TW202144820A - Image display panel and image display device - Google Patents
Image display panel and image display device Download PDFInfo
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- TW202144820A TW202144820A TW110116260A TW110116260A TW202144820A TW 202144820 A TW202144820 A TW 202144820A TW 110116260 A TW110116260 A TW 110116260A TW 110116260 A TW110116260 A TW 110116260A TW 202144820 A TW202144820 A TW 202144820A
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- polarizing film
- transparent protective
- protective film
- film
- iodine
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Images
Classifications
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Nonlinear Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Mathematical Physics (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
- Laminated Bodies (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
Description
本發明涉及影像顯示面板及影像顯示裝置。The present invention relates to an image display panel and an image display device.
以往，用於液晶顯示裝置或有機EL顯示裝置等各種影像顯示裝置之偏光膜，出於兼具高透射率與高偏光度之理由而使用經染色處理之(含有碘或二色性染料等二色性物質之)聚乙烯醇系薄膜。該偏光膜係於浴中對聚乙烯醇系薄膜施行例如膨潤、染色、交聯、延伸等各處理後，施行洗淨處理，再進行乾燥來製造。又，前述偏光膜通常係使用接著劑在其單面或兩面貼合三醋酸纖維素等保護薄膜而製成偏光薄膜(偏光板)來使用。In the past, polarizing films used in various image display devices such as liquid crystal display devices and organic EL display devices have been dyed (containing two such as iodine or dichroic dyes) for both high transmittance and high polarization degree. Color substances) polyvinyl alcohol film. This polarizing film is manufactured by subjecting a polyvinyl alcohol-based film to various treatments such as swelling, dyeing, crosslinking, and stretching in a bath, and then subjecting it to washing treatment and drying. Moreover, the said polarizing film is generally used as a polarizing film (polarizing plate) by bonding protective films, such as cellulose triacetate, on one side or both sides using an adhesive agent.
前述偏光薄膜可依需要積層其他光學層而形成積層偏光薄膜(光學積層體)來使用；又前述偏光薄膜或前述積層偏光薄膜(光學積層體)可以貼合於液晶單元或有機EL元件等影像顯示單元而形成影像顯示面板來使用；進一步前述影像顯示面板可透過黏著劑層或接著劑層貼合於視辨側之前面透明板(視窗層)或觸控面板等前面透明構件而製成上述各種影像顯示裝置來使用(專利文獻1)。The aforementioned polarizing film can be used by laminating other optical layers to form a laminated polarizing film (optical laminate); and the aforementioned polarizing film or the aforementioned laminated polarizing film (optical laminate) can be attached to image displays such as liquid crystal cells or organic EL elements The image display panel can be used as a unit to form an image display panel; further, the image display panel can be made of the above-mentioned various front transparent members such as the front transparent plate (window layer) or the touch panel through the adhesive layer or the adhesive layer. It is used as a video display device (Patent Document 1).
近年來，此般各種影像顯示裝置除了使用於行動電話或平板電腦終端等行動設備方面之外，亦使用於汽車導航裝置或後照監視器等車載用影像顯示裝置方面等，其用途廣泛。伴隨此，對於前述偏光薄膜或前述積層偏光薄膜會要求比以往所要求之更嚴酷環境下(例如高溫環境下)的高耐久性，而有提出一種以確保此種耐久性為目的之偏光薄膜或影像顯示裝置(專利文獻2-3)。 先前技術文獻 專利文獻In recent years, such various image display devices have been used not only in mobile devices such as mobile phones and tablet terminals, but also in in-vehicle image display devices such as car navigation devices and rear-view monitors, and are widely used. Along with this, the above-mentioned polarizing film or the above-mentioned laminated polarizing film is required to have high durability in a harsher environment (for example, in a high temperature environment) than previously required, and a polarizing film or Video display device (Patent Documents 2-3). prior art literature Patent Literature
專利文獻1：日本專利特開2014-102353號公報 專利文獻2：日本專利特表2012-516468號公報 專利文獻3：日本專利特開2018-101117號公報Patent Document 1: Japanese Patent Laid-Open No. 2014-102353 Patent Document 2: Japanese Patent Publication No. 2012-516468 Patent Document 3: Japanese Patent Laid-Open No. 2018-101117
發明欲解決之課題 以上述車載用影像顯示裝置來說，因近年來自動駕駛技術的發展，顯示器設計之異形化或大型化亦不斷進展。隨著所述顯示器設計之變化，對偏光膜尋求進一步提升在高溫環境下之耐久性之手段。The problem to be solved by the invention For the above-mentioned in-vehicle image display device, due to the development of automatic driving technology in recent years, the design of the display has also been advanced in special-shaped or large-scale design. With the changes in the design of such displays, a means of further enhancing the durability in high temperature environments is sought for polarizing films.
鑒於以上情事，本發明目的在於提供一種具有優異高溫耐久性之偏光膜的影像顯示面板。In view of the above, the present invention aims to provide an image display panel of a polarizing film having excellent high temperature durability.
用以解決課題之手段 即，本發明係涉及一種影像顯示面板，其係依序積層有影像顯示單元、第1透明保護薄膜、碘系偏光膜及第2透明保護薄膜者；其中前述第1透明保護薄膜之透濕度小於前述第2透明保護薄膜之透濕度，且前述第1透明保護薄膜之透濕度為200g/(m2 ・24h)以下；前述碘系偏光膜滿足下述通式(1)所示光譜面積比：通式(1)：b/a＞1(通式(1)中，在前述第1透明保護薄膜貼合於前述碘系偏光膜之單面且前述第2透明保護薄膜貼合於前述碘系偏光膜之另一面的偏光薄膜之態樣中，a表示在前述第1透明保護薄膜側之偏光膜之表面起算1µm以上且1.5µm以下之區域中，利用拉曼分光分析所得80cm-1 至130cm-1 為止之光譜面積，b表示在前述第2透明保護薄膜側之偏光膜之表面起算1µm以上且1.5µm以下之區域中，利用拉曼分光分析所得80cm-1 至130cm-1 為止之光譜面積)。The means for solving the problem, that is, the present invention relates to an image display panel in which an image display unit, a first transparent protective film, an iodine-based polarizing film, and a second transparent protective film are laminated in this order; wherein the first transparent The moisture permeability of the protective film is lower than that of the second transparent protective film, and the moisture permeability of the first transparent protective film is less than 200g/(m 2 · 24h); the iodine-based polarizing film satisfies the following general formula (1) Spectral area ratio shown: general formula (1): b/a>1 (in general formula (1), the first transparent protective film is attached to one side of the iodine-based polarizing film and the second transparent protective film In the aspect of the polarizing film attached to the other side of the above-mentioned iodine-based polarizing film, "a" indicates that the area of 1 µm or more and 1.5 µm or less from the surface of the polarizing film on the side of the first transparent protective film is analyzed by Raman spectroscopy. The obtained spectral area from 80cm -1 to 130cm -1 , b represents the area of 1µm or more and 1.5µm or less from the surface of the polarizing film on the second transparent protective film side, 80cm -1 to 130cm obtained by Raman spectroscopic analysis Spectral area up to -1).
又，本發明涉及一種影像顯示裝置，其於前述影像顯示面板之前述第2透明保護薄膜側具備前面透明構件。Furthermore, the present invention relates to an image display device including a front transparent member on the second transparent protective film side of the image display panel.
發明效果 雖本發明影像顯示面板之效果的作用機制的細節尚有不明瞭的部分，但吾等推測如下。惟，本發明不受該作用機制解釋限制。Invention effect Although the details of the action mechanism of the effect of the image display panel of the present invention are still unclear, we speculate as follows. However, the present invention is not limited by the explanation of the mechanism of action.
本發明影像顯示面板依序積層有影像顯示單元、第1透明保護薄膜、碘系偏光膜及第2透明保護薄膜；前述第1透明保護薄膜之透濕度小於前述第2透明保護薄膜之透濕度，且前述第1透明保護薄膜之透濕度為200g/(m2 ・24h)以下；前述碘系偏光膜滿足下述通式(1)所示光譜面積比：通式(1)：b/a＞1(通式(1)中，在前述第1透明保護薄膜貼合於前述碘系偏光膜之單面且前述第2透明保護薄膜貼合於前述碘系偏光膜之另一面的偏光薄膜之態樣中，a表示在前述第1透明保護薄膜側之偏光膜表面起算1µm以上且1.5µm以下之區域中，利用拉曼分光分析所得80cm-1 至130cm-1 為止之光譜面積，b表示在前述第2透明保護薄膜側之偏光膜表面起算1µm以上且1.5µm以下之區域中，利用拉曼分光分析所得80cm-1 至130cm-1 為止之光譜面積)。如日本專利特開2015-52676號公報中所記載，上述80cm-1 至130cm-1 之拉曼位移表示含碘(更具體而言為碘錯合物(I3 - )之峰值(108cm-1 )的散射強度(拉曼強度)。因此，上述a表示在前述第1透明保護薄膜側之偏光膜表面起算1µm以上且1.5µm以下之區域中的碘(碘錯合物(I3 - ))濃度，而b表示在前述第2透明保護薄膜側之偏光膜表面起算1µm以上且1.5µm以下之區域中的碘(碘錯合物(I3 - ))濃度。因此，本發明的碘系偏光膜會滿足通式(1)：b/a＞1之條件，故偏光膜所含的碘(碘錯合物(I3 - ))濃度，其在第1透明保護薄膜側(影像顯示單元側)起算固定區域中的碘濃度會比第2透明保護薄膜側(影像顯示面板之視辨側)之固定區域中的碘濃度更淡。The image display panel of the present invention is sequentially laminated with an image display unit, a first transparent protective film, an iodine-based polarizing film and a second transparent protective film; the moisture permeability of the first transparent protective film is lower than that of the second transparent protective film, And the moisture permeability of the first transparent protective film is below 200g/(m 2 · 24h); the iodine-based polarizing film satisfies the spectral area ratio shown in the following general formula (1): general formula (1): b/a> 1 (in the general formula (1), in the state of the polarizing film in which the first transparent protective film is attached to one side of the iodine-based polarizing film and the second transparent protective film is attached to the other side of the iodine-based polarizing film sample, a represents the starting 1μm or more and a surface protection film side of the polarizing film of the first transparent region of 1.5μm or less, the area up to the spectroscopically analyzing Raman spectroscopic resulting 80cm -1 to 130cm -1, b represents the polarizing surface of the second transparent protective film side of the starting 1μm or more and 1.5μm or less of the area, the area up to the use of Raman spectrum analysis of the resulting 80cm -1 to 130cm -1). As described in Japanese Patent Laid-Open Publication No. 2015-52676 described in the 80cm to 130cm -1 Raman shift of -1 denotes iodine (more specifically complexes of iodine (I 3 -) of the peak (108cm -1 ) of the scattering intensity (Raman intensity). Therefore, the above a represents the iodine (iodine complex (I 3 - )) in the region of 1 µm or more and 1.5 µm or less from the polarizing film surface on the side of the first transparent protective film. concentration, and b represents the concentration of iodine (iodine complex (I 3 - )) in the region of 1 µm or more and 1.5 µm or less from the polarizing film surface on the second transparent protective film side. Therefore, the iodine-based polarized light of the present invention The film will satisfy the general formula (1): b/a>1, so the concentration of iodine (iodine complex (I 3 - )) contained in the polarizing film is on the side of the first transparent protective film (the side of the image display unit). ), the iodine concentration in the fixed area is lighter than the iodine concentration in the fixed area on the second transparent protective film side (viewing side of the image display panel).
另一方面，偏光膜中所含之碘在高溫環境下會因聚乙烯醇之脫水反應而多烯化，因此推測會使偏光膜之單體透射率降低。又，在上述影像顯示面板暴露於高溫環境下時，前述偏光膜之影像顯示單元側由於偏光膜中之水分不易排出系統外，故會因殘存之水分而促進偏光膜劣化，因此碘系偏光膜中，前述第1透明保護薄膜側(影像顯示單元側)之表面因多烯化造成之劣化會比第2透明保護薄膜側(影像顯示面板之視辨側)之表面更明顯。本發明影像顯示面板如上述，以偏光膜所含碘(碘錯合物(I3 - ))之濃度來說，在自第1透明保護薄膜側(影像顯示單元側)起算固定區域中之碘濃度較在第2透明保護薄膜側(影像顯示面板之視辨側)之固定區域中之碘濃度更淡，故高溫耐久性優異。On the other hand, the iodine contained in the polarizing film is polyalkylated by the dehydration reaction of polyvinyl alcohol in a high temperature environment, so it is presumed that the transmittance of the polarizing film monomer decreases. In addition, when the above-mentioned image display panel is exposed to a high temperature environment, since the moisture in the polarizing film on the image display unit side of the polarizing film is not easily discharged out of the system, the remaining moisture will promote the deterioration of the polarizing film, so the iodine-based polarizing film Among them, the surface on the side of the first transparent protective film (the side of the image display unit) is more significantly deteriorated by polyolefinization than the surface on the side of the second transparent protective film (the side of the image display panel). As described above, in the image display panel of the present invention , in terms of the concentration of iodine (iodine complex (I 3 − )) contained in the polarizing film, the iodine in the fixed region from the first transparent protective film side (image display unit side) The concentration is lower than the iodine concentration in the fixed region on the second transparent protective film side (viewing side of the image display panel), so it is excellent in high temperature durability.
又，因前述第1透明保護薄膜之透濕度小於前述第2透明保護薄膜之透濕度且為200g/(m2 ・24h)以下，故偏光膜不易受設於第1透明保護薄膜之影像顯示單元側的黏著劑層等所含水分影響，且可有效地將偏光膜中之水分往第2透明保護薄膜側排出，因此前述偏光膜之高溫耐久性優異。In addition, since the water vapor transmission rate of the first transparent protective film is lower than the water vapor transmission rate of the second transparent protective film and is less than 200 g/(m 2 · 24h), the polarizing film is not easily affected by the image display unit provided on the first transparent protective film. The moisture contained in the adhesive layer on the side is affected, and the moisture in the polarizing film can be effectively discharged to the second transparent protective film side, so the high-temperature durability of the polarizing film is excellent.
圖1係顯示本發明影像顯示面板之一形態的示意截面圖。圖1中顯示影像顯示面板100之一態樣，該影像顯示面板100依序積層有影像顯示單元90、接著劑層或黏著劑層20、第1透明保護薄膜12、碘系偏光膜11及第2透明保護薄膜13。又，圖1中係顯示偏光薄膜10之一態樣，該偏光薄膜10包含第1透明保護薄膜12、碘系偏光膜11及第2透明保護薄膜13。又，圖1中顯示影像顯示裝置200之一態樣，該影像顯示裝置200於影像顯示面板100之第2透明保護薄膜側具備前面透明構件80。FIG. 1 is a schematic cross-sectional view showing one form of the image display panel of the present invention. FIG. 1 shows an aspect of the
本發明影像顯示面板依序積層有影像顯示單元、第1透明保護薄膜、碘系偏光膜及第2透明保護薄膜。又，將包含前述第1透明保護薄膜、碘系偏光膜及第2透明保護薄膜之積層體稱為偏光薄膜。The image display panel of the present invention is sequentially laminated with an image display unit, a first transparent protective film, an iodine-based polarizing film and a second transparent protective film. Moreover, the laminated body containing the said 1st transparent protective film, an iodine type polarizing film, and a 2nd transparent protective film is called a polarizing film.
＜偏光薄膜＞ ＜碘系偏光膜＞ 前述碘系偏光膜係碘吸附定向於聚乙烯醇系薄膜而形成。前述聚乙烯醇(PVA)系薄膜可無特別限制地使用在可見光區域中具有透光性且可分散吸附碘之物。又，一般作為原板使用之PVA系薄膜之厚度宜為1~100µm左右，1~50µm左右較佳，而寬度宜為100~5000mm左右。＜Polarizing film＞ ＜Iodine-based polarizing film＞ The aforementioned iodine-based polarizing film is formed by adsorbing iodine to a polyvinyl alcohol-based film. The aforementioned polyvinyl alcohol (PVA)-based film can be used without any particular limitation, having light transmittance in the visible light region and capable of dispersing and adsorbing iodine. In addition, the thickness of the PVA-based film generally used as the original plate is preferably about 1~100µm, preferably about 1~50µm, and the width is preferably about 100~5000mm.
作為前述聚乙烯醇系薄膜的材料可舉聚乙烯醇或其衍生物。前述聚乙烯醇之衍生物可舉例如聚乙烯醇縮甲醛、聚乙烯縮醛；經乙烯、丙烯等烯烴、丙烯酸、甲基丙烯酸、巴豆酸等不飽和羧酸及其烷基酯、丙烯醯胺等改質者等。前述聚乙烯醇之平均聚合度宜為100~10,000左右，1,000~10,000左右較佳，1,500~4,500左右更佳。又，前述聚乙烯醇之皂化度宜為80~100莫耳%左右，95莫耳%~99.95莫耳左右較佳。另，前述平均聚合度及前述皂化度可依循JIS K 6726求得。As a material of the said polyvinyl alcohol-type film, polyvinyl alcohol or its derivative(s) can be mentioned. Derivatives of the aforementioned polyvinyl alcohol include, for example, polyvinyl formal, polyvinyl acetal; olefins such as ethylene and propylene, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and their alkyl esters, acrylamides etc. Modifiers etc. The average degree of polymerization of the polyvinyl alcohol is preferably about 100-10,000, preferably about 1,000-10,000, more preferably about 1,500-4,500. Also, the saponification degree of the aforementioned polyvinyl alcohol is preferably about 80-100 mol%, preferably about 95-99.95 mol%. In addition, the said average polymerization degree and the said saponification degree can be calculated|required according to JIS K 6726.
前述聚乙烯醇系薄膜中亦可含有塑化劑或界面活性劑等添加劑。前述塑化劑可舉例如甘油、二甘油、三甘油、乙二醇、丙二醇、聚乙二醇等多元醇及其縮合物等。前述添加劑之使用量無特別限制，但例如宜在聚乙烯醇系薄膜中為20重量%以下左右。Additives, such as a plasticizer and a surfactant, may be contained in the said polyvinyl alcohol-type film. As said plasticizer, polyhydric alcohols, such as glycerol, diglycerol, triglycerol, ethylene glycol, propylene glycol, polyethylene glycol, and its condensate, etc. are mentioned, for example. The usage-amount of the said additive is not specifically limited, For example, in a polyvinyl alcohol-type film, it is preferable that it is about 20 weight% or less.
前述碘系偏光膜滿足下述通式(1)所示光譜面積比：通式(1)：b/a＞1(通式(1)中，在前述第1透明保護薄膜貼合於前述碘系偏光膜之單面且前述第2透明保護薄膜貼合於前述碘系偏光膜之另一面的偏光薄膜之態樣中，a表示在前述第1透明保護薄膜側之偏光膜表面起算1µm以上且1.5µm以下之區域中，利用拉曼分光分析所得80cm-1 至130cm-1 為止之光譜面積，b表示在前述第2透明保護薄膜側之偏光膜表面起算1µm以上且1.5µm以下之區域中，利用拉曼分光分析所得80cm-1 至130cm-1 為止之光譜面積)。The iodine-based polarizing film satisfies the spectral area ratio represented by the following general formula (1): General formula (1): b/a>1 (in the general formula (1), the first transparent protective film is bonded to the iodine In the form of the polarizing film that is one side of the polarizing film and the second transparent protective film is attached to the other side of the iodine-based polarizing film, a represents 1 µm or more from the surface of the polarizing film on the side of the first transparent protective film and In the region of 1.5µm or less, the spectral area from 80cm -1 to 130cm -1 obtained by Raman spectroscopic analysis, b represents the region of 1µm or more and 1.5µm or less from the polarizing film surface on the second transparent protective film side, Raman spectroscopic analysis of the resulting far spectroscopically area 80cm -1 to 130cm -1).
由提升偏光膜之高溫耐久性之觀點來看，上述b/a宜為1.2以上，且1.5以上較佳。From the viewpoint of improving the high-temperature durability of the polarizing film, the above b/a is preferably 1.2 or more, and more preferably 1.5 or more.
前述碘系偏光膜中，由在保持一定的初始光學性能之狀態下提升高溫耐久性之觀點來看，在前述第1透明保護薄膜側之偏光膜表面起算1.5µm以下至前述第2透明保護薄膜側之偏光膜表面起算1.5µm以下為止的厚度方向上，碘濃度宜增加，且碘濃度實質上單調遞增較佳。「實質上單調遞增」意指厚度方向之碘平均濃度的分布曲線不具極大值及極小值。在此，碘平均濃度係指將PVA系樹脂薄膜於厚度方向上按每1µm進行分割，並對該分割後之區域利用拉曼分光法測定而得之強度的中央值。因此，即便在碘濃度實質上單調遞增之情況下，仍會局部(即在分割後之各區域內)存在碘濃度的極大及/或極小區域。In the above-mentioned iodine-based polarizing film, from the viewpoint of improving high temperature durability while maintaining a certain initial optical performance, the surface of the polarizing film on the side of the first transparent protective film is 1.5 µm or less to the second transparent protective film. The iodine concentration is preferably increased in the thickness direction from the surface of the polarizing film on the side to 1.5 µm or less, and the iodine concentration is preferably increased substantially monotonically. "Substantially monotonically increasing" means that the distribution curve of the average concentration of iodine in the thickness direction has no maxima and minima. Here, the average iodine concentration refers to the median value of the intensity obtained by dividing the PVA-based resin film into 1 µm in the thickness direction, and measuring the divided region by Raman spectroscopy. Therefore, even in the case where the iodine concentration is substantially monotonically increasing, there may still be local (ie, within each segmented region) regions of maximal and/or minimal iodine concentration.
前述碘系偏光膜中，前述碘含量宜為1重量%以上且15重量%以下。由抑制耐久性試驗時之褪色之觀點來看，前述碘系偏光膜中，前述碘含量宜為1.5重量%以上，且2重量%以上較佳，而由防止多烯化之觀點來看，宜為12重量%以下，且10重量%以下較佳。In the iodine-based polarizing film, the iodine content is preferably 1% by weight or more and 15% by weight or less. From the viewpoint of suppressing discoloration during the durability test, the iodine content in the iodine-based polarizing film is preferably 1.5 wt % or more, and preferably 2 wt % or more, and from the viewpoint of preventing polyolefinization, it is preferable. It is 12 weight% or less, and 10 weight% or less is preferable.
前述碘系偏光膜之單體透射率宜為40.0%以上，41%以上較佳，42%以上更佳，43%以上又更佳，而由初始偏光性能之觀點來看，宜為45%以下，44%以下較佳。此外，單體透射率係使用紫外線可見光分光光度計(大塚電子製，「LPF-200」，藉由JIS Z8701之2度視野(C光源)測定並進行視感度校正所得之Y值。此外，測定波長為380~780nm(每5nm)。The monomer transmittance of the aforementioned iodine-based polarizing film should preferably be above 40.0%, preferably above 41%, more preferably above 42%, and even more preferably above 43%. , 44% or less is better. In addition, the single transmittance is the Y value obtained by measuring the 2-degree field of view (C light source) of JIS Z8701 using an ultraviolet-visible light spectrophotometer (manufactured by Otsuka Electronics Co., Ltd., "LPF-200") and corrected for visual sensitivity. The wavelength is 380~780nm (every 5nm).
又，前述碘系偏光膜之偏光度宜為99.8%以上，且99.9%以上較佳，99.95%以上更佳。In addition, the degree of polarization of the aforementioned iodine-based polarizing film is preferably 99.8% or more, more preferably 99.9% or more, and more preferably 99.95% or more.
前述碘系偏光膜例如可藉由將前述聚乙烯醇系薄膜浸漬於碘的水溶液中來進行染色，並延伸成原長的3~7倍來製成。亦可因應需求將其浸漬於硼酸或碘化鉀等的水溶液中。進一步亦可視需要在染色前，將聚乙烯醇系薄膜浸漬於水中進行水洗。藉由水洗聚乙烯醇系薄膜，可洗淨聚乙烯醇系薄膜表面的污垢或抗黏結劑，除此之外，也有使聚乙烯醇系薄膜膨潤從而防止染色參差等不均的效果。延伸可在使用碘染色之後進行，亦可以邊染色邊進行延伸，又，亦可進行延伸之後使用碘進行染色。亦可在硼酸或碘化鉀等之水溶液中或水浴中進行延伸。The iodine-based polarizing film can be produced by, for example, immersing the polyvinyl alcohol-based film in an aqueous solution of iodine, dyeing, and extending to 3 to 7 times its original length. It can also be immersed in an aqueous solution such as boric acid or potassium iodide as required. Further, before dyeing, the polyvinyl alcohol-based film may be immersed in water and washed with water if necessary. By washing the polyvinyl alcohol-based film with water, the surface of the polyvinyl alcohol-based film can be washed away from dirt and anti-adhesives, and it also has the effect of swelling the polyvinyl alcohol-based film and preventing uneven dyeing. The stretching may be carried out after dyeing with iodine, or may be carried out while dyeing, or may be dyed with iodine after stretching. The extension can also be carried out in an aqueous solution such as boric acid or potassium iodide or in a water bath.
由使偏光膜之初始偏光度提升之觀點來看，前述碘系偏光膜之厚度宜為1µm以上，2µm以上較佳，而由防止面板翹曲之觀點來看，宜為20µm以下，15µm以下較佳，10µm以下更佳，8µm以下又更佳。尤其為了獲得厚度為8µm左右以下之偏光膜，可應用以下的薄型偏光膜之製造方法，即：使用包含在熱塑性樹脂基材上製膜而成之聚乙烯醇系樹脂層的積層體來作為前述聚乙烯醇系薄膜。From the viewpoint of improving the initial polarization degree of the polarizing film, the thickness of the aforementioned iodine-based polarizing film is preferably 1 µm or more, preferably 2 µm or more, and from the viewpoint of preventing panel warpage, it is preferably 20 µm or less, preferably 15 µm or less. Better, better below 10µm, even better below 8µm. In particular, in order to obtain a polarizing film with a thickness of about 8 µm or less, the following method for producing a thin polarizing film can be applied. Vinyl alcohol film.
＜薄型碘系偏光膜之製造方法＞ 薄型碘系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形成含聚乙烯醇系樹脂(PVA系樹脂)之聚乙烯醇系樹脂層(PVA系樹脂層)，而製成積層體；及，對積層體依序施行空中輔助延伸處理、染色處理、水中延伸處理及乾燥收縮處理。尤其為了獲得滿足上述b/a＞1之條件且具有高光學特性之偏光膜，係選擇組合空中輔助延伸處理(乾式延伸)與在硼酸水溶液中之水中延伸處理的2段延伸之方法。<Method for producing thin iodine-based polarizing film> The manufacturing method of the thin iodine-based polarizing film comprises the following steps: forming a polyvinyl alcohol-based resin layer (PVA-based resin layer) containing a polyvinyl-alcohol-based resin (PVA-based resin) on one side of an elongated thermoplastic resin substrate, and A layered body is produced; and, the layered body is subjected to air-assisted stretching treatment, dyeing treatment, underwater stretching treatment and drying shrinkage treatment in this order. In particular, in order to obtain a polarizing film that satisfies the above condition of b/a>1 and has high optical properties, a two-stage stretching method combining air-assisted stretching treatment (dry stretching) and aqueous stretching treatment in boric acid aqueous solution is selected.
製作前述積層體之方法可採用任意適當之方法，可舉例如於前述熱塑性樹脂基材之表面塗佈包含前述PVA系樹脂之塗佈液並乾燥之方法。前述熱塑性樹脂基材之厚度宜為20~300µm左右，50~200µm左右較佳。前述PVA系樹脂層之厚度宜為3~40µm左右，3~20µm左右較佳。Any appropriate method can be adopted as a method of producing the above-mentioned layered product, and for example, a method of applying a coating liquid containing the above-mentioned PVA-based resin to the surface of the above-mentioned thermoplastic resin base material and drying it is exemplified. The thickness of the aforementioned thermoplastic resin substrate is preferably about 20-300µm, preferably about 50-200µm. The thickness of the aforementioned PVA-based resin layer is preferably about 3-40µm, preferably about 3-20µm.
由可吸收水而大幅降低延伸應力從而高倍率延伸之觀點來看，前述熱塑性樹脂基材的吸水率宜為0.2%左右以上，0.3%左右以上較佳。另一方面，由可防止熱塑性樹脂基材的尺寸穩定性顯著降低而造成所得偏光膜的外觀變差等不良情況之觀點來看，前述熱塑性樹脂基材之吸水率宜為3%左右以下，1%左右以下較佳。另外，前述吸水率例如可藉由將改質基導入前述熱塑性樹脂基材之構成材料中來調整。前述吸水率係依循JIS K 7209求得之值。From the viewpoint of being able to absorb water, greatly reducing the elongation stress, and extending at a high rate, the water absorption rate of the thermoplastic resin substrate is preferably about 0.2% or more, more preferably about 0.3% or more. On the other hand, from the viewpoint that the dimensional stability of the thermoplastic resin substrate can be prevented from being significantly lowered and the appearance of the obtained polarizing film can be prevented from deteriorating, the water absorption rate of the thermoplastic resin substrate is preferably about 3% or less, 1 % or less is better. In addition, the said water absorption rate can be adjusted by, for example, introducing a modified group into the constituent material of the thermoplastic resin base material. The aforementioned water absorption is a value obtained in accordance with JIS K 7209.
由可抑制PVA系樹脂層之結晶化，同時充分確保積層體之延伸性之觀點來看，前述熱塑性樹脂基材之玻璃轉移溫度(Tg)宜為120℃左右以下。並且，考慮到利用水使熱塑性樹脂基材塑化與可良好進行水中延伸，前述玻璃轉移溫度(Tg)宜為100℃左右以下，90℃左右以下較佳。另一方面，由可防止熱塑性樹脂基材在塗佈、乾燥塗佈液時變形等不良情況而製作出良好的積層體之觀點來看，熱塑性樹脂基材的玻璃轉移溫度宜為60℃左右以上。此外，前述玻璃轉移溫度例如可藉由使用可將改質基導入前述熱塑性樹脂基材之構成材料的結晶化材料進行加熱來調整。前述玻璃轉移溫度(Tg)係依循JIS K 7121求得之值。The glass transition temperature (Tg) of the thermoplastic resin substrate is preferably about 120°C or lower from the viewpoint of suppressing the crystallization of the PVA-based resin layer and ensuring sufficient extensibility of the laminate. In addition, the glass transition temperature (Tg) is preferably about 100°C or lower, preferably about 90°C or lower, considering that the thermoplastic resin substrate can be plasticized by water and can be stretched well in water. On the other hand, the glass transition temperature of the thermoplastic resin substrate is preferably about 60°C or higher, from the viewpoint of preventing defects such as deformation of the thermoplastic resin substrate during coating and drying of the coating solution and producing a good laminate. . Moreover, the said glass transition temperature can be adjusted by heating, for example, using the crystallization material which can introduce|transduce a modified group into the constituent material of the said thermoplastic resin base material. The aforementioned glass transition temperature (Tg) is a value obtained in accordance with JIS K 7121.
前述熱塑性樹脂基材之構成材料可採用任意適當的熱塑性樹脂。前述熱塑性樹脂可舉例如聚對苯二甲酸乙二酯系樹脂等酯系樹脂、降莰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、聚碳酸酯系樹脂及其等之共聚物樹脂等。該等之中又以降莰烯系樹脂、非晶質(非晶性)聚對苯二甲酸乙二酯系樹脂較佳，並且由延伸性極優異且可抑制延伸時之結晶化的觀點來看，熱塑性樹脂基材較宜使用非晶質(非晶性)聚對苯二甲酸乙二酯系樹脂。非晶質(非晶性)聚對苯二甲酸乙二酯系樹脂可舉含間苯二甲酸及/或環己烷二羧酸作為二羧酸的共聚物、或是含環己烷二甲醇或二乙二醇作為甘醇的共聚物。Any appropriate thermoplastic resin can be used as the constituent material of the thermoplastic resin substrate. Examples of the thermoplastic resin include ester-based resins such as polyethylene terephthalate-based resins, cycloolefin-based resins such as norbornene-based resins, olefin-based resins such as polypropylene, polyamide-based resins, and polycarbonate-based resins. and other copolymer resins. Among these, norbornene-based resins and amorphous (amorphous) polyethylene terephthalate-based resins are preferred, and they are excellent in elongation and can suppress crystallization during elongation. , the thermoplastic resin substrate is preferably an amorphous (amorphous) polyethylene terephthalate resin. Amorphous (non-crystalline) polyethylene terephthalate resins include isophthalic acid and/or cyclohexanedicarboxylic acid as dicarboxylic acid copolymers, or cyclohexanedimethanol-containing copolymers Or diethylene glycol as a copolymer of glycol.
前述熱塑性樹脂基材可在形成PVA系樹脂層之前施行表面處理(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。又，前述熱塑性樹脂基材亦可在形成PVA系樹脂層前經已延伸。The aforementioned thermoplastic resin substrate may be subjected to surface treatment (eg, corona treatment, etc.) before forming the PVA-based resin layer, or an easily bonding layer may be formed on the thermoplastic resin substrate. The adhesiveness between the thermoplastic resin base material and the PVA-based resin layer can be improved by performing the above-mentioned treatment. In addition, the thermoplastic resin base material described above may be stretched before forming the PVA-based resin layer.
前述塗佈液係使PVA系樹脂溶解於溶劑中之溶液。作為前述溶劑，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，而宜為水。該等可單獨使用或可將二種以上組合來使用。由可形成密著於熱塑性樹脂基材之均勻的塗佈膜之觀點來看，前述塗佈液之PVA系樹脂濃度相對於溶劑100重量份宜為3~20重量份左右。The above-mentioned coating liquid is a solution obtained by dissolving PVA-based resin in a solvent. Examples of the solvent include water, dimethylsulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, various glycols, polyhydric alcohols such as trimethylolpropane, polyols such as Ethylenediamine, diethylenetriamine and other amines, and preferably water. These may be used alone or in combination of two or more. From the viewpoint of forming a uniform coating film that adheres to the thermoplastic resin substrate, the concentration of the PVA-based resin in the coating solution is preferably about 3 to 20 parts by weight relative to 100 parts by weight of the solvent.
由可透過延伸提升聚乙烯醇分子之定向性的觀點來看，前述塗佈液中宜摻混有鹵化物。前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等。前述碘化物可舉例如碘化鉀、碘化鈉及碘化鋰等，而宜為碘化鉀。前述塗佈液中前述鹵化物之濃度相對於PVA系樹脂100重量份宜為5~20重量份左右，10~15重量份左右較佳。From the viewpoint that the orientation of the polyvinyl alcohol molecules can be improved by extension, the aforementioned coating liquid is preferably mixed with a halide. Any appropriate halide can be used as the aforementioned halide, and examples thereof include iodide, sodium chloride, and the like. As said iodide, potassium iodide, sodium iodide, lithium iodide, etc. are mentioned, for example, and potassium iodide is preferable. The concentration of the halide in the coating solution is preferably about 5 to 20 parts by weight, preferably about 10 to 15 parts by weight, relative to 100 parts by weight of the PVA resin.
又，前述塗佈液中亦可摻混添加劑。前述添加劑可舉例如乙二醇或甘油等塑化劑；非離子界面活性劑等界面活性劑等。Moreover, you may mix|blend an additive in the said coating liquid. The aforementioned additives include, for example, plasticizers such as ethylene glycol and glycerin; surfactants such as nonionic surfactants, and the like.
前述塗佈液之塗佈方法可採用任意適當之方法，可舉例如輥塗法、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。又，前述塗佈液之乾燥溫度宜為50℃左右以上。Any suitable method can be used for the coating method of the aforementioned coating solution, such as roll coating method, spin coating method, wire bar coating method, dip coating method, die coating method, curtain coating method, spray coating method, and blade coating method. Cloth method (comma coating method, etc.) and so on. In addition, the drying temperature of the coating liquid is preferably about 50°C or higher.
前述空中輔助延伸處理可一邊抑制熱塑性樹脂基材之結晶化一邊進行延伸，因此可將積層體高倍率延伸。前述空中輔助延伸處理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間進行單軸延伸之方法)，而由獲得高光學特性之觀點來看，宜為自由端延伸。The above-mentioned air-assisted stretching treatment allows stretching while suppressing crystallization of the thermoplastic resin base material, so that the laminate can be stretched at a high magnification. The stretching method of the above-mentioned aerial auxiliary stretching treatment can be fixed-end stretching (such as a method of stretching using a tenter stretching machine), or a free-end stretching (such as uniaxial stretching of the laminated body through rollers with different peripheral speeds). method), and from the viewpoint of obtaining high optical properties, the free end extension is preferable.
由滿足上述b/a＞1之條件之觀點來看，前述空中輔助延伸之延伸倍率宜為2~3.5倍左右，且2.2~2.6倍左右較佳。前述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。From the viewpoint of satisfying the above-mentioned condition of b/a>1, the stretching ratio of the above-mentioned aerial auxiliary stretching is preferably about 2 to 3.5 times, and more preferably about 2.2 to 2.6 times. The aforementioned air assist extension can be performed 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.
前述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，例如宜為熱塑性樹脂基材之玻璃轉移溫度(Tg)以上，前述玻璃轉移溫度(Tg)+10℃以上較佳，前述玻璃轉移溫度(Tg)+15℃以上更佳。另一方面，由抑制PVA系樹脂之結晶化急速進展，而可抑制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)之觀點來看，延伸溫度之上限宜為170℃左右。The stretching temperature of the above-mentioned air-assisted stretching can be set to any appropriate value according to the forming material of the thermoplastic resin substrate, the stretching method, etc. The glass transition temperature (Tg) above is more preferably +10°C or higher. On the other hand, from the viewpoint of suppressing the rapid progress of crystallization of the PVA-based resin and suppressing inconveniences caused by crystallization (for example, hindering the orientation of the PVA-based resin layer due to stretching), the upper limit of the stretching temperature is preferably around 170°C.
亦可因應需要於前述空中輔助延伸處理後且於染色處理或水中延伸處理前施行不溶解處理。前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。藉由施行不溶解處理，可賦予PVA系樹脂層耐水性，防止浸漬於水中時PVA之定向降低。該硼酸水溶液之濃度相對於水100重量份宜為1~5重量份左右。不溶解處理浴之液溫宜為20~50℃左右。Insolubility treatment can also be performed after the aforementioned air-assisted extension treatment and before dyeing treatment or water extension treatment as required. The above-mentioned insolubilization treatment is performed by immersing the PVA-based resin layer in an aqueous solution of boric acid. By performing the insolubilization treatment, water resistance can be imparted to the PVA-based resin layer, and the orientation of the PVA can be prevented from being lowered when immersed in water. The concentration of the boric acid aqueous solution is preferably about 1 to 5 parts by weight relative to 100 parts by weight of water. The liquid temperature of the insolubility treatment bath should be about 20~50℃.
前述染色處理係以碘將PVA系樹脂層染色來進行。該吸附方法可舉例如：使PVA系樹脂層(積層體)浸漬於含碘之染色液中的方法、將該染色液塗敷於PVA系樹脂層上的方法、及將該染色液噴霧至PVA系樹脂層上的方法等，而宜為使PVA系樹脂層(積層體)浸漬於含碘之染色液中的方法。The aforementioned dyeing treatment is performed by dyeing the PVA-based resin layer with iodine. The adsorption method includes, for example, a method of immersing a PVA-based resin layer (layered body) in an iodine-containing dyeing solution, a method of applying the dyeing solution to the PVA-based resin layer, and spraying the dyeing solution to PVA The method on the resin layer, etc., is preferably a method of immersing the PVA-based resin layer (layered body) in an iodine-containing dyeing solution.
前述染色浴中碘之摻混量相對於水100重量份宜為0.05~0.5重量份左右。為了提高碘對水的溶解度，宜於碘水溶液中摻混前述碘化物。相對於水100重量份，前述碘化物之摻混量宜為0.1~10重量份左右，0.3~5重量份左右較佳。為了抑制PVA系樹脂溶解，染色浴的液溫宜為20~50℃左右。又，由滿足上述b/a＞1之條件且確保PVA系樹脂層之透射率之觀點來看，浸漬時間宜為5秒~5分鐘左右，且20秒~90秒左右較佳，30~50秒左右更佳。由獲得具有良好光學特性之偏光膜的觀點來看，碘水溶液中碘及碘化物之含量比宜為1：5~1：20左右，1：5~1：10左右較佳。The mixing amount of iodine in the dyeing bath is preferably about 0.05 to 0.5 parts by weight relative to 100 parts by weight of water. In order to improve the solubility of iodine in water, it is suitable to mix the aforementioned iodide into the iodine aqueous solution. With respect to 100 parts by weight of water, the blending amount of the aforementioned iodide is preferably about 0.1 to 10 parts by weight, preferably about 0.3 to 5 parts by weight. In order to suppress the dissolution of the PVA resin, the liquid temperature of the dyeing bath is preferably about 20 to 50 °C. In addition, from the viewpoint of satisfying the above-mentioned condition of b/a>1 and ensuring the transmittance of the PVA-based resin layer, the immersion time is preferably about 5 seconds to 5 minutes, more preferably about 20 seconds to 90 seconds, and 30 to 50 seconds. Seconds or so is better. From the viewpoint of obtaining a polarizing film with good optical properties, the content ratio of iodine and iodide in the iodine aqueous solution is preferably about 1:5 to 1:20, preferably about 1:5 to 1:10.
亦可因應需要於染色處理後且於水中延伸處理前施行交聯處理。前述交聯處理代表上係藉由使PVA系樹脂層浸漬於硼酸水溶液中來進行。藉由施行交聯處理，可賦予PVA系樹脂層耐水性，防止在之後的水中延伸中浸漬於高溫的水中時PVA之定向降低。該硼酸水溶液之硼酸濃度相對於水100重量份宜為1~5重量份左右。又，進行交聯處理時，宜進一步於交聯處理之交聯浴中摻混前述碘化物。藉由摻混前述碘化物，可抑制已吸附於PVA系樹脂層之碘的溶出。前述碘化物之摻混量相對於水100重量份宜為1~5重量份左右。交聯浴(硼酸水溶液)之液溫宜為20~50℃左右。The cross-linking treatment can also be performed after the dyeing treatment and before the extension treatment in water as required. The above-mentioned crosslinking treatment is typically performed by immersing the PVA-based resin layer in a boric acid aqueous solution. By performing the crosslinking treatment, water resistance can be imparted to the PVA-based resin layer, and the orientation of the PVA can be prevented from being lowered when immersed in high-temperature water during subsequent underwater stretching. The boric acid concentration of the boric acid aqueous solution is preferably about 1 to 5 parts by weight relative to 100 parts by weight of water. In addition, when the cross-linking treatment is performed, it is preferable to further mix the aforementioned iodide in the cross-linking bath of the cross-linking treatment. By blending the aforementioned iodide, the elution of the iodine adsorbed on the PVA-based resin layer can be suppressed. The blending amount of the aforementioned iodide is preferably about 1 to 5 parts by weight relative to 100 parts by weight of water. The liquid temperature of the cross-linking bath (boric acid aqueous solution) is preferably about 20~50°C.
前述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。前述水中延伸處理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間進行單軸延伸之方法)，而由獲得高光學特性之觀點來看，宜為自由端延伸。The above-mentioned underwater stretching treatment is performed by immersing the layered body in a stretching bath. By the underwater stretching treatment, it can be stretched at a temperature lower than the glass transition temperature (about 80°C in the representative) of the thermoplastic resin substrate or the PVA-based resin layer, and the crystallization of the PVA-based resin layer can be suppressed while at the same time. Perform high magnification extension. The stretching method of the above-mentioned underwater stretching treatment can be either fixed-end stretching (such as a method of stretching using a tenter stretching machine) or free-end stretching (such as a method of uniaxial stretching of the laminated body through rolls with different peripheral speeds) ), and from the viewpoint of obtaining high optical properties, it is preferable to extend the free end.
前述水中延伸處理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施加之張力的剛性與不溶於水的耐水性。硼酸水溶液之硼酸濃度相對於水100重量份，宜為1~10重量份，2.5~6重量份較佳。又，亦可於前述延伸浴(硼酸水溶液)中摻混碘化物。延伸浴之液溫宜為40~85℃左右，60℃~75℃左右較佳。積層體浸漬於延伸浴之浸漬時間宜為15秒~5分鐘左右。The above-mentioned underwater stretching treatment is preferably performed by immersing the layered body in a boric acid aqueous solution (boric acid water stretching). By using the boric acid aqueous solution as the stretching bath, the PVA-based resin layer can be provided with rigidity and water-insoluble water resistance capable of withstanding the tension applied during stretching. The boric acid concentration of the boric acid aqueous solution is preferably 1-10 parts by weight, preferably 2.5-6 parts by weight, relative to 100 parts by weight of water. Moreover, you may mix|blend iodide in the said extension bath (boric acid aqueous solution). The liquid temperature of the extension bath is preferably about 40 to 85°C, preferably about 60°C to 75°C. The immersion time during which the layered body is immersed in the stretching bath is preferably about 15 seconds to 5 minutes.
前述水中延伸之延伸倍率宜為1.5倍左右以上，3倍左右以上較佳。The stretching magnification of the above-mentioned stretching in water is preferably about 1.5 times or more, preferably about 3 times or more.
此外，積層體之總延伸倍率相對於積層體的原長，宜為5倍左右以上，5.5倍左右以上較佳。In addition, the total stretching magnification of the laminated body is preferably about 5 times or more, preferably about 5.5 times or more, with respect to the original length of the laminated body.
前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，惟較佳係使用該兩者。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，而可製造外觀優異的偏光膜，且可在使積層體維持平整之狀態的同時進行乾燥，因此不僅可抑制捲曲，還可抑制起皺發生。且，於乾燥收縮處理時，藉由使其於寬度方向收縮，可使所得偏光膜之光學特性提升，由此觀點來看，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%左右，2~8%左右較佳。The above-mentioned drying shrinkage treatment can be performed by area heating performed by heating the entire area, or by heating a conveying roller (so-called use of a heating roller), but it is preferable to use both. By drying it with a heating roller, the heating curl of the laminate can be effectively suppressed, and a polarizing film with excellent appearance can be produced, and the laminate can be dried while maintaining a flat state, so not only can curly be suppressed, The occurrence of wrinkling can also be suppressed. In addition, during the drying shrinkage treatment, the optical properties of the obtained polarizing film can be improved by shrinking it in the width direction. From this point of view, the shrinkage rate in the width direction obtained by the drying shrinkage treatment of the laminate is preferably 1 to 10. %, preferably about 2~8%.
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℃左右，65~100℃左右較佳，70~80℃更佳。由使熱塑性樹脂之結晶化度良好地增加以可良好地抑制捲曲之觀點來看，輸送輥一般係設置2個~40個左右，且宜設置4個~30個左右。積層體與加熱輥之接觸時間(總接觸時間)宜為1~300秒左右，1~20秒較佳，1~10秒更佳。Drying conditions can be controlled by adjusting the heating temperature of the conveying rollers (the temperature of the heating rollers), the number of heating rollers, and the contact time with the heating rollers. The temperature of the heating roller is preferably about 60~120℃, preferably about 65~100℃, more preferably about 70~80℃. From the viewpoint that the degree of crystallinity of the thermoplastic resin can be favorably increased and curling can be suppressed favorably, about 2 to 40 conveying rollers are generally provided, and about 4 to 30 are preferably provided. The contact time (total contact time) between the laminate and the heating roller is preferably about 1 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，而可容易控制寬度方向之收縮。熱風乾燥之溫度宜為30~100℃左右。且，熱風乾燥時間宜為1~300秒左右。The heating roller can be installed in a heating furnace or in a general manufacturing line (under a room temperature environment). It should be installed in a heating furnace with an air supply mechanism. The rapid temperature change between the heating rollers can be suppressed by combining the drying with the heating roller and the hot air drying, and the shrinkage in the width direction can be easily controlled. The temperature of hot air drying should be about 30~100℃. In addition, the hot air drying time is preferably about 1 to 300 seconds.
宜在水中延伸處理之後且在乾燥收縮處理之前施行洗淨處理。前述洗淨處理代表上係藉由使PVA系樹脂層浸漬於碘化鉀水溶液中來進行。The washing treatment is preferably carried out after the stretching treatment in water and before the drying shrinkage treatment. The aforementioned cleaning treatment is typically performed by immersing the PVA-based resin layer in an aqueous potassium iodide solution.
又，前述染色處理步驟、前述水中延伸處理步驟、前述不溶解處理步驟、前述交聯處理步驟及前述洗淨處理步驟之各處理浴中，亦可含有如鋅鹽、pH調整劑、pH緩衝劑、其他鹽類之添加劑。前述鋅鹽可舉例如氯化鋅、碘化鋅等鹵化鋅；硫酸鋅、乙酸鋅等無機鋅鹽等。前述pH調整劑可舉例如鹽酸、硫酸、硝酸等強酸或氫氧化鈉、氫氧化鉀等強鹼。前述pH緩衝劑可舉例如乙酸、草酸、檸檬酸等羧酸及其鹽、或如磷酸、碳酸之無機弱酸及其鹽。前述其他鹽類可舉例如氯化鈉、氯化鉀、氯化鋇等氯化物、如硝酸鈉、硝酸鉀之硝酸鹽、如硫酸鈉、硫酸鉀之硫酸鹽及鹼金屬、鹼土族金屬之鹽等。In addition, each treatment bath of the dyeing treatment step, the underwater extension treatment step, the insolubilization treatment step, the cross-linking treatment step, and the washing treatment step may contain, for example, a zinc salt, a pH adjusting agent, and a pH buffering agent. , Other salt additives. Examples of the zinc salt include zinc halides such as zinc chloride and zinc iodide; inorganic zinc salts such as zinc sulfate and zinc acetate. Examples of the pH adjuster include strong acids such as hydrochloric acid, sulfuric acid, and nitric acid, and strong bases such as sodium hydroxide and potassium hydroxide. Examples of the aforementioned pH buffer include carboxylic acids such as acetic acid, oxalic acid, and citric acid, and salts thereof, or inorganic weak acids such as phosphoric acid and carbonic acid, and salts thereof. The aforementioned other salts can be exemplified by chlorides such as sodium chloride, potassium chloride, barium chloride, nitrates such as sodium nitrate, potassium nitrate, sulfates such as sodium sulfate, potassium sulfate, and salts of alkali metals and alkaline earth metals. Wait.
＜第1及第2透明保護薄膜＞ 前述第1及第2透明保護薄膜只要前述第1透明保護薄膜之透濕度小於前述第2透明保護薄膜之透濕度且前述第1透明保護薄膜之透濕度為200g/(m2 ・24h)以下則無特別限制，可使用可用於偏光薄膜之各種透明保護薄膜。構成前述透明保護薄膜之材料可使用例如透明性、機械性強度、熱穩定性、水分阻斷性、各向同性等優異之熱塑性樹脂。前述熱塑性樹脂可舉例如：三醋酸纖維素等纖維素酯系樹脂、聚對苯二甲酸乙二酯或聚萘二甲酸乙二酯等聚酯系樹脂、聚醚碸系樹脂、聚碸系樹脂、聚碳酸酯系樹脂、尼龍或芳香族聚醯胺等聚醯胺系樹脂、聚醯亞胺系樹脂、如聚乙烯、聚丙烯、乙烯・丙烯共聚物之聚烯烴系樹脂、(甲基)丙烯酸系樹脂、環系或具有降莰烯結構之環狀聚烯烴系樹脂(降莰烯系樹脂)、聚芳酯系樹脂、聚苯乙烯系樹脂、聚乙烯醇系樹脂及該等的混合物。又，前述透明保護薄膜可使用由(甲基)丙烯酸系、胺甲酸酯系、丙烯酸胺甲酸酯系、環氧系、聚矽氧系等熱硬化性樹脂或紫外線硬化型樹脂形成之硬化層。該等中宜為纖維素酯系樹脂、聚碳酸酯系樹脂、(甲基)丙烯酸系樹脂、環狀聚烯烴系樹脂、聚酯系樹脂。<1st and 2nd transparent protective film> The first and second transparent protective films are as long as the water vapor transmission rate of the first transparent protective film is less than the water vapor transmission rate of the second transparent protective film and the water vapor transmission rate of the first transparent protective film is 200g/(m 2・24h) or less is not particularly limited, and various transparent protective films that can be used for polarizing films can be used. As the material constituting the above-mentioned transparent protective film, for example, thermoplastic resins excellent in transparency, mechanical strength, thermal stability, moisture barrier properties, and isotropy can be used. Examples of the thermoplastic resin include cellulose ester-based resins such as cellulose triacetate, polyester-based resins such as polyethylene terephthalate and polyethylene naphthalate, polyether-based resins, and poly-based resins. , Polycarbonate resins, polyamide resins such as nylon or aromatic polyamide, polyamide resins, polyolefin resins such as polyethylene, polypropylene, ethylene-propylene copolymers, (methyl) Acrylic resins, cyclic or cyclic polyolefin-based resins having a norbornene structure (norbornene-based resins), polyarylate-based resins, polystyrene-based resins, polyvinyl alcohol-based resins, and mixtures thereof. Moreover, the said transparent protective film can use the hardening which consists of thermosetting resins, such as (meth)acrylic type, urethane type, acrylate urethane type, epoxy type, polysiloxane type, or UV-curable resin. Floor. Among these, cellulose ester-based resins, polycarbonate-based resins, (meth)acrylic resins, cyclic polyolefin-based resins, and polyester-based resins are preferred.
前述第1及第2透明保護薄膜之厚度可適當決定，惟一般由強度或處置性等作業性、薄層性等觀點來看，宜為1~500µm左右，1~300µm左右較佳，5~100µm左右更佳。The thicknesses of the first and second transparent protective films can be appropriately determined, but generally from the viewpoints of strength, handling properties, etc., and thin layer properties, they are preferably about 1~500µm, preferably about 1~300µm, and 5~ About 100µm is better.
前述透明保護薄膜可使用具有正面相位差為40nm以上及/或厚度方向相位差為80nm以上之相位差的相位差板。正面相位差通常係控制在40~200nm之範圍，厚度方向相位差通常係控制在80~300nm之範圍。使用相位差板作為前述透明保護薄膜時，該相位差板亦可作為透明保護薄膜發揮功能，故能謀求薄型化。As the above-mentioned transparent protective film, a retardation plate having a retardation of 40 nm or more in front phase difference and/or 80 nm or more in thickness direction retardation can be used. The front phase difference is usually controlled in the range of 40~200nm, and the thickness direction retardation is usually controlled in the range of 80~300nm. When a retardation plate is used as the above-mentioned transparent protective film, the retardation plate can also function as a transparent protective film, so that the thickness can be reduced.
作為前述相位差板，可舉例如將高分子素材進行單軸或雙軸延伸處理而成之雙折射性薄膜、液晶聚合物之定向薄膜、以薄膜支持液晶聚合物之定向層者等。相位差板之厚度無特別限制，一般為20~150µm左右。此外，亦可於不具相位差之透明保護薄膜貼合前述相位板來使用。Examples of the retardation plate include birefringent films obtained by uniaxially or biaxially stretching polymer materials, alignment films of liquid crystal polymers, and alignment layers of liquid crystal polymers supported by films. The thickness of the retardation plate is not particularly limited, generally about 20~150µm. In addition, the above-mentioned phase plate can also be used by bonding the transparent protective film with no retardation.
前述第1及第2透明保護薄膜中亦可包含有紫外線吸收劑、抗氧化劑、滑劑、塑化劑、脫模劑、抗著色劑、阻燃劑、抗靜電劑、顏料、著色劑等任意適當之添加劑。尤其於前述透明保護薄膜中包含紫外線吸收劑時，可提升偏光薄膜之耐光性。The first and second transparent protective films may contain any of ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, anti-coloring agents, flame retardants, antistatic agents, pigments, colorants, and the like. appropriate additives. Especially when the above-mentioned transparent protective film contains an ultraviolet absorber, the light resistance of the polarizing film can be improved.
前述第1透明保護薄膜之透濕度為200g/(m2 ・24h)以下。由抑制在高溫高濕環境下之偏光膜的偏光度降低之觀點來看，前述第1透明保護薄膜之透濕度宜為100g/(m2 ・24h)以下，且50/(m2 ・24h)以下較佳。由貼合偏光膜與透明保護薄膜後之乾燥步驟的生產效率之觀點來看，前述第2透明保護薄膜之透濕度宜為250g/(m2 ・24h)以上，300g/(m2 ・24h)以上較佳，而由抑制在高溫高濕環境下之偏光膜的偏光度降低之觀點來看，透濕度宜為1,000g/(m2 ・24h)以下，600g/(m2 ・24h)以下較佳。此外，透濕度可依循JIS Z0208之透濕度試驗(透濕杯法(cup method))，將切斷成直徑60mm之試樣設置於裝有約15g氯化鈣之透濕杯中，並放入溫度40℃、濕度90%R.H.之恆溫機中，測定放置24小時之前與之後的氯化鈣之重量增加，藉此來算出。The water vapor transmission rate of the first transparent protective film is 200 g/(m 2 ·24h) or less. From the viewpoint of suppressing the decrease in the degree of polarization of the polarizing film in a high temperature and high humidity environment, the moisture permeability of the first transparent protective film is preferably 100 g/(m 2 · 24h) or less, and 50/(m 2 · 24h) The following are preferred. From the viewpoint of the production efficiency of the drying step after laminating the polarizing film and the transparent protective film, the moisture permeability of the second transparent protective film should preferably be 250g/(m 2 ·24h) or more, and 300g/(m 2 ·24h) The above is preferable, and from the viewpoint of suppressing the decrease in the degree of polarization of the polarizing film in a high temperature and high humidity environment, the moisture permeability is preferably 1,000g/(m 2・24h) or less, and 600g/(m 2・24h) or less is preferable. good. In addition, the moisture permeability can follow the moisture permeability test of JIS Z0208 (the cup method), and the sample cut into a diameter of 60mm is placed in a moisture permeable cup containing about 15g of calcium chloride, and placed in In a thermostat with a temperature of 40°C and a humidity of 90% RH, it was calculated by measuring the weight increase of calcium chloride before and after being left to stand for 24 hours.
前述第1及第2透明保護薄膜之不貼合偏光膜的面上可設置硬塗層、抗反射層、抗黏層、擴散層乃至防眩層等機能層。另，上述硬塗層、抗反射層、抗黏層、擴散層或防眩層等機能層除了可設置在保護薄膜其本身以外，還可另外設置成與保護薄膜分開的個體。Functional layers such as a hard coat layer, an anti-reflection layer, an anti-adhesion layer, a diffusion layer, and an anti-glare layer can be provided on the surfaces of the first and second transparent protective films that are not attached to the polarizing film. In addition, the above-mentioned functional layers such as the hard coat layer, antireflection layer, antiadhesion layer, diffusion layer or antiglare layer may be provided not only on the protective film itself, but also separately from the protective film.
前述偏光膜與前述第1及第2透明保護薄膜、前述第1及第2透明保護薄膜與前述機能層通常係透過黏著劑層或接著劑層貼合。The said polarizing film, the said 1st and 2nd transparent protective film, the said 1st and 2nd transparent protective film, and the said functional layer are usually bonded together through an adhesive layer or an adhesive layer.
形成前述黏著劑層之黏著劑可應用可用於偏光薄膜之各種黏著劑，可舉例如橡膠系黏著劑、丙烯酸系黏著劑、聚矽氧系黏著劑、胺甲酸酯系黏著劑、乙烯基烷基醚系黏著劑、聚乙烯醇系黏著劑、聚乙烯吡咯啶酮系黏著劑、聚丙烯醯胺系黏著劑、纖維素系黏著劑等。其中宜為丙烯酸系黏著劑。Various adhesives that can be used for polarizing films can be applied to the adhesives forming the above-mentioned adhesive layer, such as rubber-based adhesives, acrylic-based adhesives, polysiloxane-based adhesives, urethane-based adhesives, vinyl alkanes Base ether-based adhesives, polyvinyl alcohol-based adhesives, polyvinylpyrrolidone-based adhesives, polypropylene amide-based adhesives, cellulose-based adhesives, etc. Among them, an acrylic adhesive is suitable.
形成黏著劑層之方法可例示如以下方法等：將前述黏著劑塗佈於經剝離處理之分離件等，並進行乾燥而形成黏著劑層後，再轉印至偏光膜等之方法；或者，將前述黏著劑塗佈於偏光膜等，並進行乾燥而形成黏著劑層之方法。前述黏著劑層之厚度無特別限制，例如為1~100µm左右，且宜為2~50µm左右。The method of forming the adhesive layer can be exemplified by the following methods: the method of applying the above-mentioned adhesive to a peeling-treated separator, etc., and drying to form an adhesive layer, and then transferring to a polarizing film or the like; or, A method of applying the above-mentioned adhesive to a polarizing film, etc., and drying it to form an adhesive layer. The thickness of the aforementioned adhesive layer is not particularly limited, for example, it is about 1 to 100 µm, and preferably about 2 to 50 µm.
形成前述接著劑層之接著劑可應用可用於偏光薄膜之各種接著劑，可舉例如異氰酸酯系接著劑、聚乙烯醇系接著劑、明膠系接著劑、乙烯基系乳膠系、水系聚酯等。該等接著劑通常係以由水溶液構成之接著劑(水系接著劑)作使用，含有0.5~60重量%之固體成分而成。該等中宜為聚乙烯醇系接著劑，且含乙醯乙醯基之聚乙烯醇系接著劑較佳。Various adhesives that can be used for polarizing films can be applied to the adhesive forming the above-mentioned adhesive layer, for example, isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, vinyl-based latex-based adhesives, and water-based polyesters. These adhesives are usually used as an adhesive (aqueous adhesive) composed of an aqueous solution, and contain a solid content of 0.5 to 60% by weight. Among these, polyvinyl alcohol-based adhesives are preferred, and polyvinyl alcohol-based adhesives containing acetylacetate groups are preferred.
前述水系接著劑亦可包含有交聯劑。前述交聯劑一般可使用1分子中具有至少2個與構成接著劑之聚合物等之成分具有反應性之官能基的化合物，可舉例如伸烷基二胺類；異氰酸酯類；環氧類；醛類；羥甲基脲、羥甲基三聚氰胺等胺-甲醛等。接著劑中交聯劑之摻混量相對於構成接著劑之聚合物等成分100重量份，一般為10~60重量份左右。The aforementioned water-based adhesive may contain a crosslinking agent. The aforementioned crosslinking agent can generally be a compound having at least two functional groups reactive with components such as polymers constituting the adhesive in one molecule, such as alkylene diamines; isocyanates; epoxies; Aldehydes; methylol urea, methylol melamine and other amines-formaldehyde, etc. The blending amount of the cross-linking agent in the adhesive is generally about 10 to 60 parts by weight relative to 100 parts by weight of components such as the polymer constituting the adhesive.
前述接著劑除上述外，還可舉紫外線硬化型接著劑、電子束硬化型接著劑等活性能量線硬化型接著劑。前述活性能量線硬化型接著劑可舉例如(甲基)丙烯酸酯系接著劑。前述(甲基)丙烯酸酯系接著劑之硬化性成分可舉例如具有(甲基)丙烯醯基之化合物、具有乙烯基之化合物。具有(甲基)丙烯醯基之化合物可舉例如碳數1~20鏈狀烷基(甲基)丙烯酸酯、脂環式烷基(甲基)丙烯酸酯、多環式烷基(甲基)丙烯酸酯等(甲基)丙烯酸烷基酯；含羥基之(甲基)丙烯酸酯；(甲基)丙烯酸環氧丙酯等含環氧基之(甲基)丙烯酸酯等。(甲基)丙烯酸酯系接著劑亦可包含有羥乙基(甲基)丙烯醯胺、N‐羥甲基(甲基)丙烯醯胺、N‐甲氧基甲基(甲基)丙烯醯胺、N‐乙氧基甲基(甲基)丙烯醯胺、(甲基)丙烯醯胺、(甲基)丙烯醯基嗎福林等含氮單體。(甲基)丙烯酸酯系接著劑中作為交聯成分亦可包含有三丙二醇二丙烯酸酯、1,9‐壬二醇二丙烯酸酯、三環癸烷二甲醇二丙烯酸酯、環狀三羥甲丙烷甲縮醛丙烯酸酯、二㗁烷二醇二丙烯酸酯、EO改質二甘油四丙烯酸酯等多官能單體。又，陽離子聚合硬化型接著劑亦可使用具有環氧基或氧雜環丁烷基之化合物。具有環氧基之化合物只要是分子內具有至少2個環氧基者，則無特別限制，可使用一般已知的各種硬化性環氧化合物。In addition to the above-mentioned adhesives, active energy ray-curable adhesives such as ultraviolet curable adhesives and electron beam curable adhesives can be mentioned. As said active energy ray hardening type adhesive agent, a (meth)acrylate type adhesive agent is mentioned, for example. As a curable component of the said (meth)acrylate type adhesive agent, the compound which has a (meth)acryloyl group, and the compound which has a vinyl group are mentioned, for example. Examples of compounds having a (meth)acryloyl group include chain alkyl (meth)acrylates having 1 to 20 carbon atoms, alicyclic alkyl (meth)acrylates, and polycyclic alkyl (meth)acrylates. Alkyl (meth)acrylates such as acrylates; (meth)acrylates containing hydroxyl groups; (meth)acrylates containing epoxy groups such as glycidyl (meth)acrylates. (Meth)acrylate type adhesive may contain hydroxyethyl (meth)acrylamide, N-methylol (meth)acrylamide, N-methoxymethyl (meth)acrylamide Nitrogen-containing monomers such as amine, N-ethoxymethyl(meth)acrylamide, (meth)acrylamide, and (meth)acryloyl mofolin. The (meth)acrylate-based adhesive may contain tripropylene glycol diacrylate, 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and cyclic trimethylolpropane as a crosslinking component Methyl acrylate, diethylene glycol diacrylate, EO modified diglycerol tetraacrylate and other multifunctional monomers. Moreover, the compound which has an epoxy group or an oxetanyl group can also be used for a cationic polymerization hardening-type adhesive agent. The compound having an epoxy group is not particularly limited as long as it has at least two epoxy groups in the molecule, and various generally known curable epoxy compounds can be used.
前述接著劑亦可視需求包含有適當的添加劑。前述添加劑可舉例如矽烷耦合劑、鈦耦合劑等矽烷耦合劑、氧化乙烯等接著促進劑、紫外線吸收劑、抗劣化劑、染料、加工助劑、離子捕捉劑、抗氧化劑、賦黏劑、充填劑、塑化劑、調平劑、發泡抑制劑、抗靜電劑、耐熱穩定劑、耐水解穩定劑等。The aforementioned adhesive may also contain appropriate additives as required. Examples of the aforementioned additives include silane coupling agents such as silane coupling agents and titanium coupling agents, adhesion promoters such as ethylene oxide, ultraviolet absorbers, anti-deterioration agents, dyes, processing aids, ion scavengers, antioxidants, tackifiers, fillers, etc. agent, plasticizer, leveling agent, foam inhibitor, antistatic agent, heat-resistant stabilizer, hydrolysis-resistant stabilizer, etc.
前述接著劑的塗佈可對前述第1及第2透明保護薄膜側(或前述機能層側)、前述偏光膜側之任一者進行，亦可對兩者進行。於貼合後，施行乾燥步驟，形成由塗佈乾燥層構成之接著劑層。可於前述乾燥步驟後，因應需要照射紫外線或電子束。前述接著劑層之厚度無特別限制，於使用水系接著劑等時，宜為30~5000nm左右，100~1000nm左右較佳，而於使用紫外線硬化型接著劑、電子束硬化型接著劑等時，宜為0.1~100µm左右，0.5~10µm左右較佳。The coating of the adhesive agent may be performed on either of the first and second transparent protective film sides (or the functional layer side) and the polarizing film side, or may be performed on both. After lamination, a drying step is performed to form an adhesive layer consisting of a coating and drying layer. After the aforementioned drying step, ultraviolet rays or electron beams may be irradiated as required. The thickness of the above-mentioned adhesive layer is not particularly limited. When using a water-based adhesive or the like, it is preferably about 30 to 5000 nm, preferably about 100 to 1000 nm, and when using an ultraviolet curable adhesive, an electron beam curable adhesive, etc., It should be about 0.1~100µm, preferably about 0.5~10µm.
尤其，由生產效率之觀點來看，貼合前述偏光膜與前述第1透明保護薄膜之接著劑宜為活性能量線硬化型接著劑。In particular, from the viewpoint of production efficiency, the adhesive for laminating the polarizing film and the first transparent protective film is preferably an active energy ray-curable adhesive.
前述偏光膜、前述第1及第2透明保護薄膜、前述機能層亦可業經表面改質處理、易接著處理。The polarizing film, the first and second transparent protective films, and the functional layer may also be subjected to surface modification treatment and easy adhesion treatment.
前述表面改質處理可舉例如電暈處理、電漿處理、底漆處理、皂化處理等。As said surface modification treatment, corona treatment, plasma treatment, primer treatment, saponification treatment, etc. are mentioned, for example.
前述易接著處理可舉例如藉由包含具有下述骨架之各種樹脂的形成材進行之處理：聚酯骨架、聚醚骨架、聚碳酸酯骨架、聚胺甲酸酯骨架、聚矽氧系、聚醯胺骨架、聚醯亞胺骨架、聚乙烯醇骨架等。The aforementioned easy-bonding treatment includes, for example, treatment with a forming material containing various resins having the following skeletons: polyester skeleton, polyether skeleton, polycarbonate skeleton, polyurethane skeleton, polysiloxane-based, poly amide skeleton, polyimide skeleton, polyvinyl alcohol skeleton, etc.
前述第1及第2透明保護薄膜與前述偏光膜、前述第1及第2透明保護薄膜與前述機能層亦可隔著阻隔層、折射率調整層等中介層而積層。The first and second transparent protective films and the polarizing film, and the first and second transparent protective films and the functional layer may be laminated via intervening layers such as a barrier layer and a refractive index adjustment layer.
前述阻隔層係具有用以防止從透明保護薄膜等溶出之寡聚物或離子等不純物移動(侵入)至偏光膜中之功能的層。前述阻隔層只要是具有透明性且可防止從透明保護薄膜等溶出之不純物的層即可，形成阻隔層之材料可舉例如胺甲酸酯預聚物系形成材、氰基丙烯酸酯系形成材、環氧系形成材等。The barrier layer is a layer having a function of preventing impurities such as oligomers and ions eluted from the transparent protective film from moving (invading) into the polarizing film. The above-mentioned barrier layer should just be a layer which has transparency and can prevent impurities eluted from the transparent protective film or the like. Materials for forming the barrier layer include, for example, urethane prepolymer-based forming materials and cyanoacrylate-based forming materials. , Epoxy-based forming materials, etc.
前述折射率調整層係為了抑制透射率隨在前述透明保護薄膜與偏光膜等折射率不同之層間的反射而降低所設置之層。形成前述折射率調整層之折射率調整材可舉例如包含具有二氧化矽系、丙烯酸系、丙烯酸-苯乙烯系、三聚氰胺系等之各種樹脂及添加劑的形成劑。The refractive index adjustment layer is a layer provided in order to suppress a decrease in transmittance due to reflection between layers having different refractive indices, such as the transparent protective film and the polarizing film. As a refractive index adjustment material which forms the said refractive index adjustment layer, the formation agent containing various resins, such as a silica type, an acryl type, an acryl-styrene type, a melamine type, and an additive, is mentioned, for example.
前述偏光薄膜亦可為前述偏光薄膜貼合於光學層之積層偏光薄膜(光學積層體)。前述光學層無特別限定，例如可使用1層或2層以上之反射板及半透射板、相位差板(包含1/2或1/4等波長板)、視角補償薄膜等可用於形成液晶顯示裝置等的光學層。作為前述積層偏光薄膜，尤可舉例如：於前述偏光薄膜上再積層反射板或半透射反射板而成的反射型偏光薄膜或半透射型偏光薄膜、於前述偏光薄膜上再積層相位差板而成的橢圓偏光薄膜或圓偏光薄膜、於前述偏光薄膜上再積層視角補償薄膜而成的廣視角偏光薄膜、或於前述偏光薄膜上再積層增亮薄膜而成的偏光薄膜。The polarizing film may be a laminated polarizing film (optical laminate) in which the polarizing film is bonded to an optical layer. The aforementioned optical layer is not particularly limited, for example, one or more layers of reflective plates and semi-transmissive plates, retardation plates (including 1/2 or 1/4 wavelength plates), viewing angle compensation films, etc. can be used to form liquid crystal displays. Optical layers of devices, etc. Examples of the above-mentioned laminated polarizing film include, for example, a reflective polarizing film or a semi-transmissive polarizing film formed by laminating a reflective plate or a semi-transmissive reflecting plate on the above-mentioned polarizing film, and a retardation film formed by laminating a retardation film on the above-mentioned polarizing film. elliptical polarizing film or circular polarizing film, a wide viewing angle polarizing film formed by laminating a viewing angle compensation film on the polarizing film, or a polarizing film formed by laminating a brightness enhancement film on the polarizing film.
前述偏光薄膜或前述積層偏光薄膜之一面或兩面亦可附設接著劑層，用來貼合液晶單元或有機EL元件等影像顯示單元與在視辨側之前面透明板或觸控面板等前面透明構件等其他構件。該接著劑層宜為黏著劑層。形成前述黏著劑層之黏著劑無特別限制，可適當選擇以丙烯酸系聚合物、聚矽氧系聚合物、聚酯、聚胺甲酸酯、聚醯胺、聚醚、氟系或橡膠系等聚合物作為基底聚合物者來使用。尤其可適宜使用如包含丙烯酸系聚合物之黏著劑般具優異光學透明性、展現適度濡濕性、凝集性與接著性並且具有優異耐候性或耐熱性等之物。An adhesive layer can also be attached to one or both sides of the polarizing film or the laminated polarizing film, which is used to attach the image display unit such as liquid crystal cell or organic EL element to the front transparent member such as the front transparent plate or touch panel on the visual side. and other components. The adhesive layer is preferably an adhesive layer. The adhesive for forming the aforementioned adhesive layer is not particularly limited, and can be appropriately selected from acrylic polymers, polysiloxane polymers, polyesters, polyurethanes, polyamides, polyethers, fluorines, or rubbers, etc. A polymer is used as a base polymer. In particular, those having excellent optical transparency such as adhesives containing an acrylic polymer, exhibiting moderate wettability, cohesion and adhesiveness, and having excellent weather resistance or heat resistance, etc. can be suitably used.
將黏著劑層附設於前述偏光薄膜或前述積層偏光薄膜之單面或兩面可透過適當方式進行。附設黏著劑層可舉例如以下方式等：調製黏著劑溶液，並以流延方式或塗佈方式等適當之展開方式將其直接附設於前述偏光薄膜或前述積層偏光薄膜上的方式；或者，於分離件上形成黏著劑層，並將其轉黏至前述偏光薄膜或前述積層偏光薄膜上的方式。前述黏著劑層之厚度可因應使用目的或接著力等來適當決定，一般為1~500µm，宜為5~200µm，較宜為10~100µm。如此一來，將於前述偏光薄膜或前述積層偏光薄膜之至少一面設有黏著劑層者稱為附黏著劑層之偏光薄膜或附黏著劑層之積層偏光薄膜。Attaching the adhesive layer to one side or both sides of the aforementioned polarizing film or the aforementioned laminated polarizing film can be performed through an appropriate method. For example, the method of attaching the adhesive layer can include the following methods: preparing an adhesive solution, and directly attaching it to the polarizing film or the laminated polarizing film by a suitable spreading method such as a casting method or a coating method; or, in The method of forming an adhesive layer on the separating piece and transferring it to the above-mentioned polarizing film or the above-mentioned laminated polarizing film. The thickness of the aforementioned adhesive layer can be appropriately determined according to the purpose of use or the adhesive force, etc., and is generally 1~500µm, preferably 5~200µm, more preferably 10~100µm. In this way, at least one side of the polarizing film or the laminated polarizing film is provided with an adhesive layer, which is called a polarizing film with an adhesive layer or a laminated polarizing film with an adhesive layer.
對於前述黏著劑層之露出面，為防止其受污染，宜在供實際使用前之期間暫時黏附分離件來覆蓋。藉此可防止黏著劑層在通例之處置狀態下受汙染等。作為前述分離件，可使用例如經將塑膠薄膜、橡膠片、紙、布、不織布、網、發泡片或金屬箔及該等之積層體等適當的單片體因應需要以聚矽氧系或長鏈烷基系、氟系或硫化鉬等適當的剝離劑進行塗佈處理者等。For the exposed surface of the aforementioned adhesive layer, in order to prevent it from being contaminated, it is advisable to temporarily adhere a separating member to cover it before the actual use. Thereby, the adhesive layer can be prevented from being contaminated or the like in the conventional disposal state. As the aforementioned separators, suitable single-piece bodies such as plastic films, rubber sheets, paper, cloth, non-woven fabrics, nets, foam sheets, metal foils, and laminates thereof can be used, as required, with polysiloxane-based or A suitable release agent such as long-chain alkyl-based, fluorine-based, or molybdenum sulfide is used for coating treatment, etc.
＜影像顯示單元＞ 前述影像顯示單元可舉例如液晶單元或有機EL單元等。前述液晶單元可使用例如利用外光之反射型液晶單元、利用來自背光等光源之光的透射型液晶單元、利用來自外部之光與來自光源之光兩者的半透射半反射型液晶單元中之任一者。當前述液晶單元為利用來自光源之光者時，影像顯示裝置(液晶顯示裝置)亦係於影像顯示單元(液晶單元)之與視辨側相反之側配置偏光薄膜，並配置光源。該光源側之偏光薄膜與液晶單元宜透過適當之接著劑層貼合。前述液晶單元的驅動方式可使用例如VA模式、IPS模式、TN模式、STN模式或彎曲定向(π型)等任意型式。<Video display unit> The aforementioned image display unit includes, for example, a liquid crystal cell, an organic EL cell, and the like. As the liquid crystal cell, for example, a reflective liquid crystal cell using external light, a transmissive liquid crystal cell using light from a light source such as a backlight, and a transflective liquid crystal cell using both light from the outside and light from a light source can be used. either. When the liquid crystal cell utilizes light from a light source, the image display device (liquid crystal display device) also arranges a polarizing film on the opposite side of the image display cell (liquid crystal cell) from the viewing side, and configures the light source. The polarizing film on the light source side and the liquid crystal cell should be bonded together through an appropriate adhesive layer. As the driving method of the liquid crystal cell, any type such as VA mode, IPS mode, TN mode, STN mode, or bend alignment (π type) can be used.
前述有機EL單元可適宜使用例如於透明基板上依序積層有透明電極、有機發光層與金屬電極而形成發光體(有機電致發光體)者等。前述有機發光層係多種有機薄膜之積層體，例如可採用以下各種層構成：由三苯胺衍生物等構成之電洞注入層與由蒽等螢光性有機固體構成之發光層的積層體；該等發光層與由苝衍生物等構成之電子注入層的積層體；或者電洞注入層、發光層及電子注入層之積層體等。As the organic EL unit, for example, a transparent electrode, an organic light-emitting layer, and a metal electrode are sequentially laminated on a transparent substrate to form a light-emitting body (organic electroluminescent body) and the like can be suitably used. The aforementioned organic light-emitting layer is a laminate of various organic thin films, for example, the following layers may be used: a laminate of a hole injection layer composed of a triphenylamine derivative and the like and a light-emitting layer composed of a fluorescent organic solid such as anthracene; the A laminate of an isoluminescent layer and an electron injection layer composed of perylene derivatives, etc.; or a laminate of a hole injection layer, a luminescent layer, and an electron injection layer, etc.
＜影像顯示裝置＞ 本發明影像顯示裝置於前述影像顯示面板之前述第2透明保護薄膜側具備前面透明構件。<Video display device> The image display device of the present invention includes a front transparent member on the second transparent protective film side of the image display panel.
配置於前述影像顯示單元之視辨側的前面透明構件可舉例如前面透明板(視窗層)或觸控面板等。前述前面透明板可使用具有適當機械強度及厚度之透明板。所述透明板例如可使用丙烯酸系樹脂或聚碳酸酯系樹脂這類的透明樹脂板、或者玻璃板等。前述觸控面板可使用例如電阻膜式、電容式、光學式、超音波式等各種觸控面板、或具備觸控感測功能之玻璃板或透明樹脂板等。在使用電容式觸控面板作為前述前面透明構件時，宜在較觸控面板更靠視辨側設置由玻璃或透明樹脂板構成之前面透明板。As a front transparent member arrange|positioned at the viewing side of the said image display unit, a front transparent plate (window layer), a touch panel, etc. are mentioned, for example. As the front transparent plate, a transparent plate having appropriate mechanical strength and thickness can be used. As the transparent plate, a transparent resin plate such as an acrylic resin or a polycarbonate resin, a glass plate, or the like can be used, for example. As the aforementioned touch panel, various touch panels such as resistive film type, capacitive type, optical type, and ultrasonic type, or a glass plate or a transparent resin plate having a touch sensing function can be used. When a capacitive touch panel is used as the front transparent member, it is preferable to provide a front transparent plate made of glass or a transparent resin plate on the visual side of the touch panel.
實施例 以下列舉實施例來更詳細說明本發明，惟本發明不僅受該等實施例所限。Example The following examples are given to illustrate the present invention in more detail, but the present invention is not limited only by these examples.
＜實施例1＞ ＜碘系偏光膜之製作＞ 對吸水率0.75%、Tg75℃之非晶質間苯二甲酸共聚聚對苯二甲酸乙二酯(IPA共聚PET)薄膜(厚度：100µm)基材的單面施加電暈處理，並在該電暈處理面上於25℃下塗佈以9：1之比包含聚乙烯醇(聚合度4200，皂化度99.2莫耳%)及乙醯乙醯基改質PVA(聚合度1200，乙醯乙醯基改質度4.6%，皂化度99.0莫耳%以上，日本合成化學工業公司製，商品名「Gohsefimer Z410」)的水溶液並乾燥，形成厚度13µm的PVA系樹脂層，而製作出積層體。將所得積層體於130℃之烘箱內在周速相異之輥間沿縱方向(長邊方向)進行自由端單軸延伸成2.4倍(空中輔助延伸處理)。接著，使積層體浸漬於液溫40℃之不溶解浴(相對於水100重量份摻混4重量份之硼酸而得之硼酸水溶液)中30秒鐘(不溶解處理)。接著，於液溫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得之碘水溶液中調整碘濃度的同時使其浸漬於其中40秒，以使最後所得偏光膜成為預定之單體透射率(染色處理)。接著，使其浸漬於液溫40℃之交聯浴(相對於水100重量份，摻混3重量份之碘化鉀並摻混5重量份之硼酸而得之硼酸水溶液)中30秒鐘(交聯處理)。其後，一邊使積層體浸漬於液溫70℃之硼酸水溶液(相對於100重量份的水摻混4重量份硼酸並摻混5重量份碘化鉀所得之水溶液)中，一邊於不同周速之輥間沿縱方向(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)。之後，使積層體浸漬於液溫20℃之洗淨浴(相對於水100重量份，摻混4重量份之碘化鉀而得之水溶液)中(洗淨處理)。之後，一邊在經保持於90℃之烘箱中乾燥，一邊使其接觸表面溫度經保持於75℃之SUS製加熱輥約2秒(乾燥收縮處理)。以上述方式獲得了包含厚度5.4µm之偏光膜的光學薄膜積層體。利用以下測定方法所得之偏光膜中的碘濃度為7.1重量%，單體透射率為43.5%。<Example 1> ＜Production of iodine-based polarizing film＞ Corona treatment was applied to one side of the substrate of amorphous isophthalic acid copolyethylene terephthalate (IPA copolyethylene terephthalate) film (thickness: 100µm) with a water absorption rate of 0.75% and a Tg of 75°C. The halo-treated surface was coated at 25°C with polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mol%) and acetylacetate modified PVA (polymerization degree 1200, acetylacetate) in a ratio of 9:1. The degree of radical modification was 4.6%, the degree of saponification was 99.0 mol% or more, and an aqueous solution of Nippon Synthetic Chemical Industry Co., Ltd., trade name "Gohsefimer Z410") was dried to form a PVA-based resin layer with a thickness of 13 µm, and a laminate was produced. The obtained layered body was uniaxially stretched by 2.4 times the free end in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds in an oven at 130°C (aerial-assisted stretching treatment). Next, the layered body was immersed in an insolubilization 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 (insolubility treatment). Next, in a dyeing bath (with respect to 100 parts by weight of water, iodine concentration was adjusted in 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, and the iodine concentration was adjusted and immersed in the dyeing bath for 40 seconds to obtain a The polarizing film finally obtained is made into a predetermined monomer transmittance (dyeing treatment). Next, it is immersed in a cross-linking bath at a liquid temperature of 40° C. (with respect to 100 parts by weight of water, 3 parts by weight of potassium iodide and 5 parts by weight of potassium iodide are mixed (cross-linking treatment) for 30 seconds (cross-linking treatment) in a boric acid aqueous solution obtained by weight parts of boric acid. Thereafter, the layered body was immersed in a boric acid aqueous solution at a liquid temperature of 70° C. (4 weight parts of boric acid was mixed with 100 weight parts of water. and blending 5 parts by weight of potassium iodide in an aqueous solution), uniaxially stretched along the longitudinal direction (long side direction) between rolls with different peripheral speeds to make the total stretching ratio reach 5.5 times (stretching in water). The body was immersed in a cleaning bath (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 (cleaning treatment). While drying, the contact surface temperature was kept at 75°C by a heating roller made of SUS for about 2 seconds (drying shrinkage treatment). An optical film laminate including a polarizing film with a thickness of 5.4 µm was obtained in the above-described manner. Obtained by the following measurement method The iodine concentration in the polarizing film was 7.1% by weight, and the monomer transmittance was 43.5%.
＜偏光膜中之碘濃度(重量%)之測定方法＞ 針對偏光膜，使用X射線螢光分析裝置(Rigaku公司製，商品名「ZSX-PRIMUS IV」，測定徑：ψ20mm)，並用下述式求得碘濃度(重量%)。 碘濃度(wt%=14.474×(X射線螢光強度)/(薄膜厚度)(kcps/µm)此外，計算濃度時之係數會依測定裝置而有所不同，而該係數可使用適當之檢量曲線求得。<Measuring method of iodine concentration (% by weight) in polarizing film> The iodine concentration (% by weight) of the polarizing film was determined by the following formula using an X-ray fluorescence analyzer (manufactured by Rigaku, trade name "ZSX-PRIMUS IV", measurement diameter: ψ20 mm). Iodine concentration (wt%=14.474×(X-ray fluorescence intensity)/(film thickness) (kcps/µm) In addition, the coefficient for calculating the concentration will vary depending on the measuring device, and the coefficient can be used with an appropriate calibration curve obtained.
＜偏光薄膜之製作＞ 利用輥貼合機透過UV硬化型接著劑以使作為第2透明保護薄膜之具有硬塗層之厚度48µm的三醋酸纖維素(TAC)薄膜(富士軟片製「TJ40UL」，透濕度300g/(m2 ・24h))之三醋酸纖維素面與上述光學薄膜積層體之偏光膜面相接之方式貼合後，照射紫外線作為活性能量線使接著劑硬化。接著，對已剝離聚對苯二甲酸乙二酯薄膜之面的偏光膜施行電暈處理，並透過上述UV硬化型接著劑以使作為第1透明保護薄膜之厚度18µm之環烯烴系(COP)薄膜(日本ZEON公司製「ZT12」，透濕度20g/(m2 ・24h))與偏光膜之電暈處理面相接之方式貼合後，照射紫外線作為活性能量線使接著劑硬化，而製作出偏光薄膜。此外，紫外線照射是使用充有鎵之金屬鹵素燈、照射裝置：Fusion UV Systems,Inc公司製的Light HAMMER10、燈泡：V燈泡、峰值照度：1600mW/cm2 、累積照射量1000/mJ/cm2 (波長380~440nm)，紫外線的照度是使用Solatell公司製的Sola-Check系統來測定。<Production of polarizing film> A 48µm thick triacetate cellulose (TAC) film with a hard coat layer (“TJ40UL” manufactured by Fujifilm, Ltd. The cellulose triacetate surface with a water vapor transmission rate of 300g/(m 2 · 24h)) was bonded to the polarizing film surface of the above-mentioned optical film laminate, and then the adhesive was cured by irradiating ultraviolet rays as active energy rays. Next, corona treatment was performed on the polarizing film on the surface of the peeled polyethylene terephthalate film, and the above-mentioned UV curable adhesive was passed through to make the first transparent protective film a cycloolefin-based (COP) film with a thickness of 18 µm. The film (“ZT12” manufactured by ZEON, Japan, moisture permeability 20g/(m 2 · 24h)) is bonded to the corona-treated surface of the polarizing film, and then irradiated with ultraviolet rays as active energy rays to harden the adhesive. polarizing film. In addition, a metal halide lamp filled with gallium was used for ultraviolet irradiation, irradiation device: Light HAMMER10 manufactured by Fusion UV Systems, Inc., bulb: V bulb, peak illuminance: 1600 mW/cm 2 , cumulative irradiation dose 1000/mJ/cm 2 (wavelength 380-440nm), the illuminance of an ultraviolet-ray was measured using the Sola-Check system made by Solatell.
＜利用拉曼分光分析進行之光譜面積比之測定＞ 利用切片機沿相對於上述所得偏光薄膜之吸收軸呈垂直之方向，製作出厚度100nm之截面切片(分析試樣)後，於偏光膜之厚度方向上按0.1µm間隔之測定點進行拉曼光譜之測定。雷射光係以與偏光膜之吸收軸方向(延伸方向)平行且與超薄切片試料之偏光膜截面呈垂直之方式入射該偏光面。接著，如圖2，針對在各測定點所得之拉曼光譜，藉由令連結在波數80cm-1 之拉曼強度與在波數130cm-1 之拉曼強度之各點的直線作為基線(以虛線顯示)，來求出在波數80cm-1 ~130cm-1 之區間的積分強度。從所得各測定點之積分強度求出偏光膜之厚度方向的積分強度分布。將結果示於圖3。並算出令自第1透明保護薄膜側之偏光膜之表層起1µm~1.5µm之80cm-1 ~130cm-1 之區間的光譜面積(積分強度)為a、且令自保護薄膜B側之偏光膜之表層起80cm-1 ~130cm-1 之區間的光譜面積(積分強度)為b時之比(b/a)。將結果列於表1。拉曼分光分析之測定條件顯示於下。 [拉曼分光分析之條件] ・測定裝置：Jobin Yvon S.A.S公司製顯微鏡雷射拉曼「LabRAM HR800」 ・測定焦點：最表面 ・測定波長：約30~600cm-1 ・雷射波長：514nm ・中性密度濾光器(Neutral Density Filter)：D4(入射雷射輸出×0.0001) ・透鏡：×100(N.A. 0.9) ・雷射輸出：6mW<Measurement of Spectral Area Ratio by Raman Spectroscopic Analysis> Using a microtome, a cross-sectional slice (analysis sample) with a thickness of 100 nm was prepared in a direction perpendicular to the absorption axis of the polarizing film obtained above, and then placed on the polarizing film. The Raman spectrum was measured at 0.1µm intervals in the thickness direction. The laser light is incident on the polarizing plane so as to be parallel to the absorption axis direction (extending direction) of the polarizing film and perpendicular to the cross section of the polarizing film of the ultrathin section sample. Next, as shown in FIG. 2, for the Raman spectrum obtained at each measurement point, a straight line connecting each point of the Raman intensity at the wavenumber of 80 cm-1 and the Raman intensity at the wavenumber of 130 cm -1 was used as the baseline ( Shown by the dotted line), to obtain the integrated intensity in the interval of wavenumber 80cm -1 ~130cm -1. The integrated intensity distribution in the thickness direction of the polarizing film was obtained from the integrated intensity at each measurement point obtained. The results are shown in FIG. 3 . And calculate the spectral area (integrated intensity) in the interval of 80cm -1 ~ 130cm -1 from 1µm to 1.5µm from the surface layer of the polarizing film on the side of the first transparent protective film, and let the polarizing film on the side of the protective film B be The spectral area (integrated intensity) in the interval from 80cm -1 to 130cm -1 from the surface layer is the ratio at time b (b/a). The results are listed in Table 1. The measurement conditions of the Raman spectroscopic analysis are shown below. [Conditions for Raman spectroscopic analysis] ・Measuring device: Microscope laser Raman "LabRAM HR800" manufactured by Jobin Yvon SAS Corporation ・Measurement focus: outermost surface ・Measurement wavelength: about 30~600cm -1・Laser wavelength: 514nm ・Middle Neutral Density Filter: D4 (incident laser output × 0.0001) ・Lens: ×100 (NA 0.9) ・Laser output: 6mW
＜模擬影像顯示面板之製作＞ 透過黏著劑將25×40mm尺寸之小片玻璃貼合於上述所得偏光膜之環烯烴系薄膜面，而製作出模擬影像顯示面板。<Production of analog video display panel> A small piece of glass with a size of 25×40 mm was attached to the cycloolefin-based film surface of the above-obtained polarizing film through an adhesive to produce an analog image display panel.
＜高溫耐久性之評估＞ 將上述所得模擬影像顯示面板投入溫度110℃之熱風烘箱內120小時，測定了投入(加熱)前後之單體透射率(ΔTs)。單體透射率係使用分光光度計(大塚電子公司製，LPF-200)測定。該單體透射率係以JIS Z 8701-1982之2度視野(C光源)進行視感度校正所得的Y值。此外，測定波長為380~780nm(每5nm)。 ΔTs(%)=Ts120 -Ts0 在此，Ts0 為初始(加熱前)之單體透射率，而Ts120 為加熱120小時後之單體透射率。 〇：ΔTs(%)為0%以上且小於3% ×：ΔTs(%)小於0%或為3%以上<Evaluation of High Temperature Durability> The simulated image display panel obtained above was put into a hot air oven at a temperature of 110° C. for 120 hours, and the single transmittance (ΔTs) before and after being put into (heated) was measured. The single transmittance was measured using a spectrophotometer (manufactured by Otsuka Electronics Co., Ltd., LPF-200). The single transmittance is a Y value obtained by performing a visual sensitivity correction with a 2-degree field of view (C light source) in JIS Z 8701-1982. In addition, the measurement wavelength is 380 to 780 nm (every 5 nm). ΔTs(%)=Ts 120 -Ts 0 Here, Ts 0 is the initial (before heating) transmittance of the monomer, and Ts 120 is the transmittance of the monomer after heating for 120 hours. 〇: ΔTs(%) is 0% or more and less than 3% ×: ΔTs(%) is less than 0% or 3% or more
＜實施例2＞
利用輥貼合機透過水系接著劑以使作為第2透明保護薄膜之具有硬塗層之厚度47µm的三醋酸纖維素(TAC)薄膜(富士軟片製「TJ40UL」，透濕度300g/(m2
・24h))之三醋酸纖維素面與上述光學薄膜積層體之偏光膜面相接之方式貼合後，於烘箱內使其加熱乾燥(溫度為60℃，時間為4分鐘)使接著劑硬化，除此之外依與實施例1相同操作，製作出偏光薄膜及模擬影像顯示面板並供於評估。此時之水系接著劑係使用以下水溶液：以重量比3:1含有含乙醯乙醯基之聚乙烯醇樹脂(平均聚合度1,200，皂化度98.5莫耳%，乙醯乙醯基化度5莫耳%)與羥甲基三聚氰胺者。將結果列於表1。<Example 2> A 47 µm thick triacetate cellulose (TAC) film (TJ40UL, manufactured by Fujifilm) with a hard coat layer as the second transparent protective film was passed through a water-based adhesive using a roll laminator, and the moisture permeability was 300 g. /(m 2 · 24h)) the triacetate cellulose surface and the polarizing film surface of the optical film laminate are bonded together, and then heated and dried in an oven (temperature is 60°C, time is 4 minutes) to make Then the agent was hardened, except that the same operation as in Example 1 was performed, and a polarizing film and a simulated image display panel were produced and used for evaluation. The water-based adhesive at this time used the following aqueous solution: a polyvinyl alcohol resin containing an acetoacetyl group at a weight ratio of 3:1 (average degree of polymerization 1,200, degree of saponification 98.5 mol%, degree of
＜比較例1＞ 將偏光膜之用來貼合第1透明保護薄膜與偏光膜之面、及用來貼合第2透明保護薄膜與偏光膜之面對調，除此之外依與實施例1相同操作，製作出偏光薄膜及模擬影像顯示面板並供於評估。將結果列於表1。<Comparative Example 1> The surface of the polarizing film used for laminating the first transparent protective film and the polarizing film, and the surface used for laminating the second transparent protective film and the polarizing film, were adjusted, except that the same operation as in Example 1 was carried out to make Polarizing films and analog image display panels were produced for evaluation. The results are listed in Table 1.
＜比較例2＞ 將偏光膜之用來貼合第1透明保護薄膜與偏光膜之面、及用來貼合第2透明保護薄膜與偏光膜之面對調，除此之外依與實施例2相同操作，製作出偏光薄膜及模擬影像顯示面板並供於評估。將結果列於表1。<Comparative Example 2> The surface of the polarizing film used for bonding the first transparent protective film and the polarizing film, and the surface used for bonding the second transparent protective film and the polarizing film to be adjusted, except that the same operation as in Example 2 was carried out to make Polarizing films and analog image display panels were produced for evaluation. The results are listed in Table 1.
[表1]
10:偏光薄膜 11:碘系偏光膜 12:第1透明保護薄膜 13:第2透明保護薄膜 20:黏著劑層 80:前面透明構件 90:影像顯示單元 100:影像顯示面板 200:影像顯示裝置10: polarizing film 11: Iodine-based polarizing film 12: The first transparent protective film 13: The second transparent protective film 20: Adhesive layer 80: Front transparent member 90: Image display unit 100: Image display panel 200: Video display device
圖1係顯示影像顯示面板及影像顯示裝置之一形態的示意截面圖。 圖2係顯示針對實施例1之超薄切片試料之偏光膜利用拉曼分光分析所得之拉曼光譜的圖表。 圖3係顯示針對實施例1之偏光膜的厚度方向，利用拉曼分光分析所得80cm-1 至130cm-1 為止之光譜面積分布(積分強度分布)的圖表。FIG. 1 is a schematic cross-sectional view showing one form of an image display panel and an image display device. FIG. 2 is a graph showing the Raman spectrum obtained by Raman spectroscopic analysis of the polarizing film of the ultrathin section sample of Example 1. FIG. FIG 3 in the thickness direction of the polarizing film for a display system of Example 1 of the embodiment, using a Raman spectroscopic analysis chart of up to 80cm -1 to 130cm -1 resultant spectral distribution area (integrated intensity distribution).
10:偏光薄膜10: polarizing film
11:碘系偏光膜11: Iodine-based polarizing film
12:第1透明保護薄膜12: The first transparent protective film
13:第2透明保護薄膜13: The second transparent protective film
20:黏著劑層20: Adhesive layer
80:前面透明構件80: Front transparent member
90:影像顯示單元90: Image display unit
100:影像顯示面板100: Image display panel
200:影像顯示裝置200: Video display device
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| TW110116260A TW202144820A (en) | 2020-05-08 | 2021-05-05 | Image display panel and image display device |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2021178508A (en) |
| KR (1) | KR20230007311A (en) |
| CN (1) | CN115516347A (en) |
| TW (1) | TW202144820A (en) |
| WO (1) | WO2021225117A1 (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006171707A (en) * | 2004-11-18 | 2006-06-29 | Nitto Denko Corp | Polarizing plate and image display using same |
| WO2010087653A2 (en) | 2009-01-30 | 2010-08-05 | 주식회사 엘지화학 | Outstandingly durable and heat-resistant polarising element, polarising plate and image-display device, and polarising-element production method |
| JP6071459B2 (en) | 2012-11-19 | 2017-02-01 | 日東電工株式会社 | Polarizing plate, image display device, and manufacturing method thereof |
| JP5615987B2 (en) * | 2013-02-07 | 2014-10-29 | 日東電工株式会社 | Optical laminate having polarizing film |
| JP5863053B2 (en) * | 2013-09-06 | 2016-02-16 | 日東電工株式会社 | Polarizing film, manufacturing method of polarizing film, and image display device using the polarizing film |
| KR102441217B1 (en) * | 2014-07-04 | 2022-09-06 | 스미또모 가가꾸 가부시키가이샤 | Method for producing polarizing plate having protective films on both surfaces thereof |
| WO2016013260A1 (en) * | 2014-07-25 | 2016-01-28 | コニカミノルタ株式会社 | Polarizing plate, method for producing polarizing plate, and liquid crystal display device |
| JP6850601B2 (en) | 2016-12-21 | 2021-03-31 | 日東電工株式会社 | Image display device |
-
2021
- 2021-04-27 JP JP2021074607A patent/JP2021178508A/en active Pending
- 2021-04-30 CN CN202180033331.3A patent/CN115516347A/en active Pending
- 2021-04-30 WO PCT/JP2021/017203 patent/WO2021225117A1/en active Application Filing
- 2021-04-30 KR KR1020227030180A patent/KR20230007311A/en unknown
- 2021-05-05 TW TW110116260A patent/TW202144820A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2021225117A1 (en) | 2021-11-11 |
| CN115516347A (en) | 2022-12-23 |
| JP2021178508A (en) | 2021-11-18 |
| KR20230007311A (en) | 2023-01-12 |
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