JP2008260879A - Active energy ray-curable adhesive composition, polarizing plate using it and its manufacturing method - Google Patents
Active energy ray-curable adhesive composition, polarizing plate using it and its manufacturing method Download PDFInfo
- Publication number
- JP2008260879A JP2008260879A JP2007105758A JP2007105758A JP2008260879A JP 2008260879 A JP2008260879 A JP 2008260879A JP 2007105758 A JP2007105758 A JP 2007105758A JP 2007105758 A JP2007105758 A JP 2007105758A JP 2008260879 A JP2008260879 A JP 2008260879A
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- Prior art keywords
- meth
- adhesive composition
- active energy
- energy ray
- film
- Prior art date
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- Granted
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 122
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- 239000003505 polymerization initiator Substances 0.000 claims abstract description 20
- 239000002985 plastic film Substances 0.000 claims abstract description 17
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- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 32
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
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- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- FYYIUODUDSPAJQ-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 2-methylprop-2-enoate Chemical compound C1C(COC(=O)C(=C)C)CCC2OC21 FYYIUODUDSPAJQ-UHFFFAOYSA-N 0.000 description 2
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- 239000004593 Epoxy Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- ZGFPUTOTEJOSAY-UHFFFAOYSA-N FC1=C([Ti])C(F)=CC=C1N1C=CC=C1 Chemical compound FC1=C([Ti])C(F)=CC=C1N1C=CC=C1 ZGFPUTOTEJOSAY-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
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- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
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- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Polarising Elements (AREA)
Abstract
Description
本発明は、活性エネルギー線硬化型接着性組成物、詳しくは、ポリビニルアルコール系偏光フィルムとポリオレフィン系樹脂フィルム、例えば熱可塑性ノルボルネン系樹脂フィルムとの接着に好適な活性エネルギー線硬化型接着性組成物、それを用いて得られる偏光板、及びその製造方法に関するものである。 The present invention relates to an active energy ray-curable adhesive composition, more specifically, an active energy ray-curable adhesive composition suitable for adhesion between a polyvinyl alcohol polarizing film and a polyolefin resin film, for example, a thermoplastic norbornene resin film. , A polarizing plate obtained using the same, and a method for producing the same.
接着剤は、包装材料分野、ラベル等の表示材料分野、電子部品分野、精密機器分野、建設材料分野等様々な分野において広く利用されている。近年では製造工程の高速化、生産性向上の目的で、紫外線、電子線などの活性エネルギー線で硬化するタイプの活性エネルギー線硬化型接着剤が広く利用されるようになってきている。光学機能性フィルムの製造においても、例えば、偏光フィルムと保護フィルムの貼り合わせには、従来ポリビニルアルコール系水性接着剤が使用されていたが、それに代わって活性エネルギー線硬化型接着剤の使用が検討されるようになってきている。特に、その傾向は、保護フィルム、位相差フィルムとしてノルボルネン系樹脂フィルムなどのポリオレフィン系樹脂フィルムが用いられるようになってから強くなってきている。 Adhesives are widely used in various fields such as packaging materials, display materials such as labels, electronic parts, precision equipment, and construction materials. In recent years, active energy ray-curable adhesives that are cured with active energy rays such as ultraviolet rays and electron beams have been widely used for the purpose of speeding up production processes and improving productivity. In the production of optical functional films, for example, polyvinyl alcohol-based water-based adhesives were conventionally used for laminating polarizing films and protective films, but instead using active energy ray-curable adhesives was examined. It has come to be. In particular, this tendency has become stronger after polyolefin resin films such as norbornene resin films are used as protective films and retardation films.
活性エネルギー線硬化性接着剤として、例えば、特許文献１には、ラジカル重合性二重結合とトリアジン骨格とを有するアミノ樹脂（ａ）と、ラジカル重合性を有さない非反応性樹脂（ｂ）、及びラジカル重合性二重結合を有する（ａ）以外の化合物（ｃ）からなる活性エネルギー線硬化性化合物を接着層とした場合、熱可塑性ノルボルネン系樹脂とＰＶＡ系偏光子の接着界面での膨れ現象や、接着力の低下などのない耐久性のある偏光板が得られることが記載されている。また、特許文献２には、（ａ）数平均分子量５，０００〜１５，０００のウレタン（メタ）アクリレート化合物、（ｂ）アクリロイルモルフォリン、ジメチルアクリルアミド、ジエチルアクリルアミド及びジイソプロピルアクリルアミドの中から選ばれる１種又は２種以上の化合物、（ｃ）フェノキシエチルアクリレート等を含む特定構造のアクリレート化合物を含有する液状硬化性粘・接着性組成物が、活性エネルギー線で硬化させるとＰＶＣフィルムやＰＥＴフィルムに対して優れた接着性を示すことが記載されており、特許文献３には、（Ａ）数平均分子量が１０，０００〜４０，０００であるウレタンアクリレートと、（Ｂ）ホモポリマーのガラス転移温度が６０℃以上であるエチレン性不飽和モノマー３０〜６０重量部を含有する液状硬化性樹脂組成物がプラスチック基板に対し優れた接着性を有することが記載されている。 As an active energy ray-curable adhesive, for example, Patent Document 1 discloses an amino resin (a) having a radical polymerizable double bond and a triazine skeleton, and a non-reactive resin (b) having no radical polymerizability. When the active energy ray-curable compound comprising the compound (c) other than (a) having a radical polymerizable double bond is used as an adhesive layer, swelling at the adhesive interface between the thermoplastic norbornene resin and the PVA polarizer It is described that a durable polarizing plate without the phenomenon and the decrease in adhesive strength can be obtained. In Patent Document 2, (a) a urethane (meth) acrylate compound having a number average molecular weight of 5,000 to 15,000, (b) acryloylmorpholine, dimethylacrylamide, diethylacrylamide and diisopropylacrylamide are selected. When a liquid curable adhesive / adhesive composition containing an acrylate compound having a specific structure including a seed or two or more kinds of compounds, (c) phenoxyethyl acrylate, and the like is cured with active energy rays, a PVC film or a PET film Patent Document 3 describes that (A) urethane acrylate having a number average molecular weight of 10,000 to 40,000 and (B) the glass transition temperature of the homopolymer are described in Patent Document 3. Contains 30-60 parts by weight of ethylenically unsaturated monomer that is 60 ° C. or higher Jo curable resin composition is described to have excellent adhesion to plastic substrates.
更に、特許文献４には、（Ａ）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共役ジエン重合体、（Ｂ）分子内に少なくとも１個のエチレン性不飽和結合を有する化合物および（Ｃ）光ラジカル重合開始剤を含有する接着剤組成物が、活性エネルギー線の照射で短時間硬化可能で、環状ポリオレフィン樹脂等の非極性基材同士や非極性基材とポリビニルアルコール系偏光フィルム等の極性基材との接着力に優れていることが記載されている。また、特許文献５には、（Ａ）数平均分子量が１０，０００〜４０，０００であるウレタン（メタ）アクリレート、及び（Ｂ）環状エーテルを持つエチレン性不飽和モノマーを含有する放射線硬化性樹脂組成物が、環状ポリオレフィンポリマーに対して優れた接着力を有していることが記載されている。
しかしながら、これらの接着剤はいずれも比較的分子量の大きい化合物を配合することを必須要件とするものであり、接着剤の粘度が高くなって接着層の厚さを薄くすることが困難であるという問題があった。
Furthermore, Patent Document 4 discloses (A) a conjugated diene polymer having at least one (meth) acryloyl group in the molecule, (B) a compound having at least one ethylenically unsaturated bond in the molecule, and ( C) Adhesive composition containing a radical photopolymerization initiator can be cured for a short time by irradiation with active energy rays, and nonpolar substrates such as cyclic polyolefin resin, nonpolar substrates and a polyvinyl alcohol polarizing film, etc. It is described that the adhesive strength with the polar substrate is excellent. Patent Document 5 discloses a radiation curable resin containing (A) a urethane (meth) acrylate having a number average molecular weight of 10,000 to 40,000 and (B) an ethylenically unsaturated monomer having a cyclic ether. It is described that the composition has excellent adhesion to cyclic polyolefin polymers.
However, all of these adhesives require that a compound having a relatively large molecular weight be blended, and it is difficult to reduce the thickness of the adhesive layer due to the increased viscosity of the adhesive. There was a problem.
一方、最近になってラジカル重合とカチオン重合の二つの重合モードで重合する接着性組成物が提案されている。例えば、特許文献６には、ラジカル重合材料とカチオン重合材料（ビスフェノールＡ型エポキシ樹脂、脂環式エポキシ樹脂等）を含有する紫外線硬化型接着剤が、有機フィルムへの接着力の向上が計れること、ＵＶ照射量をできるだけ少なくしたい場合、プロセス工法を適正化することで、接着剤の反応完結をＵＶ以外の方法で助長させることができることが記載されている。また、特許文献７には、（ａ）光カチオン重合性化合物、（ｂ）光カチオン重合開始剤、（ｃ）光ラジカル重合性化合物、（ｄ）光ラジカル重合開始剤を含む接着剤が、加熱加圧と光照射の併用により加熱温度を小さくでき、従来より低温での接続が可能になるので相対向する電極を電気的に接続する接着剤として好適であることが記載されている。
また、特許文献８には、カチオン的に硬化可能な成分と、多官能アクリレート、ラジカル光開始剤、カチオン性光開始剤を含む照射硬化可能な組成物がステレオリソグラフィーによる３次元の成型品の製造に好適であることが記載されている。
On the other hand, recently, an adhesive composition that polymerizes in two polymerization modes, radical polymerization and cationic polymerization, has been proposed. For example, Patent Document 6 discloses that an ultraviolet curable adhesive containing a radical polymerization material and a cationic polymerization material (bisphenol A type epoxy resin, alicyclic epoxy resin, etc.) can improve the adhesion to an organic film. It is described that, when it is desired to reduce the UV irradiation amount as much as possible, the reaction completion of the adhesive can be promoted by a method other than UV by optimizing the process method. Patent Document 7 discloses that an adhesive containing (a) a photocationic polymerizable compound, (b) a photocationic polymerization initiator, (c) a photoradical polymerizable compound, and (d) a photoradical polymerization initiator is heated. It is described that the combined use of pressurization and light irradiation makes it possible to reduce the heating temperature and enables connection at a lower temperature than in the prior art, so that it is suitable as an adhesive for electrically connecting opposing electrodes.
In addition, Patent Document 8 discloses that a radiation-curable composition containing a cationically curable component, a polyfunctional acrylate, a radical photoinitiator, and a cationic photoinitiator is used to produce a three-dimensional molded article by stereolithography. It is described that it is suitable.
しかしながら、単に、ラジカル重合とカチオン重合の二つの重合モードで重合する接着性組成物をポリビニルアルコール系フィルムとプラスチックフィルムとの接着に適用しても十分な接着強度が得られないという問題があった。 However, there is a problem that sufficient adhesive strength cannot be obtained even when an adhesive composition that is polymerized in two polymerization modes, radical polymerization and cationic polymerization, is applied to the adhesion between a polyvinyl alcohol film and a plastic film. .
本発明は、上記問題に鑑みてなされたもので、ポリビニルアルコール系フィルムとプラスチックフィルムとを簡便に、しかも十分な強度で接着できる活性エネルギー線硬化型接着性組成物、及びそれを用いて得られる偏光板を提供することを目的とする。 The present invention has been made in view of the above problems, and is obtained by using an active energy ray-curable adhesive composition that can easily and sufficiently bond a polyvinyl alcohol film and a plastic film with sufficient strength. An object is to provide a polarizing plate.
本発明者等は検討した結果、ポリビニルアルコール系フィルムとプラスチックフィルムとの接着に好適な活性エネルギー線硬化型接着性組成物を見いだした。すなわち、本発明は、
（１）ポリビニルアルコール系フィルムとプラスチックフィルムとを接着するための活性エネルギー線硬化型接着性組成物であって、該接着性組成物は（Ａ）（メタ）アクリル系ラジカル重合性化合物と（Ｂ）カチオン重合性化合物からなる主剤と、該主剤１００重量部に対し、（Ｃ）光ラジカル重合開始剤を０．１〜１０重量部、及び（Ｄ）光カチオン重合開始剤を０．１〜１０重量部を含有していて、２０℃における粘度が５〜１００ｍＰａ・ｓであり、前記主剤は、
（Ａ１）分子中に（メタ）アクリル基を２以上有する（メタ）アクリル系化合物５〜４０重量％
（Ａ２）分子中に水酸基と、ただ１つの（メタ）アクリル基を有する（メタ）アクリル系化合物１５〜５５重量％
（Ｂ１）分子中に（メタ）アクリル基を有するカチオン重合性化合物１５〜６５重量％を、含有していることを特徴とする活性エネルギー線硬化型接着性組成物。
As a result of investigations, the present inventors have found an active energy ray-curable adhesive composition suitable for bonding a polyvinyl alcohol film and a plastic film. That is, the present invention
(1) An active energy ray-curable adhesive composition for bonding a polyvinyl alcohol film and a plastic film, the adhesive composition comprising (A) a (meth) acrylic radical polymerizable compound and (B ) 0.1 to 10 parts by weight of (C) radical photopolymerization initiator and (D) 0.1 to 10 parts of photocationic polymerization initiator based on 100 parts by weight of the main component comprising a cationic polymerizable compound. It contains 5 parts by weight and has a viscosity at 20 ° C. of 5 to 100 mPa · s.
(A1) 5 to 40% by weight of (meth) acrylic compound having 2 or more (meth) acrylic groups in the molecule
(A2) 15 to 55% by weight of a (meth) acrylic compound having a hydroxyl group and only one (meth) acrylic group in the molecule
(B1) An active energy ray-curable adhesive composition comprising 15 to 65% by weight of a cationic polymerizable compound having a (meth) acryl group in the molecule.
（２）（Ａ２）分子中に水酸基を有し、（メタ）アクリル基をただ１つ有する（メタ）アクリル系化合物が、ヒドロキシアルキル（メタ）アクリレートであることを特徴とする（１）記載の活性エネルギー線硬化型接着性組成物。
（３）（Ｂ１）分子中に（メタ）アクリル基を有するカチオン重合性化合物が、エポキシ基またはオキセタン基を有していることを特徴とする（１）又は（２）記載の活性エネルギー線硬化型接着性組成物。
（４）（Ｂ１）分子中に（メタ）アクリル基を有するカチオン重合性化合物が、脂環式エポキシ基を有していることを特徴とする（３）記載の活性エネルギー線硬化型接着性組成物。
（５）（Ｃ）光ラジカル重合開始剤がアルキルフェノン系又はアシルフォスフィンオキサイド系の光ラジカル重合開始剤であることを特徴とする（１）〜（４）のいずれかに記載の活性エネルギー線硬化型接着性組成物。
（６）（Ｄ）光カチオン重合開始剤が、ヨードニウム塩系の光カチオン重合開始剤であることを特徴とする（１）〜（５）のいずれかに記載の活性エネルギー線硬化型接着性組成物。
（７）チオキサントン系の光増感剤を併用することを特徴とする（６）記載の活性エネルギー線硬化型接着性組成物。
（８）ポリビニルアルコール系フィルムがポリビニルアルコール系偏光フィルムであることを特徴とする（１）〜（７）のいずれかに記載の活性エネルギー線硬化型接着性組成物。
（９）プラスチックフィルムがポリオレフィン系フィルムであることを特徴とする（１）〜（８）のいずれかに記載の活性エネルギー線硬化型接着性組成物。
（１０）ポリオレフィン系フィルムが熱可塑性ノルボルネン系樹脂フィルムであることを特徴とする（９）記載の活性エネルギー線硬化型接着性組成物。
(2) (A2) The (meth) acrylic compound having a hydroxyl group in the molecule and having only one (meth) acrylic group is a hydroxyalkyl (meth) acrylate, An active energy ray-curable adhesive composition.
(3) (B1) The cationic polymerizable compound having a (meth) acryl group in the molecule has an epoxy group or an oxetane group, and the active energy ray curing according to (1) or (2) Mold adhesive composition.
(4) The active energy ray-curable adhesive composition according to (3), wherein the cationic polymerizable compound having a (meth) acrylic group in the molecule (B1) has an alicyclic epoxy group. object.
(5) The active energy ray according to any one of (1) to (4), wherein (C) the photoradical polymerization initiator is an alkylphenone-based or acylphosphine oxide-based photoradical polymerization initiator. A curable adhesive composition.
(6) The active energy ray-curable adhesive composition according to any one of (1) to (5), wherein the (D) photocationic polymerization initiator is an iodonium salt-based photocationic polymerization initiator. object.
(7) The active energy ray-curable adhesive composition according to (6), wherein a thioxanthone photosensitizer is used in combination.
(8) The active energy ray-curable adhesive composition according to any one of (1) to (7), wherein the polyvinyl alcohol film is a polyvinyl alcohol polarizing film.
(9) The active energy ray-curable adhesive composition according to any one of (1) to (8), wherein the plastic film is a polyolefin film.
(10) The active energy ray-curable adhesive composition according to (9), wherein the polyolefin-based film is a thermoplastic norbornene-based resin film.
（１１）ポリビニルアルコール系偏光フィルムと熱可塑性ノルボルネン系樹脂フィルムとを（１）〜（１０）のいずれかに記載の活性エネルギー線硬化型接着性組成物を用いて接着してなる偏光板。
（１２）ポリビニルアルコール系偏光フィルムと熱可塑性ノルボルネン系樹脂フィルムとを（１）〜（１０）のいずれかに記載の活性エネルギー線硬化型接着性組成物を介して貼合した後、活性エネルギー線を照射して、前記活性エネルギー線硬化型接着性組成物を硬化させることを特徴とする偏光板の製造方法、
を要旨とするものである。
(11) A polarizing plate formed by bonding a polyvinyl alcohol polarizing film and a thermoplastic norbornene resin film using the active energy ray-curable adhesive composition according to any one of (1) to (10).
(12) After bonding the polyvinyl alcohol polarizing film and the thermoplastic norbornene resin film through the active energy ray-curable adhesive composition according to any one of (1) to (10), the active energy ray A method of producing a polarizing plate, wherein the active energy ray-curable adhesive composition is cured
Is a summary.
本発明の活性エネルギー線硬化型接着性組成物は、特定の（メタ）アクリル系ラジカル重合性化合物とカチオン重合性化合物で構成されていて、ラジカル重合とカチオン重合の二つの重合モードで重合するのでポリビニルアルコール系フィルムとプラスチックフィルム、特に、ポリビニルアルコール系偏光フィルムとポリオレフィン系フィルムとを強固に接着することができ、また、低照度で短時間の照射で硬化させることができるという特徴も有している。更に、粘度が１００ｍＰａ・ｓ以下と低いので接着層を薄くすることができ、光学用途に利用しても接着剤層によって光学特性を損なうことがないという特徴を有している。
特に、本発明の接着剤組成物は、接着層の厚さを薄くすることができるので、従来、フィルム状の被着体を接着する場合に必須とされていた分子量の高い化合物を含有していないにもかかわらず、ポリビニルアルコール系フィルムとプラスチックフィルムとを強固に接着できると共に、貼合されたフィルムをロール状に巻き取ることが可能になるという効果を有している。
したがって、本発明の接着剤組成物は、ポリビニルアルコール系偏光フィルムと熱可塑性ノルボルネン系樹脂フィルムの貼合に好適であり、高性能な偏光板を提供することが可能となった。
The active energy ray-curable adhesive composition of the present invention is composed of a specific (meth) acrylic radical polymerizable compound and a cationic polymerizable compound, and polymerizes in two polymerization modes, radical polymerization and cationic polymerization. Polyvinyl alcohol film and plastic film, in particular, polyvinyl alcohol polarizing film and polyolefin film can be firmly bonded, and can also be cured by irradiation for a short time with low illumination. Yes. Furthermore, since the viscosity is as low as 100 mPa · s or less, the adhesive layer can be thinned, and the optical properties are not impaired by the adhesive layer even when used for optical applications.
In particular, since the adhesive composition of the present invention can reduce the thickness of the adhesive layer, it contains a compound having a high molecular weight, which has been conventionally required when adhering a film-shaped adherend. In spite of the absence, the polyvinyl alcohol film and the plastic film can be firmly bonded, and the bonded film can be wound into a roll.
Therefore, the adhesive composition of the present invention is suitable for laminating a polyvinyl alcohol polarizing film and a thermoplastic norbornene resin film, and can provide a high-performance polarizing plate.
以下に、本発明を実施するための最良の形態について詳細に説明する。なお、本発明において、「（メタ）アクリル」とは、アクリル又はメタクリルの意味で用いる。また、本発明でいう主剤とは、（Ａ）（メタ）アクリル系ラジカル重合性化合物と（Ｂ）カチオン重合性化合物の双方を合わせたものを意味している。更に、本発明でいう活性エネルギー線硬化型接着性組成物とは、活性エネルギー線を照射することで硬化可能な接着性組成物である。 The best mode for carrying out the present invention will be described in detail below. In the present invention, “(meth) acryl” means acryl or methacryl. Moreover, the main agent as used in the field of this invention means what combined (A) (meth) acrylic radically polymerizable compound and (B) cation polymerizable compound. Furthermore, the active energy ray-curable adhesive composition referred to in the present invention is an adhesive composition that can be cured by irradiation with active energy rays.
本発明の活性エネルギー線硬化型接着性組成物は、主剤中に（Ａ１）分子中に（メタ）アクリル基を２以上有する（メタ）アクリル系化合物、（Ａ２）分子中に水酸基と、ただ１つの（メタ）アクリル基を有する（メタ）アクリル系化合物、（Ｂ１）分子中に（メタ）アクリル基を有するカチオン重合性化合物を必須成分として特定量含有するものであり、主剤中に（Ａ１）、（Ａ２）、（Ｂ１）の合計量が５０〜１００重量％、特に７０〜１００重量％の範囲で含まれるようにするのが好ましい。 The active energy ray-curable adhesive composition of the present invention comprises only (A1) a (meth) acrylic compound having two or more (meth) acrylic groups in the molecule, (A2) a hydroxyl group in the molecule, (Meth) acrylic compound having two (meth) acrylic groups, (B1) a cationic polymerizable compound having a (meth) acrylic group in the molecule as a necessary component, and containing (A1) in the main component , (A2) and (B1) are preferably contained in a range of 50 to 100% by weight, particularly 70 to 100% by weight.
さて、本発明の活性エネルギー線硬化型接着性組成物を構成する（Ａ）（メタ）アクリル系ラジカル重合性化合物のうち、（Ａ１）分子中に（メタ）アクリル基を２以上有する（メタ）アクリル系化合物としては、例えば、エチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、エチレンオキシド変性ビスフェノールＡジ（メタ）アクリレート、イソシアヌル酸エチレンオキサイド変性ジアクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトール・エチレンオキシド変性トリ（メタ）アクリレート、トリメチロールプロパントリオキシエチル（メタ）アクリレート、トリス（２−ヒドロキシエチル）イソシアヌレートトリ（メタ）アクリレート、トリス（２−ヒドロキシエチル）イソシアヌレートジ（メタ）アクリレート、ε―カプロラクトン変性トリス（２−アクリロキシエチル）イソシアヌルレート、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトール・エチレンオキシド変性テトラ（メタ）アクリレート等の（メタ）アクリル系モノマーが挙げられ、これらを単独で、或いは混合して使用することができる。
特に、本発明において分子中に（メタ）アクリル基を２又は３個有する（メタ）アクリル系化合物を使用することが好ましい。更に、（Ａ１）分子中に（メタ）アクリル基を２以上有する（メタ）アクリル系化合物として、分子量が２０００以下のものを使用するのが接着性組成物の粘度を５〜１００ｍＰａ・ｓ以下とする上で好ましい。
Now, among the (A) (meth) acrylic radical polymerizable compounds constituting the active energy ray-curable adhesive composition of the present invention, (A1) the molecule has two or more (meth) acrylic groups (meth). Examples of the acrylic compound include ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, isocyanuric acid ethylene oxide Modified diacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol / ethylene oxide modified tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2-hydroxyethyl) Isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, ε-caprolactone modified tris (2-acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, pentaerythritol / ethylene oxide Examples include (meth) acrylic monomers such as modified tetra (meth) acrylate, and these can be used alone or in combination. .
In particular, in the present invention, it is preferable to use a (meth) acrylic compound having 2 or 3 (meth) acrylic groups in the molecule. Furthermore, as the (meth) acrylic compound having two or more (meth) acrylic groups in the molecule (A1), the one having a molecular weight of 2000 or less uses a viscosity of the adhesive composition of 5 to 100 mPa · s or less. This is preferable.
本発明で使用する（Ａ１）分子中に（メタ）アクリル基を２以上有する（メタ）アクリル系化合物は、主剤中に５〜４０重量％、特に、５〜２０重量％の範囲で含まれるようにするのが接着性、柔軟性、光硬化性等をバランスさせやすいので好ましい。含有量が５重量％未満では、架橋密度が少なく接着性が低下するばかりか、接着速度が遅くなるので好ましくない。また４０重量％を超えると、架橋密度が多すぎて接着層が硬くなり、得られたフィルムの柔軟性が不足すると共に接着強度も低下するので好ましくない。 (A1) The (meth) acrylic compound having 2 or more (meth) acrylic groups in the molecule used in the present invention is contained in the main agent in an amount of 5 to 40% by weight, particularly 5 to 20% by weight. It is preferable to make it easy to balance adhesiveness, flexibility, photocurability, and the like. If the content is less than 5% by weight, it is not preferable because not only the crosslinking density is low and the adhesiveness is lowered, but also the bonding speed is lowered. On the other hand, if it exceeds 40% by weight, the crosslink density is too high, the adhesive layer becomes hard, the flexibility of the obtained film is insufficient, and the adhesive strength is also unfavorable.
また、（Ａ２）分子中に水酸基を有し、（メタ）アクリル基をただ１つ有する（メタ）アクリル系化合物としては、例えば、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、４―ヒドロキシブチル（メタ）アクリレート、２―ヒドロキシブチル（メタ）アクリレート、グリセロールモノ（メタ）アクリレート、カプロラクトン変性（メタ）アクリレート、２―ヒドロキシ―３―フェノキシプロピル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、トリメチロールプロパン（モノ）アクリレートや、Ｎ−ヒドロキシエチル（メタ）アクリルアミドが挙げられ、これらを単独で、或いは混合して使用することができる。
これらの中でも、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、４―ヒドロキシブチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレートが好ましく、特に、ヒドロキシエチル（メタ）アクリレート、４−ヒドロキシブチルアクリレートが好ましいが、最も好ましいのは４−ヒドロキシブチルアクリレートである
Further, (A2) (meth) acrylic compounds having a hydroxyl group in the molecule and having only one (meth) acrylic group include, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, caprolactone-modified (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate , Trimethylolpropane (mono) acrylate, and N-hydroxyethyl (meth) acrylamide, and these can be used alone or in combination.
Among these, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate are preferable, and particularly hydroxyethyl (meth) acrylate and 4-hydroxybutyl. Acrylate is preferred, but most preferred is 4-hydroxybutyl acrylate
（Ａ２）分子中に水酸基を有し、（メタ）アクリル基をただ１つ有するアクリル系化合物は、主剤中に、１５〜５５重量％、特に２０〜５０重量％の範囲で含まれるようにするのが好ましい。これが１５重量％未満では接着性組成物全体の親水性が低下して、ポリビニルアルコール系フィルムに対する接着性が低下するので好ましくなく、４５重量％を超えると接着性組成物が硬くなるばかりか、硬化速度が遅くなるので好ましくない。 (A2) The acrylic compound having a hydroxyl group in the molecule and having only one (meth) acrylic group is contained in the main agent in the range of 15 to 55% by weight, particularly 20 to 50% by weight. Is preferred. If this is less than 15% by weight, the hydrophilicity of the entire adhesive composition is lowered, and the adhesiveness to the polyvinyl alcohol film is lowered, which is not preferable, and if it exceeds 45% by weight, the adhesive composition is not only hardened but also cured. Since the speed is slow, it is not preferable.
更に、本発明においては（Ａ３）（メタ）アクリル系ラジカル重合性化合物（Ａ１）、（Ａ２）以外の（メタ）アクリル系化合物）を併用することももちろん可能である。このような（Ａ３）（メタ）アクリル系化合物としては、例えば、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、アミル（メタ）アクリレート、イソアミル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソデシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート、ノニル（メタ）アクリレート、ドデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、２−エチルヘキシルカルビトール（メタ）アクリレート、２−アクリロイルオキシエチルコハク酸、ブトキシエチル（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、シクロヘキシルアクリレート、エトキシエチル（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、イソボルニル（メタ）アクリレート、ｔ−オクチル（メタ）アクリルアミド、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、７−アミノ−３，７−ジメチルオクチル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、ノニルフェノールエチレンオキサイド変性アクリレート、フェノールエチレンオキサイド変性アクリレートが挙げられる。 Furthermore, in the present invention, (A3) (meth) acrylic radical polymerizable compounds (A1) and (meth) acrylic compounds other than (A2)) can of course be used in combination. Examples of such (A3) (meth) acrylic compounds include propyl (meth) acrylate, isopropyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, t-butyl (meth) acrylate, and isobutyl. (Meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, octadecyl (meth) acrylate, nonyl (meth) ) Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl carbitol (meth) Acrylate, 2-acryloyloxyethyl succinic acid, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, cyclohexyl acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, Isobornyl (meth) acrylate, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, phenoxyethyl (meth) acrylate , Nonylphenol ethylene oxide modified acrylate, phenol ethylene oxide modified acrylate
更に、例えば、Ｎ，Ｎ’−ジメチルアクリルアミド、Ｎ，Ｎ’−ジエチルアクリルアミド、Ｎ，Ｎ’−ジメチルアミノエチルアクリルアミド、Ｎ，Ｎ’−ジメチルアミノプロピルアクリルアミド、Ｎ−イソプロピルアクリルアミド、Ｎ，Ｎ’−ジメチルアミノプロピルアクリルアミド等のアクリルアミド誘導体も挙げられる。 Further, for example, N, N′-dimethylacrylamide, N, N′-diethylacrylamide, N, N′-dimethylaminoethylacrylamide, N, N′-dimethylaminopropylacrylamide, N-isopropylacrylamide, N, N′— Examples include acrylamide derivatives such as dimethylaminopropylacrylamide.
これらの（Ａ３）（メタ）アクリル系化合物の配合量は、主剤中に０〜５０重量％の範囲で配合することができる。 The compounding quantity of these (A3) (meth) acrylic compounds can be mix | blended in the range of 0 to 50 weight% in a main ingredient.
一方、本発明で使用するカチオン重合性化合物（Ｂ）としての（Ｂ１）分子中に（メタ）アクリル基を有するカチオン重合性化合物とは、分子中にカチオン重合性官能基と（メタ）アクリル基の２種類の官能基を有する化合物であり、カチオン重合性化合物であるエポキシ化合物や、アルキルビニルエーテル化合物、アリールビニルエーテル化合物等のビニルエーテル化合物、或いはオキセタン化合物、テトラヒドロフラン化合物、テトラヒドロピラン化合物等の環状エーテル化合物のうち、分子中に（メタ）アクリル基を有する化合物である。
（Ｂ１）分子中に（メタ）アクリル基を有するカチオン重合性化合物は、主剤中に１５〜６５重量％、特に、２０〜５５重量％の範囲で含まれるようにするのが好ましい。この含有量が１５重量％未満ではポリビニルアルコール系フィルムとプラスチックフィルムとの接着強度が十分ではないので好ましくなく、６５重量％を超えると、重合スピードが遅くなり、連続生産に適用できなくなるので好ましくない。
本発明で用いられる（Ｂ１）分子中に（メタ）アクリル基を有するカチオン重合性化合物としては、例えば、３，４−エポキシシクロヘキシルメチル（メタ）アクリレートや３，４−エポキシシクロヘキセニルメチル―３’，４’―エポキシシクロヘキセンカルボキシレートなどの脂環式エポキシ基含有（メタ）アクリレート、グリシジル（メタ）アクリレート、オキセタン（メタ）アクリレート等が挙げられるが、特に、脂環式エポキシ基含有（メタ）アクリレートが好ましい。
On the other hand, the (B1) cationic polymerizable compound having a (meth) acryl group in the molecule as the cationic polymerizable compound (B) used in the present invention is a cationic polymerizable functional group and a (meth) acryl group in the molecule. A compound having two types of functional groups, a cationically polymerizable compound such as an epoxy compound, a vinyl ether compound such as an alkyl vinyl ether compound or an aryl vinyl ether compound, or a cyclic ether compound such as an oxetane compound, a tetrahydrofuran compound or a tetrahydropyran compound. Among them, it is a compound having a (meth) acryl group in the molecule.
(B1) The cationically polymerizable compound having a (meth) acryl group in the molecule is preferably contained in the main agent in an amount of 15 to 65% by weight, particularly 20 to 55% by weight. If the content is less than 15% by weight, the adhesive strength between the polyvinyl alcohol film and the plastic film is not sufficient, which is not preferable. If the content exceeds 65% by weight, the polymerization speed becomes slow and it is not possible to apply to continuous production. .
Examples of the cationically polymerizable compound (B1) having a (meth) acryl group in the molecule used in the present invention include 3,4-epoxycyclohexylmethyl (meth) acrylate and 3,4-epoxycyclohexenylmethyl-3 ′. , 4'-epoxycyclohexenecarboxylate and other alicyclic epoxy group-containing (meth) acrylates, glycidyl (meth) acrylates, oxetane (meth) acrylates, and the like, particularly alicyclic epoxy group-containing (meth) acrylates Is preferred.
さらに、本発明においては（Ｂ１）分子中に（メタ）アクリル基を有するカチオン重合性化合物に加えて、（Ｂ２）（メタ）アクリル基を有さないカチオン重合性化合物を併用することができる。（Ｂ）カチオン重合性化合物として、（Ｂ２）分子中に（メタ）アクリル基を有さないカチオン重合性化合物のみを使用した場合には十分な接着強度を示さないが（Ｂ１）と併用することにより良好な接着強度を付与することができる。
このような（Ｂ２）分子中に（メタ）アクリル基を有さないカチオン重合性化合物としては、例えば、３−エチル−３−エチルヒドロキシメチルオキセタンや３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレートが挙げられる。
Furthermore, in the present invention, in addition to (B1) a cationic polymerizable compound having a (meth) acryl group in the molecule, (B2) a cationic polymerizable compound having no (meth) acryl group can be used in combination. (B) When only a cationic polymerizable compound having no (meth) acrylic group in the molecule is used as the cationic polymerizable compound (B2), sufficient adhesive strength is not shown, but it is used in combination with (B1). Better adhesive strength can be imparted.
Examples of such a cationically polymerizable compound having no (meth) acryl group in the molecule (B2) include 3-ethyl-3-ethylhydroxymethyloxetane and 3,4-epoxycyclohexylmethyl-3,4- An epoxy cyclohexanecarboxylate is mentioned.
（Ｃ）光ラジカル重合開始剤としては、例えば、ベンズアルデヒド、アントラキノン、トリフェニルアミン、３−メチルアセトフェノン、４−クロロベンゾフェノン、４，４′−ジメトキシベンゾフェノン、４，４′−ジアミノベンゾフェノン、ミヒラーケトン、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、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、１−ヒドロキシシクロヘキシルフェニルケトン（ＩＲＧＡＣＵＲＥ１８４）、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン（ＤＡＲＯＣＵＲ１１７３）、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、２−ヒロドキシ−１−｛４−［４−（２−ヒドロキシ−２−メチル−プロピオニル）ベンジル］フェニル｝−２−メチルプロパン−１−オン、２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）ブタノン−１（ＩＲＧＡＣＵＲＥ３６９）、２−（ジメチルアミノ）−２−［（４−メチルフェニル）メチル］−１−［４−（４−モルホリニル）フェニル］−１−ブタノン、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（ＤＡＲＯＣＵＲ ＴＰＯ）、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド（ＩＲＧＡＣＵＲＥ８１９）、ビス（η５−２，４−シクロペンタジエン−１−イル）−ビス（２，６−ジフルオロ−３−（１Ｈ−ピロール−１−イル）フェニル）チタニウム（ＩＲＧＡＣＵＲＥ７８４）、エタノン，１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−，１−（Ｏ−アセチルオキシム）、ｐ−ジメチルアミノ安息香酸イソアミルエステル（ＫＡＹＡＣＵＲＥ ＤＭＢＩ）等が挙げられる。 (C) Examples of the photo radical polymerization initiator include benzaldehyde, anthraquinone, triphenylamine, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin Propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone (IRGACURE184), 2-hydroxy-2-methyl-1-phenylpropane -1-one (DAROCUR1173), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4 -(2 Hydroxy-2-methyl-propionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) butanone-1 (IRGACURE369), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl ] 1-butanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (DAROCUR TPO), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE819), bis (η 5 -2, 4-Cyclopentadien-1-yl) -bis (2,6-difluoro-3 -(1H-pyrrol-1-yl) phenyl) titanium (IRGACURE784), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O- Acetyloxime), p-dimethylaminobenzoic acid isoamyl ester (KAYACURE DMBI), and the like.
これらの中でも、４００ｎｍ以上の長波長側にも吸収を有する、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）ブタノン−１（ＩＲＧＡＣＵＲＥ３６９）、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド（ＩＲＧＡＣＵＲＥ８１９）、ビス（η５−２，４−シクロペンタジエン−１−イル）−ビス（２，６−ジフルオロ−３−（１Ｈ−ピロール−１−イル）フェニル）チタニウム（ＩＲＧＡＣＵＲＥ７８４）、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（ＤＡＲＯＣＵＲ ＴＰＯ）を単独で、或いは他の光ラジカル重合開始剤と組み合わせて使用することが好ましい。
これら長波長側に吸収を有する光ラジカル重合開始剤を使用した場合、メタルハライドランプのように長波長側にもスペクトルを有する紫外線ランプを使用した場合でも速やかに硬化させることができる。その場合、照射時の被着体の温度上昇を抑えることができるという利点を有している。なお、従来、４００ｎｍ以上の波長に吸収を有する光ラジカル重合開始剤を使用すると接着性組成物が僅かに着色するという問題があったが、本発明の接着性組成物は低粘度であるため極めて薄く塗布できるので問題が生じないという利点も有している。
（Ｃ）光ラジカル重合開始剤の配合割合は、主剤の合計量１００重量部に対して０．１〜１０重量部、特に０．１〜５重量部が好ましい。
Among these, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (IRGACURE 369), bis (2,4,6-trimethyl) also has absorption on the long wavelength side of 400 nm or more. Benzoyl) -phenylphosphine oxide (IRGACURE819), bis (η 5 -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium (IRGACURE784) and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (DAROCUR TPO) are preferably used alone or in combination with other photoradical polymerization initiators.
When these radical photopolymerization initiators having absorption on the long wavelength side are used, they can be cured rapidly even when an ultraviolet lamp having a spectrum on the long wavelength side, such as a metal halide lamp, is used. In that case, it has the advantage that the temperature rise of the adherend during irradiation can be suppressed. Conventionally, there has been a problem that when an optical radical polymerization initiator having absorption at a wavelength of 400 nm or longer is used, the adhesive composition is slightly colored, but the adhesive composition of the present invention is extremely low in viscosity. Since it can be applied thinly, there is an advantage that no problem occurs.
(C) The blending ratio of the radical photopolymerization initiator is preferably 0.1 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the main agent.
（Ｄ）光カチオン重合開始剤としては、例えば、ポリアリールスルホニウムヘキサフルオロホスフェート（３Ｍカンパニ−社製、商品名：Ｆｃ−５０８若しくはＦＸ−５１２）、ポリアリ−ルスルホニウムヘキサフルオロアンチモン塩（ゼネラルエレクトリック、カンパニ−社製、商品名：ＵＶＥ−１０１４）、ポリアリールスルホニウムヘキサフルオロホスフェート（旭電化（株）製、商品名：ＳＰ−１７０）、トリアリールスルホニウムヘキサフルオロホスフェート塩（ダイセル・サイテック（株）製、ＵＶＡＣＵＲＥ１５９０）、ヘキサフルオロアンチモネ−ト（旭電化（株）製、商品名：ＳＰ−１５０）、ヨードニウム（４−メチルフェニル）［４−（２−メチルプロピル）フェニル］−ヘキサフルオロフォスフェート（１−）（チバ・スペシャリティ・ケミカルズ製、商品名：ＩＲＧＡＣＵＲＥ２５０）、ビス（アルキルフェニル）ヨードニウムヘキサフルオロフォスフェート（和光純薬製、商品名：ＷＰＩ−１１７３）等のポリアリールスルホニウム錯塩、ハロゲン含有錯イオンの芳香族スルホニウム塩若しくはヨードニウム塩、並びに第ＩＩＩａ、Ｖａ及びＶＩａ族元素の芳香族オニウム塩が挙げられる。これらの中で、ヨードニウム塩系の光カチオン重合開始剤が好ましい。 (D) As a photocationic polymerization initiator, for example, polyarylsulfonium hexafluorophosphate (manufactured by 3M Company, trade name: Fc-508 or FX-512), polyarylsulfonium hexafluoroantimony salt (general electric, Company name, UVE-1014), polyarylsulfonium hexafluorophosphate (Asahi Denka Co., Ltd., trade name: SP-170), triarylsulfonium hexafluorophosphate salt (Daicel Cytec Co., Ltd.) , UVACURE1590), hexafluoroantimonate (manufactured by Asahi Denka Co., Ltd., trade name: SP-150), iodonium (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate ( 1-) (Chi -Specialty aryl chemicals, trade name: IRGACURE250), polyarylsulfonium complex salts such as bis (alkylphenyl) iodonium hexafluorophosphate (trade name: WPI-1173), aromatic sulfonium of halogen-containing complex ions Salts or iodonium salts, and aromatic onium salts of Group IIIa, Va and VIa elements. Of these, iodonium salt-based photocationic polymerization initiators are preferred.
更に、本発明においては、上記（Ｄ）光カチオン重合開始剤の性能を向上させるために光増感剤を併用することが好ましい。光増感剤としてはチオキサントン系の光ラジカル重合開始剤である２，４−ジエチルチオキサントン（日本化薬（株）製、商品名：ＫＡＹＡＣＵＲＥ ＤＴＥＸ−Ｓ）、イソプロピルチオキサントン、１−クロロ−４−プロピルチオキサントン、２−クロロチオキサントンや、ローズベンガル、エリスロシン、［４−（メチルフェニルチオ）フェニル］フェニルメタノン、４−フェニルベンゾフェノン等が挙げられる。
本発明においては、（Ｄ）光カチオン重合開始剤は主剤の合計量１００重量部に対し、通常０．１〜１０重量部、特に０．１〜５重量部配合するのが好ましい。
Furthermore, in the present invention, it is preferable to use a photosensitizer in combination in order to improve the performance of the (D) photocationic polymerization initiator. As photosensitizers, 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYACURE DTEX-S), which is a thioxanthone photoradical polymerization initiator, isopropylthioxanthone, 1-chloro-4-propyl Examples include thioxanthone, 2-chlorothioxanthone, rose bengal, erythrosine, [4- (methylphenylthio) phenyl] phenylmethanone, 4-phenylbenzophenone, and the like.
In the present invention, (D) the cationic photopolymerization initiator is preferably added in an amount of usually 0.1 to 10 parts by weight, particularly 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the main agent.
また、本発明の活性エネルギー線硬化型接着剤には、他の公知の添加剤を混合することも可能である。公知の添加剤としては、イオン系導電剤、導電性金属酸化物微粒子などの導電性付与添加剤、接着剤の屈折率と屈折率が異なる光拡散微粒子などの光拡散性付与添加剤、粘度を調整する公知の溶剤などが挙げられる。 The active energy ray-curable adhesive of the present invention can be mixed with other known additives. Known additives include ionic conductive agents, conductive conductivity additives such as conductive metal oxide fine particles, light diffusibility imparting additives such as light diffusing fine particles whose refractive index and refractive index of the adhesive are different, and viscosity. Examples include known solvents to be adjusted.
さて、本発明の接着性組成物は上述した（Ａ１）、（Ａ２）、（Ｂ１）を必須成分として配合したものであるが、この接着性組成物の粘度が２３℃で５〜１００ｍＰａの範囲となるようにする必要がある。接着性組成物の粘度を５ｍＰａ・ｓ未満とするのは実質的に困難であり、粘度が１００ｍＰａ・ｓを超えると接着剤を薄く塗布できないので好ましくない。
粘度を上記範囲とするためには、従来、プラスチックフィルムの貼合に使用する接着性組成物において、接着強度の向上と柔軟性の付与を目的として配合していた分子量の高い化合物、例えば、分子量が２０００以上のウレタン（メタ）アクリレート、ポリエステル（メタ）アクリレート、末端に（メタ）アクリロイル基を有するジエン化合物等の配合量を極力減らすか、或いは配合しないことで達成することができる。なお、その場合であっても、本発明の接着性組成物は粘度が低いため接着層の厚みが薄いので十分な柔軟性と接着強度を発揮するという特徴を有している。
Now, the adhesive composition of the present invention contains (A1), (A2) and (B1) described above as essential components. The viscosity of the adhesive composition is in the range of 5 to 100 mPa at 23 ° C. It is necessary to become. It is substantially difficult to make the viscosity of the adhesive composition less than 5 mPa · s. If the viscosity exceeds 100 mPa · s, the adhesive cannot be applied thinly, which is not preferable.
In order to make the viscosity within the above range, a compound having a high molecular weight, which has been conventionally blended for the purpose of improving adhesive strength and imparting flexibility in an adhesive composition used for bonding a plastic film, for example, molecular weight Can be achieved by reducing the amount of urethane (meth) acrylate having a molecular weight of 2000 or more, polyester (meth) acrylate, diene compound having a (meth) acryloyl group at the terminal, or the like, to the minimum or not. Even in such a case, the adhesive composition of the present invention has a characteristic that it exhibits sufficient flexibility and adhesive strength since the viscosity of the adhesive composition is low and the thickness of the adhesive layer is thin.
そして、上述した本発明の活性エネルギー線硬化型接着性組成物は、ポリビニルアルコール系フィルムとプラスチックフィルムとの貼合に用いられる。ポリビニルアルコール系フィルムとしては、通常、酢酸ビニルを重合したポリ酢酸ビニルをケン化して得られるのであるが、本発明では必ずしもこれに限定されるものではなく、少量の不飽和カルボン酸（塩、エステル、アミド、ニトリル等を含む）、炭素数２〜３０のオレフィン類（エチレン、プロピレン、ｎ−ブテン、イソブテン等）、ビニルエーテル類、不飽和スルホン酸塩等、酢酸ビニルと共重合可能な成分を含有させた変性ポリビニルアルコール系樹脂、或いはエチレン−ビニルアルコール共重合体等からなるフィルム、及びこれらのフィルムにヨウ素や二色性色素を染色・吸着させ、これを一軸延伸してなる偏光フィルムが挙げられる。また、ポリビニルアルコール系樹脂の重量平均分子量はとくに限定されないが、好ましくは６０，０００〜３００，０００、より好ましくは１２０，０００〜２６０，０００である。 And the active energy ray hardening-type adhesive composition of this invention mentioned above is used for bonding of a polyvinyl alcohol-type film and a plastic film. The polyvinyl alcohol film is usually obtained by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate, but is not necessarily limited to this in the present invention, and a small amount of unsaturated carboxylic acid (salt, ester). , Amides, nitriles, etc.), olefins having 2 to 30 carbon atoms (ethylene, propylene, n-butene, isobutene, etc.), vinyl ethers, unsaturated sulfonates, and other components copolymerizable with vinyl acetate. Examples include films made of modified polyvinyl alcohol resins or ethylene-vinyl alcohol copolymers, and polarizing films obtained by dyeing and adsorbing iodine or dichroic dyes to these films and stretching them uniaxially. . The weight average molecular weight of the polyvinyl alcohol resin is not particularly limited, but is preferably 60,000 to 300,000, more preferably 120,000 to 260,000.
一方、ポリビニルアルコール系フィルムに貼合するプラスチックフィルムとしては、特に制限はなく、通常の合成樹脂製のプラスチックフィルムが適用されるが、特に、ポリエチレン系フィルム、ポリプロピレン系フィルム、ポリ−４−メチルペンテンフィルム、環状オレフィンフィルム等のポリオレフィン系フィルムが好ましい。これらの中でも、特に、環状ポリオレフィン系フィルムである熱可塑性ノルボルネン系樹脂フィルムが好ましい。 On the other hand, the plastic film to be bonded to the polyvinyl alcohol film is not particularly limited, and a plastic film made of a normal synthetic resin is applied. In particular, a polyethylene film, a polypropylene film, and poly-4-methylpentene are used. Polyolefin films such as films and cyclic olefin films are preferred. Among these, a thermoplastic norbornene resin film which is a cyclic polyolefin film is particularly preferable.
熱可塑性ノルボルネン系樹脂フィルムは、例えば、（イ）ノルボルネン系モノマーの開環重合体もしくは開環共重合体を、必要に応じて、マレイン酸付加、シクロペンタジエン付加等の変性を行った後水素添加した樹脂、（ロ）ノルボルネン系モノマーを付加重合させた樹脂、（ハ）ノルボルネン系モノマーとエチレン、α−オレフィン等のオレフィン系モノマーとを付加重合させた樹脂、（ニ）ノルボルネン系モノマーとシクロペンテン、シクロオクテン、５，６−ジヒドロジシクロペンタジエン等の環状オレフィン系モノマーとを付加重合させた樹脂、及び、これらの変性物などの熱可塑性ノルボルネン系樹脂を成形したフィルムを意味しており、流延法、溶融押出法などの公知の方法でフィルム化したものであれば良い。熱可塑性ノルボルネン系樹脂としてはＪＳＲ社の商品名「アートン」、日本ゼオン社の商品名「ゼオノア」、三井化学社の商品名「アペル」がよく知られている。 Thermoplastic norbornene-based resin film is, for example, (i) ring-opening polymer or ring-opening copolymer of norbornene-based monomer, if necessary, after modification such as maleic acid addition or cyclopentadiene addition, hydrogenation (B) a resin obtained by addition polymerization of a norbornene monomer, (c) a resin obtained by addition polymerization of a norbornene monomer and an olefin monomer such as ethylene or α-olefin, (d) a norbornene monomer and cyclopentene, It means a resin obtained by addition polymerization of cycloolefin and cyclic olefin monomers such as 5,6-dihydrodicyclopentadiene, and a film obtained by molding a thermoplastic norbornene resin such as a modified product thereof. Any film may be used as long as it is formed into a film by a known method such as a method or a melt extrusion method. As the thermoplastic norbornene-based resin, the product name “Arton” from JSR, the product name “Zeonor” from Zeon Corporation, and the product name “Apel” from Mitsui Chemicals are well known.
本発明の接着性組成物は、ポリビニルアルコール系フィルムとしてのポリビニルアルコール系偏光フィルムに、プラスチックフィルムである熱可塑性ノルボルネン系樹脂フィルムを貼り合わせた偏光板の製造に適用するのが最も好ましい。この際、ポリビニルアルコール系偏光フィルムと貼り合せる熱可塑性ノルボルネン系樹脂フィルムは、位相差を有してもよい。位相差を示す熱可塑性ノルボルネン系樹脂フィルムを用いることにより、偏光板の上に更に位相差フィルムを貼合する工程が省かれ、より低コスト化、工程の簡略化がなされる。熱可塑性ノルボルネン系樹脂フィルムに位相差を付与する方法は、公知の方法でよく、フィルムを縦方向、または、横方向に延伸した一軸性位相差フィルム、フィルムを縦方向、および、横方向に延伸した二軸性位相差フィルムなどの延伸フィルム、熱可塑性ノルボルネン系樹脂フィルム上にディスコチック液晶などの液晶を傾斜配向させた液晶塗布型視野角補償フィルムなどが挙げられる。 The adhesive composition of the present invention is most preferably applied to the production of a polarizing plate in which a thermoplastic norbornene resin film as a plastic film is bonded to a polyvinyl alcohol polarizing film as a polyvinyl alcohol film. At this time, the thermoplastic norbornene resin film to be bonded to the polyvinyl alcohol polarizing film may have a retardation. By using the thermoplastic norbornene-based resin film exhibiting the phase difference, the step of further laminating the phase difference film on the polarizing plate is omitted, thereby further reducing the cost and simplifying the step. The method for imparting retardation to the thermoplastic norbornene-based resin film may be a known method, and a uniaxial retardation film obtained by stretching the film in the longitudinal direction or the transverse direction, and stretching the film in the longitudinal direction and the transverse direction. Examples thereof include a stretched film such as a biaxial retardation film and a liquid crystal coating type viewing angle compensation film in which a liquid crystal such as a discotic liquid crystal is tilted and oriented on a thermoplastic norbornene resin film.
次いで、本発明の活性エネルギー線硬化型接着性組成物を用いてポリビニルアルコール系偏光フィルムの両面に熱可塑性ノルボルネン系フィルムを貼り合わせてなる偏光板の製造方法の一例について説明する。
まず、ポリビニルアルコール系偏光フィルム及び／又は熱可塑性ノルボルネン系フィルムの表面に、本発明の活性エネルギー線硬化型接着性組成物をロールコーター、バーコーター、グラビアロール、接着剤塗布ノズル等の塗布装置を用いて塗布する。その際の、接着性組成物の塗布厚さは、０．５〜５μｍ、好ましくは０．５〜３μｍである。次いで接着塗布層を介してポリビニルアルコール系偏光フィルムの両面に熱可塑性ノルボルネン系樹脂フィルムを貼合した後、活性エネルギー線を照射して上記接着性組成物を硬化させ本発明の偏光板を得る。また、偏光板の製造に当たり、ポリビニルアルコール系偏光フィルムと熱可塑性ノルボルネン系樹脂フィルムとの密着性を強化するために、必要に応じてあらかじめ熱可塑性ノルボルネン系樹脂フィルム、若しくはポリビニルアルコール系偏光フィルムの表面を公知のコロナ処理、プラズマ処理、ＵＶ処理、火炎処理などで、表面を改質することも出来る。
Subsequently, an example of the manufacturing method of the polarizing plate which bonds a thermoplastic norbornene-type film on both surfaces of a polyvinyl alcohol-type polarizing film using the active energy ray hardening-type adhesive composition of this invention is demonstrated.
First, a coating apparatus such as a roll coater, a bar coater, a gravure roll, and an adhesive coating nozzle is applied to the active energy ray-curable adhesive composition of the present invention on the surface of a polyvinyl alcohol polarizing film and / or a thermoplastic norbornene film. Use to apply. In this case, the coating thickness of the adhesive composition is 0.5 to 5 μm, preferably 0.5 to 3 μm. Next, after pasting a thermoplastic norbornene resin film on both surfaces of the polyvinyl alcohol polarizing film via an adhesive coating layer, the adhesive composition is cured by irradiating active energy rays to obtain the polarizing plate of the present invention. Further, in the production of the polarizing plate, in order to enhance the adhesion between the polyvinyl alcohol polarizing film and the thermoplastic norbornene resin film, the surface of the thermoplastic norbornene resin film or the polyvinyl alcohol polarizing film in advance as necessary. The surface can be modified by a known corona treatment, plasma treatment, UV treatment, flame treatment or the like.
活性エネルギー線としては、可視光線、紫外線、電子線、Ｘ線等が挙げられるが、その中でも活性エネルギー線の発生装置が簡便で、取り扱いが容易な紫外線を使用するのが好ましい。この紫外線を照射するためのランプとしては高圧水銀ランプ、メタルハライドランプが代表的であるが、その中でも４００ｎｍ以上の領域にもスペクトルを有するメタルハライドランプを使用するのが照射時に被着体であるポリビニルアルコール系偏光フィルムの温度上昇が少ないので好ましい。本発明の活性エネルギー線硬化型接着性組成物は、メタルハライドランプを使用した場合であっても低照度で、しかも短時間の照射で硬化するという特徴を有している。
また、上述したように熱可塑性ノルボルネン系フィルム／接着性組成物／ポリビニルアルコール系偏光フィルム／接着性組成物／熱可塑性ノルボルネン系フィルムの構成となるように貼り合わせた場合で、一方の側から紫外線を照射すると照射面側の接着性組成物は十分な照度の紫外線照射を受けるが、その反対面の接着性組成物へは偏光フィルムを通過した紫外線を照射したことになるためおおよそ１／２以下、測定した結果では１／３程度の照度でしか照射されないこととなる。紫外線照射の照度をより高くすれば反対面の照度も高くすることが可能ではあるが、照度を５００ｍＷ／ｃｍ２を超えて高くすると被着物であるポリビニルアルコール系偏光フィルムの性能低下や劣化の原因となるという問題がある。よって、本発明の接着性組成物は、１００ｍＷ／ｃｍ２以下の低照度でも十分に短時間で硬化するが、硬化の際の照度は３０〜５００ｍＷ／ｃｍ２、好ましくは５０〜３００ｍＷ／ｃｍ２である。また、積算光量は３００〜１５００ｍＪ／ｃｍ２とすることが好ましい。
したがって、一方の面に紫外線吸収剤を添加した熱可塑性ノルボルネン系フィルムを使用した場合であっても、紫外線吸収剤を添加した熱可塑性ノルボルネン系フィルムの反対側からのみ紫外線を照射することによりポリビニルアルコール系偏光フィルムを挿む両方の接着性組成物を容易に硬化させることができる。
Examples of the active energy rays include visible light, ultraviolet rays, electron beams, X-rays, etc. Among them, it is preferable to use ultraviolet rays which are simple in active energy ray generating apparatus and easy to handle. Typical examples of the lamp for irradiating with ultraviolet rays include a high-pressure mercury lamp and a metal halide lamp. Among them, the use of a metal halide lamp having a spectrum in a region of 400 nm or more is a polyvinyl alcohol which is an adherend upon irradiation. This is preferable because the temperature rise of the polarizing film is small. The active energy ray-curable adhesive composition of the present invention has a feature that even when a metal halide lamp is used, it is cured with low illumination and in a short time.
In addition, as described above, when bonded to form a thermoplastic norbornene-based film / adhesive composition / polyvinyl alcohol-based polarizing film / adhesive composition / thermoplastic norbornene-based film, ultraviolet light is emitted from one side. The adhesive composition on the irradiated surface side is irradiated with ultraviolet light with sufficient illuminance, but the adhesive composition on the opposite surface is irradiated with ultraviolet light that has passed through the polarizing film, so that it is approximately 1/2 or less. As a result of the measurement, irradiation is performed only with an illuminance of about 1/3. It is possible to increase the illuminance on the opposite surface if the illuminance of ultraviolet irradiation is further increased, but if the illuminance is increased beyond 500 mW / cm 2 , the cause of performance deterioration or deterioration of the polyvinyl alcohol polarizing film as the adherend There is a problem of becoming. Therefore, although the adhesive composition of the present invention is cured in a sufficiently short time even at a low illuminance of 100 mW / cm 2 or less, the illuminance upon curing is 30 to 500 mW / cm 2 , preferably 50 to 300 mW / cm 2. It is. Moreover, it is preferable that an integrated light quantity shall be 300-1500 mJ / cm < 2 >.
Therefore, even when a thermoplastic norbornene film added with an ultraviolet absorber on one side is used, polyvinyl alcohol is irradiated by irradiating ultraviolet rays only from the opposite side of the thermoplastic norbornene film added with an ultraviolet absorber. Both adhesive compositions into which the system polarizing film is inserted can be easily cured.
更にまた、本発明によって得られる偏光板は、必要に応じて、防眩層、ハードコート層、反射防止層、低反射層、反射層、防汚層、防曇層、蓄光層、光拡散層、エレクトロルミネッセンス層等の機能層を１層若しくはそれ以上積層することもできる。
このように積層して得られる偏光板は、液晶パネルの少なくとも片面に使用されるべき偏光板として、あるいはサングラス、視力矯正用メガネ等の眼鏡用レンズの少なくとも片面に粘着される偏光板として好ましく適用される。
Furthermore, the polarizing plate obtained by the present invention includes an antiglare layer, a hard coat layer, an antireflection layer, a low reflection layer, a reflection layer, an antifouling layer, an antifogging layer, a phosphorescent layer, and a light diffusion layer as necessary. Further, one or more functional layers such as an electroluminescence layer can be laminated.
The polarizing plate obtained by laminating in this way is preferably applied as a polarizing plate to be used on at least one side of a liquid crystal panel, or as a polarizing plate adhered to at least one side of a spectacle lens such as sunglasses or eyesight correction glasses. Is done.
以下に本発明を実施例により具体的に説明するが、本発明はこれらに限定されるものではない。
本実施例においては主剤として以下の（Ａ）（メタ）アクリル系ラジカル重合性化合物及び（Ｂ）カチオン重合性化合物を使用した。
１．（Ａ）（メタ）アクリル系ラジカル重合性化合物
＜（Ａ１）分子中に（メタ）アクリル基を２以上有する（メタ）アクリル系化合物＞
（Ａ１−１） トリス（２−ヒドロキシエチル）イソシアヌレートトリ（メタ）アクリレート
（Ａ１−２） ε―カプロラクトン変性トリス（２−アクリロキシエチル）イソシアヌルレート（新中村化学（株）製、商品名：Ａ−９３００−２ＣＬ）
（Ａ１−３） エチレンオキシド変性ビスフェノールＡジメタクリレート（第一工業製薬（株）製、商品名：ＢＰＥ−４）
＜（Ａ２）分子中に水酸基と、ただ１つの（メタ）アクリル基を有する（メタ）アクリル系化合物＞
（Ａ２−１） ヒドロキシエチルメタクリレート
（Ａ２−２） ４−ヒドロキシブチルアクリレート
（Ａ２−３） 水酸基含有カプロラクトン変性アクリレート（ダイセル化学工業（株）製、商品名：プラクセルＦＡ１ＤＤＭ）
＜（Ａ３） その他の（メタ）アクリル系化合物＞
（Ａ３−１） フェノールエチレンオキサイド（ｎ＝４）変性アクリレート（東亞合成化学（株）製、商品名：Ｍ−１０２）
２．（Ｂ）カチオン重合性化合物
＜（Ｂ１） （メタ）アクリル基を有するカチオン重合性化合物＞
（Ｂ１−１） ３，４−エポキシシクロヘキシルメチルメタアクリレート
（Ｂ１−２） オキセタンメタクリレート（大阪有機化学工業（株）製、商品名：ＯＸＥ−３０）
＜（Ｂ２） （メタ）アクリル基を有さないカチオン重合性化合物＞
（Ｂ２−１） ３−エチル−３−エチルヒドロキシメチルオキセタン
（Ｂ２−２） ３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレート
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
In this example, the following (A) (meth) acrylic radical polymerizable compound and (B) cationic polymerizable compound were used as the main agent.
1. (A) (Meth) acrylic radical polymerizable compound <(A1) (meth) acrylic compound having two or more (meth) acrylic groups in the molecule>
(A1-1) Tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate (A1-2) ε-caprolactone-modified tris (2-acryloxyethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-9300-2CL)
(A1-3) Ethylene oxide modified bisphenol A dimethacrylate (Daiichi Kogyo Seiyaku Co., Ltd., trade name: BPE-4)
<(A2) (Meth) acrylic compound having hydroxyl group and only one (meth) acrylic group in molecule>
(A2-1) Hydroxyethyl methacrylate (A2-2) 4-hydroxybutyl acrylate (A2-3) Hydroxyl group-containing caprolactone-modified acrylate (manufactured by Daicel Chemical Industries, Ltd., trade name: Plaxel FA1DDM)
<(A3) Other (meth) acrylic compounds>
(A3-1) Phenolethylene oxide (n = 4) modified acrylate (manufactured by Toagosei Co., Ltd., trade name: M-102)
2. (B) Cationic polymerizable compound <(B1) Cationic polymerizable compound having (meth) acrylic group>
(B1-1) 3,4-epoxycyclohexylmethyl methacrylate (B1-2) Oxetane methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: OXE-30)
<(B2) Cationic polymerizable compound having no (meth) acrylic group>
(B2-1) 3-ethyl-3-ethylhydroxymethyloxetane (B2-2) 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate
３．光重合開始剤
光重合開始剤としてはとしては以下のものを使用した。
＜（Ｃ）光ラジカル重合開始剤＞
（Ｃ−１） ＤＡＲＯＣＵＲ４２６５（チバ・スペシャリティ・ケミカルズ（株）製）
ＤＡＲＯＣＵＲ ＴＰＯとＤＡＲＯＣＵＲ１１７３のブレンド物
（Ｃ−２） ＩＲＧＡＣＵＲＥ８１９（チバ・スペシャリティ・ケミカルズ（株）製）
（Ｃ−３） ＩＲＧＡＣＵＲＥ１８４（チバ・スペシャリティ・ケミカルズ（株）製）
＜（Ｄ）光カチオン重合開始剤＞
（Ｄ−１） ＩＲＧＡＣＵＲＥ２５０（チバ・スペシャリティ・ケミカルズ（株）製）
ヨードニウム塩系の光カチオン重合開始剤
（Ｄ−２） ＵＶＡＣＵＲＥ１５９０（ダイセル・サイテック（株）製）
スルホニウム塩系の光カチオン重合開始剤
＜（Ｅ）光増感剤＞
（Ｅ−１） ＫＡＹＡＣＵＲＥ ＤＴＥＸ―Ｓ（日本化薬（株）製）
（Ｅ−２） ４−フェニルベンゾフェノン（日本シイベルヘグナー（株）製）
3. Photopolymerization initiator The following were used as the photopolymerization initiator.
<(C) Photoradical polymerization initiator>
(C-1) DAROCUR4265 (Ciba Specialty Chemicals Co., Ltd.)
DAROCUR TPO and DAROCUR 1173 blend (C-2) IRGACURE 819 (Ciba Specialty Chemicals)
(C-3) IRGACURE 184 (manufactured by Ciba Specialty Chemicals)
<(D) Photocationic polymerization initiator>
(D-1) IRGACURE250 (Ciba Specialty Chemicals Co., Ltd.)
Iodonium salt-based photocationic polymerization initiator (D-2) UVACURE 1590 (manufactured by Daicel-Cytec)
Sulfonium salt-based photocationic polymerization initiator <(E) photosensitizer>
(E-1) KAYACURE DTEX-S (manufactured by Nippon Kayaku Co., Ltd.)
(E-2) 4-Phenylbenzophenone (manufactured by Nippon Siebel Hegner)
また、本発明にかかる接着性組成物の性能は以下の方法で評価した。
＜偏光板の製造＞
ポリビニルアルコール系フィルムとして厚み２７μｍのポリビニルアルコール系偏光フィルム（ヨウ素系偏光フィルム、以下、偏光フィルムという。）、プラスチックフィルムとして厚み６０μｍの熱可塑性ノルボルネン系フィルム（ＪＳＲ（株）社製、商品名「アートン」製フィルム、以下、保護フィルムという。）を使用し、偏光フィルムと保護フィルムの間に活性エネルギー線硬化型接着性組成物を塗布厚みが１μｍになるように塗布して、保護フィルム（表面側）／偏光フィルム／保護フィルム（裏面側）の順に積層貼合した。次いで、メタルハライドランプを光源にして、紫外線を保護フィルム（表面側）の側から照射して活性エネルギー線硬化型接着性組成物を硬化させ、偏光板を製造し、各種試験に供した。
Moreover, the performance of the adhesive composition concerning this invention was evaluated with the following method.
<Manufacture of polarizing plate>
A polyvinyl alcohol polarizing film having a thickness of 27 μm as a polyvinyl alcohol film (iodine polarizing film, hereinafter referred to as a polarizing film), and a thermoplastic norbornene film having a thickness of 60 μm as a plastic film (trade name “ARTON” manufactured by JSR Corporation) ”Film, hereinafter referred to as a protective film), and an active energy ray-curable adhesive composition is applied between the polarizing film and the protective film so that the coating thickness is 1 μm. ) / Polarizing film / protective film (back side) in this order. Next, using a metal halide lamp as a light source, ultraviolet rays were irradiated from the protective film (surface side) side to cure the active energy ray-curable adhesive composition, and a polarizing plate was produced and subjected to various tests.
＜照度及び積算光量＞
接着性組成物に対する紫外線の照度（ｍＷ／ｃｍ２）、積算光量（ｍＪ／ｃｍ２）については、保護フィルム（表面側）と偏光フィルムの間の接着性組成物については保護フィルム（表面側）表面の実測値をそのまま、保護フィルム（裏面側）と偏光フィルムの間の接着性組成物については、ブランク試験の結果より、照射した紫外線の照度、スペクトルの分布は保護フィルムを通過しても殆ど変化せず、偏光フィルムを通過した場合はスペクトルの分布は変化せずに強度のみが概ね１／３に減少したことから、保護フィルム（表面側）表面の照度及び積算光量に１／３を乗じた値を採用した。
したがって、照射面の照度が３００ｍＷ／ｃｍ２、積算光量が１５００ｍＪ／ｃｍ２の場合、裏面側の接着性組成物に対する照度は１００ｍＷ／ｃｍ２、積算光量は５００ｍＪ／ｃｍ２となる。
<Illuminance and integrated light intensity>
About the illuminance of ultraviolet rays (mW / cm 2 ) and the integrated light quantity (mJ / cm 2 ) for the adhesive composition, the protective film (surface side) for the adhesive composition between the protective film (surface side) and the polarizing film As for the adhesive composition between the protective film (back side) and the polarizing film with the actual measured value of the surface as it is, from the result of the blank test, the illuminance and spectrum distribution of the irradiated ultraviolet rays are almost passed through the protective film. When passing through the polarizing film without changing, the spectrum distribution does not change and only the intensity is reduced to approximately 1/3. Therefore, the illuminance on the surface of the protective film (surface side) and the integrated light amount are multiplied by 1/3. Values were adopted.
Therefore, the illuminance of the irradiated surface is 300 mW / cm 2, when integrated light quantity of 1500 mJ / cm 2, illuminance for the adhesive compositions of the back side 100 mW / cm 2, accumulated light quantity becomes 500 mJ / cm 2.
＜剥離強度＞
上記方法で得られた偏光板２５ｍｍ巾に裁断して試験片とし、２３℃、５０％ＲＨ環境下で、島津製作所製引張試験機「オートグラフＡＧＳ−１００Ｂ」を用い、ＪＩＳ Ｋ６８５４−４ 接着剤―はく離接着強さ試験方法―第４部：浮動ローラ法に準拠し、引張速度３００ｍｍ／分で測定した。
＜硬化状態＞
上記方法で得られた偏光板の界面を剥離し、接着性組成物の硬化状態をタックの有無で評価した。接着性組成物が十分に硬化していない場合はタックが生じる。
＜光学特性＞
得られた偏光板の光学特性と偏光フィルム自身の光学特性との差異が大きいかどうかで判断した。
○：変化なし、 ×：変化有り
＜耐屈曲性＞
得られた偏光板を直径３０ｍｍの円柱に巻き付け、その際にクラック等が発生したかどうかについて観察した。
○：クラックの発生なし、 ×：クラックの発生有り
<Peel strength>
The polarizing plate obtained by the above method is cut to a width of 25 mm to obtain a test piece, which is JIS K6854-4 adhesive using a tensile tester “Autograph AGS-100B” manufactured by Shimadzu Corporation under an environment of 23 ° C. and 50% RH. -Peeling adhesive strength test method-Part 4: Measured at a tensile speed of 300 mm / min according to the floating roller method.
<Curing state>
The interface of the polarizing plate obtained by the above method was peeled off, and the cured state of the adhesive composition was evaluated by the presence or absence of tack. If the adhesive composition is not sufficiently cured, tack will occur.
<Optical characteristics>
Judgment was made based on whether or not the difference between the optical properties of the obtained polarizing plate and the optical properties of the polarizing film itself was large.
○: No change ×: Change <Bend resistance>
The obtained polarizing plate was wound around a cylinder with a diameter of 30 mm, and it was observed whether cracks or the like occurred at that time.
○: No crack occurred, ×: Crack occurred
実施例１、２
（Ａ１−２）ε―カプロラクトン変性トリス（２−アクリロキシエチル）イソシアヌルレート２０重量％、（Ａ２−２）４−ヒドロキシブチルアクリレート４０重量％、（Ｂ１−１）３，４−エポキシシクロヘキシルメチルメタアクリレート４０重量％からなる主剤１００重量部に対して、光ラジカル重合開始剤としての（Ｃ−２）ＩＲＧＡＣＵＲＥ８１９、（Ｃ−３）ＩＲＧＡＣＵＲＥ１８４、光カチオン重合開始剤としての（Ｄ−１）ＩＲＧＡＣＵＲＥ２５０、及び光増感剤としての（Ｅ）ＫＡＹＡＣＵＲＥ ＤＴＥＸを表１に示す量配合して接着性組成物を調製し、得られた接着性組成物について紫外線の照射量、積算光量を変化させて各種性能を測定した。結果を同じく表１に示す。
Examples 1 and 2
(A1-2) ε-caprolactone-modified tris (2-acryloxyethyl) isocyanurate 20% by weight, (A2-2) 4-hydroxybutyl acrylate 40% by weight, (B1-1) 3,4-epoxycyclohexylmethyl meta (C-2) IRGACURE 819 as a photo radical polymerization initiator, (C-3) IRGACURE 184, (D-1) IRGACURE 250 as a photo cationic polymerization initiator, and 100 parts by weight of the main agent composed of 40% by weight of acrylate. (E) KAYACURE DTEX as a photosensitizer is blended in the amounts shown in Table 1 to prepare an adhesive composition, and the obtained adhesive composition has various performances by changing the irradiation amount of ultraviolet rays and the integrated light quantity. It was measured. The results are also shown in Table 1.
表１から明らかなように、本発明の実施例１にかかる活性エネルギー線硬化型接着性組成物は粘度が２０ｍＰａ・ｓ前後と低く、容易に１μｍの厚みで塗布することができ、また、４０ｍＷ／ｃｍ２から３７６ｍＷ／ｃｍ２と広い照度範囲にわたって短時間で硬化して良好な剥離強度を示した。更に、得られた偏光板は光学特性、耐屈曲性についても全く問題ないものであった。特に、実験番号Ｎｏ．１〜３のように低照度、低積算光量で紫外線照射をした場合であっても材料破壊を起こすほどの剥離強度を示すので、偏光フィルムにダメージを与えることなく活性エネルギー線硬化型接着性組成物を使用して一方向から紫外線照射することで両面に保護フィルムを貼着した偏光板を短時間で製造することが可能となった。
また、光開始剤の配合割合を半減させた実施例２の活性エネルギー線硬化型接着性組成物も同様に良好な性能を示した。
As is clear from Table 1, the active energy ray-curable adhesive composition according to Example 1 of the present invention has a viscosity as low as about 20 mPa · s and can be easily applied at a thickness of 1 μm. It cured in a short time over a wide illuminance range of from / cm 2 to 376 mW / cm 2 and showed good peel strength. Furthermore, the obtained polarizing plate had no problem with respect to optical properties and bending resistance. In particular, experiment no. Even if it is a case of ultraviolet irradiation with low illuminance and low integrated light quantity as in 1 to 3, it shows a peel strength that causes material destruction, so an active energy ray curable adhesive composition without damaging the polarizing film It became possible to produce a polarizing plate having a protective film attached to both sides in a short time by irradiating ultraviolet rays from one direction using an object.
Moreover, the active energy ray-curable adhesive composition of Example 2 in which the blending ratio of the photoinitiator was halved also showed good performance.
実施例３〜１２、比較例１、２
表２に示す配合割合で活性エネルギー線硬化型接着性組成物を調製し、得られた接着性組成物について各種性能を測定した。結果を同じく表２に示す。
Examples 3 to 12, Comparative Examples 1 and 2
An active energy ray-curable adhesive composition was prepared at a blending ratio shown in Table 2, and various performances were measured for the obtained adhesive composition. The results are also shown in Table 2.
表２からも明らかなように、本発明にかかる実施例３〜１２の接着性組成物は粘度が低いので、容易に１μｍの厚みで塗布することができ、また、短時間で硬化して良好な剥離強度を示し、光学特性、耐屈曲性についても全く問題ないものであった。また、実施例７からも明らかなように必須成分である（Ａ１）、（Ａ２）、（Ｂ１）以外の成分である（Ｂ２−２）３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレートを配合した場合であっても良好な性質を示した。一方、必須成分である（Ａ２）分子中に水酸基と、ただ１つの（メタ）アクリル基を有する（メタ）アクリル系化合物に代えて（Ａ３）その他の（メタ）アクリル系化合物を含有させた比較例１の接着性組成物や、（Ｂ１）（メタ）アクリル基を有するカチオン重合性化合物に代えて（Ｂ２）（メタ）アクリル基を有さないカチオン重合性化合物を含有させた比較例２の接着性組成物はいずれも剥離強度が弱く実用上問題があった。 As is apparent from Table 2, the adhesive compositions of Examples 3 to 12 according to the present invention have a low viscosity, so that they can be easily applied with a thickness of 1 μm, and are cured well in a short time. The peel strength was excellent, and there was no problem with respect to optical properties and bending resistance. Further, as apparent from Example 7, (B2-2) 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane, which is a component other than the essential components (A1), (A2), and (B1) Even when the carboxylate was blended, good properties were exhibited. On the other hand, in comparison with (A2) other (meth) acrylic compounds (A3) instead of (A2) (meth) acrylic compounds having only one (meth) acrylic group in the molecule (A2), which is an essential component The adhesive composition of Example 1 or (B1) of Comparative Example 2 containing a cationically polymerizable compound having no (meth) acrylic group instead of the cationically polymerizable compound having (meth) acrylic group. All of the adhesive compositions had practical problems due to their low peel strength.
本発明の接着性組成物は現在主流となっているポリビニルアルコール系偏光フィルムに対しても熱可塑性ノルボルネン系樹脂フィルムを短時間で強固に接着させることができる。特に、本発明の接着性組成物は活性エネルギー線を低照度、低積算光量で照射しても短時間で十分硬化して強固に接着するので、偏光フィルムへの両面貼合を片面からの照射のみで、偏光フィルムにダメージを与えることなく容易に行うことができる。しかも接着剤層の厚みを薄くすることができるのでポリビニルアルコール系偏光フィルムの保護フィルムの接着に好適である。 The adhesive composition of the present invention can firmly adhere a thermoplastic norbornene resin film to a polyvinyl alcohol polarizing film, which is currently mainstream, in a short time. In particular, the adhesive composition of the present invention cures sufficiently in a short time even if it is irradiated with active energy rays with low illuminance and low integrated light quantity, and adheres firmly to each other. Alone, it can be easily performed without damaging the polarizing film. And since the thickness of an adhesive bond layer can be made thin, it is suitable for adhesion | attachment of the protective film of a polyvinyl-alcohol-type polarizing film.
Claims (12)
（Ａ１）分子中に（メタ）アクリル基を２以上有する（メタ）アクリル系化合物５〜４０重量％
（Ａ２）分子中に水酸基と、ただ１つの（メタ）アクリル基を有する（メタ）アクリル系化合物１５〜５５重量％
（Ｂ１）分子中に（メタ）アクリル基を有するカチオン重合性化合物１５〜６５重量％を、含有していることを特徴とする活性エネルギー線硬化型接着性組成物。 An active energy ray-curable adhesive composition for adhering a polyvinyl alcohol film and a plastic film, the adhesive composition comprising (A) a (meth) acrylic radical polymerizable compound and (B) cationic polymerization (C) 0.1 to 10 parts by weight of a radical photopolymerization initiator and (D) 0.1 to 10 parts by weight of a cationic photopolymerization initiator with respect to 100 parts by weight of the main agent composed of a functional compound. And the viscosity at 20 ° C. is 5 to 100 mPa · s,
(A1) 5 to 40% by weight of (meth) acrylic compound having 2 or more (meth) acrylic groups in the molecule
(A2) 15 to 55% by weight of a (meth) acrylic compound having a hydroxyl group and only one (meth) acrylic group in the molecule
(B1) An active energy ray-curable adhesive composition comprising 15 to 65% by weight of a cationic polymerizable compound having a (meth) acryl group in the molecule.
After bonding the polyvinyl alcohol polarizing film and the thermoplastic norbornene resin film through the active energy ray-curable adhesive composition according to any one of claims 1 to 10, the active energy ray is irradiated, The manufacturing method of the polarizing plate characterized by hardening the said active energy ray hardening-type adhesive composition.
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