TW202129316A - Polarizing plate and phase difference layer-equipped polarizing plate, and image display device using same - Google Patents

Polarizing plate and phase difference layer-equipped polarizing plate, and image display device using same Download PDF

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TW202129316A
TW202129316A TW109137411A TW109137411A TW202129316A TW 202129316 A TW202129316 A TW 202129316A TW 109137411 A TW109137411 A TW 109137411A TW 109137411 A TW109137411 A TW 109137411A TW 202129316 A TW202129316 A TW 202129316A
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polarizing plate
iodine
polarizer
retardation layer
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TWI823029B (en
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三田聰司
村上夏紀
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日商日東電工股份有限公司
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Abstract

Provided are a thin-type polarizing plate and a phase difference layer-equipped polarizing plate that have excellent durability under a high temperature and high humidity environment. The polarizing plate according to the present invention has a polarizer, an iodine transmission suppression layer, and an adhesive layer in this order. The iodine presence index of the adhesive layer is not more than 0.050. The phase difference layer-equipped polarizing plate according to the present invention has this polarizing plate and a phase difference layer that is disposed between the polarizer and the adhesive layer. The phase difference layer is a liquid crystal compound oriented solidification layer having a circular polarization function or an elliptical polarization function.

Description

偏光板及附相位差層之偏光板以及使用該等之影像顯示裝置Polarizing plate and polarizing plate with retardation layer and image display device using them

本發明涉及偏光板及附相位差層之偏光板以及使用該等之影像顯示裝置。The present invention relates to a polarizing plate, a polarizing plate with a retardation layer, and an image display device using them.

近年來,以液晶顯示裝置及電致發光(EL)顯示裝置(例如有機EL顯示裝置、無機EL顯示裝置)為代表之影像顯示裝置急速普及。影像顯示裝置代表上係使用偏光板及相位差板。在實際應用上,廣泛使用偏光板與相位差板一體化而成的附相位差層之偏光板(例如專利文獻1),而最近隨著對於影像顯示裝置薄型化之需求增強,對於偏光板及附相位差層之偏光板的薄型化需求亦增強。但,薄型偏光板及附相位差層之偏光板卻有在高溫高濕環境下光學特性(代表上為偏光度)之變化大而耐久性不足之問題。 先前技術文獻 專利文獻In recent years, image display devices represented by liquid crystal display devices and electroluminescence (EL) display devices (for example, organic EL display devices and inorganic EL display devices) have rapidly spread. The image display device represents the use of polarizers and phase difference plates. In practical applications, polarizing plates with retardation layers formed by integrating a polarizing plate and a retardation plate are widely used (for example, Patent Document 1). Recently, as the demand for thinning of image display devices has increased, there has been an increasing demand for polarizing plates and The demand for thinner polarizers with retardation layers has also increased. However, thin polarizers and polarizers with retardation layers have the problem of large changes in optical characteristics (representatively, polarization) under high temperature and high humidity environments, and insufficient durability. Prior art literature Patent literature

專利文獻1:日本專利第3325560號公報Patent Document 1: Japanese Patent No. 3325560

發明欲解決之課題 本發明是為了解決上述以往之課題而成者,其主要目的在於提供一種在高溫高濕環境下具有優異耐久性之薄型偏光板及附相位差層之偏光板。The problem to be solved by the invention The present invention was made to solve the above-mentioned problems in the past, and its main purpose is to provide a thin polarizing plate and a polarizing plate with a retardation layer that have excellent durability in a high-temperature and high-humidity environment.

用以解決課題之手段 本發明偏光板依序具有偏光件、碘透過抑制層及黏著劑層。該黏著劑層之碘存在指數為0.050以下。 在一實施形態中,上述碘透過抑制層係樹脂之有機溶劑溶液之塗佈膜的固化物或熱硬化物。在一實施形態中,構成上述碘透過抑制層之樹脂的玻璃轉移溫度為85℃以上,且重量平均分子量Mw為25000以上。 在一實施形態中,上述碘透過抑制層係於上述偏光件與上述黏著劑層之間設有2層以上。 在一實施形態中,上述碘透過抑制層之厚度為0.05µm~10µm。 在一實施形態中,構成上述碘透過抑制層之樹脂包含藉由將單體混合物聚合而得之共聚物,且該單體混合物包含大於50重量份之(甲基)丙烯酸系單體與大於0重量份且小於50重量份之式(1)所示單體: [化學式1]

Figure 02_image001
(式中,X表示包含反應性基之官能基,且該反應性基係選自於由乙烯基、(甲基)丙烯醯基、苯乙烯基、(甲基)丙烯醯胺基、乙烯基醚基、環氧基、氧雜環丁烷基、羥基、胺基、醛基及羧基所構成群組中之至少1種反應性基,R1 及R2 分別獨立表示氫原子、可具有取代基之脂肪族烴基、可具有取代基之芳基或可具有取代基之雜環基,R1 及R2 可相互連結形成環)。 根據本發明另一面向提供一種附相位差層之偏光板。該附相位差層之偏光板具有上述偏光板及配置於上述偏光件與上述黏著劑層之間的相位差層。該相位差層係具有圓偏光機能或楕圓偏光機能之液晶化合物的定向固化層。 在一實施形態中,上述相位差層為單一層,且該相位差層的Re(550)為100nm~190nm,該相位差層之慢軸與上述偏光件之吸收軸形成之角度為40°~50°。 在一實施形態中,上述相位差層具有第1液晶化合物之定向固化層與第2液晶化合物之定向固化層的積層結構;該第1液晶化合物之定向固化層的Re(550)為200nm~300nm,且其慢軸與上述偏光件之吸收軸形成之角度為10°~20°;該第2液晶化合物之定向固化層的Re(550)為100nm~190nm,且其慢軸與該偏光件之吸收軸形成之角度為70°~80°。 在一實施形態中,上述附相位差層之偏光板的總厚度在60μm以下。 根據本發明又另一面向提供一種影像顯示裝置。該影像顯示裝置具備上述偏光板或附相位差層之偏光板。 在一實施形態中,上述影像顯示裝置係有機電致發光顯示裝置或無機電致發光顯示裝置。Means for Solving the Problem The polarizing plate of the present invention has a polarizer, an iodine permeation suppression layer, and an adhesive layer in this order. The iodine presence index of the adhesive layer is 0.050 or less. In one embodiment, the cured product or thermosetting product of the coating film of the organic solvent solution of the above-mentioned iodine permeation suppression layer resin. In one embodiment, the glass transition temperature of the resin constituting the iodine permeation suppression layer is 85° C. or higher, and the weight average molecular weight Mw is 25,000 or higher. In one embodiment, the iodine permeation suppression layer is provided with two or more layers between the polarizer and the adhesive layer. In one embodiment, the thickness of the iodine permeation suppression layer is 0.05 μm-10 μm. In one embodiment, the resin constituting the iodine permeation inhibiting layer includes a copolymer obtained by polymerizing a monomer mixture, and the monomer mixture includes more than 50 parts by weight of a (meth)acrylic monomer and more than 0 parts by weight. Parts by weight and less than 50 parts by weight of the monomer represented by formula (1): [Chemical formula 1]
Figure 02_image001
(In the formula, X represents a functional group containing a reactive group, and the reactive group is selected from the group consisting of vinyl, (meth)acryloyl, styryl, (meth)acrylamido, vinyl At least one reactive group in the group consisting of ether group, epoxy group, oxetanyl group, hydroxyl group, amino group, aldehyde group and carboxyl group, R 1 and R 2 each independently represent a hydrogen atom and may have substitution The aliphatic hydrocarbon group of the group, the aryl group which may have a substituent, or the heterocyclic group which may have a substituent, R 1 and R 2 may be connected to each other to form a ring). According to another aspect of the present invention, a polarizing plate with a retardation layer is provided. The polarizing plate with retardation layer has the polarizing plate and a retardation layer arranged between the polarizer and the adhesive layer. The retardation layer is a directional solidified layer of a liquid crystal compound with a circular polarization function or an elliptical polarization function. In one embodiment, the retardation layer is a single layer, and the Re(550) of the retardation layer is 100nm~190nm, and the angle formed by the slow axis of the retardation layer and the absorption axis of the polarizer is 40°~ 50°. In one embodiment, the above-mentioned retardation layer has a laminated structure of an oriented solidified layer of a first liquid crystal compound and an oriented solidified layer of a second liquid crystal compound; the Re(550) of the oriented solidified layer of the first liquid crystal compound is 200nm~300nm And the angle formed by the slow axis and the absorption axis of the polarizer is 10°~20°; the Re (550) of the oriented curing layer of the second liquid crystal compound is 100nm~190nm, and the slow axis and the polarizer The angle formed by the absorption axis is 70°~80°. In one embodiment, the total thickness of the polarizing plate with retardation layer is 60 μm or less. According to yet another aspect of the present invention, an image display device is provided. The image display device includes the above-mentioned polarizing plate or a polarizing plate with a retardation layer. In one embodiment, the above-mentioned image display device is an organic electroluminescence display device or an inorganic electroluminescence display device.

發明效果 根據本發明實施形態,藉由設置特定之碘透過抑制層來控制黏著劑層之碘存在指數,可實現在高溫高濕環境下具有優異耐久性之薄型偏光板及附相位差層之偏光板。本發明實施形態可使用之碘透過抑制層係樹脂之有機溶劑溶液之塗佈膜的固化物或熱硬化物,構成該碘透過抑制層之樹脂的玻璃轉移溫度為85℃以上,且重量平均分子量Mw為25000以上,並且本發明實施形態之黏著劑層的碘存在指數為0.050以下。Invention effect According to the embodiment of the present invention, by providing a specific iodine permeation suppression layer to control the iodine presence index of the adhesive layer, a thin polarizing plate with excellent durability under high temperature and high humidity environments and a polarizing plate with retardation layer can be realized. The cured product or thermosetting product of the coating film of the organic solvent solution of the iodine permeation inhibiting layer resin that can be used in the embodiment of the present invention, the glass transition temperature of the resin constituting the iodine permeation inhibiting layer is 85°C or higher, and the weight average molecular weight Mw is 25000 or more, and the iodine presence index of the adhesive layer of the embodiment of the present invention is 0.050 or less.

以下說明本發明實施形態,惟本發明不受該等實施形態限定。The following describes embodiments of the present invention, but the present invention is not limited by these embodiments.

(用語及符號之定義) 本說明書中之用語及符號之定義如下。 (1)折射率(nx、ny、nz) 「nx」為面內折射率成最大的方向(亦即慢軸方向)之折射率,「ny」為在面內與慢軸正交之方向(亦即快軸方向)之折射率,而「nz」為厚度方向之折射率。 (2)面內相位差(Re) 「Re(λ)」係於23℃下以波長λnm之光測定之面內相位差。例如,「Re(550)」係於23℃下以波長550nm之光測定之面內相位差。Re(λ)可於令層(薄膜)之厚度為d(nm)時,藉由式:Re(λ)=(nx-ny)×d求得。 (3)厚度方向之相位差(Rth) 「Rth(λ)」係於23℃下以波長λnm之光測定之厚度方向的相位差。例如,「Rth(550)」係於23℃下以波長550nm之光測定之厚度方向的相位差。Rth(λ)可於令層(薄膜)厚度為d(nm)時,藉由式:Rth(λ)=(nx-nz)×d求得。 (4)Nz係數 Nz係數可以Nz=Rth/Re求得。 (5)角度 本說明書中提及角度時,該角度包含相對於基準方向往順時針方向及逆時針方向兩者。因此,例如「45°」係指±45°。(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 where the in-plane refractive index is the largest (that is, the slow axis direction), "ny" is the refractive index in the direction orthogonal to the slow axis (that is, the fast axis direction) in the plane, and " nz" is the refractive index in the thickness direction. (2) In-plane phase difference (Re) "Re(λ)" is the in-plane phase difference measured with light of wavelength λnm at 23°C. For example, "Re(550)" is the in-plane phase difference measured with light with a wavelength of 550nm at 23°C. Re(λ) can be obtained by the formula: Re(λ)=(nx-ny)×d when the thickness of the layer (film) is d(nm). (3) Phase difference in thickness direction (Rth) "Rth(λ)" is the thickness direction retardation measured with light of wavelength λnm at 23°C. For example, "Rth(550)" is the thickness direction retardation measured with light with a wavelength of 550nm at 23°C. Rth(λ) can be obtained by formula: Rth(λ)=(nx-nz)×d when the thickness of the layer (film) is d(nm). (4) Nz coefficient The Nz coefficient can be obtained by Nz=Rth/Re. (5) Angle When referring to an angle in this specification, the angle includes both a clockwise direction and a counterclockwise direction with respect to the reference direction. Therefore, for example, "45°" means ±45°.

A.偏光板 A-1.偏光板之整體構成 圖1係本發明一實施形態之偏光板的概略截面圖。偏光板10代表上依序具有保護層12、偏光件11、碘透過抑制層40及黏著劑層30。亦可因應目的於偏光件11之與保護層12相反之側設置另一保護層(未圖示)。黏著劑層30係設置成最外層,而偏光板可貼附於影像顯示裝置(實質上為影像顯示單元)上。偏光板可在影像顯示裝置中作為視辨側偏光板來使用,亦可作為背面側偏光板來使用。A. Polarizing plate A-1. The overall composition of the polarizer Fig. 1 is a schematic cross-sectional view of a polarizing plate according to an embodiment of the present invention. The polarizer 10 has a protective layer 12, a polarizer 11, an iodine permeation suppression layer 40 and an adhesive layer 30 in this order. Another protective layer (not shown) can also be provided on the side of the polarizer 11 opposite to the protective layer 12 according to the purpose. The adhesive layer 30 is arranged as the outermost layer, and the polarizing plate can be attached to the image display device (essentially the image display unit). The polarizing plate can be used as a viewing side polarizing plate in an image display device, and can also be used as a back side polarizing plate.

本發明實施形態中,如上述於偏光件11與黏著劑層30之間設有碘透過抑制層40。碘透過抑制層代表上係樹脂之有機溶劑溶液之塗佈膜的固化物或熱硬化物。並且,構成碘透過抑制層之樹脂的玻璃轉移溫度(Tg)例如為85℃以上,且重量平均分子量Mw例如為25000以上。藉由將所述碘透過抑制層設於偏光板的預定位置,可顯著抑制在高溫高濕環境下偏光件中之碘移動至黏著劑層(最終為影像顯示裝置,實質上為影像顯示單元)。結果,可於薄型偏光板(詳細內容容後再述)實現在高溫高濕環境下優異之耐久性。並且,在將偏光板應用於影像顯示裝置之情況下,可顯著抑制影像顯示裝置之金屬構件(例如電極、感測器、配線、金屬層)之腐蝕,且可抑制在高溫高濕環境下反射率上升。此種效果為薄型偏光板特有之效果。即,本發明人等發現,關於造成薄型偏光板在高溫高濕環境下光學特性(代表上為偏光度)產生變化之要因之一的碘之移動,作為防止該碘之移動的手段,有用之方式係設置如上述之碘透過抑制層(具有特定Tg及Mw的樹脂之有機溶劑溶液之塗佈膜的固化層或熱硬化層)以使黏著劑層之碘存在指數(容後再述)為0.050以下,遂而完成本發明。並且,如後所述,碘透過抑制層可形成得非常薄,且可藉由設置碘透過抑制層來省略與視辨側相反之側的保護層,故藉由該等之加乘效果亦可有助於偏光板之進一步的薄型化。In the embodiment of the present invention, an iodine permeation suppression layer 40 is provided between the polarizer 11 and the adhesive layer 30 as described above. The iodine permeation suppression layer represents a cured product or a thermally cured product of a coating film of an organic solvent solution of the upper resin. In addition, the glass transition temperature (Tg) of the resin constituting the iodine permeation suppression layer is, for example, 85° C. or more, and the weight average molecular weight Mw is, for example, 25,000 or more. By arranging the iodine permeation suppression layer at a predetermined position of the polarizing plate, the iodine in the polarizing element can be significantly inhibited from moving to the adhesive layer under the high temperature and high humidity environment (the final image display device is essentially the image display unit) . As a result, a thin polarizer (details will be described later) can achieve excellent durability in a high temperature and high humidity environment. Moreover, when the polarizing plate is applied to the image display device, the corrosion of the metal components (such as electrodes, sensors, wiring, and metal layer) of the image display device can be significantly suppressed, and reflections under high temperature and high humidity environments can be suppressed The rate has risen. This effect is unique to thin polarizers. That is, the inventors of the present invention found that the movement of iodine, which is one of the factors that cause changes in the optical properties of a thin polarizer under a high-temperature and high-humidity environment (representatively, the degree of polarization), is useful as a means to prevent the movement of the iodine. The method is to set the above-mentioned iodine permeation suppression layer (cured layer or thermosetting layer of the coating film of the organic solvent solution of the resin with specific Tg and Mw) so that the iodine existence index of the adhesive layer (to be described later) is Below 0.050, the present invention was completed. In addition, as described later, the iodine permeation suppressing layer can be formed very thin, and the protective layer on the side opposite to the viewing side can be omitted by providing the iodine permeation suppressing layer, so the additive effect can also be achieved. Contribute to the further thinning of the polarizer.

附相位差層之偏光板中,亦可於偏光件與黏著劑層之間設置2層以上碘透過抑制層(例如圖5及圖6)。藉由附相位差層之偏光板具有2層以上碘透過抑制層,在將附相位差層之偏光板應用於影像顯示裝置時,可顯著抑制金屬構件之腐蝕。In a polarizer with a retardation layer, two or more iodine permeation suppression layers can also be provided between the polarizer and the adhesive layer (for example, FIGS. 5 and 6). Since the polarizer with retardation layer has two or more iodine transmission suppression layers, when the polarizer with retardation layer is applied to an image display device, corrosion of metal components can be significantly suppressed.

圖4所示附相位差層之偏光板中,係於偏光件與黏著劑層之間設有2層碘透過抑制層。圖5所示例中,碘透過抑制層係於偏光件11與相位差層20之間及相位差層20與黏著劑層30之間設有2層。在一實施形態中,碘透過抑制層係設置成與偏光件鄰接。在另一實施形態中,碘透過抑制層係設置成與相位差層鄰接。本說明書中「鄰接」意指不透過接著層等而直接積層。In the polarizing plate with retardation layer shown in FIG. 4, two iodine permeation suppression layers are provided between the polarizer and the adhesive layer. In the example shown in FIG. 5, the iodine permeation suppression layer is provided with two layers between the polarizer 11 and the retardation layer 20 and between the retardation layer 20 and the adhesive layer 30. In one embodiment, the iodine permeation suppression layer is provided adjacent to the polarizer. In another embodiment, the iodine permeation suppression layer is provided adjacent to the retardation layer. In this manual, "adjacent" means to directly laminate without passing through an adhesive layer or the like.

圖6所示附相位差層之偏光板中,係於偏光件與黏著劑層之間設有3層碘透過抑制層。在圖6所示例中,碘透過抑制層於偏光件11與相位差層20之間設有2層,而於相位差層20與黏著劑層30之間設有1層。偏光件11與相位差層20之間的2層碘透過抑制層之其中一者係設置成與偏光件鄰接,另一者係設置成與相位差層鄰接。In the polarizing plate with retardation layer shown in FIG. 6, three iodine permeation suppression layers are provided between the polarizer and the adhesive layer. In the example shown in FIG. 6, the iodine permeation suppression layer is provided with two layers between the polarizer 11 and the retardation layer 20, and one layer is provided between the retardation layer 20 and the adhesive layer 30. One of the two iodine penetration suppression layers between the polarizer 11 and the retardation layer 20 is arranged to be adjacent to the polarizer, and the other is arranged to be adjacent to the retardation layer.

附相位差層之偏光板中,碘透過抑制層亦可為4層以上(例如4層、5層、6層)。碘透過抑制層之數量愈多,愈可提高金屬腐蝕抑制之效果。碘透過抑制層之數量可考量成本、製造效率、附相位差層之偏光板之總厚度等來設定。In the polarizing plate with retardation layer, the iodine transmission suppression layer may be 4 or more layers (for example, 4 layers, 5 layers, and 6 layers). The greater the amount of iodine permeation inhibition layer, the more effective the metal corrosion inhibition can be improved. The number of iodine permeation suppression layers can be set in consideration of cost, manufacturing efficiency, and the total thickness of the polarizer with retardation layer.

本發明實施形態中,如上述黏著劑層30之碘存在指數為0.050以下。碘存在指數宜為0.040以下,較宜為0.030以下,更宜為0.020以下,尤宜為0.015以下。碘存在指數越小越佳,理想為零,而其下限例如可為0.001。碘存在指數係在高溫高濕環境下從偏光件移動至黏著劑層之碘的量的指標,該指數越小表示碘的移動被碘透過抑制層阻隔而偏光件中之碘量的變化越小。因此,只要碘存在指數在所述範圍內,便能抑制碘移動,而可於薄型偏光板(詳細內容容後再述)實現在高溫高濕環境下優異之耐久性。碘存在指數係對可靠性試驗(於85℃・85%RH之環境下放置240小時,之後於23℃・55%RH之環境下放置24小時)後之偏光板進行二次離子質量分析(TOF-SIMS)而求得。更詳細來說,碘存在指數可對可靠性試驗後之黏著劑層表面進行TOF-SIMS測定,從所得負二次離子中挑出源自丙烯酸(黏著劑)之C3 H3 O2 - (m/z=71)之離子強度及源自碘之I- (m/z=127)之離子強度,並用下述式算出。 碘存在指數=I- 離子強度/C3 H3 O2 - 離子強度 此外,關於黏著劑層30可採用業界周知之構成,故針對黏著劑層之詳細構成省略記載。In the embodiment of the present invention, the iodine presence index of the adhesive layer 30 as described above is 0.050 or less. The iodine presence index is preferably 0.040 or less, more preferably 0.030 or less, more preferably 0.020 or less, and particularly preferably 0.015 or less. The smaller the iodine presence index, the better, and ideally it is zero, and the lower limit thereof may be, for example, 0.001. The iodine presence index is an indicator of the amount of iodine that moves from the polarizer to the adhesive layer under a high temperature and high humidity environment. The smaller the index, the smaller the movement of iodine is blocked by the iodine permeation suppression layer, and the smaller the change in the amount of iodine in the polarizer is. . Therefore, as long as the iodine existence index is within the above range, the migration of iodine can be suppressed, and the thin polarizing plate (details will be described later) can achieve excellent durability in a high temperature and high humidity environment. The Iodine Presence Index is based on the secondary ion mass analysis (TOF) of the polarizing plate after the reliability test (placed in an environment of 85°C and 85%RH for 240 hours, and then placed in an environment of 23°C and 55%RH for 24 hours) -SIMS). More specifically, the presence of iodine index TOF-SIMS can be measured on the surface of the adhesive layer after the reliability test, pick derived from acrylic acid C (adhesive) of 3 H 3 O 2 resulting from the negative secondary ions - ( m / z = 71) and from the ionic strength of iodine I - (m / z = 127 ) of the ionic strength, and was calculated by the following formula. Iodine presence index=I - ionic strength/C 3 H 3 O 2 - ionic strength In addition, the adhesive layer 30 can have a structure known in the industry, so the detailed structure of the adhesive layer is omitted.

本發明實施形態之偏光板可為單片狀亦可為長條狀。本說明書中所謂「長條狀」意指相對於寬度而言長度足夠長的細長形狀,例如包含相對於寬度而言長度為10倍以上之細長形狀,且宜為20倍以上之細長形狀。長條狀偏光板可捲成捲狀。The polarizing plate of the embodiment of the present invention may be a single sheet or a long strip. The term "long strip" in this specification means an elongated shape having a sufficiently long length with respect to the width, and includes, for example, an elongated shape having a length of 10 times or more with respect to the width, and preferably an elongated shape having a length of 20 times or more. The long strip polarizer can be rolled into a roll.

偏光板的總厚度宜為45µm以下,較宜為40µm以下,更宜為35µm以下,尤宜為30µm以下。總厚度的下限例如可為22µm。根據本發明之實施形態,可實現如所述極薄之偏光板,並可於這種極薄之偏光板實現在高溫高濕環境下優異之耐久性。又,所述偏光板可具有極優異之可撓性及彎折耐久性。因此,所述偏光板尤可適宜應用於彎曲的影像顯示裝置及/或可彎折或可折疊之影像顯示裝置。另外,所謂偏光板的總厚度係指偏光件、保護層、碘透過抑制層及用以積層該等之接著劑層或黏著劑層的厚度之合計(即,偏光板的總厚度不包含黏著劑層30及可暫時黏附於其表面之剝離薄膜的厚度)。The total thickness of the polarizing plate should be 45 µm or less, more preferably 40 µm or less, more preferably 35 µm or less, and particularly preferably 30 µm or less. The lower limit of the total thickness may be 22 μm, for example. According to the embodiment of the present invention, an extremely thin polarizing plate as described above can be realized, and the extremely thin polarizing plate can realize excellent durability in a high temperature and high humidity environment. In addition, the polarizing plate can have extremely excellent flexibility and bending durability. Therefore, the polarizer is particularly suitable for use in curved image display devices and/or bendable or foldable image display devices. In addition, the total thickness of the polarizing plate refers to the total thickness of the polarizer, the protective layer, the iodine permeation suppression layer, and the adhesive layer or adhesive layer used to laminate them (that is, the total thickness of the polarizing plate does not include the adhesive The thickness of the layer 30 and the release film that can be temporarily adhered to its surface).

在實際應用上,黏著劑層30之表面上宜在偏光板供於使用之前暫時黏附有剝離薄膜。藉由暫時黏附剝離薄膜,可在保護黏著劑層的同時形成偏光板的捲料。In practical applications, a release film should be temporarily attached to the surface of the adhesive layer 30 before the polarizing plate is used. By temporarily adhering the release film, the roll of polarizing plate can be formed while protecting the adhesive layer.

A-2.偏光件 偏光件代表上係以含二色性物質之聚乙烯醇(PVA)系樹脂薄膜構成。偏光件的厚度宜為1µm~8µm,1µm~7µm較佳,2µm~5µm更佳。只要偏光件之厚度在所述範圍內,便可大大貢獻偏光板的薄型化。並且,在使用所述偏光件之薄型偏光板中,本發明之效果很顯著。A-2. Polarizing parts The representative of the polarizer is composed of polyvinyl alcohol (PVA) resin film containing dichroic material. The thickness of the polarizer is preferably 1µm~8µm, preferably 1µm~7µm, and more preferably 2µm~5µm. As long as the thickness of the polarizer is within the above range, it can greatly contribute to the thinning of the polarizer. Moreover, in the thin polarizing plate using the polarizer, the effect of the present invention is very significant.

偏光件的硼酸含量宜為10重量%以上,較佳為13重量%~25重量%。只要偏光件之硼酸含量在所述範圍內,便可藉由與後述碘含量之加乘效果來良好維持調整貼合時之捲曲的容易性且良好抑制加熱時之捲曲,同時改善加熱時之外觀耐久性。硼酸含量例如可由中和法使用下述式以每單位重量之偏光件所含硼酸量之形式來算出。 [數學式1]

Figure 02_image003
The boric acid content of the polarizer is preferably 10% by weight or more, preferably 13% to 25% by weight. As long as the boric acid content of the polarizer is within the above range, it is possible to maintain the ease of adjusting the curling during bonding by the additive effect of the iodine content described later, suppress curling during heating, and improve the appearance during heating. Durability. The boric acid content can be calculated as the amount of boric acid per unit weight of the polarizer by the neutralization method using the following formula. [Math 1]
Figure 02_image003

偏光件之碘含量宜為2重量%以上,較佳為2重量%~10重量%。只要偏光件之碘含量在所述範圍內,便可藉由與上述硼酸含量之加乘效果來良好維持調整貼合時之捲曲的容易性且良好抑制加熱時之捲曲,同時改善加熱時之外觀耐久性。本說明書中的「碘含量」意指偏光件(PVA系樹脂薄膜)中所含之所有碘的量。更具體而言,碘在偏光件中以碘離子(I- )、碘分子(I2 )、多碘離子(I3 - 、I5 - )等形態存在,而本說明書中的碘含量意指包含所有該等形態之碘的量。碘含量可利用例如X射線螢光分析之檢量曲線法來算出。另,多碘離子在偏光件中係在形成有PVA-碘錯合物之狀態下存在。藉由形成所述錯合物,可在可見光之波長範圍中展現吸收二色性。具體而言,PVA與三碘化物離子之錯合物(PVA・I3 - )在470nm附近具有吸光峰,而PVA與五碘化物離子之錯合物(PVA・I5 - )在600nm附近具有吸光峰。結果,多碘離子可根據其形態在可見光之寬廣範圍中吸收光。另一方面,碘離子(I- )在230nm附近具有吸光峰,其實質上與可見光之吸收無關聯。因此,在與PVA之錯合物之狀態下存在的多碘離子才主要與偏光件之吸收性能有關。The iodine content of the polarizer is preferably 2% by weight or more, preferably 2% to 10% by weight. As long as the iodine content of the polarizer is within the above range, the additive effect of the above-mentioned boric acid content can maintain the ease of adjusting the curling during bonding, suppress curling during heating, and improve the appearance during heating. Durability. The "iodine content" in this specification means the total amount of iodine contained in the polarizer (PVA-based resin film). More specifically, the iodine iodide ion (I -) is present in the form of a polarizer and the like, and the iodine content of the present specification is meant that molecular iodine (I 2), polyiodide ions (I 3 - -, I 5 ) Contains all these forms of iodine. The iodine content can be calculated by, for example, the calibration curve method of X-ray fluorescence analysis. In addition, polyiodide ions exist in a state where PVA-iodide complexes are formed in the polarizer. By forming the complex compound, it is possible to exhibit absorption dichroism in the wavelength range of visible light. Specifically, the complexes (PVA · I 3 -) PVA and tri-iodide ions having a light absorption peak around 470nm, and PVA complexes with five iodide ions (PVA · I 5 -) having in the vicinity of 600nm Absorption peak. As a result, polyiodide ions can absorb light in a wide range of visible light according to their form. On the other hand, an iodide ion (I -) having a light absorption peak around 230nm, which is associated with substantially no absorption of visible light. Therefore, the polyiodide ions present in the state of the complex with PVA are mainly related to the absorption performance of the polarizer.

偏光件宜在波長380nm~780nm的任一波長下顯示吸收二色性。偏光件之單體透射率Ts宜為40%~48%,較宜為41%~46%。偏光件的偏光度P以97.0%以上為佳,99.0%以上較佳,99.9%以上更佳。上述單體透射率代表上係使用紫外線可見光分光光度計來測定並進行視感度校正所得之Y值。上述偏光度代表上係基於使用紫外線可見光分光光度計測定並進行視感度校正所得之平行透射率Tp及正交透射率Tc,透過下述式來求得。 偏光度(%)={(Tp-Tc)/(Tp+Tc)}1/2 ×100The polarizer should exhibit absorption dichroism at any wavelength from 380nm to 780nm. The monomer transmittance Ts of the polarizer is preferably 40%~48%, more preferably 41%~46%. The degree of polarization P of the polarizer is preferably 97.0% or more, preferably 99.0% or more, and more preferably 99.9% or more. The above monomer transmittance represents the Y value obtained by measuring and calibrating the visual sensitivity using an ultraviolet-visible spectrophotometer. The above-mentioned degree of polarization is representatively calculated based on the parallel transmittance Tp and the orthogonal transmittance Tc obtained by measuring with an ultraviolet-visible light spectrophotometer and performing visual sensitivity correction, using the following equations. Polarization (%)={(Tp-Tc)/(Tp+Tc)} 1/2 ×100

偏光件在代表上可使用兩層以上之積層體來製作。使用積層體而獲得之偏光件的具體例,可舉出使用樹脂基材與塗佈形成於該樹脂基材之PVA系樹脂層的積層體而獲得之偏光件。使用樹脂基材與塗佈形成於該樹脂基材之PVA系樹脂層的積層體而獲得之偏光件,例如可透過以下方式製作: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;及,將該積層體延伸及染色以將PVA系樹脂層製成偏光件。延伸在代表上包含使積層體浸漬於硼酸水溶液中並延伸。並且視需要,延伸可更包含在硼酸水溶液中進行延伸前在高溫(例如95℃以上)下將積層體進行空中延伸。所得樹脂基材/偏光件之積層體可以直接使用(即,可將樹脂基材作為偏光件之保護層),亦可從樹脂基材/偏光件之積層體剝離樹脂基材並於該剝離面視目的積層任意適當的保護層後來使用。所述偏光件之製造方法的詳細內容記載於例如日本專利特開2012-73580號公報、日本專利第6470455號。本說明書中係援用該等公報整體之記載作為參考。The polarizer can be made by using a laminate of more than two layers. Specific examples of the polarizer obtained by using the laminate include a polarizer obtained by using a laminate of a resin substrate and a PVA-based resin layer formed on the resin substrate by coating. The polarizer 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 drying it, A PVA-based resin layer is formed on the resin substrate to obtain a laminate of the resin substrate and the PVA-based resin layer; and the laminate is extended and dyed to make the PVA-based resin layer into a polarizer. Stretching typically includes immersing the laminate in a boric acid aqueous solution and stretching. Furthermore, if necessary, stretching may further include stretching the laminated body in the air at a high temperature (for example, 95°C or higher) before stretching in a boric acid aqueous solution. The obtained resin substrate/polarizer laminate can be used directly (that is, the resin substrate can be used as a protective layer for the polarizer), or the resin substrate can be peeled from the resin substrate/polarizer laminate and placed on the peeling surface Depending on the purpose, build up any appropriate protective layer and use it later. The details of the manufacturing method of the polarizer are described in, for example, Japanese Patent Laid-Open No. 2012-73580 and Japanese Patent No. 6470455. In this manual, the entire record of these bulletins is used as a reference.

偏光件之製造方法代表上包含下列步驟:於長條狀熱塑性樹脂基材之單側形成包含鹵化物與聚乙烯醇系樹脂之聚乙烯醇系樹脂層,而製成積層體;及,對上述積層體依序施行空中輔助延伸處理、染色處理、水中延伸處理與乾燥收縮處理,該乾燥收縮處理係將上述積層體沿長邊方向輸送的同時進行加熱,藉此使其於寬度方向收縮2%以上。藉此可提供一種非常薄型且具有優異光學特性並且光學特性之參差經抑制的偏光件。亦即,藉由導入輔助延伸,即便是在將PVA塗佈於熱塑性樹脂上時仍可提升PVA之結晶性,而可達成高光學特性。又,同時事先提高PVA之定向性,可防止在之後的染色步驟或延伸步驟中浸漬於水中時,PVA之定向性降低或溶解等問題,而可達成高光學特性。並且,將PVA系樹脂層浸漬於液體中時,相較於PVA系樹脂層不含鹵化物之情況,更能抑制聚乙烯醇分子之定向紊亂及定向性之降低。藉此,可提升經由染色處理及水中延伸處理等將積層體浸漬於液體中來進行的處理步驟而得之偏光件的光學特性。並且,透過乾燥收縮處理使積層體於寬度方向上收縮,可提升光學特性。The manufacturing method of the polarizer typically includes the following steps: forming a polyvinyl alcohol-based resin layer containing a halide and a polyvinyl alcohol-based resin on one side of the elongated thermoplastic resin substrate to form a laminate; and, for the above The layered body is sequentially subjected to air-assisted stretching treatment, dyeing treatment, underwater stretching treatment and drying shrinkage treatment. The drying shrinkage treatment is to transport the above-mentioned layered body in the longitudinal direction while heating, thereby shrinking it by 2% in the width direction. above. Thereby, it is possible to provide a very thin polarizer with excellent optical characteristics and suppressed jitter in optical characteristics. That is, by introducing auxiliary extension, the crystallinity of PVA can be improved even when PVA is coated on a thermoplastic resin, and high optical properties can be achieved. In addition, at the same time, the orientation of PVA can be improved in advance to prevent problems such as degradation or dissolution of the orientation of PVA when immersed in water in the subsequent dyeing step or stretching step, and high optical properties can be achieved. In addition, when the PVA-based resin layer is immersed in a liquid, compared to the case where the PVA-based resin layer does not contain halide, it is possible to suppress the orientation disorder of the polyvinyl alcohol molecules and the decrease in orientation. Thereby, it is possible to improve the optical characteristics of the polarizer obtained by the treatment step of immersing the laminate in a liquid through dyeing treatment and underwater stretching treatment. In addition, the layered body is shrunk in the width direction through the drying shrinkage treatment, and the optical characteristics can be improved.

A-3.保護層 保護層12係以可作為偏光件之保護層使用的任意適當的薄膜形成。成為該薄膜之主成分的材料之具體例,可舉出三醋酸纖維素(TAC)等之纖維素系樹脂、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)丙烯酸系及乙酸酯系等之透明樹脂等。又,還可舉出(甲基)丙烯酸系、胺甲酸酯系、(甲基)丙烯酸胺甲酸酯系、環氧系、聚矽氧系等熱硬化型樹脂或紫外線硬化型樹脂等。其他還可舉例如矽氧烷系聚合物等之玻璃質系聚合物。並且,亦可使用日本專利特開2001-343529號公報(WO01/37007)所記載之聚合物薄膜。作為該薄膜之材料,例如可以使用含有在側鏈具有取代或非取代之醯亞胺基的熱塑性樹脂與在側鏈具有取代或非取代之苯基以及腈基的熱塑性樹脂之樹脂組成物,例如可舉出具有由異丁烯與N-甲基馬來醯亞胺構成之交替共聚物及丙烯腈-苯乙烯共聚物之樹脂組成物。該聚合物薄膜例如可為上述樹脂組成物之擠製成形物。A-3. Protective layer The protective layer 12 is formed of any suitable film that can be used as a protective layer of the polarizer. Specific examples of the material that becomes the main component of the film include cellulose resins such as cellulose triacetate (TAC), polyesters, polyvinyl alcohols, polycarbonates, polyamides, and polyamides. Transparent resins such as imine-based, polyether-based, poly-based, polystyrene, polynorbornene, polyolefin, (meth)acrylic, and acetate-based transparent resins, etc. In addition, thermosetting resins such as (meth)acrylic, urethane, (meth)acrylate urethane, epoxy, and silicone resins, or ultraviolet curable resins, etc. may also be mentioned. Other examples include glassy polymers such as silicone polymers. In addition, the polymer film described in Japanese Patent 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 iminium 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, Examples include resin compositions having alternating copolymers composed of isobutylene and N-methylmaleimide and acrylonitrile-styrene copolymers. The polymer film may be, for example, an extruded product of the above-mentioned resin composition.

偏光板在一實施形態中係配置於影像顯示裝置的視辨側,而保護層12代表上係配置於其視辨側。在所述情況下,保護層12亦可視需要施行有硬塗處理、抗反射處理、抗黏著處理、防眩處理等表面處理。並且/或者,保護層12亦可視需求施行有用以改善透過偏光太陽眼鏡視辨時之視辨性的處理(代表上為賦予(橢)圓偏光機能、賦予超高相位差)。藉由施行所述處理,即使透過偏光太陽眼鏡等偏光透鏡視辨顯示畫面時,仍可實現優異的視辨性。因此,偏光板亦可適宜用於可用於戶外之影像顯示裝置。In one embodiment, the polarizing plate is arranged on the viewing side of the image display device, and the protective layer 12 is typically arranged on the viewing side thereof. In this case, the protective layer 12 may also be subjected to surface treatments such as hard coating treatment, anti-reflection treatment, anti-adhesion treatment, and anti-glare treatment as needed. And/or, the protective layer 12 can also be processed as needed to improve the visibility through polarized sunglasses (representatively, imparting (elliptical) circular polarization function and imparting ultra-high phase difference). By performing the above processing, even when the display screen is visualized through a polarized lens such as polarized sunglasses, excellent visibility can still be achieved. Therefore, the polarizing plate can also be suitably used in image display devices that can be used outdoors.

保護層之厚度宜為10µm~50µm,較宜為10µm~30µm。另外,在施有表面處理時,外側保護層之厚度係包含表面處理層之厚度的厚度。The thickness of the protective layer should be 10µm~50µm, more preferably 10µm~30µm. In addition, when the surface treatment is applied, the thickness of the outer protective layer includes the thickness of the surface treatment layer.

A-4.碘透過抑制層 碘透過抑制層如上述,係樹脂之有機溶劑溶液之塗佈膜的固化物或熱硬化物。只要為所述構成,便可使厚度非常薄(例如製成為10μm以下)。碘透過抑制層的厚度宜為0.05µm~10µm,較宜為0.08µm~5µm,更宜為0.1µm~1µm,尤宜為0.2µm~0.7µm。並且,只要為所述構成,便可將碘透過抑制層直接(亦即不透過接著劑層或黏著劑層)形成於偏光件上。根據本發明實施形態,如上述,偏光件及碘透過抑制層非常薄且可省略用以積層碘透過抑制層之接著劑層或黏著劑,故可使偏光板之總厚度極薄。並且,由於這種碘透過抑制層之吸濕性及透濕性較水溶液或水分散體這類水系塗佈膜的固化物更小,因此具有加濕耐久性優異之優點。結果,可實現即便在高溫高濕環境下仍可維持光學特性之耐久性優異的偏光板。又,這種碘透過抑制層例如相較於紫外線硬化性樹脂之硬化物,更可抑制紫外線照射對偏光板(偏光件)造成不良影響。碘透過抑制層宜為樹脂之有機溶劑溶液之塗佈膜的固化物。固化物相較於硬化物在薄膜成形時之收縮更小、及不含殘存單體等,因此可抑制薄膜本身劣化且可抑制殘存單體等對偏光板(偏光件)造成不良影響。A-4. Iodine permeation suppression layer The iodine permeation suppression layer is a cured product or a thermal cured product of the coating film of the organic solvent solution of the resin as described above. As long as the structure is as described above, the thickness can be made very thin (for example, 10 μm or less). The thickness of the iodine permeation suppression layer should be 0.05µm~10µm, more preferably 0.08µm~5µm, more preferably 0.1µm~1µm, especially 0.2µm~0.7µm. In addition, as long as it has the above configuration, the iodine permeation suppression layer can be directly formed on the polarizing member (that is, not permeating through the adhesive layer or the adhesive layer). According to the embodiment of the present invention, as described above, the polarizer and the iodine transmission inhibiting layer are very thin, and the adhesive layer or adhesive used to laminate the iodine transmission inhibiting layer can be omitted, so the total thickness of the polarizing plate can be extremely thin. In addition, since the hygroscopicity and moisture permeability of the iodine permeation suppression layer are smaller than the cured product of an aqueous coating film such as an aqueous solution or a water dispersion, it has the advantage of excellent humidification durability. As a result, it is possible to realize a polarizing plate with excellent durability that can maintain optical characteristics even in a high-temperature and high-humidity environment. Moreover, this iodine permeation suppression layer can suppress the adverse effects of ultraviolet radiation on the polarizing plate (polarizer), for example, compared to a cured product of an ultraviolet curable resin. The iodine permeation inhibiting layer is preferably a cured product of a coating film of a resin organic solvent solution. Compared with the cured product, the cured product has smaller shrinkage during film forming and does not contain residual monomers. Therefore, the deterioration of the film itself can be suppressed and the residual monomers can be prevented from adversely affecting the polarizing plate (polarizer).

並且,構成碘透過抑制層之樹脂的玻璃轉移溫度(Tg)例如為85℃以上,且重量平均分子量Mw例如為25000以上。只要該樹脂之Tg及Mw在所述範圍內,藉由與以樹脂之有機溶劑溶液之塗佈膜的固化物或熱硬化物構成碘透過抑制層所帶來之效果的加乘效果,即便非常薄,仍可顯著抑制偏光件中之碘往黏著劑層(最終為影像顯示單元)移動。結果,可實現在高溫高濕環境下優異之耐久性。該樹脂之Tg宜為90℃以上,較宜為100℃以上,更宜為110℃以上,尤宜為120℃以上。Tg之上限例如可為200℃。又,該樹脂之Mw宜為30000以上,較宜為35000以上,更宜為40000以上。Mw之上限例如可為150000。In addition, the glass transition temperature (Tg) of the resin constituting the iodine permeation suppression layer is, for example, 85° C. or more, and the weight average molecular weight Mw is, for example, 25,000 or more. As long as the Tg and Mw of the resin are within the above-mentioned ranges, the effect of the iodine permeation inhibiting layer formed by the cured product or thermosetting product of the coating film of the organic solvent solution of the resin is multiplied by the effect of the iodine permeation inhibiting layer. It is thin, and can still significantly inhibit the iodine in the polarizer from moving to the adhesive layer (ultimately the image display unit). As a result, it is possible to realize excellent durability in a high temperature and high humidity environment. The Tg of the resin is preferably above 90°C, more preferably above 100°C, more preferably above 110°C, and particularly preferably above 120°C. The upper limit of Tg may be 200°C, for example. In addition, the Mw of the resin is preferably 30,000 or more, more preferably 35,000 or more, and more preferably 40,000 or more. The upper limit of Mw may be 150,000, for example.

作為構成碘透過抑制層之樹脂只要可形成有機溶劑溶液之塗佈膜的固化物或熱硬化物且具有如上述之Tg及Mw,便可使用任意適當之熱塑性樹脂或熱硬化性樹脂。較佳為熱塑性樹脂。熱塑性樹脂可舉例如丙烯酸系樹脂、環氧系樹脂。亦可組合丙烯酸系樹脂與環氧系樹脂來使用。以下說明可用於抑制碘透過抑制層之丙烯酸系樹脂及環氧系樹脂之代表例。As the resin constituting the iodine permeation suppression layer, any suitable thermoplastic resin or thermosetting resin can be used as long as it can form a cured product or a thermosetting product of a coating film of an organic solvent solution and has the above-mentioned Tg and Mw. Preferably it is a thermoplastic resin. Examples of the thermoplastic resin include acrylic resins and epoxy resins. It can also be used in combination with acrylic resin and epoxy resin. The following describes representative examples of acrylic resins and epoxy resins that can be used to suppress iodine permeation suppression layers.

丙烯酸系樹脂在代表上含有源自直鏈或具有支鏈結構之(甲基)丙烯酸酯系單體之重複單元作為主成分。本說明書中,(甲基)丙烯酸意指丙烯酸及/或甲基丙烯酸。丙烯酸系樹脂可含有源自因應目的之任意適當之共聚單體的重複單元。共聚單體(copolymer)可舉例如含羧基單體、含羥基單體、含醯胺基單體、含芳香環(甲基)丙烯酸酯、含雜環乙烯基系單體。藉由適當設定單體單元之種類、數量、組合及共聚比等,可獲得具有上述預定Mw之丙烯酸系樹脂。The acrylic resin typically contains a repeating unit derived from a linear or branched (meth)acrylate monomer as a main component. In this specification, (meth)acrylic acid means acrylic acid and/or methacrylic acid. The acrylic resin may contain repeating units derived from any suitable comonomers for the purpose. Copolymers include, for example, carboxyl group-containing monomers, hydroxyl group-containing monomers, amide group-containing monomers, aromatic ring-containing (meth)acrylates, and heterocyclic ring-containing vinyl monomers. By appropriately setting the type, number, combination, and copolymerization ratio of monomer units, an acrylic resin having the aforementioned predetermined Mw can be obtained.

<含硼之丙烯酸系樹脂> 在一實施形態中,丙烯酸系樹脂包含藉由將單體混合物聚合而得之共聚物(以下有時稱為含硼之丙烯酸系樹脂),且該單體混合物包含大於50重量份之(甲基)丙烯酸系單體與大於0重量份且小於50重量份之式(1)所示單體(以下有時稱為共聚單體): [化學式2]

Figure 02_image005
(式中,X表示包含反應性基之官能基,且該反應性基係選自於由乙烯基、(甲基)丙烯醯基、苯乙烯基、(甲基)丙烯醯胺基、乙烯基醚基、環氧基、氧雜環丁烷基、羥基、胺基、醛基及羧基所構成群組中之至少1種反應性基,R1 及R2 分別獨立表示氫原子、可具有取代基之脂肪族烴基、可具有取代基之芳基或可具有取代基之雜環基,R1 及R2 可相互連結形成環)。<Boron-containing acrylic resin> In one embodiment, the acrylic resin includes a copolymer obtained by polymerizing a monomer mixture (hereinafter sometimes referred to as a boron-containing acrylic resin), and the monomer mixture includes More than 50 parts by weight of (meth)acrylic monomers and more than 0 parts by weight and less than 50 parts by weight of monomers represented by formula (1) (hereinafter sometimes referred to as comonomers): [Chemical formula 2]
Figure 02_image005
(In the formula, X represents a functional group containing a reactive group, and the reactive group is selected from the group consisting of vinyl, (meth)acryloyl, styryl, (meth)acrylamido, vinyl At least one reactive group in the group consisting of ether group, epoxy group, oxetanyl group, hydroxyl group, amino group, aldehyde group and carboxyl group, R 1 and R 2 each independently represent a hydrogen atom and may have substitution The aliphatic hydrocarbon group of the group, the aryl group which may have a substituent, or the heterocyclic group which may have a substituent, R 1 and R 2 may be connected to each other to form a ring).

含硼之丙烯酸系樹脂代表上具有下述式所示重複單元。藉由將包含式(1)所示共聚單體與(甲基)丙烯酸系單體之單體混合物進行聚合,含硼之丙烯酸系樹脂於側鏈具有含硼之取代基(例如下述式中k之重複單元)。藉此,在將碘透過抑制層配置成與偏光件鄰接時,可提升與偏光件之密著性。該含硼之取代基可以與含硼之丙烯酸系樹脂連接(即塊狀)來含有,亦可以無規來含有。 [化學式3]

Figure 02_image007
(式中,R6 表示任意官能基,j及k表示1以上之整數)。The boron-containing acrylic resin typically has a repeating unit represented by the following formula. By polymerizing a monomer mixture containing a comonomer represented by formula (1) and a (meth)acrylic monomer, the boron-containing acrylic resin has a boron-containing substituent in the side chain (for example, in the following formula: Repeating unit of k). Thereby, when the iodine permeation suppression layer is arranged adjacent to the polarizer, the adhesion to the polarizer can be improved. The boron-containing substituent may be connected to the boron-containing acrylic resin (that is, in the form of a block) to be contained, or may be contained randomly. [Chemical formula 3]
Figure 02_image007
(In the formula, R 6 represents an arbitrary functional group, and j and k represent an integer of 1 or more).

<(甲基)丙烯酸系單體> 作為(甲基)丙烯酸系單體可使用任意適當的(甲基)丙烯酸系單體。可舉例如直鏈或具有支鏈結構之(甲基)丙烯酸酯系單體、及具有環狀結構之(甲基)丙烯酸酯系單體。<(Meth)acrylic monomer> As the (meth)acrylic monomer, any appropriate (meth)acrylic monomer can be used. Examples include (meth)acrylate monomers having a linear or branched structure, and (meth)acrylate monomers having a cyclic structure.

直鏈或具有支鏈結構之(甲基)丙烯酸酯系單體可舉例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸甲基2-乙基己酯、(甲基)丙烯酸2-羥乙酯等。較佳可使用(甲基)丙烯酸甲酯。(甲基)丙烯酸酯系單體可僅使用1種亦可組合2種以上來使用。Linear or branched (meth)acrylate monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (meth)acrylic acid. Isopropyl ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, methyl 2-ethylhexyl (meth)acrylate, (methyl) 2-hydroxyethyl acrylate and the like. Preferably, methyl (meth)acrylate can be used. The (meth)acrylate-based monomer may be used alone or in combination of two or more kinds.

具有環狀結構之(甲基)丙烯酸酯系單體可舉例如(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸1-金剛烷基酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧乙酯、(甲基)丙烯酸二環戊酯、聯苯(甲基)丙烯酸酯、鄰聯苯氧乙基(甲基)丙烯酸酯、鄰聯苯氧基乙氧乙基(甲基)丙烯酸酯、間聯苯氧乙基丙烯酸酯、對聯苯氧乙基(甲基)丙烯酸酯、鄰聯苯氧基-2-羥丙基(甲基)丙烯酸酯、對聯苯氧基-2-羥丙基(甲基)丙烯酸酯、間聯苯氧基-2-羥丙基(甲基)丙烯酸酯、N-(甲基)丙烯醯氧基乙基-鄰聯苯=胺甲酸酯、N-(甲基)丙烯醯氧基乙基-對聯苯=胺甲酸酯、N-(甲基)丙烯醯氧基乙基-間聯苯=胺甲酸酯、鄰苯基苯酚環氧丙基醚丙烯酸酯等含聯苯基單體、三苯(甲基)丙烯酸酯、鄰三苯氧乙基(甲基)丙烯酸酯等。較佳可使用(甲基)丙烯酸1-金剛烷基酯、(甲基)丙烯酸二環戊酯。藉由使用該等單體可獲得玻璃轉移溫度高之聚合物。該等單體可僅使用1種亦可組合2種以上來使用。The (meth)acrylate monomers having a cyclic structure include, for example, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, 1-(meth)acrylate Adamantyl ester, dicyclopentenyl (meth)acrylate, dicyclopentenoxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate, biphenyl (meth)acrylate, ortho-linked Phenoxyethyl (meth)acrylate, o-biphenoxyethoxyethyl (meth)acrylate, m-biphenoxyethyl acrylate, p-biphenoxyethyl (meth)acrylate, o-biphenoxyethyl (meth)acrylate, o-biphenoxyethyl (meth)acrylate Phenoxy-2-hydroxypropyl (meth)acrylate, p-biphenoxy-2-hydroxypropyl (meth)acrylate, m-biphenoxy-2-hydroxypropyl (meth)acrylate , N-(meth)acryloyloxyethyl-o-biphenyl=urethane, N-(meth)acryloyloxyethyl-p-biphenyl=urethane, N-(methyl) Acrylic oxyethyl-m-biphenyl = urethane, o-phenylphenol glycidyl ether acrylate and other biphenyl-containing monomers, triphenyl (meth)acrylate, o-tamoxifen (Meth)acrylate and the like. Preferably, 1-adamantyl (meth)acrylate and dicyclopentyl (meth)acrylate can be used. By using these monomers, a polymer with a high glass transition temperature can be obtained. These monomers may be used by only 1 type or in combination of 2 or more types.

又,亦可使用具有(甲基)丙烯醯基之矽倍半氧烷化合物取代上述(甲基)丙烯酸酯系單體。藉由使用矽倍半氧烷化合物,可獲得玻璃轉移溫度高之丙烯酸系聚合物。已知矽倍半氧烷化合物係具有各種骨架結構例如籠型結構、梯型結構、無規結構等之骨架者。矽倍半氧烷化合物可為僅具有1種該等結構者,亦可為具有2種以上者。矽倍半氧烷化合物可僅使用1種亦可組合2種以上來使用。In addition, a silsesquioxane compound having a (meth)acryloyl group may be used in place of the (meth)acrylate-based monomer. By using a silsesquioxane compound, an acrylic polymer with a high glass transition temperature can be obtained. It is known that silsesquioxane compounds have various framework structures such as cage structures, ladder structures, random structures and the like. The silsesquioxane compound may have only one type of these structures, or may have two or more types. The silsesquioxane compound may be used alone or in combination of two or more kinds.

含有(甲基)丙烯醯基之矽倍半氧烷化合物可使用例如東亞合成股份公司SQ系列之MAC grade及AC grade。MAC grade為含有甲基丙烯醯基之矽倍半氧烷化合物,具體可舉例如MAC-SQ TM-100、MAC-SQ SI-20、MAC-SQ HDM等。AC grade為含有丙烯醯基之矽倍半氧烷化合物,具體可舉例如AC-SQ TA-100、AC-SQ SI-20等。For the silsesquioxane compound containing (meth)acryloyl group, for example, MAC grade and AC grade of Toagosei SQ series can be used. MAC grade is a silsesquioxane compound containing a methacrylic acid group, and specific examples include MAC-SQ TM-100, MAC-SQ SI-20, MAC-SQ HDM and the like. AC grade is a silsesquioxane compound containing an acrylic group, and specific examples include AC-SQ TA-100, AC-SQ SI-20, and the like.

(甲基)丙烯酸系單體可以相對於單體混合物100重量份為大於50重量份來使用。The (meth)acrylic monomer can be used in an amount greater than 50 parts by weight with respect to 100 parts by weight of the monomer mixture.

<共聚單體> 作為共聚單體可使用上述式(1)所示單體。藉由使用所述共聚單體,可於所得聚合物之側鏈導入含硼之取代基。共聚單體可僅使用1種亦可組合2種以上來使用。<Comonomers> As a comonomer, a monomer represented by the above formula (1) can be used. By using the comonomer, a boron-containing substituent can be introduced into the side chain of the obtained polymer. A comonomer may be used by only 1 type or in combination of 2 or more types.

上述式(1)之脂肪族烴基可舉可具有取代基之碳數1~20直鏈或支鏈烷基、可具有取代基之碳數3~20環狀烷基、碳數2~20烯基。上述芳基可舉可具有取代基之碳數6~20苯基、可具有取代基之碳數10~20萘基等。雜環基可舉可具有取代基之至少包含1個雜原子的5員環基或6員環基。此外,R1 及R2 可相互連結形成環。R1 及R2 宜為氫原子或碳數1~3直鏈或支鏈烷基,較宜為氫原子。The aliphatic hydrocarbon group of the above formula (1) may include a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, and an alkene having 2 to 20 carbon atoms. base. Examples of the aryl group include a phenyl group having 6 to 20 carbon atoms, which may have a substituent, and a naphthyl group having 10 to 20 carbon atoms, which may have a substituent. Examples of the heterocyclic group include a 5-membered ring group or a 6-membered ring group containing at least one heteroatom which may have a substituent. In addition, R 1 and R 2 may be connected to each other to form a ring. R 1 and R 2 are preferably a hydrogen atom or a straight or branched chain alkyl group with 1 to 3 carbon atoms, more preferably a hydrogen atom.

X所示官能基所包含之反應性基係選自於由乙烯基、(甲基)丙烯醯基、苯乙烯基、(甲基)丙烯醯胺基、乙烯基醚基、環氧基、氧雜環丁烷基、羥基、胺基、醛基及羧基所構成群組中之至少1種。較理想的是反應性基為(甲基)丙烯醯基及/或(甲基)丙烯醯胺基。藉由具有該等反應性基,可在將碘透過抑制層配置成與偏光件鄰接時更提升與偏光件之密著性。The reactive group contained in the functional group represented by X is selected from the group consisting of vinyl, (meth)acrylic acid, styryl, (meth)acrylic amido, vinyl ether, epoxy, oxygen At least one of the group consisting of a heterocyclobutanyl group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group. Preferably, the reactive group is a (meth)acrylic acid group and/or a (meth)acrylic acid amino group. By having these reactive groups, when the iodine permeation suppression layer is arranged adjacent to the polarizer, the adhesion with the polarizer can be improved.

在一實施形態中,X所示官能基宜為以Z-Y-表示之官能基。此處,Z表示包含反應性基之官能基,且該反應性基係選自於由乙烯基、(甲基)丙烯醯基、苯乙烯基、(甲基)丙烯醯胺基、乙烯基醚基、環氧基、氧雜環丁烷基、羥基、胺基、醛基及羧基所構成群組中之至少1種反應性基,Y則表示伸苯基或伸烷基。In one embodiment, the functional group represented by X is preferably a functional group represented by Z-Y-. Here, Z represents a functional group containing a reactive group, and the reactive group is selected from the group consisting of vinyl, (meth)acryl, styryl, (meth)acrylamido, vinyl ether At least one reactive group in the group consisting of an epoxy group, an epoxy group, an oxetanyl group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group, and Y represents a phenylene group or an alkylene group.

作為共聚單體具體上可使用以下化合物。 [化學式4]

Figure 02_image009
[化學式5]
Figure 02_image011
Specifically, the following compounds can be used as a comonomer. [Chemical formula 4]
Figure 02_image009
[Chemical formula 5]
Figure 02_image011

共聚單體可以相對於單體混合物100重量份為大於0重量份且小於50重量份之含量來使用。宜為0.01重量份以上且小於50重量份,較宜為0.05重量份~20重量份,更宜為0.1重量份~10重量份,尤宜為0.5重量份~5重量份。The comonomer can be used in a content greater than 0 parts by weight and less than 50 parts by weight relative to 100 parts by weight of the monomer mixture. It is preferably 0.01 parts by weight or more and less than 50 parts by weight, more preferably 0.05 parts by weight to 20 parts by weight, more preferably 0.1 parts by weight to 10 parts by weight, and particularly preferably 0.5 parts by weight to 5 parts by weight.

<含內酯環等之丙烯酸系樹脂><Acrylic resin containing lactone ring etc.>

在另一實施形態中,丙烯酸系樹脂具有包含環結構之重複單元,該環結構係選自內酯環單元、戊二酸酐單元、戊二醯亞胺單元、馬來酸酐單元及馬來醯亞胺(N-取代馬來醯亞胺)單元。包含環結構之重複單元可僅有1種含於丙烯酸系樹脂之重複單元中,亦可有2種以上含於其中。In another embodiment, the acrylic resin has a repeating unit including a ring structure selected from the group consisting of lactone ring units, glutaric anhydride units, glutarimide units, maleic anhydride units, and maleic acid units. Amine (N-substituted maleimidine) unit. The repeating unit including the ring structure may be contained in only one type in the repeating unit of the acrylic resin, or two or more types may be contained in it.

內酯環單元宜為下述通式(2)所示:The lactone ring unit is preferably represented by the following general formula (2):

[化學式6]

Figure 02_image013
通式(2)中,R2 、R3 及R4 分別獨立表示氫原子或碳數1~20之有機殘基。此外,有機殘基亦可包含有氧原子。丙烯酸系樹脂中可僅包含有單一的內酯環單元,亦可包含有多個上述通式(2)中之R2 、R3 及R4 互異的內酯環單元。具有內酯環單元之丙烯酸系樹脂已載於例如日本專利特開2008-181078號公報中,而本說明書即援用該公報之記載作為參考。[Chemical formula 6]
Figure 02_image013
In the general formula (2), R 2 , R 3 and R 4 each independently represent a hydrogen atom or an organic residue with 1 to 20 carbon atoms. In addition, the organic residue may also contain oxygen atoms. The acrylic resin may include only a single lactone ring unit, or may include a plurality of lactone ring units in which R 2 , R 3 and R 4 in the above general formula (2) are different from each other. The acrylic resin having a lactone ring unit has been described in, for example, Japanese Patent Laid-Open No. 2008-181078, and the description of the publication is used as a reference in this specification.

戊二醯亞胺單元宜為下述通式(3)所示:The glutarimide unit is preferably represented by the following general formula (3):

[化學式7]

Figure 02_image015
[Chemical formula 7]
Figure 02_image015

通式(3)中,R11 及R12 分別獨立表示氫或碳數1~8烷基,R13 表示碳數1~18烷基、碳數3~12環烷基或碳數6~10芳基。通式(3)中,理想是R11 及R12 分別獨立為氫或甲基,R13 為氫、甲基、丁基或環己基。更理想是R11 為甲基,R12 為氫,R13 為甲基。丙烯酸系樹脂中可僅包含有單一的戊二醯亞胺單元,亦可包含有多個上述通式(3)中之R11 、R12 及R13 互異的戊二醯亞胺單元。具有戊二醯亞胺單元之丙烯酸系樹脂例如已記載於日本專利特開2006-309033號公報、日本專利特開2006-317560號公報、日本專利特開2006-328334號公報、日本專利特開2006-337491號公報、日本專利特開2006-337492號公報、日本專利特開2006-337493號公報、日本專利特開2006-337569號公報中,而本說明書即援用該公報之記載作為參考。另,戊二酸酐單元除了被上述通式(3)R13 取代之氮原子變為氧原子之外,皆適用上述有關戊二醯亞胺單元之說明。In the general formula (3), R 11 and R 12 each independently represent hydrogen or an alkyl group with 1 to 8 carbons, and R 13 represents an alkyl group with 1 to 18 carbons, a cycloalkyl group with 3 to 12 carbons, or 6 to 10 carbons. Aryl. In the general formula (3), it is desirable that R 11 and R 12 are each independently hydrogen or methyl, and R 13 is hydrogen, methyl, butyl, or cyclohexyl. More preferably, R 11 is methyl, R 12 is hydrogen, and R 13 is methyl. The acrylic resin may include only a single glutarimide unit, or may include a plurality of glutarimide units in which R 11 , R 12 and R 13 in the general formula (3) above are different from each other. Acrylic resins having pentadiimide units are described in, for example, Japanese Patent Laid-Open No. 2006-309033, Japanese Patent Laid-Open No. 2006-317560, Japanese Patent Laid-Open No. 2006-328334, and Japanese Patent Laid-Open No. 2006 -337491, Japanese Patent Laid-Open No. 2006-337492, Japanese Patent Laid-Open No. 2006-337493, and Japanese Patent Laid-Open No. 2006-337569, and this specification refers to the description of the gazette as a reference. In addition, for the glutaric anhydride unit, except that the nitrogen atom substituted by R 13 of the above general formula (3) is changed to an oxygen atom, the above description of the glutarimide unit applies.

馬來酸酐單元及馬來醯亞胺(N-取代馬來醯亞胺)單元可由名稱特定出結構,因此省略具體說明。The maleic anhydride unit and the maleimid (N-substituted maleimid) unit can specify the structure by the name, so the specific description is omitted.

丙烯酸系樹脂中包含環結構之重複單元的含有比率宜為1莫耳%~50莫耳%,較宜為10莫耳%~40莫耳%,更宜為20莫耳%~30莫耳%。另,丙烯酸系樹脂包含源自上述(甲基)丙烯酸系單體之重複單元作為主要重複單元。The content ratio of the repeating unit containing the ring structure in the acrylic resin is preferably 1 mol%~50 mol%, more preferably 10 mol%~40 mol%, more preferably 20 mol%~30 mol% . In addition, the acrylic resin contains a repeating unit derived from the above-mentioned (meth)acrylic monomer as a main repeating unit.

<環氧樹脂> 環氧樹脂較佳可使用具有芳香族環之環氧樹脂。藉由使用具有芳香族環之環氧樹脂作為環氧樹脂,可提升碘透過抑制層與偏光件之密著性。並且,將黏著劑層配置成與碘透過抑制層鄰接時,可提升黏著劑層之投錨力。具有芳香族環之環氧樹脂可舉例如雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂等雙酚型環氧樹脂;苯酚酚醛環氧樹脂、甲酚酚醛環氧樹脂、羥苯甲醛苯酚酚醛環氧樹脂等酚醛型環氧樹脂;四羥苯甲烷之環氧丙基醚、四羥基二苯基酮之環氧丙基醚、環氧化聚乙烯苯酚等多官能型環氧樹脂、萘酚型環氧樹脂、萘型環氧樹脂、聯苯型環氧樹脂等。較佳可使用雙酚A型環氧樹脂、聯苯型環氧樹脂、雙酚F型環氧樹脂。環氧樹脂可僅使用1種亦可組合2種以上來使用。<Epoxy resin> As the epoxy resin, it is preferable to use an epoxy resin having an aromatic ring. By using an epoxy resin with an aromatic ring as the epoxy resin, the adhesion between the iodine permeation suppression layer and the polarizer can be improved. In addition, when the adhesive layer is arranged adjacent to the iodine permeation suppression layer, the anchoring force of the adhesive layer can be improved. Examples of epoxy resins with aromatic rings include bisphenol-type epoxy resins such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and bisphenol S-type epoxy resin; phenol novolac epoxy resin, cresol Novolac epoxy resin, paraben phenol novolac epoxy resin, etc Multifunctional epoxy resin, naphthol epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, etc. Preferably, bisphenol A type epoxy resin, biphenyl type epoxy resin, and bisphenol F type epoxy resin can be used. The epoxy resin may be used by only 1 type or in combination of 2 or more types.

碘透過抑制層可藉由塗佈如上述之樹脂之有機溶劑溶液來形成塗佈膜,並使該塗佈膜固化或熱硬化來形成。有機溶劑可使用可將丙烯酸系樹脂溶解或均勻分散之任意適當之有機溶劑。有機溶劑之具體例可舉乙酸乙酯、甲苯、甲基乙基酮(MEK)、甲基異丁基酮(MIBK)、環戊酮、環己酮。溶液之樹脂濃度相對於溶劑100重量份宜為3重量份~20重量份。只要為所述樹脂濃度,便可形成均勻的塗佈膜。The iodine permeation inhibiting layer can be formed by applying an organic solvent solution of the resin as described above to form a coating film, and curing or thermally curing the coating film. As the organic solvent, any appropriate organic solvent that can dissolve or uniformly disperse the acrylic resin can be used. Specific examples of the organic solvent include ethyl acetate, toluene, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone, and cyclohexanone. The resin concentration of the solution is preferably 3 parts by weight to 20 parts by weight relative to 100 parts by weight of the solvent. As long as the resin concentration is the above, a uniform coating film can be formed.

溶液可塗佈於任意適當之基材上,亦可塗佈於偏光件上。當將溶液塗佈於基材時,形成於基材上之塗佈膜的固化物(碘透過抑制層)會轉印至偏光件。當將溶液塗佈於偏光件時,藉由使塗佈膜乾燥(固化),而於偏光件上直接形成保護層。較佳為溶液塗佈於偏光件上,而於偏光件上直接形成保護層。只要為所述構成,便可省略轉印所需之接著劑層或黏著劑層,故可使偏光板更薄。溶液之塗佈方法可採用任意適當的方法。具體例可舉出輥塗法、旋塗法、線棒塗佈法、浸塗法、模塗法、簾塗法、噴塗法、刮刀塗佈法(缺角輪塗佈法等)。The solution can be coated on any suitable substrate, and can also be coated on the polarizer. When the solution is applied to the substrate, the cured product (iodine permeation suppression layer) of the coating film formed on the substrate is transferred to the polarizer. When the solution is applied to the polarizer, the protective layer is directly formed on the polarizer by drying (curing) the coating film. Preferably, the solution is coated on the polarizer, and the protective layer is directly formed on the polarizer. As long as it has the above configuration, the adhesive layer or the adhesive layer required for transfer can be omitted, so the polarizing plate can be made thinner. Any appropriate method can be adopted for the coating method of the solution. Specific examples include a roll coating method, a spin coating method, a wire bar coating method, a dip coating method, a die coating method, a curtain coating method, a spray coating method, and a knife coating method (cutting wheel coating method, etc.).

藉由使溶液之塗佈膜固化或熱硬化,可形成碘透過抑制層。固化或熱硬化之加熱溫度宜為100℃以下,較宜為50℃~70℃。只要加熱溫度在所述範圍內,便可防止對偏光件造成不良影響。加熱時間可按加熱溫度變化。加熱時間例如可為1分鐘~10分鐘。By curing or thermally hardening the coating film of the solution, an iodine permeation suppression layer can be formed. The heating temperature for curing or thermal hardening should be below 100℃, more preferably 50℃~70℃. As long as the heating temperature is within the above range, adverse effects on the polarizer can be prevented. The heating time can be changed according to the heating temperature. The heating time can be, for example, 1 minute to 10 minutes.

碘透過抑制層(實質上為上述樹脂之有機溶劑溶液)亦可因應目的包含有任意適當之添加劑。添加劑之具體例可舉紫外線吸收劑;調平劑;受阻酚系、磷系、硫系等抗氧化劑;耐光穩定劑、耐候穩定劑、熱穩定劑等穩定劑;玻璃纖維、碳纖維等補強材;近紅外線吸收劑;參(二溴化丙基)磷酸酯、三烯丙基磷酸酯、氧化銻等阻燃劑;陰離子系、陽離子系、非離子系界面活性劑等抗靜電劑;無機顏料、有機顏料、染料等著色劑;有機填料或無機填料;樹脂改質劑;有機填充劑或無機填充劑;塑化劑;滑劑;抗靜電劑;阻燃劑等。添加劑之種類、數量、組合、添加量等可按目的適當設定。The iodine permeation suppression layer (essentially an organic solvent solution of the above resin) may also contain any appropriate additives according to the purpose. Specific examples of additives include ultraviolet absorbers; leveling agents; hindered phenol, phosphorus, sulfur and other antioxidants; stabilizers such as light-resistant stabilizers, weather-resistant stabilizers, and heat stabilizers; reinforcing materials such as glass fiber and carbon fiber; Near-infrared absorber; ginseng (dibromide propyl) phosphate, triallyl phosphate, antimony oxide and other flame retardants; anionic, cationic, non-ionic surfactants and other antistatic agents; inorganic pigments, Organic pigments, dyes and other colorants; organic or inorganic fillers; resin modifiers; organic or inorganic fillers; plasticizers; slip agents; antistatic agents; flame retardants, etc. The type, quantity, combination, addition amount, etc. of the additives can be appropriately set according to the purpose.

碘透過抑制層例如碘吸收指數為0.015以下。碘吸收指數宜為0.012以下,較宜為0.009以下,更宜為0.007以下,尤宜為0.005以下。碘吸收指數越小越佳,理想為零,而其下限例如可為0.001。碘吸收指數係碘透過抑制層之碘透過抑制能力的指標,該指數越小表示碘越難被碘透過抑制層吸收(亦即碘易被碘透過抑制層阻隔)。因此,只要碘吸收指數在所述範圍內,便可將黏著劑層之碘存在指數如上述設成0.050以下,而可顯著抑制偏光件中之碘移動至黏著劑層(最終為影像顯示裝置,實質上為影像顯示單元)。結果,可於薄型偏光板實現在高溫高濕環境下優異之耐久性。並且,即便在將偏光板應用於影像顯示裝置之情況下,仍可顯著抑制影像顯示裝置之金屬構件(例如電極、感測器、配線、金屬層)之腐蝕,且可抑制在高溫高濕環境下碘造成之可靠性降低,因此可抑制反射率上升。並且,碘透過抑制層如上述,鉀吸收指數宜為0.015以下。鉀吸收指數較宜為0.013以下,更宜為0.011以下,尤宜為0.009以下。鉀吸收指數越小越佳,理想為零,而其下限例如可為0.002。鉀吸收指數係碘透過抑制層之鉀透過抑制能力的指標,該指數越小表示鉀越不易被碘透過抑制層吸收,結果碘化鉀形態之碘及多碘化鉀(I3 - K+ )形態之碘越不易被碘透過抑制層吸收。因此,只要鉀吸收指數在所述範圍內,不僅碘單體即便在碘化鉀及多碘化鉀之形態下仍可抑制碘的移動。碘吸收指數可規定為碘透過抑制層利用X射線螢光分析所得之碘強度(kcps),鉀吸收指數可規定為碘透過抑制層利用X射線螢光分析所得之鉀強度(kcps)。The iodine permeation suppression layer is, for example, an iodine absorption index of 0.015 or less. The iodine absorption index is preferably less than 0.012, more preferably less than 0.009, more preferably less than 0.007, and particularly preferably less than 0.005. The smaller the iodine absorption index, the better, and ideally it is zero, and its lower limit may be, for example, 0.001. The iodine absorption index is an indicator of the iodine permeation inhibiting ability of the iodine permeation inhibiting layer. The smaller the index, the more difficult it is for iodine to be absorbed by the iodine permeation inhibiting layer (that is, the iodine is easily blocked by the iodine permeation inhibiting layer). Therefore, as long as the iodine absorption index is within the range, the iodine existence index of the adhesive layer can be set to 0.050 or less as described above, and the iodine in the polarizer can be significantly prevented from moving to the adhesive layer (in the end, the image display device, It is essentially an image display unit). As a result, the thin polarizing plate can achieve excellent durability in a high temperature and high humidity environment. Moreover, even when the polarizing plate is applied to the image display device, the corrosion of the metal components (such as electrodes, sensors, wiring, metal layer) of the image display device can be significantly suppressed, and it can be suppressed in a high temperature and high humidity environment. Reliability is reduced due to iodine, so the increase in reflectivity can be suppressed. In addition, the iodine permeation suppression layer is as described above, and the potassium absorption index is preferably 0.015 or less. The potassium absorption index is preferably less than 0.013, more preferably less than 0.011, and particularly preferably less than 0.009. The lower the potassium absorption index, the better, and it is ideally zero, and its lower limit may be 0.002, for example. Potassium absorption index is an indicator of the potassium permeation inhibition ability of iodine permeation inhibition layer. The smaller the index, the less easily potassium is absorbed by iodine permeation inhibition layer. As a result, potassium iodide form of iodine and potassium polyiodide (I 3 - K + ) form of iodine are more difficult to absorb. It is not easy to be absorbed by iodine through the suppression layer. Therefore, as long as the potassium absorption index is within the above range, not only the iodine monomer can inhibit the movement of iodine even in the form of potassium iodide and potassium polyiodide. The iodine absorption index can be defined as the iodine intensity (kcps) obtained by X-ray fluorescence analysis of the iodine permeation suppression layer, and the potassium absorption index can be defined as the potassium intensity (kcps) obtained by the X-ray fluorescence analysis of the iodine permeation suppression layer.

B.附相位差層之偏光板 B-1.附相位差層之偏光板之整體構成 本發明實施形態之附相位差層之偏光板具有偏光板與相位差層。偏光板係上述A項記載之偏光板。本發明實施形態中,相位差層配置於偏光件與黏著劑層之間。相位差層係具有圓偏光機能或楕圓偏光機能之液晶化合物的定向固化層(以下有時僅稱為液晶定向固化層)。圖2A係本發明一實施形態之附相位差層之偏光板的概略截面圖;圖2B係本發明另一實施形態之附相位差層之偏光板的概略截面圖。圖2A及圖2B之附相位差層之偏光板100、101各自自視辨側起依序具有保護層12、偏光件11、相位差層20及黏著劑層30。本發明實施形態中,碘透過抑制層40設於偏光件11與黏著劑層30之間。藉由於附相位差層之偏光板中設置碘透過抑制層,如上述關於偏光板所述,可顯著抑制偏光件中之碘移動至黏著劑層(最終為影像顯示裝置,實質上為影像顯示單元)。結果,可於薄型附相位差層之偏光板實現在高溫高濕環境下優異之耐久性。並且,在將附相位差層之偏光板應用於影像顯示裝置之情況下,可顯著抑制影像顯示裝置之金屬構件(例如電極、感測器、配線、金屬層)之腐蝕,且可抑制在高溫高濕環境下反射率上升。碘透過抑制層40可如圖2A所示設於偏光件11與相位差層20之間(即鄰接偏光件11),亦可如圖2B所示設於相位差層20與黏著劑層30之間。將碘透過抑制層設於偏光件與相位差層之間時(尤其是在使碘透過抑制層鄰接偏光件時),可抑制在高溫高濕環境下碘移動離開偏光件而具有可靠性提升之優點。將碘透過抑制層設於相位差層與黏著劑層之間時(尤其是在使碘透過抑制層鄰接黏著劑層時),亦可同時防止碘以外之可能會影響金屬腐蝕的成分(例如紫外線硬化接著劑中的殘渣單體成分、光引發劑之分解物)往黏著劑中移動,而具有更提高金屬腐蝕抑制效果之優點。B. Polarizing plate with retardation layer B-1. The overall composition of the polarizing plate with retardation layer The polarizing plate with retardation layer of the embodiment of the present invention has a polarizing plate and a retardation layer. The polarizing plate is the one described in item A above. In the embodiment of the present invention, the retardation layer is disposed between the polarizer and the adhesive layer. The retardation layer is an orientation cured layer of a liquid crystal compound having a circular polarization function or an elliptical polarization function (hereinafter, it may be simply referred to as a liquid crystal orientation cured layer). 2A is a schematic cross-sectional view of a polarizing plate with a retardation layer according to an embodiment of the present invention; FIG. 2B is a schematic cross-sectional view of a polarizing plate with a retardation layer according to another embodiment of the present invention. The polarizing plates 100 and 101 with retardation layer of FIGS. 2A and 2B each have a protective layer 12, a polarizer 11, a retardation layer 20, and an adhesive layer 30 in order from the viewing side. In the embodiment of the present invention, the iodine permeation suppression layer 40 is provided between the polarizer 11 and the adhesive layer 30. The iodine transmission suppression layer is provided in the polarizing plate with the retardation layer, as described in the above-mentioned polarizing plate, which can significantly inhibit the iodine in the polarizer from moving to the adhesive layer (the final image display device is essentially the image display unit). ). As a result, a thin polarizer with retardation layer can achieve excellent durability in a high temperature and high humidity environment. Moreover, when the polarizing plate with retardation layer is applied to the image display device, the corrosion of the metal components (such as electrodes, sensors, wiring, metal layer) of the image display device can be significantly suppressed, and it can be suppressed at high temperatures. The reflectivity increases in high humidity environments. The iodine permeation suppression layer 40 may be provided between the polarizer 11 and the retardation layer 20 as shown in FIG. 2A (ie adjacent to the polarizer 11), or may be provided between the retardation layer 20 and the adhesive layer 30 as shown in FIG. 2B between. When the iodine permeation suppression layer is provided between the polarizer and the retardation layer (especially when the iodine permeation suppression layer is adjacent to the polarizer), the iodine can be prevented from moving away from the polarizer in a high temperature and high humidity environment, thereby improving reliability advantage. When the iodine permeation inhibiting layer is placed between the retardation layer and the adhesive layer (especially when the iodine permeation inhibiting layer is adjacent to the adhesive layer), it can also prevent components other than iodine that may affect metal corrosion (such as ultraviolet rays). The residue monomer components in the hardening adhesive and the decomposition products of the photoinitiator) move into the adhesive, which has the advantage of further enhancing the metal corrosion inhibition effect.

如圖3所示,又另一實施形態之附相位差層之偏光板102中,亦可設有另一相位差層50以及/或者導電層或附導電層之各向同性基材60。另一相位差層50代表上可設於相位差20與黏著劑層30之間(即相位差層20之外側)。另一相位差層代表上折射率特性顯示nz>nx=ny之關係。導電層或附導電層之各向同性基材60代表上可設於碘透過抑制層40與黏著劑層30之間(即碘透過抑制層40之外側)。另一相位差層50以及導電層或附導電層之各向同性基材60代表上係自相位差層20側起依序設置。圖式例中,係自視辨側起依序設有碘透過抑制層40、相位差層20、另一相位差層50、以及導電層或附導電層之各向同性基材60,但只要另一相位差層50設於相位差20與黏著劑層30之間,且導電層或附導電層之各向同性基材60設於碘透過抑制層40與黏著劑層30之間,便可採用任意適當之配置順序。另一相位差層50以及導電層或附導電層之各向同性基材60代表上係可因應需要設置之任意層,可省略任一者或兩者。此外,為求方便,有時會將相位差層20稱為第1相位差層,且將另一相位差層50稱為第2相位差層。在可設置導電層或附導電層之各向同性基材時,附相位差層之偏光板可應用於在影像顯示單元(例如有機EL單元)與偏光板間組入有觸控感測器之所謂內觸控面板型輸入顯示裝置。在本發明實施形態中,藉由將導電層或附導電層之各向同性基材60設於碘透過抑制層40之外側,可顯著抑制導電層之腐蝕。As shown in FIG. 3, the polarizing plate 102 with a retardation layer of another embodiment may be provided with another retardation layer 50 and/or a conductive layer or an isotropic substrate 60 with a conductive layer. Another retardation layer 50 may be provided between the retardation 20 and the adhesive layer 30 (that is, the outer side of the retardation layer 20). The other retardation layer represents the upper refractive index characteristic showing the relationship of nz>nx=ny. The conductive layer or the isotropic substrate 60 with a conductive layer may typically be provided between the iodine permeation inhibiting layer 40 and the adhesive layer 30 (that is, the outer side of the iodine permeation inhibiting layer 40). The other retardation layer 50 and the conductive layer or the isotropic substrate 60 with a conductive layer are representatively arranged in order from the retardation layer 20 side. In the example of the drawing, an iodine permeation suppression layer 40, a retardation layer 20, another retardation layer 50, and a conductive layer or an isotropic substrate 60 with a conductive layer are provided in this order from the viewing side, but only The other retardation layer 50 is provided between the retardation 20 and the adhesive layer 30, and the conductive layer or the isotropic substrate 60 with the conductive layer is provided between the iodine permeation suppression layer 40 and the adhesive layer 30. Use any appropriate configuration sequence. The other retardation layer 50 and the conductive layer or the isotropic substrate 60 with a conductive layer represent any layers that can be provided as needed, and either or both of them can be omitted. In addition, for convenience, the retardation layer 20 may be referred to as a first retardation layer, and the other retardation layer 50 may be referred to as a second retardation layer. When a conductive layer or an isotropic substrate with a conductive layer can be provided, the polarizing plate with a retardation layer can be applied to the so-called touch sensor integrated between the image display unit (such as the organic EL unit) and the polarizing plate Internal touch panel type input display device. In the embodiment of the present invention, by disposing the conductive layer or the isotropic substrate 60 with a conductive layer on the outer side of the iodine permeation suppression layer 40, the corrosion of the conductive layer can be significantly suppressed.

如上述,第1相位差層20係液晶定向固化層。第1相位差層20可為如圖2A、圖2B及圖3所示之單一層,亦可具有如圖4所示之第1液晶定向固化層21與第2液晶定向固化層22的積層結構。As described above, the first retardation layer 20 is a liquid crystal orientation cured layer. The first retardation layer 20 may be a single layer as shown in FIG. 2A, FIG. 2B, and FIG. 3, or may have a laminated structure of the first liquid crystal orientation curing layer 21 and the second liquid crystal orientation curing layer 22 as shown in FIG. 4 .

上述實施形態可適當組合,亦可於上述實施形態之構成要素中加入業界中顯明的變更。例如,可於圖2B之附相位差層之偏光板101設置第2相位差層50以及/或者導電層或附導電層之各向同性基材60;圖2B之附相位差層之偏光板101的相位差層20亦可具有如圖4之2層結構;可於圖4之附相位差層之偏光板103設置第2相位差層50以及/或者導電層或附導電層之各向同性基材60;圖3之附相位差層之偏光板102的碘透過抑制層40亦可設於相位差層20與導電層或附導電層之各向同性基材60之間。The above-mentioned embodiments may be combined as appropriate, and obvious changes in the industry may be added to the constituent elements of the above-mentioned embodiments. For example, the second retardation layer 50 and/or the conductive layer or the isotropic substrate 60 with the conductive layer can be provided on the polarizing plate 101 with retardation layer in FIG. 2B; the polarizing plate 101 with retardation layer in FIG. 2B The retardation layer 20 of FIG. 4 may also have a two-layer structure; the second retardation layer 50 and/or a conductive layer or an isotropic base with a conductive layer can be provided on the polarizing plate 103 with a retardation layer in FIG. 4 The iodine transmission suppression layer 40 of the polarizing plate 102 with a retardation layer of FIG. 3 can also be provided between the retardation layer 20 and the conductive layer or the isotropic substrate 60 with a conductive layer.

本發明實施形態之附相位差層之偏光板亦可更包含有其他相位差層。其他相位差層之光學特性(例如折射率特性、面內相位差、Nz係數、光彈性係數)、厚度、配置位置等可按目適當設定。The polarizing plate with retardation layer of the embodiment of the present invention may further include other retardation layers. The optical properties of other retardation layers (for example, refractive index characteristics, in-plane retardation, Nz coefficient, photoelastic coefficient), thickness, arrangement position, etc. can be appropriately set according to the purpose.

附相位差層之偏光板的總厚度宜為60µm以下,較宜為55µm以下,更宜為50µm以下,尤宜為40µm以下。總厚度的下限例如可為28µm。根據本發明實施形態,可如所述實現極薄之附相位差層之偏光板,並可於這種極薄之附相位差層之偏光板實現在高溫高濕環境下優異之耐久性。並且,即便在將這種非常薄之附相位差層之偏光板應用於影像顯示裝置之情況下,仍可顯著抑制影像顯示裝置之金屬構件(例如電極、感測器、配線、金屬層)之腐蝕,且可抑制在高溫高濕環境下反射率上升。另外,所謂附相位差層之偏光板的總厚度係指偏光板、相位差層(第1相位差層及當有第2相位差層存在時之第2相位差層)、碘透過抑制層及用以積層該等之接著劑層或黏著劑層的厚度之合計(即,附相位差層之偏光板的總厚度不包含導電層或附導電層之各向同性基材60、以及黏著劑層30及可暫時黏附於其表面之剝離薄膜的厚度)。The total thickness of the polarizer with retardation layer should be less than 60 µm, more preferably less than 55 µm, more preferably less than 50 µm, especially less than 40 µm. The lower limit of the total thickness may be 28 μm, for example. According to the embodiment of the present invention, an extremely thin polarizing plate with a retardation layer can be realized as described above, and the extremely thin polarizing plate with a retardation layer can achieve excellent durability in a high temperature and high humidity environment. Moreover, even when such a very thin polarizer with a retardation layer is applied to an image display device, the metal components (such as electrodes, sensors, wiring, and metal layer) of the image display device can still be significantly suppressed. Corrosion, and can suppress the increase in reflectivity in a high temperature and high humidity environment. In addition, the total thickness of the polarizing plate with retardation layer refers to the polarizing plate, the retardation layer (the first retardation layer and the second retardation layer when the second retardation layer is present), the iodine transmission suppression layer, and The total thickness of the adhesive layer or the adhesive layer used for stacking (that is, the total thickness of the polarizing plate with the retardation layer does not include the conductive layer or the isotropic substrate 60 with the conductive layer, and the adhesive layer 30 and the thickness of the release film that can be temporarily adhered to its surface).

有關偏光板之構成、效果及用途之上述A項之記載中亦可應用於附相位差層之偏光板者可援用作為有關附相位差層之偏光板之記載。例如,有關偏光板之形狀(單片狀或長條狀)及薄型化、可應用偏光板之影像顯示裝置、剝離薄膜、以及對偏光件直接形成碘透過抑制層之記載可援用作為有關附相位差層之偏光板之記載。該等僅為例示,所援用之記載不受該等所限理應自明。同樣地,有關附相位差層之偏光板之構成、效果及用途之後述之記載中可援用於偏光板者可援用作為有關偏光板之記載。Regarding the composition, effect and use of the polarizing plate, the description of the above item A can also be applied to the polarizing plate with retardation layer, which can be cited as the description of the polarizing plate with retardation layer. For example, the description about the shape (single or long strip) and thinning of the polarizing plate, the image display device to which the polarizing plate can be applied, the release film, and the direct formation of the iodine permeation suppression layer on the polarizer can be cited as the related phase The record of the polarizing plate of the differential layer. These are only examples, and the quoted records are not subject to such restrictions and should be self-explanatory. Similarly, the description about the structure, effect, and use of the polarizing plate with retardation layer can be cited as the description about the polarizing plate in the description that can be used for the polarizing plate.

以下,針對附相位差層之偏光板之構成要素的第1相位差層、第2相位差層、及導電層或附導電層之各向同性基材進行說明。關於偏光件、保護層及碘透過抑制層係如上述A項中所說明。Hereinafter, the first retardation layer, the second retardation layer, and the conductive layer or the isotropic substrate with the conductive layer, which are the constituent elements of the polarizing plate with a retardation layer, will be described. The polarizer, protective layer, and iodine permeation suppression layer are as described in item A above.

B-2.第1相位差層 第1相位差層20如上述係液晶定向固化層。藉由使用液晶化合物,可使所得相位差層的nx與ny之差比非液晶材料大上甚多,因此可將用以獲得期望之面內相位差所需相位差層之厚度縮小甚多。結果可實現附相位差層之偏光板之進一步薄型化。本說明書中所謂「液晶定向固化層」係指液晶化合物在層內於預定方向定向,且其定向狀態已受固定之層。另外,「定向固化層」之概念包含如後述使液晶單體硬化而得的定向硬化層。在本實施形態中,代表上係棒狀液晶化合物沿第1相位差層之慢軸方向排列之狀態下定向(沿面定向)。B-2. The first retardation layer The first retardation layer 20 is a liquid crystal orientation cured layer as described above. By using a liquid crystal compound, the difference between nx and ny of the obtained retardation layer can be much larger than that of the non-liquid crystal material. Therefore, the thickness of the retardation layer required to obtain the desired in-plane retardation can be greatly reduced. As a result, the polarizing plate with retardation layer can be further thinned. The "liquid crystal orientation cured layer" in this specification refers to a layer in which the liquid crystal compound is oriented in a predetermined direction in the layer, and the orientation state of the liquid crystal compound has been fixed. In addition, the concept of "directionally hardened layer" includes an directional hardened layer obtained by hardening a liquid crystal monomer as described later. In this embodiment, it represents that the rod-shaped liquid crystal compound is aligned in the direction of the slow axis of the first retardation layer (orientated along the plane).

液晶化合物可舉例如液晶相為向列相之液晶化合物(向列型液晶)。這種液晶化合物例如可使用液晶聚合物或液晶單體。液晶化合物之液晶性的表現機構可為溶致亦可為熱致。液晶聚合物及液晶單體各自可單獨使用,也可組合。The liquid crystal compound may be, for example, 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 properties of the liquid crystal compound can be expressed by lyotropic or thermotropic. The liquid crystal polymer and the liquid crystal monomer may be used alone or in combination.

液晶化合物為液晶單體時,該液晶單體宜為聚合性單體及交聯性單體。其係因藉由使液晶單體進行聚合或交聯(亦即硬化)可固定液晶單體的定向狀態之故。在使液晶單體定向之後,例如只要使液晶單體彼此聚合或交聯,便可藉此固定上述定向狀態。在此係藉由聚合來形成聚合物,藉由交聯來形成3維網狀結構,惟該等為非液晶性。因此,所形成之第1相位差層例如不會發生液晶性化合物特有之因溫度變化而轉變為液晶相、玻璃相、結晶相之情形。結果第1相位差層會成為不受溫度變化影響而穩定性極優異的相位差層。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 (ie, hardening) the liquid crystal monomer. After aligning the liquid crystal monomers, for example, by polymerizing or crosslinking the liquid crystal monomers with each other, the above-mentioned alignment state can be fixed by this. Here, a polymer is formed by polymerization, and a three-dimensional network structure is formed by cross-linking, but these are non-liquid crystalline. Therefore, the formed first retardation layer does not change into a liquid crystal phase, a glass phase, or a crystalline phase due to temperature changes that are unique to liquid crystal compounds, for example. As a result, the first retardation layer becomes a retardation layer that is not affected by temperature changes and is extremely stable.

液晶單體展現液晶性之溫度範圍會因其種類而異。具體來說,該溫度範圍宜為40℃~120℃,更宜為50℃~100℃,最宜為60℃~90℃。The temperature range in which the liquid crystal monomer exhibits liquid crystallinity will vary depending on its type. Specifically, the temperature range is preferably 40°C to 120°C, more preferably 50°C to 100°C, and most preferably 60°C to 90°C.

上述液晶單體可採用任意適當之液晶單體。例如可使用日本專利特表2002-533742(WO00/37585)、EP358208(US5211877)、EP66137(US4388453)、WO93/22397、EP0261712、DE19504224、DE4408171及GB2280445等所記載之聚合性液晶原化合物等。所述聚合性液晶原化合物之具體例可舉例如BASF公司之商品名LC242、Merck公司之商品名E7、Wacker-Chem公司之商品名LC-Sillicon-CC3767。液晶單體宜為例如向列性液晶單體。Any appropriate liquid crystal monomer can be used as the above-mentioned liquid crystal monomer. For example, the polymerizable mesogen compounds described in Japanese Patent Special Publication 2002-533742 (WO00/37585), EP358208 (US5211877), EP66137 (US4388453), WO93/22397, EP0261712, DE19504224, DE4408171, GB2280445, etc. can be used. Specific examples of the polymerizable mesogen compound include, for example, BASF's trade name LC242, Merck's trade name E7, and Wacker-Chem's trade name LC-Sillicon-CC3767. The liquid crystal monomer is preferably, for example, a nematic liquid crystal monomer.

液晶定向固化層可藉由以下方式來形成:對預定基材之表面施行定向處理,並於該表面塗敷含液晶化合物的塗敷液使該液晶化合物於對應上述定向處理之方向定向,並固定該定向狀態。在一實施形態中,基材為任意適當之樹脂薄膜,而形成於該基材上的液晶定向固化層可轉印至鄰接層(例如偏光件、碘透過抑制層)之表面。The liquid crystal orientation curing layer can be formed by the following method: performing orientation treatment on the surface of a predetermined substrate, and coating the surface with a coating liquid containing a liquid crystal compound to orient the liquid crystal compound in the direction corresponding to the orientation treatment, and fix it The orientation state. In one embodiment, the substrate is any suitable resin film, and the liquid crystal orientation cured layer formed on the substrate can be transferred to the surface of an adjacent layer (for example, a polarizer, an iodine transmission suppression layer).

上述定向處理可採用任意適當之定向處理。具體可舉機械性定向處理、物理性定向處理、化學性定向處理。機械性定向處理的具體例可舉磨擦處理、延伸處理。物理性定向處理的具體例可舉磁場定向處理、電場定向處理。化學性定向處理的具體例可舉斜向蒸鍍法、光定向處理。各種定向處理的處理條件可按目的採用任意適當之條件。The above-mentioned orientation processing can adopt any appropriate orientation processing. Specific examples include mechanical orientation treatment, physical orientation treatment, and chemical orientation treatment. Specific examples of mechanical orientation treatment include friction treatment and stretching treatment. Specific examples of the physical orientation treatment include magnetic field orientation treatment and electric field orientation treatment. Specific examples of the chemical orientation treatment include oblique vapor deposition and light orientation treatment. The processing conditions of various directional processing can adopt any appropriate conditions according to the purpose.

液晶化合物的定向可因應液晶化合物的種類於可展現液晶相之溫度下進行處理來進行。藉由進行所述溫度處理,液晶化合物會變為液晶狀態,而該液晶化合物會因應基材表面之定向處理方向而定向。The orientation of the liquid crystal compound can be processed at a temperature that can exhibit a liquid crystal phase according to the type of the liquid crystal compound. By performing the temperature treatment, the liquid crystal compound becomes a liquid crystal state, and the liquid crystal compound is oriented according to the orientation treatment direction of the substrate surface.

在一實施形態中,定向狀態之固定係藉由冷卻已依上述方式定向之液晶化合物來進行。當液晶化合物為聚合性單體或交聯性單體時,定向狀態之固定係藉由對已依上述方式定向之液晶化合物施行聚合處理或交聯處理來進行。In one embodiment, the fixation of the orientation state is performed by cooling the liquid crystal compound that has been oriented in the above-mentioned manner. When the liquid crystal compound is a polymerizable monomer or a crosslinkable monomer, the fixation of the alignment state is performed by subjecting the liquid crystal compound aligned in the above-mentioned manner to a polymerization treatment or a crosslinking treatment.

液晶化合物之具體例及定向固化層的形成方法的詳細內容記載於日本專利特開2006-163343號公報中。本說明書中係援用該公報之記載作為參考。Specific examples of the liquid crystal compound and the details of the method for forming the oriented solidified layer are described in Japanese Patent Laid-Open No. 2006-163343. In this manual, the record in the bulletin is used as a reference.

在一實施形態中,第1相位差層20係如圖2A、圖2B及圖3所示為單一層。第1相位差層20以單一層構成時,其厚度宜為0.5µm~7µm,且1µm~5µm較佳。藉由使用液晶化合物,可以較樹脂薄膜薄上甚多的厚度實現與樹脂薄膜同等的面內相位差。In one embodiment, the first retardation layer 20 is a single layer as shown in FIGS. 2A, 2B, and 3. When the first retardation layer 20 is composed of a single layer, its thickness is preferably 0.5 μm-7 μm, and preferably 1 μm-5 μm. By using the liquid crystal compound, it is possible to achieve the same in-plane phase difference as the resin film with a much thinner thickness than the resin film.

第1相位差層如上述具有圓偏光機能或橢圓偏光機能。第1相位差層代表上折射率特性展現nx>ny=nz之關係。第1相位差層在代表上係為了賦予偏光板抗反射特性而設置,當第1相位差層為單一層時可作為λ/4板發揮功能。此時,第1相位差層的面內相位差Re(550)宜為100nm~190nm,較宜為110nm~170nm,更宜為130nm~160nm。此外,在此「ny=nz」不只ny與nz完全相同之情況,還包含實質上相同之情況。因此,在不損及本發明效果之範圍下可有ny>nz或ny<nz之情形。The first retardation layer has a circular polarization function or an elliptical polarization function as described above. The first retardation layer represents the upper refractive index characteristic exhibiting a relationship of nx>ny=nz. The first retardation layer is typically provided to impart anti-reflection properties to the polarizing plate, and when the first retardation layer is a single layer, it can function as a λ/4 plate. At this time, the in-plane retardation Re (550) of the first retardation layer is preferably 100 nm to 190 nm, more preferably 110 nm to 170 nm, and more preferably 130 nm to 160 nm. In addition, "ny=nz" here includes not only the case where ny and nz are exactly the same, but also the case where they are substantially the same. Therefore, there may be situations of ny>nz or ny<nz within a range that does not impair the effect of the present invention.

第1相位差層的Nz係數宜為0.9~1.5,較宜為0.9~1.3。藉由滿足所述關係,在將所得附相位差層之偏光板使用於影像顯示裝置時,可達成非常優異之反射色相。The Nz coefficient of the first retardation layer is preferably 0.9 to 1.5, more preferably 0.9 to 1.3. By satisfying the above relationship, when the obtained polarizing plate with retardation layer is used in an image display device, a very excellent reflection hue can be achieved.

第1相位差層可展現相位差值隨測定光之波長變大的逆分散波長特性,可展現相位差值隨測定光之波長變小的正常波長分散特性,亦可展現相位差值幾乎不隨測定光之波長變化的平坦的波長分散特性。在一實施形態中,第1相位差層展現逆分散波長特性。此時,相位差層之Re(450)/Re(550)宜為0.8以上且小於1,較宜為0.8以上且0.95以下。只要為所述構成,便可實現非常優異的抗反射特性。The first retardation layer can exhibit inverse dispersion wavelength characteristics in which the retardation value increases with the wavelength of the measurement light, and can exhibit the normal wavelength dispersion characteristics with the retardation value becoming smaller with the wavelength of the measurement light, and it can also exhibit the retardation value that hardly varies. Measure the flat wavelength dispersion characteristics of light wavelength changes. In one embodiment, the first retardation layer exhibits reverse dispersion wavelength characteristics. At this time, the Re(450)/Re(550) of the retardation layer is preferably 0.8 or more and less than 1, more preferably 0.8 or more and 0.95 or less. As long as the structure is as described above, very excellent anti-reflection characteristics can be achieved.

第1相位差層20的慢軸與偏光件11的吸收軸形成之角度θ宜為40°~50°,較宜為42°~48°,更宜為約45°。只要角度θ在所述範圍內,如上述藉由將第1相位差層製成λ/4板,可獲得具有非常優異圓偏光特性(以結果而言為非常優異的抗反射特性)的附相位差層之偏光板。The angle θ formed by the slow axis of the first retardation layer 20 and the absorption axis of the polarizer 11 is preferably 40°-50°, more preferably 42°-48°, and more preferably about 45°. As long as the angle θ is within the above range, by making the first retardation layer into a λ/4 plate as described above, it is possible to obtain a phase-attached phase with very excellent circular polarization characteristics (and as a result, very excellent anti-reflection characteristics) Polarizing plate with differential layer.

在另一實施形態中,第1相位差層20如圖4所示,具有第1液晶定向固化層21與第2液晶定向固化層22之積層結構。此時,第1液晶定向固化層21及第2液晶定向固化層22之任一者可作為λ/4板發揮功能,另一者可作為λ/2板發揮功能。因此,第1液晶定向固化層21及第2液晶定向固化層22的厚度可為了獲得λ/4板或λ/2板之所期望的面內相位差而進行調整。例如,第1液晶定向固化層21作為λ/2板發揮功能、第2液晶定向固化層22作為λ/4板發揮功能時,第1液晶定向固化層21的厚度例如為2.0µm~3.0µm,而第2液晶定向固化層22的厚度例如為1.0µm~2.0µm。此時,第1液晶定向固化層的面內相位差Re(550)宜為200nm~300nm,較宜為230nm~290nm,更宜為250nm~280nm。而第2液晶定向固化層的面內相位差Re(550)如同就上述有關單一層所說明。第1液晶定向固化層的慢軸與偏光件的吸收軸形成之角度宜為10°~20°,較宜為12°~18°,更宜為約15°。第2液晶定向固化層的慢軸與偏光件的吸收軸形成之角度宜為70°~80°,較宜為72°~78°,更宜為約75°。只要為所述構成,便可獲得接近理想之逆波長分散特性的特性,結果可實現非常優異之抗反射特性。關於構成第1液晶定向固化層及第2液晶定向固化層之液晶化合物、第1液晶定向固化層及第2液晶定向固化層之形成方法、光學特性等,如同就上述有關單一層所說明。In another embodiment, as shown in FIG. 4, the first retardation layer 20 has a layered structure of a first liquid crystal orientation cured layer 21 and a second liquid crystal orientation cured layer 22. At this time, any one of the first liquid crystal orientation curing layer 21 and the second liquid crystal orientation curing layer 22 can function as a λ/4 plate, and the other can function as a λ/2 plate. Therefore, the thicknesses of the first liquid crystal orientation curing layer 21 and the second liquid crystal orientation curing layer 22 can be adjusted in order to obtain a desired in-plane phase difference of the λ/4 plate or the λ/2 plate. For example, when the first liquid crystal orientation curing layer 21 functions as a λ/2 plate and the second liquid crystal orientation curing layer 22 functions as a λ/4 plate, the thickness of the first liquid crystal orientation curing layer 21 is, for example, 2.0 μm to 3.0 μm. The thickness of the second liquid crystal orientation curing layer 22 is, for example, 1.0 μm to 2.0 μm. At this time, the in-plane phase difference Re(550) of the first liquid crystal orientation curing layer is preferably 200nm~300nm, more preferably 230nm~290nm, and more preferably 250nm~280nm. The in-plane phase difference Re (550) of the second liquid crystal orientation cured layer is the same as that described above for the single layer. The angle formed by the slow axis of the first liquid crystal orientation curing layer and the absorption axis of the polarizer is preferably 10°-20°, more preferably 12°-18°, and more preferably about 15°. The angle formed by the slow axis of the second liquid crystal orientation curing layer and the absorption axis of the polarizer is preferably 70°~80°, more preferably 72°~78°, and more preferably about 75°. With the above configuration, characteristics close to ideal inverse wavelength dispersion characteristics can be obtained, and as a result, very excellent anti-reflection characteristics can be achieved. Regarding the liquid crystal compounds constituting the first and second liquid crystal alignment cured layers, the method of forming the first and second liquid crystal alignment cured layers, and the optical characteristics are as described above with respect to the single layer.

B-3.第2相位差層 第2相位差層如上述,可為折射率特性展現nz>nx=ny之關係的所謂正C板(Positive C-plate)。藉由使用正C板作為第2相位差層,可良好地防止斜向之反射,而可使抗反射功能廣視角化。此時,第2相位差層的厚度方向的相位差Rth(550)宜為-50nm~-300nm,較宜為-70nm~-250nm,更宜為-90nm~-200nm,尤宜為-100nm~-180nm。在此,「nx=ny」不僅包含nx與ny嚴格相等之情況,還包含nx與ny實質相等之情況。即,第2相位差層的面內相位差Re(550)可小於10nm。B-3. Second retardation layer As described above, the second retardation layer may be a so-called positive C-plate that exhibits the relationship of nz>nx=ny in refractive index characteristics. By using the positive C plate as the second retardation layer, oblique reflection can be prevented well, and the anti-reflection function can be made to widen the viewing angle. At this time, the thickness direction retardation Rth(550) of the second retardation layer is preferably -50nm~-300nm, more preferably -70nm~-250nm, more preferably -90nm~-200nm, particularly preferably -100nm~ -180nm. Here, "nx=ny" includes not only the case where nx and ny are strictly equal, but also the case where nx and ny are substantially equal. That is, the in-plane retardation Re(550) of the second retardation layer may be less than 10 nm.

具有nz>nx=ny之折射率特性的第2相位差層可以任意適當之材料形成。第2相位差層宜由包含固定為垂面定向之液晶材料的薄膜構成。可使垂面定向的液晶材料(液晶化合物)可為液晶單體亦可為液晶聚合物。該液晶化合物及該相位差層之形成方法的具體例可舉日本專利特開2002-333642號公報中段落[0020]~[0028]記載之液晶化合物及該相位差層之形成方法。此時,第2相位差層的厚度宜為0.5µm~10µm,較宜為0.5μm~8µm,更宜為0.5μm~5µm。The second retardation layer having a refractive index characteristic of nz>nx=ny can be formed of any appropriate material. The second retardation layer is preferably composed of a film containing a liquid crystal material fixed in a homeotropic orientation. The liquid crystal material (liquid crystal compound) that can align the vertical plane may be a liquid crystal monomer or a liquid crystal polymer. Specific examples of the liquid crystal compound and the method for forming the retardation layer include the liquid crystal compounds described in paragraphs [0020] to [0028] in Japanese Patent Laid-Open No. 2002-333642 and the method for forming the retardation layer. At this time, the thickness of the second retardation layer is preferably 0.5μm~10μm, more preferably 0.5μm~8μm, and more preferably 0.5μm~5μm.

B-4.導電層或附導電層之各向同性基材 導電層可利用任意適當之成膜方法(例如真空蒸鍍法、濺鍍法、CVD法、離子鍍法、噴霧法等),將金屬氧化物膜成膜於任意適當之基材上來形成。金屬氧化物可舉例如氧化銦、氧化錫、氧化鋅、銦錫複合氧化物、錫銻複合氧化物、鋅鋁複合氧化物、銦鋅複合氧化物。其中宜為銦錫複合氧化物(ITO)。B-4. Conductive layer or isotropic substrate with conductive layer The conductive layer can be formed by forming a metal oxide film on any appropriate substrate by any appropriate film forming method (for example, vacuum evaporation, sputtering, CVD, ion plating, spraying, etc.). Examples of the metal oxide include indium oxide, tin oxide, zinc oxide, indium tin composite oxide, tin antimony composite oxide, zinc aluminum composite oxide, and indium zinc composite oxide. Among them, indium tin composite oxide (ITO) is preferred.

導電層包含金屬氧化物時,該導電層的厚度宜為50nm以下,較宜為35nm以下。導電層厚度的下限宜為10nm。When the conductive layer contains a metal oxide, the thickness of the conductive layer is preferably 50 nm or less, more preferably 35 nm or less. The lower limit of the thickness of the conductive layer is preferably 10 nm.

導電層可製成為由上述基材轉印至第1相位差層(或是碘透過抑制層或有第2相位差層存在時為第2相位差層)而以導電層單獨作為附相位差層之偏光板的構成層,亦可以導電層與基材之積層體(附導電層之基材)的形式積層於第1相位差層(或是碘透過抑制層或有第2相位差層存在時為第2相位差層)。較理想的是上述基材在光學上為各向同性,因此導電層可作為附導電層之各向同性基材用於附相位差層之偏光板。The conductive layer can be made by transferring the above-mentioned substrate to the first retardation layer (or the second retardation layer when the iodine permeation suppression layer or the second retardation layer is present), and the conductive layer alone is used as the second retardation layer. The constituent layer of the polarizing plate can also be laminated on the first retardation layer in the form of a laminate of a conductive layer and a substrate (a substrate with a conductive layer) (or an iodine permeation suppression layer or a second retardation layer) It is the second retardation layer). It is more desirable that the above-mentioned substrate is optically isotropic, so the conductive layer can be used as an isotropic substrate with a conductive layer for a polarizing plate with a retardation layer.

在光學上為各向同性的基材(各向同性基材)可採用任意適當之各向同性基材。構成各向同性基材之材料可舉例如以降莰烯系樹脂或烯烴系樹脂等不具有共軛系之樹脂為主骨架的材料、於丙烯酸系樹脂之主鏈中具有內酯環或戊二醯亞胺環等環狀結構的材料等。若使用所述材料,則可將形成各向同性基材時伴隨分子鏈定向而展現之相位差抑制得較小。各向同性基材的厚度宜為50µm以下,較宜為35µm以下。各向同性基材之厚度的下限例如20µm。Any suitable isotropic substrate can be used as an optically isotropic substrate (isotropic substrate). The material constituting the isotropic substrate may include, for example, a material having a resin that does not have a conjugated system such as norbornene-based resin or olefin-based resin as the main skeleton, and a material having a lactone ring or glutaric acid in the main chain of the acrylic resin Materials with cyclic structures such as imine rings. If the material is used, the phase difference that occurs with the orientation of the molecular chain when the isotropic substrate is formed can be suppressed to be small. The thickness of the isotropic substrate is preferably 50 µm or less, more preferably 35 µm or less. The lower limit of the thickness of the isotropic substrate is, for example, 20 µm.

上述導電層及/或上述附導電層之各向同性基材的導電層可因應需要進行圖案化。藉由圖案化可形成導通部與絕緣部。結果可形成電極。電極可作為用以感測對觸控面板之接觸的觸控感測電極發揮功能。圖案化方法可採用任意適當之方法。圖案化方法的具體例可舉濕式蝕刻法、網版印刷法。The conductive layer and/or the conductive layer of the isotropic substrate with the conductive layer may be patterned as needed. The conductive part and the insulating part can be formed by patterning. As a result, electrodes can be formed. The electrode can function as a touch sensing electrode for sensing contact with the touch panel. Any appropriate method can be adopted for the patterning method. Specific examples of the patterning method include a wet etching method and a screen printing method.

C.影像顯示裝置 上述A項所記載之偏光板及上述B項所記載之附相位差層之偏光板可應用於影像顯示裝置。因此,本發明實施形態包含使用有所述偏光板或附相位差層之偏光板的影像顯示裝置。影像顯示裝置的代表例可舉液晶顯示裝置、電致發光(EL)顯示裝置(例如有機EL顯示裝置、無機EL顯示裝置)。本發明實施形態之影像顯示裝置代表上於其視辨側具備上述A項所記載之偏光板或上述B項所記載之附相位差層之偏光板。附相位差層之偏光板係以使相位差層成為影像顯示單元(例如液晶單元、有機EL單元、無機EL單元)側之方式(使偏光件成為視辨側)積層。所述影像顯示裝置雖為非常薄型,但金屬構件之腐蝕經顯著抑制。在一實施形態中,影像顯示裝置具有彎曲的形狀(實質上為彎曲的顯示畫面),及/或可彎折或可折疊。此外,上述A項所記載之偏光板亦可因應目的配置於影像顯示裝置之背面側。C. Image display device The polarizing plate described in the above item A and the polarizing plate with a retardation layer described in the above item B can be applied to an image display device. Therefore, the embodiment of the present invention includes an image display device using the polarizing plate or the polarizing plate with retardation layer. Representative examples of image display devices include liquid crystal display devices and electroluminescence (EL) display devices (for example, organic EL display devices and inorganic EL display devices). The image display device of the embodiment of the present invention is representatively provided with the polarizing plate described in the above item A or the polarizing plate with the retardation layer described in the above item B on the viewing side. The polarizing plate with retardation layer is laminated so that the retardation layer becomes the image display unit (for example, liquid crystal cell, organic EL cell, inorganic EL cell) side (the polarizer becomes the viewing side). Although the image display device is very thin, the corrosion of metal components is significantly suppressed. In one embodiment, the image display device has a curved shape (essentially a curved display screen), and/or bendable or foldable. In addition, the polarizing plate described in the above item A can also be arranged on the back side of the image display device according to the purpose.

實施例 以下,以實施例來具體說明本發明,惟本發明不受該等實施例限定。各特性之測定方法如以下所述。此外,只要無特別註記,實施例及比較例中之「份」及「%」即為重量基準。Example Hereinafter, the present invention will be specifically described with examples, but the present invention is not limited by these examples. The measuring methods of each characteristic are as follows. In addition, as long as there is no special note, the "parts" and "%" in the examples and comparative examples are the basis of weight.

(1)厚度 10μm以下的厚度係使用干涉膜厚計(大塚電子公司製,製品名「MCPD-3000」)進行測定。大於10μm的厚度係使用數位測微器(Anritsu公司製,產品名「KC-351C」)測定。(1) Thickness The thickness of 10 μm or less was measured using an interference film thickness meter (manufactured by Otsuka Electronics Co., Ltd., product name "MCPD-3000"). The thickness greater than 10 μm is measured using a digital micrometer (manufactured by Anritsu, product name "KC-351C").

(2)碘存在指數 將實施例及比較例中所得附相位差層之偏光板或偏光板貼合於無鹼玻璃,製成試驗試樣。將該試驗試樣供於可靠性試驗(於85℃・85%RH之環境下放置240小時,之後於23℃・55%RH之環境下放置24小時)後,用修整刀從無鹼玻璃整個剝離黏著劑。用IONTOF公司製「TOFSIMS5」對經剝離之試驗試樣的黏著劑表面進行二次離子質量分析(TOF-SIMS)測定。測定條件如下所述。 ・所照射之一次離子:Bi3 2+ ・一次離子加速電壓:25kV ・測定面積:100µm2 ・測定極性:負離子 從所得負二次離子中挑出源自丙烯酸(黏著劑)之C3 H3 O2 - (m/z=71)之離子強度及源自碘之I- (m/z=127)之離子強度,用下述式算出碘存在指數。 碘存在指數=I- 離子強度/C3 H3 O2 - 離子強度(2) Iodine presence index The polarizing plate with retardation layer or the polarizing plate obtained in the examples and comparative examples was bonded to the alkali-free glass to prepare a test sample. After putting the test sample in the reliability test (placed in an environment of 85℃・85%RH for 240 hours, and then placed in an environment of 23℃・55%RH for 24 hours), use a dressing knife to remove the entire alkali-free glass Peel off the adhesive. The surface of the adhesive of the peeled test sample was subjected to secondary ion mass analysis (TOF-SIMS) measurement using "TOFSIMS5" manufactured by IONTOF. The measurement conditions are as follows.・Primary ion irradiated: Bi 3 2+・Primary ion acceleration voltage: 25kV ・Measurement area: 100µm 2 ・Measurement polarity: C 3 H 3 derived from acrylic acid (adhesive) is extracted from the negative secondary ions obtained O 2 - (m / z = 71) and the ionic strength of I from iodine - (m / z = 127) of the ionic strength, the presence of iodine index was calculated by the following formula. Iodine presence index = I - ionic strength / C 3 H 3 O 2 - ionic strength

(3)碘吸收指數及鉀吸收指數 將實施例及比較例所用樹脂溶液以乾燥後之厚度成為1µm之方式塗敷於38µm之聚對苯二甲酸乙二酯(PET)薄膜上並乾燥,而獲得樹脂層/PET薄膜之試驗試樣。將所得試驗試樣浸漬於調整成23℃之碘化鉀10%水溶液(純水90重量份、碘化鉀10重量份)中24小時。浸漬後,從水溶液取出試驗試樣,擦拭表面之水滴後,對樹脂層表面進行X射線螢光測定而獲得碘及鉀之強度(kcps)。將所得碘之強度作為碘吸收指數,將鉀之強度作為鉀吸收指數。另外,X射線螢光分析之條件如下所述。 ・分析裝置:理學電機工業製 X射線螢光分析裝置(XRF),製品名「ZSX100e」 ・試驗試樣:直徑10mm之圓形試樣 ・對陰極:銠 ・分光結晶:氟化鋰 ・激發光能:40kV-90mA ・碘測定線:I-LA ・定量法:FP法 ・2θ角峰:103.078deg(碘),136.847deg(鉀) ・測定時間:40秒(3) Iodine absorption index and potassium absorption index The resin solutions used in the Examples and Comparative Examples were coated on a 38-µm polyethylene terephthalate (PET) film so that the thickness after drying became 1 µm and dried to obtain a test sample of the resin layer/PET film . The obtained test sample was immersed in a potassium iodide 10% aqueous solution (90 parts by weight of pure water, 10 parts by weight of potassium iodide) adjusted to 23°C for 24 hours. After immersion, the test sample was taken out from the aqueous solution, and after wiping the water droplets on the surface, the surface of the resin layer was subjected to X-ray fluorescence measurement to obtain the intensity of iodine and potassium (kcps). The intensity of the obtained iodine was used as the iodine absorption index, and the intensity of potassium was used as the potassium absorption index. In addition, the conditions of X-ray fluorescence analysis are as follows. ・Analysis device: X-ray fluorescence analyzer (XRF) manufactured by Rigaku Denki Kogyo, product name "ZSX100e" ・Test specimen: round specimen with a diameter of 10mm ・For cathode: Rhodium ・Spectroscopic crystal: Lithium fluoride ・Exciting light energy: 40kV-90mA ・Iodine measurement line: I-LA ・Quantitative method: FP method ・2θ angle peak: 103.078deg (iodine), 136.847deg (potassium) ・Measurement time: 40 seconds

(4)偏光度變化 將實施例及比較例中所得附相位差層之偏光板或偏光板貼合於無鹼玻璃,製成試驗試樣。藉由常法測定該試驗試樣之偏光度,將其作為初始偏光度。並將試驗試樣供於可靠性試驗(於85℃・85%RH之環境下放置240小時,之後於23℃・55% RH之環境下放置24小時)後,依與上述相同方式測定偏光度。依以下式算出偏光度變化。 偏光度變化(%)=初始偏光度(%)-可靠性試驗後之偏光度(%) 並按以下基準進行評估。 良好:偏光度變化小於5.0% 不佳:偏光度變化為5.0%以上(4) Polarization changes The polarizing plate with retardation layer or the polarizing plate obtained in the examples and comparative examples was bonded to the alkali-free glass to prepare a test sample. Measure the degree of polarization of the test sample by conventional methods, and use it as the initial degree of polarization. And after the test sample is placed in the reliability test (at 85℃・85%RH environment for 240 hours, then at 23℃・55% RH environment for 24 hours), measure the degree of polarization in the same way as above . Calculate the polarization change according to the following formula. Polarization change (%) = initial polarization (%)-polarization after reliability test (%) And evaluate according to the following benchmarks. Good: Polarization change is less than 5.0% Poor: Polarization change is more than 5.0%

(5)反射率上升 將實施例及比較例中所得附相位差層之偏光板貼合於無鹼玻璃,製成試驗試樣。將該試驗試樣置於反射率為80%之反射板上,將使用分光測色計(Konica Minolta公司製CM700D)在SCI模式下於550nm測得之數值作為反射率(%),並將其作為初始反射率。並將試驗試樣供於可靠性試驗(於60℃・90%RH之環境下放置500小時,之後於23℃・55% RH之環境下放置24小時)後,依與上述相同方式測定反射率。依以下式算出反射率上升。 反射率上升(%)=初始反射率(%)-可靠性試驗後之反射率(%) 並按以下基準進行評估。 良好:反射率上升小於0.50% 可容許:反射率上升為0.50%以上且小於1.00% 不佳:反射率上升為1.00%以上(5) Increased reflectivity The polarizing plates with retardation layer obtained in the examples and comparative examples were bonded to alkali-free glass to prepare test samples. Place the test sample on a reflector with a reflectance of 80%, and use a spectrophotometer (CM700D manufactured by Konica Minolta) in the SCI mode to measure the value at 550 nm as the reflectance (%). As the initial reflectivity. After putting the test sample in the reliability test (place it in an environment of 60℃・90%RH for 500 hours, then put it in an environment of 23℃・55% RH for 24 hours), then measure the reflectance in the same way as above . The increase in reflectance is calculated by the following formula. Increase in reflectivity (%) = initial reflectivity (%)-reflectivity after reliability test (%) And evaluate according to the following benchmarks. Good: The reflectivity rise is less than 0.50% Allowable: The reflectivity rises above 0.50% and less than 1.00% Poor: The reflectivity rises above 1.00%

(6)金屬腐蝕性(48小時) 以濕膜膜厚成為15µm之方式用線棒將銀奈米線液(MERCK公司製,奈米線尺寸:直徑115nm,長度20µm~50µm,固體成分0.5%之異丙醇(IPA)溶液)塗敷於50µm之聚對苯二甲酸乙二酯(PET)薄膜單面,並以100℃之烘箱乾燥5分鐘,而形成銀奈米線塗膜。接著,以濕膜膜厚成為10µm之方式用線棒將包含甲基異丁基酮(MIBK)99份、新戊四醇四丙烯酸酯(PETA)1份及光聚合引發劑(BASF公司製,製品名「IRGACURE 907」)0.03份之覆蓋保護液(固體成分濃度:約1%)塗敷於銀奈米線塗膜表面,並以100℃之烘箱乾燥5分鐘。接著,照射活性能量線使覆蓋保護塗膜硬化,而製作出具有PET薄膜/銀奈米線層/覆蓋保護層(厚度100nm)之構成的金屬薄膜。使用黏著劑(15µm)將該金屬薄膜貼合於厚度0.5mm之玻璃板,而獲得金屬薄膜/黏著劑/玻璃板之積層體。以非接觸式電阻測定器(Napson公司製,製品名「EC-80」)測定所得積層體之電阻值,得50Ω/□。(6) Metal corrosivity (48 hours) Coat the silver nanowire liquid (manufactured by MERCK company, nanowire size: diameter 115nm, length 20µm~50µm, solid content 0.5% isopropyl alcohol (IPA) solution) with a wire rod so that the wet film thickness becomes 15µm Spread it on one side of a 50µm polyethylene terephthalate (PET) film and dry it in an oven at 100°C for 5 minutes to form a silver nanowire coating. Next, 99 parts of methyl isobutyl ketone (MIBK), 1 part of neopentylerythritol tetraacrylate (PETA), and a photopolymerization initiator (manufactured by BASF Co., Ltd., The product name "IRGACURE 907") 0.03 parts of covering protection solution (solid content concentration: about 1%) is applied to the surface of the silver nanowire coating film and dried in an oven at 100°C for 5 minutes. Next, active energy rays were irradiated to harden the cover protective coating film to produce a metal thin film having a structure of PET film/silver nanowire layer/cover protective layer (thickness 100 nm). Use an adhesive (15 µm) to bond the metal film to a glass plate with a thickness of 0.5 mm to obtain a laminate of metal film/adhesive/glass plate. The resistance value of the obtained laminate was measured with a non-contact resistance measuring device (manufactured by Napson, product name "EC-80"), and it was 50Ω/□.

將實施例及比較例中所得附相位差層之偏光板或偏光板貼合於積層體之金屬薄膜的覆蓋保護層表面,製成試驗試樣。以非接觸式電阻測定器測定該試驗試樣之電阻值作為初始電阻值。並將試驗試樣供於可靠性試驗(於85℃・85% RH之環境下放置48小時,之後於23℃・55%RH之環境下放置2小時)後,依與上述相同方式測定電阻值。依以下式算出電阻值上升率。另,當測定值(電阻值)大於非接觸式電阻測定器之測定極限(1000Ω/□)時,將測定值假設為1500Ω/□。 電阻值上升率(%)={(可靠性試驗後之電阻值-初始電阻值)/初始電阻值}×100 並按以下基準進行評估。 良好:電阻值上升率低於200% 不佳:電阻值上升率為200%以上The polarizing plate with retardation layer or the polarizing plate obtained in the Examples and Comparative Examples was bonded to the surface of the covering protective layer of the metal thin film of the laminate to prepare a test sample. Measure the resistance value of the test sample with a non-contact resistance tester as the initial resistance value. Put the test sample in the reliability test (place it in an environment of 85°C and 85% RH for 48 hours, and then place it in an environment of 23°C and 55% RH for 2 hours), and then measure the resistance value in the same way as above . Calculate the rate of increase in resistance value according to the following formula. In addition, when the measured value (resistance value) is greater than the measurement limit (1000Ω/□) of the non-contact resistance tester, the measured value is assumed to be 1500Ω/□. Rising rate of resistance value (%)={(resistance value after reliability test-initial resistance value)/initial resistance value}×100 And evaluate according to the following benchmarks. Good: The resistance value rise rate is less than 200% Poor: The rate of increase in resistance value is more than 200%

(7)金屬腐蝕性(200小時) 將實施例及比較例中所得附相位差層之偏光板貼合於(2)所得積層體之金屬薄膜的覆蓋保護層形成面,製成試驗試樣。以非接觸式電阻測定器測定該試驗試樣之電阻值作為初始之電阻值。並將試驗試樣供於可靠性試驗(於85℃・85% RH之環境下放置200小時,之後於23℃・55%RH之環境下放置2小時)後,依與上述相同方式測定電阻值。依以下式算出電阻值上升率。另,當測定值(電阻值)大於非接觸式電阻測定器之測定極限(1000Ω/□)時,將測定值假設為1500Ω/□。 電阻值上升率(%)={(可靠性試驗後之電阻值-初始電阻值)/初始電阻值}×100 並按以下基準進行評估。 優:電阻值上升率低於200% 佳:電阻值上升率為200%以上且低於2000% 不佳:電阻值上升率為2000%以上(7) Metal corrosivity (200 hours) The polarizing plates with retardation layer obtained in the Examples and Comparative Examples were bonded to the protective layer forming surface of the metal thin film of the laminate obtained in (2) to prepare test samples. Use a non-contact resistance tester to measure the resistance value of the test sample as the initial resistance value. Put the test sample in the reliability test (place it in an environment of 85°C and 85% RH for 200 hours, and then place it in an environment of 23°C and 55% RH for 2 hours), and then measure the resistance value in the same way as above . Calculate the rate of increase in resistance value according to the following formula. In addition, when the measured value (resistance value) is greater than the measurement limit (1000Ω/□) of the non-contact resistance tester, the measured value is assumed to be 1500Ω/□. Rising rate of resistance value (%)={(resistance value after reliability test-initial resistance value)/initial resistance value}×100 And evaluate according to the following benchmarks. Excellent: The resistance value rise rate is less than 200% Good: the resistance value increase rate is more than 200% and less than 2000% Poor: The rate of increase in resistance value is more than 2000%

[實施例1] 1.製作偏光件 熱塑性樹脂基材是使用長條狀且吸水率0.75%、Tg約75℃之非晶質間苯二甲酸共聚聚對苯二甲酸乙二酯薄膜(厚度:100µm)。並對樹脂基材之單面施行了電暈處理。 在以9:1混合聚乙烯醇(聚合度4200,皂化度99.2莫耳%)及乙醯乙醯基改質PVA(日本合成化學工業公司製,商品名「GOHSEFIMER Z410」)而成之PVA系樹脂100重量份中添加碘化鉀13重量份,並將所得者溶於水中而調製出PVA水溶液(塗佈液)。 於樹脂基材之電暈處理面塗佈上述PVA水溶液並在60℃下乾燥,藉此形成厚度13μm之PVA系樹脂層,而製出積層體。 將所得積層體於130℃之烘箱內在周速相異之輥間沿縱方向(長邊方向)進行自由端單軸延伸成2.4倍(空中輔助延伸處理)。 接著,使積層體浸漬於液溫40℃的不溶解浴(相對於水100重量份摻混4重量份之硼酸而得的硼酸水溶液)中30秒鐘(不溶解處理)。 接著,調整液溫30℃的染色浴(相對於水100重量份,以1:7之重量比摻混碘與碘化鉀而獲得之碘水溶液)之濃度的同時使其浸漬於其中60秒鐘,以使最後所得偏光件的單體透射率(Ts)成為43.0%以上(染色處理)。 接著,使其浸漬於液溫40℃的交聯浴(相對於水100重量份摻混3重量份的碘化鉀並摻混5重量份的硼酸而獲得之硼酸水溶液)中30秒鐘(交聯處理)。 然後,使積層體浸漬於液溫70℃的硼酸水溶液(硼酸濃度4.0重量%,碘化鉀濃度5重量%)中,同時在周速相異的輥間沿縱向(長邊方向)進行單軸延伸以使總延伸倍率達5.5倍(水中延伸處理)。 之後,使積層體浸漬於液溫20℃的洗淨浴(相對於水100重量份摻混4重量份的碘化鉀而得之水溶液)中(洗淨處理)。 之後,一邊在維持於90℃之烘箱中乾燥,一邊使其接觸表面溫度保持於75℃之SUS製加熱輥約2秒(乾燥收縮處理)。積層體進行乾燥收縮處理所得寬度方向之收縮率為5.2%。 依上述方式而於樹脂基材上形成厚度5µm之偏光件。[Example 1] 1. Make polarized parts The thermoplastic resin substrate is an amorphous isophthalic acid copolymer polyethylene terephthalate film (thickness: 100µm) with a water absorption rate of 0.75% and a Tg of about 75°C. And applied corona treatment to one side of the resin substrate. In a 9:1 mixture of polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mol%) and acetyl acetyl modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "GOHSEFIMER Z410"). 13 parts by weight of potassium iodide was added to 100 parts by weight of resin, and the resultant was dissolved in water to prepare a PVA aqueous solution (coating liquid). The above-mentioned PVA aqueous solution was applied to the corona-treated surface of the resin substrate and dried at 60° C., thereby forming a PVA-based resin layer with a thickness of 13 μm, thereby producing a laminate. The obtained laminate was uniaxially stretched 2.4 times in the longitudinal direction (long side direction) between rollers with different peripheral speeds in an oven at 130°C (air-assisted stretching treatment). Next, the layered body was immersed in an insoluble bath (a boric acid aqueous solution obtained by mixing 4 parts by weight of boric acid with respect to 100 parts by weight of water) at a liquid temperature of 40°C for 30 seconds (insoluble treatment). Next, while adjusting the concentration of a dye bath (an iodine aqueous solution obtained by mixing iodine and potassium iodide at a weight ratio of 1:7 with respect to 100 parts by weight of water) at a liquid temperature of 30°C, it was immersed in it for 60 seconds to The monomer transmittance (Ts) of the finally obtained polarizer is 43.0% or more (dyeing treatment). Next, it was immersed in a cross-linking bath (a boric acid aqueous solution obtained by mixing 3 parts by weight of potassium iodide and 5 parts by weight of boric acid with respect to 100 parts by weight of water with a liquid temperature of 40°C) for 30 seconds (cross-linking treatment) ). Then, the layered body was immersed in a boric acid aqueous solution (4.0% by weight of boric acid concentration and 5% by weight of potassium iodide) at a liquid temperature of 70°C, while uniaxially stretched in the longitudinal direction (longitudinal direction) between rolls with different peripheral speeds. Make the total extension ratio up to 5.5 times (underwater extension treatment). After that, the layered body was immersed in a washing bath (an aqueous solution obtained by mixing 4 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 20°C (washing treatment). After that, while drying in an oven maintained at 90°C, the contact surface temperature was maintained at 75°C with a heating roller made of SUS for about 2 seconds (drying shrinkage treatment). The shrinkage rate of the laminate in the width direction obtained by the drying shrinkage treatment was 5.2%. A polarizer with a thickness of 5 µm is formed on the resin substrate in the above manner.

2.製作偏光板 於上述所得偏光件之表面(與樹脂基材相反之側的面)透過紫外線硬化型接著劑貼合HC-COP薄膜作為保護層。具體而言,是塗敷成硬化型接著劑之總厚度成為1.0μm,並使用輥軋機進行貼合。之後,從保護層側照射UV光線使接著劑硬化。此外,HC-COP薄膜係環烯烴(COP)薄膜(日本ZEON公司製,製品名「ZF12」,厚度25µm)上形成有硬塗(HC)層(厚度2µm)之薄膜,並以COP薄膜成為偏光件側之方來貼合。接著,剝離樹脂基材,而獲得具有保護層(HC層/COP薄膜)/接著劑層/偏光件之構成的偏光板。2. Making polarizing plates An HC-COP film was attached as a protective layer to the surface of the polarizer obtained above (the surface on the side opposite to the resin substrate) through an ultraviolet curable adhesive. Specifically, it is applied so that the total thickness of the hardening type adhesive becomes 1.0 μm, and is bonded using a rolling mill. After that, UV rays are irradiated from the protective layer side to harden the adhesive. In addition, the HC-COP film is a cyclic olefin (COP) film (manufactured by ZEON, Japan, product name "ZF12", thickness 25µm) with a hard coat (HC) layer (thickness 2µm) formed on it, and the COP film is used as a polarizer Fit it on the side of the piece. Next, the resin substrate is peeled off to obtain a polarizing plate having a composition of protective layer (HC layer/COP film)/adhesive layer/polarizer.

3.製作構成相位差層之第1定向固化層及第2定向固化層 將顯示向列型液晶相的聚合性液晶(BASF公司製:商品名「Paliocolor LC242」,以下述式表示)10g與對該聚合性液晶化合物的光聚合引發劑(BASF公司製:商品名「IRGACURE 907」)3g溶解至甲苯40g中,而調製出液晶組成物(塗敷液)。 [化學式8]

Figure 02_image017
使用擦拭布擦拭聚對苯二甲酸乙二酯(PET)薄膜(厚度38μm)表面,施行定向處理。定向處理之方向係設為貼合至偏光板時由視辨側觀看時相對於偏光件之吸收軸方向呈15°方向。利用棒塗機將上述液晶塗敷液塗敷至該定向處理表面,並於90℃下進行2分鐘加熱乾燥,藉此使液晶化合物定向。使用金屬鹵素燈以1mJ/cm2 的光照射依上述方式形成的液晶層,使該液晶層硬化,藉此於PET薄膜上形成液晶定向固化層A。液晶定向固化層A的厚度為2.5μm,面內相位差Re(550)為270nm。並且,液晶定向固化層A具有nx>ny=nz之折射率分布。 變更塗敷厚度,並將定向處理方向設為由視辨側觀看時相對於偏光件之吸收軸方向呈75°方向,除此之外依與上述相同方式於PET薄膜上形成液晶定向固化層B。液晶定向固化層B的厚度為1.5μm,面內相位差Re(550)為140nm。並且,液晶定向固化層B具有nx>ny=nz之折射率分布。3. Production of the first oriented cured layer and the second oriented cured layer constituting the retardation layer will show a nematic liquid crystal phase polymerizable liquid crystal (made by BASF Corporation: trade name "Paliocolor LC242", represented by the following formula) 10g and 3 g of a photopolymerization initiator (manufactured by BASF Corporation: trade name "IRGACURE 907") of this polymerizable liquid crystal compound was dissolved in 40 g of toluene to prepare a liquid crystal composition (coating liquid). [Chemical formula 8]
Figure 02_image017
Wipe the surface of a polyethylene terephthalate (PET) film (thickness 38 μm) with a wiping cloth, and perform orientation treatment. The direction of the orientation treatment is set to be 15° with respect to the absorption axis direction of the polarizer when viewed from the viewing side when attached to the polarizer. The above-mentioned liquid crystal coating liquid was applied to the alignment treatment surface using a bar coater, and heated and dried at 90° C. for 2 minutes, thereby aligning the liquid crystal compound. A metal halide lamp was used to irradiate the liquid crystal layer formed in the above manner with light of 1 mJ/cm 2 to harden the liquid crystal layer, thereby forming the liquid crystal orientation cured layer A on the PET film. The thickness of the liquid crystal orientation cured layer A was 2.5 μm, and the in-plane phase difference Re (550) was 270 nm. In addition, the liquid crystal orientation curing layer A has a refractive index distribution of nx>ny=nz. Change the coating thickness and set the orientation treatment direction to be 75° with respect to the absorption axis direction of the polarizer when viewed from the viewing side, except that the liquid crystal orientation cured layer B is formed on the PET film in the same manner as above . The thickness of the liquid crystal orientation cured layer B was 1.5 μm, and the in-plane phase difference Re (550) was 140 nm. In addition, the liquid crystal orientation curing layer B has a refractive index distribution of nx>ny=nz.

4.形成相位差層 於上述2.所得偏光板的偏光件表面依序轉印上述3.所得液晶定向固化層A及液晶定向固化層B。此時,係以偏光件之吸收軸與液晶定向固化層A之慢軸形成之角度成為15°且偏光件之吸收軸與液晶定向固化層B之慢軸形成之角度成為75°的方式進行轉印(貼合)。另外,各自之轉印(貼合)係透過上述2.所用之紫外線硬化型接著劑(厚度1.0μm)來進行。依上述方式,製作出具有保護層(HC層/COP薄膜)/接著劑層/偏光件/接著劑層/相位差層(第1液晶定向固化層/接著劑層/第2液晶定向固化層)之構成的積層體。4. Formation of retardation layer The liquid crystal orientation cured layer A and the liquid crystal orientation cured layer B obtained in 3. above are sequentially transferred onto the surface of the polarizing member of the polarizing plate obtained in the above 2. At this time, the rotation is performed such that the angle formed by the absorption axis of the polarizer and the slow axis of the liquid crystal orientation curing layer A becomes 15°, and the angle formed by the absorption axis of the polarizer and the slow axis of the liquid crystal orientation curing layer B becomes 75°. Printing (fitting). In addition, the respective transfer (bonding) was performed through the ultraviolet curable adhesive (thickness 1.0 μm) used in 2. above. According to the above method, a protective layer (HC layer/COP film)/adhesive layer/polarizer/adhesive layer/phase difference layer (first liquid crystal oriented curing layer/adhesive layer/second liquid crystal oriented curing layer) is produced The layered body composed of.

5.製作附相位差層之偏光板 將丙烯酸系樹脂(楠本化成公司製,製品名「B-811」,Tg:110℃,Mw:40000)20份溶解於甲基乙基酮80份中,而獲得樹脂溶液(20%)。將該樹脂溶液用線棒塗佈於上述4.所得積層體之第2液晶定向固化層表面,並將塗佈膜以60℃乾燥5分鐘,而形成以樹脂之有機溶劑溶液之塗佈膜的固化物的形式構成之碘透過抑制層(厚度0.5µm)。接著,於碘透過抑制層表面設置黏著劑層(厚度15µm),而獲得具有保護層(HC層/COP薄膜)/接著劑層/偏光件/接著劑層/相位差層(第1液晶定向固化層/接著劑層/第2液晶定向固化層)/碘透過抑制層/黏著劑層之構成的附相位差層之偏光板。所得附相位差層之偏光板的總厚度為39.5μm。將所得附相位差層之偏光板供於上述(4)~(7)的評估。此外,關於金屬腐蝕性,係與未形成碘透過抑制層之比較例1(後述)做比較。將結果列於表1。5. Making polarizing plate with retardation layer 20 parts of acrylic resin (manufactured by Kusumoto Chemical Co., Ltd., product name "B-811", Tg: 110°C, Mw: 40,000) was dissolved in 80 parts of methyl ethyl ketone to obtain a resin solution (20%). The resin solution was coated on the surface of the second liquid crystal orientation cured layer of the laminate obtained in the above 4. with a wire bar, and the coating film was dried at 60°C for 5 minutes to form a coating film of the organic solvent solution of the resin Iodine permeation suppression layer (thickness 0.5µm) formed in the form of a cured product. Next, an adhesive layer (thickness 15 µm) is placed on the surface of the iodine permeation suppression layer to obtain a protective layer (HC layer/COP film)/adhesive layer/polarizer/adhesive layer/phase difference layer (first liquid crystal orientation curing Layer/Adhesive layer/Second liquid crystal orientation curing layer)/Iodine permeation inhibiting layer/Adhesive layer of polarizing plate with retardation layer. The total thickness of the obtained polarizing plate with retardation layer was 39.5 μm. The obtained polarizing plate with retardation layer was used for the evaluation of (4) to (7) above. In addition, the metal corrosivity was compared with Comparative Example 1 (described later) in which an iodine permeation suppression layer was not formed. The results are listed in Table 1.

[實施例2] 將甲基丙烯酸甲酯(MMA,富士薄膜和光純藥公司製,商品名「甲基丙烯酸甲酯單體」)97.0份、上述通式(1e)所示共聚單體3.0份、聚合引發劑(富士薄膜和光純藥公司製,商品名「2,2´-偶氮雙(異丁腈)」)0.2份溶解於甲苯200份中。接著,於氮氣環境下一邊加熱至70℃一邊進行聚合反應5.5小時,而獲得含硼之丙烯酸系樹脂溶液(固體成分濃度:33%)。所得含硼之丙烯酸系聚合物之Tg為110℃,Mw為80000。使用該含硼之丙烯酸系聚合物取代丙烯酸系樹脂「B-811」、及將碘透過抑制層之厚度設為0.3µm,除此之外依與實施例1相同方式而製出附相位差層之偏光板。將所得附相位差層之偏光板供於進行與實施例1相同之評估。將結果列於表1及表2。[Example 2] 97.0 parts of methyl methacrylate (MMA, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., trade name "methyl methacrylate monomer"), 3.0 parts of the comonomer represented by the general formula (1e), and polymerization initiator ( Produced by Fuji Film Wako Pure Chemical Industries, Ltd., brand name "2,2´-Azobis(isobutyronitrile)") 0.2 part was dissolved in 200 parts of toluene. Next, the polymerization reaction was carried out for 5.5 hours while heating to 70° C. in a nitrogen atmosphere to obtain a boron-containing acrylic resin solution (solid content concentration: 33%). The obtained boron-containing acrylic polymer had a Tg of 110°C and a Mw of 80,000. The boron-containing acrylic polymer was used instead of the acrylic resin "B-811", and the thickness of the iodine permeation suppression layer was set to 0.3 µm, except that the retardation layer was produced in the same manner as in Example 1. The polarizing plate. The obtained polarizing plate with retardation layer was used for the same evaluation as in Example 1. The results are listed in Table 1 and Table 2.

[實施例3] 除了將碘透過抑制層的厚度設為0.5µm外,依與實施例2相同方式而製出附相位差層之偏光板。將所得附相位差層之偏光板供於進行與實施例1相同之評估。將結果列於表1及表2。[Example 3] Except that the thickness of the iodine permeation suppression layer was set to 0.5 µm, a polarizing plate with a retardation layer was manufactured in the same manner as in Example 2. The obtained polarizing plate with retardation layer was used for the same evaluation as in Example 1. The results are listed in Table 1 and Table 2.

[實施例4] 除了使用熱塑性環氧樹脂(Mitsubishi Chemical Co.製,商品名「jER(註冊商標)1256B40」,Tg:100℃,Mw:45000)來取代丙烯酸系樹脂「B-811」外,依與實施例1相同方式而製出附相位差層之偏光板。將所得附相位差層之偏光板供於進行與實施例1相同之評估。將結果列於表1及表2。[Example 4] Except that thermoplastic epoxy resin (manufactured by Mitsubishi Chemical Co., trade name "jER (registered trademark) 1256B40", Tg: 100°C, Mw: 45000) is used instead of the acrylic resin "B-811", the same as in Example 1 In the same way, a polarizing plate with retardation layer is produced. The obtained polarizing plate with retardation layer was used for the same evaluation as in Example 1. The results are listed in Table 1 and Table 2.

[實施例5] 使用熱塑性環氧樹脂(Mitsubishi Chemical Co.製,商品名「jER(註冊商標)YX7200B35」,Tg:150℃,Mw:30000)來取代丙烯酸系樹脂「B-811」、及將碘透過抑制層之厚度設為0.3µm,除此之外依與實施例1相同方式而製出附相位差層之偏光板。將所得附相位差層之偏光板供於進行與實施例1相同之評估。將結果列於表1及表2。[Example 5] Use thermoplastic epoxy resin (manufactured by Mitsubishi Chemical Co., trade name "jER (registered trademark) YX7200B35", Tg: 150°C, Mw: 30000) instead of acrylic resin "B-811" and pass iodine through the suppression layer The thickness was set to 0.3 µm, except that the polarizing plate with retardation layer was manufactured in the same manner as in Example 1. The obtained polarizing plate with retardation layer was used for the same evaluation as in Example 1. The results are listed in Table 1 and Table 2.

[實施例6] 除了將碘透過抑制層的厚度設為0.5µm外,依與實施例5相同方式而製出附相位差層之偏光板。將所得附相位差層之偏光板供於進行與實施例1相同之評估。將結果列於表1及表2。[Example 6] Except that the thickness of the iodine permeation suppression layer was set to 0.5 µm, a polarizing plate with a retardation layer was produced in the same manner as in Example 5. The obtained polarizing plate with retardation layer was used for the same evaluation as in Example 1. The results are listed in Table 1 and Table 2.

[實施例7] 除了使用「B-811」15份與熱塑性環氧樹脂(Mitsubishi Chemical Co.製,商品名「jER(註冊商標)YX6954BH30」)85份(固體成分換算)之摻合物來取代丙烯酸系樹脂「B-811」外,依與實施例1相同方式而製出附相位差層之偏光板。該摻合物之Tg為125℃,Mw為38000。將所得附相位差層之偏光板供於進行與實施例1相同之評估。將結果列於表1及表2。[Example 7] Except that 15 parts of "B-811" and 85 parts of thermoplastic epoxy resin (manufactured by Mitsubishi Chemical Co., trade name "jER (registered trademark) YX6954BH30") (in terms of solid content) are used instead of acrylic resin "B Except for -811", the polarizing plate with retardation layer was manufactured in the same manner as in Example 1. The Tg of this blend is 125°C and the Mw is 38,000. The obtained polarizing plate with retardation layer was used for the same evaluation as in Example 1. The results are listed in Table 1 and Table 2.

[實施例8] 於實施例1之於2.所得具有保護層(HC層/COP薄膜)/接著劑層/偏光件之構成的偏光板之偏光件側塗佈實施例7中所使用之樹脂摻合物並乾燥,而形成以樹脂之有機溶劑溶液之塗佈膜的固化物的形式構成之碘透過抑制層(厚度0.5µm)。於碘透過抑制層表面依與實施例1相同方式依序轉印液晶定向固化層A及液晶定向固化層B,而獲得具有保護層(HC層/COP薄膜)/接著劑層/偏光件/碘透過抑制層/接著劑層/相位差層(第1液晶定向固化層/接著劑層/第2液晶定向固化層)/黏著劑層之構成的附相位差層之偏光板。將所得附相位差層之偏光板供於進行與實施例1相同之評估。將結果列於表1及表2。[Example 8] Apply the resin blend used in Example 7 to the polarizer side of the polarizing plate obtained with a protective layer (HC layer/COP film)/adhesive layer/polarizer composition in Example 1 to 2. , And form an iodine permeation suppression layer (thickness 0.5μm) composed of a cured product of a coating film of a resin organic solvent solution. The liquid crystal orientation curing layer A and the liquid crystal orientation curing layer B were sequentially transferred to the surface of the iodine permeation suppression layer in the same manner as in Example 1, to obtain a protective layer (HC layer/COP film)/adhesive layer/polarizer/iodine Polarizing plate with retardation layer composed of suppression layer/adhesive layer/retardation layer (first liquid crystal oriented curing layer/adhesive layer/second liquid crystal oriented curing layer)/adhesive layer. The obtained polarizing plate with retardation layer was used for the same evaluation as in Example 1. The results are listed in Table 1 and Table 2.

[實施例9] 除了使用實施例2中含硼之丙烯酸系聚合物外,依與實施例8相同方式而製出具有保護層(HC層/COP薄膜)/接著劑層/偏光件/碘透過抑制層之構成的積層體。接著,使用實施例2中含硼之丙烯酸系聚合物15份與熱塑性環氧樹脂(Mitsubishi Chemical Co.製,商品名「jER(註冊商標)YX6954BH30」)85份(固體成分換算)之摻合物,除此之外依與實施例1相同方式而獲得具有保護層(HC層/COP薄膜)/接著劑層/偏光件/碘透過抑制層/接著劑層/相位差層(第1液晶定向固化層/接著劑層/第2液晶定向固化層)/碘透過抑制層/黏著劑層之構成的附相位差層之偏光板。所得附相位差層之偏光板的總厚度為40μm。將所得附相位差層之偏光板供於進行與實施例1相同之評估。將結果列於表2。[Example 9] Except for using the boron-containing acrylic polymer in Example 2, in the same manner as in Example 8, a protective layer (HC layer/COP film)/adhesive layer/polarizer/iodine permeation inhibiting layer was prepared. Layered body. Next, a blend of 15 parts of boron-containing acrylic polymer in Example 2 and 85 parts of thermoplastic epoxy resin (manufactured by Mitsubishi Chemical Co., trade name "jER (registered trademark) YX6954BH30") (in terms of solid content) was used Other than that, in the same manner as in Example 1, a protective layer (HC layer/COP film)/adhesive layer/polarizer/iodine transmission suppression layer/adhesive layer/phase difference layer (first liquid crystal orientation curing Layer/Adhesive layer/Second liquid crystal orientation curing layer)/Iodine permeation inhibiting layer/Adhesive layer of polarizing plate with retardation layer. The total thickness of the obtained polarizing plate with retardation layer was 40 μm. The obtained polarizing plate with retardation layer was used for the same evaluation as in Example 1. The results are listed in Table 2.

[實施例10] 於設置於偏光件與相位差層之間且鄰接偏光件之位置的碘透過抑制層採用實施例2中所得含硼之丙烯酸系聚合物15份與熱塑性環氧樹脂(Mitsubishi Chemical Co.製,商品名「jER(註冊商標)YX6954BH30」)85份(固體成分換算)之摻合物,除此之外依與實施例9相同方式而獲得附相位差層之偏光板。所得附相位差層之偏光板的總厚度為40μm。將所得附相位差層之偏光板供於進行與實施例1相同之評估。將結果列於表2。[Example 10] The iodine permeation suppressing layer provided between the polarizing member and the retardation layer and adjacent to the polarizing member used 15 parts of the boron-containing acrylic polymer obtained in Example 2 and a thermoplastic epoxy resin (manufactured by Mitsubishi Chemical Co., commercial product). Named "jER (registered trademark) YX6954BH30") a blend of 85 parts (in terms of solid content), except that the polarizing plate with retardation layer was obtained in the same manner as in Example 9. The total thickness of the obtained polarizing plate with retardation layer was 40 μm. The obtained polarizing plate with retardation layer was used for the same evaluation as in Example 1. The results are listed in Table 2.

[實施例11] 將形成於偏光件與相位差層之間且鄰接偏光件之位置的碘透過抑制層形成於偏光件與相位差層之間且鄰接相位差層之位置,除此之外依與實施例10相同方式而獲得具有保護層(HC層/COP薄膜)/接著劑層/偏光件/接著劑層/碘透過抑制層/相位差層(第1液晶定向固化層/接著劑層/第2液晶定向固化層)/碘透過抑制層/黏著劑層之構成的附相位差層之偏光板。所得附相位差層之偏光板的總厚度為40μm。將所得附相位差層之偏光板供於進行與實施例1相同之評估。將結果列於表2。[Example 11] The iodine permeation suppression layer formed between the polarizer and the retardation layer and adjacent to the polarizer is formed between the polarizer and the retardation layer and adjacent to the retardation layer, except that it is the same as in Example 10 Method to obtain a protective layer (HC layer/COP film)/adhesive layer/polarizer/adhesive layer/iodine transmission suppression layer/phase difference layer (first liquid crystal oriented curing layer/adhesive layer/second liquid crystal oriented curing Layer)/Iodine permeation suppression layer/Adhesive layer composed of polarizing plate with retardation layer. The total thickness of the obtained polarizing plate with retardation layer was 40 μm. The obtained polarizing plate with retardation layer was used for the same evaluation as in Example 1. The results are listed in Table 2.

[實施例12] 依與實施例9相同方式,於偏光件與相位差層之間且鄰接偏光件之位置進一步形成碘透過抑制層,除此之外依與實施例11相同方式而獲得具有保護層(HC層/COP薄膜)/接著劑層/偏光件/碘透過抑制層/接著劑層/碘透過抑制層/相位差層(第1液晶定向固化層/接著劑層/第2液晶定向固化層)/碘透過抑制層/黏著劑層之構成的附相位差層之偏光板。所得附相位差層之偏光板的總厚度為40.5μm。將所得附相位差層之偏光板供於進行與實施例1相同之評估。將結果列於表2。[Example 12] In the same manner as in Example 9, an iodine transmission suppression layer was further formed between the polarizing member and the retardation layer and adjacent to the polarizing member. Other than that, in the same manner as in Example 11, a protective layer (HC layer/ COP film)/adhesive layer/polarizer/iodine transmission suppression layer/adhesive layer/iodine transmission suppression layer/phase difference layer (first liquid crystal oriented cured layer/adhesive layer/second liquid crystal oriented cured layer)/iodine transmission Polarizing plate with retardation layer composed of suppression layer/adhesive layer. The total thickness of the obtained polarizing plate with retardation layer was 40.5 μm. The obtained polarizing plate with retardation layer was used for the same evaluation as in Example 1. The results are listed in Table 2.

[比較例1] 除了未形成碘透過抑制層外,依與實施例1相同方式而製出附相位差層之偏光板。將所得附相位差層之偏光板供於進行與實施例1相同之評估。將結果列於表1及表2。[Comparative Example 1] Except that the iodine permeation suppression layer was not formed, a polarizing plate with a retardation layer was produced in the same manner as in Example 1. The obtained polarizing plate with retardation layer was used for the same evaluation as in Example 1. The results are listed in Table 1 and Table 2.

[比較例2] 使用丙烯酸系樹脂「B-723」(楠本化成公司製,Tg:54℃,Mw:200000)取代丙烯酸系樹脂「B-811」,除此之外依與實施例1相同方式而製出附相位差層之偏光板。將所得附相位差層之偏光板供於進行與實施例1相同之評估。將結果列於表1及表2。[Comparative Example 2] Acrylic resin "B-723" (manufactured by Kusumoto Chemical Co., Ltd., Tg: 54°C, Mw: 200,000) was used instead of acrylic resin "B-811", except that the additional phase was produced in the same manner as in Example 1. Polarizing plate with differential layer. The obtained polarizing plate with retardation layer was used for the same evaluation as in Example 1. The results are listed in Table 1 and Table 2.

[比較例3] 使用光硬化性環氧樹脂(Mitsubishi Chemical Co.製,商品名「jER(註冊商標)828」取代丙烯酸系樹脂「B-811」,且作為光聚合引發劑使用San-Apro Ltd.製「CPI100P」),除此之外依與實施例1相同方式而製出附相位差層之偏光板。將所得附相位差層之偏光板供於進行與實施例1相同之評估。將結果列於表1及表2。[Comparative Example 3] A photocurable epoxy resin (manufactured by Mitsubishi Chemical Co., brand name "jER (registered trademark) 828" is used instead of the acrylic resin "B-811", and "CPI100P" manufactured by San-Apro Ltd. is used as a photopolymerization initiator. ), except that the polarizing plate with retardation layer was manufactured in the same manner as in Example 1. The obtained polarizing plate with retardation layer was used for the same evaluation as in Example 1. The results are listed in Table 1 and Table 2.

[比較例4] 除了使用PVA系樹脂(Mitsubishi Chemical Co.製,商品名「GOHSEFIMER Z200」,Tg:80℃,Mw:8800)取代丙烯酸系樹脂「B-811」外,依與實施例1相同方式而製出附相位差層之偏光板。將所得附相位差層之偏光板供於進行與實施例1相同之評估。將結果列於表1及表2。[Comparative Example 4] Except that PVA resin (manufactured by Mitsubishi Chemical Co., trade name "GOHSEFIMER Z200", Tg: 80°C, Mw: 8800) was used instead of acrylic resin "B-811", the attachment was produced in the same manner as in Example 1. Polarizing plate of retardation layer. The obtained polarizing plate with retardation layer was used for the same evaluation as in Example 1. The results are listed in Table 1 and Table 2.

[參考例1] 1.製作偏光板 依與實施例1相同方式而獲得具有保護層(HC層/COP薄膜)/偏光件之構成的偏光板。[Reference example 1] 1. Make a polarizing plate In the same manner as in Example 1, a polarizing plate having a protective layer (HC layer/COP film)/polarizer composition was obtained.

2.製作構成相位差層之相位差薄膜 2-1.聚酯碳酸酯系樹脂之聚合 使用具備有攪拌葉片及控制成100℃之回流冷卻器之由2台直立式反應器構成之批次聚合裝置進行聚合。饋入雙[9-(2-苯氧基羰基乙基)茀-9-基]甲烷29.60質量份(0.046mol)、異山梨醇(ISB)29.21質量份(0.200mol)、螺甘油(SPG)42.28質量份(0.139mol)、碳酸二苯酯(DPC)63.77質量份(0.298mol)及作為觸媒的乙酸鈣一水合物1.19×10-2 質量份(6.78×10-5 mol)。將反應器內進行減壓氮取代後,以加熱介質加溫,並於內部溫度達到100℃之時間點開始攪拌。於升溫開始40分鐘後使內部溫度達到220℃,控制維持該溫度的同時開始減壓,使在達到220℃後起90分鐘成13.3kPa。將隨聚合反應副生成之苯酚蒸氣導入100℃之回流冷卻器,使苯酚蒸氣中所含之些許量單體成分返回反應器,並將未凝結之苯酚蒸氣導入45℃的凝結器中回收。將氮導入第1反應器暫時使其回復到大氣壓力後,將第1反應器內之經寡聚化的反應液移至第2反應器。接著,開始進行第2反應器內的升溫及減壓,並以50分鐘使內溫成為240℃、壓力成為0.2kPa。其後,進行聚合直到達到預定之攪拌動力。在達到預定動力之時間點將氮導入反應器中使壓力回復,並將所生成之聚酯碳酸酯系樹脂擠製至水中,裁切束狀物而得到丸粒。2. Production of retardation film that constitutes the retardation layer 2-1. The polymerization of polyester carbonate resin uses a batch polymerization consisting of 2 vertical reactors equipped with a stirring blade and a reflux cooler controlled to 100°C The device is aggregated. Feed in bis[9-(2-phenoxycarbonylethyl)茀-9-yl]methane 29.60 parts by mass (0.046mol), isosorbide (ISB) 29.21 parts by mass (0.200mol), spiroglycerin (SPG) 42.28 parts by mass (0.139 mol), 63.77 parts by mass (0.298 mol) of diphenyl carbonate (DPC), and 1.19×10 -2 parts by mass (6.78×10 -5 mol) of calcium acetate monohydrate as a catalyst. After replacing the pressure with nitrogen in the reactor, it is heated with a heating medium, and stirring is started when the internal temperature reaches 100°C. The internal temperature was brought to 220°C 40 minutes after the start of the temperature increase, and the pressure was started while maintaining the temperature, so that it became 13.3 kPa 90 minutes after the temperature reached 220°C. The phenol vapor by-produced with the polymerization reaction is introduced into a reflux cooler at 100°C, a small amount of monomer components contained in the phenol vapor are returned to the reactor, and uncondensed phenol vapor is introduced into a condenser at 45°C for recovery. After nitrogen was introduced into the first reactor to temporarily return to atmospheric pressure, the oligomerization reaction solution in the first reactor was transferred to the second reactor. Next, the temperature increase and pressure reduction in the second reactor were started, and the internal temperature was set to 240° C. and the pressure was set to 0.2 kPa over 50 minutes. Thereafter, polymerization is carried out until a predetermined stirring power is reached. At the time point when a predetermined power is reached, nitrogen is introduced into the reactor to restore the pressure, and the produced polyester carbonate-based resin is extruded into water, and the bundle is cut to obtain pellets.

2-2.製作相位差薄膜 將所得聚酯碳酸酯系樹脂(丸粒)在80℃下真空乾燥5小時後,使用具備單軸擠製機(東芝機械公司製,缸筒設定溫度:250℃)、T型模(寬200mm,設定溫度:250℃)、冷卻輥(設定溫度:120~130℃)及捲取機之薄膜製膜裝置,製作出厚度135μm之長條狀樹脂薄膜。將所得長條狀樹脂薄膜以延伸溫度133℃、延伸倍率2.8倍沿寬度方向延伸,而獲得厚度53μm之相位差薄膜。所得相位差薄膜之Re(550)為141nm,Re(450)/Re(550)為0.82,且Nz係數為1.12。2-2. Making retardation film After drying the obtained polyester carbonate-based resin (pellet) in vacuum at 80°C for 5 hours, use a uniaxial extruder (manufactured by Toshiba Machine Co., Ltd., cylinder set temperature: 250°C) and T-die (width 200mm). , Setting temperature: 250℃), cooling roll (setting temperature: 120~130℃) and film forming device of the coiler to produce a long resin film with a thickness of 135μm. The obtained long resin film was stretched in the width direction at a stretching temperature of 133°C and a stretching ratio of 2.8 times to obtain a retardation film with a thickness of 53 μm. The Re(550) of the obtained retardation film is 141nm, the Re(450)/Re(550) is 0.82, and the Nz coefficient is 1.12.

3.製作附相位差層之偏光板 透過丙烯酸系黏著劑(厚度5μm)於上述1.所得偏光板的偏光件表面貼合上述2.所得相位差薄膜。此時,係以使偏光件之吸收軸與相位差薄膜之慢軸形成45°之角度的方式貼合。並於相位差層表面設置與實施例1相同之黏著劑層。依上述方式,而獲得具有保護層/接著劑層/偏光件/黏著劑層/相位差層(樹脂薄膜之延伸薄膜)/黏著劑層之構成的附相位差層之偏光板。所得附相位差層之偏光板的總厚度為91μm。將所得附相位差層之偏光板供於進行與實施例1相同之評估。將結果列於表1及表2。3. Making polarizing plate with retardation layer Adhere the retardation film obtained in 2. above on the surface of the polarizer of the polarizing plate obtained in 1. through an acrylic adhesive (thickness 5 μm). At this time, it is bonded so that the absorption axis of the polarizer and the slow axis of the retardation film form an angle of 45°. And set the same adhesive layer as in Example 1 on the surface of the retardation layer. According to the above method, a polarizing plate with a retardation layer having the composition of protective layer/adhesive layer/polarizer/adhesive layer/retardation layer (extended film of resin film)/adhesive layer is obtained. The total thickness of the obtained polarizing plate with retardation layer was 91 μm. The obtained polarizing plate with retardation layer was used for the same evaluation as in Example 1. The results are listed in Table 1 and Table 2.

[實施例13] 除了未形成相位差層外,依與實施例1相同方式而獲得具有保護層(HC層/COP薄膜)/接著劑層/偏光件/碘透過抑制層/黏著劑層之構成的偏光板。所得偏光板的總厚度為33.5μm。將所得偏光板供於與實施例1相同之評估。將結果列於表1及表2。此外,本實施例為偏光板,與附相位差層之偏光板之構成不同,故有關金屬腐蝕性並未與比較例1做比較。[Example 13] Except that the retardation layer is not formed, a polarizing plate with a protective layer (HC layer/COP film)/adhesive layer/polarizer/iodine permeation inhibiting layer/adhesive layer is obtained in the same manner as in Example 1. The total thickness of the obtained polarizing plate was 33.5 μm. The obtained polarizing plate was subjected to the same evaluation as in Example 1. The results are listed in Table 1 and Table 2. In addition, this embodiment is a polarizing plate, which is different in composition from a polarizing plate with a retardation layer, so the corrosiveness of the metal is not compared with that of Comparative Example 1.

[表1]

Figure 02_image019
[Table 1]
Figure 02_image019

[表2]

Figure 02_image021
[Table 2]
Figure 02_image021

[評估] 由表1明顯可知,本發明實施例之附相位差層之偏光板及偏光板藉由形成預定之碘透過抑制層來將黏著劑層之碘存在指數設為預定值以下,可縮小在高溫高濕環境下之偏光度變化,而具有優異之耐久性。又,本發明實施例之附相位差層之偏光板及偏光板亦可顯著抑制在高溫高濕環境下之金屬腐蝕性及反射率上升。並且,從參考例1明顯可知,所述偏光度變化、反射率上升及金屬腐蝕性為非常薄型的附相位差層之偏光板及偏光板特有的課題。此外,比較實施例1與實施例13明顯可知,液晶定向固化層(非常薄之相位差層)的有無對本發明效果無實質影響。[Evaluate] It is obvious from Table 1 that the polarizing plate with retardation layer and the polarizing plate of the embodiment of the present invention form a predetermined iodine penetration suppression layer to set the iodine existence index of the adhesive layer below a predetermined value, which can be reduced at high temperature and high temperature. The degree of polarization changes in a wet environment, and it has excellent durability. In addition, the polarizing plate with retardation layer and the polarizing plate of the embodiment of the present invention can also significantly suppress the increase in metal corrosion and reflectivity in a high-temperature and high-humidity environment. In addition, it is clear from Reference Example 1 that the aforementioned change in polarization degree, increase in reflectance, and metal corrosion are issues unique to very thin polarizers with retardation layers and polarizers. In addition, comparing Example 1 and Example 13 clearly shows that the presence or absence of the liquid crystal orientation cured layer (very thin retardation layer) has no substantial influence on the effect of the present invention.

由表2明顯可知,本發明實施例9~12之附相位差層之偏光板藉由包含2層或3層碘透過抑制層,即使在高溫高濕環境下投入長時間(200小時)之情況下,仍可顯著抑制金屬腐蝕性。因此可知,本發明實施例9~12之附相位差層之偏光板在應用於影像顯示裝置時,可顯著抑制金屬構件之腐蝕。It is obvious from Table 2 that the polarizing plates with retardation layer of Examples 9 to 12 of the present invention include two or three layers of iodine permeation suppression layer, even if they are put in for a long time (200 hours) in a high temperature and high humidity environment. It can still significantly inhibit metal corrosion. Therefore, it can be seen that the polarizing plate with retardation layer of Examples 9 to 12 of the present invention can significantly inhibit the corrosion of metal components when applied to an image display device.

產業上之可利用性 本發明偏光板可適宜使用在液晶顯示裝置、有機EL顯示裝置及無機EL顯示裝置。本發明附相位差層之偏光板可適宜用作液晶顯示裝置、有機EL顯示裝置及無機EL顯示裝置用之圓偏光板。Industrial availability The polarizing plate of the present invention can be suitably used in liquid crystal display devices, organic EL display devices, and inorganic EL display devices. The polarizing plate with retardation layer of the present invention can be suitably used as a circular polarizing plate for liquid crystal display devices, organic EL display devices and inorganic EL display devices.

10:偏光板 11:偏光件 12:保護層 20:相位差層(第1相位差層) 21:第1液晶定向固化層 22:第2液晶定向固化層 30:黏著劑層 40:碘透過抑制層 50:另一相位差層(第2相位差層) 60:導電層或附導電層之各向同性基材 100:附相位差層之偏光板 101:附相位差層之偏光板 102:附相位差層之偏光板 103:附相位差層之偏光板 104:附相位差層之偏光板 105:附相位差層之偏光板10: Polarizing plate 11: Polarizing parts 12: protective layer 20: Retardation layer (first retardation layer) 21: The first liquid crystal orientation curing layer 22: The second liquid crystal orientation curing layer 30: Adhesive layer 40: Iodine permeation suppression layer 50: Another retardation layer (second retardation layer) 60: Conductive layer or isotropic substrate with conductive layer 100: Polarizing plate with retardation layer 101: Polarizing plate with retardation layer 102: Polarizing plate with retardation layer 103: Polarizing plate with retardation layer 104: Polarizing plate with retardation layer 105: Polarizing plate with retardation layer

圖1係本發明一實施形態之偏光板的概略截面圖。 圖2A係本發明一實施形態之附相位差層之偏光板的概略截面圖。 圖2B係本發明另一實施形態之附相位差層之偏光板的概略截面圖。 圖3係本發明又另一實施形態之附相位差層之偏光板的概略截面圖。 圖4係本發明又另一實施形態之附相位差層之偏光板的概略截面圖。 圖5係本發明又另一實施形態之附相位差層之偏光板的概略截面圖。 圖6係本發明又另一實施形態之附相位差層之偏光板的概略截面圖。Fig. 1 is a schematic cross-sectional view of a polarizing plate according to an embodiment of the present invention. Fig. 2A is a schematic cross-sectional view of a polarizing plate with a retardation layer according to an embodiment of the present invention. Fig. 2B is a schematic cross-sectional view of a polarizing plate with a retardation layer according to another embodiment of the present invention. Fig. 3 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to still another embodiment of the present invention. Fig. 4 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to still another embodiment of the present invention. Fig. 5 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to still another embodiment of the present invention. Fig. 6 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to still another embodiment of the present invention.

10:偏光板 10: Polarizing plate

11:偏光件 11: Polarizing parts

12:保護層 12: protective layer

30:黏著劑層 30: Adhesive layer

40:碘透過抑制層 40: Iodine permeation suppression layer

Claims (12)

一種偏光板,依序具有偏光件、碘透過抑制層及黏著劑層,且該黏著劑層之碘存在指數為0.050以下。A polarizing plate has a polarizer, an iodine permeation inhibiting layer and an adhesive layer in sequence, and the iodine existence index of the adhesive layer is less than 0.050. 如請求項1之偏光板,其中前述碘透過抑制層係樹脂之有機溶劑溶液之塗佈膜的固化物或熱硬化物。The polarizing plate of claim 1, wherein the iodine permeation suppression layer resin is a cured product or a thermal cured product of a coating film of an organic solvent solution. 如請求項2之偏光板,其中構成前述碘透過抑制層之樹脂的玻璃轉移溫度為85℃以上,且重量平均分子量Mw為25000以上。The polarizing plate of claim 2, wherein the glass transition temperature of the resin constituting the aforementioned iodine permeation inhibiting layer is 85° C. or more, and the weight average molecular weight Mw is 25,000 or more. 如請求項1之偏光板,其中前述碘透過抑制層於前述偏光件與前述黏著劑層之間設有2層以上。The polarizing plate of claim 1, wherein the iodine transmission inhibiting layer is provided with two or more layers between the polarizing member and the adhesive layer. 如請求項1至4中任一項之偏光板,其中前述碘透過抑制層的厚度為0.05µm~10µm。The polarizing plate of any one of claims 1 to 4, wherein the thickness of the aforementioned iodine penetration suppression layer is 0.05 μm to 10 μm. 如請求項1至5中任一項之偏光板,其中構成前述碘透過抑制層之樹脂包含藉由將單體混合物聚合而得之共聚物,且該單體混合物包含大於50重量份之(甲基)丙烯酸系單體與大於0重量份且小於50重量份之式(1)所示單體: [化學式1]
Figure 03_image001
(式中,X表示包含反應性基之官能基,且該反應性基係選自於由乙烯基、(甲基)丙烯醯基、苯乙烯基、(甲基)丙烯醯胺基、乙烯基醚基、環氧基、氧雜環丁烷基、羥基、胺基、醛基及羧基所構成群組中之至少1種反應性基,R1 及R2 分別獨立表示氫原子、可具有取代基之脂肪族烴基、可具有取代基之芳基或可具有取代基之雜環基,R1 及R2 可相互連結形成環)。
The polarizing plate of any one of claims 1 to 5, wherein the resin constituting the iodine permeation inhibiting layer includes a copolymer obtained by polymerizing a monomer mixture, and the monomer mixture includes more than 50 parts by weight of (former) Base) acrylic monomer and more than 0 parts by weight and less than 50 parts by weight of the monomer represented by formula (1): [Chemical formula 1]
Figure 03_image001
(In the formula, X represents a functional group containing a reactive group, and the reactive group is selected from the group consisting of vinyl, (meth)acryloyl, styryl, (meth)acrylamido, vinyl At least one reactive group in the group consisting of ether group, epoxy group, oxetanyl group, hydroxyl group, amino group, aldehyde group and carboxyl group, R 1 and R 2 each independently represent a hydrogen atom and may have substitution The aliphatic hydrocarbon group of the group, the aryl group which may have a substituent, or the heterocyclic group which may have a substituent, R 1 and R 2 may be connected to each other to form a ring).
一種附相位差層之偏光板,具有如請求項1至6中任一項之偏光板及配置於前述偏光件與前述黏著劑層之間的相位差層;且 該相位差層係具有圓偏光機能或楕圓偏光機能之液晶化合物的定向固化層。A polarizing plate with a retardation layer, comprising the polarizing plate according to any one of claims 1 to 6 and a retardation layer disposed between the polarizer and the adhesive layer; and The retardation layer is a directional solidified layer of a liquid crystal compound with a circular polarization function or an elliptical polarization function. 如請求項7之附相位差層之偏光板,其中前述相位差層為單一層, 該相位差層的Re(550)為100nm~190nm,且 該相位差層之慢軸與前述偏光件之吸收軸形成之角度為40°~50°。For example, the polarizing plate with retardation layer of claim 7, wherein the aforementioned retardation layer is a single layer, The Re(550) of the retardation layer is 100nm~190nm, and The angle formed by the slow axis of the retardation layer and the absorption axis of the aforementioned polarizer is 40°-50°. 如請求項7之附相位差層之偏光板,其中前述相位差層具有第1液晶化合物之定向固化層與第2液晶化合物之定向固化層的積層結構; 該第1液晶化合物之定向固化層的Re(550)為200nm~300nm,且其慢軸與前述偏光件之吸收軸形成之角度為10°~20°; 該第2液晶化合物之定向固化層的Re(550)為100nm~190nm,且其慢軸與該偏光件之吸收軸形成之角度為70°~80°。The polarizing plate with retardation layer of claim 7, wherein the retardation layer has a laminated structure of a first liquid crystal compound oriented curing layer and a second liquid crystal compound oriented curing layer; The Re (550) of the orientation curing layer of the first liquid crystal compound is 200nm~300nm, and the angle formed by its slow axis and the absorption axis of the aforementioned polarizer is 10°-20°; The Re (550) of the orientation curing layer of the second liquid crystal compound is 100 nm to 190 nm, and the angle formed by its slow axis and the absorption axis of the polarizer is 70° to 80°. 如請求項7至9中任一項之附相位差層之偏光板,其總厚度在60µm以下。For example, the polarizing plate with retardation layer of any one of claims 7 to 9, the total thickness of which is less than 60 µm. 一種影像顯示裝置,具備如請求項1至6中任一項之偏光板或如請求項7至10中任一項之附相位差層之偏光板。An image display device is provided with a polarizing plate according to any one of claims 1 to 6 or a polarizing plate with a phase difference layer according to any one of claims 7 to 10. 如請求項11之影像顯示裝置,其係有機電致發光顯示裝置或無機電致發光顯示裝置。Such as the image display device of claim 11, which is an organic electroluminescence display device or an inorganic electroluminescence display device.
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