TW202238185A - Polarizing film, polarizing plate and image display device - Google Patents
Polarizing film, polarizing plate and image display device Download PDFInfo
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- TW202238185A TW202238185A TW111101823A TW111101823A TW202238185A TW 202238185 A TW202238185 A TW 202238185A TW 111101823 A TW111101823 A TW 111101823A TW 111101823 A TW111101823 A TW 111101823A TW 202238185 A TW202238185 A TW 202238185A
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Abstract
Description
本發明係關於一種偏光膜、偏光板及圖像顯示裝置。The invention relates to a polarizing film, a polarizing plate and an image display device.
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)為代表之圖像顯示裝置迅速普及。關於有機EL顯示裝置，已知藉由將包含λ/4板之圓偏光板配置於有機EL元件之視認側，而防止外界光反射及背景映入等問題(例如，專利文獻1及2)。In recent years, image display devices typified by liquid crystal display devices and electroluminescence (EL) display devices (for example, organic EL display devices, inorganic EL display devices) have spread rapidly. Regarding organic EL display devices, it is known that by arranging a circular polarizing plate including a λ/4 plate on the viewing side of an organic EL element, problems such as external light reflection and background reflection are prevented (for example, Patent Documents 1 and 2).
另一方面，由於有機EL顯示裝置用於發光之消耗電力較大，故而謀求節能化。 [先前技術文獻] [專利文獻] On the other hand, since the organic EL display device consumes a large amount of power for emitting light, energy saving is sought. [Prior Art Literature] [Patent Document]
[專利文獻1]日本專利特開2002-311239號公報 [專利文獻2]日本專利特開2002-372622號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2002-311239 [Patent Document 2] Japanese Patent Laid-Open No. 2002-372622
[發明所欲解決之問題][Problem to be solved by the invention]
本發明係為了解決上述先前之問題而成者，其主要目的在於提供一種能夠減少有機EL顯示裝置之消耗電力之偏光膜。 [解決問題之技術手段] The present invention is made to solve the above-mentioned problems, and its main purpose is to provide a polarizing film capable of reducing power consumption of an organic EL display device. [Technical means to solve the problem]
根據本發明之一態樣，提供一種偏光膜，其包含含碘之聚乙烯醇系樹脂膜，且 波長470 nm下之透過率大於波長600 nm下之透過率。 於一實施方式中，上述偏光膜之霧度為1%以下。 於一實施方式中，上述偏光膜之波長470 nm下之正交吸光度A 470為4.0以下。 於一實施方式中，上述偏光膜之波長470 nm下之正交吸光度A 470相對於波長600 nm下之正交吸光度A 600之比(A 470/A 600)為0.10～0.80。 於一實施方式中，上述偏光膜之單體透過率為42.0%～65.0%，偏光度為40.0%～99.998%。 於一實施方式中，上述偏光膜之厚度為12 μm以下。 根據本發明之另一態樣，提供一種偏光板，其包含上述偏光膜、及配置於該偏光膜之至少單側之保護層。 於一實施方式中，上述偏光板進而包含相位差層，該相位差層之波長550 nm下之面內相位差為100 nm～190 nm，該相位差層之遲相軸與上述偏光膜之吸收軸所成之角度為40°～50°。 根據本發明之另一態樣，提供一種圖像顯示裝置，其具備上述偏光板。 於一實施方式中，上述圖像顯示裝置係有機電致發光顯示裝置。 [發明之效果] According to an aspect of the present invention, a polarizing film is provided, which includes an iodine-containing polyvinyl alcohol-based resin film, and has a transmittance at a wavelength of 470 nm greater than that at a wavelength of 600 nm. In one embodiment, the haze of the polarizing film is 1% or less. In one embodiment, the orthogonal absorbance A 470 at a wavelength of 470 nm of the polarizing film is 4.0 or less. In one embodiment, the ratio (A 470 /A 600 ) of the orthogonal absorbance A 470 at a wavelength of 470 nm to the orthogonal absorbance A 600 at a wavelength of 600 nm of the polarizing film is 0.10˜0.80. In one embodiment, the single transmittance of the polarizing film is 42.0%-65.0%, and the degree of polarization is 40.0%-99.998%. In one embodiment, the thickness of the polarizing film is 12 μm or less. According to another aspect of the present invention, a polarizing plate is provided, which includes the above-mentioned polarizing film, and a protective layer disposed on at least one side of the polarizing film. In one embodiment, the above-mentioned polarizing plate further includes a retardation layer, the in-plane retardation of the retardation layer at a wavelength of 550 nm is 100 nm to 190 nm, and the slow axis of the retardation layer and the absorption of the above-mentioned polarizing film The angle formed by the axes is 40°～50°. According to another aspect of the present invention, there is provided an image display device including the above-mentioned polarizing plate. In one embodiment, the above-mentioned image display device is an organic electroluminescent display device. [Effect of Invention]
本發明之實施方式之偏光膜由於波長470 nm下之透過率大於波長600 nm下之透過率，故而能夠使短波長側之光相較於長波長側之光更積極地透過。藉由使用此種偏光膜，即便於減少消耗電力較大之藍色發光之量之情形時，亦能夠抑制短波長區域之亮度降低，結果能夠兼顧有機EL顯示裝置之節能化與高亮度化。In the polarizing film according to the embodiment of the present invention, since the transmittance at a wavelength of 470 nm is greater than that at a wavelength of 600 nm, light on the short-wavelength side can be more actively transmitted than light on the long-wavelength side. By using such a polarizing film, even when reducing the amount of blue light emission that consumes a lot of power, it is possible to suppress the decrease in luminance in the short-wavelength region, and as a result, both energy saving and high luminance of the organic EL display device can be achieved.
以下，對本發明之實施方式進行說明，但本發明並不限定於該等實施方式。Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.
(用語及記號之定義) 本說明書中之用語及記號之定義如下所述。 (1)折射率(nx、ny、nz) 「nx」係面內折射率變得最大時之方向(即，遲相軸方向)之折射率，「ny」係在面內與遲相軸正交之方向(即，進相軸方向)之折射率，「nz」係厚度方向之折射率。 (2)面內相位差(Re) 「Re(λ)」係23℃下利用波長λ nm之光測得之面內相位差。例如，「Re(550)」係23℃下利用波長550 nm之光測得之面內相位差。在將層(膜)之厚度設為d(nm)時，Re(λ)可根據式：Re(λ)＝(nx－ny)×d求出。 (3)厚度方向之相位差(Rth) 「Rth(λ)」係23℃下利用波長λ nm之光測得之厚度方向之相位差。例如，「Rth(550)」係23℃下利用波長550 nm之光測得之厚度方向之相位差。在將層(膜)之厚度設為d(nm)時，Rth(λ)可根據式：Rth(λ)＝(nx－nz)×d求出。 (4)Nz係數 Nz係數可根據Nz＝Rth/Re求出。 (5)角度 本說明書中提及角度時，該角度包括相對於基準方向之順時針方向角度及逆時針方向角度兩者。因此，例如「45°」意指±45°。 (Definition of terms and symbols) The definitions of the terms and symbols in this specification are as follows. (1) Refractive index (nx, ny, nz) "nx" is the refractive index in the direction where the in-plane refractive index becomes maximum (that is, the direction of the slow axis), and "ny" is the refractive index in the direction perpendicular to the slow axis in the plane (that is, the direction of the slow axis). Refractive index, "nz" is the refractive index in the thickness direction. (2) In-plane retardation (Re) "Re(λ)" is the in-plane retardation measured by light with a wavelength of λ nm at 23°C. For example, "Re(550)" is the in-plane retardation measured by light with a wavelength of 550 nm at 23°C. When the thickness of the layer (film) is d (nm), Re(λ) can be obtained from the formula: Re(λ)=(nx-ny)×d. (3) Phase difference in thickness direction (Rth) "Rth(λ)" is the retardation in the thickness direction measured by light with a wavelength of λ nm at 23°C. For example, "Rth(550)" is the retardation in the thickness direction measured by light with a wavelength of 550 nm at 23°C. When the thickness of the layer (film) is d (nm), Rth(λ) can be obtained from the formula: Rth(λ)=(nx-nz)×d. (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 a clockwise angle and a counterclockwise angle relative to a reference direction. Thus, for example, "45°" means ±45°.
A.偏光膜 本發明之實施方式之偏光膜包含含碘之聚乙烯醇系樹脂膜，且波長470 nm下之透過率(Ts 470)大於波長600 nm下之透過率(Ts 600)。換言之，本發明之實施方式之偏光膜滿足「1＜Ts 470/Ts 600」之關係，較佳為滿足「1.02≦Ts 470/Ts 600≦1.30」之關係。滿足此種關係之偏光膜能夠使短波長側之光相較於長波長側之光更積極地透過。 A. Polarizing film The polarizing film according to the embodiment of the present invention includes an iodine-containing polyvinyl alcohol-based resin film, and has a transmittance (Ts 470 ) at a wavelength of 470 nm greater than that at a wavelength of 600 nm (Ts 600 ). In other words, the polarizing film according to the embodiment of the present invention satisfies the relationship of “1<Ts 470 /Ts 600 ”, preferably satisfies the relationship of “1.02≦Ts 470 /Ts 600 ≦1.30”. A polarizing film that satisfies this relationship can transmit light on the short wavelength side more actively than light on the long wavelength side.
上述波長470 nm下之透過率(Ts 470)係於波長470 nm附近具有吸收之PVA(polyvinyl alcohol，聚乙烯醇)-I 3 -錯合物之含量所對應之值，通常，若PVA-I 3 -錯合物之含量增大，則波長470 nm下之透過率(Ts 470)降低。另一方面，波長600 nm下之透過率(Ts 600)係於波長600 nm附近具有吸收之PVA-I 5 -錯合物之含量所對應之值，通常，若PVA-I 5 -錯合物之含量增大，則波長600 nm下之透過率(Ts 600)降低。因此，滿足「1＜Ts 470/Ts 600」之關係之偏光膜具有如下特徵：與不滿足該關係之偏光膜相比，PVA-I 3 -錯合物相對於PVA-I 5 -錯合物之含有比較低。 The above-mentioned transmittance (Ts 470 ) at a wavelength of 470 nm is the value corresponding to the content of PVA (polyvinyl alcohol, polyvinyl alcohol) -I 3 -complex that has absorption near the wavelength of 470 nm. Usually, if PVA-I The transmittance (Ts 470 ) at a wavelength of 470 nm decreases as the content of the 3 - complex increases. On the other hand, the transmittance (Ts 600 ) at a wavelength of 600 nm is the value corresponding to the content of PVA - I 5 -complexes that absorb around the wavelength of 600 nm. Usually, if the PVA - I 5 -complexes The transmittance (Ts 600 ) at a wavelength of 600 nm decreases as the content of α increases. Therefore, a polarizing film that satisfies the relationship "1<Ts 470 /Ts 600 " has the following characteristics: Compared with a polarizing film that does not satisfy this relationship , the PVA - I 3 -complex The content is relatively low.
偏光膜之Ts 470及Ts 600可根據目的而設為任意適當之值。Ts 470例如可為40.0%以上，較佳為42.0%以上，更佳為44.0%以上，又，例如可為80.0%以下，較佳為60.0%以下。又，Ts 600例如可為40.0%以上，較佳為41.0%以上，更佳為42.0%以上，又，例如可為70.0%以下，較佳為60.0%以下，更佳為50.0%以下。 Ts 470 and Ts 600 of the polarizing film can be set to any appropriate value according to the purpose. Ts 470 may be, for example, 40.0% or more, preferably 42.0% or more, more preferably 44.0% or more, and for example, may be 80.0% or less, preferably 60.0% or less. Also, Ts 600 may be, for example, 40.0% or more, preferably 41.0% or more, more preferably 42.0% or more, and for example, may be 70.0% or less, preferably 60.0% or less, more preferably 50.0% or less.
偏光膜較佳為於波長380 nm～780 nm中任一波長下表現出吸收二色性。偏光膜之透過率(單體透過率：Ts)較佳為41.0%以上，更佳為42.0%以上，再佳的是42.5%以上。另一方面，偏光膜之透過率例如為65.0%以下，較佳為50.0%以下，更佳為48.0%以下。又，偏光膜之偏光度例如為40.0%以上，較佳為90.0%以上，更佳為94.0%以上，再佳的是96.0%以上，進而更佳為99.0%以上，進而更佳為99.5%以上，較佳為99.998%以下。代表性而言，上述透過率係使用紫外可見分光光度計進行測定，並進行視感度補正而得之Y值。代表性而言，上述偏光度可基於使用紫外可見分光光度計進行測定並進行視感度補正而得之平行透過率Tp及正交透過率Tc，根據下述式而求出。 偏光度(%)＝{(Tp－Tc)/(Tp＋Tc)} 1/2×100 The polarizing film preferably exhibits absorption dichroism at any wavelength between 380 nm and 780 nm. The transmittance of the polarizing film (single transmittance: Ts) is preferably at least 41.0%, more preferably at least 42.0%, and most preferably at least 42.5%. On the other hand, the transmittance of the polarizing film is, for example, 65.0% or less, preferably 50.0% or less, more preferably 48.0% or less. Moreover, the degree of polarization of the polarizing film is, for example, 40.0% or more, preferably 90.0% or more, more preferably 94.0% or more, even more preferably 96.0% or more, still more preferably 99.0% or more, and even more preferably 99.5% or more , preferably below 99.998%. Typically, the above-mentioned transmittance is measured with an ultraviolet-visible spectrophotometer, and the Y value is obtained by correcting the light sensitivity. Typically, the degree of polarization can be obtained from the following formula based on the parallel transmittance Tp and the cross transmittance Tc obtained by measuring with an ultraviolet-visible spectrophotometer and correcting the sensitivity. Degree of polarization (%)={(Tp－Tc)/(Tp+Tc)} 1/2 ×100
於一實施方式中，代表性而言，12 μm以下之薄型偏光膜之透過率係將偏光膜(表面之折射率：1.53)與保護層(保護膜)(折射率：1.50)之積層體作為測定對象，使用紫外可見分光光度計進行測定。存在各層之界面處之反射率根據偏光膜之表面之折射率及/或保護層之與空氣界面相接之表面之折射率而發生變化，結果導致透過率之測定值發生變化之情形。因此，例如，於使用折射率並非1.50之保護層之情形時，可根據保護層之與空氣界面相接之表面之折射率而對透過率之測定值進行補正。具體而言，透過率之補正值C係使用保護層與空氣層之界面處與透射軸平行之偏光之反射率R 1(透射軸反射率)，由以下之式表示。 C＝R 1－R 0R 0＝((1.50－1) 2/(1.50＋1) 2)×(T 1/100) R 1＝((n 1－1) 2/(n 1＋1) 2)×(T 1/100) 此處，R 0係使用折射率為1.50之保護層時之透射軸反射率，n 1係所使用之保護層之折射率，T 1係偏光膜之透過率。例如，於使用表面折射率為1.53之基材(環烯烴系膜、附硬塗層之膜等)作為保護層之情形時，補正量C約為0.2%。於此情形時，可藉由將測得之透過率加上0.2%，而將表面折射率為1.53之偏光膜換算成使用折射率為1.50之保護層時之透過率。再者，根據基於上述式之計算，使偏光膜之透過率T 1變化2%時之補正值C之變化量為0.03%以下，偏光膜之透過率對補正值C之值造成之影響有限。又，於保護層具有表面反射以外之吸收之情形時，可根據吸收量而進行適當之補正。 In one embodiment, typically, the transmittance of a thin polarizing film of 12 μm or less is a laminate of a polarizing film (refractive index of the surface: 1.53) and a protective layer (protective film) (refractive index: 1.50). Measurement objects are measured using a UV-Vis spectrophotometer. There is a situation where the reflectance at the interface of each layer changes according to the refractive index of the surface of the polarizing film and/or the refractive index of the surface of the protective layer in contact with the air interface, resulting in a change in the measured value of the transmittance. Therefore, for example, when using a protective layer with a refractive index other than 1.50, the measured value of the transmittance can be corrected based on the refractive index of the surface of the protective layer in contact with the air interface. Specifically, the correction value C of the transmittance is represented by the following formula using the reflectance R 1 (transmission axis reflectance) of polarized light parallel to the transmission axis at the interface between the protective layer and the air layer. C＝R 1 －R 0 R 0 ＝((1.50－1) 2 /(1.50＋1) 2 )×(T 1 /100) R 1 ＝((n 1 －1) 2 /(n 1 ＋1) 2 ) ×(T 1 /100) Here, R 0 is the transmission axis reflectance when using a protective layer with a refractive index of 1.50, n 1 is the refractive index of the protective layer used, and T 1 is the transmittance of the polarizing film. For example, when using a base material (cycloolefin-based film, hard-coated film, etc.) with a surface refractive index of 1.53 as a protective layer, the correction amount C is about 0.2%. In this case, by adding 0.2% to the measured transmittance, the polarizing film with a surface refractive index of 1.53 can be converted into the transmittance when using a protective layer with a refractive index of 1.50. Furthermore, according to the calculation based on the above formula, when the transmittance T1 of the polarizing film is changed by 2%, the change of the correction value C is less than 0.03%, and the influence of the transmittance of the polarizing film on the value of the correction value C is limited. Also, when the protective layer has absorption other than surface reflection, appropriate correction can be made according to the amount of absorption.
偏光膜之波長470 nm下之正交吸光度A 470較佳為4.0以下，更佳為3.5以下，再佳的是3.0以下，進而更佳為2.5以下。又，正交吸光度A 470例如為0.2以上，較佳為1.0以上，更佳為1.5以上。再者，波長λ nm下之正交吸光度A λ可基於上述正交透過率Tc，根據下述式求出。 正交吸光度＝log10(100/Tc) The orthogonal absorbance A 470 of the polarizing film at a wavelength of 470 nm is preferably at most 4.0, more preferably at most 3.5, even more preferably at most 3.0, and even more preferably at most 2.5. Also, the orthogonal absorbance A 470 is, for example, 0.2 or more, preferably 1.0 or more, more preferably 1.5 or more. In addition, the orthogonal absorbance A λ at the wavelength λ nm can be obtained from the following formula based on the above-mentioned orthogonal transmittance Tc. Orthogonal absorbance = log10(100/Tc)
偏光膜之波長470 nm下之正交吸光度A 470相對於波長600 nm下之正交吸光度A 600之比(A 470/A 600)例如為0.80以下，較佳為0.70以下，更佳為0.60以下。比(A 470/A 600)例如為0.10以上，較佳為0.30以上，更佳為0.35以上。 The ratio (A 470 /A 600 ) of the orthogonal absorbance A 470 at a wavelength of 470 nm to the orthogonal absorbance A 600 at a wavelength of 600 nm of the polarizing film is, for example, 0.80 or less, preferably 0.70 or less, more preferably 0.60 or less . The ratio (A 470 /A 600 ) is, for example, 0.10 or more, preferably 0.30 or more, more preferably 0.35 or more.
正交吸光度A 470係排列於吸收軸方向上之PVA-I 3 -錯合物之含量所對應之值，通常，正交吸光度A 470較高意味著排列於吸收軸方向上之PVA-I 3 -錯合物之含量較多。另一方面，正交吸光度A 600係排列於吸收軸方向上之PVA-I 5 -錯合物之含量所對應之值，通常，正交吸光度A 600較高意味著排列於吸收軸方向上之PVA-I 5 -錯合物之含量較多。因此，比(A 470/A 600)較低意味著排列於吸收軸方向上之PVA-I 3 -錯合物之含量相對較少，排列於吸收軸方向上之PVA-I 5 -錯合物之含量相對較多。 Orthogonal absorbance A 470 is the value corresponding to the content of PVA - I 3 -complexes arranged in the direction of the absorption axis. Usually, a higher orthogonal absorbance A 470 means that PVA-I 3 is arranged in the direction of the absorption axis - The content of complexes is relatively high. On the other hand, the orthogonal absorbance A 600 is the value corresponding to the content of the PVA - I 5 -complex arranged in the direction of the absorption axis. Generally, a higher orthogonal absorbance A 600 means that the PVA-I 5 -complexes arranged in the direction of the absorption axis The content of PVA - I 5 -complex is relatively high. Therefore, a lower ratio (A 470 /A 600 ) means that the content of PVA - I 3 -complexes arranged in the direction of the absorption axis is relatively small, and the content of PVA - I 5 -complexes arranged in the direction of the absorption axis The content is relatively high.
偏光膜之霧度較佳為1%以下，更佳為0.8%以下，再佳的是0.6%以下。若霧度處於該範圍內，則能夠獲得具有高對比率之有機EL顯示裝置。The haze of the polarizing film is preferably at most 1%, more preferably at most 0.8%, and most preferably at most 0.6%. When the haze is within this range, an organic EL display device having a high contrast ratio can be obtained.
偏光膜中之碘濃度較佳為3重量%以上，更佳為4重量%～10重量%，更佳為4重量%～8重量%。再者，本說明書中「碘濃度」意指偏光膜中所包含之所有碘之量。更具體而言，於偏光膜中，碘以I -、I 2、I 3 -、PVA-I 3 -錯合物、PVA-I 5 -錯合物等形態存在，本說明書中之碘濃度意指該等形態全部包括在內之碘之濃度。碘濃度例如可根據由螢光X射線分析所得之螢光X射線強度及膜(偏光膜)厚度而算出。 The iodine concentration in the polarizing film is preferably at least 3% by weight, more preferably 4% by weight to 10% by weight, more preferably 4% by weight to 8% by weight. In addition, "iodine concentration" in this specification means the quantity of all iodine contained in a polarizing film. More specifically, in the polarizing film, iodine exists in the form of I - , I 2 , I 3 - , PVA - I 3 -complex, PVA - I 5 -complex, etc. The concentration of iodine in this specification means Refers to the concentration of iodine inclusive of such forms. The iodine concentration can be calculated from, for example, fluorescent X-ray intensity and film (polarizing film) thickness obtained by fluorescent X-ray analysis.
代表性而言，偏光膜之厚度為25 μm以下，較佳為12 μm以下，更佳為1 μm～12 μm，再佳的是1 μm～7 μm，進而更佳為2 μm～5 μm。Typically, the thickness of the polarizing film is 25 μm or less, preferably 12 μm or less, more preferably 1 μm to 12 μm, more preferably 1 μm to 7 μm, and even more preferably 2 μm to 5 μm.
B.偏光膜之製造方法 A項所記載之偏光膜例如可藉由包括如下步驟之製造方法而獲得：使水分率為15重量%以下且吸附配向有碘之PVA系樹脂膜與水性溶劑接觸。藉由使此種PVA系樹脂膜與水性溶劑接觸，形成PVA-I 3 -錯合物之多碘離子較形成PVA-I 5 -錯合物之多碘離子更優先地脫出，而引起脫色，結果能夠簡便地獲得滿足「1＜Ts 470/Ts 600」之關係之偏光膜。於一實施方式中，與水性溶劑接觸後之PVA系樹脂膜之波長λ nm下之透過率相對於與水性溶劑接觸前之透過率的上升比(ΔTs λ＝Ts λ(接觸後)/Ts λ(接觸前))滿足ΔTs 415＞ΔTs 470＞ΔTs 600之關係。 B. Manufacturing method of polarizing film The polarizing film described in item A can be obtained, for example, by a manufacturing method including the steps of bringing a PVA-based resin film having a moisture content of 15% by weight or less and having iodine adsorbed and aligned in contact with an aqueous solvent. By contacting such a PVA-based resin film with an aqueous solvent, the polyiodide ions forming the PVA - I 3 -complex are released more preferentially than the polyiodide ions forming the PVA - I 5 -complex, thereby causing decolorization , as a result, a polarizing film satisfying the relationship of "1<Ts 470 /Ts 600 " can be easily obtained. In one embodiment, the increase ratio of the transmittance at the wavelength λ nm of the PVA-based resin film after contact with the aqueous solvent relative to the transmittance before contact with the aqueous solvent (ΔTs λ =Ts λ (after contact)/Ts λ (before contact)) satisfies the relationship of ΔTs 415 >ΔTs 470 >ΔTs 600 .
B-1.PVA系樹脂膜 代表性而言，水分率為15重量%以下且吸附配向有碘之PVA系樹脂膜(於本說明書中，亦稱為「未脫色原膜」)滿足「1≧Ts 470/Ts 600」之關係。又，未脫色原膜較佳為於波長380 nm～780 nm中任一波長下表現出吸收二色性且可作為偏光膜發揮功能之狀態。具體而言，未脫色原膜較佳為被施以延伸處理、碘染色處理、乾燥處理等各種處理之PVA系樹脂膜。 B-1. PVA-based resin film is typically a PVA-based resin film with a moisture content of 15% by weight or less and with iodine adsorbed and aligned (in this specification, also referred to as "unbleached original film") that satisfies "1≧ Ts 470 /Ts 600 "relationship. In addition, the undecolorized original film is preferably in a state in which it exhibits absorption dichroism at any wavelength between 380 nm and 780 nm and can function as a polarizing film. Specifically, the undecolorized original film is preferably a PVA-based resin film subjected to various treatments such as stretching treatment, iodine dyeing treatment, and drying treatment.
於一實施方式中，未脫色原膜之透過率(單體透過率：Ts)較佳為41.0%以上，更佳為42.0%以上，再佳的是42.5%以上。另一方面，未脫色原膜之透過率較佳為46.0%以下，更佳為45.0%以下。未脫色原膜之偏光度較佳為98.0%以上，更佳為99.0%以上，再佳的是99.9%以上。另一方面，未脫色原膜之偏光度較佳為99.998%以下。上述透過率及偏光度可以與偏光膜之透過率及偏光度相同之方式求出。In one embodiment, the transmittance (single transmittance: Ts) of the undecolorized original film is preferably 41.0% or higher, more preferably 42.0% or higher, and even more preferably 42.5% or higher. On the other hand, the transmittance of the unbleached original film is preferably 46.0% or less, more preferably 45.0% or less. The degree of polarization of the unbleached original film is preferably above 98.0%, more preferably above 99.0%, even more preferably above 99.9%. On the other hand, the degree of polarization of the unbleached original film is preferably 99.998% or less. The aforementioned transmittance and degree of polarization can be obtained in the same manner as the transmittance and degree of polarization of the polarizing film.
代表性而言，未脫色原膜之水分率為15重量%以下，較佳為12重量%以下，更佳為10重量%以下，再佳的是1重量%～5重量%。若未脫色原膜之水分率處於該範圍內，則與水性溶劑接觸時，能夠防止溶解及皺褶之產生。Typically, the moisture content of the original unbleached film is 15% by weight or less, preferably 12% by weight or less, more preferably 10% by weight or less, and most preferably 1% to 5% by weight. If the moisture content of the unbleached original film is within this range, it can prevent dissolution and wrinkles when it comes into contact with an aqueous solvent.
代表性而言，未脫色原膜之厚度為25 μm以下，較佳為12 μm以下，更佳為1 μm～12 μm，再佳的是1 μm～7 μm，進而更佳為2 μm～5 μm。Typically, the thickness of the original unbleached film is 25 μm or less, preferably 12 μm or less, more preferably 1 μm to 12 μm, even more preferably 1 μm to 7 μm, and even more preferably 2 μm to 5 μm. μm.
未脫色原膜可使用單層PVA系樹脂膜來製作，亦可使用包含PVA系樹脂層(PVA系樹脂膜)之兩層以上之積層體來製作。使用兩層以上之積層體所製作之未脫色原膜在與水性溶劑接觸後，亦能夠避免產生皺褶等，並且較好地維持優異之光學特性(代表性而言，單體透過率及偏光度)。The unbleached original film can be produced using a single-layer PVA-based resin film, or can be produced using a laminate of two or more layers including a PVA-based resin layer (PVA-based resin film). The non-decolorized original film made of more than two layers of laminates can also avoid wrinkles after contact with aqueous solvents, and maintain excellent optical properties (typically, single transmittance and polarization) Spend).
B-1-1.使用兩層以上之積層體之未脫色原膜之製作 使用兩層以上之積層體之未脫色原膜之製作例如可藉由包括如下步驟之方法來進行：將包含鹵化物及PVA系樹脂之PVA系樹脂膜在與長條狀熱塑性樹脂基材之積層體之狀態下依序供至空中輔助延伸處理、染色處理、水中延伸處理及乾燥收縮處理。熱塑性樹脂基材與PVA系樹脂膜之積層體例如可藉由如下步驟而獲得：於長條狀熱塑性樹脂基材之單側形成包含鹵化物及PVA系樹脂之PVA系樹脂層(PVA系樹脂膜)而製成積層體。乾燥收縮處理例如包括如下步驟：藉由將該長條狀熱塑性樹脂基材與PVA系樹脂膜之積層體一面沿長度方向搬送一面進行加熱，而使其於寬度方向上收縮2%以上，並且使其乾燥直至該PVA系樹脂膜之水分率為15重量%以下為止。PVA系樹脂層中之鹵化物之含量較佳為相對於PVA系樹脂100重量份為5重量份～20重量份。水中延伸處理較佳為於硼酸水溶液中進行。乾燥收縮處理較佳為使用加熱輥進行處理，加熱輥之溫度較佳為60℃～120℃。根據此種製造方法，能夠獲得PVA系樹脂之配向度較高，且具有優異光學特性之未脫色原膜。 B-1-1. Production of non-decolorized original film using laminates with more than two layers The production of an unbleached original film using a laminate of more than two layers can be carried out, for example, by a method comprising the following steps: laminating a PVA-based resin film containing a halide and a PVA-based resin on a long thermoplastic resin substrate. In the state of the body, it is sequentially subjected to air-assisted stretching treatment, dyeing treatment, underwater stretching treatment and drying shrinkage treatment. A laminate of a thermoplastic resin substrate and a PVA-based resin film can be obtained, for example, by forming a PVA-based resin layer (PVA-based resin film) containing a halide and a PVA-based resin on one side of a long thermoplastic resin substrate. ) to form a laminate. The drying shrinkage treatment includes, for example, a step of heating the laminate of the elongated thermoplastic resin substrate and the PVA-based resin film while conveying it in the longitudinal direction, shrinking it by 2% or more in the width direction, and making it This is dried until the moisture content of the PVA-based resin film is 15% by weight or less. The content of the halide in the PVA-based resin layer is preferably 5 to 20 parts by weight with respect to 100 parts by weight of the PVA-based resin. The extension treatment in water is preferably carried out in boric acid aqueous solution. The drying shrinkage treatment is preferably performed with a heating roller, and the temperature of the heating roller is preferably 60°C to 120°C. According to such a manufacturing method, it is possible to obtain an unbleached original film with a high degree of alignment of the PVA-based resin and excellent optical properties.
B-1-1-1.積層體之製作 作為熱塑性樹脂基材與PVA系樹脂層之積層體之製作方法，可採用任意適當之方法。較佳為藉由在熱塑性樹脂基材之表面塗佈包含鹵化物及PVA系樹脂之塗佈液，並進行乾燥，而於熱塑性樹脂基材上形成PVA系樹脂層。如上所述，PVA系樹脂層中之鹵化物之含量較佳為相對於PVA系樹脂100重量份為5重量份～20重量份。 B-1-1-1. Fabrication of laminated body Any appropriate method may be employed as a method for producing a laminate of the thermoplastic resin base material and the PVA-based resin layer. Preferably, the PVA-based resin layer is formed on the thermoplastic resin substrate by coating a coating solution containing a halide and a PVA-based resin on the surface of the thermoplastic resin substrate and drying the coating. As mentioned above, it is preferable that content of the halide in a PVA-type resin layer is 5 weight part - 20 weight part with respect to 100 weight part of PVA-type resin.
作為塗佈液之塗佈方法，可採用任意適當之方法。例如可例舉：輥塗法、旋轉塗佈法、線棒塗佈法、浸漬塗佈法、模嘴塗佈法、淋幕式塗佈法、噴塗法、刮塗法(缺角輪塗佈法等)等。上述塗佈液之塗佈、乾燥溫度較佳為50℃以上。Any appropriate method can be adopted as the coating method of the coating liquid. For example, roll coating method, spin coating method, wire bar coating method, dip coating method, die coating method, curtain coating method, spray coating method, blade coating method (cutting wheel coating method) law, etc.) etc. The coating and drying temperature of the above-mentioned coating solution is preferably 50°C or higher.
PVA系樹脂層之厚度較佳為3 μm～40 μm，再佳的是3 μm～20 μm。The thickness of the PVA-based resin layer is preferably from 3 μm to 40 μm, more preferably from 3 μm to 20 μm.
在形成PVA系樹脂層之前，可對熱塑性樹脂基材實施表面處理(例如，電暈處理等)，亦可於熱塑性樹脂基材上形成易接著層。藉由進行此種處理，能夠提高熱塑性樹脂基材與PVA系樹脂層之密接性。Before forming the PVA-based resin layer, the thermoplastic resin substrate can be subjected to surface treatment (for example, corona treatment, etc.), and an easy-adhesive layer can also be formed on the thermoplastic resin substrate. By performing such a process, the adhesiveness of a thermoplastic resin base material and a PVA-type resin layer can be improved.
熱塑性樹脂基材之厚度較佳為20 μm～300 μm，更佳為50 μm～200 μm。若未達20 μm，則有難以形成PVA系樹脂層之虞。若超過300 μm，則有例如在下述水中延伸處理中熱塑性樹脂基材吸收水需要之時間較長，並且延伸需要之負載過大之虞。The thickness of the thermoplastic resin substrate is preferably from 20 μm to 300 μm, more preferably from 50 μm to 200 μm. If it is less than 20 μm, it may be difficult to form a PVA-based resin layer. If it exceeds 300 μm, it may take a long time for the thermoplastic resin substrate to absorb water in, for example, the underwater stretching treatment described below, and the load required for stretching may become too large.
熱塑性樹脂基材之吸水率較佳為0.2%以上，再佳的是0.3%以上。熱塑性樹脂基材吸收水，水能夠發揮塑化劑的作用而使其塑化。結果能夠大幅降低延伸應力，能夠以高倍率進行延伸。另一方面，熱塑性樹脂基材之吸水率較佳為3.0%以下，再佳的是1.0%以下。藉由使用此種熱塑性樹脂基材，能夠防止製造時熱塑性樹脂基材之尺寸穩定性顯著降低而使所獲得之未脫色原膜之外觀變差等異常。又，能夠防止在水中延伸時基材斷裂，或者PVA系樹脂層自熱塑性樹脂基材剝離。再者，熱塑性樹脂基材之吸水率例如可藉由向構成材料中導入改性基來進行調整。吸水率係依據JIS K 7209所求出之值。The water absorption rate of the thermoplastic resin substrate is preferably above 0.2%, and more preferably above 0.3%. The thermoplastic resin substrate absorbs water, and the water acts as a plasticizer to plasticize it. As a result, elongation stress can be significantly reduced, and elongation at a high magnification can be performed. On the other hand, the water absorption of the thermoplastic resin substrate is preferably 3.0% or less, more preferably 1.0% or less. By using such a thermoplastic resin base material, it is possible to prevent abnormalities such as deterioration of the appearance of the obtained unbleached original film due to a marked reduction in the dimensional stability of the thermoplastic resin base material during production. In addition, it is possible to prevent the substrate from being broken during stretching in water, or the PVA-based resin layer to be prevented from peeling off from the thermoplastic resin substrate. Furthermore, the water absorption rate of the thermoplastic resin substrate can be adjusted, for example, by introducing a modifying group into the constituent material. The water absorption is a value obtained in accordance with JIS K 7209.
熱塑性樹脂基材之玻璃轉移溫度(Tg)較佳為120℃以下。藉由使用此種熱塑性樹脂基材，能夠抑制PVA系樹脂層之結晶化，並且充分確保積層體之延伸性。進而，考慮到良好地利用水使熱塑性樹脂基材塑化、及良好地進行水中延伸之觀點，玻璃轉移溫度更佳為100℃以下，進而更佳為90℃以下。另一方面，熱塑性樹脂基材之玻璃轉移溫度較佳為60℃以上。藉由使用此種熱塑性樹脂基材，在上述包含PVA系樹脂之塗佈液之塗佈、乾燥時，能夠防止熱塑性樹脂基材發生變形(例如，凹凸、或鬆弛、皺褶等之產生)等異常，良好地製作積層體。又，能夠於合適之溫度(例如，60℃左右)下良好地進行PVA系樹脂層之延伸。再者，熱塑性樹脂基材之玻璃轉移溫度例如可藉由向構成材料中導入改性基、使用結晶化材料進行加熱來進行調整。玻璃轉移溫度(Tg)係依據JIS K 7121所求出之值。The glass transition temperature (Tg) of the thermoplastic resin substrate is preferably below 120°C. By using such a thermoplastic resin base material, crystallization of the PVA-based resin layer can be suppressed, and the extensibility of the laminate can be sufficiently ensured. Furthermore, the glass transition temperature is more preferably 100° C. or lower, more preferably 90° C. or lower, from the viewpoint of satisfactorily plasticizing the thermoplastic resin base material with water and carrying out satisfactory underwater stretching. On the other hand, the glass transition temperature of the thermoplastic resin substrate is preferably 60° C. or higher. By using such a thermoplastic resin substrate, it is possible to prevent the thermoplastic resin substrate from being deformed (for example, unevenness, or sagging, wrinkles, etc.) during the coating and drying of the above-mentioned coating liquid containing the PVA-based resin. Abnormally, the laminate was produced well. In addition, the stretching of the PVA-based resin layer can be favorably performed at an appropriate temperature (for example, about 60° C.). Furthermore, the glass transition temperature of the thermoplastic resin substrate can be adjusted by, for example, introducing a modifying group into the constituent material and heating using the crystallization material. The glass transition temperature (Tg) is the value calculated|required based on JISK7121.
作為熱塑性樹脂基材之構成材料，可採用任意適當之熱塑性樹脂。作為熱塑性樹脂，例如可例舉：聚對苯二甲酸乙二酯系樹脂等酯系樹脂、降𦯉烯系樹脂等環烯烴系樹脂、聚丙烯等烯烴系樹脂、聚醯胺系樹脂、聚碳酸酯系樹脂、其等之共聚物樹脂等。其中，較佳為降𦯉烯系樹脂、非晶質之聚對苯二甲酸乙二酯系樹脂。Any appropriate thermoplastic resin can be used as a constituent material of the thermoplastic resin base material. Examples of thermoplastic resins include: ester resins such as polyethylene terephthalate resins, cycloolefin resins such as northylene resins, olefin resins such as polypropylene, polyamide resins, polycarbonate resins, etc. Ester resins, their copolymer resins, etc. Among them, norphthalate-based resins and amorphous polyethylene terephthalate-based resins are preferable.
於一實施方式中，較佳為使用非晶質之(未結晶化之)聚對苯二甲酸乙二酯系樹脂。其中，尤佳為使用非晶性之(不易結晶化之)聚對苯二甲酸乙二酯系樹脂。作為非晶性之聚對苯二甲酸乙二酯系樹脂之具體例，可例舉：進而包含間苯二甲酸及/或環己烷二羧酸作為二羧酸之共聚物、及進而包含環己烷二甲醇或二乙二醇作為二醇之共聚物。In one embodiment, it is preferable to use an amorphous (uncrystallized) polyethylene terephthalate resin. Among them, it is particularly preferable to use an amorphous (difficult to crystallize) polyethylene terephthalate resin. Specific examples of amorphous polyethylene terephthalate-based resins include copolymers further comprising isophthalic acid and/or cyclohexanedicarboxylic acid as dicarboxylic acids, and further comprising cyclohexanedicarboxylic acid. Copolymers of hexanedimethanol or diethylene glycol as diols.
於較佳之實施方式中，熱塑性樹脂基材包含具有間苯二甲酸單元之聚對苯二甲酸乙二酯系樹脂。其原因在於，此種熱塑性樹脂基材之延伸性極其優異，並且能夠抑制延伸時之結晶化。認為這是由於藉由導入間苯二甲酸單元而對主鏈賦予了較大彎曲。聚對苯二甲酸乙二酯系樹脂具有對苯二甲酸單元及乙二醇單元。間苯二甲酸單元之含有比率相對於全部重複單元之合計，較佳為0.1莫耳%以上，再佳的是1.0莫耳%以上。其原因在於，這樣能夠獲得延伸性極其優異之熱塑性樹脂基材。另一方面，間苯二甲酸單元之含有比率相對於全部重複單元之合計，較佳為20莫耳%以下，更佳為10莫耳%以下。藉由設為此種含有比率，能夠在下述乾燥收縮處理中良好地增加結晶度。In a preferred embodiment, the thermoplastic resin substrate includes a polyethylene terephthalate-based resin having an isophthalic acid unit. The reason for this is that such a thermoplastic resin base material is extremely excellent in elongation and can suppress crystallization during elongation. This is considered to be due to the large bend imparted to the main chain by the introduction of the isophthalic acid unit. The polyethylene terephthalate resin has a terephthalic acid unit and an ethylene glycol unit. The content ratio of the isophthalic acid unit is preferably at least 0.1 mol %, more preferably at least 1.0 mol %, based on the total of all repeating units. The reason for this is that a thermoplastic resin base material extremely excellent in extensibility can be obtained. On the other hand, the content ratio of the isophthalic acid unit is preferably 20 mol% or less, more preferably 10 mol% or less, based on the total of all repeating units. By setting it as such a content ratio, the crystallinity can be favorably increased in the drying shrinkage process mentioned later.
熱塑性樹脂基材可預先(形成PVA系樹脂層之前)進行延伸。於一實施方式中，沿長條狀熱塑性樹脂基材之橫向進行延伸。橫向較佳為與下述積層體之延伸方向正交之方向。再者，於本說明書中，所謂「正交」，亦包括實質上正交之情形。此處，所謂「實質上正交」，包括90°±5.0°之情形，較佳為90°±3.0°，再佳的是90°±1.0°。The thermoplastic resin substrate may be stretched in advance (before forming the PVA-based resin layer). In one embodiment, the elongated thermoplastic resin substrate is extended in the transverse direction. The lateral direction is preferably a direction perpendicular to the extending direction of the laminate described below. Furthermore, in this specification, the so-called "orthogonal" also includes the case of being substantially orthogonal. Here, the term "substantially orthogonal" includes the case of 90°±5.0°, preferably 90°±3.0°, more preferably 90°±1.0°.
熱塑性樹脂基材之延伸溫度相對於玻璃轉移溫度(Tg)，較佳為Tg－10℃～Tg＋50℃。熱塑性樹脂基材之延伸倍率較佳為1.5倍～3.0倍。The stretching temperature of the thermoplastic resin substrate is preferably Tg-10°C to Tg+50°C relative to the glass transition temperature (Tg). The elongation ratio of the thermoplastic resin base material is preferably 1.5 times to 3.0 times.
作為熱塑性樹脂基材之延伸方法，可採用任意適當之方法。具體而言，可為固定端延伸，亦可為自由端延伸。延伸方式可為乾式，亦可為濕式。熱塑性樹脂基材之延伸可以一階段進行，亦可以多階段進行。於以多階段進行之情形時，上述延伸倍率係各階段之延伸倍率之積。Any appropriate method can be adopted as the stretching method of the thermoplastic resin base material. Specifically, it can be extended from a fixed end, or can be extended from a free end. The extension method can be dry or wet. The stretching of the thermoplastic resin substrate can be carried out in one stage or in multiple stages. In the case of carrying out in multiple stages, the above-mentioned elongation ratio is the product of the elongation ratios of each stage.
如上所述，塗佈液包含鹵化物及PVA系樹脂。代表性而言，上述塗佈液係使上述鹵化物及上述PVA系樹脂溶解於溶劑中而成之溶液。作為溶劑，例如可例舉：水、二甲基亞碸、二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯啶酮、各種二醇類、三羥甲基丙烷等多元醇類、乙二胺、二伸乙基三胺等胺類。其等可單獨使用，或者將兩種以上組合使用。其中，較佳為水。關於溶液之PVA系樹脂濃度，相對於溶劑100重量份，較佳為3重量份～20重量份。若為此種樹脂濃度，則能夠形成與熱塑性樹脂基材密接之均勻塗佈膜。塗佈液中之鹵化物之含量較佳為相對於PVA系樹脂100重量份為5重量份～20重量份。As described above, the coating liquid contains a halide and a PVA-based resin. Typically, the said coating liquid is a solution which melt|dissolved the said halide compound and the said PVA-type resin in a solvent. Examples of solvents include: water, dimethylsulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, various glycols, trimethylolpropane, and other polyols. Alcohols, ethylenediamine, diethylenetriamine and other amines. These may be used alone or in combination of two or more. Among them, water is preferred. The concentration of the PVA-based resin in the solution is preferably 3 to 20 parts by weight with respect to 100 parts by weight of the solvent. Such a resin concentration can form a uniform coating film that is in close contact with the thermoplastic resin substrate. It is preferable that content of the halide in a coating liquid is 5 weight part - 20 weight part with respect to 100 weight part of PVA-type resins.
可於塗佈液中調配添加劑。作為添加劑，例如可例舉：塑化劑、界面活性劑等。作為塑化劑，例如可例舉乙二醇及甘油等多元醇。作為界面活性劑，例如可例舉非離子界面活性劑。為了進一步提高所獲得之PVA系樹脂層之均勻性及染色性、延伸性，可使用該等添加劑。Additives can be formulated in the coating solution. As an additive, a plasticizer, a surfactant, etc. are mentioned, for example. As a plasticizer, polyalcohols, such as ethylene glycol and glycerin, are mentioned, for example. As a surfactant, a nonionic surfactant is mentioned, for example. These additives may be used in order to further improve the uniformity, dyeability, and extensibility of the obtained PVA-based resin layer.
作為上述PVA系樹脂，可採用任意適當之樹脂。例如可例舉聚乙烯醇及乙烯-乙烯醇共聚物。聚乙烯醇可藉由使聚乙酸乙烯酯皂化而獲得。乙烯-乙烯醇共聚物可藉由使乙烯-乙酸乙烯酯共聚物皂化而獲得。PVA系樹脂之皂化度通常為85莫耳%～100莫耳%，較佳為95.0莫耳%～99.95莫耳%，再佳的是99.0莫耳%～99.93莫耳%。皂化度可依據JIS K 6726-1994而求出。藉由使用此種皂化度之PVA系樹脂，能夠獲得耐久性優異之未脫色原膜。於皂化度過高之情形時，有凝膠化之虞。Any appropriate resin can be used as the above-mentioned PVA-based resin. For example, polyvinyl alcohol and ethylene-vinyl alcohol copolymers may be mentioned. Polyvinyl alcohol can be obtained by saponifying polyvinyl acetate. The ethylene-vinyl alcohol copolymer can be obtained by saponifying an ethylene-vinyl acetate copolymer. The degree of saponification of the PVA-based resin is usually 85-100 mol%, preferably 95.0-99.95 mol%, and most preferably 99.0-99.93 mol%. The degree of saponification can be determined in accordance with JIS K 6726-1994. By using a PVA-based resin with such a degree of saponification, an unbleached original film excellent in durability can be obtained. When the saponification is too high, there is a risk of gelation.
PVA系樹脂之平均聚合度可根據目的而適當地進行選擇。平均聚合度通常為1000～10000，較佳為1200～4500，再佳的是1500～4300。再者，平均聚合度可依據JIS K 6726-1994而求出。The average degree of polymerization of the PVA-based resin can be appropriately selected according to the purpose. The average degree of polymerization is usually 1000-10000, preferably 1200-4500, more preferably 1500-4300. In addition, the average degree of polymerization can be calculated|required based on JISK6726-1994.
作為上述鹵化物，可採用任意適當之鹵化物。例如可例舉碘化物及氯化鈉。作為碘化物，例如可例舉：碘化鉀、碘化鈉、及碘化鋰。其中，較佳為碘化鉀。Any appropriate halide can be used as the above-mentioned halide. For example, iodide and sodium chloride are mentioned. As an iodide, potassium iodide, sodium iodide, and lithium iodide are mentioned, for example. Among them, potassium iodide is preferred.
塗佈液中之鹵化物之量較佳為相對於PVA系樹脂100重量份為5重量份～20重量份，更佳為相對於PVA系樹脂100重量份為10重量份～15重量份。若相對於PVA系樹脂100重量份，鹵化物之量超過20重量份，則存在鹵化物滲出，而導致最終所獲得之未脫色原膜發生白濁之情形。The amount of the halide in the coating liquid is preferably 5 to 20 parts by weight relative to 100 parts by weight of the PVA-based resin, more preferably 10 to 15 parts by weight relative to 100 parts by weight of the PVA-based resin. When the amount of the halide exceeds 20 parts by weight relative to 100 parts by weight of the PVA-based resin, the halide may bleed out, and the unbleached original film finally obtained may become cloudy.
一般而言，藉由使PVA系樹脂層延伸，PVA系樹脂層中之聚乙烯醇分子之配向性提高，但若將延伸後之PVA系樹脂層浸漬於含水液體中，則存在聚乙烯醇分子之配向紊亂，配向性降低之情形。尤其於使熱塑性樹脂基材與PVA系樹脂層之積層體於硼酸水中延伸之情形時，為了使熱塑性樹脂基材之延伸穩定而以相對較高之溫度使上述積層體於硼酸水中延伸時，上述配向度降低之傾向較為顯著。例如一般於60℃下使PVA膜單質於硼酸水中延伸，相對於此，A-PET(熱塑性樹脂基材)與PVA系樹脂層之積層體之延伸係於70℃左右之溫度這種高溫下進行，於此情形時，延伸初期之PVA之配向性可能在藉由水中延伸而提高之前之階段中降低。相對於此，藉由製作包含鹵化物之PVA系樹脂層與熱塑性樹脂基材之積層體，在使積層體於硼酸水中延伸之前在空氣中進行高溫延伸(輔助延伸)，能夠促進輔助延伸後之積層體之PVA系樹脂層中之PVA系樹脂之結晶化。其結果為，於將PVA系樹脂層浸漬於液體中之情形時，與PVA系樹脂層不含鹵化物之情形相比，能夠抑制聚乙烯醇分子之配向之紊亂、及配向性之降低。藉此，經過染色處理及水中延伸處理等將積層體浸漬於液體中而進行之處理步驟所獲得之未脫色原膜之光學特性得以提高。In general, by stretching the PVA-based resin layer, the alignment of the polyvinyl alcohol molecules in the PVA-based resin layer is improved, but when the stretched PVA-based resin layer is immersed in an aqueous liquid, the presence of polyvinyl alcohol molecules The alignment disorder and the reduction of alignment. Especially in the case of stretching the laminate of the thermoplastic resin substrate and the PVA-based resin layer in boric acid water, when the laminate is stretched in boric acid water at a relatively high temperature in order to stabilize the stretching of the thermoplastic resin substrate, the above-mentioned The tendency to reduce the degree of alignment is more significant. For example, the simple substance of PVA film is stretched in boric acid water at 60°C. In contrast, the stretching of the laminate of A-PET (thermoplastic resin substrate) and PVA-based resin layer is carried out at a temperature of about 70°C. In this case, the alignment of PVA at the initial stage of stretching may decrease in the stage before it is improved by stretching in water. On the other hand, by fabricating a laminate of a PVA-based resin layer containing a halide and a thermoplastic resin substrate, and stretching the laminate at a high temperature in air (assisted stretching) before stretching the laminate in boric acid water, the post-assisted stretching can be facilitated. Crystallization of the PVA-based resin in the PVA-based resin layer of the laminate. As a result, when the PVA-based resin layer is immersed in a liquid, the disorder of the alignment of the polyvinyl alcohol molecules and the decrease in orientation can be suppressed compared to the case where the PVA-based resin layer does not contain a halide. Thereby, the optical characteristics of the unbleached original film obtained through the processing step of immersing the laminate in liquid, such as dyeing treatment and underwater stretching treatment, can be improved.
B-1-1-2.空中輔助延伸處理 尤其是，為了獲得較高之光學特性，選擇乾式延伸(輔助延伸)與硼酸水中延伸組合而成之2階段延伸方法。藉由如2階段延伸般導入輔助延伸，能夠在抑制熱塑性樹脂基材之結晶化的同時進行延伸，能夠解決後續硼酸水中延伸中因熱塑性樹脂基材之過度結晶化而導致延伸性降低之問題，使積層體以更高倍率延伸。進而，於在熱塑性樹脂基材上塗佈PVA系樹脂之情形時，為了抑制熱塑性樹脂基材之玻璃轉移溫度之影響，需要相較於通常在金屬轉筒上塗佈PVA系樹脂之情形降低塗佈溫度，結果可能引起如下問題：PVA系樹脂之結晶化相對降低，而無法獲得充分之光學特性。相對於此，藉由導入輔助延伸，即便於在熱塑性樹脂基材上塗佈PVA系樹脂之情形時，亦能夠提高PVA系樹脂之結晶性，能夠達成較高之光學特性。又，同時，藉由事先提高PVA系樹脂之配向性，在後續染色處理及延伸處理中浸漬於水中時，能夠防止PVA系樹脂之配向性降低及溶解等問題，能夠達成較高之光學特性。 B-1-1-2. Aerial Assisted Extended Processing In particular, in order to obtain higher optical properties, a two-stage stretching method combining dry stretching (assisted stretching) and boric acid underwater stretching is selected. By introducing auxiliary stretching like two-stage stretching, stretching can be performed while suppressing the crystallization of the thermoplastic resin base material, which can solve the problem of lower elongation due to excessive crystallization of the thermoplastic resin base material in subsequent boric acid underwater stretching, Extend the laminate at a higher magnification. Furthermore, in the case of coating a PVA-based resin on a thermoplastic resin base material, in order to suppress the influence of the glass transition temperature of the thermoplastic resin base material, it is necessary to reduce the coating temperature compared to the case where the PVA-based resin is usually coated on a metal drum. As a result, the following problems may arise: the crystallization of the PVA-based resin is relatively reduced, and sufficient optical properties cannot be obtained. On the other hand, by introducing auxiliary stretching, even when a PVA-based resin is coated on a thermoplastic resin substrate, the crystallinity of the PVA-based resin can be improved, and high optical characteristics can be achieved. At the same time, by improving the alignment of the PVA-based resin in advance, when it is immersed in water during the subsequent dyeing and stretching treatments, problems such as reduction of alignment and dissolution of the PVA-based resin can be prevented, and higher optical properties can be achieved.
空中輔助延伸之延伸方法可為固定端延伸(例如，使用拉幅延伸機進行延伸之方法)，亦可為自由端延伸(例如，使積層體通過周速不同之輥間進行單軸延伸之方法)，但為了獲得較高之光學特性，可積極地採用自由端延伸。於一實施方式中，空中延伸處理包括加熱輥延伸步驟，該步驟係將上述積層體沿其長度方向搬送，同時根據加熱輥間之周速差進行延伸。代表性而言，空中延伸處理包括區域延伸步驟及加熱輥延伸步驟。再者，區域延伸步驟與加熱輥延伸步驟之順序並無限定，可先進行區域延伸步驟，亦可先進行加熱輥延伸步驟。亦可省略區域延伸步驟。於一實施方式中，依序進行區域延伸步驟及加熱輥延伸步驟。又，於另一實施方式中，藉由在拉幅延伸機中抓持積層體端部，將拉幅機間之距離在行進方向上擴大而進行延伸(拉幅機間之距離之擴大為延伸倍率)。此時，寬度方向(相對於行進方向垂直之方向)上之拉幅機之距離被設定為任意地接近。可較佳地設定為相對於行進方向之延伸倍率，藉由自由端延伸使其接近。於自由端延伸之情形時，根據寬度方向之收縮率＝(1/延伸倍率) 1/2來計算。 The stretching method of aerial auxiliary stretching can be fixed end stretching (for example, the method of stretching using a tenter stretching machine), or free end stretching (for example, the method of uniaxially stretching the laminated body through rollers with different peripheral speeds) ), but in order to obtain higher optical properties, free end extensions can be actively used. In one embodiment, the in-air stretching process includes a heating roll stretching step of extending the laminate according to the difference in circumferential speed between the heating rolls while conveying the laminate in its longitudinal direction. Typically, the in-air stretching process includes a zone stretching step and a heating roll stretching step. Furthermore, the sequence of the zone stretching step and the heating roll stretching step is not limited, the zone stretching step can be performed first, and the heating roll stretching step can also be performed first. The region extension step can also be omitted. In one embodiment, the zone stretching step and the heating roll stretching step are performed sequentially. Also, in another embodiment, stretching is carried out by enlarging the distance between tenters in the direction of travel by gripping the end of the laminate in a tenter stretching machine (the distance between tenters is extended magnification). At this time, the distance between the tenter frames in the width direction (direction perpendicular to the traveling direction) was set to be arbitrarily close. It can be preferably set as an extension magnification relative to the direction of travel, and it can be approached by extending the free end. When the free end is stretched, it is calculated based on the shrinkage ratio in the width direction = (1/stretching ratio) 1/2 .
空中輔助延伸可以一階段進行，亦可以多階段進行。於以多階段進行之情形時，延伸倍率係各階段之延伸倍率之積。空中輔助延伸中之延伸方向較佳為與水中延伸之延伸方向大致相同。Aerial assisted extension can be carried out in one stage or in multiple stages. In the case of carrying out in multiple stages, the elongation ratio is the product of the elongation ratios of each stage. The extending direction in the aerial auxiliary extending is preferably substantially the same as the extending direction in the underwater extending.
空中輔助延伸中之延伸倍率較佳為2.0倍～3.5倍。將空中輔助延伸與水中延伸組合時之最大延伸倍率相對於積層體之原本長度，較佳為5.0倍以上，更佳為5.5倍以上，再佳的是6.0倍以上。於本說明書中，所謂「最大延伸倍率」，意指積層體即將斷裂之前之延伸倍率，其係另行確認積層體斷裂時之延伸倍率，而較該值低0.2之值。The extension magnification in the air-assisted extension is preferably 2.0 times to 3.5 times. The maximum elongation magnification when aerial auxiliary elongation and underwater elongation are combined is preferably at least 5.0 times, more preferably at least 5.5 times, and most preferably at least 6.0 times the original length of the laminate. In this specification, the "maximum elongation ratio" means the elongation ratio immediately before the laminate is broken, which is a value 0.2 lower than the elongation ratio when the laminate is fractured, which is separately confirmed.
空中輔助延伸之延伸溫度可根據熱塑性樹脂基材之形成材料、延伸方式等而設定為任意適當之值。延伸溫度較佳為熱塑性樹脂基材之玻璃轉移溫度(Tg)以上，再佳的是熱塑性樹脂基材之玻璃轉移溫度(Tg)＋10℃以上，尤佳為Tg＋15℃以上。另一方面，延伸溫度之上限較佳為170℃。藉由在此種溫度下進行延伸，能夠抑制PVA系樹脂之結晶化快速進展，而抑制該結晶化所導致之異常(例如，妨礙利用延伸進行之PVA系樹脂層之配向)。空中輔助延伸後之PVA系樹脂之結晶化指數較佳為1.3～1.8，更佳為1.4～1.7。PVA系樹脂之結晶化指數可使用傅立葉變換紅外分光光度計，藉由ATR(Attenuated Total Reflectance，減弱全反射)法進行測定。具體而言，將偏光作為測定光而實施測定，使用所獲得之光譜之1141 cm -1及1440 cm -1之強度，根據下述式算出結晶化指數。 結晶化指數＝(I C/I R) 其中， I C：入射測定光進行測定時之1141 cm -1之強度 I R：入射測定光進行測定時之1440 cm -1之強度。 The stretching temperature of the in-air stretching can be set to any appropriate value according to the forming material of the thermoplastic resin substrate, the stretching method, and the like. The stretching temperature is preferably above the glass transition temperature (Tg) of the thermoplastic resin substrate, more preferably above the glass transition temperature (Tg) of the thermoplastic resin substrate + 10°C, especially preferably above Tg + 15°C. On the other hand, the upper limit of the stretching temperature is preferably 170°C. By performing stretching at such a temperature, rapid progress of crystallization of the PVA-based resin can be suppressed, and abnormalities caused by the crystallization (for example, inhibition of alignment of the PVA-based resin layer by stretching) can be suppressed. The crystallization index of the PVA-based resin after air-assisted stretching is preferably 1.3-1.8, more preferably 1.4-1.7. The crystallization index of the PVA-based resin can be measured by the ATR (Attenuated Total Reflectance) method using a Fourier transform infrared spectrophotometer. Specifically, the measurement was performed using polarized light as the measurement light, and the crystallization index was calculated from the following formula using the intensities of 1141 cm −1 and 1440 cm −1 of the obtained spectrum. Crystallization index=(I C /I R ) where, I C : the intensity at 1141 cm -1 when the measurement light is incident on it for measurement. I R : the intensity at 1440 cm -1 when the measurement light is incident on it for measurement.
B-1-1-3.不溶化處理 視需要在空中輔助延伸處理之後且水中延伸處理及染色處理之前，實施不溶化處理。代表性而言，上述不溶化處理係藉由將PVA系樹脂層浸漬於硼酸水溶液中而進行。藉由實施不溶化處理，能夠對PVA系樹脂層賦予耐水性，而防止浸漬於水中時之PVA之配向性降低。關於該硼酸水溶液之濃度，相對於水100重量份，較佳為1重量份～4重量份。不溶化浴(硼酸水溶液)之液溫較佳為20℃～50℃。 B-1-1-3. Insolubilization treatment An insolubilization treatment is performed after the air-assisted stretching treatment and before the underwater stretching treatment and the dyeing treatment as necessary. Typically, the above insolubilization treatment is performed by immersing the PVA-based resin layer in a boric acid aqueous solution. By performing insolubilization treatment, water resistance can be imparted to the PVA-based resin layer, and a reduction in the alignment of PVA at the time of immersion in water can be prevented. The concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water. The liquid temperature of the insolubilization bath (boric acid aqueous solution) is preferably from 20°C to 50°C.
B-1-1-4.染色處理 代表性而言，上述染色處理係藉由用碘將PVA系樹脂層染色而進行。具體而言，係藉由使PVA系樹脂層吸附碘而進行。作為該吸附方法，例如可例舉：使PVA系樹脂層(積層體)浸漬於含碘染色液中之方法、將該染色液塗佈於PVA系樹脂層之方法、將該染色液噴霧至PVA系樹脂層之方法等。較佳為將積層體浸漬於染色液(染色浴)中之方法。其原因在於，這樣能夠良好地吸附碘。 B-1-1-4. Dyeing treatment Typically, the above-mentioned dyeing treatment is performed by dyeing the PVA-based resin layer with iodine. Specifically, it is performed by allowing the PVA-based resin layer to adsorb iodine. As the adsorption method, for example, a method of immersing the PVA-based resin layer (laminate) in an iodine-containing dyeing solution, a method of applying the dyed solution to the PVA-based resin layer, spraying the dyed solution onto PVA, etc. The method of the resin layer, etc. A method of immersing the laminate in a dye solution (dye bath) is preferred. The reason for this is that iodine can be favorably adsorbed in this way.
上述染色液較佳為碘水溶液。碘之調配量相對於水100重量份，較佳為0.05重量份～0.5重量份。為了提高碘於水中之溶解度，較佳為於碘水溶液中調配碘化物。作為碘化物，例如可例舉：碘化鉀、碘化鋰、碘化鈉、碘化鋅、碘化鋁、碘化鉛、碘化銅、碘化鋇、碘化鈣、碘化錫、碘化鈦等。其中，較佳為碘化鉀。碘化物之調配量相對於水100重量份，較佳為0.1重量份～10重量份，更佳為0.3重量份～5重量份。為了抑制PVA系樹脂之溶解，染色液之染色時之液溫較佳為20℃～50℃。於將PVA系樹脂層浸漬於染色液中之情形時，為了確保PVA系樹脂層之透過率，浸漬時間較佳為5秒～5分鐘，更佳為30秒～90秒。The above-mentioned staining liquid is preferably iodine aqueous solution. The compounding quantity of iodine is preferably 0.05 weight part - 0.5 weight part with respect to 100 weight part of water. In order to increase the solubility of iodine in water, it is preferable to prepare iodide in aqueous iodine solution. Examples of iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, titanium iodide Wait. Among them, potassium iodide is preferred. The compounding quantity of an iodide is preferably 0.1-10 weight part with respect to 100 weight part of water, More preferably, it is 0.3-5 weight part. In order to suppress the dissolution of the PVA-based resin, the temperature of the dyeing liquid during dyeing is preferably 20°C to 50°C. When immersing the PVA-based resin layer in the dyeing solution, in order to ensure the transmittance of the PVA-based resin layer, the immersion time is preferably 5 seconds to 5 minutes, more preferably 30 seconds to 90 seconds.
染色條件(濃度、液溫、浸漬時間)可以最終所獲得之未脫色原膜之單體透過率成為期望值之方式進行設定。作為此種染色條件，較佳為使用碘水溶液作為染色液，將碘水溶液中之碘及碘化鉀之含量之比設為1：5～1：20。碘水溶液中之碘及碘化鉀之含量之比較佳為1：5～1：10。藉此，能夠獲得具有如下所述之光學特性之未脫色原膜。Dyeing conditions (concentration, liquid temperature, and immersion time) can be set so that the monomer transmittance of the finally obtained undecolorized original film becomes a desired value. As such dyeing conditions, it is preferable to use an iodine aqueous solution as a dyeing liquid, and to set the ratio of the content of the iodine and potassium iodide in an iodine aqueous solution to 1:5-1:20. The content ratio of iodine and potassium iodide in the iodine aqueous solution is preferably 1:5-1:10. Thereby, the unbleached original film which has the optical characteristic mentioned below can be obtained.
在將積層體浸漬於含有硼酸之處理浴中之處理(代表性而言，為不溶化處理)之後連續地進行染色處理之情形時，存在該處理浴中所包含之硼酸混入染色浴中而使染色浴之硼酸濃度發生經時性變化，結果導致染色性變得不穩定之情況。為了抑制如上所述之染色性之不穩定化，染色浴之硼酸濃度之上限被調整為相對於水100重量份，較佳為4重量份，更佳為2重量份。另一方面，染色浴之硼酸濃度之下限相對於水100重量份，較佳為0.1重量份，更佳為0.2重量份，再佳的是0.5重量份。於一實施方式中，使用預先調配有硼酸之染色浴進行染色處理。藉此，能夠降低上述處理浴之硼酸混入染色浴中時之硼酸濃度之變化比率。預先調配於染色浴中之硼酸之調配量(即，並非來自上述處理浴之硼酸之含量)相對於水100重量份，較佳為0.1重量份～2重量份，更佳為0.5重量份～1.5重量份。In the case where the dyeing treatment is carried out continuously after the treatment of immersing the laminate in a treatment bath containing boric acid (typically, insolubilization treatment), there is a case where the boric acid contained in the treatment bath is mixed into the dyeing bath to cause dyeing. The concentration of boric acid in the bath changes over time, resulting in unstable dyeing properties. In order to suppress the destabilization of dyeability as described above, the upper limit of the concentration of boric acid in the dyeing bath is adjusted to 100 parts by weight of water, preferably 4 parts by weight, more preferably 2 parts by weight. On the other hand, the lower limit of the concentration of boric acid in the dyeing bath is preferably 0.1 parts by weight, more preferably 0.2 parts by weight, and still more preferably 0.5 parts by weight with respect to 100 parts by weight of water. In one embodiment, the dyeing treatment is performed using a dyeing bath prepared in advance with boric acid. Thereby, the change rate of the boric-acid density|concentration when the boric acid of the said processing bath mixes in a dyeing bath can be reduced. The amount of boric acid pre-prepared in the dyeing bath (that is, the content of boric acid not derived from the above-mentioned treatment bath) is preferably 0.1 to 2 parts by weight, more preferably 0.5 to 1.5 parts by weight relative to 100 parts by weight of water. parts by weight.
B-1-1-5.交聯處理 視需要在染色處理之後且水中延伸處理之前，實施交聯處理。代表性而言，上述交聯處理係藉由將PVA系樹脂層浸漬於硼酸水溶液中而進行。藉由實施交聯處理，能夠對PVA系樹脂層賦予耐水性，而防止後續水中延伸中浸漬於高溫水中時之PVA之配向性降低。該硼酸水溶液之濃度相對於水100重量份，較佳為1重量份～5重量份。又，於上述染色處理後進行交聯處理之情形時，較佳為進而調配碘化物。藉由調配碘化物，能夠抑制被PVA系樹脂層吸附之碘之溶出。碘化物之調配量相對於水100重量份，較佳為1重量份～5重量份。碘化物之具體例如上所述。交聯浴(硼酸水溶液)之液溫較佳為20℃～50℃。 B-1-1-5. Cross-linking treatment After the dyeing treatment and before the underwater stretching treatment, a crosslinking treatment is performed as necessary. Typically, the above-mentioned crosslinking treatment is performed by immersing the PVA-based resin layer in a boric acid aqueous solution. By performing cross-linking treatment, water resistance can be imparted to the PVA-based resin layer, and the alignment of PVA when immersed in high-temperature water during subsequent underwater stretching can be prevented from being lowered. The concentration of the boric acid aqueous solution is preferably 1 to 5 parts by weight relative to 100 parts by weight of water. Moreover, when carrying out a crosslinking process after the said dyeing process, it is preferable to further mix|blend an iodide. By preparing iodide, it is possible to suppress the elution of iodine adsorbed by the PVA-based resin layer. The compounding quantity of an iodide is preferably 1-5 weight part with respect to 100 weight part of water. Specific examples of iodide are as described above. The liquid temperature of the crosslinking bath (boric acid aqueous solution) is preferably 20°C to 50°C.
B-1-1-6.水中延伸處理 水中延伸處理係將積層體浸漬於延伸浴中而進行。藉由水中延伸處理，能夠在低於上述熱塑性樹脂基材或PVA系樹脂層之玻璃轉移溫度(代表性而言，80℃左右)之溫度下進行延伸，能夠在抑制PVA系樹脂層之結晶化之同時，使其以高倍率延伸。結果能夠製造具有優異之光學特性之未脫色原膜。 B-1-1-6. Extended treatment in water The underwater stretching treatment is carried out by immersing the laminate in a stretching bath. By stretching in water, stretching can be performed at a temperature lower than the glass transition temperature (typically, about 80°C) of the above-mentioned thermoplastic resin substrate or PVA-based resin layer, and can suppress the crystallization of the PVA-based resin layer. At the same time, make it stretch at high magnification. As a result, an unbleached original film having excellent optical properties can be produced.
積層體之延伸方法可採用任意適當之方法。具體而言，可為固定端延伸，亦可為自由端延伸(例如，使積層體通過周速不同之輥間進行單軸延伸之方法)。較佳為選擇自由端延伸。積層體之延伸可以一階段進行，亦可以多階段進行。於以多階段進行之情形時，下述積層體之延伸倍率(最大延伸倍率)係各階段之延伸倍率之積。Any appropriate method can be used for the stretching method of the laminate. Specifically, it may be fixed-end stretching or free-end stretching (for example, a method of uniaxially stretching a laminate through rolls having different circumferential speeds). Preferably a free end extension is selected. The extension of the laminate may be performed in one stage or in multiple stages. In the case of carrying out in multiple stages, the elongation ratio (maximum elongation ratio) of the following laminate is the product of the elongation ratios of each stage.
水中延伸較佳為將積層體浸漬於硼酸水溶液中而進行(硼酸水中延伸)。藉由使用硼酸水溶液作為延伸浴，能夠對PVA系樹脂層賦予耐受延伸時施加之張力之剛性、及不溶於水之耐水性。具體而言，硼酸可在水溶液中生成四羥基硼酸根陰離子並藉由氫鍵與PVA系樹脂交聯。結果能夠對PVA系樹脂層賦予剛性及耐水性，而良好地進行延伸，能夠製造具有優異之光學特性之未脫色原膜。The underwater stretching is preferably carried out by immersing the laminate in an aqueous solution of boric acid (boric acid underwater stretching). By using the boric acid aqueous solution as the stretching bath, rigidity to withstand the tension applied at the time of stretching and water resistance to be insoluble in water can be imparted to the PVA-based resin layer. Specifically, boric acid can generate tetrahydroxyborate anion in aqueous solution and cross-link with PVA-based resin through hydrogen bonding. As a result, rigidity and water resistance can be imparted to the PVA-based resin layer, and stretching can be performed favorably, so that an unbleached original film having excellent optical properties can be produced.
上述硼酸水溶液較佳為藉由使硼酸及/或硼酸鹽溶解於作為溶劑之水中而獲得。關於硼酸濃度，相對於水100重量份，較佳為1重量份～10重量份，更佳為2.5重量份～6重量份，尤佳為3重量份～5重量份。藉由使硼酸濃度為1重量份以上，能夠有效地抑制PVA系樹脂層之溶解，能夠製造更高特性之未脫色原膜。再者，除了硼酸或硼酸鹽以外，亦可使用使硼砂等硼化合物、乙二醛、戊二醛等溶解於溶劑中所獲得之水溶液。The above boric acid aqueous solution is preferably obtained by dissolving boric acid and/or borate in water as a solvent. The concentration of boric acid is preferably 1 to 10 parts by weight, more preferably 2.5 to 6 parts by weight, and most preferably 3 to 5 parts by weight with respect to 100 parts by weight of water. By making the concentration of boric acid 1 part by weight or more, the dissolution of the PVA-based resin layer can be effectively suppressed, and an unbleached original film with higher characteristics can be produced. In addition, an aqueous solution obtained by dissolving boron compounds such as borax, glyoxal, glutaraldehyde, etc. in a solvent other than boric acid or borate can also be used.
較佳為於上述延伸浴(硼酸水溶液)中調配碘化物。藉由調配碘化物，能夠抑制被PVA系樹脂層吸附之碘之溶出。碘化物之具體例如上所述。碘化物之濃度相對於水100重量份，較佳為0.05重量份～15重量份，更佳為0.5重量份～8重量份。Preferably, iodide is prepared in the above-mentioned stretching bath (boric acid aqueous solution). By preparing iodide, it is possible to suppress the elution of iodine adsorbed by the PVA-based resin layer. Specific examples of iodide are as described above. The concentration of iodide is preferably 0.05 to 15 parts by weight, more preferably 0.5 to 8 parts by weight, relative to 100 parts by weight of water.
延伸溫度(延伸浴之液溫)較佳為40℃～85℃，更佳為60℃～75℃。若為此種溫度，則能夠在抑制PVA系樹脂層之溶解之同時使其以高倍率延伸。具體而言，如上所述，基於與PVA系樹脂層形成之關係考慮，熱塑性樹脂基材之玻璃轉移溫度(Tg)較佳為60℃以上。於此情形時，若延伸溫度低於40℃，則存在即便考慮到水對熱塑性樹脂基材之塑化，亦無法良好地進行延伸之虞。另一方面，延伸浴之溫度越高，PVA系樹脂層之溶解性越高，存在無法獲得優異之光學特性之虞。積層體於延伸浴中之浸漬時間較佳為15秒～5分鐘。The stretching temperature (liquid temperature of the stretching bath) is preferably from 40°C to 85°C, more preferably from 60°C to 75°C. If it is such a temperature, it can be stretched at a high ratio while suppressing dissolution of the PVA-type resin layer. Specifically, as described above, the glass transition temperature (Tg) of the thermoplastic resin substrate is preferably 60° C. or higher in consideration of the relationship with the formation of the PVA-based resin layer. In this case, if the stretching temperature is lower than 40° C., stretching may not be performed satisfactorily even in consideration of plasticization of the thermoplastic resin base material by water. On the other hand, the higher the temperature of the stretching bath, the higher the solubility of the PVA-based resin layer, and there is a possibility that excellent optical properties cannot be obtained. The immersion time of the laminate in the stretching bath is preferably 15 seconds to 5 minutes.
水中延伸之延伸倍率較佳為1.5倍以上，更佳為3.0倍以上。積層體之總延伸倍率相對於積層體之原本長度，較佳為5.0倍以上，再佳的是5.5倍以上。藉由達成此種較高之延伸倍率，能夠製造光學特性極其優異之未脫色原膜。此種較高之延伸倍率可藉由採用水中延伸方式(硼酸水中延伸)而達成。The elongation ratio of underwater elongation is preferably at least 1.5 times, more preferably at least 3.0 times. The total elongation ratio of the laminate is preferably 5.0 times or more, more preferably 5.5 times or more, relative to the original length of the laminate. By achieving such a high elongation ratio, it is possible to manufacture an unbleached original film with extremely excellent optical properties. Such a higher elongation ratio can be achieved by adopting an underwater elongation method (boric acid elongation).
B-1-1-7.乾燥收縮處理 上述乾燥收縮處理例如包括如下步驟：藉由將該長條狀熱塑性樹脂基材與PVA系樹脂膜之積層體一面沿長度方向搬送，一面進行加熱，而使其於寬度方向上收縮2%以上，並且使其乾燥直至該PVA系樹脂膜之水分率成為15重量%以下為止。就獲得穩定之外觀之觀點而言，較佳為使其乾燥直至水分率成為12重量%以下，更佳為10重量%以下，再佳的是1重量%～5重量%為止。 B-1-1-7. Drying shrinkage treatment The above-mentioned drying shrinkage treatment includes, for example, the step of shrinking the laminate of the elongated thermoplastic resin substrate and the PVA-based resin film by 2% or more in the width direction while conveying it in the longitudinal direction and heating it. And it is made to dry until the moisture content of this PVA-type resin film becomes 15 weight% or less. From the viewpoint of obtaining a stable appearance, it is preferably dried until the moisture content becomes 12% by weight or less, more preferably 10% by weight or less, and still more preferably 1% by weight to 5% by weight.
乾燥收縮處理可藉由區域加熱來進行，即，對整個區域進行加熱而進行，亦可藉由對搬送輥進行加熱(使用所謂加熱輥)而進行(加熱輥乾燥方式)。較佳為使用該兩種方式。藉由使用加熱輥進行乾燥，能夠有效率地抑制積層體之加熱捲縮，而製造外觀優異之未脫色原膜。具體而言，藉由使積層體以沿著加熱輥之狀態乾燥，能夠有效率地促進上述熱塑性樹脂基材之結晶化而增加結晶度，即便為相對較低之乾燥溫度，亦能夠良好地增加熱塑性樹脂基材之結晶度。其結果為，熱塑性樹脂基材增加了其剛性，成為可耐受乾燥引起之PVA系樹脂層之收縮之狀態，捲縮得到抑制。又，藉由使用加熱輥，能夠使積層體在維持平坦狀態的同時進行乾燥，因此，不僅能夠抑制捲縮，亦能夠抑制皺褶之產生。此時，藉由乾燥收縮處理使積層體於寬度方向上收縮，藉此能夠提高光學特性。其原因在於，這樣能夠有效地提高PVA及PVA/碘錯合物之配向性。由乾燥收縮處理所引起之積層體之寬度方向之收縮率較佳為1%～10%，更佳為2%～8%，尤佳為4%～6%。藉由使用加熱輥，能夠一面搬送積層體，一面使其連續地於寬度方向上收縮，能夠實現較高之生產性。Drying shrinkage treatment may be performed by heating the entire area, that is, by heating the entire area, or by heating the conveying roll (using a so-called heated roll) (heated roll drying method). It is preferable to use both methods. By drying with a heating roller, heat shrinkage of the laminate can be effectively suppressed, and an unbleached original film with excellent appearance can be produced. Specifically, by drying the laminate in a state along the heating roll, the crystallization of the above-mentioned thermoplastic resin substrate can be effectively promoted to increase the crystallinity, and even at a relatively low drying temperature, it can be favorably increased. Crystallinity of thermoplastic resin substrate. As a result, the rigidity of the thermoplastic resin substrate is increased, and the shrinkage of the PVA-based resin layer due to drying is resistant to shrinkage, and curling is suppressed. In addition, since the laminate can be dried while maintaining a flat state by using the heating roll, not only curling but also generation of wrinkles can be suppressed. At this time, the optical characteristics can be improved by shrinking the laminate in the width direction by drying shrinkage treatment. The reason is that this can effectively improve the alignment of PVA and PVA/iodine complex. The shrinkage in the width direction of the laminate caused by drying shrinkage is preferably 1% to 10%, more preferably 2% to 8%, and most preferably 4% to 6%. By using the heating roller, the laminate can be continuously shrunk in the width direction while being conveyed, and high productivity can be realized.
圖1係表示乾燥收縮處理之一例之概略圖。於乾燥收縮處理中，一面利用被加熱至特定溫度之搬送輥R1～R6、及導輥G1～G4來搬送積層體200，一面使其乾燥。於圖示例中，以對PVA系樹脂層之面與熱塑性樹脂基材之面交替地連續進行加熱之方式配置搬送輥R1～R6，但亦可以例如僅對積層體200之一面(例如熱塑性樹脂基材面)連續地進行加熱之方式配置搬送輥R1～R6。Fig. 1 is a schematic diagram showing an example of drying shrinkage treatment. In the drying shrinkage treatment, the laminate 200 is dried while being conveyed by the conveyance rollers R1 to R6 heated to a specific temperature and the guide rollers G1 to G4. In the illustrated example, the transfer rollers R1 to R6 are disposed so as to alternately and continuously heat the surface of the PVA-based resin layer and the surface of the thermoplastic resin substrate, but it is also possible, for example, to face only one surface of the laminate 200 (for example, a thermoplastic resin substrate). The conveyance rollers R1-R6 are arranged so that the substrate surface) is heated continuously.
可藉由調整搬送輥之加熱溫度(加熱輥之溫度)、加熱輥之數量、與加熱輥之接觸時間等，而控制乾燥條件。加熱輥之溫度較佳為60℃～120℃，再佳的是65℃～100℃，尤佳為70℃～80℃。能夠良好地增加熱塑性樹脂之結晶度，良好地抑制捲縮，並且能夠製造耐久性極其優異之光學積層體。再者，加熱輥之溫度可利用接觸式溫度計進行測定。於圖示例中，設置有6個搬送輥，但搬送輥只要為複數個即可，並無特別限制。搬送輥通常設置2個～40個，較佳為設置4個～30個。積層體與加熱輥之接觸時間(總接觸時間)較佳為1秒～300秒，更佳為1～20秒，再佳的是1～10秒。The drying conditions can be controlled by adjusting the heating temperature of the conveying roller (temperature of the heating roller), the number of the heating roller, and the contact time with the heating roller, etc. The temperature of the heating roller is preferably from 60°C to 120°C, more preferably from 65°C to 100°C, and most preferably from 70°C to 80°C. It can well increase the crystallinity of thermoplastic resin, well suppress curling, and can manufacture an optical laminate with extremely excellent durability. Furthermore, the temperature of the heating roller can be measured with a contact thermometer. In the illustrated example, six conveying rollers are provided, but there is no particular limitation as long as there are plural conveying rollers. Usually, 2 to 40 conveying rollers are installed, and it is preferable to install 4 to 30 conveyance rollers. The contact time (total contact time) between the laminate and the heating roller is preferably from 1 second to 300 seconds, more preferably from 1 to 20 seconds, and still more preferably from 1 to 10 seconds.
加熱輥可設置於加熱爐(例如，烘箱)內，亦可設置於通常之生產線(室溫環境下)。較佳為設置於具備送風機構之加熱爐內。藉由併用加熱輥乾燥與熱風乾燥，能夠抑制加熱輥間之急遽溫度變化，能夠容易地控制寬度方向上之收縮。熱風乾燥之溫度較佳為20℃～100℃。又，熱風乾燥時間較佳為1秒～300秒。熱風之風速較佳為10 m/s～30 m/s左右。再者，該風速係加熱爐內之風速，可藉由小型葉輪式數位風速計進行測定。The heating roller can be installed in a heating furnace (for example, an oven), or it can be installed in a normal production line (at room temperature). It is preferably installed in a heating furnace equipped with an air supply mechanism. By using heating roller drying and hot air drying in combination, rapid temperature changes between heating rollers can be suppressed, and shrinkage in the width direction can be easily controlled. The temperature of hot air drying is preferably 20°C to 100°C. Also, the hot air drying time is preferably from 1 second to 300 seconds. The wind speed of the hot air is preferably about 10 m/s to 30 m/s. Furthermore, the wind speed refers to the wind speed in the heating furnace, which can be measured by a small impeller-type digital anemometer.
B-1-1-8.其他處理 較佳為在水中延伸處理之後且乾燥收縮處理之前，實施洗淨處理。代表性而言，上述洗淨處理係藉由將PVA系樹脂層浸漬於碘化鉀水溶液中而進行。 B-1-1-8. Other processing It is preferable to perform the washing treatment after the underwater stretching treatment and before the drying shrinkage treatment. Typically, the above cleaning treatment is performed by immersing the PVA-based resin layer in an aqueous potassium iodide solution.
B-1-2.使用單層PVA系樹脂膜之未脫色原膜之製作 使用單層PVA系樹脂膜之未脫色原膜之製作可藉由如下步驟而進行：對具有自持性(即，無需由基材支持)之長條狀PVA系樹脂膜進行染色及延伸(代表性而言，在硼酸水溶液中使用輥延伸機之單軸延伸)，繼而，使其乾燥直至水分率成為15重量%以下，較佳為12重量%以下，更佳為10重量%以下，再佳的是1重量%～5重量%為止。上述染色例如可藉由將PVA系樹脂膜浸漬於碘水溶液中而進行。上述單軸延伸之延伸倍率較佳為3～7倍。延伸可於染色處理後進行，亦可在染色的同時進行。又，還可在延伸之後進行染色。視需要對PVA系樹脂膜實施膨潤處理、交聯處理、洗淨處理等。例如，藉由在染色之前將PVA系樹脂膜浸漬於水中進行水洗，不僅能夠將PVA系樹脂膜表面之污垢及抗黏連劑洗淨，而且能夠使PVA系樹脂膜膨潤而防止染色不均等。 B-1-2. Production of unbleached original film using single-layer PVA-based resin film The manufacture of the unbleached original film using a single-layer PVA-based resin film can be carried out by the following steps: dyeing and extending (representative For example, uniaxial stretching using a roll stretcher in a boric acid aqueous solution), and then drying until the moisture content becomes 15% by weight or less, preferably 12% by weight or less, more preferably 10% by weight or less, and more preferably It is up to 1% by weight to 5% by weight. Said dyeing can be performed, for example by immersing a PVA-type resin film in an iodine aqueous solution. The stretching ratio of the uniaxial stretching is preferably 3 to 7 times. The elongation can be carried out after the dyeing treatment or at the same time as the dyeing. Also, dyeing may be performed after elongation. Swelling treatment, crosslinking treatment, washing treatment, etc. are performed on the PVA-based resin film as necessary. For example, by immersing the PVA-based resin film in water for washing before dyeing, not only can the dirt and anti-blocking agent on the surface of the PVA-based resin film be cleaned, but also the PVA-based resin film can be swollen to prevent uneven dyeing.
B-2.水性溶劑 作為水性溶劑，可使用任意適當之溶劑，只要能夠使碘自未脫色原膜溶出即可。水性溶劑例如可為水或水與水溶性有機溶劑之混合物。作為水溶性有機溶劑，可較佳地例示：甲醇、乙醇、正丙醇、異丙醇等碳數為1個～4個之低級單醇及甘油、乙二醇等多元醇。 B-2. Aqueous solvent As the aqueous solvent, any appropriate solvent can be used as long as it can elute iodine from the undecolorized original film. The aqueous solvent can be, for example, water or a mixture of water and a water-soluble organic solvent. As the water-soluble organic solvent, preferably, lower monoalcohols having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, and isopropanol, and polyhydric alcohols such as glycerin and ethylene glycol can be exemplified.
B-3.接觸方法 作為與水性溶劑之接觸方法，並無特別限制，可採用浸漬、噴霧、塗佈等任意適當之方法。就使未脫色原膜表面之整個面與水性溶劑均勻地接觸之觀點而言，較佳為浸漬。 B-3. Contact method The contact method with the aqueous solvent is not particularly limited, and any appropriate method such as dipping, spraying, or coating can be employed. Immersion is preferred from the viewpoint of uniformly contacting the entire surface of the undecolorized original film with the aqueous solvent.
與水性溶劑之接觸時間及接觸時之水性溶劑之溫度可根據所期望之Ts 470、Ts 600、A 470、A 600等而適當地設定。藉由延長接觸時間或提高水性溶劑之溫度，透過率(尤其是Ts 470)趨於變大，又，正交吸光度(尤其是A 470)趨於變小。接觸時間例如可為10分鐘以下，較佳為60秒～9分鐘，更佳為60秒～4分鐘。水性溶劑之溫度可較佳為20℃～70℃，更佳為30℃～65℃，再佳的是40℃～60℃。 The contact time with the aqueous solvent and the temperature of the aqueous solvent during contact can be appropriately set according to desired Ts 470 , Ts 600 , A 470 , A 600 , etc. By prolonging the contact time or increasing the temperature of the aqueous solvent, the transmittance (especially Ts 470 ) tends to increase, and the orthogonal absorbance (especially A 470 ) tends to decrease. The contact time may be, for example, 10 minutes or less, preferably 60 seconds to 9 minutes, more preferably 60 seconds to 4 minutes. The temperature of the aqueous solvent may preferably be 20°C-70°C, more preferably 30°C-65°C, even more preferably 40°C-60°C.
未脫色原膜與水性溶劑之接觸可藉由僅使未脫色原膜之單面與水性溶劑接觸而進行，亦可藉由使兩面與水性溶劑接觸而進行。因此，可將使用[PVA系樹脂層/樹脂基材]之積層體所製作之[未脫色原膜/樹脂基材]之積層體或[未脫色原膜/保護層]之積層體用於與水性溶劑之接觸。或者，可將使用單層PVA系樹脂膜所製作之未脫色原膜直接用於與水性溶劑之接觸，或者以單側設置有保護層之積層體之狀態用於與水性溶劑之接觸。The contact of the non-decolorized raw film with the aqueous solvent may be performed by bringing only one side of the non-decolored raw film into contact with the aqueous solvent, or by bringing both sides into contact with the aqueous solvent. Therefore, the laminate of [unbleached original film/resin substrate] or the laminate of [unbleached original film/protective layer] produced by using the laminate of [PVA-based resin layer/resin substrate] can be used for use with Contact with aqueous solvents. Alternatively, an unbleached original film made of a single-layer PVA-based resin film can be directly used in contact with an aqueous solvent, or a laminate with a protective layer on one side can be used in contact with an aqueous solvent.
B-4.其他處理 亦可視需要將藉由與水性溶劑接觸所獲得之偏光膜供至乾燥處理。乾燥溫度例如可為20℃～100℃，較佳為30℃～80℃。代表性而言，乾燥後之偏光膜之水分率為15重量%以下，較佳為12重量%以下，更佳為10重量%以下，再佳的是1重量%～5重量%。 B-4. Other processing The polarizing film obtained by contacting with an aqueous solvent may also be subjected to drying treatment if necessary. The drying temperature may be, for example, 20°C to 100°C, preferably 30°C to 80°C. Typically, the moisture content of the polarizing film after drying is 15% by weight or less, preferably 12% by weight or less, more preferably 10% by weight or less, and more preferably 1% to 5% by weight.
C.偏光板 本發明之實施方式之偏光板包含偏光膜、及配置於該偏光膜之至少單側之保護層，可視需要進而包含相位差層。再者，於本說明書中，有時將包含相位差層之偏光板稱為附相位差層之偏光板。 C. Polarizer The polarizing plate according to the embodiment of the present invention includes a polarizing film, a protective layer arranged on at least one side of the polarizing film, and may further include a retardation layer if necessary. In addition, in this specification, a polarizing plate including a retardation layer may be referred to as a polarizing plate with a retardation layer.
偏光板之b*值例如為-3以下，較佳為-4以下，更佳為-20～-5。b*值處於該範圍內之偏光板由於短波長區域之光之透過率較高，故而呈現出帶藍色之色相。The b* value of the polarizing plate is, for example, -3 or less, preferably -4 or less, more preferably -20 to -5. Polarizing plates with a b* value within this range exhibit a bluish hue due to the high transmittance of light in the short-wavelength region.
C-1.偏光板之整體構成
圖2係本發明之一實施方式之偏光板之概略剖視圖。偏光板100包含：偏光膜10、配置於偏光膜10之一側之第1保護層12、及配置於偏光膜10之另一側之第2保護層14。
C-1. Overall composition of polarizing plate
Fig. 2 is a schematic cross-sectional view of a polarizing plate according to an embodiment of the present invention. The
圖3係本發明之另一實施方式之包含相位差層之偏光板之概略剖視圖。附相位差層之偏光板200a包含：偏光膜10、配置於偏光膜10之一側之第1保護層12、配置於偏光膜10之另一側之第2保護層14、及配置於第2保護層14之配置有偏光膜10之側之相反側的第1相位差層20。可根據目的而省略第1保護層12及第2保護層14中一者。例如，於相位差層20亦可作為偏光膜10之保護層發揮功能之情形時，亦可省略第2保護層14。3 is a schematic cross-sectional view of a polarizing plate including a retardation layer according to another embodiment of the present invention. The
圖4係本發明之又一實施方式之包含相位差層之偏光板之概略剖視圖。附相位差層之偏光板200b包含：偏光膜10、配置於偏光膜10之一側之第1保護層12、及配置於偏光膜10之另一側之第2保護層14，於第2保護層14之配置有偏光膜10之側之相反側，依序設置有第1相位差層20、第2相位差層30及導電層或附導電層之各向同性基材40。代表性而言，第2相位差層30表現出折射率特性為nz＞nx＝ny之關係。代表性而言，第2相位差層30以及導電層或附導電層之各向同性基材40係視需要設置之任意之層，可省略其中任一者或兩者。再者，於設置有導電層或附導電層之各向同性基材之情形時，附相位差層之偏光板可應用於圖像顯示元件(例如，有機EL元件)與偏光板之間組裝有觸控感測器之所謂內部觸控面板型輸入顯示裝置。4 is a schematic cross-sectional view of a polarizing plate including a retardation layer according to still another embodiment of the present invention. The
第1相位差層20之Re(550)例如為100 nm～190 nm。又，第1相位差層20之遲相軸與偏光膜10之吸收軸所成之角度例如為40°～50°。Re(550) of the
上述實施方式可適當進行組合，亦可對上述實施方式中之構成要素施加本領域中顯而易見之改變。例如，可將第2相位差層30之外側設置有附導電層之各向同性基材40的構成替換為光學等效構成(例如，第2相位差層與導電層之積層體)。The above-described embodiments may be appropriately combined, and changes that are obvious in the art may be added to the constituent elements of the above-described embodiments. For example, the structure in which the
本發明之實施方式之偏光板或附相位差層之偏光板可進而包含其他相位差層。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、配置位置等可根據目的而適當地進行設定。The polarizing plate or the polarizing plate with a retardation layer according to the embodiment of the present invention may further include another retardation layer. The optical characteristics (for example, refractive index characteristics, in-plane retardation, Nz coefficient, photoelastic coefficient), thickness, arrangement position, etc. of other retardation layers can be appropriately set according to the purpose.
本發明之偏光板可為片狀，亦可為長條狀。於本說明書中，所謂「長條狀」，意指相對於寬度，長度夠長之細長形狀，例如包括相對於寬度，長度為10倍以上，較佳為20倍以上之細長形狀。長條狀偏光板可捲繞成卷狀。於附相位差層之偏光板為長條狀之情形時，偏光板及相位差層亦為長條狀。於此情形時，偏光膜較佳為於長度方向上具有吸收軸。第1相位差層較佳為在與長度方向成40°～50°之角度之方向上具有遲相軸之斜向延伸膜。若偏光膜及第1相位差層為此種構成，則能夠利用卷對卷方式製作附相位差層之偏光板。The polarizing plate of the present invention may be in sheet form or strip form. In this specification, the term "elongated" refers to an elongated shape that is sufficiently long relative to the width, and includes, for example, an elongated shape whose length is 10 times or more, preferably 20 times or more, relative to the width. The long polarizing plate can be wound into a roll. When the polarizing plate with a retardation layer is elongated, the polarizing plate and the retardation layer are also elongated. In this case, the polarizing film preferably has an absorption axis in the longitudinal direction. The first retardation layer is preferably an obliquely stretched film having a retardation axis in a direction forming an angle of 40° to 50° with the longitudinal direction. If the polarizing film and the first retardation layer have such a configuration, a polarizing plate with a retardation layer can be produced by a roll-to-roll method.
就實用方面而言，於相位差層之與偏光板相反之側設置有黏著劑層(未圖示)，附相位差層之偏光板可貼附於圖像顯示元件。進而，較佳為在附相位差層之偏光板供使用之前，於黏著劑層之表面暫時黏貼剝離膜。藉由暫時黏貼剝離膜，能夠保護黏著劑層，並且形成捲筒。In terms of practicality, an adhesive layer (not shown) is provided on the opposite side of the phase difference layer to the polarizer, and the polarizer with the phase difference layer can be attached to the image display element. Furthermore, it is preferable to temporarily stick a peeling film to the surface of an adhesive layer before using the polarizing plate with a retardation layer. By temporarily sticking the release film, the adhesive layer can be protected, and it can be formed into a roll.
偏光板之總厚度較佳為150 μm以下，更佳為120 μm以下，再佳的是100 μm以下，進而更佳為90 μm以下，進而更佳為85 μm以下。總厚度之下限例如可為30 μm。The total thickness of the polarizing plate is preferably at most 150 μm, more preferably at most 120 μm, even more preferably at most 100 μm, still more preferably at most 90 μm, and even more preferably at most 85 μm. The lower limit of the total thickness may be, for example, 30 μm.
C-2.偏光膜 作為偏光膜，可使用A項中記載之偏光膜。 C-2. Polarizing film As the polarizing film, the polarizing film described in the item A can be used.
C-3.保護層 第1保護層及第2保護層係分別以可用作偏光膜之保護層之任意適當之膜的形式形成。作為該膜之主成分材料之具體例，可例舉：三乙醯纖維素(TAC)等纖維素系樹脂、及聚酯系、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、聚降𦯉烯系、聚烯烴系、(甲基)丙烯酸系、乙酸酯系等之透明樹脂等。又，亦可例舉：(甲基)丙烯酸系、胺基甲酸酯系、(甲基)丙烯酸胺基甲酸酯系、環氧系、矽酮系等之熱硬化型樹脂或紫外線硬化型樹脂等。除此以外，例如還可例舉矽氧烷系聚合物等玻璃質系聚合物。又，亦可使用日本專利特開2001-343529號公報(WO01/37007)中記載之聚合物膜。作為該膜之材料，例如可使用含有側鏈具有經取代或未經取代之醯亞胺基之熱塑性樹脂、以及側鏈具有經取代或未經取代之苯基及腈基之熱塑性樹脂的樹脂組合物，例如可例舉：具有包含異丁烯及N-甲基順丁烯二醯亞胺之交替共聚物、以及丙烯腈-苯乙烯共聚物的樹脂組合物。該聚合物膜例如可為上述樹脂組合物之擠出成形物。 C-3. Protective layer The first protective layer and the second protective layer are each formed as any appropriate film that can be used as a protective layer of a polarizing film. Specific examples of the main component material of the film include cellulose-based resins such as triacetyl cellulose (TAC), polyester-based, polyvinyl alcohol-based, polycarbonate-based, polyamide-based, polyamide-based resins, etc. Imide-based, polyether-based, poly-based, polystyrene-based, polynorthylene-based, polyolefin-based, (meth)acrylic-based, acetate-based transparent resins, etc. In addition, thermosetting resins such as (meth)acrylic, urethane, (meth)acrylic urethane, epoxy, silicone, etc., or ultraviolet curable resins can also be mentioned. resin etc. In addition, glassy polymers, such as a siloxane polymer, are mentioned, for example. Moreover, the polymer film described in Unexamined-Japanese-Patent No. 2001-343529 (WO01/37007) can also be used. As the material of the film, for example, a resin combination including a thermoplastic resin having a substituted or unsubstituted imide group in a side chain, and a thermoplastic resin having a substituted or unsubstituted phenyl group and a nitrile group in a side chain can be used. As an example, the resin composition which has the alternating copolymer containing isobutylene and N-methylmaleimide, and an acrylonitrile-styrene copolymer is mentioned, for example. The polymer film may be, for example, an extruded product of the aforementioned resin composition.
保護層之厚度較佳為5 μm～200 μm，更佳為10 μm～100 μm，再佳的是10 μm～60 μm。The thickness of the protective layer is preferably from 5 μm to 200 μm, more preferably from 10 μm to 100 μm, and even more preferably from 10 μm to 60 μm.
C-4.第1相位差層 第1相位差層可根據目的而具有任意適當之光學特性及/或機械特性。代表性而言，第1相位差層具有遲相軸。於一實施方式中，如上所述，第1相位差層之遲相軸與偏光膜之吸收軸所成之角度θ為40°～50°，較佳為42°～48°，再佳的是約45°。若角度θ處於此種範圍內，則如下所述藉由將第1相位差層設為λ/4板，能夠獲得具有非常優異之圓偏光特性(其結果為，非常優異之抗反射特性)之附相位差層之偏光板。 C-4. The first retardation layer The first retardation layer may have arbitrary appropriate optical properties and/or mechanical properties depending on the purpose. Typically, the first retardation layer has a slow axis. In one embodiment, as mentioned above, the angle θ formed by the retardation axis of the first retardation layer and the absorption axis of the polarizing film is 40°-50°, preferably 42°-48°, and more preferably about 45°. If the angle θ is within such a range, it is possible to obtain very excellent circular polarization characteristics (as a result, very excellent antireflection characteristics) by making the first retardation layer a λ/4 plate as described below. Polarizing plate with retardation layer.
第1相位差層較佳為表現出折射率特性為nx＞ny≧nz之關係。代表性而言，第1相位差層係為了對偏光板賦予抗反射特性而設置，於一實施方式中，可作為λ/4板發揮功能。於此情形時，第1相位差層之面內相位差Re(550)較佳為100 nm～190 nm，更佳為110 nm～170 nm，再佳的是130 nm～160 nm。再者，此處，「ny＝nz」不僅包括ny與nz完全相等之情形，亦包括實質上相等之情形。因此，在無損本發明之效果之範圍內，可能存在ny＜nz之情形。The first retardation layer preferably exhibits the relationship of nx>ny≧nz in terms of refractive index characteristics. Typically, the first retardation layer is provided to impart antireflection properties to the polarizing plate, and in one embodiment, it can function as a λ/4 plate. In this case, the in-plane retardation Re(550) of the first retardation layer is preferably from 100 nm to 190 nm, more preferably from 110 nm to 170 nm, and even more preferably from 130 nm to 160 nm. Furthermore, here, "ny=nz" includes not only the case where ny and nz are completely equal, but also the case where they are substantially equal. Therefore, ny<nz may exist in the range which does not impair the effect of this invention.
第1相位差層之Nz係數較佳為0.9～3，更佳為0.9～2.5，再佳的是0.9～1.5，尤佳為0.9～1.3。藉由滿足此種關係，於將所獲得之附相位差層之偏光板用於圖像顯示裝置之情形時，能夠達成非常優異之反射色相。The Nz coefficient of the first retardation layer is preferably from 0.9 to 3, more preferably from 0.9 to 2.5, even more preferably from 0.9 to 1.5, most preferably from 0.9 to 1.3. By satisfying such a relationship, when the obtained polarizing plate with a retardation layer is used for an image display device, a very excellent reflection hue can be achieved.
第1相位差層可表現出相位差值根據測定光之波長而變大之逆波長色散特性，亦可表現出相位差值根據測定光之波長而變小之正波長色散特性，還可表現出相位差值幾乎不根據測定光之波長而變化之平坦之波長色散特性。於一實施方式中，第1相位差層表現出逆波長色散特性。於此情形時，相位差層之Re(450)/Re(550)較佳為0.8以上且未達1，更佳為0.8以上0.95以下。若為此種構成，則能夠實現非常優異之抗反射特性。The first retardation layer can exhibit inverse wavelength dispersion characteristics in which the retardation value becomes larger according to the wavelength of the measurement light, or can exhibit positive wavelength dispersion characteristics in which the retardation value becomes smaller according to the wavelength of the measurement light, and can also exhibit A flat wavelength dispersion characteristic in which the retardation value hardly changes according to the wavelength of the measurement light. In one embodiment, the first retardation layer exhibits reverse wavelength dispersion characteristics. In this case, Re(450)/Re(550) of the retardation layer is preferably 0.8 or more and less than 1, more preferably 0.8 or more and 0.95 or less. With such a configuration, very excellent antireflection characteristics can be realized.
第1相位差層包含光彈性係數之絕對值較佳為2×10 -11m 2/N以下，更佳為2.0×10 -13m 2/N～1.5×10 -11m 2/N，再佳的是1.0×10 -12m 2/N～1.2×10 -11m 2/N之樹脂。若光彈性係數之絕對值處於此種範圍內，則於加熱時產生收縮應力之情形時，不容易發生相位差變化。結果能夠良好地防止所獲得之圖像顯示裝置之熱不均。 The absolute value of the photoelastic coefficient included in the first retardation layer is preferably 2×10 -11 m 2 /N or less, more preferably 2.0×10 -13 m 2 /N to 1.5×10 -11 m 2 /N, and then Preferably, the resin is 1.0×10 -12 m 2 /N to 1.2×10 -11 m 2 /N. When the absolute value of the photoelastic coefficient is within such a range, it is difficult to change the phase difference when shrinkage stress is generated during heating. As a result, thermal unevenness of the obtained image display device can be well prevented.
第1相位差層可為樹脂膜之延伸膜或液晶配向固化層。包含樹脂膜之延伸膜之第1相位差層之厚度較佳為70 μm以下，更佳為45 μm～60 μm。若第1相位差層之厚度處於此種範圍內，則能夠良好地抑制加熱時之捲縮，並且良好地調整貼合時之捲縮。又，於如下所述第1相位差層包含聚碳酸酯系樹脂膜之實施方式中，第1相位差層之厚度較佳為40 μm以下，更佳為10 μm～40 μm，再佳的是20 μm～30 μm。藉由使第1相位差層包含具有此種厚度之聚碳酸酯系樹脂膜，能夠抑制捲縮之發生，並且亦有助於彎折耐久性及反射色相之提高。The first retardation layer can be a stretched film of a resin film or a liquid crystal alignment solidified layer. The thickness of the first retardation layer of the stretched film including the resin film is preferably 70 μm or less, more preferably 45 μm to 60 μm. If the thickness of the first retardation layer is within such a range, curling at the time of heating can be well suppressed, and curling at the time of bonding can be well adjusted. Also, in the embodiment in which the first retardation layer includes a polycarbonate-based resin film as described below, the thickness of the first retardation layer is preferably 40 μm or less, more preferably 10 μm to 40 μm, and even more preferably 20μm～30μm. When the first retardation layer includes the polycarbonate-based resin film having such a thickness, generation of curl can be suppressed, and it also contributes to improvement of bending durability and reflection hue.
作為可形成第1相位差層之樹脂之代表例，可例舉：聚碳酸酯系樹脂、聚酯碳酸酯系樹脂、聚酯系樹脂、聚乙烯醇縮醛系樹脂、聚芳酯系樹脂、環狀烯烴系樹脂、纖維素系樹脂、聚乙烯醇系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚醚系樹脂、聚苯乙烯系樹脂、丙烯酸系樹脂。該等樹脂可單獨使用，亦可組合(例如，摻合、共聚)使用。於第1相位差層包含表現出逆波長色散特性之樹脂膜之情形時，可較佳地使用聚碳酸酯系樹脂或聚酯碳酸酯系樹脂(以下，有時簡稱為聚碳酸酯系樹脂)。Representative examples of the resin that can form the first retardation layer include polycarbonate resins, polyester carbonate resins, polyester resins, polyvinyl acetal resins, polyarylate resins, Cyclic olefin-based resins, cellulose-based resins, polyvinyl alcohol-based resins, polyamide-based resins, polyimide-based resins, polyether-based resins, polystyrene-based resins, and acrylic resins. These resins may be used alone or in combination (for example, blending, copolymerization). When the first retardation layer includes a resin film exhibiting reverse wavelength dispersion characteristics, polycarbonate-based resin or polyester-carbonate-based resin (hereinafter, sometimes abbreviated as polycarbonate-based resin) can be preferably used. .
作為上述聚碳酸酯系樹脂，可使用任意適當之聚碳酸酯系樹脂，只要能夠獲得本發明之效果即可。例如，聚碳酸酯系樹脂包含：來自茀系二羥基化合物之結構單元、來自異山梨糖醇系二羥基化合物之結構單元、以及來自選自由脂環式二醇、脂環式二甲醇、二乙二醇、三乙二醇或聚乙二醇、及伸烷基二醇或螺二醇所組成之群中之至少1種二羥基化合物的結構單元。較佳為聚碳酸酯系樹脂包含：來自茀系二羥基化合物之結構單元、來自異山梨糖醇系二羥基化合物之結構單元、以及來自脂環式二甲醇之結構單元及/或來自二乙二醇、三乙二醇或聚乙二醇之結構單元；再佳的是包含：來自茀系二羥基化合物之結構單元、來自異山梨糖醇系二羥基化合物之結構單元、及來自二乙二醇、三乙二醇或聚乙二醇之結構單元。聚碳酸酯系樹脂亦可視需要包含來自其他二羥基化合物之結構單元。再者，可較佳地用於本發明之聚碳酸酯系樹脂之詳情例如記載於日本專利特開2014-10291號公報、日本專利特開2014-26266號公報、日本專利特開2015-212816號公報、日本專利特開2015-212817號公報、日本專利特開2015-212818號公報中，該記載作為參考而援用於本說明書中。As the polycarbonate-based resin, any appropriate polycarbonate-based resin can be used as long as the effects of the present invention can be obtained. For example, the polycarbonate-based resin includes: a structural unit derived from a stilbene-based dihydroxy compound, a structural unit derived from an isosorbide-based dihydroxy compound, and a structural unit derived from alicyclic diol, alicyclic dimethanol, diethylene A structural unit of at least one dihydroxy compound selected from the group consisting of diol, triethylene glycol or polyethylene glycol, and alkylene glycol or spirodiol. Preferably, the polycarbonate-based resin comprises: structural units derived from fennel-based dihydroxy compounds, structural units derived from isosorbide-based dihydroxy compounds, and structural units derived from alicyclic dimethanol and/or derived from diethylene glycol Structural units of alcohol, triethylene glycol or polyethylene glycol; more preferably include: a structural unit derived from a stilbene-based dihydroxy compound, a structural unit derived from an isosorbide-based dihydroxy compound, and a structural unit derived from diethylene glycol , a structural unit of triethylene glycol or polyethylene glycol. The polycarbonate-based resin may optionally contain structural units derived from other dihydroxy compounds. Furthermore, the details of the polycarbonate-based resin that can be preferably used in the present invention are described in, for example, Japanese Patent Laid-Open No. 2014-10291, Japanese Patent Laid-Open No. 2014-26266, and Japanese Patent Laid-Open No. 2015-212816. In the gazette, Japanese Patent Laid-Open No. 2015-212817, and Japanese Patent Laid-Open No. 2015-212818, these descriptions are incorporated herein by reference.
上述聚碳酸酯系樹脂之玻璃轉移溫度較佳為110℃以上150℃以下，更佳為120℃以上140℃以下。若玻璃轉移溫度過低，則耐熱性趨於變差，膜成形後有可能引起尺寸變化，又，存在降低所獲得之有機EL面板之圖像品質之情形。若玻璃轉移溫度過高，則存在膜成形時之成形穩定性變差之情形，又，存在損害膜之透明性之情形。再者，玻璃轉移溫度可依據JIS K 7121(1987)而求出。The glass transition temperature of the polycarbonate-based resin is preferably from 110°C to 150°C, more preferably from 120°C to 140°C. When the glass transition temperature is too low, heat resistance tends to deteriorate, and dimensional changes may occur after film formation, and the image quality of the obtained organic EL panel may be lowered. When the glass transition temperature is too high, the molding stability at the time of film molding may deteriorate, and the transparency of the film may be impaired. In addition, glass transition temperature can be calculated|required based on JISK7121 (1987).
上述聚碳酸酯系樹脂之分子量可由比濃黏度來表示。比濃黏度係使用二氯甲烷作為溶劑，將聚碳酸酯濃度精確製備成0.6 g/dL，於溫度20.0℃±0.1℃下使用烏氏黏度管進行測定。比濃黏度之下限通常較佳為0.30 dL/g，更佳為0.35 dL/g以上。比濃黏度之上限通常較佳為1.20 dL/g，更佳為1.00 dL/g，再佳的是0.80 dL/g。若比濃黏度小於上述下限值，則有時會引起成形品機械強度變小之問題。另一方面，若比濃黏度大於上述上限值，則有時會引起成形時之流動性降低，生產性及成形性降低之問題。The molecular weight of the above-mentioned polycarbonate-based resin can be represented by reduced viscosity. The reduced viscosity uses dichloromethane as a solvent, and the concentration of polycarbonate is accurately prepared to 0.6 g/dL, and is measured with an Ubbelohde viscosity tube at a temperature of 20.0°C±0.1°C. The lower limit of the reduced viscosity is usually preferably 0.30 dL/g, more preferably 0.35 dL/g or more. The upper limit of the reduced viscosity is usually preferably 1.20 dL/g, more preferably 1.00 dL/g, even more preferably 0.80 dL/g. If the reduced viscosity is less than the above lower limit, there may be a problem that the mechanical strength of the molded product decreases. On the other hand, if the reduced viscosity exceeds the above-mentioned upper limit, the fluidity at the time of molding may decrease, and the problems of lowering productivity and moldability may arise.
可使用市售之膜作為聚碳酸酯系樹脂膜。作為市售品之具體例，可例舉：帝人公司製造之商品名「PURE-ACE WR-S」、「PURE-ACE WR-W」、「PURE-ACE WR-M」、日東電工公司製造之商品名「NRF」。A commercially available film can be used as the polycarbonate-based resin film. Specific examples of commercially available products include "PURE-ACE WR-S", "PURE-ACE WR-W", "PURE-ACE WR-M" manufactured by Teijin Corporation, and "PURE-ACE WR-M" manufactured by Nitto Denko Corporation. The product name is "NRF".
第1相位差層例如可藉由使由上述聚碳酸酯系樹脂形成之膜延伸而獲得。作為由聚碳酸酯系樹脂形成膜之方法，可採用任意適當之成形加工法。作為具體例，可例舉：壓縮成形法、轉移成形法、射出成形法、擠出成形法、吹塑成形法、粉末成形法、FRP(Fiber Reinforced Plastics，纖維強化塑膠)成形法、流延塗佈法(例如，流延法)、壓延成形法、熱壓法等。較佳為擠出成形法或流延塗佈法。其原因在於，能夠提高所獲得之膜之平滑性，獲得良好之光學均勻性。成形條件可根據所使用之樹脂之組成及種類、相位差層所需之特性等而適當地進行設定。再者，如上所述，關於聚碳酸酯系樹脂，由於膜製品多為市售品，故而可將該市售膜直接供至延伸處理。The first retardation layer can be obtained, for example, by stretching a film formed of the above-mentioned polycarbonate-based resin. As a method of forming a film from a polycarbonate-based resin, any appropriate molding method can be employed. As specific examples, compression molding method, transfer molding method, injection molding method, extrusion molding method, blow molding method, powder molding method, FRP (Fiber Reinforced Plastics, fiber reinforced plastics) molding method, cast coating Cloth method (for example, tape casting method), calendering method, hot pressing method, etc. Extrusion molding method or cast coating method is preferable. The reason for this is that the smoothness of the obtained film can be improved and good optical uniformity can be obtained. Molding conditions can be appropriately set according to the composition and type of resin to be used, the properties required for the retardation layer, and the like. In addition, as mentioned above, since many film products are commercially available about polycarbonate-type resin, this commercially available film can be directly subjected to stretching process.
樹脂膜(未延伸膜)之厚度可根據第1相位差層之所需之厚度、所需之光學特性、下述延伸條件等而設定為任意適當之值。較佳為50 μm～300 μm。The thickness of the resin film (unstretched film) can be set to any appropriate value according to the desired thickness of the first retardation layer, desired optical characteristics, stretching conditions described below, and the like. Preferably, it is 50 μm to 300 μm.
上述延伸可採用任意適當之延伸方法、延伸條件(例如，延伸溫度、延伸倍率、延伸方向)。具體而言，可單獨使用自由端延伸、固定端延伸、自由端收縮、固定端收縮等各種延伸方法，亦可同時或逐次使用該等延伸方法。關於延伸方向，亦可沿長度方向、寬度方向、厚度方向、斜向等各種方向或維度進行延伸。延伸之溫度相對於樹脂膜之玻璃轉移溫度(Tg)，較佳為Tg－30℃～Tg＋60℃，更佳為Tg－10℃～Tg＋50℃。Any appropriate stretching method and stretching conditions (for example, stretching temperature, stretching ratio, stretching direction) can be used for the above-mentioned stretching. Specifically, various stretching methods such as free-end extension, fixed-end extension, free-end shrinkage, and fixed-end shrinkage can be used alone, or these stretching methods can be used simultaneously or sequentially. Regarding the extending direction, extending can also be carried out in various directions or dimensions such as the longitudinal direction, the width direction, the thickness direction, and the oblique direction. The stretching temperature is preferably Tg-30°C to Tg+60°C relative to the glass transition temperature (Tg) of the resin film, more preferably Tg-10°C to Tg+50°C.
可藉由適當地選擇上述延伸方法、延伸條件，而獲得具有上述所需之光學特性(例如，折射率特性、面內相位差、Nz係數)之相位差膜。A retardation film having the above-mentioned desired optical characteristics (for example, refractive index characteristics, in-plane retardation, Nz coefficient) can be obtained by appropriately selecting the above-mentioned stretching method and stretching conditions.
於一實施方式中，相位差膜係藉由使樹脂膜單軸延伸或固定端單軸延伸而製作。作為固定端單軸延伸之具體例，可例舉一面使樹脂膜沿長度方向移行，一面使其沿寬度方向(橫向)延伸之方法。延伸倍率較佳為1.1倍～3.5倍。In one embodiment, the retardation film is produced by uniaxially stretching a resin film or uniaxially stretching a fixed end. As a specific example of the uniaxial extension of the fixed end, a method of extending the resin film in the width direction (transverse direction) while moving in the longitudinal direction may be mentioned. The elongation ratio is preferably from 1.1 times to 3.5 times.
於另一實施方式中，相位差膜可藉由使長條狀樹脂膜沿相對於長度方向成上述角度θ之方向連續地斜向延伸而製作。藉由採用斜向延伸，能夠獲得具有相對於膜之長度方向成角度θ之配向角(於角度θ之方向上具有遲相軸)之長條狀延伸膜，例如，與偏光膜積層時能夠實現卷對卷方式，能夠簡化製造步驟。再者，角度θ可為附相位差層之偏光板中偏光膜之吸收軸與相位差層之遲相軸所成之角度。如上所述，角度θ較佳為40°～50°，更佳為42°～48°，再佳的是約45°。In another embodiment, the retardation film can be produced by continuously extending the elongated resin film obliquely in the direction forming the above-mentioned angle θ with respect to the longitudinal direction. By adopting oblique stretching, it is possible to obtain an elongated stretched film having an alignment angle of an angle θ with respect to the longitudinal direction of the film (a slow axis in the direction of the angle θ), for example, when laminated with a polarizing film. The roll-to-roll method can simplify the manufacturing steps. Furthermore, the angle θ may be the angle formed by the absorption axis of the polarizing film in the polarizing plate with a retardation layer and the slow axis of the retardation layer. As mentioned above, the angle θ is preferably 40°-50°, more preferably 42°-48°, even more preferably about 45°.
作為用於斜向延伸之延伸機，例如可例舉：可沿橫向及/或縱向附加左右不同之速度之進給力或拉伸力或者牽引力之拉幅式延伸機。拉幅式延伸機包括橫向單軸延伸機、同時雙軸延伸機等，可採用任意適當之延伸機，只要能夠使長條狀樹脂膜連續地斜向延伸即可。As the stretching machine used for diagonal stretching, for example, a tenter stretching machine that can apply a feed force, a stretching force, or a traction force at a laterally and/or vertically different speed can be cited. The tenter stretching machine includes a horizontal uniaxial stretching machine, a simultaneous biaxial stretching machine, etc. Any suitable stretching machine can be used as long as it can continuously stretch the elongated resin film obliquely.
藉由在上述延伸機中分別適當地控制左右之速度，能夠獲得具有上述所需之面內相位差，且於上述所需之方向上具有遲相軸之相位差層(實質上為長條狀相位差膜)。By appropriately controlling the speeds of the left and right sides in the above-mentioned stretching machine, it is possible to obtain a retardation layer (essentially elongated) having the above-mentioned required in-plane phase difference and having a retardation axis in the above-mentioned required direction. retardation film).
上述膜之延伸溫度可根據相位差層所需之面內相位差值及厚度、所使用之樹脂之種類、所使用之膜之厚度、延伸倍率等而變化。具體而言，延伸溫度較佳為Tg－30℃～Tg＋30℃，再佳的是Tg－15℃～Tg＋15℃，最佳為Tg－10℃～Tg＋10℃。藉由以此種溫度進行延伸，能夠獲得本發明中具有適當特性之第1相位差層。再者，Tg係膜之構成材料之玻璃轉移溫度。The stretching temperature of the above-mentioned film can be changed according to the required in-plane retardation value and thickness of the retardation layer, the type of resin used, the thickness of the film used, and the stretching ratio. Specifically, the stretching temperature is preferably Tg-30°C to Tg+30°C, more preferably Tg-15°C to Tg+15°C, most preferably Tg-10°C to Tg+10°C. By stretching at such a temperature, the first retardation layer having appropriate characteristics in the present invention can be obtained. Furthermore, Tg is the glass transition temperature of the constituent materials of the film.
C-5.第2相位差層 如上所述，第2相位差層可為表現出折射率特性為nz＞nx＝ny之關係之所謂正C板。藉由使用正C板作為第2相位差層，能夠良好地防止斜向之反射，能夠實現抗反射功能之大視野角化。於此情形時，第2相位差層之厚度方向之相位差Rth(550)較佳為-50 nm～-300 nm，更佳為-70 nm～-250 nm，再佳的是-90 nm～-200 nm，尤佳為-100 nm～-180 nm。此處，「nx＝ny」不僅包括nx與ny嚴格相等之情形，亦包括nx與ny實質上相等之情形。即，第2相位差層之面內相位差Re(550)可未達10 nm。 C-5. The second retardation layer As described above, the second retardation layer may be a so-called positive C plate exhibiting the relationship of nz>nx=ny in refractive index characteristics. By using the positive C plate as the second retardation layer, oblique reflection can be prevented well, and the viewing angle of the antireflection function can be increased. In this case, the retardation Rth(550) in the thickness direction of the second retardation layer is preferably -50 nm to -300 nm, more preferably -70 nm to -250 nm, and even more preferably -90 nm to -200 nm, especially -100 nm to -180 nm. Here, "nx=ny" includes not only the case where nx and ny are strictly equal, but also the case where nx and ny are substantially equal. That is, the in-plane retardation Re(550) of the second retardation layer may be less than 10 nm.
具有nz＞nx＝ny之折射率特性之第2相位差層可由任意適當之材料形成。第2相位差層較佳為包含含有以垂直配向固定之液晶材料的膜。能夠垂直配向之液晶材料(液晶化合物)可為液晶單體，亦可為液晶聚合物。作為該液晶化合物及該相位差層之形成方法之具體例，可例舉日本專利特開2002-333642號公報之[0020]～[0028]中記載之液晶化合物及該相位差層之形成方法。於此情形時，第2相位差層之厚度較佳為0.5 μm～10 μm，更佳為0.5 μm～8 μm，再佳的是0.5 μm～5 μm。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 a film containing a liquid crystal material fixed in a vertical alignment. 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 liquid crystal compound and the method for forming the retardation layer include those described in [0020] to [0028] of JP-A-2002-333642 and the method for forming the retardation layer. In this case, the thickness of the second retardation layer is preferably from 0.5 μm to 10 μm, more preferably from 0.5 μm to 8 μm, and even more preferably from 0.5 μm to 5 μm.
C-6.導電層或附導電層之各向同性基材 導電層可藉由任意適當之成膜方法(例如，真空蒸鍍法、濺鍍法、CVD(Chemical Vapor Deposition，化學氣相沈積)法、離子鍍覆法、噴霧法等)於任意適當之基材上成膜金屬氧化物膜而形成。作為金屬氧化物，例如可例舉：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，較佳為銦-錫複合氧化物(ITO)。 C-6. Conductive layer or isotropic substrate with conductive layer The conductive layer can be deposited on any suitable base by any suitable film-forming method (for example, vacuum evaporation method, sputtering method, CVD (Chemical Vapor Deposition, chemical vapor deposition) method, ion plating method, spray method, etc.) It is formed by forming a metal oxide film on the material. 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 preferable.
於導電層包含金屬氧化物之情形時，該導電層之厚度較佳為50 nm以下，更佳為35 nm以下。導電層之厚度之下限較佳為10 nm。When the conductive layer includes a metal oxide, the thickness of the conductive layer is preferably not more than 50 nm, more preferably not more than 35 nm. The lower limit of the thickness of the conductive layer is preferably 10 nm.
導電層可自上述基材轉印至第1相位差層(或第2相位差層，如果存在)，僅將導電層作為附相位差層之偏光板之構成層，亦可作為與基材之積層體(附導電層之基材)積層於第1相位差層(或第2相位差層，如果存在)。較佳為上述基材具有光學各向同性，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 transferred from the above substrate to the first retardation layer (or the second retardation layer, if it exists), and the conductive layer can only be used as a constituent layer of a polarizing plate with a retardation layer, or it can be used as a layer with the substrate. The laminate (substrate with conductive layer) is laminated on the first phase difference layer (or the second phase difference layer, if it exists). It is preferable that the above substrate has optical isotropy, therefore, the conductive layer can be used as an isotropic substrate with a conductive layer for a polarizing plate with a retardation layer.
作為光學各向同性之基材(各向同性基材)，可採用任意適當之各向同性基材。作為構成各向同性基材之材料，例如可例舉：以降𦯉烯系樹脂或烯烴系樹脂等不具有共軛系之樹脂作為主骨架之材料、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之材料等。若使用此種材料，則形成各向同性基材時，能夠將分子鏈配向所伴隨之相位差之顯現抑製得較小。各向同性基材之厚度較佳為50 μm以下，更佳為35 μm以下。各向同性基材之厚度之下限例如為20 μm。Any appropriate isotropic substrate can be used as the optically isotropic substrate (isotropic substrate). As the material constituting the isotropic base material, for example, a resin having no conjugated system such as a northylene-based resin or an olefin-based resin as a main skeleton, an acrylic resin having a lactone ring in its main chain, or Materials with cyclic structures such as glutarimide rings, etc. When such a material is used, when an isotropic base material is formed, the appearance of a phase difference accompanying molecular chain alignment can be suppressed to be small. The thickness of the isotropic substrate is preferably less than 50 μm, more preferably less than 35 μm. The lower limit of the thickness of the isotropic substrate is, for example, 20 μm.
上述導電層及/或上述附導電層之各向同性基材之導電層可視需要被圖案化。藉由進行圖案化，能夠形成導通部及絕緣部。結果能夠形成電極。電極可作為感測與觸控面板之接觸之觸控感測器電極而發揮功能。作為圖案化方法，可採用任意適當之方法。作為圖案化方法之具體例，可例舉：濕式蝕刻法、網版印刷法。The above-mentioned conductive layer and/or the conductive layer of the above-mentioned isotropic substrate with a conductive layer can be patterned as required. By performing patterning, a conduction part and an insulating part can be formed. As a result, electrodes can be formed. The electrodes may function as touch sensor electrodes that sense contact with the touch panel. Any appropriate method can be adopted as a patterning method. Specific examples of the patterning method include wet etching and screen printing.
D.圖像顯示裝置 上述C項中記載之偏光板可應用於圖像顯示裝置。因此，本發明包括具備該偏光板之圖像顯示裝置。作為圖像顯示裝置之代表例，可例舉：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)。其中，就能夠藉由藍色發光量之降低而實現節能化之方面而言，較佳為有機EL顯示裝置。 [實施例] D. Image display device The polarizing plate described in the above item C can be applied to an image display device. Therefore, the present invention includes an image display device including the polarizing plate. 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). Among them, an organic EL display device is preferable at the point that energy saving can be achieved by reducing the amount of blue light emission. [Example]
以下，藉由實施例對本發明具體地進行說明，但本發明並不受到該等實施例限定。各特性之測定方法如下所述。再者，只要無特別明確記載，則實施例及比較例中之「份」及「%」係重量基準。 (1)厚度 使用製品名「Linear Gauge MODEL D-10HS」(尾崎製作所公司製造)進行測定。 (2)單體透過率、偏光度及正交吸光度 針對實施例及比較例中所獲得之PVA系樹脂膜(偏光膜或未脫色原膜)與保護層之積層體，自PVA系樹脂膜側使用紫外可見分光光度計(大塚電子公司製造之「LPF-200」)進行測定，將所測得之單體透過率Ts、平行透過率Tp、正交透過率Tc分別作為PVA系樹脂膜之Ts、Tp及Tc。針對附相位差層之偏光板，自相位差層側以相同方式測定單體透過率Ts。該等Ts、Tp及Tc係藉由JIS Z8701之2度視野(C光源)進行測定並進行視感度補正而得之Y值。再者，保護層之折射率係1.53，偏光膜之與保護層相反之側之表面之折射率為1.53。 根據所獲得之Tp及Tc，由下述式求出偏光度P。 偏光度P(%)＝{(Tp－Tc)/(Tp＋Tc)} 1/2×100 又，使用各波長下所測得之Tc，由下述式求出各波長時之正交吸光度。 正交吸光度＝log10(100/Tc) 又，將波長470 nm及600 nm下所測得之Ts分別設為Ts 470及Ts 600。 再者，關於分光光度計，亦可使用日本分光公司製造之「V-7100」等進行相同之測定，確認不管使用哪一種分光光度計，均能夠獲得相同之測定結果。 (3)水分率 將剛經過乾燥處理後之未脫色原膜(於以積層體之形式延伸之情形時，延伸基材被剝離)切成100 mm×100 mm以上之大小，利用電子天平測定處理前重量。其後，將其投入至保持為120℃之加熱烘箱內2小時，測定取出後之重量(處理後重量)，根據下述式求出水分率。 水分率[%]＝(處理前重量－處理後重量)/處理前重量×100 (4)霧度 使用日本電色工業公司製造之製品名「霧度計(NDH-5000)」，依據JISK7136進行測定。 (5)正面反射色相 使用無紫外線吸收功能之丙烯酸系黏著劑將實施例及比較例中所獲得之附相位差層之偏光板貼合於反射板(TORAY FILMS公司製造，商品名「DMS-X42」；反射率86%，無偏光板時之反射色相a*＝-0.22，b*＝0.32)上而製作測定樣本。此時，以附相位差層之偏光板之相位差層側與反射板對向之方式進行貼合。針對該測定樣本，使用分光測色計(柯尼卡美能達製造之CM-2600d)以SCE(Specular Component Exclude，排除鏡面反射分量)方式測定a*值及b*值。 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 specified, "part" and "%" in an Example and a comparative example are based on weight. (1) Thickness was measured using a product name "Linear Gauge Model D-10HS" (manufactured by Ozaki Seisakusho). (2) Monomer transmittance, polarization, and orthogonal absorbance For the laminate of the PVA-based resin film (polarizing film or unbleached original film) and protective layer obtained in Examples and Comparative Examples, from the PVA-based resin film side Use a UV-visible spectrophotometer ("LPF-200" manufactured by Otsuka Electronics Co., Ltd.) to measure, and use the measured single transmittance Ts, parallel transmittance Tp, and orthogonal transmittance Tc as Ts of the PVA-based resin film. , Tp and Tc. For the polarizing plate with a retardation layer, the single transmittance Ts was measured in the same manner from the retardation layer side. These Ts, Tp and Tc are the Y values obtained by measuring with the 2-degree field of view (C light source) of JIS Z8701 and correcting the visual sensitivity. Furthermore, the refractive index of the protective layer is 1.53, and the refractive index of the surface of the polarizing film opposite to the protective layer is 1.53. From the obtained Tp and Tc, the degree of polarization P was obtained from the following formula. Degree of polarization P(%)={(Tp-Tc)/(Tp+Tc)} 1/2 ×100 Also, using Tc measured at each wavelength, the orthogonal absorbance at each wavelength is obtained from the following formula. Orthogonal absorbance=log10(100/Tc) Also, Ts measured at wavelengths of 470 nm and 600 nm are respectively set as Ts 470 and Ts 600 . In addition, regarding the spectrophotometer, "V-7100" manufactured by JASCO Co., Ltd. was used to perform the same measurement, and it was confirmed that the same measurement results could be obtained regardless of which spectrophotometer was used. (3) Moisture content Cut the unbleached original film just after drying (in the case of stretching in the form of a laminate, the stretched substrate is peeled off) to a size of 100 mm × 100 mm or more, and use an electronic balance to measure the processing front weight. Then, it was put into the heating oven maintained at 120 degreeC for 2 hours, the weight after taking out was measured (weight after processing), and the moisture content was calculated|required from the following formula. Moisture content [%] = (weight before treatment - weight after treatment) / weight before treatment × 100 (4) haze using the product name "haze meter (NDH-5000)" manufactured by Nippon Denshoku Kogyo Co., Ltd., according to JISK7136 Determination. (5) Front reflection color using an acrylic adhesive with no ultraviolet absorption function to attach the polarizing plate with retardation layer obtained in Examples and Comparative Examples to a reflective plate (manufactured by TORAY FILMS, trade name "DMS-X42") ”; the reflectance is 86%, and the reflection hue when there is no polarizing plate is a*=-0.22, b*=0.32) to make a measurement sample. At this time, the retardation layer side of the polarizing plate with a retardation layer was bonded so that the reflection plate faced. For this measurement sample, a* value and b* value were measured by the SCE (Specular Component Exclude, specular component exclusion) method using a spectrophotometer (CM-2600d manufactured by Konica Minolta).
[實施例1-1] 1.偏光膜及偏光板之製作 將厚度30 μm之PVA系樹脂膜(可樂麗製造，製品名「PE3000」)之長條捲筒一面浸漬於30℃之水浴中，一面沿搬送方向延伸至2.2倍後，浸漬於碘濃度0.04重量%、鉀濃度0.3重量%之30℃水溶液中進行染色，與此同時以完全未延伸之膜(原本長度)為基準使其延伸至3倍。繼而，將該延伸膜一面浸漬於硼酸濃度3重量%、碘化鉀濃度3重量%之30℃之水溶液中，一面以原本長度為基準進一步延伸至3.3倍，繼而，一面浸漬於硼酸濃度4重量%、碘化鉀濃度5重量%之60℃水溶液中，一面以原本長度為基準進一步延伸至6倍，最後，於保持為60℃之烘箱內實施5分鐘之乾燥處理，藉此製作厚度12 μm之偏光膜(未脫色原膜a1)。所獲得之未脫色原膜a1之水分率為10.0重量%，單體透過率為42.5%。 [Example 1-1] 1. Production of polarizing film and polarizing plate A long roll of PVA-based resin film with a thickness of 30 μm (manufactured by Kuraray, product name "PE3000") is immersed in a water bath at 30°C on one side, stretched to 2.2 times along the conveying direction, and then immersed in an iodine concentration of 0.04 by weight. %, a potassium concentration of 0.3% by weight in an aqueous solution at 30°C, and at the same time stretch it to 3 times based on the completely unstretched film (original length). Then, the stretched film was immersed in an aqueous solution at 30° C. with a concentration of boric acid of 3% by weight and a concentration of potassium iodide of 3% by weight, and was further extended to 3.3 times the original length. In a 60°C aqueous solution with a potassium iodide concentration of 5% by weight, one side was further extended to 6 times the original length, and finally, dried in an oven kept at 60°C for 5 minutes to produce a polarizing film with a thickness of 12 μm ( Unbleached original film a1). The obtained unbleached original film a1 had a moisture content of 10.0% by weight and a monomer transmittance of 42.5%.
於所獲得之未脫色原膜a1之單面塗佈PVA系樹脂水溶液(日本合成化學工業公司製造，商品名「GOHSEFIMER(註冊商標)Z-200」，樹脂濃度：3重量%)，並貼合環烯烴系膜(日本瑞翁公司製造，Zeonor，厚度：25 μm)，而獲得具有[未脫色原膜a1/保護層]之構成之光學積層體。再者，作為保護層，可使用設置有硬塗層之保護層，作為此種保護層，例如可例示：附硬塗層之環烯烴系膜(ZEON公司製造，製品名「G-Film」，總厚度27 μm(膜厚度25 μm＋硬塗層厚度2 μm))等。A PVA-based resin aqueous solution (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "GOHSEFIMER (registered trademark) Z-200", resin concentration: 3% by weight) was coated on one side of the obtained unbleached original film a1, and bonded A cycloolefin-based film (Zeonor, manufactured by Japan Zeon Corporation, thickness: 25 μm) was used to obtain an optical laminate having the composition of [unbleached original film a1/protective layer]. Furthermore, as the protective layer, a protective layer provided with a hard coat layer can be used. As such a protective layer, for example, a cycloolefin-based film with a hard coat layer (manufactured by ZEON Corporation, product name "G-Film", The total thickness is 27 μm (film thickness 25 μm + hard coat thickness 2 μm)), etc.
將上述光學積層體切斷成50 mm×45 mm之尺寸，將其在經由丙烯酸系黏著劑層(厚度15 μm)以未脫色原膜側表面為露出面之方式貼合於玻璃板之狀態下浸漬於55℃之水中9分鐘。繼而，於50℃下乾燥5分鐘，藉此獲得具有[偏光膜A1/保護層]之構成之偏光板。Cut the above-mentioned optical laminate into a size of 50 mm×45 mm, and attach it to a glass plate through an acrylic adhesive layer (thickness 15 μm) with the surface of the non-decolorized original film exposed. Soak in water at 55°C for 9 minutes. Then, it dried at 50 degreeC for 5 minutes, and the polarizing plate which has the structure of [polarizing film A1/protective layer] was obtained.
2.構成相位差層之相位差膜之製作 2-1.聚酯碳酸酯系樹脂之聚合 使用包括2個具備攪拌翼及控制為100℃之回流冷凝器之立式反應器的批次式聚合裝置進行聚合。添加雙[9-(2-苯氧基羰基乙基)茀-9-基]甲烷29.60質量份(0.046 mol)、異山梨糖醇(ISB)29.21質量份(0.200 mol)、螺二醇(SPG)42.28質量份(0.139 mol)、碳酸二苯酯(DPC)63.77質量份(0.298 mol)及作為觸媒之乙酸鈣一水合物1.19×10 -2質量份(6.78×10 -5mol)。對反應器內進行減壓氮氣置換後，利用熱媒進行加溫，於內部溫度成為100℃之時點開始攪拌。以升溫開始40分鐘後使內部溫度達到220℃，並保持該溫度之方式進行控制，同時開始減壓，達到220℃之後耗費90分鐘使其為13.3 kPa。將伴隨著聚合反應副產之苯酚蒸氣導入至100℃之回流冷凝器中，使苯酚蒸氣中所包含之若干量之單體成分回到反應器中，將未冷凝之苯酚蒸氣導入至45℃之冷凝器中進行回收。將氮氣導入至第1反應器中，暫時先複壓至大氣壓後，將第1反應器內之經低聚化之反應液移至第2反應器內。繼而，開始第2反應器內之升溫及減壓，耗費50分鐘使內部溫度為240℃，使壓力為0.2 kPa。其後，進行聚合直至成為特定攪拌動力為止。於達到特定動力之時點將氮氣導入至反應器內進行複壓，將所生成之聚酯碳酸酯系樹脂擠出至水中，切割線料而獲得顆粒。 2. Fabrication of the 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 condenser controlled at 100°C The device is polymerized. Add 29.60 parts by mass (0.046 mol) of bis[9-(2-phenoxycarbonylethyl) fen-9-yl]methane, 29.21 parts by mass (0.200 mol) of isosorbide (ISB), spirodiol (SPG ) 42.28 parts by mass (0.139 mol), diphenyl carbonate (DPC) 63.77 parts by mass (0.298 mol), and calcium acetate monohydrate as a catalyst 1.19×10 -2 parts by mass (6.78×10 -5 mol). After the inside of the reactor was replaced with nitrogen under reduced pressure, it was heated with a heat medium, and stirring was started when the internal temperature became 100°C. 40 minutes after the start of the temperature rise, the internal temperature was controlled to reach 220° C., and the temperature was maintained. At the same time, the pressure was reduced, and it took 90 minutes after reaching 220° C. to bring it to 13.3 kPa. Introduce the by-product phenol vapor accompanying the polymerization reaction into the reflux condenser at 100°C, so that a certain amount of monomer components contained in the phenol vapor return to the reactor, and introduce the uncondensed phenol vapor into the reflux condenser at 45°C. recovered in the condenser. Nitrogen gas is introduced into the first reactor, and the pressure is temporarily reset to atmospheric pressure, then the oligomerized reaction liquid in the first reactor is transferred to the second reactor. Then, temperature rise and pressure reduction in the second reactor were started, and the internal temperature was made 240° C. and the pressure was made 0.2 kPa over 50 minutes. Thereafter, polymerization is performed until a specific stirring power is obtained. When the specific power is reached, nitrogen gas is introduced into the reactor for repressurization, the resulting polyester carbonate resin is extruded into water, and the strands are cut to obtain pellets.
2-2.相位差膜之製作
將所獲得之聚酯碳酸酯系樹脂(顆粒)於80℃下真空乾燥5小時後，使用具備單軸擠出機(東芝機械公司製造，料缸設定溫度：250℃)、T型模頭(寬度200 mm，設定溫度：250℃)、冷卻輥(設定溫度：120～130℃)及卷取機之膜制膜裝置，製作厚度130 μm之長條狀樹脂膜。將所獲得之長條狀樹脂膜一面以可獲得特定相位差之方式進行調整一面使其延伸，而獲得厚度48 μm之相位差膜。延伸條件係，於寬度方向上延伸溫度為143℃，延伸倍率為2.8倍。所獲得之相位差膜之Re(550)為141 nm，Re(450)/Re(550)為0.86，Nz係數為1.12。
2-2. Production of retardation film
After vacuum-drying the obtained polyester carbonate resin (granules) at 80° C. for 5 hours, use a single-screw extruder (manufactured by Toshiba Machinery Co., Ltd., cylinder setting temperature: 250° C.), a T-die (
3.附相位差層之偏光板之製作 經由丙烯酸系黏著劑(厚度15 μm)將上述2.中所獲得之相位差膜貼合於上述1.中所獲得之偏光板之偏光膜表面。此時，以偏光膜之吸收軸與相位差膜之遲相軸成45°之角度之方式進行貼合。以此方式獲得具有[相位差層/偏光膜A1/保護層]之構成之附相位差層之偏光板。 3. Production of polarizing plate with retardation layer The retardation film obtained in the above 2. was attached to the surface of the polarizing film of the polarizing plate obtained in the above 1. through an acrylic adhesive (thickness: 15 μm). At this time, it was bonded so that the absorption axis of the polarizing film and the slow axis of the retardation film formed an angle of 45°. In this way, a polarizing plate with a retardation layer having a composition of [retardation layer/polarizing film A1/protective layer] was obtained.
[實施例1-2] 在65℃之水中浸漬3分鐘來代替在55℃之水中浸漬9分鐘，除此以外，以與實施例1-1相同之方式獲得具有[偏光膜A2/保護層]之構成之偏光板。又，除了使用該偏光板以外，以與實施例1-1相同之方式獲得附相位差層之偏光板。 [Example 1-2] Instead of immersing in 55 degreeC water for 3 minutes in 65 degreeC water for 9 minutes, it carried out similarly to Example 1-1, and obtained the polarizing plate which has the structure of [polarizing film A2/protective layer]. Moreover, except having used this polarizing plate, it carried out similarly to Example 1-1, and obtained the polarizing plate with a retardation layer.
[實施例1-3] 在23℃之水中浸漬31小時來代替在55℃之水中浸漬9分鐘，除此以外，以與實施例1-1相同之方式獲得具有[偏光膜A3/保護層]之構成之偏光板。又，除了使用該偏光板以外，以與實施例1-1相同之方式獲得附相位差層之偏光板。 [Example 1-3] Instead of immersing in 55 degreeC water for 31 hours in 23 degreeC water for 31 hours, it carried out similarly to Example 1-1, and obtained the polarizing plate which has the structure of [polarizing film A3/protective layer]. Moreover, except having used this polarizing plate, it carried out similarly to Example 1-1, and obtained the polarizing plate with a retardation layer.
[比較例1] 將以與實施例1-1相同之方式所製作之具有[未脫色原膜a1/保護層]之構成之光學積層體用作偏光板。又，除了使用該偏光板以外，以與實施例1-1相同之方式獲得附相位差層之偏光板。 [Comparative example 1] The optical laminate having the composition of [unbleached original film a1/protective layer] produced in the same manner as in Example 1-1 was used as a polarizing plate. Moreover, except having used this polarizing plate, it carried out similarly to Example 1-1, and obtained the polarizing plate with a retardation layer.
[實施例2-1] 使用長條狀且Tg約為75℃之非晶質之間苯二甲酸共聚聚對苯二甲酸乙二酯膜(厚度：100 μm)作為熱塑性樹脂基材，對樹脂基材之單面實施電暈處理。 向聚乙烯醇(聚合度4200，皂化度99.2莫耳%)及乙醯乙醯基改性PVA(日本合成化學工業公司製造，商品名「GOHSEFIMER」)以9：1混合而成之PVA系樹脂100重量份中添加碘化鉀13重量份，使由此所得者溶解於水中，而製備PVA水溶液(塗佈液)。 於樹脂基材之電暈處理面塗佈上述PVA水溶液並於60℃下進行乾燥，藉此形成厚度13 μm之PVA系樹脂層，而製作積層體。 使所獲得之積層體於130℃之烘箱內沿縱向(長度方向)單軸延伸至2.4倍(空中輔助延伸處理)。 繼而，將積層體浸漬於液溫40℃之不溶化浴(相對於水100重量份調配硼酸4重量份所獲得之硼酸水溶液)中30秒鐘(不溶化處理)。 繼而，一面調整濃度以使最終所獲得之未脫色原膜之單體透過率(Ts)為42.3%，一面浸漬於液溫30℃之染色浴(相對於水100重量份以1：7之重量比調配碘與碘化鉀所獲得之碘水溶液)中60秒鐘(染色處理)。 繼而，將其浸漬於液溫40℃之交聯浴(相對於水100重量份調配碘化鉀3重量份並調配硼酸5重量份所獲得之硼酸水溶液)中30秒鐘(交聯處理)。 其後，將積層體一面浸漬於液溫70℃之硼酸水溶液(硼酸濃度4重量%，碘化鉀濃度5重量%)中，一面於周速不同之輥間沿縱向(長度方向)以總延伸倍率為5.5倍之方式進行單軸延伸(水中延伸處理)。 其後，將積層體浸漬於液溫20℃之洗淨浴(相對於水100重量份調配碘化鉀4重量份所獲得之水溶液)中(洗淨處理)。 其後，一面在保持為約90℃之烘箱中進行乾燥，一面使其與表面溫度保持為約75℃之SUS製加熱輥接觸(乾燥收縮處理)。由乾燥收縮處理所引起之積層體之寬度方向上之收縮率為2%。 以此方式於樹脂基材上形成水分率為4.5%，厚度為5.4 μm之未脫色原膜，藉由UV(ultraviolet，紫外線)硬化型接著劑(厚度1.0 μm)將環烯烴系膜(日本瑞翁公司製造，Zeonor，厚度：25 μm)貼合於未脫色原膜之表面，其後，將樹脂基材剝離而獲得具有[未脫色原膜b1/保護層]之構成之光學積層體。 [Example 2-1] Using a long amorphous isophthalic acid copolymerized polyethylene terephthalate film (thickness: 100 μm) with a Tg of about 75°C as the thermoplastic resin substrate, electro-electrolysis is performed on one side of the resin substrate. Halo processing. PVA-based resin mixed with polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mole%) and acetoacetyl-modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "GOHSEFIMER") at a ratio of 9:1 13 parts by weight of potassium iodide was added to 100 parts by weight, and the resultant was dissolved in water to prepare an aqueous PVA solution (coating liquid). The above-mentioned PVA aqueous solution was applied to the corona-treated surface of the resin substrate and dried at 60° C. to form a PVA-based resin layer with a thickness of 13 μm, thereby producing a laminate. The obtained laminate was uniaxially stretched to 2.4 times in the longitudinal direction (longitudinal direction) in an oven at 130° C. (in-air assisted stretching treatment). Next, the laminate was immersed in an insolubilization bath (an aqueous solution of boric acid obtained by mixing 4 parts by weight of boric acid with respect to 100 parts by weight of water) at a liquid temperature of 40° C. for 30 seconds (insolubilization treatment). Then, while adjusting the concentration so that the monomer transmittance (Ts) of the unbleached original film finally obtained is 42.3%, it is immersed in a dyeing bath with a liquid temperature of 30°C (1:7 by weight relative to 100 parts by weight of water). than the iodine aqueous solution obtained by mixing iodine and potassium iodide) for 60 seconds (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) at a liquid temperature of 40° C. for 30 seconds (crosslinking treatment). Thereafter, the laminate was immersed in a boric acid aqueous solution (boric acid concentration 4% by weight, potassium iodide concentration 5% by weight) at a liquid temperature of 70°C, and placed between rollers with different circumferential speeds in the longitudinal direction (length direction) at a total stretch ratio of 5.5 times the method of uniaxial stretching (stretching treatment in water). Thereafter, the laminate was immersed in a cleaning bath (an aqueous solution obtained by mixing 4 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 20° C. (washing treatment). Thereafter, while drying in an oven maintained at about 90° C., it was brought into contact with a heating roll made of SUS whose surface temperature was maintained at about 75° C. (drying shrinkage treatment). The shrinkage rate in the width direction of the laminate caused by the drying shrinkage treatment was 2%. In this way, a non-decolorized original film with a moisture content of 4.5% and a thickness of 5.4 μm is formed on the resin substrate, and a cycloolefin-based film (Japan Rui Manufactured by Weng Co., Zeonor, thickness: 25 μm) is pasted on the surface of the original non-decolorized film, and then the resin substrate is peeled off to obtain an optical laminate with the composition of [original non-decolorized film b1/protective layer].
將上述光學積層體切斷成50 mm×45 mm之尺寸，將其在經由丙烯酸系黏著劑層(厚度15 μm)以未脫色原膜側表面為露出面之方式貼合於玻璃板之狀態下浸漬於50℃之水中9分鐘。繼而，於50℃下乾燥5分鐘，藉此獲得具有[偏光膜B1/保護層]之構成之偏光板。又，除了使用該偏光板以外，以與實施例1-1相同之方式獲得具有[相位差層/偏光膜B1/保護層]之構成之附相位差層之偏光板。Cut the above-mentioned optical laminate into a size of 50 mm×45 mm, and attach it to a glass plate through an acrylic adhesive layer (thickness 15 μm) with the surface of the non-decolorized original film exposed. Soak in water at 50°C for 9 minutes. Then, it dried at 50 degreeC for 5 minutes, and the polarizing plate which has the structure of [polarizing film B1/protective layer] was obtained. Moreover, except having used this polarizing plate, the polarizing plate with a retardation layer which has a structure of [retardation layer/polarizing film B1/protective layer] was obtained in the same manner as Example 1-1.
[實施例2-2] 在60℃之水中浸漬3分鐘來代替在50℃之水中浸漬9分鐘，除此以外，以與實施例2-1相同之方式獲得具有[偏光膜B2/保護層]之構成之偏光板。又，除了使用該偏光板以外，以與實施例1-1相同之方式獲得附相位差層之偏光板。 [Example 2-2] Except having immersed in 60 degreeC water for 3 minutes instead of 50 degreeC water for 9 minutes, the polarizing plate which has the structure of [polarizing film B2/protective layer] was obtained in the same manner as Example 2-1. Moreover, except having used this polarizing plate, it carried out similarly to Example 1-1, and obtained the polarizing plate with a retardation layer.
[比較例2] 將以與實施例2-1相同之方式所製作之具有[未脫色原膜b1/保護層]之構成之光學積層體用作偏光板。又，除了使用該偏光板以外，以與實施例1-1相同之方式獲得附相位差層之偏光板。 [Comparative example 2] The optical laminate having the composition of [unbleached original film b1/protective layer] produced in the same manner as in Example 2-1 was used as a polarizing plate. Moreover, except having used this polarizing plate, it carried out similarly to Example 1-1, and obtained the polarizing plate with a retardation layer.
針對上述實施例及比較例中所獲得之未脫色原膜、偏光膜、附相位差層之偏光板，評價各種特性。將結果示於表1中。
[表1]
由表1表明，實施例之偏光膜滿足「1＜Ts 470/Ts 600」之關係，能夠使短波長側之光相較於長波長側之光更積極地透過。 [產業上之可利用性] Table 1 shows that the polarizing film of the embodiment satisfies the relationship of "1<Ts 470 /Ts 600 ", and can transmit light on the short-wavelength side more actively than light on the long-wavelength side. [Industrial availability]
本發明之偏光膜可較佳地用於液晶顯示裝置及EL顯示裝置等圖像顯示裝置，尤其是用於有機EL顯示裝置。The polarizing film of the present invention can be preferably used in image display devices such as liquid crystal display devices and EL display devices, especially in organic EL display devices.
10:偏光膜
12:第1保護層
14:第2保護層
20:保護層
30:相位差層
40:黏著劑層
100:偏光板
200:積層體
200a:附相位差層之偏光板
200b:附相位差層之偏光板
R1～R6:搬送輥
G1～G4:導輥
10: Polarizing film
12: The first protective layer
14: The second protective layer
20: protective layer
30: Retardation layer
40: Adhesive layer
100: polarizer
200:
圖1係表示使用加熱輥之乾燥收縮處理之一例之概略圖。 圖2係本發明之一實施方式之偏光板之概略剖視圖。 圖3係本發明之一實施方式之偏光板之概略剖視圖。 圖4係本發明之一實施方式之偏光板之概略剖視圖。 Fig. 1 is a schematic diagram showing an example of drying shrinkage treatment using a heating roll. Fig. 2 is a schematic cross-sectional view of a polarizing plate according to an embodiment of the present invention. Fig. 3 is a schematic cross-sectional view of a polarizing plate according to an embodiment of the present invention. Fig. 4 is a schematic cross-sectional view of a polarizing plate according to an embodiment of the present invention.
10:偏光膜 10: Polarizing film
12:第1保護層 12: The first protective layer
14:第2保護層 14: The second protective layer
100:偏光板 100: polarizer
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2021
- 2021-01-22 JP JP2021008757A patent/JP2022112800A/en active Pending
- 2021-12-23 CN CN202180091353.5A patent/CN116940872A/en active Pending
- 2021-12-23 WO PCT/JP2021/047760 patent/WO2022158234A1/en active Application Filing
- 2021-12-23 KR KR1020237024443A patent/KR20230130017A/en unknown
-
2022
- 2022-01-17 TW TW111101823A patent/TW202238185A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| KR20230130017A (en) | 2023-09-11 |
| WO2022158234A1 (en) | 2022-07-28 |
| JP2022112800A (en) | 2022-08-03 |
| CN116940872A (en) | 2023-10-24 |
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