TWI743179B - Polarizing plate - Google Patents

Polarizing plate Download PDF

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Publication number
TWI743179B
TWI743179B TW106128547A TW106128547A TWI743179B TW I743179 B TWI743179 B TW I743179B TW 106128547 A TW106128547 A TW 106128547A TW 106128547 A TW106128547 A TW 106128547A TW I743179 B TWI743179 B TW I743179B
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TW
Taiwan
Prior art keywords
layer
resin
polarizing element
retardation
easy
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TW106128547A
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Chinese (zh)
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TW201811564A (en
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小島理
清水享
岡田孝治
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日商日東電工股份有限公司
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    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • G02B5/3025Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • G02B5/3025Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033Polarisers, 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
    • G02B5/3041Polarisers, 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
    • G02B5/305Polarisers, 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
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363Birefringent elements, e.g. for optical compensation

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Laminated Bodies (AREA)

Abstract

本發明之偏光板之樹脂層與偏光元件之密接性優異,且還可抑制於偏光元件產生龜裂。偏光板10具有相位差層3及偏光元件1,且相位差層3與偏光元件1係經由易接著層2而積層,易接著層2於85℃下之儲存模數為1.0×106 Pa~1.0×107 Pa。The resin layer of the polarizing plate of the present invention has excellent adhesion to the polarizing element, and can also suppress the occurrence of cracks in the polarizing element. The polarizing plate 10 has a retardation layer 3 and a polarizing element 1, and the retardation layer 3 and the polarizing element 1 are laminated via the easy-to-bond layer 2. The storage modulus of the easy-to-bond layer 2 at 85°C is 1.0×10 6 Pa~ 1.0×10 7 Pa.

Description

偏光板Polarizing plate

本發明係關於一種偏光板。The present invention relates to a polarizing plate.

作為液晶顯示裝置及有機EL(電致發光,Electroluminescence)顯示裝置所使用之偏光板之製造方法,已知有將藉由對聚乙烯醇系樹脂膜進行延伸及染色所獲得之偏光元件貼附於構成相位差層或保護層等樹脂層之膜而製成偏光板的方法。又,作為偏光板之另一製造方法,揭示有藉由在樹脂基材上形成聚乙烯醇系樹脂層,並對該積層體進行延伸及染色而將聚乙烯醇系樹脂層作為偏光元件之方法。 如上所述,偏光元件可於積層於相位差層或保護層等樹脂層之狀態下使用。因此,為了於使用偏光板時偏光元件不自樹脂層剝離,要求偏光元件與樹脂層具有充分之密接性。 於專利文獻1中提出有於由樹脂基材與聚乙烯醇系樹脂層之積層體獲得偏光板之製造方法中,為了確保樹脂基材與聚乙烯醇系樹脂層之充分之密接性,將樹脂基材與聚乙烯醇系樹脂層經由包含聚乙烯醇系材料之易接著層而積層。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利第4950357號公報As a method for manufacturing polarizing plates used in liquid crystal display devices and organic EL (Electroluminescence) display devices, it is known to attach a polarizing element obtained by stretching and dyeing a polyvinyl alcohol-based resin film to A method of forming a film of a resin layer such as a retardation layer or a protective layer to produce a polarizing plate. In addition, as another manufacturing method of a polarizing plate, a method of forming a polyvinyl alcohol-based resin layer on a resin substrate and extending and dyeing the laminate is disclosed to use the polyvinyl alcohol-based resin layer as a polarizing element . As described above, the polarizing element can be used in a state where it is laminated on a resin layer such as a retardation layer or a protective layer. Therefore, in order to prevent the polarizing element from peeling off from the resin layer when the polarizing plate is used, it is required that the polarizing element and the resin layer have sufficient adhesion. Patent Document 1 proposes a method for obtaining a polarizing plate from a laminate of a resin substrate and a polyvinyl alcohol resin layer. In order to ensure sufficient adhesion between the resin substrate and the polyvinyl alcohol resin layer, the resin The base material and the polyvinyl alcohol-based resin layer are laminated via an easy-adhesion layer containing a polyvinyl alcohol-based material. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent No. 4950357

[發明所欲解決之問題] 然而,利用專利文獻1之方法製造之偏光板之偏光元件與樹脂層(樹脂基材)之密接性不充分。 本發明係鑒於上述課題而完成者,其目的在於提供一種樹脂層與偏光元件之密接性優異,進而可抑制於偏光元件產生龜裂之偏光板。 [解決問題之技術手段] 本發明之偏光板具有樹脂層及偏光元件,且上述樹脂層與上述偏光元件係經由易接著層而積層,上述易接著層於85℃下之儲存模數為1.0×106 Pa~1.0×107 Pa。 於一實施形態中,上述易接著層於交聯劑存在下以80℃、500小時之條件加熱後於85℃下之儲存模數為1.0×106 Pa~1.0×107 Pa。 於一實施形態中,上述易接著層包含聚烯烴系成分及聚乙烯醇系成分。 於一實施形態中,上述聚烯烴系成分與上述聚乙烯醇系成分之質量比為98:2~90:10。 於一實施形態中,上述易接著層之厚度為500 nm~1 μm。 於一實施形態中,上述易接著層與上述偏光元件係經由包含聚乙烯醇系樹脂之接著劑而貼合。 於一實施形態中,上述樹脂層係具有面內相位差之相位差層。 於一實施形態中,上述相位差層之面內相位差Re(550)為100 nm~180 nm,且滿足Re(450)<Re(550)之關係。 於一實施形態中,上述偏光元件之吸收軸與上述相位差層之遲相軸所成之角度為38°~52°。 於一實施形態中,上述樹脂層係具有光學各向同性之保護層。 [發明之效果] 根據本發明,提供一種樹脂層與偏光元件之密接性優異,進而可抑制於偏光元件產生龜裂之偏光板。[Problem to be Solved by the Invention] However, the adhesion between the polarizing element of the polarizing plate manufactured by the method of Patent Document 1 and the resin layer (resin base material) is insufficient. The present invention was made in view of the above-mentioned problems, and its object is to provide a polarizing plate that has excellent adhesion between the resin layer and the polarizing element, and further suppresses the occurrence of cracks in the polarizing element. [Technical Means for Solving the Problem] The polarizing plate of the present invention has a resin layer and a polarizing element, and the resin layer and the polarizing element are laminated via an easy-to-bond layer. The storage modulus of the easy-to-bond layer at 85°C is 1.0× 10 6 Pa~1.0×10 7 Pa. In one embodiment, the storage modulus of the easily adhesive layer at 85°C after heating at 80°C for 500 hours in the presence of a crosslinking agent is 1.0×10 6 Pa to 1.0×10 7 Pa. In one embodiment, the easily bonding layer includes a polyolefin-based component and a polyvinyl alcohol-based component. In one embodiment, the mass ratio of the polyolefin-based component to the polyvinyl alcohol-based component is 98:2 to 90:10. In one embodiment, the thickness of the easily bonding layer is 500 nm to 1 μm. In one embodiment, the easily bonding layer and the polarizing element are bonded via an adhesive containing a polyvinyl alcohol-based resin. In one embodiment, the above-mentioned resin layer is a retardation layer having an in-plane retardation. In one embodiment, the in-plane retardation Re(550) of the retardation layer is 100 nm to 180 nm, and satisfies the relationship of Re(450)<Re(550). In one embodiment, the angle formed by the absorption axis of the polarizing element and the retardation axis of the retardation layer is 38° to 52°. In one embodiment, the resin layer has an optically isotropic protective layer. [Effects of the Invention] According to the present invention, there is provided a polarizing plate that has excellent adhesion between the resin layer and the polarizing element, and further suppresses the occurrence of cracks in the polarizing element.

以下,對本發明之實施形態進行說明,但本發明並不限定於該等實施形態。 (用語及記號之定義) 本說明書中之用語及記號之定義如下所述。 (1)折射率(nx、ny、nz) 「nx」為面內之折射率成為最大之方向(即,遲相軸方向)之折射率,「ny」為於面內與遲相軸正交之方向(即,進相軸方向)之折射率,「nz」為厚度方向之折射率。 (2)面內相位差(Re) 「Re(λ)」為23℃下以波長λ nm之光測得之面內相位差。Re(λ)係將層(膜)之厚度設為d(nm)時,藉由式:Re=(nx-ny)×d而求出。例如,「Re(550)」係23℃下以波長550 nm之光測得之面內相位差。 A.偏光板 本發明之偏光板具有樹脂層與偏光元件,樹脂層與偏光元件係經由易接著層而接著。偏光板之易接著層於85℃下之儲存模數為1.0×106 Pa以上。藉此,能夠製成樹脂層與偏光元件之密接性優異,進而可抑制於偏光元件產生龜裂之偏光板。 於本發明之一實施形態中,上述樹脂層係具有面內相位差之相位差層。於本發明之另一實施形態中,上述樹脂層亦可為偏光元件之保護層(下述保護膜或內側保護層)。以下,主要對樹脂層為相位差層之偏光板進行說明。 圖1係本發明之一實施形態之偏光板之剖視圖。如圖1所示,偏光板10具有相位差層3作為樹脂層,相位差層3與偏光元件1經由易接著層2而積層。又,偏光板10亦可於偏光元件1之與相位差層3相反側具有保護膜(未圖示)。 B.偏光元件 作為偏光元件1,可採用任意適當之偏光元件。例如,形成偏光元件之樹脂膜可為單層之樹脂膜,亦可為兩層以上之積層體。 作為由單層樹脂膜所構成之偏光元件之具體例,可列舉:對聚乙烯醇(PVA)系膜、部分縮甲醛化PVA系膜、乙烯·乙酸乙烯酯共聚物系部分皂化膜等親水性高分子膜實施利用碘或二色性染料等二色性物質所進行之染色處理及延伸處理而成者;PVA之脫水處理物或聚氯乙烯之脫氯化氫處理物等多烯系配向膜等。就光學特性優異而言,較佳為使用利用碘將PVA系膜染色並進行單軸延伸而獲得之偏光元件。 上述利用碘之染色例如係藉由將PVA系膜浸漬於碘水溶液而進行。上述單軸延伸之延伸倍率較佳為3~7倍。延伸可於染色處理後進行,亦可一面染色一面進行。又,亦可於延伸後進行染色。視需要對PVA系膜進行膨潤處理、交聯處理、洗淨處理、乾燥處理等。例如,藉由於染色之前將PVA系膜浸漬於水來進行水洗,不僅能夠洗淨PVA系膜表面之污垢或抗黏連劑,而且能夠使PVA系膜膨潤而防止染色不均等。 作為使用積層體所獲得之偏光元件之具體例,可列舉:使用樹脂基材與積層於該樹脂基材之PVA系樹脂層(PVA系樹脂膜)之積層體、或樹脂基材與塗佈形成於該樹脂基材之PVA系樹脂層之積層體而獲得之偏光元件。使用樹脂基材與塗佈形成於該樹脂基材之PVA系樹脂層之積層體而獲得之偏光元件例如可藉由以下之方式製作:將PVA系樹脂溶液塗佈於樹脂基材,並使其乾燥而於樹脂基材上形成PVA系樹脂層,從而獲得樹脂基材與PVA系樹脂層之積層體;對該積層體進行延伸及染色而將PVA系樹脂層形成為偏光元件。於本實施形態中,延伸代表性地包括使積層體浸漬於硼酸水溶液中進行延伸。進而,延伸可視需要進而包括於在硼酸水溶液中之延伸前以高溫(例如95℃以上)對積層體進行空中延伸。所獲得之樹脂基材/偏光元件之積層體可直接使用(即,可將樹脂基材作為設置於相位差層與偏光元件之間之內側保護層),亦可將樹脂基材(樹脂層)自樹脂基材/偏光元件之積層體剝離,並將根據目的之任意適當之保護層作為內側保護層積層於該剝離面來使用。此種偏光元件之製造方法之詳細內容例如記載於日本專利特開2012-73580號公報。該公報之全部記載係作為參考而援引於本說明書中。再者,於使用樹脂基材作為設置於相位差層與偏光元件之間之內側保護層之情形時,亦可於樹脂基材與PVA系樹脂層之間設置易接著層。又,於將樹脂基材剝離,並將根據目的之任意適當之保護層作為內側保護層而積層於該剝離面之情形時,亦可於內側保護層與偏光元件之間設置易接著層。 偏光元件之厚度可根據目的及用途適當進行設計,較佳為3 μm~25 μm。 偏光元件較佳為於波長380 nm~780 nm之任一波長下表現吸收二色性。偏光元件之單體透過率較佳為42.0%~46.0%,更佳為44.5%~46.0%。偏光元件之偏光度較佳為97.0%以上,更佳為99.0%以上,進而較佳為99.9%以上。 C.相位差層 相位差層3可由根據目的具有任意適當之光學特性及/或機械特性之相位差膜構成。相位差層3代表性地具有遲相軸。於一實施形態中,相位差層3之遲相軸與偏光元件1之吸收軸所成之角度θ較佳為38°~52°,更佳為42°~48°,進而較佳為約45°。若角度θ為此種範圍,則藉由將相位差層3作為λ/4板,能夠獲得具有非常優異之圓偏光特性之偏光板10。 相位差層3較佳為表現折射率特性為nx>ny≧nz之關係。相位差層3代表性地以對偏光板賦予抗反射特性為目的而設置,於一實施形態中,可作為λ/4板發揮功能。於該情形時,相位差層3之面內相位差Re(550)較佳為80 nm~200 nm,更佳為100 nm~180 nm,進而較佳為110 nm~170 nm。再者,此處「ny=nz」不僅包含ny與nz完全相等之情況,亦包含實質上相等之情況。因此,於不損害本發明之效果之範圍內,可能存在成為ny<nz之情況。 相位差層3之雙折射Δnxy 例如為0.0025以上,較佳為0.0028以上。另一方面,雙折射Δnxy 之上限例如為0.0060,較佳為0.0050。藉由將雙折射最佳化為此種範圍,能夠獲得較薄、且具有所期望之光學特性之相位差層3。 相位差層3之Nz係數較佳為0.9~3,更佳為0.9~2.5,進而較佳為0.9~1.5,尤佳為0.9~1.3。藉由滿足此種關係,於將所獲得之偏光板用於圖像顯示裝置之情形時,能夠達成非常優異之反射色相。 相位差層3可表現相位差值對應於測定光之波長而變大之逆波長色散特性,亦可表現相位差值對應於測定光之波長而變小之正波長色散特性,亦可表現相位差值幾乎不因測定光之波長而發生變化之平坦之波長色散特性。於一實施形態中,相位差層3表現逆波長色散特性。於該情形時,相位差層3滿足Re(450)<Re(550)之關係,相位差層3之Re(450)/Re(550)較佳為0.8以上且未達1,更佳為0.8以上且0.95以下。若為此種構成,則能夠實現非常優異之抗反射特性。於另一實施形態中,相位差層3表現平坦之波長色散特性。於該情形時,相位差層3之Re(450)/Re(550)較佳為0.99~1.03,Re(650)/Re(550)較佳為0.98~1.02。於該情形時,相位差層3可具有積層構造。具體而言,藉由以特定之軸角度(例如50°~70°,較佳為約60°)配置作為λ/2板發揮功能之相位差膜與作為λ/4板發揮功能之相位差膜,能夠獲得與理想之逆波長色散特性相近之特性,結果能夠實現非常優異之抗反射特性。 相位差層3之吸水率為3%以下,較佳為2.5%以下,更佳為2%以下。藉由滿足此種吸水率,能夠抑制顯示特性之經時變化。再者,吸水率可按照JIS K 7209而求出。 相位差層3包含光彈性係數之絕對值較佳為2×10-11 m2 /N以下,更佳為2.0×10-13 m2 /N~1.6×10-11 m2 /N之樹脂。若光彈性係數之絕對值為此種範圍,則於產生加熱時之收縮應力之情形時不易產生相位差變化。其結果為,能夠良好地防止所獲得之圖像顯示裝置之熱不均。 相位差層3之厚度例如為70 μm以下,較佳為40 μm~60 μm。若為此種厚度,則可賦予作為偏光元件之保護層之適當之機械強度。 相位差層3可由能夠滿足上述特性之任意適當之樹脂膜構成。作為此種樹脂之代表例,可列舉:環狀烯烴系樹脂、聚碳酸酯系樹脂、纖維素系樹脂、聚酯系樹脂、聚乙烯醇系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚醚系樹脂、聚苯乙烯系樹脂、丙烯酸系樹脂。於由表現逆波長色散特性之樹脂膜構成相位差層3之情形時,可適當使用聚碳酸酯系樹脂。 作為上述聚碳酸酯樹脂,只要獲得本發明之效果,則可使用任意適當之聚碳酸酯樹脂。較佳為聚碳酸酯樹脂包含:源自茀系二羥基化合物之結構單元;源自異山梨酯系二羥基化合物之結構單元;以及源自選自由脂環式二醇、脂環式二甲醇、二、三或聚乙二醇、及伸烷基二醇或螺二醇所組成之群中之至少1種二羥基化合物之結構單元。較佳為聚碳酸酯樹脂包含源自茀系二羥基化合物之結構單元、源自異山梨酯系二羥基化合物之結構單元、以及源自脂環式二甲醇之結構單元及/或源自二、三或聚乙二醇之結構單元;進而較佳為包含源自茀系二羥基化合物之結構單元、源自異山梨酯系二羥基化合物之結構單元、及源自二、三或聚乙二醇之結構單元。聚碳酸酯樹脂亦可視需要包含源自其他二羥基化合物之結構單元。再者,可適當用於本發明之聚碳酸酯樹脂之詳細內容例如記載於日本專利特開2014-10291號公報、日本專利特開2014-26266號公報,該記載係作為參考而援引於本說明書中。 於一實施形態中,可使用包含源自下述通式(1)所表示之二羥基化合物之單元結構之聚碳酸酯系樹脂。 [化1]

Figure 02_image001
(上述通式(1)中,R1 ~R4 分別獨立表示氫原子、經取代或未經取代之碳數1~碳數20之烷基、經取代或未經取代之碳數6~碳數20之環烷基、或者經取代或未經取代之碳數6~碳數20之芳基,X表示經取代或未經取代之碳數2~碳數10之伸烷基、經取代或未經取代之碳數6~碳數20之伸環烷基、或者經取代或未經取代之碳數6~碳數20之伸芳基,m及n分別獨立為0~5之整數) 作為通式(1)所表示之二羥基化合物之具體例,可列舉:9,9-雙(4-羥基苯基)茀、9,9-雙(4-羥基-3-甲基苯基)茀、9,9-雙(4-羥基-3-乙基苯基)茀、9,9-雙(4-羥基-3-正丙基苯基)茀、9,9-雙(4-羥基-3-異丙基苯基)茀、9,9-雙(4-羥基-3-正丁基苯基)茀、9,9-雙(4-羥基-3-第二丁基苯基)茀、9,9-雙(4-羥基-3-第三丁基苯基)茀、9,9-雙(4-羥基-3-環己基苯基)茀、9,9-雙(4-羥基-3-苯基苯基)茀、9,9-雙(4-(2-羥基乙氧基)苯基)茀、9,9-雙(4-(2-羥基乙氧基)-3-甲基苯基)茀、9,9-雙(4-(2-羥基乙氧基)-3-異丙基苯基)茀、9,9-雙(4-(2-羥基乙氧基)-3-異丁基苯基)茀、9,9-雙(4-(2-羥基乙氧基)-3-第三丁基苯基)茀、9,9-雙(4-(2-羥基乙氧基)-3-環己基苯基)茀、9,9-雙(4-(2-羥基乙氧基)-3-苯基苯基)茀、9,9-雙(4-(2-羥基乙氧基)-3,5-二甲基苯基)茀、9,9-雙(4-(2-羥基乙氧基)-3-第三丁基-6-甲基苯基)茀、9,9-雙(4-(3-羥基-2,2-二甲基丙氧基)苯基)茀等。 上述聚碳酸酯系樹脂除了源自上述二羥基化合物之結構單元以外,亦可包含源自異山梨酯、異二縮甘露醇、異艾杜糖醇、螺二醇、二㗁烷二醇、二乙二醇(DEG)、三乙二醇(TEG)、聚乙二醇(PEG)、雙酚類等二羥基化合物之結構單元。 包含源自二羥基化合物之結構單元之聚碳酸酯系樹脂之詳細內容例如記載於日本專利5204200號、日本專利特開2012-67300號公報、日本專利第3325560號、WO2014/061677號等。該專利文獻之記載係作為參考而援引於本說明書中。 於一實施形態中,可使用包含低聚茀結構單元之聚碳酸酯系樹脂。作為包含低聚茀結構單元之聚碳酸酯系樹脂,例如可列舉包含下述通式(2)所表示之結構單元及/或下述通式(3)所表示之結構單元之樹脂。
Figure 02_image003
(上述通式(2)及上述通式(3)中,R5 及R6 分別獨立為直接鍵、經取代或未經取代之碳數1~4之伸烷基(較佳為主鏈上之碳數為2~3之伸烷基)。R7 為直接鍵、經取代或未經取代之碳數1~4之伸烷基(較佳為主鏈上之碳數為1~2之伸烷基)。R8 ~R13 分別獨立為氫原子、經取代或未經取代之碳數1~10(較佳為1~4,更佳為1~2)之烷基、經取代或未經取代之碳數4~10(較佳為4~8,更佳為4~7)之芳基、經取代或未經取代之碳數1~10(較佳為1~4,更佳為1~2)之醯基、經取代或未經取代之碳數1~10(較佳為1~4,更佳為1~2)之烷氧基、經取代或未經取代之碳數1~10(較佳為1~4,更佳為1~2)之芳氧基、經取代或未經取代之碳數1~10(較佳為1~4,更佳為1~2)之醯氧基、經取代或未經取代之胺基、經取代或未經取代之碳數1~10(較佳為1~4)之乙烯基、經取代或未經取代之碳數1~10(較佳為1~4)之乙炔基、具有取代基之硫原子、具有取代基之矽原子、鹵素原子、硝基、或氰基。R8 ~R13 中之相鄰之至少2個基亦可相互鍵結而形成環) 於一實施形態中,低聚茀結構單元中所包含之茀環具有R8 ~R13 全部為氫原子之構成,或者具有R8 及/或R13 為選自由鹵素原子、醯基、硝基、氰基、及磺基所組成之群中之任一種且R9 ~R12 為氫原子之構成。 包含低聚茀結構單元之聚碳酸酯系樹脂之詳細內容例如記載於日本專利特開2015-212816號公報等。該專利文獻之記載係作為參考而援引於本說明書中。 上述聚碳酸酯樹脂之玻璃轉移溫度較佳為110℃以上且150℃以下,更佳為120℃以上且140℃以下。若玻璃轉移溫度過低,則存在耐熱性變差之傾向,可能於膜成形後引起尺寸變化,又,存在使所獲得之圖像顯示裝置之圖像品質下降之情況。若玻璃轉移溫度過高,則存在膜成形時之成形穩定性變差之情況,又,存在損害膜之透明性之情況。再者,玻璃轉移溫度係按照JIS K 7121(1987)而求出。 上述聚碳酸酯樹脂之分子量可由比濃黏度表示。比濃黏度係使用二氯甲烷作為溶劑,將聚碳酸酯濃度精確地製備為0.6 g/dL,於溫度20.0℃±0.1℃下使用烏氏黏度管進行測定。比濃黏度之下限通常較佳為0.30 dL/g,更佳為0.35 dL/g以上。比濃黏度之上限通常較佳為1.20 dL/g,更佳為1.00 dL/g,進而較佳為0.80 dL/g。若比濃黏度小於上述下限值,則存在產生成形品之機械強度變小之問題。另一方面,若比濃黏度大於上述上限值,則存在產生成形時之流動性下降而導致生產性或成形性下降之問題之情況。 亦可使用市售之膜作為聚碳酸酯系樹脂膜。作為市售品之具體例,可列舉:帝人公司製造之商品名「PURE-ACE WR-S」、「PURE-ACE WR-W」、「PURE-ACE WR-M」、日東電工公司製造之商品名「NRF」。 相位差層3例如係藉由將由上述聚碳酸酯系樹脂形成之膜延伸而獲得。作為由聚碳酸酯系樹脂形成膜之方法,可採用任意適當之成形加工法。作為具體例,可列舉:壓縮成形法、轉移成形法、射出成形法、擠出成形法、吹塑成形法、粉末成形法、FRP(Fiber Reinforced Polymer,纖維增強複合材料)成形法、鑄塗法(例如鑄膜法)、壓延成形法、熱壓法等。較佳為擠出成形法或鑄塗法。其原因在於:能夠提高所獲得之膜之平滑性,獲得良好之光學均勻性。成形條件可根據所使用之樹脂之組成或種類、對相位差層3所期望之特性等適當進行設定。再者,如上所述,關於聚碳酸酯系樹脂,市售有較多之膜製品,因此亦可將該市售膜直接用於延伸處理。 樹脂膜(未延伸膜)之厚度可根據相位差層所期望之厚度、所期望之光學特性、下述延伸條件等設定為任意適當之值。較佳為50 μm~300 μm。 上述延伸可採用任意適當之延伸方法、延伸條件(例如延伸溫度、延伸倍率、延伸方向)。具體而言,可單獨使用亦可同時或逐次地使用自由端延伸、固定端延伸、自由端收縮、固定端收縮等各種延伸方法。關於延伸方向,亦可於長度方向、寬度方向、厚度方向、斜方向等各種方向或維度上進行。延伸溫度較佳為相對於樹脂膜之玻璃轉移溫度(Tg)為Tg-30℃~Tg+60℃,更佳為Tg-10℃~Tg+50℃。 藉由適當選擇上述延伸方法、延伸條件,能夠獲得具有上述所期望之光學特性(例如折射率特性、面內相位差、Nz係數)之相位差膜。 於一實施形態中,相位差膜係藉由對樹脂膜進行單軸延伸或固定端單軸延伸而製作。作為固定端單軸延伸之具體例,可列舉一面使樹脂膜於長度方向上移行一面於寬度方向(橫向)上延伸之方法。延伸倍率較佳為1.1倍~3.5倍。 於另一實施形態中,相位差膜可藉由使長條狀之樹脂膜相對於長度方向於上述角度θ之方向上連續地傾斜延伸而製作。藉由採用傾斜延伸,而獲得相對於膜之長度方向具有角度θ之配向角(於角度θ之方向上之遲相軸)之長條狀的延伸膜,例如與偏光元件之積層時能夠實現卷對卷式,能夠簡化製造步驟。再者,角度θ可為於偏光板中偏光元件之吸收軸與相位差層之遲相軸所成之角度。角度θ如上所述,較佳為38°~52°,更佳為42°~48°,進而較佳為約45°。 D.易接著層 易接著層2設置於相位差層3之偏光元件1側之表面。偏光板10代表性地係藉由經由接著劑將表面形成有易接著層2之相位差層3與偏光元件貼合而製造。 如上所述,易接著層2於85℃下之儲存模數為1.0×106 Pa~1.0×107 Pa。易接著層2於85℃下之儲存模數較佳為2.0×106 Pa~7.0×106 Pa。藉此,能夠製成相位差層3與偏光元件1之密接性優異,進而可抑制於偏光元件1產生龜裂之偏光板10。以下進行具體說明。因於加熱環境下使用偏光板,而使整個樹脂層膨脹,偏光元件收縮,因此存在對易接著層施加剪力之情況。於易接著層於85℃下之儲存模數未達1.0×106 Pa之情形時,易接著層柔軟,相對於所施加之應力之變形較大。因此,因對易接著層施加剪力,而存在產生於與偏光元件1之界面之密接性下降、或易接著層之凝聚破壞之情況。尤其是於在與偏光元件之界面易接著層發生剝離之情形時,偏光元件露出,可能產生偏光元件產生龜裂之問題。進而,於易接著層於85℃下之儲存模數未達1.0×106 Pa之情形時,存在無法抑制偏光元件產生之微小龜裂進展之情況。於易接著層於85℃下之儲存模數大於1.0×107 Pa之情形時,易接著層脆,易接著層之應力緩和之功能不足。因此,導因於對易接著層施加剪力,而有相位差層與偏光元件之間之密接力下降,而發生相位差層之破壞及/或易接著層之凝聚破壞之情況的結果之情形。對此,藉由使易接著層2於85℃下之儲存模數為1.0×106 Pa~1.0×107 Pa,能夠獲得相位差層3與偏光元件1之間之密接力優異,且抑制相位差層3之破壞及/或易接著層2之凝聚破壞之偏光板10。 於交聯劑存在下以80℃、500小時之條件加熱後之易接著層2於85℃下的儲存模數較佳為1.0×106 Pa~1.0×107 Pa。較佳為易接著層2於交聯劑存在下以80℃、500小時加熱前之85℃下之儲存模數為1.0×106 Pa~1.0×107 Pa,並且於交聯劑存在下以80℃、500小時加熱後之85℃下之儲存模數為1.0×106 Pa~1.0×107 Pa。即,較佳為易接著層2於交聯劑存在下以80℃、500小時加熱前後之85℃下之儲存模數之變化量為9.0×106 Pa以下。於經由以聚乙烯醇系樹脂為主成分之接著劑將相位差層3與偏光元件1貼合時使用包含聚乙烯醇系成分之先前之易接著層的情形時,因接著劑所含之交聯劑之影響而導致易接著層所含之聚乙烯醇系成分之交聯進展,其結果為,易接著層之儲存模數經時性上升,相位差層與偏光元件之密接性有可能下降。對此,藉由使用於交聯劑存在下以80℃、500小時加熱前後之85℃下之儲存模數之變化量為9.0×106 Pa以下的易接著層2,而降低使相位差層3與偏光元件1貼合後之易接著層2之儲存模數之經時性上升,能夠抑制相位差層3與偏光元件1之密接性下降。 作為易接著層2之構成材料,可採用能夠使85℃下之儲存模數為上述範圍內之任意適當之材料。易接著層2代表性地包含聚烯烴系成分及聚乙烯醇系成分。於該情形時,聚烯烴系成分與聚乙烯醇系成分之質量比較佳為86:14~99:1,更佳為90:10~98:2。藉由調整聚烯烴系成分與聚乙烯醇系成分之質量比,能夠控制易接著層2(實質上為形成易接著層2之易接著劑組合物)於85℃下之儲存模數。 易接著層2代表性地係藉由將易接著劑組合物塗佈於相位差層3之單側並使之乾燥而形成。作為易接著層之構成材料之塗佈方法,可採用任意適當之方法。例如可列舉:棒式塗佈法、輥塗法、凹版塗佈法、桿式塗佈法、孔縫式塗佈法、淋幕式塗佈法、噴注式塗佈法等。作為乾燥溫度,代表性地為50℃以上,較佳為70℃以上,進而較佳為90℃以上。藉由將乾燥溫度設為此種範圍,能夠提供耐色性(尤其是高溫高濕下)優異之偏光板。乾燥溫度較佳為120℃以下,進而較佳為100℃以下。 易接著層2之厚度可設定為任意適當之值。易接著層2之厚度較佳為500 nm~1 μm,進而較佳為700 nm~800 nm。藉由設定為此種範圍,可使與偏光元件1之密接性優異,能夠抑制於易接著層2顯現相位差。 E.接著劑層 相位差層3及偏光元件1代表性地經由形成於易接著層2上之接著劑層而貼合。接著劑層可由任意適當之接著劑構成。接著劑層之厚度較佳為10 nm~300 nm,進而較佳為10 nm~200 nm,尤佳為20 nm~150 nm。 接著劑較佳為具有透明性及光學各向同性。作為接著劑之形態,可採用任意適當之形態。作為具體例,可列舉:水性接著劑、溶劑型接著劑、乳液系接著劑、無溶劑型接著劑、活性能量線硬化型接著劑、熱硬化型接著劑。作為活性能量線硬化型接著劑,可列舉:電子束硬化型接著劑、紫外線硬化型接著劑、可見光線硬化型接著劑。可適當使用水性接著劑。 作為水性接著劑之具體例,可列舉:異氰酸酯系接著劑、聚乙烯醇系接著劑、明膠系接著劑、乙烯系乳膠系、水系聚胺基甲酸酯、水系聚酯。較佳為聚乙烯醇或改性聚乙烯醇等聚乙烯醇系接著劑,進而較佳為以具有乙醯乙醯基之聚乙烯醇為主成分之接著劑。此種接著劑被市售,作為市售品之具體例,可列舉日本合成化學(股)製造(商品名「GOHSEFIMER Z」)。 F.保護膜 保護膜係由可作為偏光元件之保護膜使用之任意適當的膜形成。作為成為該膜之主成分之材料之具體例,可列舉:三乙醯纖維素(TAC)等纖維素系樹脂;或聚酯系、聚乙烯醇系、聚碳酸酯系、聚醯胺系、聚醯亞胺系、聚醚碸系、聚碸系、聚苯乙烯系、聚降莰烯系、聚烯烴系、(甲基)丙烯酸系、乙酸酯系等透明樹脂等。又,亦可列舉:(甲基)丙烯酸系、胺基甲酸酯系、(甲基)丙烯酸胺基甲酸酯系、環氧系、矽酮系等熱硬化型樹脂或紫外線硬化型樹脂等。此外,例如亦可列舉矽氧烷系聚合物等玻璃質系聚合物。又,亦可使用日本專利特開2001-343529號公報(WO01/37007)中記載之聚合物膜。作為該膜之材料,例如可使用含有側鏈具有經取代或未經取代之亞胺基之熱塑性樹脂、以及側鏈具有經取代或未經取代之苯基及腈基之熱塑性樹脂的樹脂組合物,例如可列舉:具有包含異丁烯與N-甲基順丁烯二醯亞胺之交替共聚物、及丙烯腈·苯乙烯共聚物之樹脂組合物。該聚合物膜例如可為上述樹脂組合物之擠出成形物。 本發明之偏光板代表性地配置於圖像顯示裝置之視認側,保護膜代表性地配置於該視認側。因此,亦可視需要對保護膜實施硬塗處理、抗反射處理、抗沾黏處理、防眩處理等表面處理。 關於保護膜之厚度,只要獲得本發明之效果,則可採用任意適當之厚度。保護膜之厚度例如為10 μm~100 μm,較佳為30 μm~90 μm。再者,於實施表面處理之情形時,保護膜之厚度為包含表面處理層之厚度在內之厚度。 G.另一保護層 又,視需要配置之另一保護層(內側保護層)亦由能夠作為偏光元件之保護層使用之任意適當的膜形成。成為該膜之主成分之材料係如在上述F項中保護膜有關之說明。內側保護層之厚度例如為15 μm~35 μm,較佳為20 μm~30 μm。內側保護層較佳為光學各向同性。於本說明書中,所謂「光學各向同性」係指面內相位差Re(550)為0 nm~10 nm,且厚度方向之相位差Rth(550)為-10 nm~+10 nm。 H.其他 如上所述,作為本發明之一實施形態,列舉上述樹脂層為相位差層3之偏光板10為例進行了說明,但本發明之實施形態並不限定於此。即,於本發明之另一實施形態之偏光板中,上述樹脂層可為能夠設置於偏光元件1之相位差層3側之內側保護層,亦可經由易接著層將偏光元件1與內側保護層接著。又,於本發明之又一實施形態之偏光板中,上述樹脂層可為能夠設置於偏光元件1之與相位差層3相反側之保護膜,亦可經由易接著層將偏光元件1與保護膜接著。 I.顯示裝置 上述A項至H項中記載之偏光板可應用於液晶顯示裝置及有機EL顯示裝置等顯示裝置。因此,本發明包含使用上述偏光板之顯示裝置。本發明之實施形態之顯示裝置具備顯示元件、及配置於顯示元件之視認側之上述A項至H項中記載之偏光板。偏光板係以相位差層成為顯示元件側之方式配置。 [實施例] 以下,利用實施例對本發明進行具體說明,但本發明並不由該等實施例限定。 <實施例1> 1.偏光元件之製作 於下述(1)~(5)條件之5個浴中,對厚度60 μm之以聚乙烯醇系樹脂為主成分之高分子膜(可樂麗(股)製造,商品名「VF-PE#6000」)一面於膜長度方向上賦予張力一面進行浸漬,以最終之延伸倍率相對於膜原長成為6.2倍之方式延伸。使該延伸膜於40度之空氣循環式乾燥烘箱內乾燥1分鐘,從而製作偏光元件。 <條件> (1)膨潤浴:30度之純水。 (2)染色浴:包含相對於100重量份之水為0.035重量份之碘及相對於100重量份之水為0.2重量份之碘化鉀之30度之水溶液。 (3)第1交聯浴:包含3重量%之碘化鉀及3重量%之硼酸之40度之水溶液。 (4)第2交聯浴:包含5重量%之碘化鉀及4重量%之硼酸之60度之水溶液。 (5)水洗浴:包含3重量%之碘化鉀之25度之水溶液。 2.構成相位差層之相位差膜之製作 (聚碳酸酯樹脂膜之製作) 將38.06重量份(0.059 mol)之雙[9-(2-苯氧基羰基乙基)茀-9-基]甲烷、53.73重量份(0.368 mol)之異山梨酯(ROQUETTE FRERES公司製造,商品名「POLYSORB」)、9.64重量份(0.067 mol)之1,4-環己烷二甲醇(順式、反式混合物,SK化學公司製造)、81.28重量份(0.379 mol)之碳酸二苯酯(三菱化學公司製造)、及3.83×10-4 重量份(2.17×10-6 mol)之作為觸媒之乙酸鈣一水合物放入至反應容器,並對反應裝置內進行減壓氮氣置換。於氮氣氛圍下,於150℃下約10分鐘一面進行攪拌一面使原料溶解。作為反應第1階段之步驟,歷時30分鐘升溫至220℃,並於常壓下反應60分鐘。然後,歷時60分鐘將壓力自常壓減壓至13.3 kPa,於13.3 kPa下保持30分鐘將產生之苯酚向反應系統外抽出。然後,作為反應第2階段之步驟,一面歷時15分鐘將熱媒溫度升溫至240℃,一面歷時15分鐘將壓力減壓至0.10 kPa以下,將產生之苯酚向反應系統外抽出。於達到特定之攪拌轉矩後,利用氮氣複壓至常壓而使反應停止,將生成之聚酯碳酸酯擠出至水中,切割線料而獲得聚碳酸酯樹脂顆粒。 (相位差膜之製作) 將包含上述聚碳酸酯樹脂顆粒之膜傾斜延伸而獲得相位差膜(厚度:57 μm、光彈性係數:16×10-12 Pa、Re(450):120 nm、Re(550):140 nm、Re(450)/Re(550):0.86)。此時,延伸方向相對於膜之長度方向設為45°。又,為了使得所獲得之相位差膜顯現λ/4之相位差,延伸倍率調整為2~3倍。又,延伸溫度設為148℃(即,未延伸改性聚碳酸酯膜之Tg+5℃)。 3.易接著層之形成 以聚烯烴系成分與聚乙烯醇系成分之質量比成為98:2之方式將8重量份之改性聚烯烴樹脂(Unitika(股)製造,商品名「Arrow Base SE-1030N」)、0.9重量份之聚乙烯醇系樹脂(日本合成化學工業公司製造,商品名「GOHSEFIMER Z200」)之水溶液、及27.0重量份之純水進行混合,從而獲得易接著劑組合物。 使用動態黏彈性測定裝置(TA Instruments公司製造,商品名「RSA-G2」)將負載模式設為拉伸模式,且設為升溫速度10℃/min、頻率1 Hz、初始應變0.1%,對所獲得之易接著劑組合物之儲存模數進行測定。所獲得之易接著劑組合物於85℃下之儲存模數為2.4×106 Pa。又,於交聯劑存在下以80℃、500小時之條件進行加熱後之易接著劑組合物於85℃下的儲存模數為6.7×106 Pa。 利用棒式塗佈機(#6)將所獲得之易接著劑組合物以乾燥後之厚度成為500 nm之方式塗佈於相位差膜的一面。其後,將聚碳酸酯系樹脂膜放入至熱風乾燥機(90℃),使易接著劑組合物乾燥約5分鐘,藉此於相位差膜之一面形成易接著層(厚度500 nm)。 4.偏光板之製作 將偏光元件經由以聚乙烯醇系樹脂為主成分之水溶性接著劑(日本合成化學工業公司製造,商品名「GOHSEFIMER Z200」)而貼合於相位差膜之易接著層形成面。再者,偏光元件與相位差膜係以偏光元件之吸收軸與相位差膜之遲相軸所成之角度成為45°之方式貼合。然後,將作為保護膜之TAC膜(大日本印刷公司製造,商品名「DSG-03」,厚度70 μm)經由以聚乙烯醇系樹脂為主成分之水溶性接著劑(日本合成化學工業公司製造,商品名「GOHSEFIMER Z200」)而貼合於偏光元件之與相位差層為相反側的面,從而獲得偏光板。 <實施例2> 以聚烯烴系成分與聚乙烯醇系成分之質量比成為90:10之方式將改性聚烯烴樹脂、聚乙烯醇系樹脂、及純水進行混合而獲得易接著劑組合物,除此以外,以與實施例1相同之方式製作偏光板。再者,所獲得之易接著劑組合物於85℃下之儲存模數為6.4×106 Pa。又,於交聯劑存在下以80℃、500小時之條件進行加熱後之易接著劑組合物於85℃下的儲存模數為8.2×106 Pa。 <比較例1> 以聚烯烴系成分與聚乙烯醇系成分之質量比成為10:0之方式不使用聚乙烯醇系樹脂而將改性聚烯烴樹脂與純水進行混合而獲得易接著劑組合物,除此以外,以與實施例1相同之方式製作偏光板。再者,所獲得之易接著劑組合物於85℃下之儲存模數為8.8×105 Pa。又,於交聯劑存在下以80℃、500小時之條件進行加熱後之易接著劑組合物於85℃下的儲存模數為8.9×105 Pa。 <比較例2> 以聚烯烴系成分與聚乙烯醇系成分之質量比成為85:15之方式將改性聚烯烴樹脂、聚乙烯醇系樹脂、及純水進行混合而獲得易接著劑組合物,除此以外,以與實施例1相同之方式製作偏光板。再者,所獲得之易接著劑組合物於85℃下之儲存模數為1.6×107 Pa。又,於交聯劑存在下以80℃、500小時之條件進行加熱後之易接著劑組合物於85℃下的儲存模數為8.2×108 Pa。 <比較例3> 以聚烯烴系成分與聚乙烯醇系成分之質量比成為70:30之方式將改性聚烯烴樹脂、聚乙烯醇系樹脂、及純水進行混合而獲得易接著劑組合物,除此以外,以與實施例1相同之方式製作偏光板。再者,所獲得之易接著劑組合物於85℃下之儲存模數為4.5×107 Pa。又,於交聯劑存在下以80℃、500小時之條件進行加熱後之易接著劑組合物於85℃下的儲存模數為8.8×108 Pa。 <比較例4> 以聚烯烴系成分與聚乙烯醇系成分之質量比成為0:10之方式不使用改性聚烯烴樹脂而將聚乙烯醇系樹脂與純水進行混合而獲得易接著劑組合物,除此以外,以與實施例1相同之方式製作偏光板。再者,所獲得之易接著劑組合物於85℃下之儲存模數為2.3×108 Pa。又,於交聯劑存在下以80℃、500小時之條件進行加熱後之易接著劑組合物於85℃下的儲存模數為9.5×109 Pa。 <比較例5> 將10重量份之水系聚胺基甲酸酯樹脂(第一工業製藥(股)製造,商品名「Superflex 210」)、1.8重量份之㗁唑啉系交聯劑(日本觸媒(股)製造,商品名「Epocros WS700」)、及83重量份之純水進行混合而獲得易接著劑組合物,除此以外,以與實施例1相同之方式製作偏光板。所獲得之易接著劑組合物於85℃下之儲存模數為2.0×108 Pa。又,以80℃、500小時之條件進行加熱後之易接著劑組合物於85℃下的儲存模數為4.1×108 Pa。 (評價) 對上述實施例及比較例進行以下之評價。將評價結果示於表1。 (1)初始密接性試驗 將黏著劑塗佈於上述實施例及比較例中所獲得之偏光板之相位差層側並貼合於玻璃基板,從而製作測定用樣品。利用截切刀於該測定用樣品之偏光元件與易接著層之間切出切口,將偏光元件及保護膜以相對於相位差層之表面呈角度90°之方式豎立,利用角度自如型黏著/皮膜剝離解析裝置(共和界面化學股份有限公司製造,商品名「VPA-2」)對以剝離速度3000 mm/min剝離時所需之力(剝離力:N/15 mm)進行測定。再者,為了作為偏光板加以實用,剝離力必須為1 N/15 mm以上。 (2)加濕試驗後之偏光元件之剝落 以60℃、95%RH將上述實施例及比較例中所獲得之偏光板加濕500小時後,使用光學顯微鏡觀察偏光元件之剝落之有無。 (3)熱休克試驗後之偏光元件之龜裂 於-40℃與85℃之溫度環境下分別將上述實施例及比較例中所獲得之偏光板保持30分鐘,重複該操作300個週期,之後使用光學顯微鏡觀察偏光元件之龜裂之有無。 (4)加熱試驗後之偏光元件之剝落 以80℃對上述實施例及比較例中所獲得之偏光板加熱500小時後,使用光學顯微鏡觀察偏光元件之剝落之有無。 [表1]
Figure 106128547-A0304-0001
[產業上之可利用性] 本發明之偏光板例如適宜用於圖像顯示裝置。具體而言,適宜用作液晶電視、液晶顯示器、行動電話、數位相機、攝錄影機、攜帶型遊戲機、汽車導航、影印機、印表機、傳真機、時鐘、微波爐等液晶面板、有機EL裝置之抗反射板等。Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments. (Definition of terms and symbols) The definitions of terms and symbols in this manual are as follows. (1) Refractive index (nx, ny, nz) "nx" is the refractive index in the direction in which the in-plane refractive index becomes the largest (ie, the direction of the slow axis), and "ny" is the in-plane perpendicular to the slow axis The refractive index in the direction (ie, the direction of the advancing axis), and "nz" is the refractive index in the thickness direction. (2) In-plane retardation (Re) "Re(λ)" is the in-plane retardation measured with light of wavelength λ nm at 23°C. Re(λ) is calculated by the formula: Re=(nx-ny)×d when the thickness of the layer (film) is d (nm). For example, "Re(550)" is the in-plane phase difference measured with light with a wavelength of 550 nm at 23°C. A. Polarizing plate The polarizing plate of the present invention has a resin layer and a polarizing element, and the resin layer and the polarizing element are connected via an easy-to-bond layer. The storage modulus of the easy bonding layer of the polarizing plate at 85°C is 1.0×10 6 Pa or more. Thereby, it is possible to produce a polarizing plate with excellent adhesion between the resin layer and the polarizing element, and furthermore, it is possible to suppress the occurrence of cracks in the polarizing element. In one embodiment of the present invention, the above-mentioned resin layer is a retardation layer having an in-plane retardation. In another embodiment of the present invention, the above-mentioned resin layer may also be a protective layer of the polarizing element (the protective film or the inner protective layer described below). Hereinafter, the polarizing plate in which the resin layer is a retardation layer is mainly demonstrated. Fig. 1 is a cross-sectional view of a polarizing plate according to an embodiment of the present invention. As shown in FIG. 1, the polarizing plate 10 has a retardation layer 3 as a resin layer, and the retardation layer 3 and the polarizing element 1 are laminated via the easy-adhesive layer 2. In addition, the polarizing plate 10 may have a protective film (not shown) on the side of the polarizing element 1 opposite to the retardation layer 3. B. Polarizing element As the polarizing element 1, any suitable polarizing element can be used. For example, the resin film forming the polarizing element may be a single-layer resin film or a laminate of two or more layers. Specific examples of the polarizing element composed of a single-layer resin film include: hydrophilicity such as polyvinyl alcohol (PVA)-based film, partially formalized PVA-based film, ethylene-vinyl acetate copolymer-based partially saponified film, etc. Polymer films are those made by dyeing and stretching using dichroic substances such as iodine or dichroic dyes; polyene-based alignment films such as dehydrated PVA or dehydrochlorinated polyvinyl chloride. In terms of excellent optical properties, it is preferable to use a polarizing element obtained by dyeing a PVA-based film with iodine and performing uniaxial stretching. The above-mentioned dyeing with iodine is performed, for example, by immersing the PVA-based film in an iodine aqueous solution. The stretching magnification of the above-mentioned uniaxial stretching is preferably 3 to 7 times. Stretching can be done after dyeing, or it can be done while dyeing. Also, dyeing may be performed after stretching. If necessary, the PVA-based film is subjected to swelling treatment, cross-linking treatment, washing treatment, drying treatment, etc. For example, by immersing the PVA-based film in water for washing before dyeing, not only can the dirt or anti-blocking agent on the surface of the PVA-based film be cleaned, but also the PVA-based film can be swollen to prevent uneven dyeing. As a specific example of a polarizing element obtained by using a laminate, a laminate of a resin substrate and a PVA-based resin layer (PVA-based resin film) laminated on the resin substrate, or a resin substrate and coating formation can be cited The polarizing element obtained by the laminate of the PVA-based resin layer of the resin substrate. A polarizing element obtained by using a laminate of a resin substrate and a PVA-based resin layer formed on the resin substrate can be produced, for example, by applying a PVA-based resin solution to the resin substrate and making it The PVA-based resin layer is formed on the resin substrate by drying to obtain a laminate of the resin substrate and the PVA-based resin layer; the laminate is stretched and dyed to form the PVA-based resin layer as a polarizing element. In this embodiment, stretching typically includes stretching the laminate by immersing the laminate in an aqueous boric acid solution. Furthermore, the stretching may be further included in the air stretching of the laminated body at a high temperature (for example, 95° C. or higher) before stretching in the boric acid aqueous solution, if necessary. The obtained resin substrate/polarizing element laminate can be used directly (that is, the resin substrate can be used as the inner protective layer between the retardation layer and the polarizing element), or the resin substrate (resin layer) It is peeled from the laminate of the resin substrate/polarizing element, and any appropriate protective layer according to the purpose is laminated on the peeling surface as an inner protective layer. The details of the manufacturing method of such a polarizing element are described in, for example, Japanese Patent Laid-Open No. 2012-73580. All the descriptions in this gazette are cited in this specification as a reference. Furthermore, when a resin substrate is used as the inner protective layer provided between the retardation layer and the polarizing element, an easy-adhesion layer may also be provided between the resin substrate and the PVA-based resin layer. In addition, when the resin substrate is peeled off, and any suitable protective layer according to the purpose is laminated on the peeling surface as the inner protective layer, an easy-adhesion layer may be provided between the inner protective layer and the polarizing element. The thickness of the polarizing element can be appropriately designed according to the purpose and application, and is preferably 3 μm to 25 μm. The polarizing element preferably exhibits absorption dichroism at any wavelength from 380 nm to 780 nm. The monomer transmittance of the polarizing element is preferably 42.0%-46.0%, more preferably 44.5%-46.0%. The degree of polarization of the polarizing element is preferably 97.0% or more, more preferably 99.0% or more, and still more preferably 99.9% or more. C. Retardation layer The retardation layer 3 can be composed of a retardation film having any appropriate optical properties and/or mechanical properties according to the purpose. The retardation layer 3 typically has a slow axis. In one embodiment, the angle θ formed by the slow axis of the retardation layer 3 and the absorption axis of the polarizing element 1 is preferably 38°~52°, more preferably 42°~48°, and still more preferably about 45° °. If the angle θ is in such a range, by using the retardation layer 3 as a λ/4 plate, a polarizing plate 10 having very excellent circular polarization characteristics can be obtained. The retardation layer 3 preferably exhibits the relationship of refractive index characteristics of nx>ny≧nz. The retardation layer 3 is typically provided for the purpose of imparting anti-reflection properties to the polarizing plate, and in one embodiment, it can function as a λ/4 plate. In this case, the in-plane retardation Re(550) of the retardation layer 3 is preferably 80 nm to 200 nm, more preferably 100 nm to 180 nm, and still more preferably 110 nm to 170 nm. Furthermore, "ny=nz" here includes not only the case where ny and nz are completely equal, but also the case where they are substantially equal. Therefore, in the range which does not impair the effect of this invention, there may be a case where ny<nz. The birefringence Δn xy of the retardation layer 3 is, for example, 0.0025 or more, preferably 0.0028 or more. On the other hand, the upper limit of the birefringence Δn xy is , for example, 0.0060, preferably 0.0050. By optimizing the birefringence to such a range, it is possible to obtain the retardation layer 3 that is thinner and has desired optical characteristics. The Nz coefficient of the retardation layer 3 is preferably 0.9 to 3, more preferably 0.9 to 2.5, still more preferably 0.9 to 1.5, and particularly preferably 0.9 to 1.3. By satisfying this relationship, when the obtained polarizing plate is used in an image display device, a very excellent reflection hue can be achieved. The retardation layer 3 can express the reverse wavelength dispersion characteristic that the retardation value increases in accordance with the wavelength of the measurement light, and it can also express the positive wavelength dispersion characteristic that the retardation value becomes smaller corresponding to the wavelength of the measurement light, and it can also express the retardation. A flat wavelength dispersion characteristic whose value hardly changes due to the wavelength of the measured light. In one embodiment, the retardation layer 3 exhibits reverse wavelength dispersion characteristics. In this case, the retardation layer 3 satisfies the relationship of Re(450)<Re(550), and the Re(450)/Re(550) of the retardation layer 3 is preferably 0.8 or more and less than 1, more preferably 0.8 Above and below 0.95. With this structure, very excellent anti-reflection characteristics can be realized. In another embodiment, the retardation layer 3 exhibits flat wavelength dispersion characteristics. In this case, the Re(450)/Re(550) of the retardation layer 3 is preferably 0.99-1.03, and the Re(650)/Re(550) is preferably 0.98-1.02. In this case, the retardation layer 3 may have a laminated structure. Specifically, by arranging a retardation film that functions as a λ/2 plate and a retardation film that functions as a λ/4 plate at a specific axis angle (for example, 50° to 70°, preferably about 60°) , Can obtain characteristics close to the ideal reverse wavelength dispersion characteristics, and as a result can achieve very excellent anti-reflection characteristics. The water absorption rate of the retardation layer 3 is 3% or less, preferably 2.5% or less, and more preferably 2% or less. By satisfying such a water absorption rate, it is possible to suppress changes in the display characteristics over time. In addition, the water absorption rate can be determined in accordance with JIS K 7209. 3 the absolute value of the retardation layer comprising a photoelastic coefficient is preferably 2 × 10 -11 m 2 / N or less, more preferably 2.0 × 10 -13 m 2 /N~1.6×10 -11 m 2 / N of the resin. If the absolute value of the photoelastic coefficient is in this range, the phase difference will not change easily when the shrinkage stress during heating occurs. As a result, the thermal unevenness of the obtained image display device can be prevented satisfactorily. The thickness of the retardation layer 3 is, for example, 70 μm or less, preferably 40 μm to 60 μm. If it is such a thickness, it can provide proper mechanical strength as a protective layer of a polarizing element. The retardation layer 3 may be composed of any appropriate resin film that can satisfy the above-mentioned characteristics. Representative examples of such resins include: cyclic olefin resins, polycarbonate resins, cellulose resins, polyester resins, polyvinyl alcohol resins, polyamide resins, and polyimide resins. Resin, polyether resin, polystyrene resin, acrylic resin. When the retardation layer 3 is composed of a resin film exhibiting reverse wavelength dispersion characteristics, a polycarbonate resin can be suitably used. As the aforementioned polycarbonate resin, any appropriate polycarbonate resin can be used as long as the effects of the present invention are obtained. Preferably, the polycarbonate resin comprises: a structural unit derived from a stilbene-based dihydroxy compound; a structural unit derived from an isosorbide-based dihydroxy compound; and a structural unit derived from alicyclic diol, alicyclic dimethanol, 2. A structural unit of at least one dihydroxy compound in the group consisting of two, three or polyethylene glycol, and alkylene glycol or spirodiol. Preferably, the polycarbonate resin contains structural units derived from stilbene-based dihydroxy compounds, structural units derived from isosorbide-based dihydroxy compounds, and structural units derived from alicyclic dimethanol and/or derived from two, Tri-or polyethylene glycol structural unit; further preferably comprising structural units derived from stilbene-based dihydroxy compounds, structural units derived from isosorbide-based dihydroxy compounds, and structural units derived from di-, tri-, or polyethylene glycols The structural unit. The polycarbonate resin may optionally contain structural units derived from other dihydroxy compounds. In addition, the details of the polycarbonate resin that can be suitably used in the present invention are described in, for example, Japanese Patent Laid-Open No. 2014-10291 and Japanese Patent Laid-Open No. 2014-26266, and this description is incorporated into this specification by reference. middle. In one embodiment, a polycarbonate resin containing a unit structure derived from a dihydroxy compound represented by the following general formula (1) can be used. [化1]
Figure 02_image001
(In the above general formula (1), R 1 to R 4 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbons, a substituted or unsubstituted carbon number 6 to carbon A cycloalkyl group of 20, or a substituted or unsubstituted aryl group of 6 to 20 carbons, X represents a substituted or unsubstituted alkylene of 2 to 10 carbons, substituted or For unsubstituted cycloalkylene groups having 6 to 20 carbon atoms, or substituted or unsubstituted arylalkylene groups having 6 to 20 carbon atoms, m and n are each independently an integer of 0 to 5) as Specific examples of the dihydroxy compound represented by the general formula (1) include: 9,9-bis(4-hydroxyphenyl)sulfuron, 9,9-bis(4-hydroxy-3-methylphenyl)sulfuron , 9,9-bis(4-hydroxy-3-ethylphenyl) pyridium, 9,9-bis(4-hydroxy-3-n-propylphenyl) pyridium, 9,9-bis(4-hydroxy- 3-isopropylphenyl) pyrene, 9,9-bis(4-hydroxy-3-n-butylphenyl) pyrene, 9,9-bis(4-hydroxy-3-second-butylphenyl) pyrene , 9,9-bis(4-hydroxy-3-tert-butylphenyl) pyridium, 9,9-bis(4-hydroxy-3-cyclohexylphenyl) pyridium, 9,9-bis(4-hydroxyl -3-Phenylphenyl) pyridium, 9,9-bis(4-(2-hydroxyethoxy)phenyl)pyridium, 9,9-bis(4-(2-hydroxyethoxy)-3- Methylphenyl) quince, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl) quince, 9,9-bis(4-(2-hydroxyethoxy) -3-isobutylphenyl) quince, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl) quince, 9,9-bis(4-(2- Hydroxyethoxy)-3-cyclohexylphenyl)sulfuron, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)sulfuron, 9,9-bis(4-( 2-Hydroxyethoxy)-3,5-Dimethylphenyl)茀, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butyl-6-methylphenyl ) 茀, 9,9-bis(4-(3-hydroxy-2,2-dimethylpropoxy)phenyl) 茀, etc. In addition to the structural units derived from the above-mentioned dihydroxy compounds, the polycarbonate resins may also contain isosorbide, isomannide, isoidide, spirodiol, diethylene glycol, and dihydroxy compounds. The structural unit of ethylene glycol (DEG), triethylene glycol (TEG), polyethylene glycol (PEG), bisphenols and other dihydroxy compounds. The details of the polycarbonate resin containing a structural unit derived from a dihydroxy compound are described in, for example, Japanese Patent No. 5204200, Japanese Patent Laid-Open No. 2012-67300, Japanese Patent No. 3325560, WO2014/061677, and the like. The description of this patent document is cited in this specification as a reference. In one embodiment, a polycarbonate resin containing oligomeric fluoride structural units can be used. Examples of the polycarbonate resin containing an oligomeric fluoride structural unit include a resin containing a structural unit represented by the following general formula (2) and/or a structural unit represented by the following general formula (3).
Figure 02_image003
(In the above general formula (2) and the above general formula (3), R 5 and R 6 are each independently a direct bond, a substituted or unsubstituted alkylene group with 1 to 4 carbon atoms (preferably on the main chain) R 7 is a direct bond, a substituted or unsubstituted alkylene group with 1 to 4 carbon atoms (preferably one with a carbon number of 1 to 2 in the main chain). Alkylene). R 8 to R 13 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 (preferably 1 to 4, more preferably 1 to 2) carbon atoms, substituted or Unsubstituted aryl groups with 4 to 10 carbons (preferably 4 to 8, more preferably 4 to 7), substituted or unsubstituted carbons 1 to 10 (preferably 1 to 4, more preferably 1~2) acyl group, substituted or unsubstituted alkoxy group with 1~10 (preferably 1~4, more preferably 1~2) carbon number, substituted or unsubstituted carbon number 1 to 10 (preferably 1 to 4, more preferably 1 to 2) aryloxy group, substituted or unsubstituted carbon number 1 to 10 (preferably 1 to 4, more preferably 1 to 2) The acyloxy group, substituted or unsubstituted amine group, substituted or unsubstituted vinyl group with 1 to 10 (preferably 1 to 4) carbons, substituted or unsubstituted carbon number from 1 to 10 (preferably 1 to 4) ethynyl group, substituted sulfur atom, substituted silicon atom, halogen atom, nitro group, or cyano group. At least two adjacent ones of R 8 to R 13 Groups can also be bonded to each other to form a ring) In one embodiment, the sulphuric acid ring contained in the oligomeric sulphuric acid structural unit has a structure in which all of R 8 to R 13 are hydrogen atoms, or R 8 and/or R 13 are Any one selected from the group consisting of a halogen atom, an acyl group, a nitro group, a cyano group, and a sulfo group, wherein R 9 to R 12 are hydrogen atoms. The details of the polycarbonate-based resin containing the oligomeric fluoride structural unit are described in, for example, Japanese Patent Laid-Open No. 2015-212816 and the like. The description of this patent document is cited in this specification as a reference. The glass transition temperature of the polycarbonate resin is preferably 110°C or higher and 150°C or lower, more preferably 120°C or higher and 140°C or lower. If the glass transition temperature is too low, the heat resistance tends to deteriorate, which may cause dimensional changes after the film is formed, and may also degrade the image quality of the obtained image display device. If the glass transition temperature is too high, the forming stability during film forming may deteriorate, and the transparency of the film may be impaired. In addition, the glass transition temperature is calculated|required in accordance with JIS K 7121 (1987). The molecular weight of the above polycarbonate resin can be represented by reduced viscosity. The reduced viscosity is determined by using dichloromethane as the solvent to accurately prepare the polycarbonate concentration to 0.6 g/dL and using a Ubbelohde viscosity tube at a temperature of 20.0℃±0.1℃. The lower limit of the concentrated viscosity is generally preferably 0.30 dL/g, more preferably 0.35 dL/g or more. The upper limit of the reduced viscosity is generally preferably 1.20 dL/g, more preferably 1.00 dL/g, and still more preferably 0.80 dL/g. If the reduced viscosity is less than the above-mentioned lower limit, there is a problem that the mechanical strength of the molded product becomes small. On the other hand, if the reduced viscosity is greater than the above upper limit, there may be a problem of a decrease in fluidity during molding, resulting in a decrease in productivity or moldability. A commercially available film can also be used as the polycarbonate resin film. Specific examples of commercially available products include: "PURE-ACE WR-S", "PURE-ACE WR-W", "PURE-ACE WR-M" manufactured by Teijin, and products manufactured by Nitto Denko Corporation The name is "NRF". The retardation layer 3 is obtained, for example, by stretching a film formed of the above-mentioned polycarbonate resin. As a method of forming a film from a polycarbonate-based resin, any appropriate forming method can be adopted. Specific examples include: compression molding method, transfer molding method, injection molding method, extrusion molding method, blow molding method, powder molding method, FRP (Fiber Reinforced Polymer, fiber reinforced composite material) molding method, cast coating method (For example, film casting method), calendering method, hot pressing method, etc. Preferably, it is an extrusion molding method or a cast coating method. The reason is that the smoothness of the obtained film can be improved, and good optical uniformity can be obtained. The molding conditions can be appropriately set according to the composition or type of the resin used, the characteristics desired for the retardation layer 3, and the like. Furthermore, as described above, regarding polycarbonate-based resins, many film products are commercially available, so the commercially available film can also be directly used for the stretching treatment. The thickness of the resin film (unstretched film) can be set to any appropriate value according to the desired thickness of the retardation layer, the desired optical properties, the following stretching conditions, and the like. It is preferably 50 μm to 300 μm. Any appropriate stretching method and stretching conditions (e.g. stretching temperature, stretching magnification, stretching direction) can be used for the above-mentioned stretching. Specifically, various extension methods such as free end extension, fixed end extension, free end contraction, and fixed end contraction can be used alone or simultaneously or sequentially. Regarding the extension direction, it may be performed in various directions or dimensions such as the length direction, the width direction, the thickness direction, and the oblique direction. The stretching temperature is preferably Tg-30°C to Tg+60°C relative to the glass transition temperature (Tg) of the resin film, more preferably Tg-10°C to Tg+50°C. By appropriately selecting the above-mentioned stretching method and stretching conditions, a retardation film having the above-mentioned desired optical characteristics (for example, refractive index characteristics, in-plane retardation, and Nz coefficient) can be obtained. In one embodiment, the retardation film is produced by uniaxially stretching a resin film or uniaxially stretching a fixed end. As a specific example of the uniaxial extension of the fixed end, a method of extending the resin film in the width direction (lateral direction) while moving the resin film in the longitudinal direction can be cited. The stretching ratio is preferably 1.1 to 3.5 times. In another embodiment, the retardation film can be produced by continuously extending a long resin film obliquely in the direction of the above-mentioned angle θ with respect to the longitudinal direction. By adopting oblique stretching, a long stretched film having an alignment angle of angle θ (the lagging axis in the direction of angle θ) with respect to the longitudinal direction of the film is obtained. The roll-to-roll type can simplify the manufacturing steps. Furthermore, the angle θ may be the angle formed by the absorption axis of the polarizing element in the polarizer and the retardation axis of the retardation layer. The angle θ is as described above, and is preferably 38° to 52°, more preferably 42° to 48°, and still more preferably about 45°. D. Easy-adhesive layer Easy-adhesive layer 2 is provided on the surface of the phase difference layer 3 on the side of the polarizing element 1. The polarizing plate 10 is typically manufactured by bonding the retardation layer 3 on which the easily bonding layer 2 is formed on the surface and the polarizing element through an adhesive. As mentioned above, the storage modulus of the easy bonding layer 2 at 85°C is 1.0×10 6 Pa to 1.0×10 7 Pa. The storage modulus of the easy bonding layer 2 at 85° C. is preferably 2.0×10 6 Pa to 7.0×10 6 Pa. Thereby, it is possible to produce the polarizing plate 10 having excellent adhesion between the retardation layer 3 and the polarizing element 1 and further suppress the occurrence of cracks in the polarizing element 1. A specific description will be given below. Because the polarizing plate is used in a heated environment, the entire resin layer expands and the polarizing element shrinks, so there is a case of applying shear to the easy-to-bond layer. When the storage modulus of the easy-adhesive layer at 85°C does not reach 1.0×10 6 Pa, the easy-adhesive layer is soft and deforms relatively large with respect to the applied stress. Therefore, due to the application of shear to the easy-to-adhesive layer, there are cases in which the adhesion at the interface with the polarizing element 1 decreases, or the adhesion of the easy-to-adhesive layer is broken. Especially when the easy-to-adhesive layer at the interface with the polarizing element is peeled off, the polarizing element is exposed, which may cause cracks in the polarizing element. Furthermore, when the storage modulus of the easy-adhesive layer at 85° C. does not reach 1.0×10 6 Pa, there is a case where the progress of micro cracks generated by the polarizing element cannot be suppressed. When the storage modulus of the easy-adhesive layer at 85°C is greater than 1.0×10 7 Pa, the easy-adhesive layer is brittle, and the stress-relieving function of the easy-adhesive layer is insufficient. Therefore, due to the application of shear to the easy-to-bond layer, the adhesion between the retardation layer and the polarizing element is reduced, and the failure of the retardation layer and/or the cohesion failure of the easy-to-bond layer occurs. . In this regard, by setting the storage modulus of the easily bonding layer 2 at 85°C to 1.0×10 6 Pa to 1.0×10 7 Pa, it is possible to obtain excellent adhesion between the retardation layer 3 and the polarizing element 1 and suppress The polarizing plate 10 for the destruction of the retardation layer 3 and/or the aggregation destruction of the easy-to-bond layer 2. The storage modulus of the easily bonding layer 2 at 85°C after heating at 80°C for 500 hours in the presence of a crosslinking agent is preferably 1.0×10 6 Pa to 1.0×10 7 Pa. Preferably, the easy-adhesive layer 2 has a storage modulus of 1.0×10 6 Pa~1.0×10 7 Pa at 80° C. and at 85° C. before 500 hours of heating in the presence of a cross-linking agent. The storage modulus at 85°C after heating at 80°C for 500 hours is 1.0×10 6 Pa~1.0×10 7 Pa. That is, it is preferable that the change in the storage modulus of the easily bonding layer 2 at 85°C before and after heating at 80°C for 500 hours in the presence of a crosslinking agent is 9.0×10 6 Pa or less. When bonding the retardation layer 3 to the polarizing element 1 via an adhesive mainly composed of polyvinyl alcohol-based resins, when the previous easy-to-bond layer containing polyvinyl alcohol-based components is used, the adhesive contained The influence of the linking agent leads to the progress of crosslinking of the polyvinyl alcohol-based components contained in the easy-to-bond layer. As a result, the storage modulus of the easy-to-bond layer increases with time, and the adhesion between the retardation layer and the polarizing element may decrease . In this regard, by using the easily bonding layer 2 whose storage modulus at 85°C before and after heating at 80°C for 500 hours in the presence of a crosslinking agent is 9.0×10 6 Pa or less, the retardation layer is reduced 3 The storage modulus of the easy bonding layer 2 after being bonded to the polarizing element 1 increases with time, and it is possible to suppress the deterioration of the adhesion between the retardation layer 3 and the polarizing element 1. As the constituent material of the easily bonding layer 2, any suitable material that can make the storage modulus at 85°C within the above-mentioned range can be used. The easy-adhesive layer 2 typically contains a polyolefin-based component and a polyvinyl alcohol-based component. In this case, the mass ratio of the polyolefin-based component and the polyvinyl alcohol-based component is preferably 86:14 to 99:1, and more preferably 90:10 to 98:2. By adjusting the mass ratio of polyolefin-based components and polyvinyl alcohol-based components, the storage modulus of the easy-adhesive layer 2 (essentially the easy-adhesive composition forming the easy-adhesive layer 2) at 85°C can be controlled. The easy-adhesive layer 2 is typically formed by applying an easy-adhesive composition to one side of the retardation layer 3 and drying it. As the coating method of the constituent material of the easy-to-bond layer, any appropriate method can be adopted. For example, a bar coating method, a roll coating method, a gravure coating method, a rod coating method, a slot coating method, a curtain coating method, a jet coating method, etc. can be mentioned. The drying temperature is typically 50°C or higher, preferably 70°C or higher, and more preferably 90°C or higher. By setting the drying temperature in such a range, it is possible to provide a polarizing plate having excellent color resistance (especially under high temperature and high humidity). The drying temperature is preferably 120°C or lower, and more preferably 100°C or lower. The thickness of the easy bonding layer 2 can be set to any appropriate value. The thickness of the easy bonding layer 2 is preferably 500 nm to 1 μm, and more preferably 700 nm to 800 nm. By setting it to such a range, the adhesiveness with the polarizing element 1 can be excellent, and the phase difference can be suppressed in the easy-adhesive layer 2. E. Adhesive layer The retardation layer 3 and the polarizing element 1 are typically bonded via an adhesive layer formed on the easy-adhesive layer 2. The adhesive layer can be composed of any suitable adhesive. The thickness of the adhesive layer is preferably 10 nm to 300 nm, more preferably 10 nm to 200 nm, and particularly preferably 20 nm to 150 nm. The adhesive preferably has transparency and optical isotropy. As the form of the adhesive, any appropriate form can be adopted. Specific examples include aqueous adhesives, solvent-based adhesives, emulsion-based adhesives, solvent-free adhesives, active energy ray-curable adhesives, and thermosetting adhesives. Examples of the active energy ray curable adhesive include electron beam curable adhesives, ultraviolet curable adhesives, and visible light curable adhesives. Aqueous adhesives can be used appropriately. Specific examples of the aqueous adhesive include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, ethylene-based emulsions, water-based polyurethanes, and water-based polyesters. A polyvinyl alcohol-based adhesive such as polyvinyl alcohol or modified polyvinyl alcohol is preferable, and an adhesive mainly composed of polyvinyl alcohol having an acetyl acetyl group is more preferable. Such an adhesive is commercially available, and as a specific example of a commercially available product, a product made by Nippon Synthetic Chemical Co., Ltd. (trade name "GOHSEFIMER Z") can be cited. F. Protective film The protective film is formed of any suitable film that can be used as a protective film for polarizing elements. Specific examples of the material that becomes the main component of the film include: cellulose resins such as triacetyl cellulose (TAC); or polyester, polyvinyl alcohol, polycarbonate, polyamide, Transparent resins such as polyimide-based, polyether-based, poly-based, polystyrene, polynorbornene, polyolefin, (meth)acrylic, acetate, etc. In addition, examples include thermosetting resins such as (meth)acrylic, urethane, (meth)acrylate urethane, epoxy, and silicone resins, or ultraviolet curing resins, etc. . In addition, for example, glassy polymers such as silicone polymers can also be cited. In addition, the polymer film described in Japanese Patent Application Laid-Open No. 2001-343529 (WO01/37007) can also be used. As the material of the film, for example, a resin composition containing a thermoplastic resin having a substituted or unsubstituted imine group in the side chain, and a thermoplastic resin having a substituted or unsubstituted phenyl group and a nitrile group in the side chain can be used For example, a resin composition having an alternating copolymer containing isobutylene and N-methylmaleimide and an acrylonitrile·styrene copolymer can be cited. The polymer film may be, for example, an extrusion molded product of the above-mentioned resin composition. The polarizing plate of the present invention is typically arranged on the viewing side of the image display device, and the protective film is typically arranged on the viewing side. Therefore, surface treatments such as hard coating treatment, anti-reflection treatment, anti-sticking treatment, and anti-glare treatment can also be applied to the protective film as needed. Regarding the thickness of the protective film, any appropriate thickness can be adopted as long as the effect of the present invention is obtained. The thickness of the protective film is, for example, 10 μm to 100 μm, preferably 30 μm to 90 μm. Furthermore, in the case of surface treatment, the thickness of the protective film is the thickness including the thickness of the surface treatment layer. G. Another protective layer In addition, the other protective layer (inner protective layer) arranged as needed is also formed of any suitable film that can be used as a protective layer of a polarizing element. The material that becomes the main component of the film is as described in the above item F regarding the protective film. The thickness of the inner protective layer is, for example, 15 μm to 35 μm, preferably 20 μm to 30 μm. The inner protective layer is preferably optically isotropic. In this specification, the so-called "optical isotropy" means that the in-plane retardation Re (550) is 0 nm to 10 nm, and the thickness direction retardation Rth (550) is -10 nm to +10 nm. H. Others As described above, as an embodiment of the present invention, the polarizing plate 10 in which the above-mentioned resin layer is the retardation layer 3 has been described as an example, but the embodiment of the present invention is not limited to this. That is, in the polarizing plate of another embodiment of the present invention, the above-mentioned resin layer may be an inner protective layer that can be provided on the side of the retardation layer 3 of the polarizing element 1, or the polarizing element 1 and the inner side may be protected by an easy-to-bond layer. Layer then. Furthermore, in the polarizing plate of another embodiment of the present invention, the resin layer may be a protective film that can be provided on the side of the polarizing element 1 opposite to the retardation layer 3, or the polarizing element 1 and the protective film may be connected via an easy-to-bond layer. Film then. I. Display device The polarizing plate described in the above items A to H can be applied to display devices such as liquid crystal display devices and organic EL display devices. Therefore, the present invention includes a display device using the above-mentioned polarizing plate. The display device of the embodiment of the present invention includes a display element, and the polarizing plate described in the above A to H, which is arranged on the viewing side of the display element. The polarizing plate is arranged so that the retardation layer becomes the display element side. [Examples] Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited by these examples. <Example 1> 1. The polarizing element was produced in 5 baths under the following conditions (1) to (5), and a polymer film (Kuraray (Kuraray ( Strand), trade name "VF-PE#6000"), while applying tension in the length direction of the film, immerse it so that the final stretching ratio becomes 6.2 times the original length of the film. The stretched film was dried in an air-circulating drying oven at 40 degrees for 1 minute to fabricate a polarizing element. <Conditions> (1) Swelling bath: pure water at 30 degrees. (2) Dyeing bath: a 30-degree aqueous solution containing 0.035 parts by weight of iodine relative to 100 parts by weight of water and 0.2 parts by weight of potassium iodide relative to 100 parts by weight of water. (3) The first cross-linking bath: a 40-degree aqueous solution containing 3% by weight of potassium iodide and 3% by weight of boric acid. (4) The second cross-linking bath: a 60°C aqueous solution containing 5 wt% potassium iodide and 4 wt% boric acid. (5) Water bath: 25°C aqueous solution containing 3% by weight of potassium iodide. 2. Production of retardation film constituting the retardation layer (production of polycarbonate resin film) 38.06 parts by weight (0.059 mol) of bis[9-(2-phenoxycarbonylethyl)茀-9-yl] Methane, 53.73 parts by weight (0.368 mol) of isosorbide (manufactured by ROQUETTE FRERES, trade name "POLYSORB"), 9.64 parts by weight (0.067 mol) of 1,4-cyclohexanedimethanol (cis and trans mixtures) , SK Chemical Company), 81.28 parts by weight (0.379 mol) of diphenyl carbonate (manufactured by Mitsubishi Chemical Company), and 3.83×10 -4 parts by weight (2.17×10 -6 mol) of calcium acetate as a catalyst The hydrate is put into the reaction vessel, and the inside of the reaction device is replaced with nitrogen under reduced pressure. Under a nitrogen atmosphere, dissolve the raw materials while stirring at 150°C for about 10 minutes. As the first step of the reaction, the temperature was raised to 220°C over 30 minutes and reacted under normal pressure for 60 minutes. Then, the pressure was reduced from normal pressure to 13.3 kPa over a period of 60 minutes, and the pressure was maintained at 13.3 kPa for 30 minutes to extract the generated phenol to the outside of the reaction system. Then, as the second step of the reaction, the temperature of the heat medium was raised to 240°C over 15 minutes, and the pressure was reduced to below 0.10 kPa over 15 minutes, and the generated phenol was extracted out of the reaction system. After reaching a specific stirring torque, the reaction is stopped by recompressing with nitrogen to normal pressure, the resulting polyester carbonate is extruded into water, and the strands are cut to obtain polycarbonate resin pellets. (Production of retardation film) A retardation film (thickness: 57 μm, photoelastic coefficient: 16×10 -12 Pa, Re(450): 120 nm, Re) was obtained by obliquely extending the film containing the polycarbonate resin particles (550): 140 nm, Re(450)/Re(550): 0.86). At this time, the extending direction was set to 45° with respect to the longitudinal direction of the film. In addition, in order to make the obtained retardation film exhibit a retardation of λ/4, the stretching magnification is adjusted to 2 to 3 times. In addition, the stretching temperature was set to 148°C (that is, the Tg of the unstretched modified polycarbonate film + 5°C). 3. Formation of the easy-adhesive layer. 8 parts by weight of modified polyolefin resin (Unitika (stock), trade name "Arrow Base SE -1030N"), 0.9 parts by weight of polyvinyl alcohol-based resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "GOHSEFIMER Z200") aqueous solution, and 27.0 parts by weight of pure water were mixed to obtain an easy-adhesive composition. Use a dynamic viscoelasticity measuring device (manufactured by TA Instruments, trade name "RSA-G2") to set the load mode to the tensile mode, and set the heating rate to 10°C/min, frequency 1 Hz, and initial strain 0.1%. The storage modulus of the obtained easy-adhesive composition was measured. The storage modulus of the obtained easy-adhesive composition at 85°C was 2.4×10 6 Pa. In addition, the storage modulus of the easy-adhesive composition at 85°C after heating at 80°C for 500 hours in the presence of a crosslinking agent was 6.7×10 6 Pa. Use a bar coater (#6) to coat the obtained easy-adhesive composition on one side of the retardation film so that the thickness after drying becomes 500 nm. After that, the polycarbonate resin film was put into a hot air dryer (90°C), and the easy-adhesive composition was dried for about 5 minutes, thereby forming an easy-adhesive layer (thickness 500 nm) on one side of the retardation film. 4. Production of polarizing plate The polarizing element is bonded to the easy-adhesive layer of the retardation film through a water-soluble adhesive (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "GOHSEFIMER Z200") mainly composed of polyvinyl alcohol resin Form the surface. Furthermore, the polarizing element and the retardation film are bonded so that the angle formed by the absorption axis of the polarizing element and the retardation axis of the retardation film becomes 45°. Then, the TAC film (manufactured by Dainippon Printing Co., Ltd., brand name "DSG-03", thickness 70 μm) as a protective film was passed through a water-soluble adhesive (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) mainly composed of polyvinyl alcohol resin. , Trade name "GOHSEFIMER Z200") and bonded to the surface of the polarizing element on the opposite side of the retardation layer to obtain a polarizing plate. <Example 2> The modified polyolefin resin, the polyvinyl alcohol resin, and pure water were mixed so that the mass ratio of the polyolefin component to the polyvinyl alcohol component became 90:10 to obtain an easy-adhesive composition Except for this, a polarizing plate was produced in the same manner as in Example 1. Furthermore, the obtained adhesive composition has a storage modulus of 6.4×10 6 Pa at 85°C. In addition, the storage modulus at 85°C of the easy-adhesive composition after heating at 80°C for 500 hours in the presence of a crosslinking agent was 8.2×10 6 Pa. <Comparative Example 1> Modified polyolefin resin and pure water were mixed without using polyvinyl alcohol resin so that the mass ratio of polyolefin component to polyvinyl alcohol component became 10:0 to obtain an easy-adhesive combination Except for this, a polarizing plate was produced in the same manner as in Example 1. Furthermore, the storage modulus of the obtained easy-adhesive composition at 85°C was 8.8×10 5 Pa. In addition, the storage modulus at 85°C of the easy-adhesive composition after heating at 80°C for 500 hours in the presence of a crosslinking agent was 8.9×10 5 Pa. <Comparative Example 2> The modified polyolefin resin, the polyvinyl alcohol resin, and pure water were mixed so that the mass ratio of the polyolefin component to the polyvinyl alcohol component became 85:15 to obtain an easy-adhesive composition Except for this, a polarizing plate was produced in the same manner as in Example 1. Furthermore, the obtained adhesive composition has a storage modulus of 1.6×10 7 Pa at 85°C. In addition, the storage modulus of the easy-adhesive composition at 85°C after heating at 80°C for 500 hours in the presence of a crosslinking agent was 8.2×10 8 Pa. <Comparative Example 3> The modified polyolefin resin, the polyvinyl alcohol resin, and pure water were mixed so that the mass ratio of the polyolefin component to the polyvinyl alcohol component became 70:30 to obtain an easy-adhesive composition Except for this, a polarizing plate was produced in the same manner as in Example 1. Furthermore, the obtained adhesive composition has a storage modulus of 4.5×10 7 Pa at 85°C. In addition, the storage modulus of the easy-adhesive composition at 85°C after heating at 80°C for 500 hours in the presence of a crosslinking agent was 8.8×10 8 Pa. <Comparative Example 4> The polyvinyl alcohol-based resin and pure water were mixed without using modified polyolefin resin so that the mass ratio of the polyolefin-based component to the polyvinyl alcohol-based component became 0:10 to obtain an easy-adhesive combination Except for this, a polarizing plate was produced in the same manner as in Example 1. Furthermore, the obtained adhesive composition has a storage modulus of 2.3×10 8 Pa at 85°C. In addition, the storage modulus of the easy-adhesive composition at 85°C after heating at 80°C for 500 hours in the presence of a crosslinking agent was 9.5×10 9 Pa. <Comparative Example 5> 10 parts by weight of water-based polyurethane resin (manufactured by Daiichi Kogyo Co., Ltd., trade name "Superflex 210"), and 1.8 parts by weight of azoline-based crosslinking agent (Nippon Contact Except that it is manufactured by Media (Stock), trade name "Epocros WS700"), and 83 parts by weight of pure water are mixed to obtain an easy-adhesive composition, a polarizing plate is produced in the same manner as in Example 1, except that it is mixed. The storage modulus of the obtained easy-adhesive composition at 85°C was 2.0×10 8 Pa. In addition, the storage modulus of the easy-adhesive composition at 85°C after heating at 80°C for 500 hours was 4.1×10 8 Pa. (Evaluation) The following evaluations were performed on the above-mentioned Examples and Comparative Examples. The evaluation results are shown in Table 1. (1) Initial adhesion test The adhesive was applied to the retardation layer side of the polarizing plate obtained in the above-mentioned Examples and Comparative Examples and bonded to a glass substrate to prepare a sample for measurement. Use a cutter to cut an incision between the polarizing element and the easy bonding layer of the sample for measurement, and erect the polarizing element and the protective film at an angle of 90° with respect to the surface of the retardation layer, using an angle-free adhesive/film The peeling analysis device (manufactured by Kyowa Interface Chemical Co., Ltd., trade name "VPA-2") measures the force required for peeling at a peeling speed of 3000 mm/min (peeling force: N/15 mm). Furthermore, in order to be practical as a polarizing plate, the peeling force must be 1 N/15 mm or more. (2) Peeling of the polarizing element after humidification test After humidifying the polarizing plate obtained in the above-mentioned Examples and Comparative Examples at 60° C. and 95% RH for 500 hours, the presence or absence of peeling of the polarizing element was observed using an optical microscope. (3) Cracking of the polarizing element after the heat shock test. Keep the polarizing plates obtained in the above-mentioned examples and comparative examples for 30 minutes under a temperature environment of -40°C and 85°C, and repeat the operation for 300 cycles, after which Use an optical microscope to observe the presence or absence of cracks in the polarizing element. (4) Peeling of the polarizing element after the heating test After heating the polarizing plate obtained in the above examples and comparative examples at 80°C for 500 hours, the presence of peeling of the polarizing element was observed using an optical microscope. [Table 1]
Figure 106128547-A0304-0001
[Industrial Applicability] The polarizing plate of the present invention is suitable for use in, for example, image display devices. Specifically, it is suitable for LCD TVs, LCD monitors, mobile phones, digital cameras, camcorders, portable game consoles, car navigation systems, photocopiers, printers, fax machines, clocks, microwave ovens and other LCD panels, organic Anti-reflection board of EL device, etc.

1‧‧‧偏光元件2‧‧‧易接著層3‧‧‧相位差層(樹脂層)10‧‧‧偏光板1‧‧‧Polarizing element 2‧‧‧Easy bonding layer 3‧‧‧Phase difference layer (resin layer) 10‧‧‧Polarizer

圖1係本發明之一實施形態之偏光板之剖視圖。Fig. 1 is a cross-sectional view of a polarizing plate according to an embodiment of the present invention.

1‧‧‧偏光元件 1‧‧‧Polarizing element

2‧‧‧易接著層 2‧‧‧Easy bonding layer

3‧‧‧相位差層(樹脂層) 3‧‧‧Phase difference layer (resin layer)

10‧‧‧偏光板 10‧‧‧Polarizer

Claims (7)

一種偏光板,其具有樹脂層及偏光元件,且上述樹脂層與上述偏光元件係經由易接著層而積層,上述易接著層於85℃下之儲存模數為1.0×106Pa~1.0×107Pa,上述樹脂層係具有面內相位差之相位差層,上述相位差層包含聚碳酸酯系樹脂膜,上述相位差層之面內相位差Re(550)為100nm~180nm,且滿足Re(450)<Re(550)之關係;此處,Re(450)及Re(550)分別表示23℃下以波長450nm及550nm之光測得之面內相位差。 A polarizing plate having a resin layer and a polarizing element, and the resin layer and the polarizing element are laminated via an easy-to-bond layer, the storage modulus of the easy-to-bond layer at 85°C is 1.0×10 6 Pa~1.0×10 7 Pa, the resin layer is a retardation layer with in-plane retardation, the retardation layer includes a polycarbonate resin film, the in-plane retardation Re (550) of the retardation layer is 100nm~180nm, and satisfies Re The relationship of (450)<Re(550); here, Re(450) and Re(550) represent the in-plane phase difference measured with light of wavelength 450nm and 550nm at 23°C, respectively. 如請求項1之偏光板,其中上述易接著層於交聯劑存在下以80℃、500小時之條件加熱後於85℃下之儲存模數為1.0×106Pa~1.0×107Pa。 The polarizing plate of claim 1, wherein the easy-adhesive layer has a storage modulus of 1.0×10 6 Pa to 1.0×10 7 Pa after being heated at 80° C. for 500 hours in the presence of a crosslinking agent at 85° C. 如請求項1或2之偏光板,其中上述易接著層包含聚烯烴系成分及聚乙烯醇系成分。 The polarizing plate of claim 1 or 2, wherein the easily bonding layer includes a polyolefin-based component and a polyvinyl alcohol-based component. 如請求項3之偏光板,其中上述聚烯烴系成分與上述聚乙烯醇系成分之質量比為98:2~90:10。 Such as the polarizing plate of claim 3, wherein the mass ratio of the polyolefin-based component to the polyvinyl alcohol-based component is 98:2 to 90:10. 如請求項1或2之偏光板,其中上述易接著層之厚度為500nm~1μm。 Such as the polarizing plate of claim 1 or 2, wherein the thickness of the easily bonding layer is 500nm~1μm. 如請求項1或2之偏光板,其中上述易接著層與上述偏光元件係經由包含聚乙烯醇系樹脂之接著劑而貼合。 The polarizing plate of claim 1 or 2, wherein the easily bonding layer and the polarizing element are bonded via an adhesive containing a polyvinyl alcohol-based resin. 如請求項1或2之偏光板,其中上述偏光元件之吸收軸與上述相位差層之遲相軸所成之角度為38°~52°。 The polarizing plate of claim 1 or 2, wherein the angle formed by the absorption axis of the polarizing element and the late axis of the retardation layer is 38°~52°.
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