JP2019191282A - Polarizing plate with retardation layer and organic EL display device - Google Patents
Polarizing plate with retardation layer and organic EL display device Download PDFInfo
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- JP2019191282A JP2019191282A JP2018081257A JP2018081257A JP2019191282A JP 2019191282 A JP2019191282 A JP 2019191282A JP 2018081257 A JP2018081257 A JP 2018081257A JP 2018081257 A JP2018081257 A JP 2018081257A JP 2019191282 A JP2019191282 A JP 2019191282A
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- retardation layer
- polarizing plate
- layer
- weight
- sensitive adhesive
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- 238000011002 quantification Methods 0.000 description 1
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- 239000005268 rod-like liquid crystal Substances 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
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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
-
- 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]
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3016—Polarising elements involving passive liquid crystal elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- 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
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/50—OLEDs integrated with light modulating elements, e.g. with electrochromic elements, photochromic elements or liquid crystal elements
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- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polarising Elements (AREA)
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Abstract
Description
本発明は、位相差層付き偏光板および有機EL表示装置に関する。 The present invention relates to a polarizing plate with a retardation layer and an organic EL display device.
近年、薄型ディスプレイの普及と共に、有機ELパネルを搭載した画像表示装置(有機EL表示装置)が提案されている。有機ELパネルは反射性の高い金属層を有しており、外光反射や背景の映り込み等の問題を生じやすい。そこで、位相差層付き偏光板(円偏光板)を視認側に設けることにより、これらの問題を防ぐことが知られている。しかしながら、このような位相差層付き偏光板の位相差層として、液晶化合物を含む2層の位相差層を粘着剤で貼り合せた積層体を用いた場合、高温環境下において位相差層にクラックが発生する場合がある。 In recent years, with the widespread use of thin displays, image display devices (organic EL display devices) equipped with organic EL panels have been proposed. The organic EL panel has a highly reflective metal layer, and is likely to cause problems such as external light reflection and background reflection. Therefore, it is known to prevent these problems by providing a polarizing plate with a retardation layer (circular polarizing plate) on the viewing side. However, when a laminate in which two retardation layers containing a liquid crystal compound are bonded with an adhesive is used as a retardation layer of such a polarizing plate with a retardation layer, the retardation layer is cracked in a high temperature environment. May occur.
本発明は上記従来の課題を解決するためになされたものであり、その主たる目的は、高温環境下での位相差層のクラックの発生を抑制した位相差層付き偏光板、および、そのような位相差層付き偏光板を用いた有機EL表示装置を提供することにある。 The present invention has been made to solve the above-described conventional problems, and its main purpose is to provide a polarizing plate with a retardation layer that suppresses the generation of cracks in the retardation layer under a high-temperature environment, and such a polarizing plate. An object of the present invention is to provide an organic EL display device using a polarizing plate with a retardation layer.
本発明の位相差層付き偏光板は、偏光板と、第1の位相差層と、粘着剤層と、第2の位相差層と、をこの順に有し、上記第1の位相差層および上記第2の位相差層が液晶化合物を含み、上記粘着剤層を構成する粘着剤が、ベースポリマー100重量部に対してイソシアネート架橋剤を0.05重量部以上含む。
1つの実施形態においては、上記ベースポリマーが(メタ)アクリル系ポリマーである。
1つの実施形態においては、上記ベースポリマーが、モノマー成分としてカルボキシル基含有モノマーを含む。
1つの実施形態においては、上記粘着剤層を構成する粘着剤が、紫外線吸収剤をさらに含む。
1つの実施形態においては、上記紫外線吸収剤が、分子構造中に水酸基を0個〜3個有する。
1つの実施形態においては、上記粘着剤層を構成する粘着剤が、吸収スペクトルの最大吸収波長が380nm〜430nmの波長領域に存在する色素化合物をさらに含む。
本発明の別の局面によれば、有機EL表示装置が提供される。この有機EL表示装置は、上記位相差層付き偏光板を有する。
The polarizing plate with a retardation layer of the present invention has a polarizing plate, a first retardation layer, a pressure-sensitive adhesive layer, and a second retardation layer in this order, and the first retardation layer and The second retardation layer contains a liquid crystal compound, and the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer contains 0.05 parts by weight or more of an isocyanate crosslinking agent with respect to 100 parts by weight of the base polymer.
In one embodiment, the base polymer is a (meth) acrylic polymer.
In one embodiment, the base polymer includes a carboxyl group-containing monomer as a monomer component.
In one embodiment, the adhesive which comprises the said adhesive layer further contains a ultraviolet absorber.
In one embodiment, the said ultraviolet absorber has 0-3 hydroxyl groups in molecular structure.
In one embodiment, the adhesive which comprises the said adhesive layer further contains the pigment | dye compound which exists in the wavelength range whose maximum absorption wavelength of an absorption spectrum is 380 nm-430 nm.
According to another aspect of the present invention, an organic EL display device is provided. This organic EL display device has the above polarizing plate with a retardation layer.
本発明によれば、2つの位相差層の間に配置される粘着剤層を構成する粘着剤が、ベースポリマー100重量部に対してイソシアネート架橋剤を0.05重量部以上含むことにより、高温環境下での位相差層のクラックの発生を抑制した位相差層付き偏光板を実現することができた。 According to the present invention, the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer disposed between the two retardation layers contains 0.05 parts by weight or more of the isocyanate cross-linking agent with respect to 100 parts by weight of the base polymer. It was possible to realize a polarizing plate with a retardation layer that suppressed the occurrence of cracks in the retardation layer under the environment.
以下、本発明の実施形態について説明するが、本発明はこれらの実施形態には限定されない。 Hereinafter, although embodiment of this invention is described, this invention is not limited to these embodiment.
A.位相差層付き偏光板
図1は、本発明の1つの実施形態に係る位相差層付き偏光板の概略断面図である。図1に示すように、位相差層付き偏光板100は、偏光板10と、第1の位相差層20と、粘着剤層30と、第2の位相差層40と、をこの順に有する。すなわち、第1の位相差層20と第2の位相差層40とは、粘着剤層30を介して積層されている。第1の位相差層20および第2の位相差層40は、液晶化合物を含んで構成されている。粘着剤層30を構成する粘着剤は、ベースポリマー100重量部に対してイソシアネート架橋剤を0.05重量部以上含む。これにより、高温環境下での第1の位相差層20および/または第2の位相差層30のクラックの発生が抑制され得る。第2の位相差層40の粘着剤層30とは反対側には、別の粘着剤層50が積層され得る。これにより、例えば有機ELパネルへの貼り合せが容易になる。
A. FIG. 1 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to one embodiment of the present invention. As illustrated in FIG. 1, the retardation layer-attached polarizing
上記粘着剤のベースポリマーは、好ましくは(メタ)アクリル系ポリマーである。上記粘着剤のベースポリマーは、好ましくは、モノマー成分としてカルボキシル基含有モノマーを含む。1つの実施形態においては、粘着剤層30を構成する粘着剤は、紫外線吸収剤をさらに含む。この場合、紫外線吸収剤は、好ましくは、分子構造中に水酸基を0個〜3個有する。また、1つの実施形態においては、粘着剤層30を構成する粘着剤は、吸収スペクトルの最大吸収波長が380nm〜430nmの波長領域に存在する色素化合物をさらに含む。上記の構成によれば、粘着剤層30に紫外線吸収機能を付与することができ、これにより、位相差層付き偏光板を有機EL表示装置に用いた場合の有機EL素子の劣化を抑制することができる。
The base polymer of the pressure-sensitive adhesive is preferably a (meth) acrylic polymer. The base polymer of the pressure-sensitive adhesive preferably contains a carboxyl group-containing monomer as a monomer component. In one embodiment, the pressure-sensitive adhesive constituting the pressure-sensitive
以下、位相差層付き偏光板100を構成する各層について、詳細に説明する。
Hereinafter, each layer which comprises the polarizing
B.偏光板
偏光板10は、代表的には、偏光子と、偏光子の片側に配置された第1の保護層と、偏光子のもう一方の側に配置された第2の保護層とを有する。偏光子は、代表的には吸収型偏光子である。第1の保護層および第2の保護層のうち一方は省略されてもよい。
B. Polarizing plate The polarizing
B−1.偏光子
偏光子としては、任意の適切な偏光子が採用され得る。例えば、偏光子を形成する樹脂フィルムは、単層の樹脂フィルムであってもよく、二層以上の積層体であってもよい。
B-1. Polarizer Any appropriate polarizer may be adopted as the polarizer. For example, the resin film forming the polarizer may be a single-layer resin film or a laminate of two or more layers.
単層の樹脂フィルムから構成される偏光子の具体例としては、ポリビニルアルコール(PVA)系フィルム、部分ホルマール化PVA系フィルム、エチレン・酢酸ビニル共重合体系部分ケン化フィルム等の親水性高分子フィルムに、ヨウ素や二色性染料等の二色性物質による染色処理および延伸処理が施されたもの、PVAの脱水処理物やポリ塩化ビニルの脱塩酸処理物等ポリエン系配向フィルム等が挙げられる。好ましくは、光学特性に優れることから、PVA系フィルムをヨウ素で染色し一軸延伸して得られた偏光子が用いられる。 Specific examples of polarizers composed of a single-layer resin film include hydrophilic polymer films such as polyvinyl alcohol (PVA) films, partially formalized PVA films, and ethylene / vinyl acetate copolymer partially saponified films. In addition, there may be mentioned polyene-based oriented films such as those subjected to dyeing treatment and stretching treatment with dichroic substances such as iodine and dichroic dyes, PVA dehydrated products and polyvinyl chloride dehydrochlorinated products. Preferably, a polarizer obtained by dyeing a PVA film with iodine and uniaxially stretching is used because of excellent optical properties.
上記ヨウ素による染色は、例えば、PVA系フィルムをヨウ素水溶液に浸漬することにより行われる。上記一軸延伸の延伸倍率は、好ましくは3〜7倍である。延伸は、染色処理後に行ってもよいし、染色しながら行ってもよい。また、延伸してから染色してもよい。必要に応じて、PVA系フィルムに、膨潤処理、架橋処理、洗浄処理、乾燥処理等が施される。例えば、染色の前にPVA系フィルムを水に浸漬して水洗することで、PVA系フィルム表面の汚れやブロッキング防止剤を洗浄することができるだけでなく、PVA系フィルムを膨潤させて染色ムラなどを防止することができる。 The dyeing with iodine is performed, for example, by immersing a PVA film in an iodine aqueous solution. The stretching ratio of the uniaxial stretching is preferably 3 to 7 times. The stretching may be performed after the dyeing treatment or may be performed while dyeing. Moreover, you may dye | stain after extending | stretching. If necessary, the PVA film is subjected to swelling treatment, crosslinking treatment, washing treatment, drying treatment and the like. For example, by immersing the PVA film in water and washing it before dyeing, not only can the surface of the PVA film be cleaned of dirt and anti-blocking agents, but the PVA film can be swollen to cause uneven staining. Can be prevented.
積層体を用いて得られる偏光子の具体例としては、樹脂基材と当該樹脂基材に積層されたPVA系樹脂層(PVA系樹脂フィルム)との積層体、あるいは、樹脂基材と当該樹脂基材に塗布形成されたPVA系樹脂層との積層体を用いて得られる偏光子が挙げられる。樹脂基材と当該樹脂基材に塗布形成されたPVA系樹脂層との積層体を用いて得られる偏光子は、例えば、PVA系樹脂溶液を樹脂基材に塗布し、乾燥させて樹脂基材上にPVA系樹脂層を形成して、樹脂基材とPVA系樹脂層との積層体を得ること;当該積層体を延伸および染色してPVA系樹脂層を偏光子とすること;により作製され得る。本実施形態においては、延伸は、代表的には積層体をホウ酸水溶液中に浸漬させて延伸することを含む。さらに、延伸は、必要に応じて、ホウ酸水溶液中での延伸の前に積層体を高温(例えば、95℃以上)で空中延伸することをさらに含み得る。得られた樹脂基材/偏光子の積層体はそのまま用いてもよく(すなわち、樹脂基材を偏光子の保護層としてもよく)、樹脂基材/偏光子の積層体から樹脂基材を剥離し、当該剥離面に目的に応じた任意の適切な保護層を積層して用いてもよい。このような偏光子の製造方法の詳細は、例えば特開2012−73580号公報に記載されている。当該公報は、その全体の記載が本明細書に参考として援用される。 As a specific example of a polarizer obtained by using a laminate, a laminate of a resin substrate and a PVA resin layer (PVA resin film) laminated on the resin substrate, or a resin substrate and the resin Examples thereof include a polarizer obtained by using a laminate with a PVA resin layer applied and formed on a substrate. For example, a polarizer obtained by using a laminate of a resin base material and a PVA resin layer applied and formed on the resin base material may be obtained by, for example, applying a PVA resin solution to a resin base material and drying it. A PVA-based resin layer is formed thereon to obtain a laminate of a resin base material and a PVA-based resin layer; the laminate is stretched and dyed to make the PVA-based resin layer a polarizer; obtain. In the present embodiment, stretching typically includes immersing the laminate in an aqueous boric acid solution and stretching. Furthermore, the stretching may further include, if necessary, stretching the laminate in the air at a high temperature (for example, 95 ° C. or higher) before stretching in the aqueous boric acid solution. The obtained resin base material / polarizer laminate may be used as it is (that is, the resin base material may be used as a protective layer of the polarizer), and the resin base material is peeled from the resin base material / polarizer laminate. Any appropriate protective layer according to the purpose may be laminated on the release surface. Details of a method for manufacturing such a polarizer are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580. This publication is incorporated herein by reference in its entirety.
偏光子の厚みは、例えば1μm〜35μmである。1つの実施形態においては、偏光子の厚みは、好ましくは1μm〜15μmであり、さらに好ましくは3μm〜10μmであり、特に好ましくは3μm〜8μmである。偏光子の厚みがこのような範囲であれば、加熱時のカールを良好に抑制することができ、および、良好な加熱時の外観耐久性が得られる。 The thickness of the polarizer is, for example, 1 μm to 35 μm. In one embodiment, the thickness of the polarizer is preferably 1 μm to 15 μm, more preferably 3 μm to 10 μm, and particularly preferably 3 μm to 8 μm. When the thickness of the polarizer is in such a range, curling during heating can be satisfactorily suppressed, and good appearance durability during heating can be obtained.
B−2.保護層
第1および第2の保護層は、偏光子を保護するフィルムとして使用できる任意の適切な保護フィルムで形成される。当該保護フィルムの主成分となる材料の具体例としては、トリアセチルセルロース(TAC)等のセルロース系樹脂や、ポリエステル系、ポリビニルアルコール系、ポリカーボネート系、ポリアミド系、ポリイミド系、ポリエーテルスルホン系、ポリスルホン系、ポリスチレン系、ポリノルボルネン系、ポリオレフィン系、(メタ)アクリル系、アセテート系等の透明樹脂等が挙げられる。また、(メタ)アクリル系、ウレタン系、(メタ)アクリルウレタン系、エポキシ系、シリコーン系等の熱硬化型樹脂または紫外線硬化型樹脂等も挙げられる。この他にも、例えば、シロキサン系ポリマー等のガラス質系ポリマーも挙げられる。また、特開2001−343529号公報(WO01/37007)に記載のポリマーフィルムも使用できる。このフィルムの材料としては、例えば、側鎖に置換または非置換のイミド基を有する熱可塑性樹脂と、側鎖に置換または非置換のフェニル基ならびにニトリル基を有する熱可塑性樹脂を含有する樹脂組成物が使用でき、例えば、イソブテンとN−メチルマレイミドからなる交互共重合体と、アクリロニトリル・スチレン共重合体とを有する樹脂組成物が挙げられる。当該ポリマーフィルムは、例えば、上記樹脂組成物の押出成形物であり得る。
B-2. Protective layer The first and second protective layers are formed of any suitable protective film that can be used as a film for protecting the polarizer. Specific examples of the material that is the main component of the protective film include cellulose resins such as triacetyl cellulose (TAC), polyester-based, polyvinyl alcohol-based, polycarbonate-based, polyamide-based, polyimide-based, polyethersulfone-based, and polysulfone-based materials. And transparent resins such as those based on polystyrene, polystyrene, polynorbornene, polyolefin, (meth) acryl, and acetate. Further, thermosetting resins such as (meth) acrylic, urethane-based, (meth) acrylurethane-based, epoxy-based, and silicone-based or ultraviolet curable resins are also included. In addition to this, for example, a glassy polymer such as a siloxane polymer is also included. Moreover, the polymer film as described in Unexamined-Japanese-Patent No. 2001-343529 (WO01 / 37007) can also be used. As a material for this film, for example, a resin composition containing a thermoplastic resin having a substituted or unsubstituted imide group in the side chain and a thermoplastic resin having a substituted or unsubstituted phenyl group and nitrile group in the side chain For example, a resin composition having an alternating copolymer composed of isobutene and N-methylmaleimide and an acrylonitrile / styrene copolymer can be mentioned. The polymer film can be, for example, an extruded product of the resin composition.
保護フィルムの厚みは、好ましくは10μm〜100μmである。保護フィルムは、接着層(具体的には、接着剤層、粘着剤層)を介して偏光子に積層されていてもよく、偏光子に密着(接着層を介さずに)積層されていてもよい。接着剤層は、任意の適切な接着剤で形成される。接着剤としては、例えば、ポリビニルアルコール系樹脂を主成分とする水溶性接着剤が挙げられる。ポリビニルアルコール系樹脂を主成分とする水溶性接着剤は、好ましくは、金属化合物コロイドをさらに含有し得る。金属化合物コロイドは、金属化合物微粒子が分散媒中に分散しているものであり得、微粒子の同種電荷の相互反発に起因して静電的安定化し、永続的に安定性を有するものであり得る。金属化合物コロイドを形成する微粒子の平均粒子径は、偏光特性等の光学特性に悪影響を及ぼさない限り、任意の適切な値であり得る。好ましくは1nm〜100nm、さらに好ましくは1nm〜50nmである。微粒子を接着剤層中に均一に分散させ得、接着性を確保し、かつクニックを抑え得るからである。なお、「クニック」とは、偏光子と保護フィルムの界面で生じる局所的な凹凸欠陥のことをいう。粘着剤層は、任意の適切な粘着剤で構成される。 The thickness of the protective film is preferably 10 μm to 100 μm. The protective film may be laminated to the polarizer via an adhesive layer (specifically, an adhesive layer or an adhesive layer), or may be adhered to the polarizer (without an adhesive layer). Good. The adhesive layer is formed of any appropriate adhesive. As an adhesive agent, the water-soluble adhesive agent which has a polyvinyl alcohol-type resin as a main component is mentioned, for example. The water-soluble adhesive mainly composed of a polyvinyl alcohol-based resin can preferably further contain a metal compound colloid. The metal compound colloid can be one in which metal compound fine particles are dispersed in a dispersion medium, and can be electrostatically stabilized due to mutual repulsion of the same kind of charge of the fine particles, and can have permanent stability. . The average particle size of the fine particles forming the metal compound colloid can be any appropriate value as long as it does not adversely affect the optical properties such as polarization properties. Preferably they are 1 nm-100 nm, More preferably, they are 1 nm-50 nm. This is because the fine particles can be uniformly dispersed in the adhesive layer, the adhesion can be ensured, and the nick can be suppressed. The “knic” refers to a local uneven defect generated at the interface between the polarizer and the protective film. The pressure-sensitive adhesive layer is composed of any appropriate pressure-sensitive adhesive.
C.位相差層
上記のとおり、第1および第2の位相差層は、液晶化合物を含んで構成されている。代表的には、第1および第2の位相差層は、液晶化合物を含有する液晶性組成物の配向固化層により構成され得る。本明細書において「配向固化層」とは、液晶化合物が層内で所定の方向に配向し、その配向状態が固定されている層をいう。液晶化合物の配向固化層は、所定の基材の表面に配向処理を施し、当該表面に液晶化合物を含む塗工液を塗工して当該液晶化合物を上記配向処理に対応する方向に配向させ、当該配向状態を固定することにより形成され得る。1つの実施形態においては、基材は任意の適切な樹脂フィルムであり、当該基材上に形成された配向固化層は、位相差層付き偏光板を構成する他の層の表面に転写され得る。液晶化合物の具体例および配向固化層の形成方法の詳細は、特開2006−163343号公報に記載されている。当該公報の記載は本明細書に参考として援用される。
C. Retardation layer As described above, the first and second retardation layers include a liquid crystal compound. Typically, the first and second retardation layers can be constituted by an alignment solidified layer of a liquid crystal composition containing a liquid crystal compound. In the present specification, the “alignment solidified layer” refers to a layer in which a liquid crystal compound is aligned in a predetermined direction in the layer and the alignment state is fixed. The alignment solidified layer of the liquid crystal compound is subjected to an alignment treatment on the surface of a predetermined substrate, and a coating liquid containing the liquid crystal compound is applied to the surface to align the liquid crystal compound in a direction corresponding to the alignment treatment, It can be formed by fixing the alignment state. In one embodiment, the substrate is any suitable resin film, and the alignment solidified layer formed on the substrate can be transferred to the surface of the other layer constituting the polarizing plate with a retardation layer. . Specific examples of the liquid crystal compound and details of the method for forming the alignment solidified layer are described in JP-A No. 2006-163343. The description in this publication is incorporated herein by reference.
1つの実施形態においては、第1の位相差層の面内位相差Re(550)は、好ましくは200nm〜300nmであり、第2の位相差層の面内位相差Re(550)は、好ましくは100nm〜150nmである。したがって、この場合、第1の位相差層はλ/2板として機能し得、第2の位相差層はλ/4板として機能し得る。偏光子の吸収軸と第1の位相差層の遅相軸とのなす角度は、好ましくは5°〜25°であり、特に好ましくは約15°である。偏光子の吸収軸と第2の位相差層の遅相軸とのなす角度は、好ましくは65°〜85°であり、特に好ましくは約75°である。別の実施形態においては、第1の位相差層の面内位相差Re(550)は、好ましくは120nm〜160nmであり、第2の位相差層は、屈折率楕円体がnz>nx=nyの関係を満たす。したがって、この場合、第1の位相差層はλ/4板として機能し得、第2の位相差層はいわゆるポジティブCプレートとして機能し得る。偏光子の吸収軸と第1の位相差層の遅相軸とのなす角度は、好ましくは39°〜51°であり、特に好ましくは約45°である。 In one embodiment, the in-plane retardation Re (550) of the first retardation layer is preferably 200 nm to 300 nm, and the in-plane retardation Re (550) of the second retardation layer is preferably Is 100 nm to 150 nm. Therefore, in this case, the first retardation layer can function as a λ / 2 plate, and the second retardation layer can function as a λ / 4 plate. The angle formed by the absorption axis of the polarizer and the slow axis of the first retardation layer is preferably 5 ° to 25 °, and particularly preferably about 15 °. The angle formed by the absorption axis of the polarizer and the slow axis of the second retardation layer is preferably 65 ° to 85 °, and particularly preferably about 75 °. In another embodiment, the in-plane retardation Re (550) of the first retardation layer is preferably 120 nm to 160 nm, and the second retardation layer has a refractive index ellipsoid of nz> nx = ny. Satisfy the relationship. Therefore, in this case, the first retardation layer can function as a λ / 4 plate, and the second retardation layer can function as a so-called positive C plate. The angle formed between the absorption axis of the polarizer and the slow axis of the first retardation layer is preferably 39 ° to 51 °, particularly preferably about 45 °.
C−1.第1の位相差層
1つの実施形態においては、第1の位相差層は、実質的に垂直に配向させたディスコティック液晶化合物を含有する液晶性組成物の配向固化層により構成され得る。本明細書において、「ディスコティック液晶化合物」とは、分子構造中に、円板状のメソゲン基を有し、該メソゲン基に2〜8本の側差が、エーテル結合やエステル結合で放射状に結合しているものをいう。第1の位相差層の厚みは、所望の面内位相差が得られるように設定され得、好ましくは1μm〜20μmであり、より好ましくは1μm〜12μmである。上記のディスコティック液晶化合物を含有する液晶性組成物は、ディスコティック液晶化合物を含み、液晶性を示すものであれば特に制限はない。上記液晶性組成物中のディスコティック液晶化合物の含有量は、液晶性組成物の全固形分100重量部に対して、好ましくは40重量部以上100重量部未満である。上記実質的に垂直に配向させたディスコティック液晶化合物を含有する液晶性組成物の配向固化層からなる位相差フィルムとしては、特開2001−56411号公報に記載の方法によって得ることができる。
C-1. First Retardation Layer In one embodiment, the first retardation layer may be constituted by an alignment solidified layer of a liquid crystalline composition containing a discotic liquid crystal compound aligned substantially vertically. In the present specification, the “discotic liquid crystal compound” has a disc-shaped mesogenic group in the molecular structure, and 2 to 8 side differences in the mesogenic group are radially formed by an ether bond or an ester bond. This is what is connected. The thickness of the first retardation layer can be set so as to obtain a desired in-plane retardation, and is preferably 1 μm to 20 μm, more preferably 1 μm to 12 μm. The liquid crystalline composition containing the above discotic liquid crystal compound is not particularly limited as long as it contains a discotic liquid crystal compound and exhibits liquid crystallinity. The content of the discotic liquid crystal compound in the liquid crystal composition is preferably 40 parts by weight or more and less than 100 parts by weight with respect to 100 parts by weight of the total solid content of the liquid crystal composition. The retardation film comprising an alignment solidified layer of a liquid crystalline composition containing the substantially vertically aligned discotic liquid crystal compound can be obtained by the method described in JP-A-2001-56411.
別の実施形態においては、第1の位相差層は、棒状の液晶化合物が位相差層の遅相軸方向に並んだ状態で配向した(ホモジニアス配向)配向固化層により構成され得る。液晶化合物としては、例えば、液晶相がネマチック相である液晶化合物(ネマチック液晶)が挙げられる。このような液晶化合物として、例えば、液晶ポリマーや液晶モノマーが使用可能である。液晶化合物の液晶性の発現機構は、リオトロピックでもサーモトロピックでもどちらでもよい。液晶化合物が液晶モノマーである場合、当該液晶モノマーは、重合性モノマーおよび架橋性モノマーであることが好ましい。液晶モノマーを重合または架橋させることにより、液晶モノマーの配向状態を固定できるからである。上記液晶モノマーとしては、任意の適切な液晶モノマーが採用され得る。例えば、特表2002−533742(WO00/37585)、EP358208(US5211877)、EP66137(US4388453)、WO93/22397、EP0261712、DE19504224、DE4408171、およびGB2280445等に記載の重合性メソゲン化合物等が使用できる。このような重合性メソゲン化合物の具体例としては、例えば、BASF社の商品名LC242、Merck社の商品名E7、Wacker−Chem社の商品名LC−Sillicon−CC3767が挙げられる。第1の位相差層の厚みは、所望の面内位相差が得られるように設定され得、好ましくは1μm〜10μmであり、より好ましくは1μm〜6μmである。 In another embodiment, the first retardation layer may be constituted by an alignment solidified layer in which rod-like liquid crystal compounds are aligned in a state of being aligned in the slow axis direction of the retardation layer (homogeneous alignment). Examples of the liquid crystal compound include a liquid crystal compound (nematic liquid crystal) whose liquid crystal phase is a nematic phase. As such a liquid crystal compound, for example, a liquid crystal polymer or a liquid crystal monomer can be used. The liquid crystal compound may exhibit liquid crystallinity either lyotropic or thermotropic. When the liquid crystal compound is a liquid crystal monomer, the liquid crystal monomer is preferably a polymerizable monomer and a crosslinkable monomer. This is because the alignment state of the liquid crystal monomer can be fixed by polymerizing or crosslinking the liquid crystal monomer. Any appropriate liquid crystal monomer can be adopted as the liquid crystal monomer. For example, polymerizable mesogenic compounds described in JP-T-2002-533742 (WO00 / 37585), EP358208 (US52111877), EP66137 (US4388453), WO93 / 22397, EP02661712, DE195504224, DE44081171, and GB2280445 can be used. Specific examples of such a polymerizable mesogenic compound include, for example, the trade name LC242 from BASF, the trade name E7 from Merck, and the trade name LC-Silicon-CC3767 from Wacker-Chem. The thickness of the first retardation layer can be set so as to obtain a desired in-plane retardation, and is preferably 1 μm to 10 μm, more preferably 1 μm to 6 μm.
C−2.第2の位相差層
λ/4板として機能し得る第2の位相差層は、第1の位相差層について上記C−1項で説明した材料および方法により形成され得る。
C-2. Second Retardation Layer The second retardation layer that can function as a λ / 4 plate can be formed by the materials and methods described in the above section C-1 for the first retardation layer.
ポジティブCプレートとして機能し得る第2の位相差層は、屈折率楕円体がnz>nx=nyの関係を満たす限り、任意の適切な液晶化合物で構成され得る。このような液晶化合物の詳細は、特許第4186980号公報および特許第6055569号公報に記載されている。当該公報の記載は本明細書に参考として援用される。1つの実施形態においては、第2の位相差層は、下記化学式(I)(式中の数字65および35はモノマーユニットのモル%を示し、便宜的にブロックポリマー体で表している:重量平均分子量5000)で示される側鎖型液晶ポリマーと、ネマチック液晶相を示す重合性液晶とにより構成され得る。 The second retardation layer that can function as a positive C plate can be composed of any appropriate liquid crystal compound as long as the refractive index ellipsoid satisfies the relationship of nz> nx = ny. Details of such a liquid crystal compound are described in Japanese Patent No. 4186980 and Japanese Patent No. 6055569. The description in this publication is incorporated herein by reference. In one embodiment, the second retardation layer has the following chemical formula (I) (numbers 65 and 35 in the formula indicate mol% of the monomer unit, and are represented by a block polymer body for convenience: weight average) A side chain type liquid crystal polymer represented by a molecular weight of 5000) and a polymerizable liquid crystal exhibiting a nematic liquid crystal phase.
D.粘着剤層
上記のとおり、粘着剤は、ベースポリマー100重量部に対してイソシアネート架橋剤を0.05重量部以上含み、好ましくは、紫外線吸収剤および/または色素化合物をさらに含む。
D. Adhesive Layer As described above, the adhesive contains 0.05 parts by weight or more of an isocyanate crosslinking agent with respect to 100 parts by weight of the base polymer, and preferably further contains an ultraviolet absorber and / or a dye compound.
粘着剤層の厚みは、例えば、2μm〜50μmであり、好ましくは5μm〜30μmである。粘着剤層のゲル分率は、好ましくは40%〜95%であり、より好ましくは50%〜95%であり、さらに好ましくは65%〜93%であり、特に好ましくは80%〜93%であり、最も好ましくは85〜93%である。粘着剤層のゲル分率が小さい場合には凝集力に劣り、加工性やハンドリング性に問題が出る場合がある。また、粘着剤層を形成した直後のゲル分率は、糊打痕等の外観不具合を防止する観点から、60%以上であることが好ましく、63%以上であることがより好ましく、66%以上であることがさらに好ましく、70%以上であることが特に好ましい。 The thickness of the pressure-sensitive adhesive layer is, for example, 2 μm to 50 μm, preferably 5 μm to 30 μm. The gel fraction of the pressure-sensitive adhesive layer is preferably 40% to 95%, more preferably 50% to 95%, still more preferably 65% to 93%, and particularly preferably 80% to 93%. Yes, most preferably 85 to 93%. When the gel fraction of the pressure-sensitive adhesive layer is small, the cohesive force is inferior and there may be a problem in workability and handling properties. Further, the gel fraction immediately after forming the pressure-sensitive adhesive layer is preferably 60% or more, more preferably 63% or more, and 66% or more from the viewpoint of preventing appearance defects such as glue marks. It is more preferable that it is 70% or more.
D−1.ベースポリマー
ベースポリマーとしては、必要とされる接着性および粘着性を発揮し得るかぎり、任意の適切なポリマーが採用され得る。ベースポリマーの具体例としては、(メタ)アクリル系ポリマー、ゴム系ポリマー等が挙げられる。好ましくは、ベースポリマーは(メタ)アクリル系ポリマーである。
D-1. Base polymer Any appropriate polymer can be adopted as the base polymer as long as the required adhesiveness and tackiness can be exhibited. Specific examples of the base polymer include (meth) acrylic polymers and rubber polymers. Preferably, the base polymer is a (meth) acrylic polymer.
(メタ)アクリル系ポリマーは、モノマー単位として、アルキル(メタ)アクリレートを主成分として含有する。アルキル(メタ)アクリレートとしては、直鎖状又は分岐鎖状の炭素数1〜24のアルキル基をエステル末端に有するものが挙げられる。アルキル(メタ)アクリレートは1種を単独で又は2種以上を組み合わせて用いることができる。なお、「アルキル(メタ)アクリレート」は、アルキルアクリレート及び/又はアルキルメタクリレートをいう。 The (meth) acrylic polymer contains alkyl (meth) acrylate as a main component as a monomer unit. Examples of the alkyl (meth) acrylate include those having a linear or branched alkyl group having 1 to 24 carbon atoms at the ester terminal. Alkyl (meth) acrylate can be used individually by 1 type or in combination of 2 or more types. “Alkyl (meth) acrylate” refers to alkyl acrylate and / or alkyl methacrylate.
炭素数1〜24のアルキル基をエステル末端に有するアルキル(メタ)アクリレートは、(メタ)アクリル系ポリマーを形成する単官能性モノマー成分の全量に対して40重量%以上であることが好ましく、50重量%以上がより好ましく、60重量%以上がさらに好ましい。 The alkyl (meth) acrylate having an alkyl group having 1 to 24 carbon atoms at the ester terminal is preferably 40% by weight or more based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer, More preferably, it is more than 60% by weight.
上記モノマー成分には、単官能性モノマー成分として、アルキル(メタ)アクリレート以外の共重合モノマーが含まれ得る。共重合モノマーは、モノマー成分におけるアルキル(メタ)アクリレートの残部として用いることができる。共重合モノマーとしては、例えば、環状窒素含有モノマーを含み得る。上記環状窒素含有モノマーとしては、(メタ)アクリロイル基又はビニル基等の不飽和二重結合を有する重合性の官能基を有し、かつ環状窒素構造を有するものを特に制限なく用いることができる。環状窒素構造は、環状構造内に窒素原子を有するものが好ましい。環状窒素含有モノマーの含有量は、(メタ)アクリル系ポリマーを形成する単官能性モノマー成分の全量に対して、好ましくは0.5〜50重量%であり、より好ましくは0.5〜40重量%であり、さらにより好ましくは0.5〜30重量%である。 The monomer component may contain a copolymerization monomer other than alkyl (meth) acrylate as a monofunctional monomer component. A copolymerization monomer can be used as the remainder of the alkyl (meth) acrylate in a monomer component. As the copolymerization monomer, for example, a cyclic nitrogen-containing monomer may be included. As said cyclic nitrogen containing monomer, what has a polymerizable functional group which has unsaturated double bonds, such as a (meth) acryloyl group or a vinyl group, and has a cyclic nitrogen structure can be especially used without a restriction | limiting. The cyclic nitrogen structure preferably has a nitrogen atom in the cyclic structure. The content of the cyclic nitrogen-containing monomer is preferably 0.5 to 50% by weight, more preferably 0.5 to 40% by weight based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer. %, Even more preferably 0.5 to 30% by weight.
(メタ)アクリル系ポリマーを形成するモノマー成分には、その他の官能基含有モノマーが含まれ得る。このようなモノマーとして、例えば、カルボキシル基含有モノマー、環状エーテル基を有するモノマーが挙げられる。カルボキシル基含有モノマーを含有する場合、含有量は、好ましくは0.05〜10重量%であり、より好ましくは0.1〜8重量%であり、さらに好ましくは0.2〜6重量%である。カルボキシル基含有モノマーを含むことにより、粘着剤層のゲル分率を好ましい範囲内の値とすることができ、その結果、位相差層におけるクラックの発生を抑制することができる。 The monomer component that forms the (meth) acrylic polymer may include other functional group-containing monomers. Examples of such a monomer include a carboxyl group-containing monomer and a monomer having a cyclic ether group. When the carboxyl group-containing monomer is contained, the content is preferably 0.05 to 10% by weight, more preferably 0.1 to 8% by weight, and further preferably 0.2 to 6% by weight. . By including a carboxyl group-containing monomer, the gel fraction of the pressure-sensitive adhesive layer can be set to a value within a preferable range, and as a result, generation of cracks in the retardation layer can be suppressed.
また、上記モノマー成分には、ヒドロキシル基含有モノマーが含まれ得る。ヒドロキシル基含有モノマーとしては、(メタ)アクリロイル基又はビニル基等の不飽和二重結合を有する重合性の官能基を有し、かつヒドロキシル基を有するものを特に制限なく用いることができる。上記ヒドロキシル基含有モノマーの含有量は、接着力、凝集力を高める点から、(メタ)アクリル系ポリマーを形成する単官能性モノマー成分の全量に対して、好ましくは0.08重量%以上であり、より好ましくは0.3重量%以上であり、さらに好ましくは1重量%以上である。一方、ヒドロキシル基含有モノマーの含有量の上限は、(メタ)アクリル系ポリマーを形成する単官能性モノマー成分の全量に対して、好ましくは30重量%であり、より好ましくは27重量%であり、さらに好ましくは25重量%である。ヒドロキシル基含有モノマーが多くなりすぎると、粘着剤層が固くなり、接着力が低下する場合があり、また、粘着剤の粘度が高くなりすぎる場合がある。 The monomer component may include a hydroxyl group-containing monomer. As the hydroxyl group-containing monomer, a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a hydroxyl group can be used without particular limitation. The content of the hydroxyl group-containing monomer is preferably 0.08% by weight or more based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer, from the viewpoint of enhancing the adhesive force and cohesive force. More preferably, it is 0.3% by weight or more, and further preferably 1% by weight or more. On the other hand, the upper limit of the content of the hydroxyl group-containing monomer is preferably 30% by weight, more preferably 27% by weight, based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer, More preferably, it is 25% by weight. If the amount of the hydroxyl group-containing monomer is too large, the pressure-sensitive adhesive layer becomes hard, the adhesive force may be reduced, and the viscosity of the pressure-sensitive adhesive may become too high.
(メタ)アクリル系ポリマーを形成するモノマー成分には、上述の単官能性モノマーの他に、粘着剤の凝集力を調整するために、必要に応じて、任意の適切な多官能性モノマーを含有することができる。 In addition to the above-mentioned monofunctional monomer, the monomer component that forms the (meth) acrylic polymer contains any appropriate multifunctional monomer as necessary to adjust the cohesive strength of the pressure-sensitive adhesive. can do.
(メタ)アクリル系ポリマーは、通常、重量平均分子量が50万〜300万の範囲のものが用いられる。耐久性、特に耐熱性を考慮すれば、重量平均分子量は70万〜270万であるものを用いることが好ましい。さらには80万〜250万であることが好ましい。重量平均分子量が50万よりも小さいと、耐熱性の点で好ましくない。また、重量平均分子量が300万よりも大きくなると、塗工に適した粘度に調整するために多量の希釈溶剤が必要となり、コストアップとなることから好ましくない。なお、重量平均分子量は、GPC(ゲル・パーミエーション・クロマトグラフィー)により測定し、ポリスチレン換算により算出された値をいう。 As the (meth) acrylic polymer, those having a weight average molecular weight in the range of 500,000 to 3,000,000 are usually used. In view of durability, particularly heat resistance, it is preferable to use those having a weight average molecular weight of 700,000 to 2,700,000. Furthermore, it is preferable that it is 800,000-2.5 million. A weight average molecular weight of less than 500,000 is not preferable in terms of heat resistance. On the other hand, if the weight average molecular weight is more than 3 million, a large amount of a diluting solvent is required to adjust the viscosity to be suitable for coating, which is not preferable. The weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.
(メタ)アクリル系ポリマーの製造方法として、溶液重合、紫外線(UV)重合等の放射線重合、塊状重合、乳化重合等の各種ラジカル重合等の任意の適切な方法を採用することができる。また、得られる(メタ)アクリル系ポリマーは、ランダム共重合体、ブロック共重合体、グラフト共重合体等のいずれでもよい。 As a method for producing the (meth) acrylic polymer, any appropriate method such as radiation polymerization such as solution polymerization and ultraviolet (UV) polymerization, various radical polymerizations such as bulk polymerization and emulsion polymerization can be employed. Further, the (meth) acrylic polymer obtained may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.
(メタ)アクリル系ポリマーをラジカル重合により製造する場合には、モノマー成分に、ラジカル重合に用いられる重合開始剤、連鎖移動剤、乳化剤等を適宜添加して、重合を行うことができる。ラジカル重合に用いられる重合開始剤、連鎖移動剤、乳化剤等は特に限定されず適宜選択して使用することができる。なお、(メタ)アクリル系ポリマーの重量平均分子量は、重合開始剤、連鎖移動剤の使用量、反応条件により制御可能であり、これらの種類に応じて適宜その使用量が調整される。 When a (meth) acrylic polymer is produced by radical polymerization, polymerization can be carried out by appropriately adding a polymerization initiator, a chain transfer agent, an emulsifier and the like used for radical polymerization to the monomer component. The polymerization initiator, chain transfer agent, emulsifier and the like used for radical polymerization are not particularly limited and can be appropriately selected and used. In addition, the weight average molecular weight of a (meth) acrylic-type polymer can be controlled by the usage-amount of a polymerization initiator and a chain transfer agent, and reaction conditions, and the usage-amount is suitably adjusted according to these kinds.
(メタ)アクリル系ポリマーを放射線重合により製造する場合には、モノマー成分に、電子線、紫外線(UV)等の放射線を照射することにより重合して製造することができる。これらの中でも、紫外線重合が好ましい。紫外線重合を行う際には、重合時間を短くすることができる利点等から、モノマー成分に光重合開始剤を含有させることが好ましい。 When the (meth) acrylic polymer is produced by radiation polymerization, it can be produced by polymerizing the monomer component by irradiating the monomer component with radiation such as an electron beam or ultraviolet rays (UV). Among these, ultraviolet polymerization is preferable. When performing the ultraviolet polymerization, it is preferable to contain a photopolymerization initiator in the monomer component because of the advantage that the polymerization time can be shortened.
光重合開始剤としては、特に限定されないが、波長400nm以上に吸収帯を有する光重合開始剤であることが好ましい。このような光重合開始剤としては、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(BASF社製、製品名「Irgacure819」)、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(BASF社製、「LUCIRIN TPO」)等を挙げることができる。 Although it does not specifically limit as a photoinitiator, It is preferable that it is a photoinitiator which has an absorption band in wavelength 400nm or more. As such a photopolymerization initiator, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF, product name “Irgacure 819”), 2,4,6-trimethylbenzoyl-diphenyl-phos Examples include fin oxide (manufactured by BASF, “LUCIRIN TPO”).
光重合開始剤には、波長400nm未満に吸収帯を有する光重合開始剤を含有することができる。このような光重合開始剤としては、紫外線によりラジカルを発生し、光重合を開始するものであって、波長400nm未満に吸収帯を有するものであれば特に制限されず、通常用いられる光重合開始剤をいずれも好適に用いることができる。例えば、ベンゾインエーテル系光重合開始剤、アセトフェノン系光重合開始剤、α−ケトール系光重合開始剤、光活性オキシム系光重合開始剤、ベンゾイン系光重合開始剤、ベンジル系光重合開始剤、ベンゾフェノン系光重合開始剤、ケタール系光重合開始剤、チオキサントン系光重合開始剤、アシルフォスフィンオキサイド系光重合開始剤等を用いることができる。 The photopolymerization initiator can contain a photopolymerization initiator having an absorption band at a wavelength of less than 400 nm. Such a photopolymerization initiator is not particularly limited as long as it generates radicals by ultraviolet rays and initiates photopolymerization and has an absorption band at a wavelength of less than 400 nm. Any agent can be suitably used. For example, benzoin ether photopolymerization initiator, acetophenone photopolymerization initiator, α-ketol photopolymerization initiator, photoactive oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone A photopolymerization initiator, a ketal photopolymerization initiator, a thioxanthone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, or the like can be used.
D−2.イソシアネート架橋剤
粘着剤において、ベースポリマー100重量部に対するイソシアネート架橋剤の含有量は、好ましくは0.1重量部〜12重量部である。ベースポリマー100重量部に対するイソシアネート架橋剤の含有量の下限は、好ましくは0.5重量部であり、さらに好ましくは1重量部であり、特に好ましくは2重量部である。これにより、高温環境下での位相差層におけるクラックの発生を効果的に抑制することができる。また、ベースポリマー100重量部に対するイソシアネート架橋剤の含有量の上限は、好ましくは8重量部であり、より好ましくは5重量部である。これにより、粘着剤層の白濁化を抑制することができる。
D-2. Isocyanate crosslinking agent In the pressure-sensitive adhesive, the content of the isocyanate crosslinking agent with respect to 100 parts by weight of the base polymer is preferably 0.1 to 12 parts by weight. The lower limit of the content of the isocyanate crosslinking agent with respect to 100 parts by weight of the base polymer is preferably 0.5 parts by weight, more preferably 1 part by weight, and particularly preferably 2 parts by weight. Thereby, generation | occurrence | production of the crack in a phase difference layer in a high temperature environment can be suppressed effectively. Moreover, the upper limit of the content of the isocyanate crosslinking agent with respect to 100 parts by weight of the base polymer is preferably 8 parts by weight, more preferably 5 parts by weight. Thereby, the cloudiness of an adhesive layer can be suppressed.
イソシアネート架橋剤は、イソシアネート基(イソシアネート基をブロック剤または数量体化等により一時的に保護したイソシアネート再生型官能基を含む)を1分子中に2つ以上有する化合物をいう。イソシアネート架橋剤としては、トリレンジイソシアネート、キシレンジイソシアネート等の芳香族イソシアネート、イソホロンジイソシアネート等の脂環族イソシアネート、ヘキサメチレンジイソシアネート等の脂肪族イソシアネート等が挙げられる。好ましくは、トリレンジイソシアネートである。粘着剤層のゲル分率を高めることができるからである。 An isocyanate cross-linking agent refers to a compound having two or more isocyanate groups (including isocyanate-regenerating functional groups in which isocyanate groups are temporarily protected by blocking agents or quantification) in one molecule. Examples of the isocyanate crosslinking agent include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate. Tolylene diisocyanate is preferable. This is because the gel fraction of the pressure-sensitive adhesive layer can be increased.
より具体的には、例えば、ブチレンジイソシアネート、ヘキサメチレンジイソシアネート等の低級脂肪族ポリイソシアネート類、シクロペンチレンジイソシアネート、シクロヘキシレンジイソシアネート、イソホロンジイソシアネート等の脂環族イソシアネート類、2,4−トリレンジイソシアネート、4,4’−ジフェニルメタンジイソシアネート、キシレンジイソシアネート、ポリメチレンポリフェニルイソシアネート等の芳香族ジイソシアネート類、トリメチロールプロパン/トリレンジイソシアネート3量体付加物(日本ポリウレタン工業株式会社製、製品名「コロネートL」)、トリメチロールプロパン/ヘキサメチレンジイソシアネート3量体付加物(日本ポリウレタン工業株式会社製、製品名「コロネートHL」)、ヘキサメチレンジイソシアネートのイソシアヌレート体(日本ポリウレタン工業株式会社製、製品名「コロネートHX」)等のイソシアネート付加物、キシレンジイソシアネートのトリメチロールプロパン付加物(三井化学株式会社製、製品名「D110N」)、ヘキサメチレンジイソシアネートのトリメチロールプロパン付加物(三井化学株式会社製、製品名「D160N」);ポリエーテルポリイソシアネート、ポリエステルポリイソシアネート、ならびにこれらと各種のポリオールとの付加物、イソシアヌレート結合、ビューレット結合、アロファネート結合等で多官能化したポリイソシアネート等が挙げられる。 More specifically, for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, 2,4-tolylene diisocyanate, Aromatic diisocyanates such as 4,4′-diphenylmethane diisocyanate, xylene diisocyanate, polymethylene polyphenyl isocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (product name “Coronate L” manufactured by Nippon Polyurethane Industry Co., Ltd.) , Trimethylolpropane / hexamethylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., product name “Coronate HL”), hexame Isocyanurate of diisocyanate (product name “Coronate HX” manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane adduct of xylene diisocyanate (product name “D110N” manufactured by Mitsui Chemicals), hexa Trimethylolpropane adduct of methylene diisocyanate (product name “D160N” manufactured by Mitsui Chemicals, Inc.); polyether polyisocyanate, polyester polyisocyanate, and adducts of these with various polyols, isocyanurate bond, burette bond, Polyisocyanate polyfunctionalized by allophanate bond etc. is mentioned.
D−3.紫外線吸収剤
紫外線吸収剤としては、任意の適切な紫外線吸収剤を用いることができる。紫外線吸収剤は、好ましくは、分子構造中に水酸基を0個〜3個有する。具体的には、トリアジン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、オキシベンゾフェノン系紫外線吸収剤、サリチル酸エステル系紫外線吸収剤、シアノアクリレート系紫外線吸収剤等を挙げることができ、これらを1種単独で又は2種以上を組み合わせて用いることができる。これらの中でも、トリアジン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤が好ましく、1分子中にヒドロキシル基を2個以下有するトリアジン系紫外線吸収剤、及び、1分子中にベンゾトリアゾール骨格を1個有するベンゾトリアゾール系紫外線吸収剤からなる群から選択される少なくとも1種の紫外線吸収剤であることが、アクリル系粘着剤組成物の形成に用いられるモノマーへの溶解性が良好であり、かつ、波長380nm付近での紫外線吸収能力が高いため好ましい。紫外線吸収剤は、単独で使用してもよく、また2種以上を混合して使用してもよい。
D-3. Ultraviolet absorber Any appropriate ultraviolet absorber can be used as the ultraviolet absorber. The ultraviolet absorber preferably has 0 to 3 hydroxyl groups in the molecular structure. Specific examples include triazine UV absorbers, benzotriazole UV absorbers, benzophenone UV absorbers, oxybenzophenone UV absorbers, salicylic acid ester UV absorbers, and cyanoacrylate UV absorbers. These can be used singly or in combination of two or more. Among these, triazine-based UV absorbers and benzotriazole-based UV absorbers are preferable, triazine-based UV absorbers having 2 or less hydroxyl groups in one molecule, and benzones having one benzotriazole skeleton in one molecule. It is at least one ultraviolet absorber selected from the group consisting of triazole-based ultraviolet absorbers, has good solubility in monomers used for forming an acrylic pressure-sensitive adhesive composition, and has a wavelength of around 380 nm This is preferable because of its high ultraviolet absorption ability. An ultraviolet absorber may be used independently and may mix and use 2 or more types.
紫外線吸収剤の含有量は、ベースポリマー100重量部に対して、好ましくは0.1〜20重量部であり、より好ましくは0.1〜10重量部であり、さらに好ましくは0.1〜5重量部であり、特に好ましくは0.5〜3重量部である。 The content of the ultraviolet absorber is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and further preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the base polymer. Parts by weight, particularly preferably 0.5 to 3 parts by weight.
紫外線吸収剤の吸収スペクトルの最大吸収波長は、好ましくは300nm〜400nmの波長領域に存在し、より好ましくは320nm〜380nmの波長領域に存在する。最大吸収波長は、紫外可視分光光度計を用いて測定することができる。 The maximum absorption wavelength of the absorption spectrum of the ultraviolet absorber is preferably in the wavelength region of 300 nm to 400 nm, more preferably in the wavelength region of 320 nm to 380 nm. The maximum absorption wavelength can be measured using an ultraviolet-visible spectrophotometer.
紫外線吸収剤物としては、市販されているものを好適に用いることができ、Tinosorb S(BASF社製)、SeeSorb106(シプロ化成株式会社製)等が挙げられる。 As the ultraviolet absorbent product, commercially available products can be suitably used, and examples thereof include Tinosorb S (manufactured by BASF) and Seesorb 106 (manufactured by Sipro Kasei Co., Ltd.).
D−4.色素化合物
色素化合物は、上記のとおり、吸収スペクトルの最大吸収波長が380nm〜430nmの波長領域に存在する。色素化合物の吸収スペクトルの最大吸収波長は、好ましくは380nm〜420nmの波長領域に存在する。このような色素化合物と紫外線吸収剤とを組み合わせて用いることで、有機EL素子の発光に影響しない領域(波長380nm〜430nm)の光を十分に吸収することができ、かつ、有機EL素子の発光領域(430nmよりも長波長側)は十分に透過することができる。
D-4. As mentioned above, the dye compound is present in the wavelength region of the absorption spectrum having a maximum absorption wavelength of 380 nm to 430 nm. The maximum absorption wavelength of the absorption spectrum of the dye compound is preferably in the wavelength region of 380 nm to 420 nm. By using a combination of such a dye compound and an ultraviolet absorber, light in a region (wavelength 380 nm to 430 nm) that does not affect the light emission of the organic EL element can be sufficiently absorbed, and the light emission of the organic EL element. The region (longer wavelength side than 430 nm) can be sufficiently transmitted.
色素化合物の半値幅は、好ましくは80nm以下であり、より好ましくは5nm〜70nmであり、さらに好ましくは10nm〜60nmである。これにより、有機EL素子の発光に影響しない領域の光を十分に吸収しつつ、430nmよりも長波長側の光は十分に透過させることができる。色素化合物の半値幅は、紫外可視分光光度計(株式会社日立ハイテクサイエンス製、製品名「U−4100」)を使用し、以下の測定条件で色素化合物の溶液の透過吸光スペクトルから測定することができる。代表的には、最大吸収波長の吸光度が1.0となるよう濃度を調整して測定した分光スペクトルから、ピーク値の50%になる2点間の波長の間隔(半値全幅)をその色素化合物の半値幅とする。
(測定条件)
溶媒:トルエン又はクロロホルム
セル:石英セル
光路長:10mm
The full width at half maximum of the dye compound is preferably 80 nm or less, more preferably 5 nm to 70 nm, and still more preferably 10 nm to 60 nm. Thereby, the light of the long wavelength side more than 430 nm can fully be permeate | transmitted, fully absorbing the light of the area | region which does not influence the light emission of an organic EL element. The full width at half maximum of the dye compound can be measured from the transmission absorption spectrum of the solution of the dye compound under the following measurement conditions using an ultraviolet-visible spectrophotometer (manufactured by Hitachi High-Tech Science Co., Ltd., product name “U-4100”). it can. Typically, from the spectrum measured by adjusting the concentration so that the absorbance at the maximum absorption wavelength is 1.0, the wavelength interval (full width at half maximum) between two points at 50% of the peak value is expressed as the dye compound. The full width at half maximum.
(Measurement condition)
Solvent: Toluene or chloroform Cell: Quartz cell Optical path length: 10 mm
色素化合物としては、吸収スペクトルの最大吸収波長が上記波長領域に存在する化合物であればよく、その構造等は特に限定されるものではない。色素化合物としては、例えば、有機系色素化合物や無機系色素化合物を挙げることができるが、これらの中でも、ベースポリマー等の樹脂成分への分散性と透明性の維持の観点から、有機系色素化合物が好ましい。 The dye compound is not particularly limited as long as it is a compound having a maximum absorption wavelength in the absorption spectrum in the above wavelength region. Examples of the dye compound include an organic dye compound and an inorganic dye compound. Among these, from the viewpoint of maintaining dispersibility and transparency in a resin component such as a base polymer, the organic dye compound is used. Is preferred.
有機系色素化合物としては、アゾメチン系化合物、インドール系化合物、けい皮酸系化合物、ピリミジン系化合物、ポルフィリン系化合物、ポリメチン化合物等を挙げることができる。 Examples of organic dye compounds include azomethine compounds, indole compounds, cinnamic acid compounds, pyrimidine compounds, porphyrin compounds, and polymethine compounds.
有機色素化合物としては、市販されているものを好適に用いることができ、具体的には、インドール系化合物としては、BONASORB UA3911(オリエント化学工業株式会社製、吸収スペクトルの最大吸収波長:398nm、半値幅:48nm)、BONASORB UA3912(オリエント化学工業株式会社製、吸収スペクトルの最大吸収波長:386nm、半値幅:53nm)、けい皮酸系化合物としては、SOM−5−0106(オリエント化学工業株式会社製、吸収スペクトルの最大吸収波長:416nm、半値幅:50nm)、ピリミジン系化合物としては、FDB−009(山田化学工業株式会社製、吸収スペクトルの最大吸収波長:394nm、半値幅:43nm)、ポルフィリン系化合物としては、FDB−001(山田化学工業株式会社製、吸収スペクトルの最大吸収波長:420nm、半値幅:14nm)、ポリメチン化合物としては、DAA247(山田化学工業株式会社製、吸収スペクトルの最大吸収波長:389nm、半値幅:49.5nm)等が挙げられる。 What is marketed can be used suitably as an organic pigment | dye compound, Specifically, as an indole-type compound, BONASORB UA3911 (Orient Chemical Industries Ltd. make, absorption spectrum maximum absorption wavelength: 398nm, half Value range: 48 nm), BONASORB UA3912 (manufactured by Orient Chemical Industry Co., Ltd., maximum absorption wavelength of absorption spectrum: 386 nm, half-value width: 53 nm), and cinnamic acid compounds as SOM-5-0106 (manufactured by Orient Chemical Industry Co., Ltd.) Absorption spectrum maximum absorption wavelength: 416 nm, half-value width: 50 nm), as pyrimidine compounds, FDB-009 (manufactured by Yamada Chemical Co., Ltd., absorption spectrum maximum absorption wavelength: 394 nm, half-value width: 43 nm), porphyrin series As a compound, FDB-00 1 (manufactured by Yamada Chemical Co., Ltd., absorption spectrum maximum absorption wavelength: 420 nm, half width: 14 nm), as a polymethine compound, DAA247 (manufactured by Yamada Chemical Industry Co., Ltd., absorption spectrum maximum absorption wavelength: 389 nm, half width: 49.5 nm).
D−5.その他の成分
粘着剤組成物は、必要に応じて、シランカップリング剤、酸化防止剤、老化防止剤、可塑剤などの他の成分を含み得る。酸化防止剤としては、例えば、フェノール系、リン系、イオウ系、アミン系の酸化防止剤が挙げられる。シランカップリング剤としては、例えば、3−グリシドキシプロピルトリメトキシシラン等のエポキシ基含有シランカップリング剤、3−アミノプロピルトリメトキシシラン等のアミノ基含有シランカップリング剤、3−アクリロキシプロピルトリメトキシシラン等の(メタ)アクリル基含有シランカップリング剤、3−イソシアネートプロピルトリエトキシシラン等のイソシアネート基含有シランカップリング剤、アセトアセチル基含有シランカップリング剤が挙げられる。
D-5. Other Components The pressure-sensitive adhesive composition may contain other components such as a silane coupling agent, an antioxidant, an anti-aging agent, and a plasticizer as necessary. Examples of the antioxidant include phenol-based, phosphorus-based, sulfur-based, and amine-based antioxidants. Examples of the silane coupling agent include epoxy group-containing silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, amino group-containing silane coupling agents such as 3-aminopropyltrimethoxysilane, and 3-acryloxypropyl. (Meth) acrylic group-containing silane coupling agents such as trimethoxysilane, isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane, and acetoacetyl group-containing silane coupling agents.
E.有機EL表示装置
上記AからD項に記載の位相差層付き偏光板は、画像表示装置に用いられ得る。したがって、本発明は、そのような光学積層体を用いた画像表示装置も包含する。画像表示装置の代表例としては、液晶表示装置、有機エレクトロルミネセンス(EL)表示装置が挙げられる。本発明の実施形態による画像表示装置(有機EL表示装置)は、上記A項からD項に記載の光学積層体を備える。
E. Organic EL Display Device The polarizing plate with a retardation layer described in the above items A to D can be used in an image display device. Therefore, the present invention also includes an image display device using such an optical laminate. Typical examples of the image display device include a liquid crystal display device and an organic electroluminescence (EL) display device. An image display device (organic EL display device) according to an embodiment of the present invention includes the optical layered body described in the items A to D.
以下、実施例によって本発明を具体的に説明するが、本発明はこれら実施例によって限定されるものではない。なお、各特性の測定方法は以下の通りである。
(1)厚み
位相差層の厚みを、干渉膜厚計(大塚電子株式会社製、MCPD2000)を用いて測定した。また、位相差層以外の層の厚みを、デジタルマイクロメーター(アンリツ株式会社製、KC−351C)を用いて測定した。
(2)位相差値
位相差層の屈折率nx、nyおよびnzを、自動複屈折測定装置(王子計測機器株式会社製,自動複屈折計KOBRA−WPR)により計測し、面内位相差Reおよび厚み方向位相差Rthを算出した。
(3)粘着剤層の透過率
実施例及び比較例で得られた各粘着剤層のセパレータを剥離して、粘着剤層を測定用治具に取り付け、分光光度計(株式会社日立ハイテクノロジーズ製、製品名「U4100」)で測定した。透過率は、波長300nm〜450nmの範囲における透過率を測定した。
(4)粘着剤層のゲル分率
実施例及び比較例で得られた各粘着剤層(粘着剤組成物)を0.2gとり、あらかじめ重量を測定したフッ素樹脂(日東電工株式会社製、製品名「TEMISH NTF−1122」、重量:Wa)に包み、粘着剤が漏れないように縛った後、重量(Wb)を測定し、サンプル瓶にいれた。酢酸エチルを40cc加えて7日間放置した。その後、フッ素樹脂を取り出し、アルミカップ上で130℃、2時間乾燥させ、サンプルを含むフッ素樹脂の重量(Wc)を測定し、次式(I)によりゲル分率を求めた。
式(I):ゲル分率=(Wc−Wa)/(Wb−Wa)×100(重量%)
ゲル分率の測定は、粘着剤層を形成した後、室温(23℃)で1週間放置した後に行った。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these Examples. In addition, the measuring method of each characteristic is as follows.
(1) Thickness The thickness of the retardation layer was measured using an interference film thickness meter (MCPD2000, manufactured by Otsuka Electronics Co., Ltd.). Moreover, the thickness of layers other than a phase difference layer was measured using the digital micrometer (The Anritsu Co., Ltd. make, KC-351C).
(2) Retardation value Refractive indexes nx, ny and nz of the retardation layer are measured by an automatic birefringence measuring device (manufactured by Oji Scientific Instruments, automatic birefringence meter KOBRA-WPR), and in-plane retardation Re and The thickness direction retardation Rth was calculated.
(3) Transmittance of pressure-sensitive adhesive layer The separator of each pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was peeled off, and the pressure-sensitive adhesive layer was attached to a measuring jig, and a spectrophotometer (manufactured by Hitachi High-Technologies Corporation) , Product name “U4100”). As for the transmittance, the transmittance in a wavelength range of 300 nm to 450 nm was measured.
(4) Gel fraction of the pressure-sensitive adhesive layer 0.2 g of each pressure-sensitive adhesive layer (pressure-sensitive adhesive composition) obtained in Examples and Comparative Examples, and the weight of the fluororesin (manufactured by Nitto Denko Corporation, product) After wrapping in the name “TEMISH NTF-1122”, weight: Wa) and binding the adhesive so that it does not leak, the weight (Wb) was measured and placed in a sample bottle. 40 cc of ethyl acetate was added and left for 7 days. Thereafter, the fluororesin was taken out, dried on an aluminum cup at 130 ° C. for 2 hours, the weight (Wc) of the fluororesin including the sample was measured, and the gel fraction was determined by the following formula (I).
Formula (I): Gel fraction = (Wc−Wa) / (Wb−Wa) × 100 (% by weight)
The gel fraction was measured after the pressure-sensitive adhesive layer was formed and left at room temperature (23 ° C.) for 1 week.
<製造例1>
(偏光板の作製)
厚み30μmのポリビニルアルコールフィルム(クラレ製 製品名「PE3000」)の長尺ロールを、ロール延伸機により長尺方向に5.9倍になるように長尺方向に一軸延伸しながら同時に膨潤、染色、架橋、洗浄処理を施し、最後に乾燥処理を施すことにより厚み12μmの偏光子を作製した。
具体的には、膨潤処理は20℃の純水で処理しながら2.2倍に延伸した。次いで、染色処理は作製される偏光膜の透過率が45.0%になるようにヨウ素濃度が調整されたヨウ素とヨウ化カリウムの重量比が1:7である30℃の水溶液中において処理しながら1.4倍に延伸した。更に、架橋処理は、2段階の架橋処理を採用し、1段階目の架橋処理は40℃のホウ酸とヨウ化カリウムを溶解した水溶液において処理しながら1.2倍に延伸した。1段階目の架橋処理の水溶液のホウ酸含有量は5.0重量%で、ヨウ化カリウム含有量は3.0重量%とした。2段階目の架橋処理は65℃のホウ酸とヨウ化カリウムとを溶解した水溶液において処理しながら1.6倍に延伸した。2段階目の架橋処理の水溶液のホウ酸含有量は4.3重量%で、ヨウ化カリウム含有量は5.0重量%とした。また、洗浄処理は、20℃のヨウ化カリウム水溶液で処理した。洗浄処理の水溶液のヨウ化カリウム含有量は2.6重量%とした。最後に、乾燥処理は70℃で5分間乾燥させて偏光子を得た。
得られた偏光子の両面に、それぞれ、ポリビニルアルコール系接着剤を介して、コニカミノルタ株式会社製のTACフィルム(製品名:KC2UA 厚み:25μm)及び当該TACフィルムの片面にHC層を有するHC−TACフィルム(厚み:32μm)を貼り合せて偏光子の両面に保護フィルムが貼り合わされた偏光板1を得た。
<Production Example 1>
(Preparation of polarizing plate)
A long roll of polyvinyl alcohol film (product name “PE3000” manufactured by Kuraray Co., Ltd.) having a thickness of 30 μm is simultaneously swollen and dyed while being uniaxially stretched in the longitudinal direction so as to be 5.9 times in the longitudinal direction by a roll stretching machine. A cross-linking and cleaning treatment was performed, and finally a drying treatment was performed to produce a polarizer having a thickness of 12 μm.
Specifically, the swelling treatment was stretched 2.2 times while being treated with pure water at 20 ° C. Next, the dyeing treatment is performed in an aqueous solution at 30 ° C. in which the weight ratio of iodine and potassium iodide is 1: 7 and the iodine concentration is adjusted so that the transmittance of the produced polarizing film is 45.0%. The film was stretched 1.4 times. Furthermore, the crosslinking treatment employed a two-stage crosslinking treatment, and the first-stage crosslinking treatment was stretched 1.2 times while being treated in an aqueous solution in which boric acid and potassium iodide were dissolved at 40 ° C. The boric acid content of the aqueous solution of the first-stage crosslinking treatment was 5.0% by weight, and the potassium iodide content was 3.0% by weight. In the second-stage crosslinking treatment, the film was stretched 1.6 times while being treated in an aqueous solution in which boric acid and potassium iodide were dissolved at 65 ° C. The boric acid content of the aqueous solution of the second crosslinking treatment was 4.3% by weight, and the potassium iodide content was 5.0% by weight. In addition, the cleaning treatment was performed with an aqueous potassium iodide solution at 20 ° C. The potassium iodide content of the aqueous solution for the washing treatment was 2.6% by weight. Finally, the drying process was performed at 70 ° C. for 5 minutes to obtain a polarizer.
A TAC film (product name: KC2UA thickness: 25 μm) manufactured by Konica Minolta Co., Ltd. and an HC layer on one side of the TAC film on both sides of the obtained polarizer via a polyvinyl alcohol adhesive, respectively. A TAC film (thickness: 32 μm) was bonded to obtain polarizing plate 1 having protective films bonded to both sides of the polarizer.
<製造例2>
(位相差層Aの作製)
ネマチック液晶相を示す重合性液晶(BASF社製、製品名「PaliocolorLC242」、下記式で表される)10gと、当該重合性液晶化合物に対する光重合開始剤(チバスペシャリティーケミカルズ社製、製品名「イルガキュア907」)3gとを、トルエン40gに溶解して、液晶組成物(塗工液)を調製した。
(Preparation of retardation layer A)
10 g of a polymerizable liquid crystal exhibiting a nematic liquid crystal phase (manufactured by BASF, product name “Paliocolor LC242”, represented by the following formula) and a photopolymerization initiator (product name “Ciba Specialty Chemicals, product name”) 3 g of Irgacure 907 ") was dissolved in 40 g of toluene to prepare a liquid crystal composition (coating solution).
配向処理の方向は、偏光板と貼り付ける際に偏光子の吸収軸の方向に対して視認側から見て−75°方向となるようにした。この配向処理表面に、上記塗工液をバーコーターにより塗工し、90℃で2分間加熱乾燥することによって液晶化合物を配向させた。条件(a)〜(c)では液晶化合物の配向状態が非常に良好であった。条件(d)および(e)では液晶化合物の配向に若干の乱れが生じたが、実用上は問題のないレベルであった。このようにして形成された液晶層に、メタルハライドランプを用いて1mJ/cm2の光を照射し、当該液晶層を硬化させることによって、PETフィルム上に位相差層Aを形成した。位相差層Aの厚みは2μm、面内位相差Reは270nmであった。さらに、位相差層Aは、nx>ny=nzの屈折率分布を有していた。 The direction of the orientation treatment was set to a −75 ° direction when viewed from the viewing side with respect to the direction of the absorption axis of the polarizer when being attached to the polarizing plate. The liquid coating compound was aligned by applying the coating liquid onto the alignment-treated surface with a bar coater and heating and drying at 90 ° C. for 2 minutes. Under the conditions (a) to (c), the alignment state of the liquid crystal compound was very good. Under the conditions (d) and (e), a slight disturbance occurred in the alignment of the liquid crystal compound, but the level was not problematic for practical use. The liquid crystal layer thus formed was irradiated with 1 mJ / cm 2 of light using a metal halide lamp to cure the liquid crystal layer, thereby forming a retardation layer A on the PET film. The thickness of the retardation layer A was 2 μm, and the in-plane retardation Re was 270 nm. Furthermore, the retardation layer A had a refractive index distribution of nx> ny = nz.
<製造例3>
(位相差層Bの作製)
ポリエチレンテレフタレート(PET)フィルム(厚み38μm)表面を、ラビング布を用いてラビングし、配向処理を施した。配向処理の方向は、偏光板と貼り付ける際に偏光子の吸収軸の方向に対して視認側から見て−15°方向となるようにした。この配向処理表面に、上記と同様の液晶塗工液を塗工し、上記と同様に液晶を配向および硬化させて、PETフィルム上に位相差層Bを形成した。位相差層Bの厚みは1.2μm、面内位相差Reは140nmであった。さらに、位相差層Bは、nx>ny=nzの屈折率分布を有していた。
<Production Example 3>
(Preparation of retardation layer B)
The surface of a polyethylene terephthalate (PET) film (thickness 38 μm) was rubbed with a rubbing cloth and subjected to orientation treatment. The direction of the orientation treatment was set to a −15 ° direction when viewed from the viewing side with respect to the direction of the absorption axis of the polarizer when pasted to the polarizing plate. A liquid crystal coating liquid similar to that described above was applied to the surface subjected to the alignment treatment, and the liquid crystal was aligned and cured in the same manner as described above to form a retardation layer B on the PET film. The thickness of the retardation layer B was 1.2 μm, and the in-plane retardation Re was 140 nm. Further, the retardation layer B had a refractive index distribution of nx> ny = nz.
[実施例1]
1.粘着剤層の作製
<(メタ)アクリル系ポリマー(1)の調製>
冷却管、窒素導入管、温度計及び撹拌装置を備えた反応容器に、アクリル酸ブチル99部、アクリル酸4−ヒドロキシブチル1.0部および2,2´−アゾビスイソブチロニトリル0.3部を酢酸エチルと共に加えて窒素ガス気流下、60℃で4時間反応させた後、その反応液に酢酸エチルを加えて、重量平均分子量160万のアクリル系ポリマーを含有する溶液(固形分濃度30%)を得た。
<粘着剤組成物の調製>
上記アクリル系ポリマーをベースポリマーとして、アクリル系ポリマー溶液の固形分100部あたり0.3部のベンゾイルパーオキシド(日本油脂株式会社製、製品名「ナイパーBMT」)と、0.1部のトリメチロールプロパンキシレンジイソシアネート(三井化学株式会社製、製品名「タケネートD110N」)と、0.2部のシランカップリング剤(綜研化学株式会社製、製品名「A−100」、アセトアセチル基含有シランカップリング剤)を配合して、粘着剤組成物A(溶液)を得た。
<粘着剤層の作製>
上記粘着剤組成物Aを、シリコーン系剥離剤で表面処理したポリエステルフィルムからなるセパレータに塗工し155℃で3分間加熱処理することにより、厚さ20μmの粘着剤層を得た。
2.位相差層付き偏光板の作製
上記の偏光板のTACフィルム面と位相差層Aとを、偏光板の吸収軸と位相差層Aの遅相軸の角度が75°となるように紫外線硬化型接着剤を介して貼り合わせた。次に、位相差層Aと位相差層Bとを、偏光板の吸収軸と位相差層Bの遅相軸の角度が15°となるように上記粘着剤層を介して貼り合わせることにより、位相差層付き偏光板を得た。
[Example 1]
1. Preparation of pressure-sensitive adhesive layer <Preparation of (meth) acrylic polymer (1)>
In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer and a stirrer, 99 parts of butyl acrylate, 1.0 part of 4-hydroxybutyl acrylate and 2,2′-azobisisobutyronitrile 0.3 After adding a part with ethyl acetate and making it react at 60 degreeC under nitrogen gas stream for 4 hours, ethyl acetate was added to the reaction liquid, and the solution (solid content concentration 30) containing a weight average molecular weight 1.6 million. %).
<Preparation of pressure-sensitive adhesive composition>
Based on the above acrylic polymer as a base polymer, 0.3 part of benzoyl peroxide (manufactured by NOF Corporation, product name “Nyper BMT”) and 100 parts of trimethylol per 100 parts of solid content of the acrylic polymer solution Propane xylene diisocyanate (Mitsui Chemicals, product name “Takenate D110N”) and 0.2 part silane coupling agent (Soken Chemicals, product name “A-100”, acetoacetyl group-containing silane coupling A pressure-sensitive adhesive composition A (solution) was obtained.
<Preparation of adhesive layer>
The pressure-sensitive adhesive composition A was applied to a separator made of a polyester film surface-treated with a silicone release agent and heat-treated at 155 ° C. for 3 minutes to obtain a pressure-sensitive adhesive layer having a thickness of 20 μm.
2. Preparation of Polarizing Plate with Retardation Layer The TAC film surface of the polarizing plate and the retardation layer A are UV curable so that the angle between the absorption axis of the polarizing plate and the slow axis of the retardation layer A is 75 °. It bonded together through the adhesive agent. Next, by laminating the retardation layer A and the retardation layer B through the pressure-sensitive adhesive layer so that the angle between the absorption axis of the polarizing plate and the slow axis of the retardation layer B is 15 °, A polarizing plate with a retardation layer was obtained.
[実施例2]
紫外線吸収剤として、2,4−ビス−[{4−(4−エチルヘキシルオキシ)−4−ヒドロキシ}−フェニル]−6−(4−メトキシフェニル)−1,3,5-トリアジン(BASFジャパン社製、製品名「Tinosorb S」、表1中の「a1」)を2重量部(固形分重量)添加したこと以外は実施例1と同様にして粘着剤組成物Bを得た。
上記粘着剤組成物Bを用いたこと以外は実施例1と同様にして、粘着剤層および位相差層付き偏光板を得た。
[Example 2]
As a UV absorber, 2,4-bis-[{4- (4-ethylhexyloxy) -4-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine (BASF Japan Ltd.) A pressure-sensitive adhesive composition B was obtained in the same manner as in Example 1 except that 2 parts by weight (solid content weight) of the product name “Tinosorb S” and “a1” in Table 1 were added.
Except having used the said adhesive composition B, it carried out similarly to Example 1, and obtained the polarizing plate with an adhesive layer and a phase difference layer.
[実施例3]
トリメチロールプロパンキシレンジイソシアネートの添加量を、アクリル系ポリマー溶液の固形分100部に対して0.5部としたこと以外は実施例2と同様にして粘着剤組成物Cを得た。
上記粘着剤組成物Cを用いたこと以外は実施例1と同様にして、粘着剤層および位相差層付き偏光板を得た。
[Example 3]
A pressure-sensitive adhesive composition C was obtained in the same manner as in Example 2, except that the amount of trimethylolpropane xylene diisocyanate added was 0.5 parts with respect to 100 parts of the solid content of the acrylic polymer solution.
Except having used the said adhesive composition C, it carried out similarly to Example 1, and obtained the adhesive layer and the polarizing plate with retardation layer.
[実施例4]
紫外線吸収剤として、紫外線吸収剤a1に代えて、2,2´,4,4´−テトラヒドロキシベンゾフェノン(シプロ化成株式会社製、製品名「SeeSorb106」、表1中の「a2」)を2重量部(固形分重量)添加したこと以外は実施例3と同様にして粘着剤組成物Dを得た。
上記粘着剤組成物Dを用いたこと以外は実施例1と同様にして、粘着剤層および位相差層付き偏光板を得た。
[Example 4]
2 weights of 2,2 ′, 4,4′-tetrahydroxybenzophenone (manufactured by Cypro Kasei Co., Ltd., product name “SeeSorb106”, “a2” in Table 1) is used as the ultraviolet absorber instead of the ultraviolet absorber a1. A pressure-sensitive adhesive composition D was obtained in the same manner as in Example 3 except that part (solid content weight) was added.
Except having used the said adhesive composition D, it carried out similarly to Example 1, and obtained the adhesive layer and the polarizing plate with retardation layer.
[実施例5]
紫外線吸収剤a1の添加量を3重量部としたこと、および、色素化合物としてピリミジン系化合物(山田化学工業株式会社製、製品名「FDB−009」、表1中の「b1」)を3重量部(固形分重量)添加したこと以外は実施例3と同様にして粘着剤組成物Eを得た。
上記粘着剤組成物Eを用いたこと以外は実施例1と同様にして、粘着剤層および位相差層付き偏光板を得た。
[Example 5]
The addition amount of the ultraviolet absorber a1 was 3 parts by weight, and a pyrimidine compound (manufactured by Yamada Chemical Co., Ltd., product name “FDB-009”, “b1” in Table 1) as a pigment compound was 3% by weight. A pressure-sensitive adhesive composition E was obtained in the same manner as in Example 3 except that part (solid weight) was added.
Except having used the said adhesive composition E, it carried out similarly to Example 1, and obtained the polarizing plate with an adhesive layer and a phase difference layer.
[実施例6]
紫外線吸収剤a2の添加量を3重量部としたこと、および、色素化合物としてインドール系化合物(オリエント化学工業株式会社製、製品名「BONASORB UA3912」、表1中の「b3」)を2重量部(固形分重量)添加したこと以外は実施例4と同様にして粘着剤組成物Fを得た。
上記粘着剤組成物Fを用いたこと以外は実施例1と同様にして、粘着剤層および位相差層付き偏光板を得た。
[Example 6]
The addition amount of the ultraviolet absorber a2 was 3 parts by weight, and 2 parts by weight of an indole compound (made by Orient Chemical Industry Co., Ltd., product name “BONASORB UA3912”, “b3” in Table 1) as a pigment compound) A pressure-sensitive adhesive composition F was obtained in the same manner as in Example 4 except that (solid content weight) was added.
Except having used the said adhesive composition F, it carried out similarly to Example 1, and obtained the polarizing plate with an adhesive layer and a phase difference layer.
[実施例7]
冷却管、窒素導入管、温度計及び撹拌装置を備えた反応容器に、アクリル酸ブチル95部、アクリル酸4.9部、アクリル酸2−ヒドロキシエチル0.1部、及びジベンゾイルパーオキシドをモノマー(固形分)100部に対して0.3部を酢酸エチルと共に加えて窒素ガス気流下、60℃で7時間反応させた後、その反応液に酢酸エチルを加えて、重量平均分子量220万のアクリル系ポリマーを含有する溶液(固形分濃度30重量%)を得た。
上記アクリル系ポリマーをベースポリマーとして、アクリル系ポリマー溶液の固形分100部あたり0.5部のトリメチロールプロパントリレンジイソシアネート(日本ポリウレタン株式会社製、製品名「コロネートL」)と、0.075部のγ−グリシドキシプロピルメトキシシラン(信越化学工業株式会社製、製品名「KBM−403」)と、3重量部の紫外線吸収剤a1とを配合して、粘着剤組成物Gを得た。
上記粘着剤組成物Gを用いたこと以外は実施例1と同様にして、粘着剤層および位相差層付き偏光板を得た。
[Example 7]
In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirring device, 95 parts of butyl acrylate, 4.9 parts of acrylic acid, 0.1 part of 2-hydroxyethyl acrylate, and dibenzoyl peroxide are monomers (Solid content) 0.3 parts per 100 parts was added with ethyl acetate and reacted at 60 ° C. for 7 hours under a nitrogen gas stream. Then, ethyl acetate was added to the reaction solution to give a weight average molecular weight of 2.2 million. A solution containing an acrylic polymer (solid content concentration: 30% by weight) was obtained.
Using the acrylic polymer as a base polymer, 0.5 part of trimethylolpropane tolylene diisocyanate (product name “Coronate L”, manufactured by Nippon Polyurethane Co., Ltd.) per 100 parts of solid content of the acrylic polymer solution, and 0.075 part Γ-glycidoxypropylmethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM-403”) and 3 parts by weight of an ultraviolet absorber a1 were blended to obtain an adhesive composition G.
Except having used the said adhesive composition G, it carried out similarly to Example 1, and obtained the polarizing plate with an adhesive layer and a phase difference layer.
[実施例8]
色素化合物b1を3重量部(固形分重量)添加したこと以外は実施例7と同様にして粘着剤組成物Hを得た。
上記粘着剤組成物Hを用いたこと以外は実施例1と同様にして、粘着剤層および位相差層付き偏光板を得た。
[Example 8]
A pressure-sensitive adhesive composition H was obtained in the same manner as in Example 7 except that 3 parts by weight (solid weight) of the dye compound b1 was added.
Except having used the said adhesive composition H, it carried out similarly to Example 1, and obtained the adhesive layer and the polarizing plate with retardation layer.
[実施例9]
色素化合物b3を3重量部(固形分重量)添加したこと以外は実施例7と同様にして粘着剤組成物Iを得た。
上記粘着剤組成物Iを用いたこと以外は実施例1と同様にして、粘着剤層および位相差層付き偏光板を得た。
[Example 9]
A pressure-sensitive adhesive composition I was obtained in the same manner as Example 7 except that 3 parts by weight (solid content weight) of the dye compound b3 was added.
Except having used the said adhesive composition I, it carried out similarly to Example 1, and obtained the adhesive layer and the polarizing plate with retardation layer.
[実施例10]
色素化合物として、ポリメチン化合物(山田化学工業株式会社製、製品名「DAA247」、表1中の「b2」)を3重量部(固形分重量)添加したこと以外は実施例7と同様にして粘着剤組成物Jを得た。
上記粘着剤組成物Jを用いたこと以外は実施例1と同様にして、粘着剤層および位相差層付き偏光板を得た。
[Example 10]
Adhesive in the same manner as in Example 7 except that 3 parts by weight (solid weight) of polymethine compound (manufactured by Yamada Chemical Co., Ltd., product name “DAA247”, “b2” in Table 1) was added as the dye compound. Agent composition J was obtained.
Except having used the said adhesive composition J, it carried out similarly to Example 1, and obtained the adhesive layer and the polarizing plate with retardation layer.
[実施例11]
トリメチロールプロパントリレンジイソシアネートの添加量を、アクリル系ポリマー溶液の固形分100部に対して0.8部としたこと以外は実施例10と同様にして粘着剤組成物Kを得た。
上記粘着剤組成物Kを用いたこと以外は実施例1と同様にして、粘着剤層および位相差層付き偏光板を得た。
[Example 11]
A pressure-sensitive adhesive composition K was obtained in the same manner as in Example 10 except that the amount of trimethylolpropane tolylene diisocyanate added was 0.8 parts relative to 100 parts of the solid content of the acrylic polymer solution.
Except having used the said adhesive composition K, it carried out similarly to Example 1, and obtained the adhesive layer and the polarizing plate with retardation layer.
[実施例12]
トリメチロールプロパントリレンジイソシアネートの添加量を、アクリル系ポリマー溶液の固形分100部に対して2.5部としたこと以外は実施例10と同様にして粘着剤組成物Lを得た。
上記粘着剤組成物Lを用いたこと以外は実施例1と同様にして、粘着剤層および位相差層付き偏光板を得た。
[Example 12]
A pressure-sensitive adhesive composition L was obtained in the same manner as in Example 10 except that the amount of trimethylolpropane tolylene diisocyanate added was 2.5 parts with respect to 100 parts of the solid content of the acrylic polymer solution.
Except having used the said adhesive composition L, it carried out similarly to Example 1, and obtained the adhesive layer and the polarizing plate with retardation layer.
[実施例13]
トリメチロールプロパントリレンジイソシアネートの添加量を、アクリル系ポリマー溶液の固形分100部に対して10部としたこと以外は実施例10と同様にして粘着剤組成物Mを得た。
上記粘着剤組成物Mを用いたこと以外は実施例1と同様にして、粘着剤層および位相差層付き偏光板を得た。
[Example 13]
A pressure-sensitive adhesive composition M was obtained in the same manner as in Example 10 except that the amount of trimethylolpropane tolylene diisocyanate added was 10 parts with respect to 100 parts of the solid content of the acrylic polymer solution.
Except having used the said adhesive composition M, it carried out similarly to Example 1, and obtained the polarizing plate with an adhesive layer and a phase difference layer.
[比較例1]
トリメチロールプロパンキシレンジイソシアネートの添加量を、アクリル系ポリマー溶液の固形分100部に対して0.02部としたこと以外は実施例2と同様にして粘着剤組成物Nを得た。
上記粘着剤組成物Nを用いたこと以外は実施例1と同様にして、粘着剤層および位相差層付き偏光板を得た。
[Comparative Example 1]
A pressure-sensitive adhesive composition N was obtained in the same manner as in Example 2, except that the amount of trimethylolpropane xylene diisocyanate added was 0.02 part with respect to 100 parts of the solid content of the acrylic polymer solution.
Except having used the said adhesive composition N, it carried out similarly to Example 1, and obtained the polarizing plate with an adhesive layer and retardation layer.
(評価)
実施例および比較例で得られた位相差層付き偏光板について、下記の評価を行った。結果を表2に示す。
<耐熱性>
位相差層付き偏光板を120mm×60mmのサイズに裁断し、実施例1で用いた粘着剤を介して位相差層B側の面をガラスに貼り合せて試験サンプルとした。この試験サンプルを85℃のオーブンに投入して500時間保管後に、光学顕微鏡で位相差層におけるクラックの有無を確認した。
以下の基準で耐熱性を評価した。
◎◎・・・位相差層にクラックが生じなかった。
◎・・・位相差層の一部に貼り合せ異物を起点としたクラックが発生しているのみであった。
○・・・位相差層の一部にクラックが発生しているが、目視では視認できないレベルであった。
△・・・位相差層の一部にクラックが発生し、目視で確認できるレベルであった。
×・・・位相差層の全面にクラックが多発していた。
(Evaluation)
The following evaluation was performed about the polarizing plate with a phase difference layer obtained by the Example and the comparative example. The results are shown in Table 2.
<Heat resistance>
The polarizing plate with a retardation layer was cut into a size of 120 mm × 60 mm, and the surface on the retardation layer B side was bonded to glass through the adhesive used in Example 1 to prepare a test sample. The test sample was put into an oven at 85 ° C. and stored for 500 hours, and then the presence or absence of cracks in the retardation layer was confirmed with an optical microscope.
The heat resistance was evaluated according to the following criteria.
A: No crack occurred in the retardation layer.
A: Only cracks originating from the bonded foreign material occurred in a part of the retardation layer.
○: Cracks occurred in a part of the retardation layer, but it was a level that could not be visually recognized.
Δ: A crack occurred in a part of the retardation layer, which was a level that can be visually confirmed.
X: Many cracks occurred on the entire surface of the retardation layer.
表2から明らかなように、実施例の位相差層付き偏光板は、位相差層のクラックが抑制される。また、粘着剤組成物として紫外線吸収剤を含む実施例2〜13は、紫外線吸収特性に優れ、中でも、色素化合物をさらに含む実施例5〜6および8〜13は、紫外線吸収特性に特に優れている。 As can be seen from Table 2, the retardation layer-attached polarizing plate of the example suppresses cracks in the retardation layer. Moreover, Examples 2-13 which contain an ultraviolet absorber as an adhesive composition are excellent in an ultraviolet absorption characteristic, and especially Examples 5-6 and 8-13 which further contain a pigment | dye compound are especially excellent in an ultraviolet absorption characteristic. Yes.
本発明の光学積層体は、有機EL表示装置などの画像表示装置に好適に用いられる。 The optical layered body of the present invention is suitably used for an image display device such as an organic EL display device.
10 偏光板
20 第1の位相差層
30 粘着剤層
40 第2の位相差層
50 粘着剤層
100 位相差層付き偏光板
DESCRIPTION OF
Claims (7)
前記第1の位相差層および前記第2の位相差層が液晶化合物を含み、
前記粘着剤層を構成する粘着剤が、ベースポリマー100重量部に対してイソシアネート架橋剤を0.05重量部以上含む、位相差層付き偏光板。 It has a polarizing plate, a first retardation layer, an adhesive layer, and a second retardation layer in this order,
The first retardation layer and the second retardation layer contain a liquid crystal compound,
The polarizing plate with a retardation layer, wherein the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer contains 0.05 parts by weight or more of an isocyanate crosslinking agent with respect to 100 parts by weight of the base polymer.
An organic EL display device comprising the polarizing plate with a retardation layer according to claim 1.
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JP2018081257A JP2019191282A (en) | 2018-04-20 | 2018-04-20 | Polarizing plate with retardation layer and organic EL display device |
KR1020207025303A KR20210002457A (en) | 2018-04-20 | 2019-04-04 | Polarizing plate and organic EL display device with retardation layer |
CN201980020646.7A CN111886526A (en) | 2018-04-20 | 2019-04-04 | Polarizing plate with retardation layer and organic EL display device |
PCT/JP2019/014960 WO2019203008A1 (en) | 2018-04-20 | 2019-04-04 | Polarizing plate provided with phase difference layer, and organic el display device |
TW108113372A TW201943818A (en) | 2018-04-20 | 2019-04-17 | Polarizing plate provided with phase difference layer, and organic el display device |
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WO2021182340A1 (en) * | 2020-03-11 | 2021-09-16 | 日東電工株式会社 | Multilayered pressure-sensitive adhesive layer, multilayered pressure-sensitive adhesive layer with separator attached thereto and production method therefor, tack-type optical film, tack-type optical film with separator attached thereto and production method therefor, and image display device |
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KR20210002457A (en) | 2021-01-08 |
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