JP5459128B2 - Polarizing plate and light curable adhesive for polarizing plate formation - Google Patents
Polarizing plate and light curable adhesive for polarizing plate formation Download PDFInfo
- Publication number
- JP5459128B2 JP5459128B2 JP2010164200A JP2010164200A JP5459128B2 JP 5459128 B2 JP5459128 B2 JP 5459128B2 JP 2010164200 A JP2010164200 A JP 2010164200A JP 2010164200 A JP2010164200 A JP 2010164200A JP 5459128 B2 JP5459128 B2 JP 5459128B2
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- polymerizable compound
- mass
- polarizing plate
- radical polymerizable
- radical
- Prior art date
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Images
Classifications
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- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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Description
本発明は、液晶表示装置等に用いられる偏光板及び該偏光板形成用の光硬化性接着剤に関する。 The present invention relates to a polarizing plate used for a liquid crystal display device or the like and a photocurable adhesive for forming the polarizing plate.
時計、携帯電話、個人用の携帯情報端末(PDA)、ノートパソコン、パソコン用モニタ、DVDプレーヤー、TVなどでは液晶表示装置が急速に市場に広まっている。液晶表示装置は、液晶のスイッチングによる偏光状態を可視化させたものであり、その表示原理から、偏光子が用いられる。特に、TV等の用途では、ますます高輝度、高コントラスト、広い視野角が求められ、偏光板においてもますます高透過率、高偏光度、高い色再現性などが求められている。 Liquid crystal display devices are rapidly spreading in the market for watches, mobile phones, personal digital assistants (PDAs), notebook computers, personal computer monitors, DVD players, TVs, and the like. The liquid crystal display device visualizes the polarization state by switching of the liquid crystal, and a polarizer is used from the display principle. In particular, in applications such as TV, higher brightness, higher contrast, and wider viewing angle are required, and polarizing plates are also required to have higher transmittance, higher degree of polarization, and higher color reproducibility.
液晶表示関連分野などに用いられる偏光子は、通常ポリビニルアルコール(PVA)にヨウ素や染料を吸着させたものを一軸延伸して製造される。このポリビニルアルコール系偏光子は、熱や水分により収縮し、偏光性能の低下をきたす。そこで、PVA系偏光子の表面に保護フィルムを貼合せたものが偏光板として用いられる。 A polarizer used in a liquid crystal display-related field or the like is usually manufactured by uniaxially stretching a material obtained by adsorbing iodine or a dye on polyvinyl alcohol (PVA). This polyvinyl alcohol-based polarizer shrinks due to heat and moisture, resulting in a decrease in polarization performance. Then, what stuck the protective film on the surface of the PVA type | system | group polarizer is used as a polarizing plate.
偏光子に保護フィルムを貼着するための接着剤としては、従来からポリビニルアルコール系樹脂の水溶液(PVA系接着剤)が広く使用されている(特許文献1、2参照)。
また、特許文献3には、水性ウレタン系接着剤を用いてなる偏光板が開示されている。
As an adhesive for sticking a protective film to a polarizer, an aqueous solution (PVA adhesive) of a polyvinyl alcohol resin has been widely used (see
Patent Document 3 discloses a polarizing plate using a water-based urethane adhesive.
ところで、特にTVで代表されるように、近年、画像表示装置の大画面化が進むにつれ、偏光板に対しても大型化の要求が高まり、重要な課題になっている。
しかし、前述の水系接着剤を用いた偏光板では、バックライトの熱により偏光板の寸法が変化し、その寸法変化に起因するひずみが画面の一部に局在化し、その結果、本来画面全体が黒く表示されるべき場合に、部分的に光がもれてしまう、いわゆる光抜け(ムラ)が顕著になってくるという問題がある。
By the way, as represented by TV in particular, as the screen size of image display devices has been increasing in recent years, the demand for larger polarizing plates has increased, which has become an important issue.
However, in the polarizing plate using the water-based adhesive described above, the size of the polarizing plate changes due to the heat of the backlight, and the distortion caused by the change in size is localized in a part of the screen. When the image is to be displayed in black, there is a problem that so-called light omission (unevenness) that partly leaks light becomes noticeable.
上記のような理由から、水系接着剤の代わりに、カチオン重合性紫外線硬化型接着剤を使用することが提案されている(特許文献4参照)。
しかし、カチオン重合性紫外線硬化型接着剤では、紫外線照射後に暗反応(後重合)が生じるので、長尺の硬化物を巻取りロール状にした場合、保管時に巻き癖がつきやすいという問題がある。しかも、カチオン重合性紫外線硬化型接着剤は、硬化時の湿度の影響を受けやすく、硬化状態がバラつきやすいという問題がある。そこで、均一な硬化状態を発現するためには、環境湿度は言うに及ばず、PVA系偏光子の含水率を厳しく管理する必要がある。
ラジカル重合性紫外線硬化型接着剤には、このような問題が比較的少ないという点で優れる。
For the reasons described above, it has been proposed to use a cationic polymerizable ultraviolet curable adhesive instead of the water-based adhesive (see Patent Document 4).
However, in the case of a cationic polymerizable UV curable adhesive, a dark reaction (post-polymerization) occurs after UV irradiation. Therefore, when a long cured product is formed into a take-up roll, there is a problem that curling tends to occur during storage. . In addition, the cationic polymerizable ultraviolet curable adhesive is susceptible to the influence of humidity during curing and has a problem that the cured state tends to vary. Therefore, in order to develop a uniform cured state, it is necessary to strictly control the moisture content of the PVA polarizer, not to mention the environmental humidity.
Radical polymerizable ultraviolet curable adhesives are excellent in that these problems are relatively small.
ところで、液晶表示装置は、その用途が拡大するにつれて、さまざまな環境で使用されるようになり、液晶表示装置を構成する偏光板には高い耐環境性が要求されている。
例えば、携帯電話に代表されるモバイル用途の液晶表示装置では、高い耐湿熱耐久性が要求されている。
By the way, liquid crystal display devices are used in various environments as their applications expand, and high environmental resistance is required for polarizing plates constituting liquid crystal display devices.
For example, a liquid crystal display device for mobile use typified by a mobile phone is required to have high moisture and heat resistance.
上記したように、ラジカル重合性紫外線硬化型接着剤はカチオン重合性硬化型接着剤に比して、種々の点で優れる。
しかし、ラジカル重合性紫外線硬化型接着剤を用いた場合、湿熱環境下に長時間暴露されると、偏光性能が低下しやすく、切断端部ではヨウ素や染料で着色した偏光子の色抜けが発生しやすいという問題がある。
また、湿熱環境下よりもさらに過酷な条件(例えば、60℃の温水に浸漬)においては、偏光子の色抜けが顕著に発生する。
すなわち、偏光板の使用環境がさらに過酷になっている今日、従来の偏光板を更に上回る耐湿熱性を持った偏光板が望まれているのが実情である。
As described above, the radical polymerizable ultraviolet curable adhesive is superior in various respects as compared with the cationic polymerizable curable adhesive.
However, when a radical polymerizable UV curable adhesive is used, if it is exposed to a humid heat environment for a long time, the polarization performance is likely to deteriorate, and color loss of a polarizer colored with iodine or dye occurs at the cut end. There is a problem that it is easy to do.
Moreover, under severer conditions (for example, immersed in hot water at 60 ° C.) than in a humid heat environment, color loss of the polarizer is remarkably generated.
That is, in the present situation where the usage environment of the polarizing plate is more severe, it is the actual situation that a polarizing plate having a heat and humidity resistance that exceeds the conventional polarizing plate is desired.
さらに、偏光板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充分な強度で接着するために、(メタ)アクリル系のラジカル重合性化合物とカチオン重合性化合物を併用する接着性組成物も提案されている(特許文献5)。しかし、この技術では、打ち抜き加工性においてさらなる改善が求められる。 Furthermore, an adhesive composition using a (meth) acrylic radical polymerizable compound and a cationic polymerizable compound has been proposed in order to easily bond a polarizing film polyvinyl alcohol film and a plastic film with sufficient strength. (Patent Document 5). However, this technique requires further improvement in punching workability.
本発明は、ポリビニルアルコール系偏光子と保護フィルムとを構成層とし、保護フィルムと偏光子との接着性および打ち抜き加工性に優れ、耐水性にも優れる偏光板を提供することを目的とする。 An object of the present invention is to provide a polarizing plate having a polyvinyl alcohol-based polarizer and a protective film as constituent layers, excellent adhesion between the protective film and the polarizer and punching workability, and excellent water resistance.
本発明者らは前記課題を解決すべく鋭意検討を重ねた結果、以下に示す偏光板により前記目標達成できることを見出し、本発明を完成するに至った。
すなわち、本発明は、 ポリビニルアルコール系偏光子と、光硬化性接着剤を硬化してなる接着層と、保護フィルムとを含み、前記偏光子の両面が前記接着層を介して保護フィルムでそれぞれ被覆されてなる偏光板であって、
前記光硬化性接着剤は、ラジカル重合性化合物およびカチオン重合性化合物からなる主剤と、光ラジカル重合開始剤と、光カチオン重合開始剤とを含み、
前記ラジカル重合性化合物として、ガラス転移温度が−80℃〜0℃のホモポリマーを形成するラジカル重合性化合物(a)を前記主剤中に60〜99.8質量%含み、
前記カチオン重合性化合物として、(メタ)アクリロイル基を有しないカチオン重合性化合物(c)を前記主剤中に0.02〜40質量%含み、
前記主剤100質量部に対して、前記光ラジカル重合開始剤を1〜10質量部、前記光カチオン重合開始剤を0.5〜5質量部の範囲でそれぞれ含むことを特徴とする偏光板に関する。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned target can be achieved by the polarizing plate shown below, and have completed the present invention.
That is, the present invention includes a polyvinyl alcohol polarizer, an adhesive layer formed by curing a photocurable adhesive, and a protective film, and both surfaces of the polarizer are respectively covered with a protective film via the adhesive layer. A polarizing plate,
The photo-curable adhesive includes a main agent composed of a radical polymerizable compound and a cationic polymerizable compound, a photo radical polymerization initiator, and a photo cationic polymerization initiator,
As the radical polymerizable compound, the radical polymerizable compound (a) that forms a homopolymer having a glass transition temperature of −80 ° C. to 0 ° C. is contained in the main agent in an amount of 60 to 99.8% by mass,
As the cationic polymerizable compound, containing 0.02 to 40% by mass of a cationic polymerizable compound (c) having no (meth) acryloyl group in the main agent,
The present invention relates to a polarizing plate comprising 1 to 10 parts by mass of the radical photopolymerization initiator and 0.5 to 5 parts by mass of the cationic photopolymerization initiator with respect to 100 parts by mass of the main agent.
さらに、本発明は、ラジカル重合性化合物およびカチオン重合性化合物からなる主剤と、光ラジカル重合開始剤と、光カチオン重合開始剤とを含み、
前記ラジカル重合性化合物として、ガラス転移温度が−80℃〜0℃のホモポリマーを形成するラジカル重合性化合物(a)を前記主剤中に60〜99.8質量%含み、
前記カチオン重合性化合物として、(メタ)アクリロイル基を有しないカチオン重合性化合物(c)を前記主剤中に0.02〜40質量%含み、
前記主剤100質量部に対して、前記光ラジカル重合開始剤を1〜10質量部、前記光カチオン重合開始剤を0.5〜5質量部の範囲でそれぞれ含むことを特徴とする、偏光板形成用光硬化性接着剤に関する。
Furthermore, the present invention includes a main agent composed of a radical polymerizable compound and a cationic polymerizable compound, a radical photopolymerization initiator, and a cationic photopolymerization initiator,
As the radical polymerizable compound, the radical polymerizable compound (a) that forms a homopolymer having a glass transition temperature of −80 ° C. to 0 ° C. is contained in the main agent in an amount of 60 to 99.8% by mass,
As the cationic polymerizable compound, containing 0.02 to 40% by mass of a cationic polymerizable compound (c) having no (meth) acryloyl group in the main agent,
Forming a polarizing plate, comprising 1 to 10 parts by mass of the radical photopolymerization initiator and 0.5 to 5 parts by mass of the cationic photopolymerization initiator with respect to 100 parts by mass of the main agent. The present invention relates to a photocurable adhesive for use.
本発明によれば、ポリビニルアルコール系偏光子と保護フィルムとを構成層とする偏光板であって、接着性、打ち抜き加工性、及び耐水性に優れる偏光板を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, it is a polarizing plate which uses a polyvinyl alcohol-type polarizer and a protective film as a structural layer, Comprising: The polarizing plate which is excellent in adhesiveness, stamping workability, and water resistance can be provided.
以下、本発明の好ましい実施形態について説明する。
[接着層]
以下、本発明の偏光板を構成する接着層(または接着剤層)について説明する。
接着層(図1および2において符号2,4)は、光硬化性接着剤を硬化してなるものである。
光硬化性接着剤は、光硬化性化合物からなる主剤と、重合開始剤とを含む。主剤は、ラジカル重合性成分(ラジカル重合性化合物)とカチオン重合性成分(カチオン重合性化合物)を含む。
ラジカル重合性成分は、ガラス転移温度が−80℃〜0℃のホモポリマーを形成し得るラジカル重合性化合物(a)(以下、これを「ラジカル重合性化合物(a)」または「低Tgラジカル重合性化合物(a)」とも記す。)を必須成分とし、さらにガラス転移温度が60℃〜250℃のホモポリマーを形成し得るラジカル重合性化合物(b)(以下、これを「ラジカル重合性化合物(b)」または「高Tgラジカル重合性化合物(b)」とも記す。)を含有し得る。すなわち、ラジカル重合性成分として、ホモポリマーのガラス転移温度が−80℃〜0℃であるラジカル重合性化合物(a)を含み、ホモポリマーのガラス転移温度が60℃〜250℃であるラジカル重合性化合物(b)を任意に含む。
Hereinafter, preferred embodiments of the present invention will be described.
[Adhesive layer]
Hereinafter, the adhesive layer (or adhesive layer) constituting the polarizing plate of the present invention will be described.
The adhesive layer (reference numerals 2 and 4 in FIGS. 1 and 2) is formed by curing a photocurable adhesive.
A photocurable adhesive contains the main ingredient which consists of a photocurable compound, and a polymerization initiator. The main agent contains a radical polymerizable component (radical polymerizable compound) and a cationic polymerizable component (cation polymerizable compound).
The radical polymerizable component is a radical polymerizable compound (a) capable of forming a homopolymer having a glass transition temperature of −80 ° C. to 0 ° C. (hereinafter referred to as “radical polymerizable compound (a)” or “low Tg radical polymerization”). Radical polymerizable compound (b) (hereinafter referred to as “radical polymerizable compound (hereinafter referred to as“ radical polymerizable compound (”)”), which can form a homopolymer having a glass transition temperature of 60 ° C. to 250 ° C. b) "or" high Tg radical polymerizable compound (b) "). That is, the radical polymerizable component (a) having a glass transition temperature of −80 ° C. to 0 ° C. as the radical polymerizable component and the glass transition temperature of the homo polymer being 60 ° C. to 250 ° C. Compound (b) is optionally included.
低Tgラジカル重合性化合物(a)のうち、単官能のものとしては、例えば、
2−ヒドロキシエチルアクリレート(ホモポリマーのTg:−9℃、以下同様)、
2−ヒドロキシプロピルアクリレート(−7℃)、および
4−ヒドロキシブチルアクリレート(−55℃)、
に代表される水酸基末端アルキル(メタ)アクリレート;
2−メトキシエチルアクリレート(−43℃)、
3−メトキシブチルアクリレート(−47℃)、
トリデシルアクリレート(−65℃)、および
トリデシルメタアクリレート(−37℃)、
に代表されるアルキル基末端アルキル(メタ)アクリレート;
ジエチレングリコールモノエチルエーテルアクリレート(−54℃)、
エトキシジエチレングリコールアクリレート(−51℃)、
メトキシポリエチレングリコール(n=9)アクリレート(−71℃)、および
メトキシトリプロピレングリコールアクリレート(−75℃)、
に代表されるアルキル基末端(ポリ)アルキレングリコール系(メタ)アクリレート;
フェノキシエチルアクリレート(−15℃)、
トリフルオロエチルアクリレート(−10℃)、
ω-カルボキシ-ポリカプロラクトンアクリレート(−46℃)、などが挙げられる。
Among the low Tg radical polymerizable compounds (a), as monofunctional ones, for example,
2-hydroxyethyl acrylate (Tg of homopolymer: −9 ° C., the same applies hereinafter),
2-hydroxypropyl acrylate (−7 ° C.), and 4-hydroxybutyl acrylate (−55 ° C.),
A hydroxyl-terminated alkyl (meth) acrylate represented by
2-methoxyethyl acrylate (−43 ° C.),
3-methoxybutyl acrylate (−47 ° C.),
Tridecyl acrylate (−65 ° C.), and tridecyl methacrylate (−37 ° C.),
An alkyl-terminated alkyl (meth) acrylate represented by:
Diethylene glycol monoethyl ether acrylate (−54 ° C.),
Ethoxydiethylene glycol acrylate (−51 ° C.),
Methoxypolyethylene glycol (n = 9) acrylate (−71 ° C.), and methoxytripropylene glycol acrylate (−75 ° C.),
An alkyl group-terminated (poly) alkylene glycol-based (meth) acrylate represented by:
Phenoxyethyl acrylate (−15 ° C.),
Trifluoroethyl acrylate (−10 ° C.),
ω-carboxy-polycaprolactone acrylate (−46 ° C.), and the like.
また、低Tgラジカル重合性化合物(a)のうち、多官能のものとしては、
ポリエチレングリコール(400)ジアクリレート(−28℃)、
ポリエチレングリコール(600)ジアクリレート(−42℃)、
トリエチレングリコールジメタクリレート(−5℃)、
エトキシ化(9)トリメチロールプロパントリアクリレート(−19℃)、などが挙げられる。
In addition, among the low Tg radical polymerizable compound (a), as a polyfunctional one,
Polyethylene glycol (400) diacrylate (−28 ° C.),
Polyethylene glycol (600) diacrylate (−42 ° C.),
Triethylene glycol dimethacrylate (−5 ° C.),
Ethoxylated (9) trimethylolpropane triacrylate (-19 ° C), and the like.
本発明における光硬化性接着剤は、これらの材料を適宜組み合わせて使うことができる。
低Tgラジカル重合性化合物(a)としては、単官能のものが好ましい。低Tgラジカル重合性化合物(a)ではあっても、多官能のものだけを使用することは、後述するカッター試験性能の点で好ましくない場合がある。そこで、このカッター試験性能も良好なものとするためには、低Tgラジカル重合性化合物(a)として多官能のものを併用する場合に、低Tgラジカル重合性化合物(a)(100質量%とする)中に40質量%未満程度、好ましくは10質量%未満程度に抑えることが好ましい。
The photocurable adhesive in the present invention can be used by appropriately combining these materials.
As the low Tg radical polymerizable compound (a), a monofunctional compound is preferable. Even if it is a low Tg radically polymerizable compound (a), it may be unpreferable from the point of the cutter test performance mentioned later to use only a polyfunctional thing. Therefore, in order to improve the cutter test performance, when a polyfunctional compound is used as the low Tg radical polymerizable compound (a), the low Tg radical polymerizable compound (a) (100% by mass and It is preferable to suppress the content to less than 40% by mass, preferably less than 10% by mass.
さらに、後述する高Tgラジカル重合性化合物(b)を用いる場合は、この高Tgラジカル重合性化合物(b)も、多官能ではなく単官能であることが好ましい。換言すると、ラジカル重合性化合物((a)または(a)+(b))として多官能ラジカル重合性化合物を用いる場合、その割合は主剤(100質量%とする)中に40質量%未満程度、好ましくは10質量%未満程度であることが好ましい。
あるいは、ラジカル重合性化合物中の単官能ラジカル重合性化合物(単官能のラジカル重合性化合物(a)、または、単官能のラジカル重合性化合物(a)および(b)の合計)の割合は、60質量%以上であることが好ましく、70質量%以上であることがより好ましく、90質量%以上であることが一層好ましい。
Furthermore, when using the high Tg radical polymerizable compound (b) described later, the high Tg radical polymerizable compound (b) is also preferably monofunctional rather than polyfunctional. In other words, when a polyfunctional radical polymerizable compound is used as the radical polymerizable compound ((a) or (a) + (b)), the proportion thereof is less than about 40% by mass in the main agent (100% by mass), Preferably it is less than about 10% by mass.
Alternatively, the ratio of the monofunctional radical polymerizable compound (monofunctional radical polymerizable compound (a) or the sum of monofunctional radical polymerizable compounds (a) and (b)) in the radical polymerizable compound is 60 It is preferably at least mass%, more preferably at least 70 mass%, and even more preferably at least 90 mass%.
このラジカル重合性化合物(a)は、ホモポリマーのガラス転移温度が−60℃〜−20℃のものがより好ましく、ホモポリマーのガラス転移温度が−60℃〜−40℃のものが一層好ましい。 The radical polymerizable compound (a) preferably has a homopolymer glass transition temperature of −60 ° C. to −20 ° C., more preferably a homopolymer glass transition temperature of −60 ° C. to −40 ° C.
これら低Tgラジカル重合性化合物(a)のうち、PVA系偏光子との接着性向上の点から、ヒドロキシアルキル(メタ)アクリレートなどの水酸基を有するものが好ましく、なかでも4−ヒドロキシブチルアクリレートが好ましい。硬化物のTgを低くしにくいという点では、水酸基を有してはいても、2−ヒドロキシエチルアクリレート、2−ヒドロキシプロピルアクリレートは使用しないことが好ましい。すなわち、ヒドロキシアルキル(メタ)アクリレートのアルキル基の炭素数は、4〜40程度であることが好ましい。 Among these low Tg radical polymerizable compounds (a), those having a hydroxyl group such as hydroxyalkyl (meth) acrylate are preferable from the viewpoint of improving the adhesion to a PVA polarizer, and 4-hydroxybutyl acrylate is particularly preferable. . In view of making it difficult to lower the Tg of the cured product, it is preferable not to use 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate even if it has a hydroxyl group. That is, it is preferable that the alkyl group of hydroxyalkyl (meth) acrylate has about 4 to 40 carbon atoms.
また、硬化後の接着剤層の凝集力を高め、接着力を向上させる点で、低Tgラジカル重合性化合物(a)として、ω-カルボキシ-ポリカプロラクトンモノ(メタ)アクリレートをさらに用いることが好ましい。但し、ω-カルボキシ-ポリカプロラクトンモノ(メタ)アクリレートは硬化性があまり良くないので、ラジカル重合開始剤の種類や量を適宜選択したり、紫外線照射装置のランプを適宜選択したり、照射強度や照射線量等の硬化条件を適宜選択したり、保護フィルムの種類や厚み等を適宜選択したりすることによって、硬化性を補うことができる。ω-カルボキシ-ポリカプロラクトンモノ(メタ)アクリレートのカプロラクトンの重合度(n)は特に限定されないが、n=2〜20程度であることが好ましい。 In addition, it is preferable to further use ω-carboxy-polycaprolactone mono (meth) acrylate as the low Tg radical polymerizable compound (a) in terms of enhancing the cohesive force of the adhesive layer after curing and improving the adhesive force. . However, since ω-carboxy-polycaprolactone mono (meth) acrylate is not very curable, the type and amount of the radical polymerization initiator is appropriately selected, the lamp of the ultraviolet irradiation device is appropriately selected, the irradiation intensity is Curability can be supplemented by appropriately selecting curing conditions such as irradiation dose, or by appropriately selecting the type and thickness of the protective film. The polymerization degree (n) of caprolactone of ω-carboxy-polycaprolactone mono (meth) acrylate is not particularly limited, but it is preferably about n = 2 to 20.
たとえば、主剤の合計を100質量%として60〜99.8質量%であるラジカル重合性化合物(a)は、4−ヒドロキシブチルアクリレート等のヒドロキシアルキル(メタ)アクリレートを10〜99.8質量%、ω-カルボキシ-ポリカプロラクトンモノ(メタ)アクリレートを0〜50質量%の各範囲で組み合わせることが好ましい。
また、ω-カルボキシ-ポリカプロラクトンモノ(メタ)アクリレートを配合する場合は、ヒドロキシアルキル(メタ)アクリレートを10〜99.7質量%、ω-カルボキシ-ポリカプロラクトンモノ(メタ)アクリレートを0.01〜50質量%の範囲で用いることがさらに好ましい。
For example, the radically polymerizable compound (a) that is 60 to 99.8% by mass with respect to 100% by mass of the main agent is 10 to 99.8% by mass of hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl acrylate, It is preferable to combine ω-carboxy-polycaprolactone mono (meth) acrylate in each range of 0 to 50% by mass.
Moreover, when mix | blending omega-carboxy-polycaprolactone mono (meth) acrylate, 10-99.7 mass% of hydroxyalkyl (meth) acrylate and 0.01- of omega-carboxy-polycaprolactone mono (meth) acrylate are included. More preferably, it is used in the range of 50% by mass.
任意で配合される高Tgラジカル重合性化合物(b)としては、例えば、
ジシクロペンタニルメタクリレート(ホモポリマーのTg:180℃、以下同様)、
トリフルオロエチルメタクリレート(81℃)、
t−ブチルメタクリレート(113℃)、
エチルメタクリレート(65℃)、
テトラヒドロフルフリルメタクリレート(68℃)、
イソボルニルアクリレート(85℃)、および
アクリロイルモルホリン(106℃)等が挙げられる。なかでも、耐熱性の観点からイソボルニルアクリレート、アクリロイルモルホリンを使用することが好ましい。
このラジカル重合性化合物(b)は、ホモポリマーのガラス転移温度が60℃〜200℃のものがより好ましく、ホモポリマーのガラス転移温度が80℃〜150℃のものが一層好ましい。
本発明における光硬化性接着剤は、これらの材料を適宜組み合わせて使うことができる。
Examples of the optionally compounded high Tg radical polymerizable compound (b) include:
Dicyclopentanyl methacrylate (Tg of homopolymer: 180 ° C., the same shall apply hereinafter),
Trifluoroethyl methacrylate (81 ° C.),
t-butyl methacrylate (113 ° C.),
Ethyl methacrylate (65 ° C.),
Tetrahydrofurfuryl methacrylate (68 ° C.),
And isobornyl acrylate (85 ° C.) and acryloylmorpholine (106 ° C.). Of these, isobornyl acrylate and acryloylmorpholine are preferably used from the viewpoint of heat resistance.
The radical polymerizable compound (b) preferably has a homopolymer glass transition temperature of 60 ° C. to 200 ° C., and more preferably a homo polymer glass transition temperature of 80 ° C. to 150 ° C.
The photocurable adhesive in the present invention can be used by appropriately combining these materials.
なお、前記の低Tgラジカル重合性化合物(a)、高Tgラジカル重合性化合物(b)から形成され得る各ホモポリマーのTgは、以下のようにして求められる値である。
各化合物と開始剤とを適当量プラスチック製の容器に入れ、紫外線を照射し、硬化させたもの、10mgを測定用試料とし、示差走査熱量計(DSC)を用いて、10℃/分又は20℃/分の昇温速度で測定した。
In addition, Tg of each homopolymer which can be formed from the said low Tg radically polymerizable compound (a) and high Tg radically polymerizable compound (b) is a value calculated | required as follows.
An appropriate amount of each compound and initiator are put in a plastic container, irradiated with ultraviolet rays, and cured, 10 mg as a measurement sample, and 10 ° C./min or 20 using a differential scanning calorimeter (DSC) Measured at a rate of temperature rise of ° C / min.
(メタ)アクリロイル基を有しないカチオン重合性化合物(c)(以下、これを「カチオン重合性化合物(c)」とも記す。)は、カチオン重合性の官能基を有し且つ(メタ)アクリロイル基を有しない化合物であり、例えば、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、2−(3,4−エポキシシクロヘキシル−5,5−スピロ−3,4−エポキシ)シクロヘキサン−メタ−ジオキサン、ビス(3,4−エポキシシクロヘキシルメチル)アジペート、ビス(3,4−エポキシ−6−メチルシクロヘキシルメチル)アジペート、ビニルシクロヘキセンモノオキサイド 1,2−エポキシ−4−ビニルシクロヘキサンなどの、1分子中に1個以上の脂環式エポキシ基を有する化合物やオキセタニル基を有する化合物が挙げられる。カチオン重合性化合物(c)は、硬化した接着層の耐水性向上の役割を担う。
脂環式エポキシ基を有する化合物のうち、反応性の点から、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使用することが好ましい。
The cationically polymerizable compound (c) having no (meth) acryloyl group (hereinafter also referred to as “cationic polymerizable compound (c)”) has a cationically polymerizable functional group and is a (meth) acryloyl group. Such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane- 1 such as meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate,
Of the compounds having an alicyclic epoxy group, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is preferably used from the viewpoint of reactivity.
本発明においては、カチオン重合性化合物(c)は、接着力を確保し且つ打ち抜き加工性を良好なものとする観点から、(メタ)アクリロイル基を有しないものを選択する。(メタ)アクリロイル基を有するカチオン重合性化合物を上記(c)と併用することもできるが、その場合の(メタ)アクリロイル基を有するカチオン重合性化合物の配合量は、主剤100質量%中に20質量%未満程度、好ましくは10質量%未満程度に抑える必要がある。
あるいは、カチオン重合性化合物全体に占める(メタ)アクリロイル基を有しないカチオン重合性化合物(c)の割合は50質量%以上であることが好ましく、75質量%以上であることがより好ましい。
In the present invention, the cationically polymerizable compound (c) is selected from those having no (meth) acryloyl group from the viewpoint of securing adhesive force and improving punchability. A cationically polymerizable compound having a (meth) acryloyl group can be used in combination with the above (c). In this case, the amount of the cationically polymerizable compound having a (meth) acryloyl group is 20 in 100% by mass of the main agent. It is necessary to suppress to less than about 10% by mass, preferably less than about 10% by mass.
Alternatively, the proportion of the cationic polymerizable compound (c) having no (meth) acryloyl group in the entire cationic polymerizable compound is preferably 50% by mass or more, and more preferably 75% by mass or more.
光硬化性接着剤の主剤は、ラジカル重合性化合物(a)を60〜99.8質量%、カチオン重合性化合物(c)を0.02〜40質量%の範囲で含み、ラジカル重合性化合物(a):60〜99質量%、カチオン重合性化合物(c):1〜40質量%であることが好ましく、ラジカル重合性化合物(a):90〜99質量%、カチオン重合性化合物(c):1〜10質量%であることがより好ましい。
低Tgラジカル重合性化合物(a)が60質量%よりも少ないと、形成される接着層が固くなりすぎて、接着力を確保できないばかりでなく、打ち抜き加工性が悪化してしまう。
一方、低Tgラジカル重合性化合物(a)が99.8質量%よりも多い、つまり、カチオン重合性化合物(c)がほとんど含まれない場合、形成される接着層の耐水性が悪くなり、偏光板を温水に浸漬するとPVA偏光子の色が抜けてしまう。
The main component of the photocurable adhesive contains the radical polymerizable compound (a) in the range of 60 to 99.8% by mass and the cationic polymerizable compound (c) in the range of 0.02 to 40% by mass. a): 60 to 99% by mass, cation polymerizable compound (c): preferably 1 to 40% by mass, radical polymerizable compound (a): 90 to 99% by mass, cation polymerizable compound (c): More preferably, it is 1-10 mass%.
When the amount of the low Tg radical polymerizable compound (a) is less than 60% by mass, the formed adhesive layer becomes too hard, and the adhesive strength cannot be ensured, and the punching processability is deteriorated.
On the other hand, when the amount of the low Tg radical polymerizable compound (a) is more than 99.8% by mass, that is, when the cationic polymerizable compound (c) is hardly contained, the water resistance of the formed adhesive layer is deteriorated, and the polarization When the plate is immersed in warm water, the color of the PVA polarizer is lost.
高Tgラジカル重合性化合物(b)は、保護フィルムとして、トリアセチルセルロース等のアセチルセルロース系樹脂フィルムを用いる場合に、接着力向上に寄与する。
高Tgラジカル重合性化合物(b)を用いる場合には、低Tgラジカル重合性化合物(a):60〜75質量%、高Tgラジカル重合性化合物(b):0.01〜39.98質量%、カチオン重合性化合物(c):0.02〜24.99質量%であることが好ましく、低Tgラジカル重合性化合物(a):60〜70質量%、高Tgラジカル重合性化合物(b):10〜35質量%、カチオン重合性化合物(c):5〜20質量%であることがより好ましい。
The high Tg radical polymerizable compound (b) contributes to improvement in adhesive strength when an acetylcellulose-based resin film such as triacetylcellulose is used as the protective film.
When the high Tg radical polymerizable compound (b) is used, the low Tg radical polymerizable compound (a): 60 to 75% by mass, the high Tg radical polymerizable compound (b): 0.01 to 39.98% by mass. Cationic polymerizable compound (c): 0.02 to 24.99% by mass is preferable, low Tg radical polymerizable compound (a): 60 to 70% by mass, high Tg radical polymerizable compound (b): It is more preferable that they are 10-35 mass%, cationically polymerizable compound (c): 5-20 mass%.
あるいは、好ましい一実施形態における光硬化性接着剤は、主剤として、ガラス転移温度が−80℃〜0℃のホモポリマーを形成する単官能のラジカル重合性化合物(a):60〜99.8質量%と、
ガラス転移温度が60℃〜250℃のホモポリマーを形成する単官能のラジカル重合性化合物(b):0〜39.98質量%と、
カチオン重合性の官能基を有し(メタ)アクリロイル基を有しないカチオン重合性化合物(c):0.02〜40質量%(但し、前記(a)〜(c)の合計を100質量%とする)とを含み、
重合開始剤として、光ラジカル重合開始剤(d):1〜10質量部(前記(a)〜(c)の合計100質量部に対して)と、
光カチオン重合開始剤(e):0.5〜5質量部(前記(a)〜(c)の合計100質量部に対して)とを含むものである。
さらに好ましくは、低Tgラジカル重合性化合物(a):60〜99質量%、高Tgラジカル重合性化合物(b):0〜39質量%、及びカチオン重合性化合物(c):1〜40質量%を含む。
Alternatively, the photocurable adhesive in a preferred embodiment is a monofunctional radically polymerizable compound (a) that forms a homopolymer having a glass transition temperature of −80 ° C. to 0 ° C. as the main agent: 60 to 99.8 mass %When,
Monofunctional radically polymerizable compound (b) that forms a homopolymer having a glass transition temperature of 60 ° C to 250 ° C: 0 to 39.98% by mass;
Cationic polymerizable compound having a cationic polymerizable functional group and not having a (meth) acryloyl group (c): 0.02 to 40% by mass (provided that the total of the above (a) to (c) is 100% by mass) And)
As a polymerization initiator, radical photopolymerization initiator (d): 1 to 10 parts by mass (based on a total of 100 parts by mass of the above (a) to (c)),
Photocationic polymerization initiator (e): 0.5-5 mass parts (with respect to the total 100 mass parts of said (a)-(c)).
More preferably, the low Tg radical polymerizable compound (a): 60 to 99% by mass, the high Tg radical polymerizable compound (b): 0 to 39% by mass, and the cationic polymerizable compound (c): 1 to 40% by mass. including.
本発明における光硬化性接着剤には、低Tgラジカル重合性化合物(a)や高Tgラジカル重合性化合物(b)の他に、さらに別のラジカル重合性化合物を添加してもよい。その他のラジカル重合性化合物としてはウレタンアクリレート、エポキシアクリレート、ポリエステルアクリレート、ポリエーテルアクリレートが挙げられる。しかし、上述のように、ラジカル重合性化合物は、限られた配合範囲で用いることが好ましい。
また、本発明における光硬化性接着剤には、必要であれば適宜添加剤を添加してもよい。添加剤としては、保護フィルムとの接着力を大きくでき、偏光板の収縮を抑制できるという点で、シランカップリング剤が好ましい。シランカップリング剤としては、アクリロイル基を有するものが好ましい。
In addition to the low Tg radical polymerizable compound (a) and the high Tg radical polymerizable compound (b), another radical polymerizable compound may be added to the photocurable adhesive in the present invention. Examples of other radical polymerizable compounds include urethane acrylate, epoxy acrylate, polyester acrylate, and polyether acrylate. However, as described above, the radically polymerizable compound is preferably used in a limited blending range.
Moreover, you may add an additive suitably to the photocurable adhesive agent in this invention as needed. As the additive, a silane coupling agent is preferable in that the adhesive force with the protective film can be increased and shrinkage of the polarizing plate can be suppressed. As the silane coupling agent, those having an acryloyl group are preferable.
本発明における光硬化性接着剤は、光ラジカル重合開始剤(d)を含む。
光ラジカル重合開始剤(d)としては特に制限はなく、例えばイルガキュアー184,907,651,1700,1800,819,369,261、DAROCUR-TPO(チバ・スペシャルティ・ケミカルズ社製)、ダロキュア-1173(メルク社製)、エザキュアーKIP150、TZT(日本シイベルヘグナー社製)、カヤキュアBMS、カヤキュアDMBI、(日本化薬製)等が挙げられる。
これらの中でも、光硬化後の接着剤層の透明性を高める点で、フォトブリーチするDAROCUR-TPOを使用することが好ましい。
光ラジカル重合開始剤(d)の配合割合は、前記ラジカル重合性化合物(a)、(b)及びカチオン重合性化合物(c)の合計100質量部に対して、1〜10質量部であり、1〜5質量部であることが好ましい。
The photocurable adhesive in the present invention contains a photoradical polymerization initiator (d).
There is no restriction | limiting in particular as radical photopolymerization initiator (d), For example, Irgacure 184,907,651,1700,1800,819,369,261, DAROCUR-TPO (Ciba Specialty Chemicals company make), Darocur-1173 (Merck), Ezacure KIP150, TZT (Nihon Shibel Hegner), Kayacure BMS, Kayacure DMBI, (Nippon Kayaku).
Among these, it is preferable to use DAROCUR-TPO that is photobleached in terms of enhancing the transparency of the adhesive layer after photocuring.
The blending ratio of the radical photopolymerization initiator (d) is 1 to 10 parts by mass with respect to a total of 100 parts by mass of the radical polymerizable compounds (a) and (b) and the cationic polymerizable compound (c). It is preferable that it is 1-5 mass parts.
本発明における光硬化性接着剤は、光カチオン重合開始剤(e)を含む。
光カチオン重合開始剤(e)としては、例えばUVACURE1590(ダイセル・サイテック製)、CPI−110P(サンアプロ製)、などのスルホニウム塩やIRGACURE250(チバ・スペシャルティ・ケミカルズ製)、WPI−113(和光純薬製)、Rp−2074(ローディア・ジャパン製)等のヨードニウム塩が挙げられる。
光カチオン重合開始剤(e)の配合割合は、前記ラジカル重合性化合物(a)、(b)及びカチオン重合性化合物(c)の合計100質量部に対して、0.5〜10質量部であり、0.5〜5質量部であることが好ましい。
The photocurable adhesive in the present invention contains a photocationic polymerization initiator (e).
Examples of the cationic photopolymerization initiator (e) include sulfonium salts such as UVACURE1590 (manufactured by Daicel Cytec) and CPI-110P (manufactured by San Apro), IRGACURE250 (manufactured by Ciba Specialty Chemicals), and WPI-113 (Wako Pure Chemical Industries). And iodonium salts such as Rp-2074 (manufactured by Rhodia Japan).
The blending ratio of the photo cationic polymerization initiator (e) is 0.5 to 10 parts by mass with respect to 100 parts by mass in total of the radical polymerizable compounds (a) and (b) and the cationic polymerizable compound (c). Yes, it is preferably 0.5 to 5 parts by mass.
光硬化性接着剤は、上記主剤および重合開始剤に加え、重合禁止剤、重合開始助剤、紫外線吸収剤、可塑剤、着色剤、酸化防止剤、消泡剤、可塑剤等の各種の公知の添加剤を、必要に応じて、本発明の効果を阻害しない範囲内で含むことができる。 In addition to the above-mentioned main agent and polymerization initiator, the photocurable adhesive is known in various ways such as a polymerization inhibitor, a polymerization initiation assistant, an ultraviolet absorber, a plasticizer, a colorant, an antioxidant, an antifoaming agent, and a plasticizer. These additives can be included as needed within a range not inhibiting the effects of the present invention.
[偏光子]
本発明の偏光板に用いられるポリビニルアルコール系偏光子(図1、2において符号3)について説明する。
偏光子を形成する、すなわち偏光子の基材となるポリビニルアルコール系樹脂としては、ポリビニルアルコール、エチレン・ビニルアルコール共重合体などが挙げられるが、耐水性の点から、エチレン・ビニルアルコール共重合体が好ましい。ポリビニルアルコールとしては、酢酸基が数十%残存している部分ケン化ポリビニルアルコールや、酢酸基が残存しない完全ケン化ポリビニルアルコールや、水酸基が変性された変性ポリビニルアルコールなどが挙げられるが、特に限定されるものではない。ポリビニルアルコール系樹脂は、1種単独で使用することも、あるいは2種以上を併用することもできる。
[Polarizer]
A polyvinyl alcohol polarizer (reference numeral 3 in FIGS. 1 and 2) used in the polarizing plate of the present invention will be described.
Examples of the polyvinyl alcohol-based resin that forms the polarizer, that is, the base material of the polarizer, include polyvinyl alcohol and ethylene / vinyl alcohol copolymer. From the viewpoint of water resistance, the ethylene / vinyl alcohol copolymer is used. Is preferred. Examples of polyvinyl alcohol include partially saponified polyvinyl alcohol in which several tens of percent of acetate groups remain, fully saponified polyvinyl alcohol in which acetate groups do not remain, and modified polyvinyl alcohol in which hydroxyl groups have been modified. Is not to be done. A polyvinyl alcohol-type resin can be used individually by 1 type, or can also use 2 or more types together.
上記ポリビニルアルコールの具体例としては、(株)クラレ製のRSポリマーであるRS−110(ケン化度=99%、重合度=1,000)、同社製のクラレポバールLM−20SO(ケン化度=40%、重合度=2,000)、日本合成化学工業(株)製のゴーセノールNM−14(ケン化度=99%、重合度=1.400)などが挙げられる。ポリビニルアルコールは、例えば、酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル等の脂肪酸ビニルエステルの重合体を、アルカリ触媒等を用いてケン化して得られる。 Specific examples of the polyvinyl alcohol include RS-110 (degree of saponification = 99%, degree of polymerization = 1,000) manufactured by Kuraray Co., Ltd., and Kuraray Poval LM-20SO (degree of saponification) manufactured by the same company. = 40%, polymerization degree = 2,000), Gohsenol NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, polymerization degree = 1.400), and the like. Polyvinyl alcohol is obtained, for example, by saponifying a polymer of a fatty acid vinyl ester such as vinyl acetate, vinyl propionate or vinyl pivalate using an alkali catalyst or the like.
上記エチレン・ビニルアルコール共重合体は、エチレンと酢酸ビニルとの共重合体のケン化物、すなわち、エチレン−酢酸ビニルランダム共重合体をケン化して得られるものであり、酢酸基が数十モル%残存している部分ケン化物から、酢酸基が数モル%しか残存していないかまたは酢酸基が残存しない完全ケン化物まで含み、特に限定されない。 The ethylene-vinyl alcohol copolymer is obtained by saponifying a copolymer of ethylene and vinyl acetate, that is, an ethylene-vinyl acetate random copolymer, and has an acetate group of several tens mol%. The remaining saponified product is not particularly limited, and includes a partially saponified product in which only a few mol% of acetic acid groups remain or no acetic acid group remains.
偏光子は、公知の方法に従い、上述のポリビニルアルコール系樹脂をキャスティング成形法等の方法によってフィルム化し、ヨウ素または二色染料(二色性色素)を吸着配向させることにより得られる。前記偏光子は、ホウ酸等による架橋や、延伸をされたものであってもよい。延伸を行なう場合、染色の前・染色と同時・染色の後の、いずれの段階で行なってもよい、偏光子の形状としては、特に限定されないが、例えば、フィルム等が挙げられる。なお、本明細書において、「フィルム」の語は、厚みが小さいもの(厚みが1mm未満のもの)の他、厚手のシート(例えば、厚みが1〜5mmのもの)も含むものとする。偏光子の厚さは、特に限定されないが、例えば、10〜40μm程度が好ましい。 The polarizer can be obtained by forming a film of the above-described polyvinyl alcohol resin by a casting molding method or the like according to a known method, and adsorbing and orienting iodine or a dichroic dye (dichroic dye). The polarizer may be cross-linked or stretched with boric acid or the like. When stretching is performed, the shape of the polarizer may be performed at any stage before dyeing, simultaneously with dyeing, or after dyeing. The shape of the polarizer is not particularly limited, and examples thereof include a film. In this specification, the term “film” includes not only a sheet having a small thickness (thickness of less than 1 mm) but also a thick sheet (for example, having a thickness of 1 to 5 mm). Although the thickness of a polarizer is not specifically limited, For example, about 10-40 micrometers is preferable.
[保護フィルム]
本発明の偏光板に用いられる保護フィルム(図1、2において符号1,5)について説明する。
保護フィルムは特に限定されず、具体的には、現在偏光板の保護フィルムとして最も広く用いられているトリアセチルセルロース(TAC)等のアセチルセルロース系樹脂フィルムや、トリアセチルセルロースよりも透湿度の低い透明樹脂フィルムを用いることができる。
トリアセチルセルロースよりも透湿度の低い保護フィルムを構成する材料としては、例えば透明性、機械的強度、熱安定性、水分遮断性、等方性などに優れる熱可塑性樹脂が用いられる。このような熱可塑性樹脂の具体例としては、シクロオレフィン系樹脂、アクリル系樹脂が挙げられる。
[Protective film]
The protective film (
The protective film is not particularly limited. Specifically, the moisture permeability is lower than that of an acetylcellulose-based resin film such as triacetylcellulose (TAC) that is currently most widely used as a protective film for polarizing plates, or triacetylcellulose. A transparent resin film can be used.
As a material constituting the protective film having a moisture permeability lower than that of triacetyl cellulose, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is used. Specific examples of such thermoplastic resins include cycloolefin resins and acrylic resins.
シクロオレフィン系樹脂は、環状オレフィンを重合単位として重合される樹脂の総称である。具体例としては、環状オレフィンの開環(共)重合体、環状オレフィンの付加重合体、環状オレフィンとエチレン、プロピレン等のα−オレフィンとその共重合体(代表的にはランダム共重合体)、および、これらを不飽和カルボン酸やその誘導体で変性したグラフト重合体、ならびに、それらの水素化物などが挙げられ、ノルボルネン系樹脂が好ましい。ノルボルネン系樹脂フィルムは、特開2005−164632号公報、特開2006−201736号公報、特開2008−233279号公報等に記載された公知の方法により得ることができる。 The cycloolefin-based resin is a general term for resins that are polymerized using a cyclic olefin as a polymerization unit. Specific examples include ring-opening (co) polymers of cyclic olefins, addition polymers of cyclic olefins, cyclic olefins and α-olefins such as ethylene and propylene (typically random copolymers), And a graft polymer obtained by modifying these with an unsaturated carboxylic acid or a derivative thereof, a hydride thereof, or the like, and a norbornene-based resin is preferable. The norbornene resin film can be obtained by a known method described in JP-A No. 2005-164632, JP-A No. 2006-201736, JP-A No. 2008-233279, and the like.
シクロオレフィン系樹脂としては、種々の製品が市販されている。具体例としては、日本ゼオン株式会社製の商品名「ゼオノア」、JSR株式会社製の商品名「アートン」、TICONA社製の商品名「トーパス」、三井化学株式会社製の商品名「APEL」が挙げられる。 Various products are commercially available as cycloolefin resins. Specific examples include the product name “ZEONOR” manufactured by ZEON CORPORATION, the product name “ARTON” manufactured by JSR Corporation, the product name “TOPAS” manufactured by TICONA, and the product name “APEL” manufactured by Mitsui Chemicals, Inc. Can be mentioned.
アクリル系樹脂は、ポリメチルメタクリレートをはじめ、メチルメタクリレートやブチルメタクリレート等のアルキルエステル類の(メタ)アクリレートを主成分とする樹脂(=共重合体)である。場合によっては、他の樹脂とブレンドされて、フィルム化される。
アクリル系フィルムは、特開2002−361712号公報等に記載された公知の方法により得ることができる。
アクリル系フィルムは、種々の製品が市販されている。具体例としては、三菱レイヨン社製の商品名「アクリプレン」や、カネカ社製の商品名「サンデュレン」が挙げられる。
The acrylic resin is a resin (= copolymer) mainly composed of (meth) acrylate of alkyl esters such as methyl methacrylate and butyl methacrylate as well as polymethyl methacrylate. In some cases, it is blended with another resin to form a film.
The acrylic film can be obtained by a known method described in JP-A No. 2002-361712.
Various products are commercially available for the acrylic film. Specific examples include the product name “Acryprene” manufactured by Mitsubishi Rayon Co., Ltd. and the product name “Sanduren” manufactured by Kaneka Corporation.
本発明の偏光板に使用される保護フィルムは、(1)、(5)の両面とも同一組成であっても異なっていても良い。例えば、(1)にシクロオレフィン系樹脂フィルムを使用し、(5)に、アクリル系樹脂フィルムを使用しても何ら差し支えは無い。 The protective film used for the polarizing plate of the present invention may be the same or different on both sides of (1) and (5). For example, a cycloolefin resin film can be used for (1) and an acrylic resin film can be used for (5).
保護フィルムの厚さは、適宜に決定しうるが、一般には強度や取扱性等の作業性、薄層性などの点より1〜500μm程度である。特に1〜300μmが好ましく、5〜200μmがより好ましい。保護フィルム(1)と(5)の厚みは、同一であっても異なっていてもよい。
なお、偏光子の両側に保護フィルムを設ける場合、その表裏で同じポリマー材料からなる保護フィルムを用いてもよく、異なるポリマー材料等からなる保護フィルムを用いてもよい。たとえば、偏光子の両面にアクリル系フィルムを使用する場合でも、アクリル系ポリマーの種類が互いに異なっていてもよいし、配合する添加剤が互いに異なっていてもよく、何ら限定はされない。
Although the thickness of a protective film can be determined suitably, generally it is about 1-500 micrometers from points, such as workability | operativity, such as intensity | strength and handleability, and thin layer property. 1-300 micrometers is especially preferable, and 5-200 micrometers is more preferable. The thicknesses of the protective films (1) and (5) may be the same or different.
In addition, when providing a protective film in the both sides of a polarizer, the protective film which consists of the same polymer material may be used by the front and back, and the protective film which consists of a different polymer material etc. may be used. For example, even when an acrylic film is used on both surfaces of a polarizer, the types of acrylic polymers may be different from each other, and additives to be blended may be different from each other, and there is no limitation.
本発明の偏光板は、以下のようにして得ることができる。
即ち、第1の保護フィルム(1)の一方の面に、第1の光硬化性接着剤を塗工し、第1の硬化性接着剤層(2’)を形成し、
第2の保護フィルム(5)の一方の面に、第2の光硬化性接着剤を塗工し、第2の硬化性接着剤層(4’)を形成し、
次いで、ポリビニルアルコール系偏光子(3)の各面に、第1の硬化性接着剤層(2’)及び第2の硬化性接着剤層(4’)を、同時に/または順番に重ね合わせ、
第2の保護フィルム(5)の側から活性エネルギー線を照射し、第1の硬化性接着剤層(2’)及び第2の硬化性接着剤層(4’)を硬化することによって製造することが好ましい。
The polarizing plate of the present invention can be obtained as follows.
That is, a first photocurable adhesive is applied to one surface of the first protective film (1) to form a first curable adhesive layer (2 ′),
A second photocurable adhesive is applied to one surface of the second protective film (5) to form a second curable adhesive layer (4 ′),
Next, the first curable adhesive layer (2 ′) and the second curable adhesive layer (4 ′) are simultaneously and / or sequentially overlapped on each surface of the polyvinyl alcohol polarizer (3),
It is produced by irradiating active energy rays from the second protective film (5) side and curing the first curable adhesive layer (2 ′) and the second curable adhesive layer (4 ′). It is preferable.
上記硬化性接着剤層(2’)および(4’)、保護フィルム(1)および(5)は、それぞれ、互いに同一でも異なっていてもよい。すなわち、硬化性接着剤層(2’)と硬化性接着剤層(4’)(換言すると第1の光硬化性接着剤と第2の光硬化性接着剤)は、同一組成であってもよいし、異なる組成であってもよい。形成される接着剤層(2)および(4)の厚みは、互いに同一でも異なっていてもよく、特に限定されないが、一般に、0.1μm〜50μmであることが好ましく、より好ましくは0.5μm〜20μmである。 The curable adhesive layers (2 ') and (4') and the protective films (1) and (5) may be the same as or different from each other. That is, the curable adhesive layer (2 ′) and the curable adhesive layer (4 ′) (in other words, the first photocurable adhesive and the second photocurable adhesive) have the same composition. It may be a different composition. The thicknesses of the adhesive layers (2) and (4) to be formed may be the same or different from each other, and are not particularly limited, but are generally preferably 0.1 μm to 50 μm, more preferably 0.5 μm. ˜20 μm.
以下、図2に基づいて、工程ごとに説明する。
[工程(a)]
工程(a)は、図2の(a)に示されるように、保護フィルム(1)および(5)のそれぞれ片面に、接着剤層形成用の光硬化性接着剤を塗布し、必要に応じて乾燥等を行って、硬化性接着剤層(2’)、(4’)を具備する積層体(1’)、(5’)を得る工程である。
光硬化性接着剤の塗布方法としては、特に限定されないが、例えばダイコート法、ロールコート法、グラビアコート法、スピンコート法などが挙げられる。
Hereafter, it demonstrates for every process based on FIG.
[Step (a)]
In step (a), as shown in FIG. 2 (a), a photocurable adhesive for forming an adhesive layer is applied to one side of each of the protective films (1) and (5), and if necessary, And drying, etc. to obtain laminates (1 ′) and (5 ′) having curable adhesive layers (2 ′) and (4 ′).
The method for applying the photocurable adhesive is not particularly limited, and examples thereof include a die coating method, a roll coating method, a gravure coating method, and a spin coating method.
[工程(b)]
工程(b)は、図2の(b)に示されるように、ポリビニルアルコール系偏光子(3)の一方の面(図では上面)に、保護フィルム(1)と硬化性接着剤層(2’)とを具備する積層体(1’)を、
ポリビニルアルコール系偏光子(3)の他方の面(図では下面)に、保護フィルム(5)と硬化性接着剤層(4’)とを具備する積層体(5’)を、それぞれ重ね合わせる工程である。
[Step (b)]
In step (b), as shown in FIG. 2 (b), the protective film (1) and the curable adhesive layer (2) are formed on one surface (upper surface in the figure) of the polyvinyl alcohol polarizer (3). A laminate (1 ') comprising:
A step of superimposing a laminate (5 ′) comprising a protective film (5) and a curable adhesive layer (4 ′) on the other surface (lower surface in the figure) of the polyvinyl alcohol polarizer (3). It is.
[工程(c)]
工程(c)は、図2の(c)に示されるように、活性エネルギー線(6)を照射することにより、保護フィルム(1)、(5)とポリビニルアルコール系偏光子(3)とに挟まれた硬化性接着剤層(2’)、(4’)を硬化させ、接着剤層(2),(4)を形成させる工程である。
図では、保護フィルム(5)の側から活性エネルギー線(6)を照射する場合を示すが、保護フィルム(1)の側から活性エネルギー線(6)を照射してもよいし、両側から同時に、または両側から順次、活性エネルギー線(6)を照射してもよい。
[Step (c)]
In the step (c), as shown in FIG. 2 (c), the active energy rays (6) are irradiated to the protective films (1) and (5) and the polyvinyl alcohol polarizer (3). This is a step of curing the sandwiched curable adhesive layers (2 ′) and (4 ′) to form adhesive layers (2) and (4).
Although the figure shows the case where the active energy ray (6) is irradiated from the protective film (5) side, the active energy ray (6) may be irradiated from the protective film (1) side or simultaneously from both sides. Alternatively, the active energy rays (6) may be irradiated sequentially from both sides.
活性エネルギー線の照射量は、特に限定されるものではないが、波長200〜450nm、照度1〜500mW/cm2の光を、照射量が10〜5000mJ/cm2となるように照射して露光することが好ましい。照射量が10mJ/cm2より低い場合、紫外線硬化性組成物の硬化が促進せず、欲する性能が発揮できないことがあり、照射量が5000mJ/cm2より高い場合は、照射時間が非常に長くなり、生産性に問題がある。照射する活性エネルギー線の種類としては、可視光、紫外線、赤外線、X線、α線、β線、γ線等が挙げられるが、特に紫外線が好ましい。光の照射装置としては、例えば、高圧水銀ランプ、低圧水銀ランプ、メタルハライドランプ、エキシマランプ等を用いることが好ましい。
活性エネルギー線(6)照射後、室温で1週間程度エージングすることもできる。
工程(c)を経ることにより、硬化性接着剤層(2’)、(4’)を硬化させて接着剤層(2),(4)とし、偏光子(3)と保護フィルム(1)および(5)とが接着剤層(2),(4)を介して接着されてなる偏光板が完成する(図1、図2中の(d)参照)。
The dose of the active energy ray is not particularly limited, wavelength 200 to 450 nm, the
After irradiation with the active energy ray (6), it can be aged at room temperature for about one week.
Through the step (c), the curable adhesive layers (2 ′) and (4 ′) are cured to form adhesive layers (2) and (4), and the polarizer (3) and the protective film (1). And (5) are bonded through the adhesive layers (2) and (4) to complete a polarizing plate (see (d) in FIGS. 1 and 2).
また、本発明の偏光板は、ポリビニルアルコール系偏光子(3)の一方の面に、光硬化性接着剤を塗工し、第1の硬化性接着剤層(2’)を形成し、形成された第1の硬化性接着剤層(2’)の表面を第1の保護フィルム(1)で覆い、次いでポリビニルアルコール系偏光子(3)の他方の面に、光硬化性接着剤を塗工し、第2の硬化性接着剤層(4’)を形成し、形成された第2の硬化性接着剤層(4’)の表面を第2の保護フィルム(5)で覆い、それから、第2の保護フィルム(5)の側から活性エネルギー線を照射し、第1の硬化性接着剤層(2’)及び第2の硬化性接着剤層(4’)を硬化することによって製造することもできる。 The polarizing plate of the present invention is formed by applying a photocurable adhesive to one surface of the polyvinyl alcohol polarizer (3) to form a first curable adhesive layer (2 ′). Cover the surface of the first curable adhesive layer (2 ′) thus formed with the first protective film (1), and then apply a photocurable adhesive to the other surface of the polyvinyl alcohol polarizer (3). Forming a second curable adhesive layer (4 ′), covering the surface of the formed second curable adhesive layer (4 ′) with a second protective film (5), and It is produced by irradiating active energy rays from the second protective film (5) side and curing the first curable adhesive layer (2 ′) and the second curable adhesive layer (4 ′). You can also.
偏光板は、上記のように、偏光子と接着層と保護フィルムとを必須の構成として含むものであるが、その他の任意の構成を含んでいてもよい。たとえば、任意の位置に必要に応じて反射層、反射防止層、ハードコート層、防汚層、防曇層、スティッキング防止層等を含むことができる。 As described above, the polarizing plate includes the polarizer, the adhesive layer, and the protective film as essential components, but may include other optional components. For example, a reflection layer, an antireflection layer, a hard coat layer, an antifouling layer, an antifogging layer, an antisticking layer, and the like can be included at an arbitrary position as required.
[ポリビニルアルコール系偏光子]の製造例
ホウ酸20質量部、ヨウ素0.2質量部、ヨウ化カリウム0.5質量部を水480質量部に溶解させて染色液を調整した。この染色液にPVAフィルム(ビニロンフィルム#40、アイセロ社製)を、30秒浸漬した後、フィルムを一方向に2倍に延伸し、乾燥させて、膜厚30μmのPVA偏光子を得た。
Production Example of [Polyvinyl Alcohol Polarizer] A staining solution was prepared by dissolving 20 parts by mass of boric acid, 0.2 parts by mass of iodine, and 0.5 parts by mass of potassium iodide in 480 parts by mass of water. A PVA film (Vinylon film # 40, manufactured by Aicello) was immersed in this dyeing solution for 30 seconds, and then the film was stretched twice in one direction and dried to obtain a PVA polarizer having a thickness of 30 μm.
[実施例1]
保護フィルム(1)として、三菱レイヨン(株)製の紫外線吸収剤を含有するアクリルフィルム:HBD−002(50μm)を用い、保護フィルム(5)として、日本ゼオン社製の紫外線吸収剤を含有しないシクロオレフィンフィルム、ゼオノアフィルム「ZF−14」(100μm)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った。表面処理後1時間以内に、保護フィルム(1)と(5)のそれぞれに、表1に示す光重合組成物をワイヤーバーコーター#3を用いて塗工し、硬化性接着剤層(2’)、(4’)を形成し、その硬化性接着剤層(2’)と(4’)との間に上記のPVA偏光子を挟み、保護フィルム(1)/硬化性接着剤層(2’)/PVA系偏光子(3)/硬化性接着剤層(4’)/保護フィルム(5)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。
UV照射装置(東芝社製 高圧水銀灯)で最大照度500mW/cm2、積算光量800mJ/cm2の紫外線を保護フィルム(5)側から照射して、偏光板を作製した。形成された各接着剤層の厚みは、3〜4μmであった。
[Example 1]
The protective film (1) is an acrylic film containing an ultraviolet absorber manufactured by Mitsubishi Rayon Co., Ltd .: HBD-002 (50 μm), and the protective film (5) does not contain an ultraviolet absorber manufactured by Nippon Zeon. A cycloolefin film and ZEONOR film “ZF-14” (100 μm) were used, and each surface was subjected to corona treatment with a discharge amount of 300 W · min / m 2 . Within 1 hour after the surface treatment, each of the protective films (1) and (5) was coated with the photopolymerization composition shown in Table 1 using a wire bar coater # 3, and a curable adhesive layer (2 ′ ), (4 ′), the PVA polarizer is sandwiched between the curable adhesive layers (2 ′) and (4 ′), and the protective film (1) / curable adhesive layer (2 A laminate comprising ') / PVA polarizer (3) / curable adhesive layer (4') / protective film (5) was obtained.
Four sides of this laminate were fixed with cellophane tape so that the protective film (1) was in contact with the tin plate, and was fixed to the tin plate.
A polarizing plate was produced by irradiating ultraviolet rays having a maximum illuminance of 500 mW / cm 2 and an integrated light amount of 800 mJ / cm 2 from the protective film (5) side with a UV irradiation apparatus (high pressure mercury lamp manufactured by Toshiba Corporation). The thickness of each formed adhesive layer was 3 to 4 μm.
[実施例2〜8、比較例1〜7]
光硬化性重合組成物を表1および表2のように変えた以外は実施例1と同様にして偏光板を作製し、後述する方法に従って、その性能を評価した。
[Examples 2 to 8, Comparative Examples 1 to 7]
A polarizing plate was produced in the same manner as in Example 1 except that the photocurable polymer composition was changed as shown in Tables 1 and 2, and its performance was evaluated according to the method described later.
[実施例9および10]
実施例9では、保護フィルム(1)を富士フィルム(株)製の紫外線吸収剤含有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)に、実施例10では保護フィルム(1)を日本ゼオン社製の紫外線吸収剤を含有しないシクロオレフィンフィルム、ゼオノアフィルム「ZF−14」(100μm)にそれぞれ代えた以外は、実施例3と同様にして偏光板を得、同様に評価した。
[Examples 9 and 10]
In Example 9, the protective film (1) is an ultraviolet absorber-containing triacetylcellulose-based film manufactured by Fuji Film Co., Ltd .: trade name “Fujitac” (80 μm), and in Example 10, the protective film (1) is ZEON A polarizing plate was obtained and evaluated in the same manner as in Example 3 except that it was replaced with a cycloolefin film and a ZEONOR film “ZF-14” (100 μm) which did not contain an ultraviolet absorber manufactured by the company.
[実施例11]
保護フィルム(1)を富士フィルム(株)製の紫外線吸収剤含有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)に代え、保護フィルム(5)を、紫外線吸収剤を含まないトリアセチルセルロース系フィルム:商品名「TACPHAN N882GL」(80μm)に代えた以外は、実施例3と同様にして偏光板を得、同様に評価した。
[Example 11]
The protective film (1) is replaced with an ultraviolet absorbent-containing triacetyl cellulose film manufactured by Fuji Film Co., Ltd .: trade name “Fujitac” (80 μm), and the protective film (5) is a triacetyl cellulose containing no ultraviolet absorbent. System film: A polarizing plate was obtained and evaluated in the same manner as in Example 3 except that the product name was changed to “TACPHAN N882GL” (80 μm).
[実施例12]
保護フィルム(1)、(5)を実施例11と同様にし、表1に示すように高Tgラジカル重合性化合物(b)を含む光硬化性接着剤を用い、実施例3と同様にして偏光板を得、同様に評価した。
[Example 12]
The protective films (1) and (5) were prepared in the same manner as in Example 11, and as shown in Table 1, a photocurable adhesive containing a high Tg radical polymerizable compound (b) was used. Plates were obtained and evaluated similarly.
[実施例13]
保護フィルム(1)、(5)を日本ゼオン社製の紫外線吸収剤を含有しないシクロオレフィンフィルム、ゼオノアフィルム「ZF−14」(100μm)にした以外は、実施例12と同様の光硬化性接着剤を用い、偏光板を得、同様に評価した。
[Example 13]
Photocurable adhesion similar to Example 12 except that the protective films (1) and (5) were changed to a cycloolefin film and ZEONOR film “ZF-14” (100 μm) which do not contain an ultraviolet absorber manufactured by Nippon Zeon. A polarizing plate was obtained using an agent and evaluated in the same manner.
[実施例14および15]
保護フィルム(1)、(5)を実施例13と同様にし、表1に示すように多官能アクリレート(b)又はアクリロイル基を有するカチオン重合性化合物(x)を含む光硬化性接着剤を用い、実施例13と同様にして偏光板を得、同様に評価した。
[Examples 14 and 15]
The protective films (1) and (5) were used in the same manner as in Example 13, and a photocurable adhesive containing a polyfunctional acrylate (b) or a cationically polymerizable compound (x) having an acryloyl group as shown in Table 1 was used. A polarizing plate was obtained in the same manner as in Example 13 and evaluated in the same manner.
[比較例8〜11]
保護フィルム(1)、(5)を日本ゼオン社製の紫外線吸収剤を含有しないシクロオレフィンフィルム、ゼオノアフィルム「ZF−14」(100μm)にし、表2に記載の光硬化性接着剤を用い、偏光板を得、同様に評価した。
[Comparative Examples 8 to 11]
Protective films (1) and (5) were made into a cycloolefin film and ZEONOR film “ZF-14” (100 μm) containing no UV absorber made by Nippon Zeon Co., Ltd., and the photocurable adhesives listed in Table 2 were used. A polarizing plate was obtained and evaluated in the same manner.
<接着力(剥離強度)>
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サンプルとした。サンプルを両面粘着テープ(東洋インキ製造株式会社製DF8712S)により金属板上に貼り付けた。サンプル(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、23℃、50%RH環境下で、ピール速度:300mm/minにて接着力を測定した。表中の接着力は、以下の基準に従って評価した。
2.5(N/25mm)以上・・・◎
1.5(N/25mm)以上〜2.5(N/25mm)未満・・・○
1.0(N/25mm)以上〜1.5(N/25mm)未満・・・△
1.0(N/25mm)未満・・・×
<Adhesive strength (peel strength)>
The obtained polarizing plate was cut into a size of 25 mm × 150 mm using a cutter to obtain a sample. The sample was affixed on the metal plate with a double-sided adhesive tape (DF8712S manufactured by Toyo Ink Manufacturing Co., Ltd.). The sample (polarizing plate) was previously provided with a peeling peel between the protective film and the polarizer, and the adhesive force was measured at a peel rate of 300 mm / min in an environment of 23 ° C. and 50% RH. The adhesive strength in the table was evaluated according to the following criteria.
2.5 (N / 25mm) or more ... ◎
1.5 (N / 25mm) or more to less than 2.5 (N / 25mm)
1.0 (N / 25mm) or more to less than 1.5 (N / 25mm) ・ ・ ・ △
Less than 1.0 (N / 25mm) ... ×
<カッター試験(密着力試験)>
得られた偏光板の、保護フィルムと偏光子の間にカッターの刃を入れ、刃を押し進めたときの刃の入り方を以下の基準で評価した。
カッターの刃がフィルム間に容易に入らない・・・◎
カッターの刃を押し進めたときに、刃がフィルム間に4〜5mm入ったところで止まる・・・○
カッターの刃がフィルム間に無理なく入る・・・×
<Cutter test (adhesion test)>
The blade of a cutter was put between the protective film and the polarizer of the obtained polarizing plate, and how the blade entered when the blade was pushed forward was evaluated according to the following criteria.
The cutter blade does not easily fit between the films ... ◎
When the blade of the cutter is pushed forward, it stops when the blade enters 4-5 mm between the films ...
The blade of the cutter fits between the films without difficulty ... ×
<打ち抜き加工性>
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がれ状態を目視で観察した。
偏光板の面積(100cm2)に対して剥がれた面積の割合(%)が0〜1%未満のものを◎、1〜2%未満のものを○、2〜3%未満のものを△、剥離面積が3%以上のものを×とした。
<Punching workability>
The produced polarizing plate was punched out from the protective film (1) side using a 100 mm × 100 mm blade manufactured by Dumbbell.
The state of peeling around the punched polarizing plate was visually observed.
The ratio (%) of the peeled area with respect to the area (100 cm 2 ) of the polarizing plate is 0 to less than 1% ◎, less than 1 to 2% ○, less than 2 to 3% Δ, Those having a peeled area of 3% or more were evaluated as x.
<温水浸漬試験(耐水性)>
得られた偏光板を、25mm×50mmのサイズにカッターを用いて裁断してサンプルとし、これを恒温水(60℃)中に24時間、及び72時間それぞれ浸漬させた後、サンプル(偏光板)の色抜け度合いを目視で観察した。
偏光板の面積に対して色抜けした面積の割合(%)が、0〜10%未満のものを◎、10〜30%未満のものを○、30%以上のものを×とした。
評価結果を表1および表2に示す。使用した化合物および保護フィルムについては、表1の下にその詳細を記載した。
<Hot water immersion test (water resistance)>
The obtained polarizing plate was cut into a size of 25 mm × 50 mm with a cutter to obtain a sample, which was immersed in constant temperature water (60 ° C.) for 24 hours and 72 hours, respectively, and then a sample (polarizing plate) The degree of color loss was visually observed.
When the ratio (%) of the lost color area to the polarizing plate area was 0 to less than 10%, ◎, 10 to less than 30% were evaluated as ◯, and 30% or more were evaluated as ×.
The evaluation results are shown in Tables 1 and 2. Details of the compounds and protective films used are listed below Table 1.
表1に示すように、いずれの実施例でも、接着性、打ち抜き加工性、および耐水性に優れた偏光子を形成することができた。
実施例3と実施例6はいずれも、高Tgラジカル重合性化合物(b)を含まず、低Tgラジカル重合性化合物(a)の含有量が90質量%の光硬化性接着剤を用いる場合であり、低Tgラジカル重合性化合物(a)として、4-ヒドロキシブチルアクリレートの他にω-カルボキシ-ポリカプロラクトンアクリレートを併用する実施例3は、実施例6よりも凝集力が高く、接着力の点で優れている。
As shown in Table 1, in any of the examples, a polarizer excellent in adhesiveness, punching workability, and water resistance could be formed.
Example 3 and Example 6 are both cases where a high-Tg radical polymerizable compound (b) is not used and a photo-curing adhesive having a low Tg radical polymerizable compound (a) content of 90% by mass is used. In Example 3, in which ω-carboxy-polycaprolactone acrylate is used in combination with 4-hydroxybutyl acrylate in addition to 4-hydroxybutyl acrylate as the low Tg radical polymerizable compound (a), the cohesive force is higher than that in Example 6, and the adhesive strength is high. Is excellent.
また、実施例12は、高Tgラジカル重合性化合物(b)を含む光硬化性接着剤を用いる場合であり、高Tgラジカル重合性化合物(b)を含まない実施例11に比して、保護フィルムのトリアセチルセルロース系フィルムに対する接着性の点で優れているので、接着力及び耐水性の点で優れている。 Moreover, Example 12 is a case where the photocurable adhesive agent containing a high Tg radically polymerizable compound (b) is used, and compared with Example 11 which does not contain a high Tg radically polymerizable compound (b). Since it is excellent in the adhesiveness with respect to the triacetylcellulose-type film of a film, it is excellent in the point of adhesive force and water resistance.
さらに、実施例13は、実施例12に比して、保護フィルムに透湿性の低いシクロオレフィンフィルムを用いた場合であり、耐水性の点でより優れている。 Furthermore, Example 13 is a case where a cycloolefin film having low moisture permeability is used for the protective film as compared with Example 12, and is more excellent in terms of water resistance.
一方、カチオン重合性化合物(c)を含有しない光硬化性接着剤を用いる比較例1は、24時間の耐水性すらも不良である。
また、低Tgラジカル重合性化合物(a)の含有量の少ない比較例2〜5および10は、いずれも硬化した接着層が固くなりすぎるためか、接着力が小さく、打ち抜き加工性も良くない。
On the other hand, Comparative Example 1 using a photocurable adhesive that does not contain the cationically polymerizable compound (c) has poor water resistance even for 24 hours.
In Comparative Examples 2 to 5 and 10 having a low content of the low Tg radical polymerizable compound (a), the cured adhesive layer is too hard, or the adhesive force is small and the punching processability is not good.
さらに、比較例6、7は、低Tgラジカル重合性化合物(a)の含有量が少なく、単官能高Tgラジカル重合性化合物(b)の代わりに3官能のラジカル重合性化合物と、カチオン重合性化合物(c)の代わりにカチオン重合性官能基及び(メタ)アクリロイル基を有する化合物を用いた場合であり、接着力が極めて小さかった。 Further, Comparative Examples 6 and 7 have a low content of the low Tg radical polymerizable compound (a), and instead of the monofunctional high Tg radical polymerizable compound (b), a trifunctional radical polymerizable compound and a cationic polymerizable compound are used. In this case, a compound having a cationic polymerizable functional group and a (meth) acryloyl group was used instead of the compound (c), and the adhesive force was extremely small.
比較例8および9は、低Tgラジカル重合性化合物(a)の含有量は十分ではあるが、カチオン重合性化合物(c)の代わりにカチオン重合性官能基及び(メタ)アクリロイル基を有する化合物を用いた場合であり、接着力が極めて小さかった。
なお、比較例4〜9は、接着力が極めて小さかったにも関わらず、耐水性が良好だったのは、カッター試験による密着性が良好であったことが原因の1つと考察される。
In Comparative Examples 8 and 9, although the content of the low Tg radical polymerizable compound (a) is sufficient, a compound having a cationic polymerizable functional group and a (meth) acryloyl group is used instead of the cationic polymerizable compound (c). In this case, the adhesive strength was extremely small.
In Comparative Examples 4 to 9, although the adhesive force was very small, the water resistance was considered to be one of the reasons that the adhesiveness by the cutter test was good.
1,5 保護フィルム
2 第1の接着剤層
3 ポリビニルアルコール系偏光子
4 第2の接着剤層
1’ 保護フィルム(1)と硬化性組成物からなる層(2’)との積層体
5’ 保護フィルム(5)と硬化性組成物からなる層(4’)との積層体
6 活性エネルギー線
DESCRIPTION OF
Claims (11)
前記光硬化性接着剤は、ラジカル重合性化合物およびカチオン重合性化合物からなる主剤と、光ラジカル重合開始剤と、光カチオン重合開始剤とを含み、
前記ラジカル重合性化合物として、ガラス転移温度が−80℃〜0℃のホモポリマーを形成するラジカル重合性化合物(a)を前記主剤中に60〜99.8質量%含み、
前記ラジカル重合性化合物(a)は4−ヒドロキシブチルアクリレートを含み、
前記カチオン重合性化合物として、(メタ)アクリロイル基を有しないカチオン重合性化合物(c)を前記主剤中に0.02〜40質量%含み、
前記主剤100質量部に対して、前記光ラジカル重合開始剤を1〜10質量部、前記光カチオン重合開始剤を0.5〜5質量部の範囲でそれぞれ含む、
ことを特徴とする偏光板。 A polarizing plate comprising a polyvinyl alcohol polarizer, an adhesive layer obtained by curing a photocurable adhesive, and a protective film, wherein both sides of the polarizer are respectively covered with a protective film via the adhesive layer There,
The photo-curable adhesive includes a main agent composed of a radical polymerizable compound and a cationic polymerizable compound, a photo radical polymerization initiator, and a photo cationic polymerization initiator,
As the radical polymerizable compound, the radical polymerizable compound (a) that forms a homopolymer having a glass transition temperature of −80 ° C. to 0 ° C. is contained in the main agent in an amount of 60 to 99.8% by mass,
The radical polymerizable compound (a) contains 4-hydroxybutyl acrylate,
As the cationic polymerizable compound, containing 0.02 to 40% by mass of a cationic polymerizable compound (c) having no (meth) acryloyl group in the main agent,
1 to 10 parts by mass of the radical photopolymerization initiator and 100 to 5 parts by mass of the cationic photopolymerization initiator, respectively, with respect to 100 parts by mass of the main agent.
A polarizing plate characterized by that.
前記ラジカル重合性化合物として、ガラス転移温度が−80℃〜0℃のホモポリマーを形成するラジカル重合性化合物(a)を前記主剤中に60〜99.8質量%含み、
前記ラジカル重合性化合物(a)は4−ヒドロキシブチルアクリレートを含み、
前記カチオン重合性化合物として、(メタ)アクリロイル基を有しないカチオン重合性化合物(c)を前記主剤中に0.02〜40質量%含み、
前記主剤100質量部に対して、前記光ラジカル重合開始剤を1〜10質量部、前記光カチオン重合開始剤を0.5〜5質量部の範囲でそれぞれ含むことを特徴とする、偏光板形成用光硬化性接着剤。 A main agent composed of a radical polymerizable compound and a cationic polymerizable compound, a photo radical polymerization initiator, and a photo cationic polymerization initiator,
As the radical polymerizable compound, the radical polymerizable compound (a) that forms a homopolymer having a glass transition temperature of −80 ° C. to 0 ° C. is contained in the main agent in an amount of 60 to 99.8% by mass,
The radical polymerizable compound (a) contains 4-hydroxybutyl acrylate,
As the cationic polymerizable compound, containing 0.02 to 40% by mass of a cationic polymerizable compound (c) having no (meth) acryloyl group in the main agent,
Forming a polarizing plate, comprising 1 to 10 parts by mass of the radical photopolymerization initiator and 0.5 to 5 parts by mass of the cationic photopolymerization initiator with respect to 100 parts by mass of the main agent. Photo-curable adhesive.
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