TWI823029B - Polarizing plates and polarizing plates with retardation layers and image display devices using the same - Google Patents
Polarizing plates and polarizing plates with retardation layers and image display devices using the same Download PDFInfo
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- TWI823029B TWI823029B TW109137411A TW109137411A TWI823029B TW I823029 B TWI823029 B TW I823029B TW 109137411 A TW109137411 A TW 109137411A TW 109137411 A TW109137411 A TW 109137411A TW I823029 B TWI823029 B TW I823029B
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- Taiwan
- Prior art keywords
- layer
- polarizing plate
- iodine
- liquid crystal
- polarizer
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Images
Landscapes
- Polarising Elements (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Electroluminescent Light Sources (AREA)
- Liquid Crystal (AREA)
Abstract
本發明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。本發明偏光板依序具有偏光件、碘透過抑制層及黏著劑層。黏著劑層之碘存在指數為0.050以下。本發明附相位差層之偏光板具有所述偏光板及配置於偏光件與黏著劑層之間的相位差層,且相位差層為具有圓偏光機能或橢圓偏光機能之液晶化合物的定向固化層。The present invention provides a thin polarizing plate and a polarizing plate with a retardation layer that have excellent durability in high-temperature and high-humidity environments. The polarizing plate of the present invention has a polarizer, an iodine transmission inhibition layer and an adhesive layer in sequence. The iodine presence index of the adhesive layer is 0.050 or less. The polarizing plate with a retardation layer of the present invention has the polarizing plate and a retardation layer arranged between the polarizer and the adhesive layer, and the retardation layer is a directionally solidified layer of a liquid crystal compound with circular polarization function or elliptical polarization function. .
Description
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 polarizing plates, polarizing plates with retardation layers, and image display devices using these.
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 (eg, organic EL display devices, inorganic EL display devices) have rapidly become popular. Typical image display devices use polarizing plates and phase difference plates. In practical applications, polarizing plates with retardation layers in which a polarizing plate and a retardation plate are integrated are widely used (for example, Patent Document 1). Recently, as the demand for thinner image display devices has increased, polarizing plates and The demand for thinning polarizing plates with retardation layers is also increasing. However, thin polarizers and polarizers with retardation layers have problems such as large changes in optical properties (typically polarization) and insufficient durability in high temperature and high humidity environments. Prior technical literature patent documents
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 conventional problems, and its main purpose is to provide a thin polarizing plate and a polarizing plate with a retardation layer that have excellent durability in high temperature and high humidity environments.
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] (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 Problems The polarizing plate of the present invention has a polarizer, an iodine transmission inhibiting 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 iodine permeation inhibiting layer is a cured product or a thermosetting product of a coating film of an organic solvent solution of resin. In one embodiment, the glass transition temperature of the resin constituting the iodine transmission inhibiting layer is 85° C. or higher, and the weight average molecular weight Mw is 25,000 or higher. In one embodiment, two or more layers of the iodine transmission inhibiting layer are provided between the polarizer and the adhesive layer. In one embodiment, the thickness of the iodine transmission inhibition layer is 0.05µm~10µm. In one embodiment, the resin constituting the iodine transmission 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 and less than 50 parts by weight of the monomer represented by formula (1): [Chemical Formula 1] (In the formula, At least one reactive group in the group consisting of an ether group, an epoxy group, an oxetanyl group, a hydroxyl group, an amine group, an aldehyde group and a carboxyl group. R 1 and R 2 each independently represent a hydrogen atom and may be substituted. The base is an aliphatic hydrocarbon group, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent, and 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 a retardation layer includes the above-mentioned polarizing plate and a retardation layer arranged between the above-mentioned polarizer and the above-mentioned adhesive layer. The retardation layer is a directionally solidified layer of a liquid crystal compound having a circular polarizing function or an eccentric polarizing function. In one embodiment, the above-mentioned 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 above-mentioned polarizer is 40°~ 50°. In one embodiment, the retardation layer has a laminated structure of a directionally solidified layer of a first liquid crystal compound and a directionally solidified layer of a second liquid crystal compound; Re (550) of the directionally solidified layer of the first liquid crystal compound is 200 nm to 300 nm. , and the angle formed by its slow axis and the absorption axis of the above-mentioned polarizer is 10°~20°; the Re(550) of the orientationally solidified layer of the second liquid crystal compound is 100nm~190nm, and the angle between its slow axis and the absorption axis of the polarizer is The angle formed by the absorption axis is 70°~80°. In one embodiment, the total thickness of the polarizing plate with the 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 image display device is an organic electroluminescent display device or an inorganic electroluminescent 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 transmission inhibition layer to control the iodine presence index of the adhesive layer, it is possible to realize a thin polarizing plate and a polarizing plate with a retardation layer that have excellent durability in high temperature and high humidity environments. The cured product or thermosetting product of the coating film of the organic solvent solution of the iodine permeation inhibiting layer-based resin that can be used in the embodiment of the present invention has a glass transition temperature of 85° C. or higher and a weight average molecular weight of the resin constituting the iodine permeation inhibiting layer. Mw is 25,000 or more, and the iodine presence index of the adhesive layer according to 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。Embodiments of the present invention will be described below, but the present invention is not limited to 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 maximum (i.e., the slow axis direction), "ny" is the refractive index in the direction orthogonal to the slow axis in the plane (i.e., the fast axis direction), 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 using light with a wavelength of 550 nm 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 phase difference in the thickness direction measured with light of wavelength λnm at 23°C. For example, "Rth(550)" is the phase difference in the thickness direction measured at 23°C using light with a wavelength of 550 nm. Rth(λ) can be obtained by the formula: Rth(λ)=(nx-nz)×d when the layer (film) thickness is d(nm). (4)Nz coefficient The Nz coefficient can be obtained by Nz=Rth/Re. (5)Angle When an angle is mentioned in this specification, the angle includes both clockwise and counterclockwise directions relative to the reference direction. So, 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. Overall composition of polarizing plate
FIG. 1 is a schematic cross-sectional view of a polarizing plate according to an embodiment of the present invention. The representative polarizing
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, as mentioned above, the iodine
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 polarizing plate with a retardation layer, two or more iodine transmission inhibiting layers can also be provided between the polarizer and the adhesive layer (for example, Figure 5 and Figure 6). By having the polarizing plate with the retardation layer having two or more iodine transmission inhibiting layers, when the polarizing plate with the retardation layer is used in an image display device, the corrosion of metal components can be significantly inhibited.
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 a retardation layer shown in Figure 4, two layers of iodine transmission inhibition layers are provided between the polarizer and the adhesive layer. In the example shown in FIG. 5 , two iodine transmission inhibition layers are provided between the polarizer 11 and the
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 a retardation layer shown in Figure 6, there are three layers of iodine transmission inhibition layers between the polarizer and the adhesive layer. In the example shown in FIG. 6 , two iodine transmission inhibiting layers are provided between the polarizer 11 and the
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 a retardation layer, the iodine transmission inhibiting layer may also be 4 or more layers (for example, 4 layers, 5 layers, or 6 layers). The greater the amount of iodine that penetrates the inhibition layer, the greater the metal corrosion inhibition effect. The number of iodine transmission inhibition layers can be set by taking into account cost, manufacturing efficiency, the total thickness of the polarizing plate with the retardation layer, etc.
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 an embodiment of the present invention, the iodine presence index of the above-mentioned
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 in the embodiment of the present invention may be in a single sheet shape or in a long strip shape. The term "elongated shape" in this specification means an elongated shape with a length that is sufficiently long relative to the width. For example, it includes an elongated shape with a length that is 10 times or more relative to the width, and preferably an elongated shape with a length that is 20 times or more. Long strip polarizing plates can be rolled into rolls.
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 is preferably 45µm or less, more preferably 40µm or less, more preferably 35µm or less, especially 30µm or less. The lower limit of the total thickness may be, for example, 22 μm. According to the embodiment of the present invention, it is possible to realize an extremely thin polarizing plate as described above, and to achieve excellent durability in a high temperature and high humidity environment in such an extremely thin polarizing plate. In addition, the polarizing plate can have extremely excellent flexibility and bending durability. Therefore, the polarizing plate is particularly suitable for use in curved image display devices and/or bendable or foldable image display devices. In addition, the so-called total thickness of the polarizing plate refers to the total thickness of the polarizer, protective layer, iodine transmission inhibitory 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
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, it is preferable that a release film is temporarily adhered to the surface of the
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.Polarizer Polarizers are typically made of polyvinyl alcohol (PVA) resin films containing dichroic substances. The thickness of the polarizer should be 1µm~8µm, 1µm~7µm is better, and 2µm~5µm is better. As long as the thickness of the polarizer is within the above range, it can greatly contribute to the thinning of the polarizing plate. Furthermore, the effect of the present invention is very remarkable in a thin polarizing plate using the above-mentioned polarizing element.
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] The boric acid content of the polarizer is preferably more than 10% by weight, preferably 13% to 25% by weight. As long as the boric acid content of the polarizer is within the above range, the synergistic effect with the iodine content described below can maintain the ease of adjusting the curling during lamination and effectively suppress the curling during heating, and at the same time improve the appearance during heating. Durability. The boric acid content can be calculated, for example, by the neutralization method using the following formula as the amount of boric acid contained per unit weight of the polarizer. [Mathematical formula 1]
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 polarizing element is preferably more than 2% by weight, preferably 2% to 10% by weight. As long as the iodine content of the polarizer is within the above range, the synergistic effect with the above-mentioned boric acid content can maintain the ease of adjusting the curling during lamination and effectively suppress the curling during heating, while improving the appearance during heating. Durability. The "iodine content" in this specification means the amount of all iodine contained in the polarizer (PVA-based resin film). More specifically, iodine exists in the polarizer in the form of iodine ions (I - ), iodine molecules (I 2 ), polyiodide ions (I 3 - , I 5 - ), etc., and the iodine content in this specification means Amounts containing all such forms of iodine. The iodine content can be calculated using, for example, the calibration curve method of X-ray fluorescence analysis. In addition, polyiodide ions exist in a state of forming a PVA-iodine complex in the polarizer. By forming the complex, absorption dichroism can be exhibited in the wavelength range of visible light. Specifically, the complex of PVA and triiodide ions (PVA·I 3 - ) has an absorption peak near 470 nm, while the complex of PVA and pentaiodide ions (PVA·I 5 - ) has an absorption peak near 600 nm. Absorption peak. As a result, polyiodide ions can absorb light in a wide range of visible light depending on their morphology. On the other hand, iodide ions (I − ) have an absorption peak near 230 nm, which is essentially irrelevant to the absorption of visible light. Therefore, the polyiodide ions existing in the state of 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 show absorption dichroism at any wavelength from 380nm to 780nm. The single transmittance Ts of the polarizer should be 40% to 48%, more preferably 41% to 46%. The polarization degree P of the polarizer is preferably 97.0% or more, more preferably 99.0% or more, and even more preferably 99.9% or more. The above-mentioned monomer transmittance represents the Y value obtained by measuring it using an ultraviolet-visible light spectrophotometer and correcting the visual sensitivity. The above-mentioned degree of polarization is represented by the following formula based on the parallel transmittance Tp and the orthogonal transmittance Tc measured using an ultraviolet-visible spectrophotometer and corrected for visual sensitivity. Polarization degree (%)={(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。Polarizers can typically be produced using a laminate of two or more layers. Specific examples of polarizers obtained using a laminate include polarizers obtained using a laminate of a resin base material and a PVA-based resin layer coated on the resin base material. A polarizer obtained by using a laminate of a resin base material and a PVA-based resin layer coated on the resin base material can be produced, for example, by applying a PVA-based resin solution to the resin base material and drying it. and forming a PVA-based resin layer on the resin base material to obtain a laminated body of the resin base material and the PVA-based resin layer; and extending and dyeing the laminated body to make the PVA-based resin layer into a polarizer. The stretching typically includes immersing the laminate in a boric acid aqueous solution and stretching. And if necessary, stretching may further include stretching the laminate in the air at a high temperature (for example, 95° C. or higher) before stretching in a boric acid aqueous solution. The obtained laminated body of the resin base material/polarizing element can be used directly (that is, the resin base material can be used as a protective layer of the polarizing element), or the resin base material can be peeled off from the laminated body of the resin base material/polarizing element and placed on the peeling surface. Laminate any appropriate protective layer for later use depending on the purpose. Details of the manufacturing method of the polarizer are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580 and Japanese Patent No. 6470455. The entire description of these publications is quoted in this specification 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 a 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 a long thermoplastic resin base material to form a laminate; and, for the above The laminated body is sequentially subjected to air-assisted stretching treatment, dyeing treatment, water stretching treatment and drying shrinkage treatment. The drying and shrinking treatment is to transport the above-mentioned laminated body in the longitudinal direction while heating it, thereby shrinking it by 2% in the width direction. above. This makes it possible to provide a polarizer that is very thin and has excellent optical properties with suppressed variation in optical properties. That is, by introducing auxiliary stretching, the crystallinity of PVA can be improved even when PVA is coated on a thermoplastic resin, and high optical properties can be achieved. At the same time, improving the orientation of PVA in advance can prevent problems such as the decrease in orientation or dissolution of PVA when immersed in water in the subsequent dyeing step or stretching step, thereby achieving high optical properties. In addition, when the PVA-based resin layer is immersed in a liquid, compared with the case where the PVA-based resin layer does not contain halides, the orientation disorder and decrease in orientation of polyvinyl alcohol molecules can be suppressed. Thereby, the optical characteristics of the polarizing element obtained by immersing the laminate in a liquid, such as dyeing treatment and water stretching treatment, can be improved. In addition, the optical properties can be improved by shrinking the laminate in the width direction through drying and shrinkage treatment.
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 appropriate film that can be used as a protective layer of the polarizer. Specific examples of the material that is the main component of the film include cellulose-based resins such as triacetylcellulose (TAC), polyester-based, polyvinyl alcohol-based, polycarbonate-based, polyamide-based, and polyamide-based resins. Imine-based, polyether-based, polystyrene-based, polystyrene-based, polynorbornene-based, polyolefin-based, (meth)acrylic-based and acetate-based transparent resins, etc. Furthermore, thermosetting resins such as (meth)acrylic-based, urethane-based, (meth)acrylic-urethane-based, epoxy-based, and polysiloxane-based resins, or ultraviolet curable resins can also be cited. Other examples include glassy polymers such as siloxane polymers. Furthermore, the polymer film described in Japanese Patent Application Laid-Open No. 2001-343529 (WO01/37007) can also be used. As the material of the film, for example, a resin composition containing a thermoplastic resin having a substituted or unsubstituted acyl imine group in the side chain and a thermoplastic resin having a substituted or unsubstituted phenyl group and a nitrile group in the side chain can be used, for example Examples include resin compositions having an alternating copolymer composed of isobutylene and N-methylmaleimide and an acrylonitrile-styrene copolymer. 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 disposed on the viewing side of the image display device, and the protective layer 12 is typically disposed on the viewing side. 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 if necessary. And/or, if necessary, the protective layer 12 may also be subjected to processing to improve the visibility when viewed through polarized sunglasses (typically, imparting (elliptical) polarization function and imparting ultra-high phase difference). By performing the above processing, excellent visibility can be achieved even when the display screen is viewed through polarized lenses such as polarized sunglasses. 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 surface treatment is provided, 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 penetration inhibition layer As mentioned above, the iodine permeation inhibiting layer is a cured product or a thermally cured product of a coating film of an organic solvent solution of resin. As long as it has the above structure, the thickness can be made very thin (for example, 10 μm or less). The thickness of the iodine penetration inhibition layer is preferably 0.05µm~10µm, more preferably 0.08µm~5µm, more preferably 0.1µm~1µm, especially 0.2µm~0.7µm. Furthermore, as long as it has the above structure, the iodine transmission inhibiting layer can be formed directly on the polarizer (that is, without passing through the adhesive layer or adhesive layer). According to the embodiment of the present invention, as described above, the polarizing element and the iodine transmission inhibiting layer are very thin, and the adhesive layer or adhesive for laminating the iodine transmission inhibiting layer can be omitted, so that the total thickness of the polarizing plate can be made extremely thin. In addition, since the hygroscopicity and moisture permeability of this iodine permeation inhibiting layer are smaller than those of cured products of water-based coating films such as aqueous solutions or water dispersions, it has the advantage of excellent humidification durability. As a result, a polarizing plate with excellent durability that can maintain optical characteristics even in a high-temperature and high-humidity environment can be realized. In addition, such an iodine transmission inhibiting layer can suppress the adverse effects of ultraviolet irradiation on a polarizing plate (polarizer) compared to, for example, 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 cured products, the cured product shrinks less during film formation and does not contain residual monomers. Therefore, it can suppress the deterioration of the film itself and prevent the negative effects of residual monomers on 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。Furthermore, the glass transition temperature (Tg) of the resin constituting the iodine transmission suppressing layer is, for example, 85° C. or higher, and the weight average molecular weight Mw is, for example, 25,000 or higher. As long as the Tg and Mw of the resin are within the above ranges, the synergistic effect of constituting the iodine transmission inhibiting layer with the cured product or thermosetting product of the coating film using the organic solvent solution of the resin can be achieved even if it is extremely Thin, it can still significantly inhibit the iodine in the polarizer from moving to the adhesive layer (eventually the image display unit). As a result, excellent durability in high temperature and high humidity environments can be achieved. The Tg of the resin is preferably 90°C or higher, more preferably 100°C or higher, more preferably 110°C or higher, especially 120°C or higher. The upper limit of Tg may be, for example, 200°C. Furthermore, 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, for example, 150,000.
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 inhibiting layer, any appropriate 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. Thermoplastic resin is preferred. Examples of the thermoplastic resin include acrylic resin and epoxy resin. Acrylic resin and epoxy resin can also be used in combination. Representative examples of acrylic resins and epoxy resins that can be used to inhibit iodine permeation inhibition layers are described below.
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。Acrylic resins typically contain repeating units derived from (meth)acrylic acid ester monomers having a linear or branched structure as a main component. In this specification, (meth)acrylic acid means acrylic acid and/or methacrylic acid. Acrylic resins may contain repeating units derived from any suitable comonomer suited to the purpose. Examples of the copolymer (copolymer) include carboxyl group-containing monomers, hydroxyl group-containing monomers, amide group-containing monomers, aromatic ring-containing (meth)acrylate, and heterocyclic ring-containing vinyl-based monomers. By appropriately setting the type, quantity, combination, copolymerization ratio, etc. of monomer units, an acrylic resin having the above-mentioned 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] (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 contains a copolymer obtained by polymerizing a monomer mixture (hereinafter sometimes referred to as boron-containing acrylic resin), and the monomer mixture contains More than 50 parts by weight of (meth)acrylic monomer and more than 0 parts by weight and less than 50 parts by weight of the monomer represented by formula (1) (hereinafter sometimes referred to as comonomer): [Chemical Formula 2] (In the formula, At least one reactive group in the group consisting of an ether group, an epoxy group, an oxetanyl group, a hydroxyl group, an amine group, an aldehyde group and a carboxyl group. R 1 and R 2 each independently represent a hydrogen atom and may be substituted. The base is an aliphatic hydrocarbon group, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent, and 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] (式中,R6 表示任意官能基,j及k表示1以上之整數)。Boron-containing acrylic resins typically have repeating units represented by the following formula. By polymerizing a monomer mixture including 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 k repeating unit). Thereby, when the iodine transmission suppressing layer is arranged adjacent to the polarizer, the adhesion with 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) or may be contained randomly. [Chemical formula 3] (In the formula, R 6 represents any functional group, j and k represent integers above 1).
<(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 thereof 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。Examples of (meth)acrylate monomers having a linear or branched structure include 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, (meth)acrylate 2-hydroxyethyl acrylate, etc. Preferably, methyl (meth)acrylate can be used. (Meth)acrylate-based monomers may be used alone or in combination of two or more types.
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。Examples of the (meth)acrylate monomer having a cyclic structure include cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isocamphenyl (meth)acrylate, and 1-(meth)acrylate. Adamantyl ester, dicyclopentenyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate, biphenyl (meth)acrylate, ortho- Phenoxyethyl (meth)acrylate, o-biphenoxyethyl (meth)acrylate, m-biphenoxyethyl acrylate, p-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)acryloxyethyl-o-biphenyl=carbamate, N-(meth)acryloxyethyl-p-biphenyl=carbamate, N-(methyl) Acryloxyethyl-m-biphenyl = urethane, o-phenylphenol glycidyl ether acrylate and other biphenyl-containing monomers, triphenyl (meth)acrylate, o-triphenoxyethyl (meth)acrylate, etc. Preferably, 1-adamantyl (meth)acrylate and dicyclopentyl (meth)acrylate can be used. By using these monomers, polymers with high glass transition temperatures can be obtained. These monomers may be used 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。Furthermore, a silsesquioxane compound having a (meth)acrylyl group may be used instead of the (meth)acrylate 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 skeleton 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. As for the silsesquioxane compound, only one type may be used or two or more types may be used in combination.
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。As the silsesquioxane compound containing (meth)acrylyl group, for example, MAC grade and AC grade of Toa Gosei Co., Ltd.'s SQ series can be used. MAC grade is a silsesquioxane compound containing methacrylyl groups. Specific examples include MAC-SQ TM-100, MAC-SQ SI-20, MAC-SQ HDM, etc. AC grade is a silsesquioxane compound containing an acryl group. Specific examples include AC-SQ TA-100, AC-SQ SI-20, etc.
(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 of more than 50 parts by weight relative 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。<Comonomer> As the copolymerizable monomer, a monomer represented by the above formula (1) can be used. By using the comonomer, boron-containing substituents can be introduced into the side chains of the resulting polymer. As the comonomer, only one type may be used or two or more types may be used in combination.
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。Examples of the aliphatic hydrocarbon group of the above formula (1) include linear or branched alkyl groups having 1 to 20 carbon atoms which may have substituents, cyclic alkyl groups having 3 to 20 carbon atoms or alkenes having 2 to 20 carbon atoms which may have substituents. base. Examples of the aryl group include a phenyl group having 6 to 20 carbon atoms which may have a substituent, a naphthyl group having 10 to 20 carbon atoms which may have a substituent, and the like. Examples of the heterocyclic group include a 5-membered cyclic group or a 6-membered cyclic group containing at least 1 heteroatom which may have a substituent. In addition, R 1 and R 2 may be linked to each other to form a ring. R 1 and R 2 are preferably a hydrogen atom or a linear or branched alkyl group having 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 included in the functional group represented by At least one kind from the group consisting of heterocyclobutanyl group, hydroxyl group, amine group, aldehyde group and carboxyl group. Preferably, the reactive group is a (meth)acrylyl group and/or a (meth)acrylamide group. By having such reactive groups, when the iodine transmission inhibiting layer is arranged adjacent to the polarizer, the adhesion to the polarizer can be further 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)acrylyl, styryl, (meth)acrylamide, vinyl ether At least one reactive group in the group consisting of a group, an epoxy group, an oxetanyl group, a hydroxyl group, an amine 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] [化學式5] Specifically, the following compounds can be used as comonomers. [Chemical formula 4] [Chemical formula 5]
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 may be used in a content of 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 more than 0.01 parts by weight and less than 50 parts by weight, more preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, especially 0.5 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 repeating units including a ring structure selected from the group consisting of lactone ring units, glutaric anhydride units, glutadiryl imine units, maleic anhydride units and maleic anhydride units. Amine (N-substituted maleimine) unit. Only one type of repeating unit including a ring structure may be contained in the repeating unit of the acrylic resin, or two or more types may be contained therein.
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] 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] In the general formula (2), R 2 , R 3 and R 4 each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms. In addition, organic residues may also contain oxygen atoms. The acrylic resin may contain only a single lactone ring unit, or may contain a plurality of lactone ring units in which R 2 , R 3 and R 4 in the general formula (2) are different from each other. Acrylic resins having a lactone ring unit are described in, for example, Japanese Patent Application Laid-Open No. 2008-181078, and the description of this 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 glutadirylimine unit is preferably represented by the following general formula (3):
[化學式7] [Chemical Formula 7]
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 independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 13 represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a cycloalkyl group having 6 to 10 carbon atoms. Aryl. In the general formula (3), it is desirable that R 11 and R 12 are 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 contain only a single glutarimide unit, or may contain a plurality of glutarimide units in which R 11 , R 12 and R 13 in the general formula (3) are different from each other. Acrylic resins having a glutadirylimine unit 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 Application Publication No. 2006-337492, Japanese Patent Application Publication No. 2006-337493, and Japanese Patent Application Publication No. 2006-337569, and the descriptions of these publications are cited in this specification. 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 about the glutaric imine unit is applicable.
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 structure of the maleic anhydride unit and the maleimide (N-substituted maleimide) unit can be identified by their names, so detailed descriptions are 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% to 50 mol%, more preferably 10 mol% to 40 mol%, and more preferably 20 mol% to 30 mol%. . In addition, the acrylic resin contains repeating units derived from the above-mentioned (meth)acrylic monomer as main repeating units.
<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, an epoxy resin having an aromatic ring is preferably used. By using an epoxy resin having an aromatic ring as the epoxy resin, the adhesion between the iodine transmission inhibiting layer and the polarizer can be improved. In addition, when the adhesive layer is arranged adjacent to the iodine transmission inhibiting layer, the anchoring force of the adhesive layer can be improved. Examples of epoxy resins having 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, and cresol Phenolic epoxy resins such as phenolic epoxy resin, hydroxybenzaldehyde phenol phenolic epoxy resin and other phenolic epoxy resins; glycidyl ether of tetrahydroxyphenylmethane, epoxypropyl ether of tetrahydroxydiphenylketone, epoxidized polyvinyl phenol, etc. Multifunctional epoxy resin, naphthol-type epoxy resin, naphthalene-type epoxy resin, biphenyl-type epoxy resin, etc. Preferably, bisphenol A-type epoxy resin, biphenyl-type epoxy resin, and bisphenol F-type epoxy resin can be used. As for the epoxy resin, only one type may be used or two or more types may be used in combination.
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 coating an organic solvent solution of the above-mentioned resin to form a coating film, and solidifying or thermally hardening 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 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 appropriate substrate or on a polarizer. When the solution is applied to the base material, the cured product of the coating film formed on the base material (iodine transmission inhibiting layer) is transferred to the polarizer. When the solution is applied to the polarizer, the coating film is dried (cured) to form a protective layer directly on the polarizer. Preferably, the solution is coated on the polarizer, and a protective layer is directly formed on the polarizer. With the above configuration, the adhesive layer or adhesive layer required for transfer can be omitted, so the polarizing plate can be made thinner. The solution may be applied by any appropriate method. Specific examples include roll coating, spin coating, wire bar coating, dip coating, die coating, curtain coating, spray coating, and blade coating (notched wheel coating, 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 solidifying or thermally hardening the coating film of the solution, the iodine transmission inhibiting layer can be formed. The heating temperature for curing or thermal hardening should be below 100°C, preferably 50°C to 70°C. 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 inhibition layer (essentially an organic solvent solution of the above-mentioned resin) may also contain any appropriate additives according to the purpose. Specific examples of additives include ultraviolet absorbers; leveling agents; antioxidants such as hindered phenol series, phosphorus series, and sulfur series; stabilizers such as light stabilizers, weathering stabilizers, and heat stabilizers; reinforcing materials such as glass fiber and carbon fiber; Near-infrared absorbers; flame retardants such as ginseng (propyl dibromide) phosphate, triallyl phosphate, and antimony oxide; antistatic agents such as anionic, cationic, and nonionic surfactants; inorganic pigments, Colorants such as organic pigments and dyes; organic fillers or inorganic fillers; resin modifiers; organic fillers or inorganic fillers; plasticizers; slip agents; antistatic agents; flame retardants, etc. The type, quantity, combination, addition amount, etc. of 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 inhibition layer has, for example, an iodine absorption index of 0.015 or less. The iodine absorption index is preferably 0.012 or less, more preferably 0.009 or less, more preferably 0.007 or less, especially 0.005 or less. The smaller the iodine absorption index, the better, and ideally is zero, and the lower limit thereof may be, for example, 0.001. The iodine absorption index is an indicator of the iodine penetration inhibition ability of the iodine penetration inhibition layer. The smaller the index, the more difficult it is for iodine to be absorbed by the iodine penetration inhibition layer (that is, iodine is easily blocked by the iodine penetration inhibition layer). Therefore, as long as the iodine absorption index is within the above range, the iodine presence index of the adhesive layer can be set to less than 0.050 as mentioned above, which can significantly inhibit the movement of iodine in the polarizer to the adhesive layer (and ultimately the image display device, Essentially an image display unit). As a result, it is possible to achieve excellent durability in high-temperature and high-humidity environments in thin polarizing plates. Moreover, even when a polarizing plate is applied to an image display device, corrosion of metal components (such as electrodes, sensors, wiring, and metal layers) of the image display device can still be significantly suppressed, and corrosion in high temperature and high humidity environments can be suppressed. The reliability is reduced due to the presence of iodine, so the increase in reflectivity can be suppressed. Furthermore, the iodine permeation inhibiting layer is as described above, and the potassium absorption index is preferably 0.015 or less. The potassium absorption index is preferably below 0.013, more preferably below 0.011, especially below 0.009. The smaller the potassium absorption index, the better, and ideally is zero, and the lower limit thereof may be, for example, 0.002. The potassium absorption index is an indicator of the potassium penetration inhibition ability of the iodine penetration inhibition layer. The smaller the index, the less easily potassium is absorbed by the iodine penetration inhibition layer. As a result, the iodine in the form of potassium iodide and the iodine in the form of polyiodide (I 3 - K + ) are more It is not easily absorbed by the iodine penetration inhibition layer. Therefore, as long as the potassium absorption index is within the above range, not only iodine monomer but also in the form of potassium iodide and potassium polyiodide can inhibit the movement of iodine. The iodine absorption index can be defined as the iodine intensity (kcps) obtained by X-ray fluorescence analysis of iodine passing through the suppression layer, and the potassium absorption index can be defined as the potassium intensity (kcps) obtained by X-ray fluorescence analysis of iodine passing through the 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 phase difference layer
B-1. Overall composition of polarizing plate with retardation layer
A polarizing plate with a retardation layer according to an embodiment of the present invention includes a polarizing plate and a retardation layer. The polarizing plate is the polarizing plate described in item A above. In the embodiment of the present invention, the retardation layer is arranged between the polarizer and the adhesive layer. The retardation layer is a directionally solidified layer of a liquid crystal compound with a circular polarizing function or an elliptical circular polarizing function (hereinafter sometimes simply referred to as a liquid crystal directional solidifying layer). FIG. 2A is a schematic cross-sectional view of a polarizing plate with a retardation layer according to one 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 layers in FIGS. 2A and 2B each have a protective layer 12, a polarizer 11, a
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 in another embodiment may also be provided with another retardation layer 50 and/or a conductive layer or an isotropic base material 60 with a conductive layer. Another retardation layer 50 can be typically provided between the
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 mentioned above, the
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 appropriately, and changes evident 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 a retardation layer in Figure 2B; the polarizing plate 101 with a retardation layer in Figure 2B The
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 a retardation layer according to the embodiment of the present invention may further include other retardation layers. The optical properties (such as refractive index properties, in-plane phase difference, Nz coefficient, photoelastic coefficient), thickness, arrangement position, etc. of other retardation layers 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 polarizing plate with the retardation layer should be 60µm or less, more preferably 55µm or less, more preferably 50µm or less, especially 40µm or less. The lower limit of the total thickness may be, for example, 28 µm. According to the embodiment of the present invention, an extremely thin polarizing plate with a retardation layer can be realized as described above, and excellent durability in a high temperature and high humidity environment can be achieved in such an extremely thin polarizing plate with a retardation layer. Moreover, even when such a very thin polarizing plate with a retardation layer is applied to an image display device, it can still significantly suppress the degradation of metal components (such as electrodes, sensors, wiring, and metal layers) of the image display device. Corrosion, and can inhibit the increase in reflectivity in high temperature and high humidity environments. In addition, the total thickness of the polarizing plate with a retardation layer refers to the polarizing plate, the retardation layer (the first retardation layer and the second retardation layer when there is a second retardation layer), the iodine transmission suppression layer and The total thickness of the adhesive layer or adhesive layer used to laminate these layers (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
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。The descriptions in item A above regarding the composition, effects, and uses of polarizing plates that can also be applied to polarizing plates with retardation layers can be cited as the descriptions of polarizing plates with retardation layers. For example, records on the shape (monolithic or strip-like) and thinning of polarizers, image display devices that can use polarizers, release films, and the direct formation of iodine transmission inhibiting layers on polarizers can be cited as relevant phase attachments. Recording of polarizing plates with different layers. These are only examples, and it should be self-evident that the records cited are not limited by these. Similarly, any descriptions regarding the structure, effects, and uses of the polarizing plate with a retardation layer that can be cited in the following descriptions can be cited as descriptions of 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 base material 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 transmission inhibiting layer are as described in the above item A.
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. 1st phase difference layer
The
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。Examples of the liquid crystal compound include a liquid crystal compound whose liquid crystal phase is a nematic phase (nematic liquid crystal). As such a liquid crystal compound, for example, a liquid crystal polymer or a liquid crystal monomer can be used. The liquid crystallinity expression mechanism of the liquid crystal compound may be either lyotropic or thermotropic. The liquid crystal polymer and the liquid crystal monomer can each 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 orientation state of the liquid crystal monomer can be fixed by polymerizing or crosslinking (that is, hardening) the liquid crystal monomer. After the liquid crystal monomers are oriented, for example, the liquid crystal monomers are polymerized or cross-linked with each other, thereby fixing the above-mentioned orientation state. Here, the polymer is formed by polymerization, and the three-dimensional network structure is formed by cross-linking, but these are non-liquid crystalline. Therefore, the formed first retardation layer does not undergo transformation into a liquid crystal phase, a glass phase, or a crystal phase due to temperature changes, which is unique to liquid crystalline compounds. As a result, the first retardation layer becomes a retardation layer that is not affected by temperature changes and has extremely excellent stability.
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 liquid crystal monomers exhibit liquid crystallinity varies depending on their 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, polymerizable mesogen compounds described in Japanese Patent List 2002-533742 (WO00/37585), EP358208 (US5211877), EP66137 (US4388453), WO93/22397, EP0261712, DE19504224, DE4408171, and GB2280445 can be used. . Specific examples of the polymerizable mesogen compound include LC242, a trade name of BASF, E7, a trade name of Merck, and LC-Sillicon-CC3767, a trade name of Wacker-Chem. The liquid crystal monomer is preferably a nematic liquid crystal monomer, for example.
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 solidified layer can be formed by performing orientation treatment on the surface of a predetermined base material, and coating a coating liquid containing a liquid crystal compound on the surface so that the liquid crystal compound is oriented in a direction corresponding to the orientation treatment and fixed. the orientation status. In one embodiment, the base material is any appropriate resin film, and the liquid crystal alignment solidified layer formed on the base material can be transferred to the surface of an adjacent layer (eg, polarizer, iodine transmission inhibition 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 orientation processing may 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 physical orientation processing include magnetic field orientation processing and electric field orientation processing. Specific examples of chemical orientation treatment include oblique evaporation and photo-orientation treatment. The processing conditions for various targeted treatments can be any appropriate conditions depending on 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 carried out by treating the liquid crystal compound 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 will change into a liquid crystal state, and the liquid crystal compound will be oriented according to the direction of the orientation treatment on the surface of the substrate.
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 alignment state is fixed by cooling the liquid crystal compound that has been aligned in the above manner. When the liquid crystal compound is a polymerizable monomer or a cross-linking monomer, the alignment state is fixed by subjecting the liquid crystal compound that has been aligned in the above manner to a polymerization treatment or a cross-linking 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 details of the formation method of the orientationally solidified layer are described in Japanese Patent Application Laid-Open No. 2006-163343. The records in this publication are cited in this specification 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
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 phase difference layer has a circular polarization function or an elliptical polarization function as described above. The refractive index characteristics of the first phase difference layer represent the relationship of nx>ny=nz. The first retardation layer is typically provided to impart anti-reflective properties to the polarizing plate. When the first retardation layer is a single layer, it can function as a λ/4 plate. At this time, the in-plane phase difference 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, the situation may be ny>nz or ny<nz as long as the effect of the present invention is not impaired.
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 phase difference layer is preferably 0.9~1.5, more preferably 0.9~1.3. By satisfying the above relationship, when the obtained polarizing plate with a 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 phase difference layer can exhibit inverse wavelength dispersion characteristics in which the phase difference value becomes larger with the wavelength of the measurement light, can exhibit normal wavelength dispersion characteristics in which the phase difference value becomes smaller with the wavelength of the measurement light, and can also exhibit that the phase difference value hardly varies with the wavelength of the measurement light. Flat wavelength dispersion characteristics that measure changes in wavelength of light. In one embodiment, the first retardation layer exhibits reverse dispersion wavelength characteristics. At this time, Re(450)/Re(550) of the phase difference layer is preferably 0.8 or more and less than 1, and more preferably 0.8 or more and 0.95 or less. As long as it has the above configuration, very excellent anti-reflection properties 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
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
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 phase difference layer As mentioned above, the second retardation layer may be a so-called positive C-plate whose refractive index characteristics exhibit the relationship nz>nx=ny. By using the positive C plate as the second retardation layer, oblique reflection can be effectively prevented, and the anti-reflection function can be widened to a wider viewing angle. At this time, the retardation Rth (550) in the thickness direction of the second retardation layer is preferably -50nm~-300nm, more preferably -70nm~-250nm, more preferably -90nm~-200nm, especially -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 phase difference 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 the refractive index characteristic of nz>nx=ny can be formed of any appropriate material. The second retardation layer is preferably composed of a thin film containing a liquid crystal material fixed in a homeotropic orientation. The liquid crystal material (liquid crystal compound) capable of vertical alignment can be a liquid crystal monomer or a liquid crystal polymer. Specific examples of the method of forming the liquid crystal compound and the retardation layer include the liquid crystal compound and the method of forming the retardation layer described in paragraphs [0020] to [0028] of Japanese Patent Application Laid-Open No. 2002-333642. 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 using any appropriate film forming method (such as vacuum evaporation, sputtering, CVD, ion plating, spraying, etc.). Examples of metal oxides 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 suitable.
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 base material to the first retardation layer (or the iodine transmission inhibition layer or the second retardation layer when there is a second retardation layer), and the conductive layer alone serves as the attached retardation layer. The constituent layers of the polarizing plate can also be laminated in the form of a laminate of a conductive layer and a base material (a base material with a conductive layer) on the first retardation layer (or the iodine transmission suppression layer or the second retardation layer) is the second phase difference layer). It is preferable that the above-mentioned base material is optically isotropic, so the conductive layer can be used as an isotropic base material 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 appropriate isotropic base material can be used as the optically isotropic base material (isotropic base material). Examples of materials constituting the isotropic base material include materials having a main skeleton of a resin without a conjugated system, such as norbornene resin or olefin resin, and acrylic resin having a lactone ring or glutaryl ring in the main chain. Materials with cyclic structures such as imine rings, etc. If such a material is used, the phase difference caused by the orientation of molecular chains when forming an isotropic base material can be suppressed to a small size. The thickness of the isotropic substrate should be 50µm or less, more preferably 35µm or less. The lower limit of the thickness of the isotropic substrate is, for example, 20µm.
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 can be patterned as needed. Conductive portions and insulating portions can be formed through patterning. As a result, electrodes can be formed. The electrodes may function as touch sensing electrodes for sensing contact with the touch panel. The patterning method may employ any suitable method. Specific examples of the patterning method include wet etching and screen printing.
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, embodiments of the present invention include an image display device using the polarizing plate or the polarizing plate with a 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). An image display device according to an embodiment of the present invention typically includes the polarizing plate described in Item A above or the polarizing plate with a retardation layer described in Item B above on its viewing side. The polarizing plate with the retardation layer is laminated so that the retardation layer becomes the side of the image display unit (for example, liquid crystal unit, organic EL unit, inorganic EL unit) (the polarizer becomes the viewing side). Although the image display device is very thin, corrosion of metal components is significantly suppressed. In one embodiment, the image display device has a curved shape (substantially a curved display screen), and/or is 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 reference to examples, but the present invention is not limited by these examples. The measurement method of each characteristic is as follows. In addition, unless otherwise noted, "parts" and "%" in the examples and comparative examples are based on 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 is measured using an interference film thickness meter (manufactured by Otsuka Electronics Co., Ltd., product name "MCPD-3000"). The thickness of more than 10 μm is measured using a digital micrometer (manufactured by Anritsu Co., Ltd., 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 a retardation layer or the polarizing plate obtained in the Examples and Comparative Examples was bonded to alkali-free glass to prepare a test sample. After subjecting the test sample to a reliability test (leaving it in an environment of 85°C and 85%RH for 240 hours and then in an environment of 23°C and 55%RH for 24 hours), use a trimming knife to remove the entire alkali-free glass. Peel off the adhesive. Secondary ion mass analysis (TOF-SIMS) measurement was performed on the adhesive surface of the peeled test sample using "TOFSIMS5" manufactured by IONTOF Corporation. The measurement conditions are as follows.・Primary ion irradiated: Bi 3 2+・Primary ion acceleration voltage: 25kV ・Measurement area: 100µm 2・Measurement polarity: Negative ions pick out C 3 H 3 derived from acrylic acid (adhesive) from the obtained negative secondary ions The iodine presence index was calculated using the following formula based on the ionic strength of O 2 - (m/z=71) and the ionic strength of I - (m/z=127) derived from iodine. 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 dried thickness became 1 µm and dried to obtain a test sample of the resin layer/PET film. . The obtained test sample was immersed in a 10% potassium iodide 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 is taken out from the aqueous solution, and after wiping the water droplets on the surface, X-ray fluorescence measurement is performed on the surface of the resin layer to obtain the intensity of iodine and potassium (kcps). The strength of the obtained iodine was taken as the iodine absorption index, and the strength of the potassium was taken as the potassium absorption index. In addition, the conditions for X-ray fluorescence analysis are as follows. ・Analysis device: Rigaku Denki Industrial X-ray fluorescence analysis device (XRF), product name "ZSX100e" ・Test sample: circular sample with diameter 10mm ・Counter cathode: rhodium ・Spectral crystallization: lithium fluoride ・Excitation 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) Changes in polarization degree The polarizing plate with a retardation layer or the polarizing plate obtained in the Examples and Comparative Examples was bonded to alkali-free glass to prepare a test sample. The polarization degree of the test sample is measured by a conventional method and is used as the initial polarization degree. After the test sample is subjected to a reliability test (placed in an environment of 85℃・85%RH for 240 hours, and then placed in an environment of 23°C・55%RH for 24 hours), the polarization degree is measured in the same manner as above. . The change in polarization degree is calculated according to the following formula. Polarization change (%) = initial polarization (%) - polarization after reliability test (%) and evaluated against the following benchmarks. Good: Polarization change is less than 5.0% Poor: Polarization change is 5.0% or more
(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) Reflectivity increases The polarizing plate with the retardation layer obtained in the Example and the Comparative Example was bonded to the alkali-free glass to prepare a test sample. The test sample was placed on a reflective plate with a reflectance of 80%, and the value measured at 550nm in SCI mode using a spectrophotometer (CM700D manufactured by Konica Minolta Co., Ltd.) was taken as the reflectance (%). as the initial reflectivity. After the test sample is subjected to a reliability test (placed in an environment of 60°C・90%RH for 500 hours, and then placed in an environment of 23°C・55%RH for 24 hours), the reflectance is measured in the same manner as above . The reflectance increase is calculated according to the following equation. Reflectivity increase (%) = initial reflectivity (%) - reflectivity after reliability test (%) and evaluated against the following benchmarks. Good: Reflectivity increase is less than 0.50% Allowable: the reflectivity rises above 0.50% and is less than 1.00% Poor: Reflectivity increased 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 corrosion (48 hours) Coat the silver nanowire solution (manufactured by MERCK, 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. Apply to 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, a wet film containing 99 parts of methyl isobutyl ketone (MIBK), 1 part of neopentyl tetraacrylate (PETA), and a photopolymerization initiator (manufactured by BASF Corporation) was used with a wire rod so that the wet film thickness became 10 μm. Product name "IRGACURE 907") 0.03 parts of covering protection liquid (solid content concentration: about 1%) is applied on 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 protective coating film, thereby producing a metal thin film composed of a PET film/silver nanowire layer/protective coating layer (thickness: 100 nm). Use an adhesive (15µm) to bond the metal film to a glass plate with a thickness of 0.5mm to obtain a laminated body of metal film/adhesive/glass plate. The resistance value of the obtained laminated body was measured with a non-contact resistance measuring instrument (manufactured by Napson Corporation, product name "EC-80") and found to be 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 a retardation layer or the polarizing plate obtained in the Examples and Comparative Examples was bonded to the surface of the protective layer of the metal film of the laminate to prepare a test sample. Use a non-contact resistance measuring device to measure the resistance value of the test sample as the initial resistance value. After the test sample is subjected to a reliability test (placed in an environment of 85°C・85%RH for 48 hours, and then placed in an environment of 23°C・55%RH for 2 hours), the resistance value is measured in the same manner as above . Calculate the resistance value increase rate according to the following formula. In addition, when the measured value (resistance value) is greater than the measurement limit of the non-contact resistance measuring device (1000Ω/□), the measured value is assumed to be 1500Ω/□. Resistance value increase rate (%) = {(resistance value after reliability test - initial resistance value)/initial resistance value} × 100 and evaluated against the following benchmarks. Good: The resistance value rise rate is less than 200% Poor: Resistance value increase rate 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 corrosion (200 hours) The polarizing plate with the retardation layer obtained in the Example and the Comparative Example was bonded to the protective layer-forming surface of the metal film of the laminate obtained in (2) to prepare a test sample. Use a non-contact resistance measuring device to measure the resistance value of the test sample as the initial resistance value. After the test sample is subjected to a reliability test (placed in an environment of 85°C・85%RH for 200 hours, and then placed in an environment of 23°C・55%RH for 2 hours), the resistance value is measured in the same manner as above . Calculate the resistance value increase rate according to the following formula. In addition, when the measured value (resistance value) is greater than the measurement limit of the non-contact resistance measuring device (1000Ω/□), the measured value is assumed to be 1500Ω/□. Resistance value increase rate (%) = {(resistance value after reliability test - initial resistance value)/initial resistance value} × 100 and evaluated against the following benchmarks. Excellent: The resistance value increase rate is less than 200% Good: The resistance value increase rate is above 200% and below 2000% Poor: The resistance value increase rate 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 polarizers The thermoplastic resin base material is a long amorphous isophthalic acid copolymer polyethylene terephthalate film (thickness: 100µm) with a water absorption rate of 0.75% and a Tg of approximately 75°C. And corona treatment is applied to one side of the resin substrate. A PVA system made by mixing polyvinyl alcohol (degree of polymerization 4200, saponification degree 99.2 mol%) and acetyl-acetyl modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "GOHSEFIMER Z410") at a ratio of 9:1 13 parts by weight of potassium iodide was added to 100 parts by weight of the 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 base material and dried at 60° C. to form a PVA-based resin layer with a thickness of 13 μm, thereby producing a laminate. The obtained laminate was uniaxially stretched in the longitudinal direction (long side direction) at the free end between rollers with different circumferential speeds in an oven at 130° C. to 2.4 times (air-assisted stretching treatment). Next, the laminated body was immersed in an insolubilization bath (a boric acid aqueous solution in which 4 parts by weight of boric acid was mixed with 100 parts by weight of water) having a liquid temperature of 40° C. for 30 seconds (insolubilization 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) with a liquid temperature of 30° C., the dye bath was immersed in it for 60 seconds. The single transmittance (Ts) of the finally obtained polarizing element is 43.0% or more (dyeing treatment). Next, it was immersed in a crosslinking 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 (crosslinking treatment) ). Then, the laminated body was immersed in a boric acid aqueous solution with a liquid temperature of 70°C (boric acid concentration 4.0% by weight, potassium iodide concentration 5% by weight), and uniaxially stretched in the longitudinal direction (longitudinal direction) between rollers with different circumferential speeds. Make the total extension ratio reach 5.5 times (extension treatment in water). Thereafter, the laminated body was immersed in a cleaning bath (an aqueous solution in which 4 parts by weight of potassium iodide was mixed with 100 parts by weight of water) having a liquid temperature of 20° C. (washing treatment). Thereafter, it was dried in an oven maintained at 90° C. while keeping the surface temperature in contact with a SUS heated roller at 75° C. for about 2 seconds (drying shrinkage treatment). The laminate was subjected to drying and shrinkage treatment, and the shrinkage rate in the width direction was 5.2%. According to the above method, a polarizer with a thickness of 5 μm is formed on the resin substrate.
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. Make polarizing plates An HC-COP film was bonded to the surface of the polarizer obtained above (the surface opposite to the resin base material) through an ultraviolet curable adhesive as a protective layer. Specifically, the hardening adhesive is applied so that the total thickness becomes 1.0 μm and bonded using a roller. After that, UV light is irradiated from the protective layer side to harden the adhesive. In addition, the HC-COP film is a film with a hard coat (HC) layer (thickness 2µm) formed on a cyclic olefin (COP) film (manufactured by ZEON Corporation of Japan, product name "ZF12", thickness 25µm), and the COP film becomes polarized Fit the side of the piece. Next, the resin base material is peeled off to obtain a polarizing plate having a structure 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] 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. Prepare the first orientationally solidified layer and the second orientationally solidified layer constituting the retardation layer. 10 g of polymerizable liquid crystal showing the nematic liquid crystal phase (manufactured by BASF: trade name "Paliocolor LC242", represented by the following formula) and 3 g of the photopolymerization initiator of this polymerizable liquid crystal compound (manufactured by BASF: trade name "IRGACURE 907") was dissolved in 40 g of toluene, and a liquid crystal composition (coating liquid) was prepared. [Chemical formula 8] Wipe the surface of 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° relative to the absorption axis direction of the polarizer when viewed from the viewing side when attached to the polarizing plate. The above-mentioned liquid crystal coating liquid was applied to the orientation-treated surface using a bar coater, and the liquid crystal compound was oriented by heating and drying at 90° C. for 2 minutes. A metal halide lamp is 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 a liquid crystal orientation solidified layer A on the PET film. The thickness of the liquid crystal orientation solidified layer A is 2.5 μm, and the in-plane phase difference Re (550) is 270 nm. Furthermore, the liquid crystal alignment solidified layer A has a refractive index distribution of nx>ny=nz. Change the coating thickness and set the orientation treatment direction to be 75° relative to the absorption axis direction of the polarizer when viewed from the viewing side. In addition, form the liquid crystal orientation solidified layer B on the PET film in the same manner as above. . The thickness of the liquid crystal orientation solidified layer B is 1.5 μm, and the in-plane phase difference Re (550) is 140 nm. Furthermore, the liquid crystal alignment solidified 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. Form a phase difference layer The liquid crystal orientation solidified layer A and the liquid crystal orientation solidified layer B obtained in the above 3. are sequentially transferred to the surface of the polarizer of the polarizing plate obtained in the above 2.. At this time, the rotation is performed in such a way that the angle formed by the absorption axis of the polarizer and the slow axis of the liquid crystal alignment solidified layer A becomes 15° and the angle formed by the absorption axis of the polarizer and the slow axis of the liquid crystal alignment solidified layer B becomes 75°. Print (fit). In addition, each transfer (bonding) is performed through the ultraviolet curable adhesive (thickness 1.0 μm) used in 2. above. In the above manner, a protective layer (HC layer/COP film)/adhesive layer/polarizer/adhesive layer/retardation layer (first liquid crystal orientation solidified layer/adhesive layer/second liquid crystal orientation solidified layer) is produced. The layered body composed of it.
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. Make a polarizing plate with a
[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 Fujifilm Wako Pure Chemical Industries, Ltd., trade name "methyl methacrylate monomer"), 3.0 parts of the comonomer represented by the above general formula (1e), and a polymerization initiator ( Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "2,2´-azobis(isobutyronitrile)") 0.2 part was dissolved in 200 parts of toluene. Next, a polymerization reaction was performed for 5.5 hours while heating to 70° C. in a nitrogen atmosphere, and a boron-containing acrylic resin solution (solid content concentration: 33%) was obtained. 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 transmission inhibition layer was set to 0.3 µm. The retardation layer was produced in the same manner as in Example 1. The polarizing plate. The obtained polarizing plate with a retardation layer was subjected to 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] A polarizing plate with a retardation layer was produced in the same manner as in Example 2, except that the thickness of the iodine transmission inhibition layer was set to 0.5 μm. The obtained polarizing plate with a retardation layer was subjected to 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] The same procedure as in Example 1 was performed except that thermoplastic epoxy resin (manufactured by Mitsubishi Chemical Co., trade name "jER (registered trademark) 1256B40", Tg: 100°C, Mw: 45000) was used instead of the acrylic resin "B-811". In the same way, a polarizing plate with a retardation layer is produced. The obtained polarizing plate with a retardation layer was subjected to 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) to replace the acrylic resin "B-811", and add iodine permeation inhibition layer to the The thickness was set to 0.3 μm, except that a polarizing plate with a retardation layer was produced in the same manner as in Example 1. The obtained polarizing plate with a retardation layer was subjected to 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] A polarizing plate with a retardation layer was produced in the same manner as in Example 5, except that the thickness of the iodine transmission inhibition layer was set to 0.5 μm. The obtained polarizing plate with a retardation layer was subjected to 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] In place of the acrylic resin "B", a blend of 15 parts of "B-811" and 85 parts of a thermoplastic epoxy resin (manufactured by Mitsubishi Chemical Co., trade name "jER (registered trademark) YX6954BH30") (in terms of solid content) was used. -811", a polarizing plate with a retardation layer was produced in the same manner as in Example 1. The blend had a Tg of 125°C and a Mw of 38,000. The obtained polarizing plate with a retardation layer was subjected to 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] The resin blend used in Example 7 was coated on the polarizer side of the polarizing plate having the structure of protective layer (HC layer/COP film)/adhesive layer/polarizer obtained in Example 1 and 2 and dried. , to form an iodine transmission inhibiting layer (thickness 0.5µm) in the form of a cured product of a coating film of a resin organic solvent solution. Sequentially transfer the liquid crystal orientation solidification layer A and the liquid crystal orientation solidification layer B on the surface of the iodine transmission inhibition layer in the same manner as in Example 1 to obtain a protective layer (HC layer/COP film)/adhesive layer/polarizer/iodine A polarizing plate with a retardation layer composed of a transmission inhibition layer/adhesive layer/retardation layer (first liquid crystal alignment solidified layer/adhesive layer/second liquid crystal alignment solidification layer)/adhesive layer. The obtained polarizing plate with a retardation layer was subjected to 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 using the boron-containing acrylic polymer in Example 2, a protective layer (HC layer/COP film)/adhesive layer/polarizer/iodine transmission inhibiting layer was produced in the same manner as in Example 8. Laminated body. Next, a blend of 15 parts of the boron-containing acrylic polymer in Example 2 and 85 parts of a thermoplastic epoxy resin (manufactured by Mitsubishi Chemical Co., trade name "jER (registered trademark) YX6954BH30") (in terms of solid content) was used. , except that the protective layer (HC layer/COP film)/adhesive layer/polarizer/iodine transmission inhibition layer/adhesive layer/retardation layer (the first liquid crystal orientation solidification layer) was obtained in the same manner as in Example 1. A polarizing plate with a retardation layer composed of layer/adhesive layer/second liquid crystal orientation solidification layer)/iodine transmission inhibiting layer/adhesive layer. The total thickness of the obtained polarizing plate with a retardation layer was 40 μm. The obtained polarizing plate with a retardation layer was subjected to 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 transmission suppression layer disposed between the polarizer and the retardation layer and adjacent to the polarizer was made of 15 parts of the boron-containing acrylic polymer obtained in Example 2 and a thermoplastic epoxy resin (manufactured by Mitsubishi Chemical Co., commercial product). A polarizing plate with a retardation layer was obtained in the same manner as in Example 9 except that 85 parts (in terms of solid content) of the blend (named "jER (registered trademark) YX6954BH30") was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 40 μm. The obtained polarizing plate with a retardation layer was subjected to 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]
An iodine transmission inhibition layer is formed between the polarizer and the retardation layer and adjacent to the polarizer. The iodine transmission inhibition layer is formed between the polarizer and the retardation layer and adjacent to the retardation layer. Otherwise, it is the same as in
[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 inhibition layer is further formed between the polarizer and the retardation layer and adjacent to the polarizer. In addition, 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/retardation layer (first liquid crystal orientation solidified layer/adhesive layer/second liquid crystal orientation solidification layer)/iodine transmission A polarizing plate with a retardation layer composed of an inhibition layer/adhesive layer. The total thickness of the polarizing plate with the retardation layer obtained was 40.5 μm. The obtained polarizing plate with a retardation layer was subjected to 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] A polarizing plate with a retardation layer was produced in the same manner as in Example 1 except that the iodine transmission inhibiting layer was not formed. The obtained polarizing plate with a retardation layer was subjected to 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] The acrylic resin "B-723" (manufactured by Kusumoto Chemical Co., Ltd., Tg: 54°C, Mw: 200000) was used instead of the acrylic resin "B-811", and a phase-attached phase was produced in the same manner as in Example 1. Differential layer of polarizing plate. The obtained polarizing plate with a retardation layer was subjected to 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., trade name "jER (registered trademark) 828") was used instead of the acrylic resin "B-811", and "CPI100P" manufactured by San-Apro Ltd. was used as the photopolymerization initiator. ), except that a polarizing plate with a retardation layer was produced in the same manner as in Example 1. The obtained polarizing plate with a retardation layer was subjected to 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 using PVA-based resin (manufactured by Mitsubishi Chemical Co., trade name "GOHSEFIMER Z200", Tg: 80°C, Mw: 8800) instead of the acrylic resin "B-811", the attachment was produced in the same manner as in Example 1. Polarizing plate with phase difference layer. The obtained polarizing plate with a retardation layer was subjected to 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 polarizing plates A polarizing plate having a structure of protective layer (HC layer/COP film)/polarizer was obtained in the same manner as in Example 1.
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. Preparation of retardation film constituting the retardation layer 2-1. Polymerization of polyester carbonate resin Batch polymerization using two vertical reactors equipped with stirring blades and a reflux cooler controlled to 100°C device for aggregation. Feed in 29.60 parts by mass (0.046 mol) of bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane, 29.21 parts by mass (0.200 mol) of isosorbide (ISB), and spiroglycerol (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 the reactor was replaced with nitrogen under reduced pressure, it was heated with a heating medium, and stirring was started when the internal temperature reached 100°C. The internal temperature was brought to 220°
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. Preparation of retardation film The obtained polyester carbonate resin (pellets) was vacuum-dried at 80°C for 5 hours, and then used a single-screw extruder (manufactured by Toshiba Machine Co., Ltd., cylinder set temperature: 250°C) and a T-die (width 200mm). , set temperature: 250℃), cooling roller (set temperature: 120~130℃) and film forming device of the winding machine 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 phase difference film with a thickness of 53 μm. The Re(550) of the obtained retardation film was 141 nm, Re(450)/Re(550) was 0.82, and the Nz coefficient was 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. Make a polarizing plate with a phase difference layer The retardation film obtained in the above 2. was bonded to the surface of the polarizer of the polarizing plate obtained in the above 1. through an acrylic adhesive (thickness: 5 μm). At this time, the polarizer is bonded so that the absorption axis and the slow axis of the retardation film form an angle of 45°. And the same adhesive layer as in Example 1 is provided on the surface of the retardation layer. In the above manner, a polarizing plate with a retardation layer composed of a protective layer/adhesive layer/polarizer/adhesive layer/retardation layer (a stretched film of a resin film)/adhesive layer is obtained. The total thickness of the polarizing plate with the retardation layer obtained was 91 μm. The obtained polarizing plate with a retardation layer was subjected to 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 was not formed, a polarizing plate having a protective layer (HC layer/COP film)/adhesive layer/polarizer/iodine transmission inhibition layer/adhesive layer was 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 from a polarizing plate with a retardation layer in structure, so the metal corrosion properties are not compared with Comparative Example 1.
[表1] [Table 1]
[表2] [Table 2]
[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 can be clearly seen from Table 1 that the polarizing plate with a retardation layer and the polarizing plate according to the embodiment of the present invention can reduce the iodine presence index of the adhesive layer below a predetermined value by forming a predetermined iodine transmission inhibition layer, and can reduce the temperature under high temperature and high temperature. It has excellent durability despite changes in polarization in wet environments. In addition, the polarizing plate with a retardation layer and the polarizing plate according to embodiments of the present invention can also significantly suppress metal corrosion and increase in reflectivity in high temperature and high humidity environments. Furthermore, as is apparent from Reference Example 1, the change in polarization degree, increase in reflectivity, and metal corrosion are issues unique to very thin polarizing plates with retardation layers and polarizing plates. In addition, comparing Example 1 and Example 13, it is obvious that the presence or absence of the liquid crystal alignment solidified 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 can be clearly seen from Table 2 that the polarizing plates with retardation layers in Examples 9 to 12 of the present invention include two or three layers of iodine transmission inhibiting layers, even if they are put into use for a long time (200 hours) in a high temperature and high humidity environment. down, metal corrosion can still be significantly inhibited. Therefore, it can be seen that when the polarizing plates with retardation layers in Embodiments 9 to 12 of the present invention are used in image display devices, they can significantly inhibit corrosion of metal components.
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 a 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:Polarizer 12:Protective layer 20: Phase difference layer (first phase difference layer) 21: The first liquid crystal orientation solidification layer 22: The second liquid crystal orientation solidification layer 30: Adhesive layer 40: Iodine penetration inhibition layer 50: Another phase difference layer (second phase difference layer) 60: Conductive layer or isotropic substrate with conductive layer 100: Polarizing plate with phase difference layer 101: Polarizing plate with phase difference layer 102: Polarizing plate with phase difference layer 103: Polarizing plate with phase difference layer 104: Polarizing plate with phase difference layer 105: Polarizing plate with phase difference 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. 2A is a schematic cross-sectional view of a polarizing plate with a retardation layer according to an embodiment of the present invention. 2B is a schematic cross-sectional view of a polarizing plate with a retardation layer according to another embodiment of the present invention. 3 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to yet another embodiment of the present invention. 4 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to yet another embodiment of the present invention. FIG. 5 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to yet another embodiment of the present invention. 6 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to yet another embodiment of the present invention.
10:偏光板 10:Polarizing plate
11:偏光件 11:Polarizer
12:保護層 12:Protective layer
30:黏著劑層 30: Adhesive layer
40:碘透過抑制層 40: Iodine penetration inhibition layer
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