TW202108383A - Polarizing film, polarizing plate, and method for producing said polarizing film - Google Patents
Polarizing film, polarizing plate, and method for producing said polarizing film Download PDFInfo
- Publication number
- TW202108383A TW202108383A TW109118842A TW109118842A TW202108383A TW 202108383 A TW202108383 A TW 202108383A TW 109118842 A TW109118842 A TW 109118842A TW 109118842 A TW109118842 A TW 109118842A TW 202108383 A TW202108383 A TW 202108383A
- Authority
- TW
- Taiwan
- Prior art keywords
- polarizing film
- treatment
- based resin
- manufacturing
- pva
- Prior art date
Links
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
- B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Polarising Elements (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本發明涉及偏光膜、偏光板、及該偏光膜之製造方法。The present invention relates to a polarizing film, a polarizing plate, and a manufacturing method of the polarizing film.
在代表性之影像顯示裝置的液晶顯示裝置中,依據其影像形成方式而於液晶單元的兩側配置有偏光膜。作為偏光膜之製造方法,例如已提出有一種將具有樹脂基材與聚乙烯醇(PVA)系樹脂層之積層體延伸,接著施以染色處理,以在樹脂基材上獲得偏光膜的方法(例如專利文獻1)。藉由這種方法可獲得厚度較薄的偏光膜,所以能對近年之影像顯示裝置的薄型化有所貢獻而備受矚目。但,對薄型偏光膜要求在高溫高濕環境下之耐久性能更提升。In the liquid crystal display device, which is a representative image display device, polarizing films are arranged on both sides of the liquid crystal cell according to the image forming method. As a manufacturing method of a polarizing film, for example, a method has been proposed in which a laminate having a resin substrate and a polyvinyl alcohol (PVA) resin layer is stretched, and then dyed to obtain a polarizing film on the resin substrate ( For example, Patent Document 1). By this method, a thinner polarizing film can be obtained, so it can contribute to the thinning of image display devices in recent years and has attracted attention. However, thin polarizing films are required to have higher durability in high temperature and high humidity environments.
先前技術文獻 專利文獻 專利文獻1:日本特開2001-343521號公報Prior art literature Patent literature Patent Document 1: Japanese Patent Application Publication No. 2001-343521
發明欲解決之課題 本發明是為了解決上述以往之課題而成者,其主要目的在於提供一種在高溫高濕環境下之耐久性優異的偏光膜、偏光板、及所述偏光膜之製造方法。The problem to be solved by the invention The present invention was made in order to solve the aforementioned problems in the past, and its main purpose is to provide a polarizing film, a polarizing plate, and a method for manufacturing the polarizing film that are excellent in durability in a high-temperature and high-humidity environment.
用以解決課題之手段 本發明之偏光膜係以含碘之聚乙烯醇系樹脂薄膜構成;並且,其在溫度60℃及相對濕度95%下進行240小時之耐久試驗後,波長600nm下之吸光度Abs240 相對於該耐久試驗前之吸光度Abs0 滿足以下關係: Abs240 /Abs0 >1.00 在一實施形態中,上述偏光膜之單體透射率為43.0%以上。 在一實施形態中,上述偏光膜的厚度為8μm以下。 根據本發明之另一面向提供一種偏光板。該偏光板具有上述偏光膜與配置於該偏光膜之至少一側的保護層。 根據本發明之又另一面向提供一種上述偏光膜之製造方法。該方法包含以下步驟:於長條狀熱塑性樹脂基材之單側形成聚乙烯醇系樹脂層而製成積層體;將該積層體延伸及染色,以將該聚乙烯醇系樹脂層製成偏光膜;及,使該偏光膜接觸pH在3.0以下之處理液。 在一實施形態中,上述製造方法包含:於上述偏光膜塗佈上述處理液。在另一實施形態中,上述製造方法包含:將上述偏光膜浸漬於上述處理液中。 在一實施形態中,上述製造方法係於上述熱塑性樹脂基材之單側形成含碘化物或氯化鈉與聚乙烯醇系樹脂之聚乙烯醇系樹脂層。 在一實施形態中,上述製造方法包含下述步驟:對上述積層體依序施行空中輔助延伸處理、染色處理、水中延伸處理與乾燥收縮處理,該乾燥收縮處理係一邊將上述積層體沿長邊方向輸送一邊加熱,藉此使其於寬度方向收縮2%以上。 在一實施形態中,上述乾燥收縮處理係使用加熱輥來進行。此時,上述加熱輥之溫度譬如為60℃~120℃。 本發明之另一偏光膜之製造方法包含以下步驟:將聚乙烯醇系樹脂薄膜延伸及染色,以將該聚乙烯醇系樹脂薄膜製成偏光膜;及,使該偏光膜接觸pH在3.0以下之處理液。Means to Solve the Problem The polarizing film of the present invention is composed of a polyvinyl alcohol resin film containing iodine; and after 240 hours of durability test at a temperature of 60°C and a relative humidity of 95%, the absorbance at a wavelength of 600nm Abs 240 satisfies the following relationship with respect to the absorbance Abs 0 before the endurance test: Abs 240 /Abs 0 >1.00 In one embodiment, the monomer transmittance of the polarizing film is 43.0% or more. In one embodiment, the thickness of the polarizing film is 8 μm or less. According to another aspect of the present invention, a polarizing plate is provided. The polarizing plate has the above-mentioned polarizing film and a protective layer arranged on at least one side of the polarizing film. According to yet another aspect of the present invention, a manufacturing method of the above-mentioned polarizing film is provided. The method includes the following steps: forming a polyvinyl alcohol-based resin layer on one side of a long-shaped thermoplastic resin substrate to form a laminated body; extending and dyeing the laminated body to make the polyvinyl alcohol-based resin layer into a polarized light Film; and, make the polarizing film contact a treatment solution with a pH below 3.0. In one embodiment, the above-mentioned manufacturing method includes applying the above-mentioned treatment liquid to the above-mentioned polarizing film. In another embodiment, the above-mentioned manufacturing method includes immersing the above-mentioned polarizing film in the above-mentioned treatment liquid. In one embodiment, the manufacturing method described above is to form a polyvinyl alcohol-based resin layer containing iodide or sodium chloride and a polyvinyl alcohol-based resin on one side of the thermoplastic resin substrate. In one embodiment, the above-mentioned manufacturing method includes the steps of sequentially performing aerial auxiliary stretching treatment, dyeing treatment, underwater stretching treatment, and drying shrinkage treatment on the layered body. It is heated while conveying in the direction, so that it shrinks by more than 2% in the width direction. In one embodiment, the above-mentioned drying and shrinking treatment is performed using a heated roller. At this time, the temperature of the heating roller is, for example, 60°C to 120°C. Another method of manufacturing a polarizing film of the present invention includes the following steps: stretching and dyeing a polyvinyl alcohol-based resin film to make the polyvinyl alcohol-based resin film into a polarizing film; and making the polarizing film contact pH below 3.0的处理液。 The treatment fluid.
發明效果 根據本發明,藉由使偏光膜接觸pH在3.0以下之處理液,可獲得在高溫高濕環境下之耐久性優異的偏光膜。具體而言,本發明之實施形態之偏光膜在溫度60℃及相對濕度95%下進行240小時之耐久試驗後,波長600nm下之吸光度Abs240 相對於該耐久試驗前之吸光度Abs0 滿足以下關係: Abs240 /Abs0 >1.00 亦即,本發明之實施形態之偏光膜在波長600nm下之吸光度經加熱加濕耐久試驗會增加。此意味著本發明之實施形態之偏光膜之偏光性能在高溫高濕環境下會提升。一般預想偏光膜之偏光性能通常在高溫高濕環境下會降低,但本發明之實施形態之偏光膜在高溫高濕環境下之耐久性的提升乃不可預期且很優異。Effects of the Invention According to the present invention, by contacting the polarizing film with a treatment solution having a pH of 3.0 or less, a polarizing film having excellent durability under a high temperature and high humidity environment can be obtained. Specifically, after the polarizing film of the embodiment of the present invention is subjected to an endurance test at a temperature of 60°C and a relative humidity of 95% for 240 hours, the absorbance Abs 240 at a wavelength of 600 nm relative to the absorbance Abs 0 before the endurance test satisfies the following relationship : Abs 240 /Abs 0 >1.00 That is, the absorbance of the polarizing film of the embodiment of the present invention at a wavelength of 600 nm will increase after heating and humidifying durability test. This means that the polarization performance of the polarizing film of the embodiment of the present invention will be improved in a high temperature and high humidity environment. It is generally expected that the polarization performance of the polarizing film will generally decrease in a high temperature and high humidity environment, but the improvement of the durability of the polarizing film of the embodiment of the present invention in a high temperature and high humidity environment is unexpected and excellent.
以下說明本發明之實施形態,惟本發明不受該等實施形態限定。The following describes embodiments of the present invention, but the present invention is not limited by these embodiments.
A.偏光膜 本發明之實施形態之偏光膜係以含碘之聚乙烯醇(PVA)系樹脂薄膜構成;並且其在溫度60℃及相對濕度95%下進行240小時之耐久試驗後,波長600nm下之吸光度Abs240 相對於該耐久試驗前之吸光度Abs0 滿足以下關係。 Abs240 /Abs0 >1.00 其表示本發明之實施形態之偏光膜中,在600nm附近具有吸收的PVA-I5 - 錯合物即便在加熱加濕耐久試驗中亦不會被破壞,反而還會增加。PVA-I5 - 錯合物在高溫高濕環境下會被破壞,而預想偏光膜之偏光性能通常在高溫高濕環境下會降低,但本發明之實施形態之偏光膜的上述優異之耐久性乃不可預期且很優異。理論上雖尚不明確,但所述優異耐久性可藉由使偏光膜接觸pH在3.0以下之處理液來實現。Abs240 /Abs0 宜為1.05以上,較宜為1.10以上,更宜為1.15以上,尤宜為1.20以上,特別宜為1.25以上。Abs240 /Abs0 之上限可為例如2.00。此外,吸光度代表上為正交吸光度。正交吸光度可基於後述求取偏光度時測定之正交透射率Tc,利用下述式來求得。 正交吸光度=log10(100/Tc) 另,耐久試驗前之吸光度Abs0 係偏光膜在一般狀態下之吸光度,偏光膜在波長600nm下之Abs0 例如小於5.0,宜為4.3以下,更宜為4.0以下。Abs0 之下限可為例如2.0。A. Polarizing film The polarizing film of the embodiment of the present invention is composed of a polyvinyl alcohol (PVA) resin film containing iodine; and after being subjected to a durability test at a temperature of 60°C and a relative humidity of 95% for 240 hours, the wavelength is 600nm The absorbance Abs 240 below satisfies the following relationship with respect to the absorbance Abs 0 before the endurance test. Abs 240 / Abs 0> 1.00 which represents a polarizing film of the embodiment of the present invention having absorption in the vicinity of 600nm PVA-I 5 - complexes will not be damaged even in the heated humidification durability test, but also increase. PVA-I 5 - complexes will be destroyed at high temperature and high-humidity environment, and the expected polarization of the polarized film typically decreases at high temperature and high-humidity environment, but the durability of the polarizing film is excellent in the above-described embodiment of the present invention It is unpredictable and excellent. Although it is not clear in theory, the excellent durability can be achieved by contacting the polarizing film with a treatment solution with a pH of 3.0 or less. Abs 240 /Abs 0 is preferably 1.05 or more, more preferably 1.10 or more, more preferably 1.15 or more, particularly preferably 1.20 or more, particularly preferably 1.25 or more. The upper limit of Abs 240 /Abs 0 can be, for example, 2.00. In addition, the absorbance represents the orthogonal absorbance. The cross absorbance can be obtained by the following formula based on the cross transmittance Tc measured when obtaining the polarization degree described later. Orthogonal absorbance = log10 (100 / Tc) Also, the absorbance Abs 0 based polarizing absorbance before the durability test under the general condition of the polarizing film at a wavelength of 600nm Abs 0 for example less than 5.0, should be 4.3 or less, more suitably from Below 4.0. The lower limit of Abs 0 may be 2.0, for example.
偏光膜之厚度宜為8µm以下,7µm以下較佳,5µm以下更佳,3µm以下尤佳。偏光膜厚度之下限在一實施形態中可為1µm,在另一實施形態中可為2µm。所述厚度,如後述可藉由使用例如樹脂基材與塗佈形成於該樹脂基材之PVA系樹脂層的積層體來製作偏光膜來實現。由單一樹脂薄膜製作偏光膜時,偏光膜之厚度例如可為12µm~35µm。The thickness of the polarizing film is preferably 8 µm or less, preferably 7 µm or less, more preferably 5 µm or less, and particularly preferably 3 µm or less. The lower limit of the thickness of the polarizing film may be 1 μm in one embodiment, and may be 2 μm in another embodiment. The thickness can be achieved by producing a polarizing film using, for example, a laminate of a resin substrate and a PVA-based resin layer formed on the resin substrate by coating, as described later. When the polarizing film is made from a single resin film, the thickness of the polarizing film can be, for example, 12µm~35µm.
偏光膜宜在波長380nm~780nm之任一波長下顯示吸收二色性。偏光膜的單體透射率宜為42.0%以上,較宜為42.5%以上,更宜為43.0%以上,尤宜為43.5%以上,特別宜為44.0%以上。另一方面,單體透射率宜為47.0%以下,更宜為46.0%以下。偏光膜的偏光度宜為99.95%以上,較宜為99.99%以上。另一方面,偏光度宜為99.998%以下。根據本發明之實施形態,如此一來可兼顧高單體透射率與高偏光度,且如上述可實現在高溫高濕環境下優異之耐久性。上述單體透射率代表上係使用紫外線可見光分光光度計來測定並進行視感度校正所得之Y值。又,單體透射率是將偏光板之一表面之折射率換算為1.50,並將另一表面之折射率換算為1.53時的值。上述偏光度代表上係基於使用紫外線可見光分光光度計測定並進行視感度校正所得之平行透射率Tp及正交透射率Tc,透過下述式來求得。 偏光度(%)={(Tp-Tc)/(Tp+Tc)}1/2 ×100The polarizing film should exhibit absorption dichroism at any wavelength from 380nm to 780nm. The monomer transmittance of the polarizing film is preferably 42.0% or more, more preferably 42.5% or more, more preferably 43.0% or more, particularly preferably 43.5% or more, particularly preferably 44.0% or more. On the other hand, the transmittance of the monomer is preferably 47.0% or less, and more preferably 46.0% or less. The degree of polarization of the polarizing film is preferably over 99.95%, more preferably over 99.99%. On the other hand, the degree of polarization is preferably 99.998% or less. According to the embodiment of the present invention, it is possible to achieve both high monomer transmittance and high polarization degree, and as described above, it is possible to achieve excellent durability in a high temperature and high humidity environment. The above monomer transmittance represents the Y value obtained by measuring and calibrating the visual sensitivity using an ultraviolet-visible spectrophotometer. In addition, the single transmittance is a value obtained when the refractive index of one surface of the polarizing plate is converted to 1.50, and the refractive index of the other surface is converted to 1.53. The above-mentioned degree of polarization is representatively calculated based on the parallel transmittance Tp and the orthogonal transmittance Tc obtained by measuring with an ultraviolet-visible light spectrophotometer and performing visual sensitivity correction, using the following equations. Polarization (%)={(Tp-Tc)/(Tp+Tc)} 1/2 ×100
在一實施形態中,8µm以下的薄型偏光膜之透射率(單體透射率)代表上係以偏光膜(表面之折射率:1.53)與保護層(保護薄膜)(折射率:1.50)之積層體為測定對象,使用紫外線可見光分光光度計來測定。依偏光膜表面之折射率及/或保護層之與空氣界面接觸的表面之折射率,在各層界面上的反射率會有所變化,結果會有透射率之測定值產生變化之情形。因此,舉例而言在使用折射率非1.50之保護層時,亦可依保護層之與空氣界面接觸的表面之折射率來校正透射率之測定值。具體而言,透射率之校正值C係使用保護層與空氣層之界面上與透射軸平行的偏光之反射率R1 (透射軸反射率),利用以下式來表示。 C=R1 -R0 R0 =((1.50-1)2 /(1.50+1)2 )×(T1 /100) R1 =((n1 -1)2 /(n1 +1)2 )×(T1 /100) 在此,R0 為使用折射率為1.50之保護層時之透射軸反射率,n1 為所使用之保護層的折射率,而T1 為偏光膜之透射率。舉例而言,在使用表面折射率為1.53之基材(環烯烴系薄膜、附硬塗層之薄膜等)作為保護層時,校正量C為約0.2%。此時,將測得之透射率加上0.2%,可將表面折射率為1.53之偏光膜換算成使用表面折射率為1.50之保護層時之透射率。另,經依上述式進行計算,在使偏光膜之透射率T1 變化了2%後之校正值C的變化量為0.03%以下,故而偏光膜之透射率對校正值C之值的影響是有限的。又,保護層具有表面反射以外之吸收時,可因應吸收量來進行適當的校正。In one embodiment, the transmittance (single transmittance) of a thin polarizing film of 8 µm or less represents a combination of a polarizing film (surface refractive index: 1.53) and a protective layer (protective film) (refractive index: 1.50) The body is the object of measurement, and it is measured using an ultraviolet-visible spectrophotometer. Depending on the refractive index of the polarizing film surface and/or the refractive index of the surface of the protective layer in contact with the air interface, the reflectance at the interface of each layer will vary, and as a result, the measured value of the transmittance will change. Therefore, for example, when a protective layer with a refractive index other than 1.50 is used, the measured value of transmittance can also be corrected according to the refractive index of the surface of the protective layer in contact with the air interface. Specifically, the transmittance correction value C uses the reflectance R 1 (transmission axis reflectance) of polarized light parallel to the transmission axis on the interface between the protective layer and the air layer, and is expressed by the following formula. 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 reflectance of the transmission axis when a protective layer with a refractive index of 1.50 is used, n 1 is the refractive index of the protective layer used, and T 1 is the transmission of the polarizing film rate. For example, when a substrate with a surface refractive index of 1.53 (a cycloolefin-based film, a film with a hard coat layer, etc.) is used as a protective layer, the correction amount C is about 0.2%. At this time, 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 a protective layer with a surface refractive index of 1.50 is used. In addition, after calculating according to the above formula, the change amount of the correction value C after changing the transmittance T 1 of the polarizing film by 2% is 0.03% or less, so the influence of the transmittance of the polarizing film on the value of the correction value C is limited. In addition, when the protective layer has absorption other than surface reflection, it can be appropriately corrected according to the amount of absorption.
偏光膜可用單一樹脂薄膜來製作,亦可用二層以上之積層體來製作。使用積層體獲得之偏光膜的具體例,可舉出使用樹脂基材與經塗佈形成於該樹脂基材之PVA系樹脂層的積層體而獲得之偏光膜。使用樹脂基材與經塗佈形成於該樹脂基材之PVA系樹脂層的積層體而獲得之偏光膜,例如可以藉由以下方式來製作:將PVA系樹脂溶液塗佈於樹脂基材,並使其乾燥而於樹脂基材上形成PVA系樹脂層,而獲得樹脂基材與PVA系樹脂層的積層體;及,將該積層體延伸及染色而將PVA系樹脂層製成偏光膜。在本發明之實施形態中,係使偏光膜接觸pH在3.0以下之處理液。藉此,可實現上述之在高溫高濕環境下優異之耐久性。宜於樹脂基材之單側形成包含鹵化物與聚乙烯醇系樹脂之聚乙烯醇系樹脂層。延伸在代表上包含使積層體浸漬於硼酸水溶液中並延伸。並且視需要,延伸可更包含在硼酸水溶液中進行延伸前在高溫(例如95℃以上)下將積層體進行空中延伸。並且,在本實施形態中,較佳為積層體係供於一邊沿長邊方向輸送一邊加熱藉此使其於寬度方向收縮2%以上之乾燥收縮處理。代表上,本實施形態之製造方法包含對積層體依序施行空中輔助延伸處理、染色處理、水中延伸處理與乾燥收縮處理。藉由導入輔助延伸,即便是在將PVA塗佈於熱塑性樹脂上時仍可提升PVA之結晶性,而可達成高光學特性。又,同時事先提高PVA之定向性,可防止在之後的染色步驟或延伸步驟中浸漬於水中時,PVA之定向性降低或溶解等問題,而可達成高光學特性。並且,將PVA系樹脂層浸漬於液體中時,相較於PVA系樹脂層不含鹵化物之情況,更能抑制聚乙烯醇分子之定向紊亂及定向性之降低。因此,可提升經由染色處理及水中延伸處理等將積層體浸漬於液體中來進行的處理步驟而獲得之偏光膜的光學特性。並且,透過乾燥收縮處理使積層體於寬度方向收縮,可提升光學特性。可以直接使用所得樹脂基材/偏光膜之積層體(即,亦可將樹脂基材作為偏光膜之保護層),亦可從樹脂基材/偏光膜之積層體剝離樹脂基材並於該剝離面按目的積層任意適當的保護層後來使用。關於偏光膜之製造方法的詳細內容將於C項說明。The polarizing film can be made of a single resin film, or a laminate of two or more layers. Specific examples of the polarizing film obtained using the laminate include a polarizing film obtained using a laminate of a resin substrate and a PVA-based resin layer formed on the resin substrate by coating. A polarizing film obtained by using a laminate of a resin substrate and a PVA-based resin layer formed on the resin substrate by coating can be produced by, for example, applying a PVA-based resin solution to the resin substrate, and It is dried to form a PVA-based resin layer on the resin substrate to obtain a laminate of the resin substrate and the PVA-based resin layer; and the laminate is stretched and dyed to form the PVA-based resin layer into a polarizing film. In the embodiment of the present invention, the polarizing film is brought into contact with a treatment solution whose pH is below 3.0. Thereby, the above-mentioned excellent durability under high temperature and high humidity environment can be realized. It is suitable to form a polyvinyl alcohol resin layer containing halide and polyvinyl alcohol resin on one side of the resin substrate. Stretching typically includes immersing the laminate in a boric acid aqueous solution and stretching. Furthermore, if necessary, stretching may further include stretching the laminated body in the air at a high temperature (for example, 95° C. or higher) before stretching in a boric acid aqueous solution. In addition, in this embodiment, it is preferable that the laminated system is subjected to a drying shrinkage treatment in which it is heated while being transported in the longitudinal direction to shrink it by 2% or more in the width direction. Representatively, the manufacturing method of this embodiment includes sequentially performing aerial auxiliary stretching treatment, dyeing treatment, underwater stretching treatment, and drying shrinkage treatment on the laminate. By introducing auxiliary extension, the crystallinity of PVA can be improved even when PVA is coated on the thermoplastic resin, and high optical properties can be achieved. In addition, at the same time, the orientation of PVA can be improved in advance to prevent problems such as degradation or dissolution of the orientation of PVA when immersed in water in the subsequent dyeing step or stretching step, and high optical properties can be achieved. In addition, when the PVA-based resin layer is immersed in a liquid, compared to the case where the PVA-based resin layer does not contain halide, it is possible to suppress the orientation disorder of the polyvinyl alcohol molecules and the decrease in orientation. Therefore, it is possible to improve the optical properties of the polarizing film obtained by the treatment step of immersing the laminate in a liquid, such as dyeing treatment and underwater stretching treatment. In addition, by drying and shrinking the laminate in the width direction, the optical properties can be improved. The obtained resin substrate/polarizing film laminate can be used directly (that is, the resin substrate can also be used as the protective layer of the polarizing film), or the resin substrate can be peeled from the resin substrate/polarizing film laminate and then peeled off. Lay any appropriate protective layer according to the purpose and use it later. The detailed content of the manufacturing method of the polarizing film will be explained in item C.
B.偏光板
圖1係本發明一實施形態之偏光板的概略截面圖。偏光板100具有:偏光膜10、配置於偏光膜10之一側的第1保護層20及配置於偏光膜10之另一側的第2保護層30。偏光膜10係於上述A項所說明之本發明之偏光膜。亦可省略第1保護層20及第2保護層30之中其中一保護層。另,如上述,第1保護層及第2保護層之中,亦可有一者為用於上述偏光膜之製造的樹脂基材。B. Polarizing plate
Fig. 1 is a schematic cross-sectional view of a polarizing plate according to an embodiment of the present invention. The
第1及第2保護薄膜係以可作為偏光膜之保護層使用的任意適當的薄膜形成。成為該薄膜之主成分的材料之具體例,可舉出三醋酸纖維素(TAC)等之纖維素系樹脂、聚酯系、聚乙烯醇系、聚碳酸酯系、聚醯胺系、聚醯亞胺系、聚醚碸系、聚碸系、聚苯乙烯系、聚降莰烯系、聚烯烴系、(甲基)丙烯酸系及乙酸酯系等之透明樹脂等。又,還可舉出(甲基)丙烯酸系、胺甲酸酯系、(甲基)丙烯酸胺甲酸酯系、環氧系、聚矽氧系等熱硬化型樹脂或紫外線硬化型樹脂等。其他還可舉出例如矽氧烷系聚合物等之玻璃質系聚合物。並且,亦可使用日本特開2001-343529號公報(WO01/37007)所記載之聚合物薄膜。作為該薄膜之材料,例如可以使用含有在側鏈具有取代或非取代之醯亞胺基的熱塑性樹脂與在側鏈具有取代或非取代之苯基以及腈基的熱塑性樹脂之樹脂組成物,例如可舉出具有由異丁烯與N-甲基馬來醯亞胺構成之交替共聚物及丙烯腈-苯乙烯共聚物之樹脂組成物。該聚合物薄膜例如可為上述樹脂組成物之擠製成形物。The first and second protective films are formed of any suitable film that can be used as a protective layer of a polarizing film. Specific examples of the material that becomes the main component of the film include cellulose resins such as cellulose triacetate (TAC), polyesters, polyvinyl alcohols, polycarbonates, polyamides, and polyamides. Transparent resins such as imine-based, polyether-based, poly-based, polystyrene, polynorbornene, polyolefin, (meth)acrylic, and acetate-based transparent resins, etc. In addition, thermosetting resins such as (meth)acrylic, urethane, (meth)acrylate urethane, epoxy, and silicone resins, or ultraviolet curable resins, etc. may also be mentioned. Other examples include glassy polymers such as silicone polymers. In addition, the polymer film described in JP 2001-343529 A (WO01/37007) can also be used. As the material of the film, for example, a resin composition containing a thermoplastic resin having a substituted or unsubstituted iminium group in the side chain and a thermoplastic resin having a substituted or unsubstituted phenyl group and a nitrile group in the side chain can be used, for example, Examples include resin compositions having alternating copolymers composed of isobutylene and N-methylmaleimide and acrylonitrile-styrene copolymers. The polymer film may be, for example, an extruded product of the above-mentioned resin composition.
在將偏光板100應用於影像顯示裝置時,配置於與顯示面板相反之側的保護層(外側保護層)之厚度代表上為300μm以下,宜為100μm以下,更宜為5μm~80μm,又更宜為10μm~60μm。另外,在施有表面處理時,外側保護層之厚度係包含表面處理層之厚度的厚度。When the
在將偏光板100應用於影像顯示裝置時,配置於顯示面板側的保護層(內側保護層)之厚度宜為5μm~200μm,更宜為10μm~100μm,又更宜為10μm~60μm。在一實施形態中,內側保護層係具有任意適當之相位差值的相位差層。此時,相位差層之面內相位差Re(550)例如為110nm~150nm。「Re(550)」為在23℃下以波長550nm的光測定之面內相位差,可藉由式:Re=(nx-ny)×d來求得。在此,「nx」為面內折射率成最大之方向(亦即慢軸方向)的折射率,「ny」為在面內與慢軸正交之方向(亦即快軸方向)的折射率,「nz」為厚度方向的折射率,「d」為層(薄膜)之厚度(nm)。When the
C.偏光膜之製造方法 本發明一實施形態之偏光膜之製造方法包含以下步驟:於長條狀熱塑性樹脂基材之單側塗佈PVA系樹脂溶液並乾燥,形成PVA系樹脂層,而製成積層體;將該積層體延伸及染色,以將PVA系樹脂層製成偏光膜;及,使該偏光膜接觸pH在3.0以下之處理液。藉由使偏光膜接觸pH在3.0以下之處理液,可實現在高溫高濕環境下之耐久性優異的偏光膜。較佳為PVA系樹脂溶液更包含鹵化物。較佳為上述製造方法包含下述步驟:對積層體依序施行空中輔助延伸處理、染色處理、水中延伸處理與乾燥收縮處理,該乾燥收縮處理係一邊將該積層體沿長邊方向輸送一邊加熱,藉此使其於寬度方向收縮2%以上。PVA系樹脂溶液(結果而言為PVA系樹脂層)中之鹵化物含量相對於PVA系樹脂100重量份宜為5重量份~20重量份。乾燥收縮處理宜使用加熱輥進行處理,且加熱輥溫度宜為60℃~120℃。積層體進行乾燥收縮處理所得寬度方向之收縮率宜為2%以上。根據所述製造方法可獲得在上述A項所說明之偏光膜。尤其是藉由下述方式可獲得具有優異光學特性(代表上為單體透射率及單位偏光度)之偏光膜:製作包含含有鹵化物之PVA系樹脂層的積層體後,將上述積層體之延伸進行包含空中輔助延伸及水中延伸的多階段延伸,再將延伸後之積層體以加熱輥進行加熱。C. Manufacturing method of polarizing film The manufacturing method of the polarizing film of one embodiment of the present invention includes the following steps: apply a PVA-based resin solution on one side of a long-shaped thermoplastic resin substrate and dry to form a PVA-based resin layer to form a laminate; Body extension and dyeing to make the PVA-based resin layer into a polarizing film; and, contacting the polarizing film with a treatment solution with a pH below 3.0. By contacting the polarizing film with a treatment solution with a pH below 3.0, a polarizing film with excellent durability under high temperature and high humidity environments can be realized. Preferably, the PVA-based resin solution further contains a halide. Preferably, the above-mentioned manufacturing method includes the following steps: sequentially performing aerial auxiliary stretching treatment, dyeing treatment, underwater stretching treatment, and drying shrinkage treatment on the layered body, and the drying and shrinking treatment system heats the layered body while conveying the layered body in the longitudinal direction. , Thereby making it shrink by more than 2% in the width direction. The halide content in the PVA-based resin solution (the PVA-based resin layer as a result) is preferably 5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the PVA-based resin. The drying shrinkage should be treated with a heating roller, and the temperature of the heating roller should be 60°C~120°C. The shrinkage rate in the width direction of the laminate after drying and shrinking is preferably 2% or more. According to the manufacturing method, the polarizing film described in the above item A can be obtained. In particular, a polarizing film with excellent optical properties (representatively, monomer transmittance and unit polarization) can be obtained by the following method: After making a laminate containing a PVA-based resin layer containing a halide, the laminate The stretching performs multi-stage stretching including aerial auxiliary stretching and underwater stretching, and then the stretched laminate is heated by heating rollers.
C-1.製作積層體 製作熱塑性樹脂基材與PVA系樹脂層之積層體的方法可採用任意適當之方法。較宜為將含有鹵化物與PVA系樹脂之塗佈液塗佈於熱塑性樹脂基材之表面並乾燥,藉此於熱塑性樹脂基材上形成PVA系樹脂層。如上述,PVA系樹脂層中之鹵化物含量宜相對於PVA系樹脂100重量份為5重量份~20重量份。C-1. Making multilayer body Any appropriate method can be adopted as a method of producing a laminate of a thermoplastic resin base material and a PVA-based resin layer. Preferably, a coating solution containing halide and PVA-based resin is applied to the surface of the thermoplastic resin substrate and dried, thereby forming a PVA-based resin layer on the thermoplastic resin substrate. As mentioned above, the halide content in the PVA-based resin layer is preferably 5 parts by weight to 20 parts by weight relative to 100 parts by weight of the PVA-based resin.
塗佈液之塗佈方法可採用任意適當的方法。例如可舉出輥塗法、旋塗法、線棒塗佈法、浸塗法、模塗法、簾塗法、噴塗法、刮刀式塗佈法(逗號塗佈法等)等。上述塗佈液之塗佈、乾燥溫度宜為50℃以上。Any appropriate method can be adopted for the coating method of the coating liquid. For example, a roll coating method, a spin coating method, a wire bar coating method, a dip coating method, a die coating method, a curtain coating method, a spray coating method, a knife coating method (comma coating method, etc.) etc. are mentioned. The coating and drying temperature of the above-mentioned coating liquid is preferably 50°C or higher.
PVA系樹脂層之厚度宜為3μm~40μm,更宜為3μm~20μm。The thickness of the PVA-based resin layer is preferably 3μm-40μm, more preferably 3μm-20μm.
在形成PVA系樹脂層之前,可對熱塑性樹脂基材施行表面處理(例如電暈處理等),也可於熱塑性樹脂基材上形成易接著層。藉由進行所述處理,可提升熱塑性樹脂基材與PVA系樹脂層之密著性。Before forming the PVA-based resin layer, the thermoplastic resin substrate may be subjected to surface treatment (for example, corona treatment, etc.), or an easy-adhesion layer may be formed on the thermoplastic resin substrate. By performing the above treatment, the adhesion between the thermoplastic resin substrate and the PVA-based resin layer can be improved.
C-1-1.熱塑性樹脂基材 熱塑性樹脂基材可採用任意適當的熱塑性樹脂薄膜。關於熱塑性樹脂薄膜基材的詳細內容,例如記載於日本特開2012-73580號公報。本說明書中係援用該公報整體之記載作為參考。C-1-1. Thermoplastic resin substrate As the thermoplastic resin substrate, any appropriate thermoplastic resin film can be used. The details of the thermoplastic resin film substrate are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580. In this manual, the entirety of the bulletin is cited as a reference.
C-1-2.塗佈液 塗佈液係如上述包含鹵化物與PVA系樹脂。上述塗佈液代表上係使上述鹵化物及上述PVA系樹脂溶解於溶劑而成之溶液。作為溶劑,可舉例如水、二甲亞碸、二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯啶酮、各種甘醇類、三羥甲丙烷等多元醇類、伸乙二胺、二伸乙三胺等胺類。該等可單獨使用或可將二種以上組合來使用。該等中又以水為佳。相對於溶劑100重量份,溶液之PVA系樹脂濃度宜為3重量份~20重量份。只要為所述樹脂濃度,便可形成密著於熱塑性樹脂基材且均勻的塗佈膜。塗佈液中之鹵化物含量相對於PVA系樹脂100重量份宜為5重量份~20重量份。C-1-2. Coating liquid The coating liquid system contains a halide and a PVA-based resin as described above. The above-mentioned coating liquid represents a solution obtained by dissolving the above-mentioned halide and the above-mentioned PVA-based resin in a solvent. As the solvent, for example, water, dimethyl sulfide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, various glycols, trimethylolpropane and other polyols, ethylene oxide Amines such as diamine and diethylenetriamine. These can be used alone or in combination of two or more kinds. Among these, water is better. Relative to 100 parts by weight of the solvent, the concentration of the PVA-based resin in the solution is preferably 3 parts by weight to 20 parts by weight. As long as it is the resin concentration, a uniform coating film that adheres to the thermoplastic resin substrate can be formed. The halide content in the coating liquid is preferably 5 parts by weight to 20 parts by weight relative to 100 parts by weight of the PVA-based resin.
塗佈液中亦可摻混添加劑。添加劑可舉如塑化劑、界面活性劑等。可塑劑可舉例如乙二醇或丙三醇等多元醇。界面活性劑可舉例如非離子性界面活性劑。該等可為了進一步提升所得PVA系樹脂層的均勻性或染色性、延伸性而使用。Additives can also be blended in the coating liquid. Examples of additives include plasticizers and surfactants. Examples of the plasticizer include polyhydric alcohols such as ethylene glycol and glycerol. Examples of the surfactant include nonionic surfactants. These can be used in order to further improve the uniformity, dyeability, and extensibility of the obtained PVA-based resin layer.
上述PVA系樹脂可採用任意適當的樹脂。可舉例如聚乙烯醇及乙烯-乙烯醇共聚物。聚乙烯醇可藉由將聚乙酸乙烯酯皂化而得。乙烯-乙烯醇共聚物可藉由將乙烯-乙酸乙烯酯共聚物皂化而得。PVA系樹脂之皂化度通常為85莫耳%~100莫耳%,宜為95.0莫耳%~99.95莫耳%,更宜為99.0莫耳%~99.93莫耳%。皂化度可依JIS K 6726-1994而求得。藉由使用所述皂化度的PVA系樹脂,可獲得耐久性優異的偏光膜。皂化度太高時,會有膠化之虞。Any appropriate resin can be adopted for the above-mentioned PVA-based resin. Examples include polyvinyl alcohol and ethylene-vinyl alcohol copolymers. 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 saponification degree of PVA resin is usually 85 mol%~100 mol%, preferably 95.0 mol%~99.95 mol%, and more preferably 99.0 mol%~99.93 mol%. The degree of saponification can be determined in accordance with JIS K 6726-1994. By using the PVA-based resin with the degree of saponification, a polarizing film with excellent durability can be obtained. When the saponification degree is too high, there is a risk of gelation.
PVA系樹脂的平均聚合度可按目的適當選擇。平均聚合度通常為1000~10000,宜為1200~4500,更宜為1500~4300。另,平均聚合度可按JIS K 6726-1994而求得。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 obtained in accordance with JIS K 6726-1994.
上述鹵化物可採用任意適當之鹵化物。可舉例如碘化物及氯化鈉。碘化物可舉例如碘化鉀、碘化鈉及碘化鋰。該等之中又以碘化鉀為佳。Any appropriate halide can be used as the above-mentioned halide. Examples include iodide and sodium chloride. Examples of iodides include potassium iodide, sodium iodide, and lithium iodide. Among these, potassium iodide is preferred.
塗佈液中之鹵化物量相對於PVA系樹脂100重量份宜為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。若鹵化物量相對於PVA系樹脂100重量份為大於20重量份,則會有鹵化物溢出而使最後獲得之偏光膜變白濁之情形。The amount of halide in the coating liquid is preferably 5 parts by weight to 20 parts by weight relative to 100 parts by weight of the PVA-based resin, and more preferably 10 parts by weight to 15 parts by weight relative to 100 parts by weight of the PVA-based resin. If the amount of halide is greater than 20 parts by weight relative to 100 parts by weight of the PVA-based resin, the halide may overflow and the resulting polarizing film may become cloudy.
一般而言,PVA系樹脂層經延伸,會使PVA樹脂層中之聚乙烯醇分子之定向性變高,但若將延伸後之PVA系樹脂層浸漬於含水之液體中,則會有聚乙烯醇分子之定向紊亂而定向性降低之情形。尤其是在對熱塑性樹脂與PVA系樹脂層之積層體進行硼酸水中延伸時,為了穩定熱塑性樹脂之延伸而在相對較高溫度下在硼酸水中將上述積層體進行延伸時,上述定向度降低之傾向很顯著。舉例而言,PVA薄膜單體在硼酸水中之延伸一般而言係在60℃下進行,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在70℃前後之溫度即較高溫度下進行,此時,延伸初始之PVA的定向性會在因水中延伸而上升之前的階段便降低。對此,藉由製作含有鹵化物之PVA系樹脂層與熱塑性樹脂基材之積層體,並將積層體於在硼酸水中進行延伸前在空氣中進行高溫延伸(輔助延伸),可促進輔助延伸後之積層體之PVA系樹脂層中的PVA系樹脂之結晶化。結果,在將PVA系樹脂層浸漬於液體中時,相較於PVA系樹脂層不含鹵化物之情況,更能抑制聚乙烯醇分子之定向紊亂及定向性之降低。藉此,可提升經染色處理及水中延伸處理等將積層體浸漬於液體中來進行的處理步驟而得之偏光膜的光學特性。Generally speaking, the extension of the PVA-based resin layer will increase the orientation of the polyvinyl alcohol molecules in the PVA resin layer. However, if the extended PVA-based resin layer is immersed in a water-containing liquid, there will be polyethylene A situation where the orientation of the alcohol molecules is disordered and the orientation is reduced. Especially when the laminate of thermoplastic resin and PVA-based resin layer is stretched in boric acid water, in order to stabilize the elongation of the thermoplastic resin, when the laminate is stretched in boric acid water at a relatively high temperature, the degree of orientation tends to decrease It's remarkable. For example, the extension of the PVA film monomer in boric acid water is generally performed at 60°C. In contrast, the extension of the laminate of A-PET (thermoplastic resin substrate) and PVA-based resin layer is performed at 70°C. The temperature before and after is performed at a higher temperature. At this time, the orientation of the PVA at the beginning of the extension will decrease in the stage before it rises due to the extension in the water. In this regard, by making a laminate of a halide-containing PVA-based resin layer and a thermoplastic resin substrate, and stretching the laminate in the air at a high temperature before stretching in boric acid water (assisted extension), the post-assisted extension can be promoted. Crystallization of the PVA resin in the PVA resin layer of the laminate. As a result, when the PVA-based resin layer is immersed in a liquid, compared to the case where the PVA-based resin layer does not contain a halide, it is possible to suppress the orientation disorder of the polyvinyl alcohol molecules and the decrease in orientation. Thereby, it is possible to improve the optical properties of the polarizing film obtained by the treatment step of immersing the laminate in a liquid, such as dyeing treatment and underwater stretching treatment.
C-2.空中輔助延伸處理 尤其為了獲得高光學特性,會選擇組合乾式延伸(輔助延伸)與硼酸水中延伸之2段延伸之方法。如2段延伸之方式,藉由導入輔助延伸,可一邊抑制熱塑性樹脂基材之結晶化一邊進行延伸,解決在之後的硼酸水中延伸中因熱塑性樹脂基材之過度結晶化造成延伸性降低之問題,從而可以更高倍率延伸積層體。並且,在將PVA系樹脂塗佈於熱塑性樹脂基材上時,為了抑制熱塑性樹脂基材之玻璃轉移溫度之影響,必須使塗佈溫度比將PVA系樹脂塗佈於一般的金屬滾筒上之情況更低,結果會產生PVA系樹脂之結晶化相對變低而無法獲得充分光學特性之問題。對此,藉由導入輔助延伸,即使是在將PVA系樹脂塗佈於熱塑性樹脂上時仍可提升PVA系樹脂之結晶性,而可達成高光學特性。又,同時事先提高PVA系樹脂之定向性,可防止在之後的染色步驟或延伸步驟中浸漬於水中時,PVA系樹脂之定向性降低或溶解等問題,而可達成高光學特性。C-2. Air auxiliary extension processing Especially in order to obtain high optical properties, a two-stage extension method combining dry extension (auxiliary extension) and extension in boric acid water is selected. Like the two-stage extension method, by introducing the auxiliary extension, the extension can be performed while suppressing the crystallization of the thermoplastic resin substrate, which solves the problem of the extension of the thermoplastic resin substrate due to the excessive crystallization of the thermoplastic resin substrate in the subsequent boric acid extension. , So that the laminate can be stretched at a higher magnification. In addition, when applying PVA-based resin to a thermoplastic resin substrate, in order to suppress the influence of the glass transition temperature of the thermoplastic resin substrate, the coating temperature must be higher than that when PVA-based resin is applied to a general metal roller. Lower, as a result, the crystallization of the PVA-based resin is relatively low and the problem that sufficient optical properties cannot be obtained. In this regard, by introducing auxiliary extension, the crystallinity of the PVA-based resin can be improved even when the PVA-based resin is coated on the thermoplastic resin, and high optical properties can be achieved. In addition, at the same time, the orientation of the PVA-based resin is improved in advance to prevent problems such as the decrease in orientation or dissolution of the PVA-based resin when immersed in water in the subsequent dyeing step or the stretching step, and high 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相異之輥件間進行單軸延伸之方法),惟為了獲得高光學特性,可積極採用自由端延伸。在一實施形態中,空中延伸處理包含加熱輥延伸步驟,該步驟係將上述積層體一邊沿其長邊方向輸送一邊利用加熱輥間之周速差進行延伸。空中延伸處理代表上係包含區域(zone)延伸步驟與加熱輥延伸步驟。另,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。在一實施形態中,係依序進行區域延伸步驟及加熱輥延伸步驟。又,在另一實施形態中,係於拉幅延伸機中把持薄膜端部,並將拉幅機間之距離往行進方向擴大來進行延伸(拉幅機間距離的增幅即為延伸倍率)。此時,寬度方向(相對於行進方向為垂直方向)之拉幅機的距離係設定成可任意接近。較佳可設定成相對於行進方向之延伸倍率來利用自由端延伸作接近。為自由端延伸時,係以寬度方向之收縮率=(1/延伸倍率)1/2 來計算。The extension method of aerial auxiliary extension can be fixed-end extension (for example, using a tenter stretcher for extension) or free end extension (for example, a method of uniaxial extension by passing the laminated body between rollers with different peripheral speeds) ), but in order to obtain high optical characteristics, free end extension can be actively used. In one embodiment, the in-flight stretching process includes a heating roller stretching step in which the laminate is conveyed in the longitudinal direction and stretched using the difference in peripheral speed between the heating rollers. The air extension process means that the above system includes a zone extension step and a heating roller extension step. In addition, the sequence of the area extension step and the heating roller extension step is not limited, and the area extension step may be performed first, or the heating roller extension step may be performed first. The area extension step can also be omitted. In one embodiment, the area extension step and the heating roller extension step are sequentially performed. In another embodiment, the end of the film is gripped in a tenter stretcher, and the distance between the tenters is expanded in the direction of travel to stretch (the increase in the distance between the tenters is the stretch magnification). At this time, the distance of the tenter in the width direction (vertical to the direction of travel) is set to be arbitrarily close. Preferably, it can be set to a stretch magnification relative to the direction of travel so that the free end stretch can be used for approaching. When the free end is extended, it is calculated as the shrinkage rate in the width direction=(1/stretching ratio) 1/2.
空中輔助延伸可在一階段中進行亦可分多階段進行。分多階段進行時,延伸倍率為各階段之延伸倍率之積。空中輔助延伸中之延伸方向宜與水中延伸之延伸方向大致相同。Air assist extension can be carried out in one stage or in multiple stages. When it is carried out in multiple stages, the stretching ratio is the product of the stretching ratios of each stage. The extension direction of the aerial auxiliary extension should be approximately the same as the extension direction of the underwater extension.
空中輔助延伸之延伸倍率宜為2.0倍~3.5倍。組合空中輔助延伸與水中延伸時之最大延伸倍率,相對於積層體之原長以5.0倍以上為宜,以5.5倍以上為佳,以6.0倍以上為更佳。本說明書中「最大延伸倍率」意指積層體將要斷裂前的延伸倍率,係另外確認積層體斷裂的延伸倍率後比其值低0.2之值。The extension ratio of aerial auxiliary extension should be 2.0 to 3.5 times. The maximum extension ratio when combining aerial auxiliary extension and underwater extension is preferably 5.0 times or more relative to the original length of the laminate, preferably 5.5 times or more, and more preferably 6.0 times or more. In this specification, the "maximum extension ratio" means the extension ratio before the laminate body breaks, and it is a value that is 0.2 lower than the value after confirming the extension ratio at which the laminate body fractures.
空中輔助延伸之延伸溫度可因應熱塑性樹脂基材之形成材料、延伸方式等設定成任意適當之值。延伸溫度宜為熱塑性樹脂基材之玻璃轉移溫度(Tg)以上,熱塑性樹脂基材之玻璃轉移溫度(Tg)+10℃以上更適宜,Tg+15℃以上特別適宜。另一方面,延伸溫度的上限宜為170℃。藉由在所述溫度下延伸可抑制PVA系樹脂之結晶化急速進展,從而可抑制該結晶化所造成的不良情況(例如,因延伸而妨礙PVA系樹脂層之定向)。The extension temperature of the air-assisted extension can be set to any appropriate value according to the forming material and extension method of the thermoplastic resin substrate. The elongation temperature is preferably higher than the glass transition temperature (Tg) of the thermoplastic resin substrate. The glass transition temperature (Tg) of the thermoplastic resin substrate (Tg) + 10°C or higher is more suitable, and the Tg + 15°C or higher is particularly suitable. On the other hand, the upper limit of the stretching temperature is preferably 170°C. Stretching at the temperature can suppress the rapid progress of the crystallization of the PVA-based resin, thereby suppressing defects caused by the crystallization (for example, hindering the orientation of the PVA-based resin layer due to the stretching).
C-3.不溶解處理、染色處理及交聯處理 視需要在空中輔助延伸處理之後且在水中延伸處理或染色處理之前,施行不溶解處理。上述不溶解處理代表上係將PVA系樹脂層浸漬於硼酸水溶液中來進行。上述染色處理代表上係以二色性物質(代表上為碘)將PVA系樹脂層染色來進行。視需要在染色處理之後且在水中延伸處理之前,施行交聯處理。上述交聯處理代表上可藉由使PVA系樹脂層浸漬於硼酸水溶液中來進行。關於不溶解處理、染色處理及交聯處理的詳細內容,例如記載於日本特開2012-73580號公報(上述)。C-3. Insoluble treatment, dyeing treatment and cross-linking treatment If necessary, after the aerial auxiliary extension treatment and before the underwater extension treatment or dyeing treatment, an insolubilization treatment is performed. The above-mentioned insolubilization treatment means that the PVA-based resin layer is immersed in an aqueous boric acid solution. The dyeing process described above is performed by dyeing the PVA-based resin layer with a dichroic substance (iodine in representative). If necessary, a cross-linking treatment is performed after the dyeing treatment and before the water extension treatment. The above-mentioned crosslinking treatment can typically be performed by immersing the PVA-based resin layer in an aqueous boric acid solution. The details of the insolubilization treatment, the dyeing treatment, and the cross-linking treatment are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580 (mentioned above).
C-4.水中延伸處理 水中延伸處理係使積層體浸漬於延伸浴來進行。藉由水中延伸處理,可在比上述熱塑性樹脂基材或PVA系樹脂層之玻璃轉移溫度(代表上為80℃左右)更低的溫度下延伸,而可在抑制PVA系樹脂層結晶化的同時進行高倍率延伸。結果可製出具有優異光學特性之偏光膜。C-4. Water extension treatment The underwater stretching treatment is performed by immersing the laminate in a stretching bath. The stretching treatment in water can stretch at a temperature lower than the glass transition temperature of the thermoplastic resin substrate or PVA resin layer (typically around 80°C), and can suppress the crystallization of the PVA resin layer at the same time Perform high-magnification extension. As a result, a polarizing film with excellent optical properties can be produced.
積層體之延伸方法可採用任意適當的方法。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相異之輥件間進行單軸延伸的方法)。較佳為選擇自由端延伸。積層體之延伸可在一階段中進行亦可分多階段進行。分多階段進行時,後述積層體之延伸倍率(最大延伸倍率)為各階段之延伸倍率之積。Any appropriate method can be adopted for the extension method of the laminate. Specifically, it may be a fixed-end extension or a free-end extension (for example, a method of uniaxially extending the laminate through rollers with different peripheral speeds). Preferably, the free end extension is selected. The extension of the laminated body can be carried out in one stage or in multiple stages. When it is carried out in multiple stages, the stretching magnification (maximum stretching magnification) of the laminate described later is the product of the stretching magnifications of each stage.
水中延伸宜使積層體浸漬於硼酸水溶液中來進行(硼酸水中延伸)。藉由使用硼酸水溶液作為延伸浴,可對PVA系樹脂層賦予得以承受延伸時所受張力的剛性及不溶解於水的耐水性。具體上,硼酸在水溶液中會生成四羥基硼酸陰離子而可藉由氫鍵與PVA系樹脂交聯。結果可賦予PVA系樹脂層剛性與耐水性,進行良好地延伸,從而製出具有優異光學特性之偏光膜。The stretching in water is preferably carried out by immersing the layered body in an aqueous boric acid solution (extending in boric acid in water). By using an aqueous solution of boric acid as a stretching bath, the PVA-based resin layer can be imparted with rigidity that can withstand tension during stretching and water resistance that is insoluble in water. Specifically, boric acid generates tetrahydroxyborate anions in an aqueous solution and can be cross-linked with PVA-based resins through hydrogen bonds. As a result, rigidity and water resistance can be imparted to the PVA-based resin layer, and the PVA-based resin layer can be stretched well, thereby producing a polarizing film with excellent optical properties.
上述硼酸水溶液宜使硼酸及/或硼酸鹽溶解於屬溶劑的水而獲得。硼酸濃度相對於水100重量份宜為1重量份~10重量份,更宜為2.5重量份~6重量份,尤宜為3重量份~5重量份。藉由將硼酸濃度設為1重量份以上,可有效抑制PVA系樹脂層之溶解,製造特性更高之偏光膜。此外,除硼酸或硼酸鹽外,亦可使用將硼砂等之硼化合物、乙二醛、戊二醛等溶解於溶劑而得之水溶液。The above-mentioned boric acid aqueous solution is preferably obtained by dissolving boric acid and/or borate in water which is a solvent. The concentration of boric acid is preferably 1 part by weight to 10 parts by weight relative to 100 parts by weight of water, more preferably 2.5 parts by weight to 6 parts by weight, and particularly preferably 3 parts by weight to 5 parts by weight. By setting the concentration of boric acid to 1 part by weight or more, the dissolution of the PVA-based resin layer can be effectively suppressed, and a polarizing film with higher characteristics can be produced. In addition to boric acid or borate, an aqueous solution obtained by dissolving boron compounds such as borax, glyoxal, glutaraldehyde, etc. in a solvent can also be used.
宜於上述延伸浴(硼酸水溶液)中摻混碘化物。藉由摻混碘化物,可抑制已吸附於PVA系樹脂層之碘的溶出。碘化物之具體例如上所述。碘化物之濃度相對於水100重量份宜為0.05重量份~15重量份,更宜為0.5重量份~8重量份。It is suitable to mix iodide in the above-mentioned extension bath (aqueous boric acid solution). By blending iodide, the elution of iodine that has been adsorbed on the PVA-based resin layer can be suppressed. Specific examples of iodide are as described above. The concentration of iodide relative to 100 parts by weight of water is preferably 0.05 to 15 parts by weight, more preferably 0.5 to 8 parts by weight.
延伸溫度(延伸浴之液溫)宜為40℃~85℃,較宜為60℃~75℃。只要為所述溫度,便可抑制PVA系樹脂層溶解,同時可高倍率地延伸。具體而言如上所述,以與形成PVA系樹脂層之關係來說,熱塑性樹脂基材之玻璃轉移溫度(Tg)以60℃以上為宜。此時,延伸溫度若低於40℃,則即使考慮以水將熱塑性樹脂基材塑化,也恐無法良好地延伸。另一方面,延伸浴之溫度愈高溫,PVA系樹脂層之溶解性就愈高,而恐無法獲得優異的光學特性。積層體浸漬於延伸浴之浸漬時間宜為15秒~5分鐘。The extension temperature (liquid temperature of the extension bath) is preferably 40℃~85℃, more preferably 60℃~75℃. As long as the temperature is above, the dissolution of the PVA-based resin layer can be suppressed, and at the same time, it can be extended at a high rate. Specifically, as described above, in relation to the formation of the PVA-based resin layer, the glass transition temperature (Tg) of the thermoplastic resin substrate is preferably 60°C or higher. At this time, if the stretching temperature is lower than 40°C, even if it is considered that the thermoplastic resin base material is plasticized with water, it may not be stretched well. On the other hand, the higher the temperature of the stretching bath, the higher the solubility of the PVA-based resin layer, and it may not be possible to obtain excellent optical properties. The immersion time of the laminate in the extension bath is preferably 15 seconds to 5 minutes.
水中延伸所行之延伸倍率宜為1.5倍以上,較佳為3.0倍以上。積層體之總延伸倍率相對於積層體的原長宜為5.0倍以上,更宜為5.5倍以上。藉由達成所述高延伸倍率,可製造出光學特性極優異的偏光膜。所述高延伸倍率可藉由採用水中延伸方式(硼酸水中延伸)來達成。The stretching magnification performed in water stretching is preferably 1.5 times or more, preferably 3.0 times or more. The total extension ratio of the laminate is preferably 5.0 times or more, and more preferably 5.5 times or more relative to the original length of the laminate. By achieving the high stretching magnification, a polarizing film with extremely excellent optical properties can be manufactured. The high stretch magnification can be achieved by using an underwater stretch method (boric acid stretch in water).
C-5.乾燥收縮處理 上述乾燥收縮處理可透過將區域整體加熱所進行之區域加熱來進行,亦可透過將輸送輥加熱(所謂使用加熱輥)來進行(加熱輥乾燥方式)。較佳為使用這兩者。藉由使用加熱輥使其乾燥,可有效率地抑制積層體之加熱捲曲,而製造出外觀優異的偏光膜。具體而言,藉由在使積層體沿著加熱輥之狀態下進行乾燥,可有效率地促進上述熱塑性樹脂基材之結晶化使結晶化度增加,即使是在相對較低的乾燥溫度下,仍能良好地增加熱塑性樹脂基材之結晶化度。結果熱塑性樹脂基材之剛性增加而成為得以承受PVA系樹脂層因乾燥而收縮的狀態,從而捲曲受到抑制。又,藉由使用加熱輥,可在將積層體維持平坦狀態的同時進行乾燥,因此不只能抑制捲曲的產生,亦能抑制起皺的產生。此時,積層體可透過乾燥收縮處理使其於寬度方向收縮,來提升光學特性。其係因可有效提升PVA及PVA/碘錯合物之定向性之故。積層體進行乾燥收縮處理所得寬度方向之收縮率宜為1%~10%,更宜為2%~8%,尤宜為4%~6%。C-5. Drying shrinkage treatment The above-mentioned drying and shrinking treatment may be performed by heating the area by heating the entire area, or may be performed by heating the conveying roller (so-called heating roller) (heat roller drying method). It is preferable to use both. By using a heating roller to dry it, heating and curling of the laminate can be effectively suppressed, and a polarizing film with excellent appearance can be produced. Specifically, by drying the laminate in a state where the laminate is moved along the heating roller, the crystallization of the thermoplastic resin substrate can be efficiently promoted and the degree of crystallinity can be increased, even at a relatively low drying temperature. It can still increase the crystallinity of the thermoplastic resin substrate. As a result, the rigidity of the thermoplastic resin base material is increased and the PVA-based resin layer can withstand the shrinkage of the PVA-based resin layer due to drying, so that curling is suppressed. In addition, by using a heating roller, the layered body can be dried while maintaining a flat state. Therefore, not only can the generation of curls be suppressed, but also the generation of wrinkles can be suppressed. At this time, the laminated body can be shrunk in the width direction through a drying shrinkage treatment to improve optical properties. It is because it can effectively improve the orientation of PVA and PVA/iodine complexes. The shrinkage rate of the laminate in the width direction obtained by drying and shrinking is preferably 1%~10%, more preferably 2%~8%, especially 4%~6%.
圖2係顯示乾燥收縮處理之一例的概略圖。在乾燥收縮處理中,係利用已加熱至預定溫度的輸送輥R1~R6與導輥G1~G4來一邊輸送積層體200一邊使其乾燥。在圖式例中,係將輸送輥R1~R6配置成可交替連續加熱PVA樹脂層之面與熱塑性樹脂基材之面,但例如亦可將輸送輥R1~R6配置成僅連續加熱積層體200的其中一面(例如熱塑性樹脂基材面)。Fig. 2 is a schematic diagram showing an example of drying shrinkage treatment. In the drying and shrinking treatment, the
藉由調整輸送輥之加熱溫度(加熱輥之溫度)、加熱輥之數量及與加熱輥的接觸時間等,可控制乾燥條件。加熱輥之溫度宜為60℃~120℃,更宜為65℃~100℃,尤宜為70℃~80℃。可在可良好地增加熱塑性樹脂之結晶化度而良好地抑制捲曲的同時,製造出耐久性極優異的光學積層體。另,加熱輥之溫度可以接觸式溫度計來測定。在圖式例中設置有6個輸送輥,惟輸送輥只要為多數個即無特別限制。輸送輥通常為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)以1秒~300秒為宜,以1~20秒為佳,以1~10秒更佳。By adjusting the heating temperature of the conveying roller (temperature of the heating roller), the number of heating rollers and the contact time with the heating roller, etc., the drying conditions can be controlled. The temperature of the heating roller is preferably 60℃~120℃, more preferably 65℃~100℃, especially 70℃~80℃. The degree of crystallinity of the thermoplastic resin can be increased well and curling can be well suppressed, and an optical laminate with extremely excellent durability can be produced. In addition, the temperature of the heating roller can be measured with a contact thermometer. In the example of the drawing, there are 6 conveying rollers, but there is no particular limitation as long as there are a plurality of conveying rollers. The number of conveying rollers is usually 2-40, preferably 4-30. The contact time (total contact time) between the laminate and the heating roller is preferably 1 second to 300 seconds, preferably 1 to 20 seconds, and more preferably 1 to 10 seconds.
加熱輥可設置於加熱爐(例如烘箱)內,亦可設置於一般的製造產線(室溫環境下)。宜設置於具備送風機構的加熱爐內。藉由併用以加熱輥進行之乾燥與熱風乾燥,可抑制在加熱輥間急遽的溫度變化,而可易控制寬度方向之收縮。熱風乾燥之溫度宜為30℃~100℃。且,熱風乾燥時間宜為1秒~300秒。熱風之風速宜為10m/s~30m/s左右。另,該風速係在加熱爐內之風速,可以迷你扇葉型數位風速計來測定。The heating roller can be installed in a heating furnace (such as an oven), or can be installed in a general manufacturing line (at room temperature). It is suitable to be installed in a heating furnace with an air supply mechanism. By combining drying with heating rollers and hot air drying, sudden temperature changes between the heating rollers can be suppressed, and the shrinkage in the width direction can be easily controlled. The temperature of hot air drying should be 30℃~100℃. Moreover, the hot air drying time is preferably 1 second to 300 seconds. The wind speed of the hot air should be about 10m/s~30m/s. In addition, the wind speed is the wind speed in the heating furnace, which can be measured by a mini fan blade type digital anemometer.
C-6.與處理液之接觸 依上述方式,可獲得熱塑性樹脂基材與偏光膜之積層體。在本發明之實施形態中,係使偏光膜接觸pH在3.0以下之處理液。在一實施形態中,藉由使該積層體直接與處理液接觸,可使偏光膜與處理液接觸。此時,代表上熱塑性樹脂基材可直接作為偏光膜之保護層來使用。或者,亦可於經與處理液接觸之積層體的偏光膜表面貼合樹脂薄膜(成為保護層)來製作保護層/偏光膜/熱塑性樹脂基材之積層體,並從該積層體剝離熱塑性樹脂基材,而製作出具有保護層/偏光膜之構成的偏光板。在另一實施形態中,係於積層體的偏光膜表面貼合樹脂薄膜(成為保護層)來製作保護層/偏光膜/熱塑性樹脂基材之積層體,並從該積層體剝離熱塑性樹脂基材,而製作出保護層/偏光膜之積層體(偏光板)。藉由使所得偏光板與處理液接觸,可使偏光膜與處理液接觸。C-6. Contact with treatment liquid In the above manner, a laminate of a thermoplastic resin substrate and a polarizing film can be obtained. In the embodiment of the present invention, the polarizing film is brought into contact with a treatment solution whose pH is below 3.0. In one embodiment, by directly contacting the layered body with the processing liquid, the polarizing film can be brought into contact with the processing liquid. At this time, it means that the thermoplastic resin substrate can be directly used as the protective layer of the polarizing film. Alternatively, a resin film (to become a protective layer) can be bonded to the surface of the polarizing film of the laminate that is in contact with the treatment liquid to produce a laminate of protective layer/polarizing film/thermoplastic resin substrate, and the thermoplastic resin may be peeled from the laminate Base material to produce a polarizing plate with a protective layer/polarizing film composition. In another embodiment, a resin film (which becomes a protective layer) is attached to the surface of the polarizing film of the laminate to produce a laminate of protective layer/polarizing film/thermoplastic resin substrate, and the thermoplastic resin substrate is peeled from the laminate , And produced a protective layer/polarizing film laminate (polarizing plate). By bringing the obtained polarizing plate into contact with the processing liquid, the polarizing film can be brought into contact with the processing liquid.
偏光膜與處理液之接觸可利用任意適當之方法進行。代表例可舉將處理液塗佈至偏光膜、將偏光膜(實質上為積層體或偏光板)浸漬於處理液中。塗佈方法可採用任意適當之方法。具體例可舉作為塗佈液之塗佈方法在C-1項中所說明之方法。浸漬亦可藉由任意適當之態樣進行。例如,可於洗淨處理之洗淨浴中添加處理液、可使用處理液之浴來取代洗淨浴、亦可與洗淨浴不同另外設置處理液之浴。另,洗淨處理代表上係於水中延伸處理後且在乾燥收縮處理前進行。另外設置處理液之浴時,處理液之浴可設置於洗淨浴與乾燥收縮處理設備之間(亦即,與處理液之接觸亦可在洗淨處理與乾燥收縮處理之間進行),亦可設置在剝離熱塑性樹脂基材之機構的下游(亦即,與處理液之接觸亦可在剝離熱塑性樹脂基材後進行)。The contact between the polarizing film and the treatment liquid can be performed by any appropriate method. Representative examples include applying a treatment liquid to a polarizing film, and immersing a polarizing film (substantially a laminate or a polarizing plate) in the treatment liquid. Any appropriate method can be adopted as the coating method. Specific examples include the method described in the section C-1 as the coating method of the coating liquid. The impregnation can also be performed in any appropriate manner. For example, the treatment liquid may be added to the washing bath of the washing treatment, a bath of the treatment liquid may be used instead of the washing bath, or a bath of the treatment liquid may be provided separately from the washing bath. In addition, the washing treatment is typically carried out after the underwater stretching treatment and before the drying shrinkage treatment. In addition, when the treatment liquid bath is set, the treatment liquid bath can be set between the washing bath and the drying shrinkage treatment equipment (that is, the contact with the treatment liquid can also be carried out between the washing treatment and the drying shrinkage treatment). It can be installed downstream of the mechanism for peeling the thermoplastic resin substrate (that is, contact with the treatment liquid may be performed after peeling the thermoplastic resin substrate).
處理液之pH只要在3.0以下,便可使用任意適當之酸性液體。處理液之具體例可舉鹽酸、硫酸、硝酸、磷酸、檸檬酸。處理液宜為強酸水溶液。強酸之具體例可舉鹽酸、硫酸、硝酸。處理液之pH愈小(酸性愈強)愈佳。具體而言,pH宜為2.7以下,較宜為2.5以下,更宜為2.0以下,尤宜為1.5以下。Any appropriate acidic liquid can be used as long as the pH of the treatment liquid is below 3.0. Specific examples of the treatment liquid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and citric acid. The treatment liquid is preferably a strong acid aqueous solution. Specific examples of strong acids include hydrochloric acid, sulfuric acid, and nitric acid. The lower the pH of the treatment solution (the stronger the acidity), the better. Specifically, the pH is preferably 2.7 or less, more preferably 2.5 or less, more preferably 2.0 or less, and particularly preferably 1.5 or less.
處理液之酸濃度宜為0.02重量%~3.0重量%,較宜為0.04重量%~2.0重量%,更宜為0.1重量%~1.0重量%。The acid concentration of the treatment liquid is preferably 0.02% by weight to 3.0% by weight, more preferably 0.04% by weight to 2.0% by weight, and more preferably 0.1% by weight to 1.0% by weight.
處理液亦可包含有水溶性樹脂(譬如PVA系樹脂)。水溶性樹脂可作為黏結劑發揮功能。處理液中之水溶性樹脂濃度宜為3重量%~5重量%。此時,可藉由將處理液予以塗佈、乾燥來形成處理層。藉由形成所述處理層,亦可獲得具有上述所期望之耐久性的偏光膜。處理層的厚度宜為1.7µm以下,更宜為0.2µm~1.4µm。The treatment liquid may also contain water-soluble resin (for example, PVA-based resin). Water-soluble resin can function as a binder. The concentration of the water-soluble resin in the treatment solution is preferably 3% by weight to 5% by weight. In this case, the treatment layer can be formed by coating and drying the treatment liquid. By forming the treatment layer, a polarizing film having the aforementioned desired durability can also be obtained. The thickness of the treatment layer should be less than 1.7µm, more preferably 0.2µm~1.4µm.
與處理液接觸後,可視需求進行乾燥。乾燥溫度宜為40℃~90℃,更宜為50℃~70℃。After contacting with the treatment liquid, it can be dried as required. The drying temperature is preferably 40°C to 90°C, more preferably 50°C to 70°C.
C-7.變形例 在C-1項~C-6中說明了使用樹脂基材與塗佈形成於該樹脂基材之PVA系樹脂層的積層體之製造方法,惟本發明亦可應用於使用單一之PVA系樹脂薄膜之製造方法。所述製造方法代表上包含以下步驟:利用輥延伸機將長條狀PVA系樹脂薄膜沿長條方向單軸延伸,同時施行膨潤、染色、交聯及洗淨處理,最後施行乾燥處理。與處理液之接觸代表上可藉由浸漬於添加有處理液之洗淨浴中、浸漬於洗淨處理後之處理浴中或塗佈洗淨處理後之處理液來進行。 實施例C-7. Modifications Sections C-1 to C-6 describe the manufacturing method of a laminate using a resin substrate and a PVA-based resin layer formed on the resin substrate. However, the present invention can also be applied to the use of a single PVA-based resin The manufacturing method of the film. The manufacturing method typically includes the following steps: using a roll stretcher to uniaxially stretch a long PVA-based resin film in the longitudinal direction, simultaneously perform swelling, dyeing, crosslinking, and washing treatments, and finally perform a drying treatment. The contact with the treatment liquid can typically be performed by immersing in a washing bath to which the treatment liquid is added, immersing in a treatment bath after the washing treatment, or applying the treatment liquid after the washing treatment. Example
以下,以實施例來具體說明本發明,惟本發明不受該等實施例限定。各特性之測定方法如以下所述。此外,只要無特別註記,實施例及比較例中之「份」及「%」即為重量基準。 (1)厚度 使用干涉膜厚計(大塚電子公司製,製品名「MCPD-3000」)進行測定。 (2)單體透射率及正交吸光度 針對實施例及比較例之偏光板(保護層/偏光膜),使用紫外線可見光分光光度計(大塚電子製LPF-200)進行測定,並將測定之單體透射率Ts、平行透射率Tp、正交透射率Tc分別作為偏光膜之Ts、Tp及Tc。該等之Ts、Tp及Tc係依JIS Z8701之2度視野(C光源)進行測定並進行視感度校正所得之Y值。另,保護薄膜之折射率為1.50,而偏光膜之與保護薄膜相反之側的表面之折射率為1.53。 又,使用在各波長下測得之Tc,利用下述式求得正交吸光度。 正交吸光度=log10(100/Tc) 使用大塚電子公司製「LPF-200」從測定波長600nm之正交透射率Tc求出正交吸光度Abs0 。另,關於Abs0 ,亦可使用日本分光製「V-7100」等進行同樣的測定。 接著,將偏光板供於在溫度60℃及相對濕度95%下240小時之耐久試驗。依上述相同方式求出耐久試驗後的正交吸光度Abs240 。Hereinafter, the present invention will be specifically described with examples, but the present invention is not limited by these examples. The measuring methods of each characteristic are as follows. In addition, as long as there is no special note, the "parts" and "%" in the examples and comparative examples are the basis of weight. (1) The thickness was measured using an interference film thickness meter (manufactured by Otsuka Electronics Co., Ltd., product name "MCPD-3000"). (2) Monomer transmittance and orthogonal absorbance For the polarizing plates (protective layer/polarizing film) of the examples and comparative examples, the ultraviolet-visible light spectrophotometer (LPF-200 manufactured by Otsuka Electronics) was used to measure, and the measured single The volume transmittance Ts, the parallel transmittance Tp, and the orthogonal transmittance Tc are respectively used as the Ts, Tp, and Tc of the polarizing film. These Ts, Tp, and Tc are Y values obtained by measuring and calibrating the visual sensitivity according to the 2-degree field of view (C light source) of JIS Z8701. In addition, the refractive index of the protective film is 1.50, and the refractive index of the surface of the polarizing film on the opposite side of the protective film is 1.53. In addition, using the Tc measured at each wavelength, the orthogonal absorbance was obtained by the following formula. Orthogonal absorbance=log10(100/Tc) Using "LPF-200" manufactured by Otsuka Electronics Co., Ltd., the orthogonal absorbance Abs 0 was obtained from the orthogonal transmittance Tc at a measurement wavelength of 600 nm. In addition, for Abs 0 , the same measurement can be performed using JASCO Corporation "V-7100" or the like. Next, the polarizing plate was subjected to an endurance test at a temperature of 60° C. and a relative humidity of 95% for 240 hours. Obtain the orthogonal absorbance Abs 240 after the endurance test in the same manner as above.
[實施例1] 熱塑性樹脂基材是使用長條狀且吸水率0.75%、Tg約75℃之非晶質間苯二甲酸共聚聚對苯二甲酸乙二酯薄膜(厚度:100μm)。並對樹脂基材之單面施行電暈處理(處理條件:55W・min/m2 )。 在以9:1混合聚乙烯醇(聚合度4200,皂化度99.2莫耳%)及乙醯乙醯基改質PVA(日本合成化學工業公司製,商品名「GOHSEFIMER Z410」)而成之PVA系樹脂100重量份中,添加碘化鉀13重量份,而調製出PVA水溶液(塗佈液)。 於樹脂基材之電暈處理面塗佈上述PVA水溶液並在60℃下乾燥,藉此形成厚度20μm之PVA系樹脂層,而製作出積層體。 將所獲得之積層體於130℃之烘箱內在不同周速之輥件間沿縱方向(長邊方向)進行自由端單軸延伸2.4倍(空中輔助延伸處理)。 接著,使積層體浸漬於液溫40℃的不溶解浴(相對於水100重量份摻混4重量份之硼酸而得的硼酸水溶液)中30秒(不溶解處理)。 接著,一邊調整液溫30℃的染色浴(相對於水100重量份,以1:7之重量比摻混碘與碘化鉀而獲得之碘水溶液)之濃度,以使最後所得偏光板的單體透射率(Ts)成為45.0%,一邊浸漬於其中60秒(染色處理)。 接著,使其浸漬於液溫40℃的交聯浴(相對於水100重量份,摻混3重量份的碘化鉀並摻混5重量份的硼酸而得之硼酸水溶液)中30秒(交聯處理)。 然後,一邊使積層體浸漬於液溫70℃的硼酸水溶液(硼酸濃度4.0重量%,碘化鉀5重量%)中,一邊在周速相異的輥件間沿縱向(長邊方向)進行單軸延伸以使總延伸倍率達5.5倍(水中延伸處理)。 之後,使積層體浸漬於液溫20℃的洗淨浴(相對於水100重量份,摻混4重量份的碘化鉀而得之水溶液,pH=6)中(洗淨處理)。 之後,一邊在保持於90℃之烘箱中乾燥,一邊使其接觸表面溫度保持於75℃之SUS製加熱輥約2秒(乾燥收縮處理)。積層體進行乾燥收縮處理所得寬度方向之收縮率為2%。 依上述方式,於樹脂基材上形成厚度5.0µm之偏光膜,並於偏光膜表面透過UV硬化型接著劑(厚度1.0µm)貼合作為保護層(保護薄膜)之環烯烴系薄膜(ZEON公司製,製品名「G-Film」),之後剝離樹脂基材而獲得具有保護層/偏光膜之構成的積層體。所得積層體之單體透射率(Ts)為45.0%,其係因構成該積層體之偏光膜/保護層之表面折射率為1.53/1.53,故於實際測定值+0.2%進行校正,換算成1.53/1.50之狀態的值。 接著,將0.3重量%之鹽酸、3.5重量%之PVA(JC-25)溶解於水而獲得處理液(pH=1.3)並將其以厚度成為0.6um之方式塗敷於積層體之偏光膜表面,在60℃下乾燥4分鐘而形成處理層。 依上述方式而獲得本實施例之偏光板。[Example 1] As the thermoplastic resin substrate, an amorphous isophthalic acid copolymer polyethylene terephthalate film (thickness: 100 μm) with a water absorption rate of 0.75% and a Tg of about 75° C. was used. And apply corona treatment to one side of the resin substrate (treatment condition: 55W·min/m 2 ). In a 9:1 mixture of polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mol%) and acetyl acetyl modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "GOHSEFIMER Z410"). To 100 parts by weight of resin, 13 parts by weight of potassium iodide was added to prepare a PVA aqueous solution (coating liquid). The above-mentioned PVA aqueous solution was applied to the corona-treated surface of the resin substrate and dried at 60° C., thereby forming a PVA-based resin layer with a thickness of 20 μm to produce a laminate. The obtained laminate was subjected to uniaxial extension of the free end 2.4 times in the longitudinal direction (long side direction) between rollers of different peripheral speeds in an oven at 130°C (air-assisted extension treatment). Next, the layered body was immersed in an insoluble bath (a boric acid aqueous solution obtained by blending 4 parts by weight of boric acid with respect to 100 parts by weight of water) at a liquid temperature of 40°C for 30 seconds (insoluble treatment). Next, adjust the concentration of the dyeing bath (an iodine aqueous solution obtained by mixing iodine and potassium iodide at a weight ratio of 1:7 with respect to 100 parts by weight of water) at a liquid temperature of 30°C, so that the monomers of the polarizing plate obtained finally are transmitted The rate (Ts) became 45.0%, and it was immersed in it for 60 seconds (dyeing treatment). Next, it was immersed in a cross-linking bath (a boric acid aqueous solution obtained by mixing 3 parts by weight of potassium iodide and 5 parts by weight of boric acid with respect to 100 parts by weight of water) at a liquid temperature of 40°C for 30 seconds (cross-linking treatment ). Then, while immersing the layered body in an aqueous boric acid solution (4.0% by weight of boric acid concentration and 5% by weight of potassium iodide) at a liquid temperature of 70°C, uniaxially stretched in the longitudinal direction (longitudinal direction) between rollers with different peripheral speeds In order to make the total extension ratio up to 5.5 times (in water extension treatment). After that, the layered body was immersed in a washing bath (an aqueous solution obtained by mixing 4 parts by weight of potassium iodide with respect to 100 parts by weight of water, pH=6) at a liquid temperature of 20°C (washing treatment). After that, while drying in an oven maintained at 90°C, the contact surface temperature was maintained at 75°C with a heating roller made of SUS for about 2 seconds (drying shrinkage treatment). The shrinkage rate of the laminate in the width direction obtained by the drying shrinkage treatment is 2%. According to the above method, a polarizing film with a thickness of 5.0 µm is formed on the resin substrate, and a cycloolefin-based film (Zeon Co., Ltd.) is bonded as a protective layer (protective film) through a UV curable adhesive (1.0 µm) on the surface of the polarizing film. Manufacture, product name "G-Film"), and then peel off the resin substrate to obtain a laminate with a protective layer/polarizing film composition. The monomer transmittance (Ts) of the obtained laminate is 45.0%, which is because the surface refractive index of the polarizing film/protective layer constituting the laminate is 1.53/1.53, so the actual measurement value + 0.2% is corrected and converted into The value of the state of 1.53/1.50. Next, 0.3% by weight of hydrochloric acid and 3.5% by weight of PVA (JC-25) were dissolved in water to obtain a treatment solution (pH=1.3) and applied to the surface of the polarizing film of the laminate so that the thickness became 0.6um , Dried at 60°C for 4 minutes to form a treated layer. In the above manner, the polarizing plate of this embodiment is obtained.
針對所得偏光板(實質上為偏光膜),於表1顯示單體透射率及Abs240 /Abs0 。For the obtained polarizing plate (essentially a polarizing film), Table 1 shows the monomer transmittance and Abs 240 /Abs 0 .
[實施例2] 調整染色浴之濃度以將偏光膜之單體透射率(Ts)設為44.0%,除此之外依與實施例1相同方式而製作出偏光板。針對所得偏光板(實質上為偏光膜),於表1顯示單體透射率及Abs240 /Abs0 。[Example 2] The concentration of the dyeing bath was adjusted to set the monomer transmittance (Ts) of the polarizing film to 44.0%, except that the polarizing plate was produced in the same manner as in Example 1. For the obtained polarizing plate (essentially a polarizing film), Table 1 shows the monomer transmittance and Abs 240 /Abs 0 .
[實施例3~19] 將偏光膜之單體透射率、與處理液接觸之方法、處理液之pH、處理液中所含酸之種類以及處理層之厚度調整成表1所示來製作偏光板。針對所得偏光板(實質上為偏光膜),於表1顯示單體透射率及Abs240 /Abs0 。[Examples 3-19] The monomer transmittance of the polarizing film, the method of contact with the treatment liquid, the pH of the treatment liquid, the type of acid contained in the treatment liquid, and the thickness of the treatment layer were adjusted as shown in Table 1 to produce polarized light board. For the obtained polarizing plate (essentially a polarizing film), Table 1 shows the monomer transmittance and Abs 240 /Abs 0 .
[實施例20] 未使處理液包含PVA系樹脂(亦即未形成處理層)及將處理液的pH設為0.9,除此之外依與實施例2相同方式製出偏光板。針對所得偏光板(實質上為偏光膜),於表1顯示單體透射率及Abs240 /Abs0 。[Example 20] A polarizing plate was produced in the same manner as in Example 2 except that the treatment liquid was not made to contain PVA-based resin (that is, the treatment layer was not formed) and the pH of the treatment liquid was set to 0.9. For the obtained polarizing plate (essentially a polarizing film), Table 1 shows the monomer transmittance and Abs 240 /Abs 0 .
[實施例21] 依與實施例2相同方式,將熱塑性樹脂基材/PVA系樹脂層之積層體供於空中輔助延伸處理、不溶解處理、染色處理、交聯處理及水中延伸處理。使水中延伸處理後之積層體浸漬於液溫20℃之處理浴(pH=1.6)中(與處理液之接觸)。另,處理液係於一般的洗淨浴(相對於水100重量份,摻混4重量份的碘化鉀而獲得之水溶液)中添加鹽酸來調製。 之後,一邊在保持於90℃之烘箱中乾燥,一邊使其接觸表面溫度保持於75℃之SUS製加熱輥約2秒(乾燥收縮處理)。積層體進行乾燥收縮處理所得寬度方向之收縮率為2%。 接著,於偏光膜表面透過UV硬化型接著劑(厚度1.0μm)貼合作為保護層(保護薄膜)之環烯烴系薄膜(ZEON公司製,製品名「G-Film」),之後剝離樹脂基材而獲得具有保護層/偏光膜之構成的偏光板。針對所得偏光板(實質上為偏光膜),於表1顯示單體透射率及Abs240 /Abs0 。[Example 21] In the same manner as in Example 2, a laminate of a thermoplastic resin substrate/PVA-based resin layer was subjected to aerial auxiliary stretching treatment, insolubilization treatment, dyeing treatment, cross-linking treatment, and underwater stretching treatment. The layered body after the water extension treatment is immersed in a treatment bath (pH=1.6) with a liquid temperature of 20°C (in contact with the treatment liquid). In addition, the treatment liquid was prepared by adding hydrochloric acid to a general washing bath (an aqueous solution obtained by mixing 4 parts by weight of potassium iodide with respect to 100 parts by weight of water). After that, while drying in an oven maintained at 90°C, the contact surface temperature was maintained at 75°C with a heating roller made of SUS for about 2 seconds (drying shrinkage treatment). The shrinkage rate of the laminate in the width direction obtained by the drying shrinkage treatment is 2%. Next, a protective layer (protective film) of cycloolefin-based film (manufactured by ZEON, product name "G-Film") is pasted on the surface of the polarizing film through a UV curable adhesive (thickness 1.0μm), and then the resin substrate is peeled off A polarizing plate with a protective layer/polarizing film composition is obtained. For the obtained polarizing plate (essentially a polarizing film), Table 1 shows the monomer transmittance and Abs 240 /Abs 0 .
<比較例1~2> 除了不進行與處理液之接觸以外,分別依與實施例1~2相同方式製作出偏光板。針對所得偏光板(實質上為偏光膜),於表1顯示單體透射率及Abs240 /Abs0 。<Comparative Examples 1-2> Except not making contact with the treatment liquid, polarizing plates were produced in the same manner as in Examples 1-2, respectively. For the obtained polarizing plate (essentially a polarizing film), Table 1 shows the monomer transmittance and Abs 240 /Abs 0 .
[比較例3] 將偏光膜之單體透射率設為43.0%,除此之外依與比較例1相同方式而製作出偏光板。針對所得偏光板(實質上為偏光膜),於表1顯示單體透射率及Abs240 /Abs0 。[Comparative Example 3] A polarizing plate was produced in the same manner as in Comparative Example 1, except that the single transmittance of the polarizing film was 43.0%. For the obtained polarizing plate (essentially a polarizing film), Table 1 shows the monomer transmittance and Abs 240 /Abs 0 .
<比較例4~9> 將偏光膜之單體透射率、與處理液接觸之方法、處理液之pH、處理液中所含酸之種類以及處理層(有形成時)之厚度調整成表1所示來製作偏光板。針對所得偏光板(實質上為偏光膜),於表1顯示單體透射率及Abs240 /Abs0 。<Comparative Examples 4-9> The monomer transmittance of the polarizing film, the method of contact with the treatment liquid, the pH of the treatment liquid, the type of acid contained in the treatment liquid, and the thickness of the treatment layer (when formed) are adjusted to Table 1 The polarizing plate is made as shown. For the obtained polarizing plate (essentially a polarizing film), Table 1 shows the monomer transmittance and Abs 240 /Abs 0 .
[實施例22] 將厚度55μm之PVA系樹脂薄膜(日本合成公司製,製品名「PS7500」)的長條捲料,利用輥延伸機沿長條方向進行單軸延伸使總延伸倍率達6.0倍,同時施以膨潤、染色、交聯及洗淨處理,最後施以乾燥處理而製出厚度23μm之偏光膜。於洗淨處理後及乾燥處理前,將與實施例2相同的處理液依與實施例2相同方式塗佈於PVA系樹脂薄膜(偏光膜)之一面。針對所得偏光膜,於表1顯示單體透射率及Abs240 /Abs0 。[Example 22] A long roll of PVA-based resin film (manufactured by Nippon Gosei Co., Ltd., product name "PS7500") with a thickness of 55 μm was uniaxially stretched in the longitudinal direction using a roll stretcher to achieve a total stretch ratio of 6.0 times , Simultaneously apply swelling, dyeing, cross-linking and washing treatments, and finally apply drying treatment to produce a polarizing film with a thickness of 23μm. After the washing treatment and before the drying treatment, the same treatment liquid as in Example 2 was applied to one side of the PVA-based resin film (polarizing film) in the same manner as in Example 2. For the obtained polarizing film, the monomer transmittance and Abs 240 /Abs 0 are shown in Table 1.
[實施例23] 替代洗淨處理之洗淨浴,使PVA系樹脂薄膜(偏光膜)通過與實施例21相同的處理浴(因此於洗淨處理後未進行塗佈處理液),除此之外依與實施例22相同方式製作出厚度23µm之偏光膜。針對所得偏光膜,於表1顯示單體透射率及Abs240 /Abs0 。[Example 23] In place of the washing bath of the washing treatment, the PVA-based resin film (polarizing film) was passed through the same treatment bath as in Example 21 (therefore, the treatment liquid was not applied after the washing treatment), except for this In the same manner as in Example 22, a polarizing film with a thickness of 23 µm was produced. For the obtained polarizing film, the monomer transmittance and Abs 240 /Abs 0 are shown in Table 1.
[表1] [Table 1]
由表1明顯可知,本發明之實施例之偏光膜在耐久試驗後的Abs240 /Abs0 大於1.00,在高溫高濕環境下之耐久性優異。未進行與處理液接觸之比較例1~3之偏光膜、以及有與pH大於3.0之處理液接觸之比較例4~9之偏光膜之Abs240 /Abs0 皆小於1.00。另,使用硼酸作為處理液之比較例7,其處理液膠化而無法接觸其。 It can be clearly seen from Table 1 that the Abs 240 /Abs 0 of the polarizing film of the embodiment of the present invention after the durability test is greater than 1.00, and it has excellent durability in a high temperature and high humidity environment. The Abs 240 /Abs 0 of the polarizing films of Comparative Examples 1 to 3 that were not in contact with the treatment liquid and the polarizing films of Comparative Examples 4 to 9 that were in contact with the treatment liquid of pH greater than 3.0 were all less than 1.00. In addition, in Comparative Example 7 in which boric acid was used as the treatment liquid, the treatment liquid was gelled and could not be contacted.
產業上之可利用性 本發明之偏光膜及偏光板可適宜用於液晶顯示裝置。Industrial availability The polarizing film and polarizing plate of the present invention can be suitably used in a liquid crystal display device.
10:偏光膜 20:第1保護層 30:第2保護層 100:偏光板 200:積層體 R1~R6:輸送輥 G1~G4:導輥10: Polarizing film 20: The first protective layer 30: The second protective layer 100: Polarizing plate 200: layered body R1~R6: Conveying roller G1~G4: guide roller
圖1係本發明一實施形態之偏光板的概略截面圖。 圖2係顯示使用加熱輥之乾燥收縮處理之一例的概略圖。Fig. 1 is a schematic cross-sectional view of a polarizing plate according to an embodiment of the present invention. Fig. 2 is a schematic diagram showing an example of drying shrinkage treatment using a heating roller.
10:偏光膜 10: Polarizing film
20:第1保護層 20: The first protective layer
30:第2保護層 30: The second protective layer
100:偏光板 100: Polarizing plate
Claims (12)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019117770A JP7421276B2 (en) | 2019-06-25 | 2019-06-25 | Polarizing film, polarizing plate, and method for manufacturing the polarizing film |
JP2019-117770 | 2019-06-25 |
Publications (1)
Publication Number | Publication Date |
---|---|
TW202108383A true TW202108383A (en) | 2021-03-01 |
Family
ID=74060870
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW109118842A TW202108383A (en) | 2019-06-25 | 2020-06-04 | Polarizing film, polarizing plate, and method for producing said polarizing film |
Country Status (5)
Country | Link |
---|---|
JP (2) | JP7421276B2 (en) |
KR (1) | KR20220025733A (en) |
CN (1) | CN114026471A (en) |
TW (1) | TW202108383A (en) |
WO (1) | WO2020261776A1 (en) |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001343521A (en) | 2000-05-31 | 2001-12-14 | Sumitomo Chem Co Ltd | Polarizing plate and method for manufacturing the same |
JP2005062458A (en) | 2003-08-12 | 2005-03-10 | Fuji Photo Film Co Ltd | Polarizing plate and liquid crystal display device |
TWI388888B (en) | 2005-03-10 | 2013-03-11 | Nippon Kayaku Kk | Iodine systemic polarizing film, manufacturing method thereof and polarizing plate using the same, and liquid crystal display device using the polarizing plate |
JP4919403B2 (en) * | 2006-09-14 | 2012-04-18 | 日本化薬株式会社 | High durability polarizing plate |
JP4691205B1 (en) | 2010-09-03 | 2011-06-01 | 日東電工株式会社 | Method for producing optical film laminate including thin high-performance polarizing film |
JP2014089465A (en) * | 2013-12-25 | 2014-05-15 | Nitto Denko Corp | Polarizing coat and polarizing film |
JP2016071349A (en) * | 2014-09-30 | 2016-05-09 | 住友化学株式会社 | Production method of polarizing laminate film and polarizing plate |
WO2018159376A1 (en) * | 2017-02-28 | 2018-09-07 | 日東電工株式会社 | Polarizing plate and method for producing polarizing plate |
TWI743373B (en) * | 2017-09-13 | 2021-10-21 | 日商日東電工股份有限公司 | Polarizing film, polarizing plate, and manufacturing method of polarizing film |
-
2019
- 2019-06-25 JP JP2019117770A patent/JP7421276B2/en active Active
-
2020
- 2020-05-11 CN CN202080046221.6A patent/CN114026471A/en active Pending
- 2020-05-11 WO PCT/JP2020/018819 patent/WO2020261776A1/en active Application Filing
- 2020-05-11 KR KR1020217041728A patent/KR20220025733A/en active Search and Examination
- 2020-06-04 TW TW109118842A patent/TW202108383A/en unknown
-
2023
- 2023-10-27 JP JP2023185055A patent/JP2024010124A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
KR20220025733A (en) | 2022-03-03 |
JP2021004942A (en) | 2021-01-14 |
JP7421276B2 (en) | 2024-01-24 |
CN114026471A (en) | 2022-02-08 |
WO2020261776A1 (en) | 2020-12-30 |
JP2024010124A (en) | 2024-01-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI775940B (en) | Polarizing plate, polarizing plate roll material and polarizing film manufacturing method | |
TWI748108B (en) | Polarizing film, polarizing plate, and manufacturing method of polarizing film | |
TWI775939B (en) | Polarizing plate, polarizing plate roll material and polarizing film manufacturing method | |
TWI762667B (en) | Polarizing film, polarizing plate, polarizing plate roll, and manufacturing method of polarizing film | |
TWI743373B (en) | Polarizing film, polarizing plate, and manufacturing method of polarizing film | |
TWI749242B (en) | Polarizing film, polarizing plate, and manufacturing method of polarizing film | |
WO2020262213A1 (en) | Polarization plate production method | |
TWI821519B (en) | Polarizing film, polarizing plate and manufacturing method of the polarizing film | |
TW201915063A (en) | Polarizing plate, polarizing plate roll, and method for producing polarizing film | |
TWI824113B (en) | Polarizing film, polarizing plate, and manufacturing method of the polarizing film | |
TW202101044A (en) | Polarizing film, polarizing plate, and method for producing said polarizing film | |
TW202039599A (en) | Polarizing film, polarizing plate, and polarizing film production method | |
TW202108383A (en) | Polarizing film, polarizing plate, and method for producing said polarizing film | |
TW202108384A (en) | Polarizing film, polarizing plate, and method for producing said polarizing film | |
CN113646676A (en) | Polarizing film, polarizing plate, and method for producing polarizing film | |
TW201915062A (en) | Polarizing plate, polarizing plate roll, and method for manufacturing polarizing film | |
TWI805911B (en) | Polarizing film, polarizing plate, and manufacturing method of the polarizing film | |
JP7267396B2 (en) | Polarizing film, polarizing plate, and method for producing the polarizing film | |
TW202108386A (en) | Polarizing plate and method for producing polarizing plate | |
TW202100364A (en) | Polarizing plate and method for producing said polarizing plate | |
JP2023050226A (en) | Method for producing polarizing film | |
JP2023050227A (en) | Method for producing polarizing film |