって、重合硬化塗膜の凝集力が向上し、耐熱性や耐湿熱性等の耐久性向上を図ることが容易となる。また、アミノ基に伴う水素結合の形成により、後述の基材(G)との密着性や接着性を向上させることが容易となる。特に限定するものではないが、アミン系化合物(C)として使用可能な化合物としては、以下が挙げられる。
全量100重量%中、化合物(A)と化合物(C)が、それぞれ0.5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、全量100重量%中、化合物(A)と化合物(C)が、30重量%以下であると、樹脂組成物をコート剤、あるいは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。
本発明の樹脂組成物の一実施形態において、樹脂組成物は、上記必須成分に加えて、オリゴマー(D)を含んでもよい。オリゴマー(D)を使用することによって、樹脂組成物をコート剤又は接着剤として使用した時に、基材に対する接着性及び密着性をより向上させることができる。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。
ポリエステル系オリゴマー(d1)としては、主鎖骨格に多塩基酸と多価アルコールを重縮合して得られるポリエステルの末端あるいはポリエステル鎖中の水酸基と(メタ)アクリル酸、マレイン酸などの分子内に1個以上のカルボキシル基を有するα,β−エチレン性不飽和二重結合基含有化合物とのエステル化によって得られる化合物、あるいはポリエステルの末端あるいはポリエステル鎖中のカルボキシル基と(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などの前述の化合物(b1)とのエステル化によって得られる化合物である。その他、酸無水物と(メタ)アクリル酸グリシジルと少なくとも1個の水酸基を有する化合物とから得られるポリエステルオリゴマー等もポリエステルオリゴマー(d1)として使用可能である。
比較的高分子量のポリオール類としては、より具体的には、例えば、高分子量ポリエステルポリオール、高分子量ポリアミドポリオール、高分子量ポリカーボネートポリオール及び高分子量ポリウレタンポリオールが挙げられる。高分子量ポリカーボネートポリオールは、上記の比較的低分子量のジオールと炭酸エステル又はホスゲンとの反応によって得られる。
上記高分子量ポリアミドポリオールの市販品としては、富士化成工業社製のTPAE617等を使用できる。
上記高分子量ポリカーボネートポリオールの市販品としては、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。
その他に、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として使用できる高分子量ポリオールに含まれる。
ポリウレタン系オリゴマー(d2)は、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と前記化合物(b1)を反応させて得られる化合物、あるいは少なくとも1個のイソシアネート基を有する化合物と上述の多価アルコールとを反応させて得られる末端イソシアネート基のウレタンプレポリマーと前記化合物(b1)を反応させて得られる化合物、あるいは少なくとも1個のイソシアネート基を有する化合物と多価アルコールとを反応させて得られる末端イソシアネート基のウレタンプレポリマーと、更に少なくとも1個以上のアミノ基を有する化合物とを反応させて得られる末端イソシアネート基のウレタンプレポリマーと前記化合物(b1)とを反応させて得られる化合物である。また、イソシアネート基とアミノ基とを反応させて得られるウレア結合基を含有したものもポリウレタン系オリゴマー(d2)に含む。
また、アミノ基を有するアミン類としては、上述したアミン系化合物(c1)、あるいは(c2)が利用できる。
ポリエポキシ系オリゴマー(c3)は、グリシジル基を有する化合物とヒドロキシエチル(メタ)アクリレート、(メタ)アクリル酸、マレイン酸などの分子内に1個以上の水酸基や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との反応により得られる化合物であり、実質的にグリシジル基を有さず、かつα,β−不飽和二重結合基含有化合物を有する化合物である。代表例としてビスフェノール型、エポキシ化油型、フェノールノボラック型、脂環型が挙げられる。ビスフェノール型ポリエポキシ系オリゴマーとしては、ビスフェノール類とエピクロルヒドリンとを反応させて得られるビスフェノール型ジグリシジルエーテルと(メタ)アクリル酸などの分子内に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とを反応して得られるものである。
本発明では、オリゴマー(D)として、アクリル系オリゴマー(d4)を使用することもできる。使用可能な化合物の具体例として、α,β−不飽和二重結合基を有する変性ポリエーテル、アミン変性されたα,β−不飽和二重結合基含有化合物、並びに、アルキッド樹脂、スピロアセタール樹脂、ポリブタジエン樹脂、ポリチオールポリエン樹脂及び多価アルコール等の各種化合物にα,β−不飽和二重結合基を付加させた変性α,β−不飽和二重結合基含有化合物、からなる群より選択される1以上の化合物の、オリゴマーまたはプレポリマーを使用することができる。
なお、数平均分子量(Mn)、重量平均分子量(Mw)、酸価(AV)及び水酸基価(OHV)の測定方法については後述する。
本発明の樹脂組成物は、各種活性化エネルギー線の照射によって重合反応が進行し、硬化可能である。しかし、上記樹脂組成物は、成分(A)、(B)、及び(C)の必須成分に加えて、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、重合反応を促進することができる。本発明の一実施形態において、上記活性化エネルギーは紫外線であることが好ましく、紫外線の照射によって重合反応を進行させる場合、樹脂組成物は、活性エネルギー線重合開始剤(E)を含むことが好ましい。
具体例として、例えば、以下が挙げられる。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−チオキサントン、カンファーキノン、及び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。
また、市販品としては、例えば、以下が挙げられる。イルガキュアー184,907,651,1700,1800,819,369,及び261(BASF社製)、DAROCUR−TPO(BASF社製、2,4,6−トリメチルベンゾイル−ジフェニル−ホ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,及びTZT(日本シイベルヘグナー社製)、カヤキュアBMS,及びカヤキュアDMBI(日本化薬社製)等。
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を使用することもできる。
また、α,β−エチレン性不飽和二重結合基含有化合物(B)として、(メタ)アクリル酸グリシジル、4−(グリシジルオキシ)ブチル(メタ)アクリレート、(メタ)アクリル酸(3−メチル−3−オキセタニル)メチル、(メタ)アクリル酸−3,4−エポキシシクロヘキシルメチルなどの3員環または4員環の酸素原子を有するヘテロ環含有(メタ)アクリル酸エステル類を使用した場合には、活性エネルギー線重合開始剤として、必要に応じて公知の光酸発生剤を含有することが好ましい。光酸発生剤としては、例えば、UVACURE1590(ダイセル・サイテック社製)、CPI−110P(サンアプロ社製)、などのスルホニウム塩やIRGACURE250(チバ・スペシャルティ・ケミカルズ社製)、WPI−113(和光純薬社製)、Rp−2074(ローディア・ジャパン社製)等のヨードニウム塩などに例示されるものが挙げられ、併用使用する事で、重合架橋が進み、熱や湿度に対する耐久性に優れる接着層を形成するため好ましい。
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活性エネルギー線重合開始剤を使用することもできる。
本発明では、上記成分(E)として、上述の化合物を単独で、又は2種類以上組合せて使用することができる。
本発明の樹脂組成物は、本発明による効果を損なわない範囲であれば、各種添加剤を適宜配合することも可能である。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、シランカップリング剤、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、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、樹脂組成物中に、溶解、半溶解又はミクロ分散させることも可能である。
(I)第1の透明フィルム(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の重合性接着層を形成する。また、第2の透明フィルム(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両主面に、上記第1の重合性接着層と第2の重合性接着層とを、同時に/又は順番に、重ね合わせる。次いで、得られた積層体に活性エネルギー線を照射し、第1及び第2の接着層を重合硬化させる。
[配合例1〜40]
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(A)、分子内にカルボニル基を有しないα,β−不飽和二重結合基含有化合物(B)、アミン系化合物(C)、オリゴマー(D)、活性エネルギー線重合開始剤(E)及びその他の添加剤(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。
・成分(A)
MCMA:アクリル酸(メトキシカルボニル)メチル、AAEA:アクリル酸2−オキソブタノイルエチル、AAEM:メタクリル酸2−オキソブタノイルエチル、DAAM:N−(2−オキソブタノイルエチル)アクリルアミド、AVAC:アセト酢酸ビニル
・成分(b1−1)
4HBA:アクリル酸4−ヒドロキシブチル、2HEA:アクリル酸2−ヒドロキシエチル
・成分(b1−2)
CHDMA:アクリル酸1,4−シクロヘキサンジメタノール、HPPA:アクリル酸2−ヒドロキシ−3−フェノキシプロピル
・成分(b2−1)
IBXA:アクリル酸イソボルニル、DCPA:アクリル酸ジシクロペンタニル、ADCP:ジアクリル酸ジシクロペンタニル
・成分(b2−2)
ACMO:4−アクリロイルモルホリン、GMA:メクリル酸グリシジル
・成分(b3)
NPGDA:ジアクリル酸ネオペンチルグリコール、BA:アクリル酸ブチル
・成分(c1)
AN:アニリン
・成分(c2)
IPDA:イソホロンジアミン、ADH:アジピン酸ジヒドラジド
・成分(c3)
MAEA:アクリル酸N−メチルアミノエチル、AAH:アクリル酸ヒドラジド
・成分(d1)
885:ダイセルサイテック社製 ポリエステルアクリレート 「Ebecryl 885」
・成分(d2)
3000B:日本合成化学工業社製 ポリウレタン系オリゴマー(ウレタンアクリレート) 「紫光UV3000B」
・成分(d3)
600:ダイセルサイテック社製 ポリエポキシ系オリゴマー(エポキシアクリレート) 「Ebecryl600」
・成分(E)
TPO: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ト゛(BASF社製,DAROCUR TPO)、CPI−110P:p-フェニルチオフェニルジフェニルスルホニウムPF6塩
本発明では、上述の成分に限定されることなく、各種特性に優れた活性エネルギー線重合性樹脂組成物を提供することができる。
各配合例で得られた樹脂組成物の外観を観察し、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を、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1〜42][比較例1〜9]
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、配合例に示す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、接着層を形成し、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、接着層を形成した。さらに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。
[実施例101〜150][比較例11〜19]
表1及び表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、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の紫外線をコート剤層側から照射して、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106〜150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101〜105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11〜19では、特に密着性、あるいは耐熱性に劣ることがわかる。
Claims (8)
- 分子内にアルデヒド基、オキシカルボニル基、オキシカルボニルオキシ基、あるいはアシル基(ただし、エステル基中のアシル基は除く)を有するα,β−不飽和二重結合基含有化合物(A)(ただし、オリゴマー(D)を除く、また、ここでいうカルボニル基は、α,β−不飽和二重結合基に直接結合しているカルボニル基を除く。)と、
分子内にカルボニル基を有しないα,β−不飽和二重結合基含有化合物(B)(ただし、ここでいうカルボニル基は、α,β−不飽和二重結合基に直接結合しているカルボニル基を除く。また、1級及び/または2級アミノ基を有するα,β−不飽和二重結合基含有化合物を除く。)と、
1級及び/または2級アミノ基を有するアミン系化合物(C)と、を必須成分とし、N−メチロール(メタ)アクリルアミドおよびN−アルコキシメチル(メタ)アクリルアミドは含まない、活性エネルギー線重合性接着剤。 - 活性エネルギー線重合性接着剤全量中、
化合物(A)を0.5〜30重量%、
化合物(B)を40〜99重量%、
化合物(C)を0.5〜30重量%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接着剤。 - 化合物(A)に含まれるα,β−不飽和二重結合基が、アクリロイル基、またはメタクリロイル基であることを特徴とする請求項1又は2記載の活性エネルギー線重合性接着剤。
- 化合物(C)が有するアミノ基が2個以上であ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接着剤。
- 基材(G)と、該基材(G)の少なくとも一方の主面に設けられた、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接着剤からなる樹脂層とを有する積層体。
- 前記基材(G)が、透明フィルム(H)である請求項5記載の積層体。
- 前記、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、及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6記載の積層体。
- 光学フィルムと、該光学フィルムの少なくとも一方の主面に設けられた、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接着剤からなる樹脂層とを有する光学素子用積層体。
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