TW202116563A - Polarization film, layered polarization film, image display panel, and image display device - Google Patents
Polarization film, layered polarization film, image display panel, and image display device Download PDFInfo
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- TW202116563A TW202116563A TW109129381A TW109129381A TW202116563A TW 202116563 A TW202116563 A TW 202116563A TW 109129381 A TW109129381 A TW 109129381A TW 109129381 A TW109129381 A TW 109129381A TW 202116563 A TW202116563 A TW 202116563A
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- polarizing film
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- image display
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- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
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Classifications
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- 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
-
- 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
-
- 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
- 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
- G02F1/133528—Polarisers
-
- 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
- G02F1/13363—Birefringent elements, e.g. for optical compensation
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Polarising Elements (AREA)
Abstract
Description
本發明涉及偏光薄膜、積層偏光薄膜、影像顯示面板及影像顯示裝置。The invention relates to a polarizing film, a laminated polarizing film, 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，施行洗淨處理然後進行乾燥來製造。又，前述偏光膜通常係製成於其單面或兩面使用接著劑貼合有三醋酸纖維素等之保護薄膜而成的偏光薄膜(偏光板)來使用。In the past, polarizing films used in various image display devices such as liquid crystal display devices or organic EL display devices have been dyed (containing iodine or dichroic dyes, etc.) for the reason of having both high transmittance and high polarization. Color material) polyvinyl alcohol film. This polarizing film is manufactured by subjecting the polyvinyl alcohol-based film to various treatments such as swelling, dyeing, crosslinking, and stretching in a bath, followed by washing treatment and drying. In addition, the aforementioned polarizing film is usually used as a polarizing film (polarizing plate) in which a protective film such as cellulose triacetate is bonded to one or both sides using an adhesive.
前述偏光薄膜可因應需要與其他光學層積層而製成積層偏光薄膜(光學積層體)來使用，而前述偏光薄膜或前述積層偏光薄膜(光學積層體)係透過黏著劑層或接著劑層貼合於液晶單元或有機EL元件等影像顯示單元與在視辨側之前面透明板(視窗層)或觸控面板等前面透明構件之間，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 laminated with other optical layers to form a laminated polarizing film (optical laminate) to use, and the aforementioned polarizing film or the aforementioned laminated polarizing film (optical laminate) is bonded through an adhesive layer or an adhesive layer. Between the image display unit such as a liquid crystal cell or an organic EL element and a front transparent member such as a front transparent plate (window layer) or a touch panel on the viewing side, the various image display devices described above are used (Patent Document 1).
近年來，所述各種影像顯示裝置除了製成行動電話或平板電腦終端等行動設備使用之外，亦製成汽車導航裝置或後照監視器等車載用影像顯示裝置使用等，其用途廣泛。因此，要求前述影像顯示裝置在比以往即要求的更嚴酷之環境下(例如高溫環境下)有高耐久性，而提出一種以確保所述耐久性為目的之影像顯示裝置(專利文獻2)。 先前技術文獻 專利文獻In recent years, the various image display devices described above have been used in mobile devices such as mobile phones or tablet terminals, as well as in-vehicle image display devices such as car navigation devices and rear-illuminated monitors, and have a wide range of applications. Therefore, the aforementioned image display device is required to have high durability in a harsher environment (for example, under a high temperature environment) than conventionally required, and an image display device for the purpose of ensuring the durability is proposed (Patent Document 2). 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：日本專利特開2018-101117號公報Patent Document 1: Japanese Patent Laid-Open No. 2014-102353 Patent Document 2: Japanese Patent Laid-Open No. 2018-101117
發明欲解決之課題 使用碘系偏光膜之偏光薄膜或積層偏光薄膜在暴露於高溫環境下時，構成偏光膜之聚乙烯醇會因脫水反應而多烯化，使偏光膜產生著色，而有其單體透射率降低之問題。The problem to be solved by the invention When the polarizing film or laminated polarizing film using iodine-based polarizing film is exposed to high temperature, the polyvinyl alcohol that constitutes the polarizing film will be polyalkenized due to the dehydration reaction, causing the polarizing film to be colored, and its monomer transmittance is reduced. The problem.
本發明人等經過積極研討，發現碘系偏光膜中所含之碘在高溫環境下會促進多烯化。因此，若欲抑制在高溫環境下偏光膜著色造成單體透射率降低，有效的是使偏光膜中的碘濃度(含量)減少，但在使用這種偏光膜時，伴隨影像顯示裝置之面板的大型化，有容易發生偏光薄膜或積層偏光薄膜在加熱時剝落之傾向。Through active research, the inventors of the present invention found that iodine contained in the iodine-based polarizing film promotes polyethylenization under a high-temperature environment. Therefore, if it is desired to suppress the reduction of the monomer transmittance caused by the coloring of the polarizing film in a high-temperature environment, it is effective to reduce the iodine concentration (content) in the polarizing film. However, when such a polarizing film is used, it is accompanied by the deterioration of the panel of the image display device. The larger the size, there is a tendency for the polarizing film or laminated polarizing film to peel off when heated.
又，偏光薄膜或積層偏光薄膜在高溫高濕環境下時，偏光膜中的硼酸交聯會脫落，造成碘錯合物被破壞，而有偏光度降低之問題。In addition, when the polarizing film or the laminated polarizing film is in a high temperature and high humidity environment, the crosslinking of boric acid in the polarizing film will fall off, causing the iodine complex to be destroyed, and there is a problem that the degree of polarization decreases.
鑒於以上情事，本發明之目的在於提供一種具有以下偏光膜之偏光薄膜，該偏光膜之初始偏光度良好，且在高溫環境下抑制偏光膜著色造成單體透射率降低之效果佳，並且在高溫高濕環境下抑制偏光度降低之效果(加濕耐久性)佳。In view of the above situation, the object of the present invention is to provide a polarizing film with the following polarizing film, the initial polarization of the polarizing film is good, and the effect of suppressing the coloring of the polarizing film to reduce the monomer transmittance under high temperature environment is good, and at high temperature The effect of suppressing the decrease of polarization degree (humidification durability) is good in high humidity environment.
且，本發明之目的在於提供使用上述偏光薄膜的積層偏光薄膜、影像顯示面板及影像顯示裝置。Moreover, an object of the present invention is to provide a laminated polarizing film, an image display panel, and an image display device using the above-mentioned polarizing film.
用以解決課題之手段 亦即，本發明涉及一種偏光薄膜，其係於偏光膜之兩面貼合有透明保護薄膜者；前述偏光膜係碘吸附定向於聚乙烯醇系薄膜而形成，且碘濃度為3重量%以上且10重量%以下；前述透明保護薄膜之至少一者的透濕度為200g/(m2 ・24h)以下；前述偏光薄膜滿足通式(1)：ΔTs(%)=Ts750 -Ts0 所示單體透射率的變化量(ΔTs)為0%以上且5%以下之條件(前述通式(1)中，Ts0 為於前述偏光薄膜之單面透過黏著劑層貼合有玻璃板之積層體的單體透射率，Ts750 表示前述積層體以105℃、750小時進行加熱處理後之單體透射率)。The means to solve the problem, that is, the present invention relates to a polarizing film, which is laminated with a transparent protective film on both sides of the polarizing film; the polarizing film is formed by adsorbing and oriented iodine on the polyvinyl alcohol film, and the iodine concentration 3% by weight or more and 10% by weight or less; the moisture permeability of at least one of the aforementioned transparent protective films is 200g/(m 2 ·24h) or less; the aforementioned polarizing film satisfies the general formula (1): ΔTs(%)=Ts 750 -Ts 0 shows that the monomer transmittance change (ΔTs) is 0% or more and 5% or less (in the above general formula (1), Ts 0 is attached to the single side of the polarizing film through the adhesive layer) The transmittance of the monomer of the laminated body with glass plates, Ts 750 represents the transmittance of the monomer after the above-mentioned laminated body is heat-treated at 105°C for 750 hours).
且，本發明涉及一種積層偏光薄膜，其係前述偏光薄膜貼合於光學層者。In addition, the present invention relates to a laminated polarizing film obtained by bonding the aforementioned polarizing film to an optical layer.
且，本發明涉及一種影像顯示面板，其係於影像顯示單元貼合有前述偏光薄膜或前述積層偏光薄膜者。In addition, the present invention relates to an image display panel, which is bonded with the aforementioned polarizing film or the aforementioned laminated polarizing film to an image display unit.
且，本發明涉及一種影像顯示裝置，其係於前述影像顯示面板的偏光薄膜或積層偏光薄膜側具備前面透明構件者。Furthermore, the present invention relates to an image display device which is provided with a front transparent member on the polarizing film or laminated polarizing film side of the aforementioned image display panel.
發明效果 雖本發明偏光薄膜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，本發明亦可不限定於該作用機制解釋。Invention effect Although the details of the mechanism of the effect of the polarizing film of the present invention are still unclear, we speculate as follows. However, the present invention may not be limited to the explanation of the mechanism of action.
本發明之偏光薄膜，係於偏光膜之兩面貼合有透明保護薄膜者；前述偏光膜係碘吸附定向於聚乙烯醇系薄膜而形成，且碘濃度為3重量%以上且10重量%以下；前述透明保護薄膜之至少一者的透濕度為200g/(m2 ・24h)以下；前述偏光薄膜滿足通式(1)：ΔTs(%)=Ts750 -Ts0 所示單體透射率的變化量(ΔTs)為0%以上且5%以下之條件(前述通式(1)中，Ts0 為於前述偏光薄膜之單面透過黏著劑層貼合有玻璃板之積層體的單體透射率，Ts750 表示前述積層體以105℃、750小時進行加熱處理後之單體透射率)。本發明之偏光薄膜於上述加熱處理後(高溫環境下)之單體透射率的變化量(ΔTs)小，故可抑制偏光膜著色造成單體透射率降低。因此，吾等推測加熱處理前後之單體透射率的變化量(ΔTs)小之理由係因引發本發明之偏光膜多烯化而導致脫水反應的溫度較以往之偏光膜更高溫所致。尤其，上述加熱處理係作為車載顯示器之耐熱性指標的加熱耐久性試驗，比以往之加熱耐久性試驗更嚴苛。並且，本發明之偏光薄膜係將偏光膜中之碘濃度設定在一定範圍內，藉此可將引發多烯化而導致脫水反應的溫度控制在高溫側，並且初始偏光度良好。The polarizing film of the present invention is one with transparent protective films laminated on both sides of the polarizing film; the aforementioned polarizing film is formed by iodine adsorption and orientation on the polyvinyl alcohol film, and the iodine concentration is 3% by weight or more and 10% by weight or less; The moisture permeability of at least one of the aforementioned transparent protective films is less than 200g/(m 2 ·24h); the aforementioned polarizing film satisfies the general formula (1): ΔTs (%)=Ts 750 -Ts 0 shows the change in monomer transmittance The amount (ΔTs) is 0% or more and 5% or less (in the aforementioned general formula (1), Ts 0 is the monomer transmittance of the laminated body with the glass plate bonded to the adhesive layer on one side of the polarizing film) , Ts 750 represents the monomer transmittance of the aforementioned laminate after heat treatment at 105°C for 750 hours). The polarizing film of the present invention has a small change in monomer transmittance (ΔTs) after the above-mentioned heat treatment (under a high temperature environment), so it can suppress the coloring of the polarizing film to reduce the monomer transmittance. Therefore, we speculate that the reason why the change in monomer transmittance (ΔTs) before and after the heat treatment is small is that the temperature of the dehydration reaction caused by the polyolefinization of the polarizing film of the present invention is higher than that of the conventional polarizing film. In particular, the above-mentioned heating treatment is a heating endurance test as an index of heat resistance of a vehicle display, which is more stringent than the conventional heating endurance test. In addition, the polarizing film of the present invention sets the iodine concentration in the polarizing film within a certain range, so that the temperature of initiating polyolefinization and leading to the dehydration reaction can be controlled to the high temperature side, and the initial polarization degree is good.
且，本發明之偏光薄膜中，前述透明保護薄膜之至少一者的透濕度為200g/(m2 ・24h)以下，故能防止水侵入偏光膜，藉此即使在高溫高濕環境下抑制偏光度降低之效果(加濕耐久性)仍佳。In addition, in the polarizing film of the present invention, the moisture permeability of at least one of the transparent protective films is 200g/(m 2 · 24h) or less, so water can be prevented from entering the polarizing film, thereby suppressing polarized light even in a high temperature and high humidity environment The effect of lowering the degree of humidity (humidification durability) is still good.
用以實施發明之形態 ＜偏光膜＞ 本發明偏光膜係碘吸附定向於聚乙烯醇系薄膜而形成之碘系偏光膜，且碘濃度為3重量%以上且10重量%以下。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。The form used to implement the invention ＜Polarizing film＞ The polarizing film of the present invention is an iodine-based polarizing film formed by adsorption and orientation of iodine on a polyvinyl alcohol-based film, and the iodine concentration is 3% by weight or more and 10% by weight or less. The above-mentioned polyvinyl alcohol (PVA)-based film can be used without particular limitation, which has translucency in the visible light region and can dispersely adsorb iodine. In addition, the thickness of the PVA-based film generally used as the original plate is preferably about 1 to 100 μm, preferably about 1 to 50 μm, and the width is preferably about 100 to 5000 mm.
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、丙烯酸醯胺等改質者等。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。Examples of the material of the polyvinyl alcohol-based film include polyvinyl alcohol or derivatives thereof. Examples of the aforementioned derivatives of polyvinyl alcohol include polyvinyl formal and polyvinyl acetal; olefins such as ethylene and propylene, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid and their alkyl esters, and amide acrylates. Waiting for reformers, etc. The average degree of polymerization of the aforementioned polyvinyl alcohol is preferably about 100 to 10,000, preferably about 1,000 to 10,000, and more preferably about 1,500 to 4,500. In addition, the degree of saponification of the aforementioned polyvinyl alcohol is preferably about 80 to 100 mol%, preferably about 95 mol% to 99.95 mol%. In addition, the aforementioned average polymerization degree and the aforementioned saponification degree can be obtained in accordance with 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。The aforementioned polyvinyl alcohol-based film may also contain additives such as plasticizers and surfactants. Examples of the plasticizer include polyhydric alcohols such as glycerin, diglycerin, triglycerin, ethylene glycol, propylene glycol, and polyethylene glycol, and condensates thereof. The use amount of the aforementioned additives is not particularly limited, but for example, it is preferably about 20% by weight or less in a polyvinyl alcohol-based film.
前述偏光膜中，由使偏光膜之初始偏光度良好、且使引發多烯化而導致脫水反應的溫度成為高溫的觀點來看，前述碘濃度(含量)為3重量%以上且10重量%以下。前述偏光膜中，由提升偏光膜之初始偏光度的觀點來看，前述碘濃度(含量)宜為3.5重量%以上，4重量%以上較佳，而由使引發多烯化而導致脫水反應的溫度成為高溫之觀點來看，宜為9重量%以下，7重量%以下較佳，6重量%以下更佳，5重量%以下最佳。In the aforementioned polarizing film, the iodine concentration (content) is 3% by weight or more and 10% by weight or less from the viewpoint of making the initial polarization degree of the polarizing film good and the temperature at which the polyolefinization is initiated and the dehydration reaction becomes high. . In the aforementioned polarizing film, from the viewpoint of increasing the initial polarization degree of the polarizing film, the aforementioned iodine concentration (content) is preferably 3.5% by weight or more, preferably 4% by weight or more. From the viewpoint that the temperature becomes a high temperature, it is preferably 9% by weight or less, preferably 7% by weight or less, more preferably 6% by weight or less, and most preferably 5% by weight or less.
前述偏光膜宜包含具有自由基捕捉功能之化合物。吾等推測前述具有自由基捕捉功能之化合物會捕捉偏光膜之聚乙烯醇因加熱而產生的自由基，而可將引發多烯化之脫水反應的溫度設定在高溫側。前述具有自由基捕捉功能之化合物可舉例如受阻酚系、受阻胺系、磷系、硫系、苯并***系、二苯基酮系、羥胺系、水楊酸酯系、三
前述具有氮氧自由基或氮氧基之化合物由具有在室溫、空氣中較穩定之自由基之觀點來看，可舉N-氧基化合物(具有C-N(-C)-O・作為官能基之化合物(O・表示氧自由基))，且可使用公知者。前述具有氮氧自由基或氮氧基之化合物可舉例如具有以下結構之有機基的化合物等。
[化學式1]
具有上述有機基之化合物可舉例如以下通式(2)~(5)所示化合物等。
[化學式2]
前述通式(1)~(5)中，R2 至R5 由取得容易度之觀點來看，宜為碳原子數1~6烷基，碳原子數1~3烷基較佳。又，前述通式(2)中，由取得容易度之觀點來看，R6 宜為氫原子或碳原子數1~10烷基，氫原子較佳。又，前述通式(3)中，由取得容易度之觀點來看，R7 及R8 宜獨立為氫原子或碳原子數1~10烷基，氫原子較佳。又，前述通式(4)中，由取得容易度之觀點來看，R9 至R11 宜為氫原子或碳原子數1~10烷基。又，前述通式(5)中，由取得容易度之觀點來看，R12 宜為羥基、胺基或烷氧基。前述通式(1)~(5)中，n由取得容易度之觀點來看宜為1。In the aforementioned general formulas (1) to (5), R 2 to R 5 are preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms, from the viewpoint of ease of acquisition. Furthermore, in the aforementioned general formula (2), from the viewpoint of ease of acquisition, R 6 is preferably a hydrogen atom or an alkyl group with 1 to 10 carbon atoms, and a hydrogen atom is more preferred. Moreover, in the aforementioned general formula (3), from the viewpoint of ease of acquisition, R 7 and R 8 are preferably independently a hydrogen atom or an alkyl group with 1 to 10 carbon atoms, and a hydrogen atom is preferred. In addition, in the aforementioned general formula (4), R 9 to R 11 are preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms from the viewpoint of ease of acquisition. In addition, in the aforementioned general formula (5), R 12 is preferably a hydroxyl group, an amino group or an alkoxy group from the viewpoint of ease of acquisition. In the aforementioned general formulas (1) to (5), n is preferably 1 from the viewpoint of ease of acquisition.
又，前述具有氮氧自由基或氮氧基之化合物可舉例如以下化合物等。
[化學式6]
又，由可有效率地捕捉在多烯化反應中產生的自由基之觀點來看，前述具有自由基捕捉功能之化合物之分子量宜為1000以下，500以下較佳，300以下更佳。In addition, from the viewpoint of efficiently trapping free radicals generated in the polyolefination reaction, the molecular weight of the aforementioned compound having a radical trapping function is preferably 1000 or less, preferably 500 or less, and more preferably 300 or less.
又，前述具有自由基捕捉功能之化合物由容易移動至偏光膜中之水分之觀點來看，宜為相對於25℃之水100重量份可溶解1重量份以上的水溶性化合物，相對於25℃之水100重量份可溶解2重量份以上的水溶性化合物較佳，相對於25℃之水100重量份可溶解5重量份以上的水溶性化合物更佳。In addition, the aforementioned compound with a radical trapping function is preferably a water-soluble compound that can dissolve at least 1 part by weight with respect to 100 parts by weight of water at 25°C from the viewpoint of water that easily moves into the polarizing film. It is preferable that 100 parts by weight of water can dissolve 2 parts by weight or more of water-soluble compounds, and it is more preferable to dissolve more than 5 parts by weight of water-soluble compounds relative to 100 parts by weight of water at 25°C.
由抑制在高溫環境下偏光膜著色造成單體透射率降低之觀點來看，前述偏光膜在包含前述具有自由基捕捉功能之化合物時，前述具有自由基捕捉功能之化合物的含量在前述偏光膜中宜為0.01重量%以上，0.02重量%以上較佳，0.05重量%以上更佳，而由外觀之觀點來看，宜為10重量%以下，7重量%以下較佳，3重量%以下更佳。From the viewpoint of suppressing the decrease in the transmittance of the monomer due to the coloring of the polarizing film in a high temperature environment, when the polarizing film contains the compound having the free radical trapping function, the content of the compound having the free radical trapping function is in the polarizing film It is preferably 0.01% by weight or more, preferably 0.02% by weight or more, more preferably 0.05% by weight or more. From the viewpoint of appearance, it is preferably 10% by weight or less, preferably 7% by weight or less, and more preferably 3% by weight or less.
前述偏光膜宜包含氯離子(氯化物離子)。吾等推測前述氯離子為潮解性，能使偏光膜之聚乙烯醇因加熱而產生的脫水反應延遲，從而可將引發多烯化之脫水反應的溫度設定在高溫側。The aforementioned polarizing film preferably contains chloride ions (chloride ions). We speculate that the aforementioned chloride ions are deliquescent, which can delay the dehydration reaction of the polyvinyl alcohol of the polarizing film due to heating, so that the temperature of the dehydration reaction that initiates polyolefinization can be set to the high temperature side.
前述偏光膜包含氯離子(氯化物離子)時，由抑制在高溫環境下偏光膜著色造成單體透射率降低之觀點來看，前述氯離子之含量在前述偏光膜中宜大於2重量%，2.5重量%以上較佳，3重量%以上更佳，而由在高溫環境下之偏光膜的色相變化之觀點來看，宜為10重量%以下，7重量%以下較佳，5重量%以下更佳。When the aforementioned polarizing film contains chloride ions (chloride ions), the content of the aforementioned chloride ions in the aforementioned polarizing film should preferably be greater than 2% by weight, from the viewpoint of suppressing the reduction of monomer transmittance caused by the coloring of the polarizing film in a high temperature environment. The weight% or more is preferable, and 3 weight% or more is more preferable. From the viewpoint of the hue change of the polarizing film in a high temperature environment, it is preferably 10 weight% or less, 7 weight% or less is preferable, and 5 weight% or less is more preferable .
＜偏光膜之製造方法＞ 前述偏光膜之製造方法係對前述聚乙烯醇系薄膜施行任意之膨潤步驟及洗淨步驟，以及至少施行染色步驟、交聯步驟及延伸步驟而得。前述偏光膜中所含前述碘之含量可透過膨潤步驟、染色步驟、交聯步驟、延伸步驟及洗淨步驟中的各處理浴中之任一者所含前述碘以及碘化鉀等碘化物之濃度、上述各處理浴之處理溫度及處理時間來控制。＜Manufacturing method of polarizing film＞ The manufacturing method of the aforementioned polarizing film is obtained by subjecting the aforementioned polyvinyl alcohol-based film to any swelling step and washing step, and at least performing a dyeing step, a cross-linking step, and a stretching step. The content of the aforementioned iodine contained in the aforementioned polarizing film can be determined by the concentration of the aforementioned iodine and potassium iodide and other iodides contained in any one of the treatment baths in the swelling step, the dyeing step, the cross-linking step, the stretching step, and the washing step. The treatment temperature and treatment time of each treatment bath mentioned above are controlled.
又，於製造包含前述具有自由基捕捉功能之化合物的偏光膜時，只要前述膨潤步驟、前述洗淨步驟、前述染色步驟、前述交聯步驟及前述延伸步驟中之任1個以上處理浴中含有前述具有自由基捕捉功能之化合物即可。前述各處理浴中之任一者所含前述具有自由基捕捉功能之化合物之濃度會受各處理之處理次數、處理時間、處理溫度等影響故不能一概決定，惟由可有效率地控制偏光膜中的前述具有自由基捕捉功能之化合物之含量的觀點來看，通常宜為0.03重量%以上，0.05重量%以上較佳，0.1重量%以上更佳，並且，宜為15重量%以下，10重量%以下較佳，5重量%以下更佳。In addition, when manufacturing a polarizing film containing the compound having a radical trapping function, any one or more of the swelling step, the washing step, the dyeing step, the crosslinking step, and the stretching step need to be contained in any one or more treatment baths. The aforementioned compound having the function of capturing radicals is sufficient. The concentration of the aforementioned compound with free radical trapping function contained in any of the aforementioned treatment baths will be affected by the number of treatments, treatment time, treatment temperature, etc., so it cannot be determined unambiguously, but the polarizing film can be controlled efficiently From the viewpoint of the content of the compound having a free radical trapping function in the above, it is usually preferably 0.03% by weight or more, preferably 0.05% by weight or more, more preferably 0.1% by weight or more, and preferably 15% by weight or less, 10% by weight % Or less is preferable, and 5% by weight or less is more preferable.
尤其在施行染色步驟、交聯步驟及延伸步驟後施行洗淨步驟之情況下，在考慮到染色步驟、交聯步驟及延伸步驟等之處理條件的前提下，由使碘或前述具有自由基捕捉功能之化合物等成分從聚乙烯醇系薄膜溶出或吸附至聚乙烯醇系薄膜之觀點來看，洗淨步驟易將前述碘或前述具有自由基捕捉功能之化合物之含量調整成所期望範圍。Especially when the washing step is performed after the dyeing step, the cross-linking step, and the extension step, taking into account the processing conditions of the dyeing step, cross-linking step, and extension step, the iodine or the aforementioned free radical trapping From the viewpoint of elution or adsorption of functional compounds and other components to the polyvinyl alcohol-based film, the cleaning step can easily adjust the content of the aforementioned iodine or the aforementioned compound having a radical-trapping function to a desired range.
又，於製造包含前述具有自由基捕捉功能之化合物的偏光膜時，亦可塗佈包含前述具有自由基捕捉功能之化合物的水溶液，使其浸潤至偏光膜中。塗佈步驟可設於上述膨潤步驟、染色步驟、交聯步驟、延伸步驟及洗淨處理中之任一步驟前後，尤其由可易將前述具有自由基捕捉功能之化合物之含量調整成所期望之範圍之觀點來看，宜設於洗淨步驟後。塗佈方式並無特別限制，可舉例如線棒塗佈法、凹版塗佈法、噴塗法等。In addition, when manufacturing a polarizing film containing the aforementioned compound having a radical trapping function, it is also possible to apply an aqueous solution containing the aforementioned compound having a radical trapping function to infiltrate the polarizing film. The coating step can be set before and after any one of the above-mentioned swelling step, dyeing step, cross-linking step, extension step, and washing treatment. In particular, the content of the aforementioned compound with free radical trapping function can be easily adjusted to the desired level. From the point of view of scope, it should be set after the washing step. The coating method is not particularly limited, and examples thereof include a wire bar coating method, a gravure coating method, and a spray coating method.
並且，前述膨潤步驟、前述染色步驟、前述交聯步驟、前述延伸步驟及前述洗淨步驟中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。尤其是由獲得可抑制在高溫環境下偏光膜著色造成單體透射率降低之偏光膜之觀點來看，宜使上述各處理浴中之1個以上的處理浴含有氯化物。In addition, each treatment bath in the aforementioned swelling step, the aforementioned dyeing step, the aforementioned cross-linking step, the aforementioned extension step, and the aforementioned washing step may also contain additives such as zinc salt, pH adjusting agent, pH buffering agent, and other salts. Examples of the aforementioned zinc salt include zinc halides such as zinc chloride and zinc iodide; and 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, or strong bases such as sodium hydroxide and potassium hydroxide. Examples of the aforementioned pH buffering agent include carboxylic acids and their salts such as acetic acid, oxalic acid, and citric acid, or weak inorganic acids such as phosphoric acid and carbonic acid and their salts. The aforementioned other salts include, for example, chlorides such as sodium chloride, potassium chloride, and 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. In particular, from the viewpoint of obtaining a polarizing film capable of suppressing the decrease in the transmittance of the monomer due to coloring of the polarizing film in a high-temperature environment, it is preferable that one or more of the above-mentioned treatment baths contain a chloride.
前述膨潤步驟係將聚乙烯醇系薄膜浸漬於膨潤浴中之處理步驟，其可去除聚乙烯醇系薄膜表面的污垢及抗結塊劑，且可使聚乙烯醇系薄膜膨潤以抑制染色參差。前述膨潤浴一般可使用水、蒸餾水、純水等以水為主成分之介質。前述膨潤浴亦可依循一般方法適當添加有界面活性劑、醇等。The aforementioned swelling step is a processing step of immersing the polyvinyl alcohol-based film in a swelling bath, which can remove dirt and anti-caking agents on the surface of the polyvinyl alcohol-based film, and can swell the polyvinyl alcohol-based film to suppress uneven dyeing. The aforementioned swelling bath generally can use water, distilled water, pure water and other media with water as the main component. The aforementioned swelling bath can also be appropriately added with surfactants, alcohols, etc. according to general methods.
前述膨潤浴之溫度宜為10~60℃左右，15~45℃左右較佳，18~30℃左右更佳。又，因聚乙烯醇系薄膜之膨潤程度會受膨潤浴溫度的影響，故浸漬於前述膨潤浴之浸漬時間不能一概決定，而宜為5~300秒鐘左右，10~200秒鐘左右較佳，20~100秒鐘左右更佳。前述膨潤步驟可僅實施1次，亦可因應需要實施複數次。The temperature of the aforementioned swelling bath is preferably about 10-60°C, preferably about 15-45°C, and more preferably about 18-30°C. In addition, since the degree of swelling of the polyvinyl alcohol-based film is affected by the temperature of the swelling bath, the immersion time for immersion in the aforementioned swelling bath cannot be determined uniformly. It is preferably about 5 to 300 seconds, preferably about 10 to 200 seconds. , 20~100 seconds is better. The aforementioned swelling step can be implemented only once, or multiple times as needed.
前述染色步驟係將聚乙烯醇系薄膜浸漬於染色浴(碘溶液)之處理步驟，其可使碘吸附、定向於聚乙烯醇系薄膜。前述碘溶液一般宜為碘水溶液，且含有碘及作為溶解助劑之碘化物。此外，前述碘化物可舉：碘化鉀、碘化鋰、碘化鈉、碘化鋅、碘化鋁、碘化鉛、碘化銅、碘化鋇、碘化鈣、碘化錫、碘化鈦等。該等中，由控制前述偏光膜中之鉀含量之觀點來看，以碘化鉀為宜。The aforementioned dyeing step is a processing step of immersing the polyvinyl alcohol-based film in a dyeing bath (iodine solution), which can adsorb and orient iodine to the polyvinyl alcohol-based film. The aforementioned iodine solution is generally an iodine aqueous solution, and contains iodine and iodide as a dissolution aid. In addition, the aforementioned iodide may include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, titanium iodide, etc. . Among these, from the viewpoint of controlling the potassium content in the aforementioned polarizing film, potassium iodide is preferable.
前述染色浴中，碘濃度宜為0.01~1重量%左右，0.02~0.5重量%左右較佳。前述染色浴中，前述碘化物之濃度宜為0.01~20重量%左右，0.05~10重量%左右較佳，0.1~5重量%左右更佳。In the aforementioned dyeing bath, the iodine concentration is preferably about 0.01 to 1% by weight, preferably about 0.02 to 0.5% by weight. In the aforementioned dyeing bath, the concentration of the aforementioned iodide is preferably about 0.01-20% by weight, preferably about 0.05-10% by weight, and more preferably about 0.1-5% by weight.
前述染色浴之溫度宜為10~50℃左右，15~45℃左右較佳，18~30℃左右更佳。又，因聚乙烯醇系薄膜之染色程度會受染色浴溫度的影響，故浸漬於前述染色浴之浸漬時間不能一概決定，而宜為10~300秒鐘左右，20~240秒鐘左右較佳。前述染色步驟可僅實施1次，亦可因應需要實施複數次。The temperature of the aforementioned dyeing bath is preferably about 10-50°C, preferably about 15-45°C, and more preferably about 18-30°C. In addition, since the degree of dyeing of the polyvinyl alcohol-based film is affected by the temperature of the dyeing bath, the immersion time for immersion in the aforementioned dyeing bath cannot be determined uniformly, and it is preferably about 10 to 300 seconds, preferably about 20 to 240 seconds . The aforementioned dyeing step can be performed only once, or multiple times as needed.
前述交聯步驟係將聚乙烯醇系薄膜浸漬於含硼化合物之處理浴(交聯浴)中的處理步驟，可透過硼化合物使聚乙烯醇系薄膜交聯而將碘分子或染料分子吸附至該交聯結構。前述硼化合物可舉例如硼酸、硼酸鹽、硼砂等。前述交聯浴一般為水溶液，但例如亦可為與水有混合性之有機溶劑及水的混合溶液。又，由控制前述偏光膜中之鉀含量之觀點來看，前述交聯浴宜包含有碘化鉀。The aforementioned cross-linking step is a treatment step in which the polyvinyl alcohol-based film is immersed in a treatment bath (cross-linking bath) containing a boron compound. The polyvinyl alcohol-based film can be cross-linked through the boron compound to adsorb iodine molecules or dye molecules to The cross-linked structure. Examples of the aforementioned boron compound include boric acid, borate, and borax. The aforementioned crosslinking bath is generally an aqueous solution, but for example, it may be a mixed solution of an organic solvent and water that is miscible with water. In addition, from the viewpoint of controlling the potassium content in the polarizing film, the cross-linking bath preferably contains potassium iodide.
前述交聯浴中，前述硼化合物之濃度宜為1~15重量%左右，1.5~10重量%左右較佳，2~5重量%左右更佳。又，於前述交聯浴中使用碘化鉀時，前述交聯浴中碘化鉀之濃度宜為1~15重量%左右，1.5~10重量%左右較佳，2~5重量%左右更佳。In the aforementioned crosslinking bath, the concentration of the aforementioned boron compound is preferably about 1 to 15% by weight, preferably about 1.5 to 10% by weight, and more preferably about 2 to 5% by weight. Furthermore, when potassium iodide is used in the cross-linking bath, the concentration of potassium iodide in the cross-linking bath is preferably about 1 to 15% by weight, preferably about 1.5 to 10% by weight, and more preferably about 2 to 5% by weight.
前述交聯浴之溫度宜為20~70℃左右，30~60℃左右較佳。又，因聚乙烯醇系薄膜之交聯程度會受交聯浴溫度的影響，故浸漬於前述交聯浴之浸漬時間不能一概決定，而宜為5~300秒鐘左右，10~200秒鐘左右較佳。前述交聯步驟可僅實施1次，亦可因應需要實施複數次。The temperature of the aforementioned crosslinking bath is preferably about 20 to 70°C, preferably about 30 to 60°C. In addition, since the degree of crosslinking of the polyvinyl alcohol-based film is affected by the temperature of the crosslinking bath, the immersion time for immersion in the aforementioned crosslinking bath cannot be determined uniformly, but is preferably about 5 to 300 seconds, 10 to 200 seconds Left and right are better. The aforementioned cross-linking step can be performed only once, or multiple times as needed.
前述延伸步驟係將聚乙烯醇系薄膜沿至少一方向延伸預定倍率的處理步驟。一般而言，係將聚乙烯醇系薄膜沿輸送方向(長邊方向)進行單軸延伸。前述延伸方法並無特別限制，可採用濕潤延伸法與乾式延伸法中之任一方法。前述延伸步驟可僅實施1次，亦可因應需要實施複數次。前述延伸步驟可於偏光膜之製造中在任一階段進行。The aforementioned stretching step is a processing step of stretching the polyvinyl alcohol-based film in at least one direction at a predetermined magnification. In general, the polyvinyl alcohol-based film is uniaxially stretched in the conveying direction (long-side direction). The aforementioned extension method is not particularly limited, and any one of a wet extension method and a dry extension method can be used. The aforementioned extension step can be performed only once, or multiple times as needed. The aforementioned stretching step can be performed at any stage in the manufacture of the polarizing film.
前述濕潤延伸法之處理浴(延伸浴)一般可使用水或與水有混合性之有機溶劑及水的混合溶液等之溶劑。由控制前述偏光膜中之前述鉀含量之觀點來看，前述延伸浴亦可包含有碘化鉀。於前述延伸浴中使用碘化鉀時，該延伸浴中之碘化鉀之濃度宜為1~15重量%左右，2~10重量%左右較佳，3~6重量%左右更佳。又，由抑制延伸中薄膜斷裂之觀點來看，前述處理浴(延伸浴)中可包含前述硼化合物，此時該延伸浴中前述硼化合物之濃度宜為1~15重量%左右，1.5~10重量%左右較佳，2~5重量%左右更佳。The treatment bath (extension bath) of the aforementioned wet extension method generally can use a solvent such as water or an organic solvent miscible with water and a mixed solution of water. From the viewpoint of controlling the potassium content in the polarizing film, the stretching bath may also contain potassium iodide. When potassium iodide is used in the aforementioned extension bath, the concentration of potassium iodide in the extension bath is preferably about 1-15% by weight, preferably about 2-10% by weight, and more preferably about 3-6% by weight. In addition, from the viewpoint of suppressing film breakage during stretching, the treatment bath (stretching bath) may contain the boron compound. In this case, the concentration of the boron compound in the stretching bath is preferably about 1-15% by weight, 1.5-10 About weight% is preferable, and about 2 to 5 weight% is more preferable.
前述延伸浴之溫度宜為25~80℃左右，40~75℃左右較佳，50~70℃左右更佳。又，因聚乙烯醇系薄膜之延伸程度會受延伸浴溫度之影響，故浸漬於前述延伸浴之浸漬時間不能一概決定，而宜為10~800秒鐘左右，30~500秒鐘左右較佳。此外，前述濕潤延伸法之延伸處理亦可與前述膨潤步驟、前述染色步驟、前述交聯步驟及前述洗淨步驟中之任1個以上處理步驟一同施行。The temperature of the aforementioned extension bath is preferably about 25-80°C, preferably about 40-75°C, and more preferably about 50-70°C. Also, since the degree of extension of the polyvinyl alcohol-based film is affected by the temperature of the extension bath, the immersion time for immersion in the aforementioned extension bath cannot be determined at all. It is preferably about 10 to 800 seconds, preferably about 30 to 500 seconds. . In addition, the stretching treatment of the aforementioned wet stretching method can also be performed together with any one or more treatment steps of the aforementioned swelling step, the aforementioned dyeing step, the aforementioned cross-linking step, and the aforementioned washing step.
前述乾式延伸法可舉例如輥間延伸方法、加熱輥延伸方法、壓縮延伸方法等。此外，前述乾式延伸法亦可與前述乾燥步驟一同施行。Examples of the aforementioned dry stretching method include an inter-roll stretching method, a heated roll stretching method, and a compression stretching method. In addition, the aforementioned dry stretching method can also be performed together with the aforementioned drying step.
施於前述聚乙烯醇系薄膜之總延伸倍率(累積延伸倍率)可因應目的適當設定，而宜為2~7倍左右，3~6.8倍左右較佳，3.5~6.5倍左右更佳。The total stretching ratio (cumulative stretching ratio) applied to the aforementioned polyvinyl alcohol-based film can be appropriately set according to the purpose, and is preferably about 2 to 7 times, preferably about 3 to 6.8 times, and more preferably about 3.5 to 6.5 times.
前述洗淨步驟係將聚乙烯醇系薄膜浸漬於洗淨浴中的處理步驟，其可去除殘存於聚乙烯醇系薄膜表面等的異物。前述洗淨浴一般可使用水、蒸餾水、純水等以水為主成分之介質。又，由控制前述偏光膜中之鉀含量之觀點來看，前述洗淨浴中亦可包含有碘化鉀，此時前述洗淨浴中碘化鉀之濃度宜為1~10重量%左右，1.5~4重量%左右較佳，1.8~3.8重量%左右更佳。The aforementioned washing step is a processing step of immersing the polyvinyl alcohol-based film in a washing bath, which can remove foreign substances remaining on the surface of the polyvinyl alcohol-based film. The aforementioned washing bath generally can use a medium containing water as the main component, such as water, distilled water, and pure water. In addition, from the viewpoint of controlling the potassium content in the polarizing film, the washing bath may also contain potassium iodide. At this time, the concentration of potassium iodide in the washing bath is preferably about 1-10% by weight, 1.5-4% by weight About% is preferable, and about 1.8 to 3.8% by weight is more preferable.
前述洗淨浴之溫度宜為5~50℃左右，10~40℃左右較佳，15~30℃左右更佳。又，因聚乙烯醇系薄膜之洗淨程度會受洗淨浴溫度之影響，故浸漬於前述洗淨浴之浸漬時間不能一概決定，而宜為1~100秒鐘左右，2~50秒鐘左右較佳，3~20秒鐘左右更佳。前述膨潤步驟可僅實施1次，亦可因應需要實施複數次。The temperature of the aforementioned washing bath is preferably about 5-50°C, preferably about 10-40°C, and more preferably about 15-30°C. In addition, since the degree of washing of the polyvinyl alcohol-based film is affected by the temperature of the washing bath, the immersion time for immersion in the aforementioned washing bath cannot be determined uniformly. It is preferably about 1-100 seconds, 2-50 seconds Left and right are better, preferably about 3 to 20 seconds. The aforementioned swelling step can be implemented only once, or multiple times as needed.
本發明偏光膜之製造方法亦可設置乾燥步驟。前述乾燥步驟係將經前述洗淨步驟洗淨過之聚乙烯醇系薄膜進行乾燥而獲得偏光膜之步驟，可藉由乾燥獲得具有所期望之水分率的偏光膜。前述乾燥可利用任意適當之方法進行，可舉例如自然乾燥、送風乾燥、加熱乾燥。The manufacturing method of the polarizing film of the present invention can also be provided with a drying step. The aforementioned drying step is a step of drying the polyvinyl alcohol-based film washed in the aforementioned washing step to obtain a polarizing film, and a polarizing film having a desired moisture content can be obtained by drying. The aforementioned drying can be performed by any appropriate method, and examples thereof include natural drying, air blowing drying, and heat drying.
前述乾燥溫度宜為20~150℃左右，25~100℃左右較佳。又，因偏光膜之乾燥程度會受乾燥溫度之影響，故前述乾燥時間不能一概決定，而宜為10~600秒鐘左右，30~300秒鐘左右較佳。前述乾燥步驟可僅實施1次，亦可因應需要實施複數次。The aforementioned drying temperature is preferably about 20 to 150°C, preferably about 25 to 100°C. In addition, since the degree of drying of the polarizing film will be affected by the drying temperature, the aforementioned drying time cannot be determined at all. It is preferably about 10 to 600 seconds, preferably about 30 to 300 seconds. The aforementioned drying step can be performed only once, or multiple times as needed.
由使偏光膜之初始偏光度提升之觀點來看，前述偏光膜之厚度宜為1μm以上，2μm以上較佳，而由防止加熱剝落之觀點來看，宜為20μm以下，18μm以下較佳，15μm以下更佳。尤其為了獲得厚度為8μm左右以下之偏光膜，可應用以下薄型偏光膜之製造方法，該薄型偏光膜係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作為前述聚乙烯醇系薄膜。From the viewpoint of increasing the initial polarization degree of the polarizing film, the thickness of the aforementioned polarizing film is preferably 1 μm or more, preferably 2 μm or more, and from the viewpoint of preventing heat peeling, it is preferably 20 μm or less, preferably 18 μm or less, 15 μm The following is better. In particular, in order to obtain a polarizing film with a thickness of about 8μm or less, the following thin polarizing film manufacturing method can be applied. The thin polarizing film uses a laminate including a polyvinyl alcohol-based resin layer formed by forming a film on a thermoplastic resin substrate as the aforementioned Polyvinyl alcohol-based film.
＜薄型偏光膜之製造方法＞ 薄型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。＜Manufacturing method of thin polarizing film＞ The manufacturing method of the thin polarizing film includes the following steps: forming a polyvinyl alcohol resin layer (PVA resin layer) containing a polyvinyl alcohol resin (PVA resin) on one side of a long-shaped thermoplastic resin substrate, and the product is made Laminated body; and, the laminated body is sequentially subjected to aerial auxiliary stretching treatment, dyeing treatment, underwater stretching treatment and drying shrinkage treatment. Especially in order to obtain a polarizing film with high optical properties, a two-stage stretching method combining aerial auxiliary stretching treatment (dry stretching) and water stretching treatment in a 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 for the method of producing the laminate. For example, a method of applying a coating liquid containing the PVA-based resin to the surface of the thermoplastic resin substrate and drying it can be mentioned. The thickness of the aforementioned thermoplastic resin substrate is preferably about 20 to 300 μm, preferably about 50 to 200 μm. The thickness of the aforementioned PVA-based resin layer is preferably about 3-40 μm, preferably about 3-20 μm.
前述熱塑性樹脂基材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，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 standpoint of the aforementioned thermoplastic resin substrate that can absorb water and greatly reduce the elongation stress so as to extend at a high magnification, the water absorption is preferably about 0.2% or more, preferably about 0.3% or more. On the other hand, from the viewpoint of preventing the dimensional stability of the thermoplastic resin substrate from being significantly reduced and causing the deterioration of the appearance of the polarizing film obtained, the water absorption rate of the thermoplastic resin substrate is preferably about 3% or less. About% or less is better. In addition, the water absorption rate can be adjusted, for example, by introducing a modifying group into the constituent material of the thermoplastic resin substrate. 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、以及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。另外，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。From the viewpoint of suppressing the crystallization of the PVA-based resin layer and ensuring the extensibility of the laminate, the glass transition temperature (Tg) of the aforementioned thermoplastic resin substrate is preferably about 120°C or less. In addition, considering the use of water to plasticize the thermoplastic resin substrate and the ability to stretch well in water, the glass transition temperature (Tg) is preferably about 100°C or less, and preferably about 90°C or less. On the other hand, 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, the glass transition temperature of the thermoplastic resin substrate is preferably about 60°C or higher . In addition, the glass transition temperature can be adjusted by heating, for example, by using a crystallization material that can introduce a modifying group into the constituent material of the thermoplastic resin substrate. 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有間苯二甲酸及/或環己烷二羧酸作為二羧酸的共聚物、或是含有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 aforementioned thermoplastic resin substrate. The aforementioned thermoplastic resins include, for example, ester resins such as polyethylene terephthalate resins, cycloolefin resins such as norbornene resins, olefin resins such as polypropylene, polyamide resins, and polycarbonate resins. And other copolymer resins. Among them, norbornene-based resins and amorphous (amorphous) polyethylene terephthalate-based resins are preferred, and from the viewpoint of excellent extensibility and suppression of crystallization during stretching For the thermoplastic resin substrate, it is better to use amorphous (amorphous) polyethylene terephthalate resin. Amorphous (amorphous) polyethylene terephthalate resins may include copolymers containing isophthalic acid and/or cyclohexanedicarboxylic acid as dicarboxylic acids, or containing cyclohexanedimethanol 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。且，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 (for example, corona treatment, etc.) before forming the PVA-based resin layer, or an easy-adhesion layer may be formed on the thermoplastic resin substrate. By performing the treatment, the adhesion between the thermoplastic resin substrate and the PVA-based resin layer can be improved. In addition, the aforementioned thermoplastic resin substrate 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 aforementioned coating liquid is a solution in which PVA-based resin is dissolved in a solvent. Examples of the aforementioned solvent include water, dimethyl sulfide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, various glycols, trimethylolpropane and other polyols, extensions Amines such as ethylenediamine and diethylenetriamine are preferably water. These can be used alone or in combination of two or more kinds. From the viewpoint of forming a uniform coating film adhered 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 polyvinyl alcohol molecules can be improved by extension, it is preferable to blend a halide in the aforementioned coating liquid. Any appropriate halide can be used as the aforementioned halide, and examples thereof include iodide and sodium chloride. Examples of the aforementioned iodide include potassium iodide, sodium iodide, and lithium iodide, and potassium iodide is preferred. The concentration of the halide in the coating solution is preferably about 5-20 parts by weight, preferably about 10-15 parts by weight, relative to 100 parts by weight of the PVA-based 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丙三醇等塑化劑；非離子界面活性劑等界面活性劑等。In addition, additives may be blended in the aforementioned coating liquid. Examples of the aforementioned additives include plasticizers such as ethylene glycol or glycerol; and surfactants such as nonionic surfactants.
前述塗佈液之塗佈方法之例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。As an example of the coating method of the aforementioned coating liquid, any appropriate method can be used, such as roll coating, spin coating, wire bar coating, dip coating, die coating, curtain coating, spray coating, and doctor blade. Type coating method (comma coating method, etc.) and so on. In addition, the drying temperature of the aforementioned coating liquid is preferably about 50°C or higher.
前述空中輔助延伸處理步驟可一邊抑制熱塑性樹脂基材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 aforementioned air-assisted stretching treatment step can stretch while suppressing the crystallization of the thermoplastic resin base material, so that the laminate can be stretched at a high magnification. The stretching method of the aforementioned aerial auxiliary stretching treatment can be fixed-end stretching (for example, stretching using a tenter stretching machine) or free-end stretching (for example, uniaxial stretching of the laminated body through rollers with different peripheral speeds) Method), and from the viewpoint of obtaining high optical characteristics, it is better to extend the free end.
前述空中輔助延伸之延伸倍率宜為2~3.5倍左右。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。The extension ratio of the aforementioned aerial auxiliary extension should be about 2~3.5 times. The aforementioned aerial auxiliary 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.
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 aforementioned aerial auxiliary stretching can be set to any appropriate value according to the forming material of the thermoplastic resin substrate, the stretching method, etc., for example, preferably above the glass transition temperature (Tg) of the thermoplastic resin substrate, the aforementioned glass transition temperature (Tg) +10°C or higher is preferable, and the aforementioned glass transition temperature (Tg) +15°C or higher is more preferable. On the other hand, from the viewpoint of suppressing the rapid progress of the crystallization of the PVA-based resin and suppressing the defects caused by the crystallization (for example, hindering the orientation of the PVA-based resin layer due to extension), the upper limit of the extension 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。It is also possible to perform the insolubilization treatment after the aforementioned aerial auxiliary extension treatment and before the dyeing treatment or the underwater extension treatment according to needs. The aforementioned insolubilization treatment means that the PVA-based resin layer is immersed in an aqueous boric acid solution. The insolubilization treatment can impart water resistance to the PVA-based resin layer and prevent the orientation of the PVA from decreasing 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 insoluble 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 the PVA-based resin layer (layered body) in a dyeing solution containing iodine, a method of coating the dyeing solution on the PVA-based resin layer, and spraying the dyeing solution onto the PVA The method on the resin layer, etc., is preferably a method of immersing the PVA resin layer (layered body) in a dyeing solution containing iodine.
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，30秒~90秒左右較佳。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 blending amount of iodine in the aforementioned dyeing bath is preferably about 0.05 to 0.5 parts by weight with respect to 100 parts by weight of water. In order to improve the solubility of iodine in water, it is advisable to mix the aforementioned iodide with the iodine aqueous solution. 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, relative to 100 parts by weight of water. In order to prevent the PVA-based resin from dissolving, the liquid temperature of the dyeing bath is preferably about 20-50°C. In addition, from the viewpoint of ensuring the transmittance of the PVA-based resin layer, the immersion time is preferably about 5 seconds to 5 minutes, and more preferably about 30 seconds to 90 seconds. 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。It can also be cross-linked after dyeing treatment and before extension treatment in water as needed. The aforementioned crosslinking treatment is typically performed by immersing the PVA-based resin layer in a boric acid aqueous solution. The cross-linking treatment can impart water resistance to the PVA-based resin layer and prevent the orientation of the PVA from being reduced when it is immersed in high-temperature water in the subsequent water extension. 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 crosslinking treatment is performed, it is preferable to further blend the aforementioned iodide in the crosslinking bath of the crosslinking treatment. By blending the aforementioned iodide, it is possible to suppress the elution of iodine that has been adsorbed on the PVA-based resin layer. 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 temperature of the cross-linking bath (aqueous solution of boric acid) should be around 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 aforementioned 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. The stretching method of the aforementioned underwater stretching treatment can be fixed-end stretching (for example, a method of stretching using a tenter stretcher) or free-end stretching (for example, a method of uniaxially stretching the laminated body through rollers with different peripheral speeds) ), and from the viewpoint of obtaining high optical properties, it is better 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 aforementioned underwater stretching treatment is preferably performed by immersing the layered body in a boric acid aqueous solution (boric acid aqueous stretching). By using an aqueous solution of boric acid as a stretching bath, rigidity and water-insoluble water resistance can be imparted to the PVA-based resin layer to withstand 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. In addition, iodide may be blended in the aforementioned stretching bath (aqueous boric acid solution). The temperature of the extension bath should be about 40~85℃, preferably about 60℃~75℃. The immersion time for the laminate to be immersed in the extension 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 ratio of the aforementioned underwater stretching 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 ratio of the laminated body is preferably about 5 times or more, and more preferably about 5.5 times or more relative 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。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，還可抑制其發生起皺。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，積層體因進行乾燥收縮處理所致之寬度方向之收縮率宜為1~10%左右，2~8%左右較佳。The aforementioned drying and shrinking treatment can be performed by heating the area by heating the entire area, or by heating the conveying roller (so-called using a heating roller). It is preferable to use both. By using a heating roller to dry it, heating and curling of the laminated body can be effectively suppressed, and a polarizing film with excellent appearance can be produced. The laminated body can be dried while maintaining a flat state, so not only curling can be suppressed. It can also suppress wrinkling. In addition, during the drying and shrinking treatment, by shrinking it in the width direction, the optical properties of the obtained polarizing film can be improved. From this point of view, the shrinkage rate in the width direction of the laminate due to the drying and shrinking treatment is preferably About 1~10%, 2~8% is better.
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。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 around 60~120℃, preferably around 65~100℃, more preferably 70~80℃. From the viewpoint of improving the degree of crystallinity of the thermoplastic resin and suppressing curling well, the conveyor rollers are generally set at about 2 to 40, and preferably set at about 4 to 30. 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 room temperature). It is suitable to be installed in a heating furnace equipped 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 around 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。It is advisable to perform a washing treatment after the water extension treatment and before the drying shrinkage treatment. The aforementioned washing treatment is typically performed by immersing the PVA-based resin layer in a potassium iodide aqueous solution.
又，於製造含有前述具有自由基捕捉功能之化合物的薄型偏光膜時，只要染色處理、水中延伸處理、不溶解處理、交聯處理及洗淨處理中之任1個以上處理浴中含有前述具有自由基捕捉功能之化合物即可。前述各處理浴中之任一者所含前述具有自由基捕捉功能之化合物之濃度會受各處理之處理次數、處理時間、處理溫度等影響故不能一概決定，惟由可有效率地控制偏光膜中的前述具有自由基捕捉功能之化合物之含量的觀點來看，通常宜為0.03重量%以上，0.05重量%以上較佳，0.1重量%以上更佳，並且，宜為15重量%以下，10重量%以下較佳，5重量%以下更佳。In addition, when manufacturing a thin polarizing film containing the compound with the aforementioned free radical trapping function, it is only necessary that any one or more of the dyeing treatment, underwater stretching treatment, insolubilization treatment, cross-linking treatment, and cleaning treatment contains the aforementioned compound Compounds with free radical capture function are sufficient. The concentration of the aforementioned compound with free radical trapping function contained in any of the aforementioned treatment baths will be affected by the number of treatments, treatment time, treatment temperature, etc., so it cannot be determined unambiguously, but the polarizing film can be controlled efficiently From the viewpoint of the content of the compound having a free radical trapping function in the above, it is usually preferably 0.03% by weight or more, preferably 0.05% by weight or more, more preferably 0.1% by weight or more, and preferably 15% by weight or less, 10% by weight % Or less is preferable, and 5% by weight or less is more preferable.
尤其在施行洗淨處理之情況下，在考慮到染色處理、水中延伸處理等之處理條件的前提下，由可使碘或前述具有自由基捕捉功能之化合物等成分從聚乙烯醇系薄膜溶出或吸附至聚乙烯醇系薄膜之觀點來看，洗淨處理易將前述碘或前述具有自由基捕捉功能之化合物之含量調整成所期望範圍。Especially in the case of washing treatment, taking into account the treatment conditions such as dyeing treatment, water extension treatment, etc., components such as iodine or the aforementioned free radical trapping function can be eluted from the polyvinyl alcohol-based film or From the viewpoint of adsorption to the polyvinyl alcohol-based film, it is easy to adjust the content of the aforementioned iodine or the aforementioned compound having a radical trapping function to a desired range in the washing treatment.
又，於製造包含前述具有自由基捕捉功能之化合物的薄型偏光膜時，亦可塗佈包含前述具有自由基捕捉功能之化合物的水溶液，使其浸潤至偏光膜中。塗佈步驟可設於上述染色處理、水中延伸處理、不溶解處理、交聯處理及洗淨處理中之任一處理前後，尤其由可將前述具有自由基捕捉功能之化合物之含量調整成所期望之範圍之觀點來看，宜設於洗淨處理後。塗佈方式並無特別限制，可舉例如線棒塗佈法、凹版塗佈法、噴塗法等。In addition, when manufacturing a thin polarizing film containing the aforementioned compound having a radical trapping function, it is also possible to apply an aqueous solution containing the aforementioned compound having a radical trapping function to infiltrate the polarizing film. The coating step can be set before and after any one of the above-mentioned dyeing treatment, water extension treatment, insolubilization treatment, cross-linking treatment and washing treatment, especially by adjusting the content of the aforementioned compound with free radical trapping function to the desired From the point of view of the range, it should be set after the washing treatment. The coating method is not particularly limited, and examples thereof include a wire bar coating method, a gravure coating method, and a spray coating method.
又，上述染色處理、水中延伸處理、不溶解處理、交聯處理及洗淨處理等之各處理浴中，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。尤其是由獲得可抑制在高溫環境下偏光膜著色造成單體透射率降低之偏光膜之觀點來看，宜使上述各處理浴中之1個以上的處理浴含有氯化物。In addition, the above-mentioned dyeing treatment, water extension treatment, insolubilization treatment, cross-linking treatment, and washing treatment may also contain additives such as zinc salt, pH adjuster, pH buffer, and other salts. Examples of the aforementioned zinc salt include zinc halides such as zinc chloride and zinc iodide; and 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, or strong bases such as sodium hydroxide and potassium hydroxide. Examples of the aforementioned pH buffering agent include carboxylic acids and their salts such as acetic acid, oxalic acid, and citric acid, or weak inorganic acids such as phosphoric acid and carbonic acid and their salts. The aforementioned other salts include, for example, chlorides such as sodium chloride, potassium chloride, and 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. In particular, from the viewpoint of obtaining a polarizing film capable of suppressing the decrease in the transmittance of the monomer due to coloring of the polarizing film in a high-temperature environment, it is preferable that one or more of the above-mentioned treatment baths contain a chloride.
＜偏光薄膜＞ 本發明偏光薄膜係於前述偏光膜之兩面貼合有透明保護薄膜者；前述透明保護薄膜之至少一者的透濕度為200g/(m2 ・24h)以下；該偏光薄膜滿足通式(1)：ΔTs(%)=Ts750 -Ts0 所示單體透射率的變化量(ΔTs)為0%以上且5%以下之條件(前述通式(1)中，Ts0 為於前述偏光薄膜之單面透過黏著劑層貼合有玻璃板之積層體的單體透射率，Ts750 表示前述積層體以105℃、750小時進行加熱處理後之單體透射率)。<Polarizing film> The polarizing film of the present invention is one with transparent protective films laminated on both sides of the aforementioned polarizing film; the moisture permeability of at least one of the aforementioned transparent protective films is 200g/(m 2 · 24h) or less; the polarizing film satisfies Formula (1): ΔTs (%)=Ts 750 -Ts 0 shows that the change in monomer transmittance (ΔTs) is 0% or more and 5% or less (in the aforementioned general formula (1), Ts 0 is The monomer transmittance of the laminated body in which the glass plate is bonded to one side of the polarizing film through the adhesive layer. Ts 750 represents the monomer transmittance of the laminated body after heat treatment at 105°C for 750 hours).
＜透明保護薄膜＞ 前述透明保護薄膜只要是貼合於前述偏光膜之至少一面的透明保護薄膜之透濕度為200g/(m2 ・24h)以下即無特別限制，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。<Transparent protective film> As long as the transparent protective film is bonded to at least one side of the polarizing film, the moisture permeability of the transparent protective film is 200g/(m 2・24h) or less. There is no particular limitation. Various types of polarizing films can be used. Transparent protective film. As the material constituting the aforementioned 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 resins such as cellulose triacetate, polyester resins such as polyethylene terephthalate or polyethylene naphthalate, polyether-based resins, and poly-based resins. , Polycarbonate resins, polyamide resins such as nylon or aromatic polyamides, polyimide resins, polyolefin resins such as polyethylene, polypropylene, ethylene and propylene copolymers, (methyl) Acrylic resin, cyclic or cyclic polyolefin resin having a norbornene structure (norbornene resin), polyarylate resin, polystyrene resin, polyvinyl alcohol resin, and mixtures thereof. In addition, the aforementioned transparent protective film can be cured using thermosetting resins such as (meth)acrylic, urethane, acrylic urethane, epoxy, polysilicone, or ultraviolet curable resins. Floor. Among these, cellulose ester resins, polycarbonate resins, (meth)acrylic resins, cyclic polyolefin resins, and polyester resins are preferable.
前述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 thickness of the aforementioned transparent protective film can be appropriately determined, but generally from the viewpoints of workability such as strength or handling, thin layer properties, etc., it is preferably about 1 to 500 μm, preferably about 1 to 300 μm, and more preferably about 5 to 100 μm.
前述透明保護薄膜之至少一者(偏光件之單面側的第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，透濕度宜為180g/(m2 ・24h)以下，150g/(m2 ・24h)以下較佳。又，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，另一透明保護薄膜(偏光件之另一面側的第2透明保護薄膜)之透濕度宜為200g/(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1200g/(m2 ・24h)以下，1000g/(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))，將裁切為直徑60mm之試樣設置於裝有約15g氯化鈣之透濕杯，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。At least one of the aforementioned transparent protective films (the first transparent protective film on one side of the polarizer) has a moisture permeability of 200g/(m 2 · 24h) or less, which suppresses the degree of polarization of the polarizing film in a high-temperature and high-humidity environment From the viewpoint of reduction, the moisture permeability is preferably 180g/(m 2 ·24h) or less, preferably 150g/(m 2 ·24h) or less. In addition, from the viewpoint of production efficiency in the drying step after bonding the polarizing film and the transparent protective film, the moisture permeability of the other transparent protective film (the second transparent protective film on the other side of the polarizing member) is preferably 200 g/( m 2 ·24h) or more, 300g/(m 2 ·24h) or more is preferable. 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 1200g/(m 2 · 24h) or less, preferably 1000g/(m 2 ·24h) or less. In addition, the moisture permeability can follow the moisture permeability test of JIS Z0208 (cup method). The sample cut to a diameter of 60mm is placed in a moisture permeable cup containing about 15g of calcium chloride and placed in the temperature In a thermostat with a temperature of 40°C and a humidity of 90%RH, the weight gain of calcium chloride before and after being left for 24 hours was measured to calculate it.
將前述透明保護薄膜貼合於前述偏光膜之兩面時，其兩面之透明保護薄膜可相同亦可互異。When the transparent protective film is attached to both sides of the polarizing film, the transparent protective films on both sides may be the same or different.
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 aforementioned transparent protective film, a retardation plate having a frontal retardation of 40 nm or more and/or a retardation of 80 nm or more in the thickness direction can be used. The frontal phase difference is usually controlled in the range of 40~200nm, and the thickness direction phase difference is usually controlled in the range of 80~300nm. When a phase difference plate is used as the above-mentioned transparent protective film, the phase difference plate can also function as a transparent protective film, so that it can be reduced in thickness.
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。相位差板之厚度並無特別限制，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。As the above-mentioned retardation plate, for example, a birefringent film obtained by uniaxially or biaxially stretching a polymer material, an oriented film of a liquid crystal polymer, a film supporting an oriented layer of a liquid crystal polymer, etc. are mentioned. The thickness of the phase difference plate is not particularly limited, and is generally about 20 to 150 μm. In addition, it can also be used by pasting the aforementioned phase plate on a transparent protective film without phase difference.
前述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。The aforementioned transparent protective film may also contain any appropriate additives such as ultraviolet absorbers, antioxidants, slip agents, plasticizers, release agents, anti-colorants, flame retardants, antistatic agents, pigments, and colorants.
前述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、抗黏著層、擴散層或防眩層等機能層。另，上述硬塗層、抗反射層、抗黏著層、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 or an anti-glare layer can be provided on the surface of the aforementioned transparent protective film that is not attached to the polarizing film. In addition, functional layers such as the above-mentioned hard coat layer, anti-reflection layer, anti-adhesion layer, diffusion layer, or anti-glare layer may be provided in addition to the protective film itself, or may be separately provided as an individual from the protective film.
前述偏光膜與前述透明保護薄膜、或前述偏光膜與前述機能層一般係透過黏著劑層或接著劑層貼合。The aforementioned polarizing film and the aforementioned transparent protective film, or the aforementioned polarizing film and the aforementioned functional layer are generally bonded 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、聚乙烯基吡咯啶酮系黏著劑、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。The adhesive that forms the aforementioned adhesive layer can be applied to various adhesives that can be used for polarizing films, such as rubber-based adhesives, acrylic adhesives, silicone-based adhesives, urethane-based adhesives, and vinyl alkanes. Base ether-based adhesives, polyvinyl alcohol-based adhesives, polyvinylpyrrolidone-based adhesives, polyacrylamide-based adhesives, cellulose-based adhesives, etc. Among them, acrylic adhesive is preferable.
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；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。前述黏著劑層的厚度無特別限制，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 method: the aforementioned adhesive is applied to a peeled-off part, etc., dried to form an adhesive layer, and then transferred to a polarizing film, etc.; The adhesive is applied to a polarizing film, etc., and dried to form an adhesive layer. The thickness of the aforementioned adhesive layer is not particularly limited, and is, for example, 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來使用，含有0.5~60重量%之固體成分而成。Various adhesives that can be used for polarizing films can be applied to the adhesive forming the aforementioned adhesive layer, and examples thereof include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, vinyl-based latex-based, water-based polyesters, and the like. These adhesives are usually used as an adhesive composed of an aqueous solution and contain 0.5 to 60% by weight of solid content.
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射線硬化型接著劑。前述活性能量射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。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 cited. Examples of the active energy ray-curable adhesive agent include (meth)acrylate-based adhesive agents. Examples of the curable component of the (meth)acrylate-based adhesive include a compound having a (meth)acryloyl group and a compound having a vinyl group. Moreover, the cationic polymerization hardening type adhesive agent can also use the compound which has an epoxy group or an oxetanyl group. 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.
前述接著劑的塗佈可對前述透明保護薄膜側(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 application of the adhesive may be performed on either the transparent protective film side (or the functional layer side) and the polarizing film side, or both. After bonding, a drying step is performed to form an adhesive layer composed of a coated dry layer. After the aforementioned drying step, ultraviolet light or electron beam can be irradiated as needed. The thickness of the aforementioned adhesive layer is not particularly limited. When using water-based adhesives, etc., it is preferably about 30 to 5000 nm, preferably about 100 to 1000 nm. When using ultraviolet curing type adhesives, electron beam curing type adhesives, etc., It is preferably about 0.1 to 100 μm, preferably about 0.5 to 10 μm.
前述透明保護薄膜與前述偏光膜、或前述偏光膜與前述機能層亦可隔著表面改質處理層、易接著劑層、阻隔層、折射率調整層等中介層而積層。The transparent protective film and the polarizing film, or the polarizing film and the functional layer may also be laminated via intermediary layers such as a surface modification layer, an easy-adhesive layer, a barrier layer, and a refractive index adjustment layer.
形成前述表面改質層之表面改質處理可舉例如電暈處理、電漿處理、底塗處理、皂化處理等。The surface modification treatment for forming the aforementioned surface modification layer includes, for example, corona treatment, plasma treatment, primer treatment, saponification treatment, and the like.
形成前述易接著層之易接著劑可舉例如包含具有下述骨架之各種樹脂的形成材：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。前述易接著層通常會事先設於保護薄膜上，並藉由前述黏著劑層或前述接著劑層將該保護薄膜之易接著層側與偏光膜積層。Examples of the easy-adhesive agent forming the aforementioned easy-adhesive layer include forming materials containing various resins having the following skeletons: polyester skeleton, polyether skeleton, polycarbonate skeleton, polyurethane skeleton, polysiloxane, poly Amide skeleton, polyimide skeleton, polyvinyl alcohol skeleton, etc. The aforementioned easy-adhesive layer is usually provided on the protective film in advance, and the easy-adhesive layer side of the protective film and the polarizing film are laminated by the aforementioned adhesive layer or the aforementioned adhesive 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 aforementioned barrier layer has a function of preventing impurities such as oligomers or ions eluted from the transparent protective film from moving (intruding) into the polarizing film. The aforementioned barrier layer may be a layer that has transparency and can prevent impurities eluted from a transparent protective film, etc. The material for forming the barrier layer includes, for example, a urethane prepolymer-based forming material and a cyanoacrylate-based forming material. , Epoxy-based forming materials, etc.
前述折射率調整層係為了抑制透射率伴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 prevent the transmittance from being lowered due to reflection between layers having different refractive indexes such as the transparent protective film and the polarizing film. Examples of the refractive index adjusting material that forms the refractive index adjusting layer include forming agents containing various resins and additives such as silica-based, acrylic-based, acrylic-styrene-based, and melamine-based resins.
本發明之偏光薄膜滿足通式(1)：ΔTs(%)=Ts750 -Ts0 所示單體透射率的變化量(ΔTs)為0%以上且5%以下之條件(前述通式(1)中，Ts0 為於前述偏光薄膜之單面透過黏著劑層貼合有玻璃板之積層體的單體透射率，Ts750 表示前述積層體以105℃、750小時進行加熱處理後之單體透射率)。此外，前述單體透射率之變化量(ΔTs)宜為0%以上且3%以下，0%以上且2%以下較佳。The polarizing film of the present invention satisfies the general formula (1): ΔTs (%) = Ts 750 -Ts 0 shows that the change in monomer transmittance (ΔTs) is 0% or more and 5% or less (the aforementioned general formula (1) In ), Ts 0 is the monomer transmittance of the laminated body with the glass plate bonded to the adhesive layer on one side of the polarizing film, and Ts 750 means the monomer after the laminated body is heated at 105°C for 750 hours Transmittance). In addition, the amount of change (ΔTs) of the aforementioned monomer transmittance is preferably 0% or more and 3% or less, preferably 0% or more and 2% or less.
前述偏光薄膜之偏光度宜為99.98%以上，偏光度為99.99%以上較佳。The degree of polarization of the aforementioned polarizing film is preferably 99.98% or more, and the degree of polarization is preferably 99.99% or more.
＜積層偏光薄膜＞ 本發明積層偏光薄膜(光學積層體)係前述偏光薄膜貼合於光學層者。前述光學層無特別限定，例如可使用1層或2層以上之例如反射板及半透射板、相位差板(包含1/2及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。＜Layered Polarizing Film＞ The laminated polarizing film (optical laminate) of the present invention is obtained by bonding the aforementioned polarizing film to the optical layer. The aforementioned optical layer is not particularly limited. For example, one layer or two or more layers such as reflective plates and semi-transmissive plates, retardation plates (including 1/2 and 1/4 wavelength plates), viewing angle compensation films, etc. can be used to form liquid crystals. Optical layer for display devices, etc. As the laminated polarizing film, for example, a reflective polarizing film or a semi-transmissive polarizing film formed by laminating a reflective plate or a semi-transmissive reflective plate on the polarizing film, and a retardation plate is laminated on the polarizing film. Elliptically 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並無特別限制，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。Adhesive layers can also be attached to one or both sides of the aforementioned polarizing film or the aforementioned multilayer polarizing film, which can be used to bond image display units such as liquid crystal cells or organic EL elements with transparent components such as front transparent plates or touch panels on the viewing side. And other components. The adhesive layer is preferably an adhesive layer. The adhesive forming the aforementioned adhesive layer is not particularly limited, and can be appropriately selected from acrylic polymer, silicone polymer, polyester, polyurethane, polyamide, polyether, fluorine-based or rubber-based Such polymers are used as the base polymer. In particular, it can be suitably used, such as an acrylic polymer-containing adhesive, which has excellent optical transparency, exhibits moderate wettability, cohesiveness, and adhesiveness, and has excellent weather resistance or heat resistance.
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；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 multilayer polarizing film can be carried out by an appropriate method. The adhesive layer can be attached by, for example, the following methods: preparing an adhesive solution, and directly attaching it to the aforementioned polarizing film or the aforementioned multilayer polarizing film by a suitable spreading method such as a casting method or a coating method; A method of forming an adhesive layer on the surface and transferring it to the aforementioned polarizing film or the aforementioned multilayer polarizing film. The thickness of the aforementioned adhesive layer can be appropriately determined according to the purpose of use or adhesion, etc., generally 1~500μm, preferably 5~200μm, more preferably 10~100μm. In this way, the polarizing film or the laminated polarizing film provided with an adhesive layer on at least one surface is called an adhesive layer-attached polarizing film or an adhesive layer-attached laminated polarizing film.
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薄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 to prevent it from being contaminated, it is advisable to temporarily stick a separator to cover it before actual use. This can prevent the adhesive layer from being contaminated in the usual disposal state. As the aforementioned separating member, for example, suitable thin films such as plastic films, rubber sheets, paper, cloth, non-woven fabrics, nets, foam sheets or metal foils, and laminates of these can be used. Those who apply appropriate release agents such as alkyl group, fluorine or molybdenum sulfide, etc.
＜影像顯示面板及影像顯示裝置＞ 本發明影像顯示面板係於影像顯示單元貼合有前述偏光薄膜或前述積層偏光薄膜者。又，本發明影像顯示裝置係於前述影像顯示面板的偏光薄膜或積層偏光薄膜側(視辨側)具備前面透明構件者。<Image display panel and image display device> The image display panel of the present invention is one in which the aforementioned polarizing film or the aforementioned laminated polarizing film is attached to the image display unit. In addition, the image display device of the present invention is provided with a front transparent member on the polarizing film or laminated polarizing film side (viewing side) of the aforementioned image display panel.
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。在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)亦會於影像顯示單元(液晶單元)之與視辨側相反之側配置偏光薄膜，並會配置光源。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。The aforementioned image display unit may be, for example, a liquid crystal cell or an organic EL unit. The aforementioned liquid crystal cell may use, 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 external light and light from a light source. Either. When the aforementioned liquid crystal cell uses light from a light source, the image display device (liquid crystal display device) will also arrange a polarizing film on the side of the image display unit (liquid crystal cell) opposite to the viewing side, and will also arrange a light source. The polarizing film on the light source side and the liquid crystal cell should be attached through a suitable adhesive layer. The driving method of the aforementioned liquid crystal cell may use any type such as VA mode, IPS mode, TN mode, STN mode, or bend orientation (π-type).
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所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；或電洞注入層、發光層及電子注入層之積層體等。The aforementioned organic EL unit can be suitably used, 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). The aforementioned organic light-emitting layer is a laminate of a variety of organic thin films. For example, the following various layers can be used: a laminate of a hole injection layer composed of triphenylamine derivatives and a light-emitting layer composed of a fluorescent organic solid such as anthracene; A laminate of the light-emitting layer and an electron injection layer composed of a perylene derivative, etc.; or a laminate of a hole injection layer, a light-emitting layer, and an electron injection layer, etc.
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透明板時，宜在較觸控面板更靠視辨側設置玻璃或由透明樹脂板構成之前面透明板。The front transparent member arranged on the viewing side of the aforementioned image display unit may, for example, be a front transparent plate (window layer) or a touch panel. For the aforementioned front transparent plate, a transparent plate with appropriate mechanical strength and thickness can be used. As the transparent plate, for example, a transparent resin plate such as an acrylic resin or a polycarbonate resin, a glass plate, or the like can be used. As the aforementioned touch panel, various touch panels such as resistive film type, capacitive type, optical type, ultrasonic type, etc., or glass plate or transparent resin plate with touch sensing function can be used. When a capacitive touch panel is used as the aforementioned transparent plate, it is advisable to provide a glass or a transparent resin plate on the front surface of the transparent plate on the side closer to the visibility than the touch panel.
本發明偏光薄膜具有以下偏光膜，因此本發明偏光薄膜、以及使用該偏光薄膜之積層偏光薄膜、影像顯示面板及影像顯示裝置適宜用於汽車導航裝置或後照監視器等車載用影像顯示裝置之用途，本發明偏光薄膜具有之偏光膜之初始偏光度良好且在高溫環境下抑制偏光膜著色造成單體透射率降低之效果佳，並且在高溫高濕環境下抑制偏光度降低之效果佳。The polarizing film of the present invention has the following polarizing film. Therefore, the polarizing film of the present invention, and the laminated polarizing film, image display panel, and image display device using the polarizing film are suitable for use in car navigation devices or rear-illuminated monitors and other vehicle-mounted image display devices Purpose: The polarizing film of the present invention has a good initial polarization degree and a good effect of inhibiting the reduction of the monomer transmittance caused by the coloring of the polarizing film in a high temperature environment, and a good effect of inhibiting the decrease of the polarization degree under a high temperature and high humidity environment.
實施例
以下列舉實施例來更詳細說明本發明，惟本發明不僅受限於該等實施例。
＜實施例1＞
＜製作偏光膜＞
準備平均聚合度為2,400、皂化度為99.9莫耳%且厚度為30μm之聚乙烯醇薄膜。於周速比相異之輥間一邊將聚乙烯醇薄膜浸漬於20℃之膨潤浴(水浴)中30秒進行膨潤，一邊沿輸送方向延伸成2.2倍(膨潤步驟)，接著，在30℃之染色浴(相對於水100重量份將碘與碘化鉀以1：7之重量比摻混而得之碘水溶液)中調整濃度並浸漬30秒進行染色，以使最後所得偏光膜之碘濃度成為3.8重量%，並一邊以原本的聚乙烯醇薄膜(完全未沿輸送方向延伸過的聚乙烯醇薄膜)為基準沿輸送方向延伸成3.3倍(染色步驟)。接著，將已染色之聚乙烯醇薄膜在40℃之交聯浴(硼酸濃度為3.5重量%、碘化鉀濃度為3.0重量%、硫酸鋅濃度為3.6重量%之水溶液)中浸漬28秒，並以原本的聚乙烯醇薄膜為基準沿輸送方向延伸至3.6倍為止(交聯步驟)。再將所得聚乙烯醇薄膜於64℃之延伸浴(硼酸濃度為4.5重量%、碘化鉀濃度為5.0重量%、硫酸鋅濃度為5.0重量%之水溶液)中浸漬60秒，並以原本的聚乙烯醇薄膜為基準沿輸送方向延伸至6.0倍為止(延伸步驟)後，在27℃之洗淨浴(碘化鉀濃度為2.3重量%且作為具有自由基捕捉功能之化合物的下述通式(9)所示化合物濃度為1.0重量%之水溶液)中浸漬10秒(洗淨步驟)。將已洗淨之聚乙烯醇薄膜在40℃下乾燥30秒而製出偏光膜。偏光膜之碘濃度係利用以下測定方法求得。又，所得偏光膜之多烯化之脫水溫度(以逸出氣分析法檢測出之水的最大強度之峰值溫度)為210℃，偏光膜中的下述通式(9)所示化合物之含量為0.3重量%，偏光膜之厚度為12μm。
[化學式9]
[偏光膜中之碘濃度(重量%)之測定方法] 針對偏光膜，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)另，算出濃度時之係數會依測定裝置而有所不同，但該係數可使用適當之檢量曲線求得。[Measurement method of iodine concentration (wt%) in polarizing film] For the polarizing film, an X-ray fluorescence analyzer (manufactured by Rigaku, trade name "ZSX-PRIMUS IV", measurement diameter: ψ20 mm) was used, and the iodine concentration (% by weight) was determined by the following formula. Iodine concentration (wt%)=14.4474×(X-ray fluorescence intensity)/(film thickness)(kcps/μm) In addition, the coefficient when calculating the concentration will be different depending on the measuring device, but the coefficient can be checked by appropriate Calculated by the volume curve.
[多烯化之脫水溫度的測定方法] 將偏光膜導入加熱爐型熱解器(Frontier Laboratories製，PY-2020iD)中，再將所產生之氣體直接導入TOFMS(JEOL製，MS-T100GCV)中，利用逸出氣分析(EGA/TOFMS)法進行測定，求得所檢測之水的最大強度之峰值溫度，並將該溫度作為多烯化之脫水溫度。 [測定條件] 升溫條件：40℃→＋10℃/min→350℃ 介面：非活性熔融石英管，2.5m×0.15mm id 載氣：He(1.0mL/min) 注入口溫度：300℃ 注入口：分流比 20：1 介面溫度：300℃ 質量分析計：TOFMS 離子化法：EI法 質量範圍：m/z=18[Determination method of dehydration temperature for polyolefination] The polarizing film is introduced into a furnace-type pyrolyzer (Frontier Laboratories, PY-2020iD), and then the generated gas is directly introduced into TOFMS (JEOL, MS-T100GCV), using outgas analysis (EGA/TOFMS) Method to determine the peak temperature of the maximum intensity of the detected water, and use this temperature as the dehydration temperature for polyolefination. [Measurement conditions] Heating conditions: 40℃→＋10℃/min→350℃ Interface: Inactive fused silica tube, 2.5m×0.15mm id Carrier gas: He(1.0mL/min) Note inlet temperature: 300℃ Note inlet: split ratio 20:1 Interface temperature: 300℃ Quality Analyzer: TOFMS Ionization method: EI method Mass range: m/z=18
[偏光膜中之具有自由基捕捉功能之化合物之含量(重量%)的測定方法] 採取約20mg的偏光膜並定量，於水1mL中加熱溶解後，以甲醇4.5mL稀釋，再將所得萃取液以膜濾器過濾，並將濾液使用HPLC(Waters公司製 ACQUITY UPLC H-class Bio)測定具有自由基捕捉功能之化合物之濃度。[Method for measuring the content (wt%) of the compound with free radical trapping function in the polarizing film] About 20 mg of the polarizing film was taken and quantified. After heating and dissolving in 1 mL of water, it was diluted with 4.5 mL of methanol, and the obtained extract was filtered with a membrane filter, and the filtrate was measured by HPLC (ACQUITY UPLC H-class Bio manufactured by Waters) Concentration of compounds with free radical capture function.
＜製作偏光薄膜＞ 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。使用該接著劑，以輥貼合機於上述所得偏光膜之一面(視辨側)貼合三醋酸纖維素薄膜(富士軟片製，商品名「TJ40UL」)上形成有HC之厚度47μm的透明保護薄膜(透濕度為380g/(m2 ・24h))作為第2透明保護薄膜，並於另一面(影像顯示單元側)上貼合由(甲基)丙烯酸系樹脂(具有內酯環結構之改質丙烯酸系聚合物)構成之厚度30μm的透明保護薄膜(日本觸媒製，透濕度為125g/(m2 ・24h))作為第1透明保護薄膜後，接著於烘箱內使其加熱乾燥(溫度為90℃，時間為10分鐘)，而製作出偏光膜之兩面貼合有透明保護薄膜的偏光薄膜。<Preparation of polarizing film> The following aqueous solution is used as the adhesive: a weight ratio of 3:1 containing polyvinyl alcohol resin containing acetyl group (average degree of polymerization 1,200, degree of saponification 98.5 mol%, degree of acetylation degree 5 mol%) and methylol melamine. Using this adhesive, a cellulose triacetate film (manufactured by Fujifilm, trade name "TJ40UL") was laminated on one side (viewing side) of the polarizing film obtained above with a roll laminator to form a transparent protection of 47μm in thickness with HC The film (with a moisture permeability of 380g/(m 2 · 24h)) is used as the second transparent protective film, and on the other side (the side of the image display unit) is laminated a (meth)acrylic resin (with a lactone ring structure). A transparent protective film with a thickness of 30μm (made by Nippon Shokubai, with a moisture permeability of 125g/(m 2 · 24h)) composed of acrylic polymer) is used as the first transparent protective film, and then it is heated and dried in an oven (temperature The temperature is 90°C and the time is 10 minutes), and a polarizing film with a transparent protective film attached to both sides of the polarizing film is produced.
[在高溫環境下之單體透射率的測定方法] 將上述獲得之偏光薄膜以使偏光膜之吸收軸與長邊平行之方式裁切成5.0×4.5cm之尺寸，並透過厚度20μm之丙烯酸系黏著劑層將玻璃板(模擬影像顯示單元)貼合於偏光薄膜的影像顯示單元側之保護薄膜面，再於50℃、0.5MPa下進行15分鐘高壓釜處理，而製作出積層體。將所得積層體靜置於溫度105℃之熱風烘箱內750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(日本分光製，製品名「V7100」)測定，並以以下基準評估。此外，測定波長為380~700nm(每5nm)。將結果列於表1。 ΔTs(%)=Ts750 -Ts0 在此，Ts0 為加熱前的積層體的單體透射率，Ts750 為加熱750小時後的積層體的單體透射率。[Method for measuring monomer transmittance under high temperature environment] The polarizing film obtained above was cut into a size of 5.0×4.5 cm so that the absorption axis of the polarizing film was parallel to the long side, and passed through an acrylic with a thickness of 20 μm Adhesive layer The glass plate (analog image display unit) is attached to the protective film surface of the polarizing film on the side of the image display unit, and then autoclaved at 50°C and 0.5MPa for 15 minutes to produce a laminate. The resulting laminate was left in a hot air oven at a temperature of 105°C for 750 hours, and the monomer transmittance (ΔTs) before and after the input (heating) was measured. The monomer transmittance was measured using a spectrophotometer (manufactured by JASCO Corporation, product name "V7100"), and evaluated based on the following criteria. In addition, the measurement wavelength is 380 to 700 nm (every 5 nm). The results are listed in Table 1. ΔTs (%)=Ts 750 −Ts 0 Here, Ts 0 is the monomer transmittance of the laminate before heating, and Ts 750 is the monomer transmittance of the laminate after heating for 750 hours.
[評估偏光度] 偏光薄膜之偏光度可使用分光光度計(日本分光製，製品名「V7100」)來測定。偏光度之具體測定方法，係測定偏光膜之平行透射率(H0)及正交透射率(H90)，可由式：偏光度(%)={(H0-H90)/(H0+H90)}1/2×100來求得。平行透射率(H0)係平行型積層偏光膜的透射率之值，該平行型積層偏光膜係將兩片相同偏光膜疊合成雙方的吸收軸平行而製成者。又，正交透射率(H90)係正交型積層偏光膜的透射率之值，該正交型積層偏光膜係將兩片相同偏光膜疊合成雙方的吸收軸正交而製成者。此外，該等透射率係以JIS Z 8701-1982之2度視野(C光源)進行視感度校正所得之Y值。將結果列於表1。[Assess the degree of polarization] The degree of polarization of the polarizing film can be measured using a spectrophotometer (manufactured by JASCO, product name "V7100"). The specific measurement method of polarization degree is to measure the parallel transmittance (H0) and orthogonal transmittance (H90) of the polarizing film, which can be determined by the formula: polarization degree (%)={(H0-H90)/(H0+H90)}1 /2×100 to find. The parallel transmittance (H0) is the value of the transmittance of the parallel-type laminated polarizing film, which is made by stacking two identical polarizing films so that the absorption axes of both sides are parallel. In addition, the cross transmittance (H90) is the value of the transmittance of the cross-type laminated polarizing film, which is made by stacking two identical polarizing films so that the absorption axes of both sides are orthogonal to each other. In addition, the transmittance is the Y value obtained by the visual sensitivity correction of the 2 degree field of view (C light source) of JIS Z 8701-1982. The results are listed in Table 1.
[評估加濕耐久性] 將上述積層體試樣靜置於85℃、85%RH之濕熱烘箱內500小時後，以上述分光光度計(日本分光製，製品名「V7100」)評估偏光度。將結果列於表1。 ○：偏光度90%以上 ×：偏光度低於90%[Evaluation of humidification durability] After placing the laminate sample in a humid heat oven at 85° C. and 85% RH for 500 hours, the degree of polarization was evaluated by the spectrophotometer (Japan Spectrophotometer, product name "V7100"). The results are listed in Table 1. ○: Polarization degree above 90% ×: The degree of polarization is less than 90%
[評估加熱剝落] 以偏光薄膜之吸收軸與長邊平行之方式裁切成680×250mm之尺寸，並透過厚度20μm之丙烯酸系黏著劑層於偏光薄膜的影像顯示單元側之保護薄膜面上製作出玻璃板(模擬影像顯示單元)。將所得積層體試樣在105℃的熱風烘箱內靜置750小時後，依下述基準以肉眼評估其外觀。將結果列於表1。 〇：雖然極少但於端部有些許剝落或發泡，不過實際使用上無問題。 △：於端部觀察到剝落或發泡，但只要非為特別用途(例如偏光板端部至顯示影像之主動區為止之距離短的窄邊框顯示器等)，則實際使用上無問題。 ×：端部有顯著剝落，實際使用上有問題。[Assess heat spalling] Cut into a size of 680×250mm with the absorption axis of the polarizing film parallel to the long side, and make a glass plate (simulation) on the protective film surface of the image display unit side of the polarizing film through an acrylic adhesive layer with a thickness of 20μm. Image display unit). After leaving the obtained laminate sample in a hot-air oven at 105°C for 750 hours, its appearance was evaluated visually based on the following criteria. The results are listed in Table 1. ○: Although there is very little peeling or foaming at the ends, there is no problem in actual use. △: Peeling or foaming is observed at the end, but as long as it is not for special purposes (for example, a narrow border display with a short distance from the end of the polarizing plate to the active area where the image is displayed, etc.), there is no problem in actual use. ×: There was significant peeling at the end, which was problematic in actual use.
＜實施例2＞ ＜製作偏光膜、偏光薄膜＞ 在製作偏光膜時，將染色浴之碘濃度調整成最後獲得之偏光膜的碘濃度成為4.3重量%，除此之外以與實施例1相同操作而製出偏光膜及偏光薄膜。所得偏光膜以逸出氣分析法檢測出之水的最大強度之峰值溫度為208℃，偏光膜中的上述通式(9)所示化合物之含量為0.3重量%，偏光膜之厚度為12μm。<Example 2> <Production of polarizing film and polarizing film> When producing the polarizing film, the iodine concentration of the dye bath was adjusted so that the iodine concentration of the finally obtained polarizing film became 4.3% by weight, except that the same operation as in Example 1 was performed to prepare the polarizing film and the polarizing film. The peak temperature of the maximum intensity of water detected by the outgas analysis method of the obtained polarizing film was 208°C, the content of the compound represented by the general formula (9) in the polarizing film was 0.3% by weight, and the thickness of the polarizing film was 12 μm.
＜實施例3＞ ＜製作偏光膜、偏光薄膜＞ 在製作偏光膜時，對厚度為45μm之聚乙烯醇薄膜，將染色浴之碘濃度調整成最後獲得之偏光膜的碘濃度成為3.5重量%，除此之外以與實施例1相同操作而製出偏光膜及偏光薄膜。所得偏光膜以逸出氣分析法檢測出之水的最大強度之峰值溫度為210℃，偏光膜中的上述通式(9)所示化合物之含量為0.2重量%，偏光膜之厚度為18μm。<Example 3> <Production of polarizing film and polarizing film> When making the polarizing film, the iodine concentration of the dyeing bath was adjusted to the iodine concentration of the polarizing film finally obtained to be 3.5% by weight for the polyvinyl alcohol film with a thickness of 45μm, except that it was prepared by the same operation as in Example 1 Out polarizing film and polarizing film. The peak temperature of the maximum intensity of water detected by the outgas analysis method of the obtained polarizing film was 210°C, the content of the compound represented by the general formula (9) in the polarizing film was 0.2% by weight, and the thickness of the polarizing film was 18 μm.
＜實施例4＞ ＜製作偏光膜、偏光薄膜＞ 於作成偏光膜時，將染色浴之碘濃度調整成使最後獲得之偏光膜的碘濃度成為4.8重量%，且於洗淨浴中調整成碘化鉀濃度成為3.6重量%、取代上述通式(9)之上述通式(8)所示化合物成為1.5重量%，除此之外以與實施例1相同操作方法而製出偏光膜及偏光薄膜。所得偏光膜以逸出氣分析法檢測出之水的最大強度之峰值溫度為210℃，偏光膜中的上述通式(8)所示化合物之含量為0.4重量%，偏光膜之厚度為12μm。<Example 4> <Production of polarizing film and polarizing film> When making the polarizing film, adjust the iodine concentration of the dye bath so that the iodine concentration of the polarizing film finally obtained becomes 4.8% by weight, and in the washing bath, adjust the potassium iodide concentration to 3.6% by weight, instead of the above general formula (9) The compound represented by the above general formula (8) was 1.5% by weight, except that the polarizing film and the polarizing film were prepared by the same operation method as in Example 1. The peak temperature of the maximum intensity of water detected by the outgas analysis method of the obtained polarizing film was 210° C., the content of the compound represented by the general formula (8) in the polarizing film was 0.4% by weight, and the thickness of the polarizing film was 12 μm.
＜實施例5＞
＜製作偏光膜、偏光薄膜＞
於作成偏光膜時，將染色浴之碘濃度調整成使最後獲得之偏光膜的碘濃度成為2.5重量%，且於洗淨浴中調整成碘化鉀濃度成為1.8重量%、取代上述通式(9)之下述通式(10)所示化合物成為1.0重量%、氯化鈉成為15重量%，除此之外以與實施例1相同操作方法而製出偏光膜及偏光薄膜。所得偏光膜以逸出氣分析法檢測出之水的最大強度之峰值溫度為209℃，偏光膜中的下述通式(10)所示化合物之含量為0.3重量%，氯離子之含量為3.1重量%，偏光膜之厚度為12μm。又，氯離子係利用以下測定方法求得。
[化學式10]
[氯離子(氯化物離子)之測定方法] 將試料採取5mg至多烯丙烯容器中，並加入超純水20mL後蓋上蓋子。接著，以120℃、1小時進行加溫萃取後，將所得萃取液以膜濾器與有機物去除筒過濾，並利用離子層析儀進行定量分析，算出氯離子。 [測定條件] 裝置(陰離子)：Thermo Fisher Scientific製 ICS-3000 分離管柱：Dionex IonPac AS18-fast(4mm×150mm) 保護管柱：Dionex IonPac AG18-fast(4mm×30mm) 去除系統：Dionex AERS-500(external mode) 檢測器：導電度檢測器 溶析液：KOH水溶液(使用溶析液產生器EGCIII) 溶析液流量：1.2mL/min 試料注入量：250μL[Measurement method of chloride ion (chloride ion)] Take 5 mg of the sample into a polyene propylene container, add 20 mL of ultrapure water, and close the lid. Next, after heating and extracting at 120° C. for 1 hour, the obtained extract was filtered with a membrane filter and an organic substance removal cartridge, and quantitatively analyzed by an ion chromatograph to calculate chloride ions. [Measurement conditions] Device (anion): ICS-3000 manufactured by Thermo Fisher Scientific Separation column: Dionex IonPac AS18-fast (4mm×150mm) Protection column: Dionex IonPac AG18-fast(4mm×30mm) Removal system: Dionex AERS-500 (external mode) Detector: conductivity detector Eluent: KOH aqueous solution (using the eluent generator EGCIII) Eluent flow rate: 1.2mL/min Sample injection volume: 250μL
＜實施例6＞ ＜製作偏光膜、偏光薄膜＞ 在製作偏光膜時，未添加上述通式(10)所示化合物，除此之外以與實施例5相同操作方法而製出偏光膜及偏光薄膜。所得偏光膜以逸出氣分析法檢測出之水的最大強度之峰值溫度為209℃，偏光膜中的氯離子之含量為3.2重量%，偏光膜之厚度為12μm。<Example 6> <Production of polarizing film and polarizing film> In the production of the polarizing film, the compound represented by the above general formula (10) was not added, except that the polarizing film and the polarizing film were prepared by the same operation method as in Example 5. The peak temperature of the maximum intensity of water detected by the outgas analysis method of the obtained polarizing film was 209°C, the content of chloride ions in the polarizing film was 3.2% by weight, and the thickness of the polarizing film was 12 μm.
＜比較例1＞ ＜製作偏光膜、偏光薄膜＞ 在製作偏光膜時，未於洗淨浴中添加上述通式(9)所示化合物作為具有自由基捕捉功能之化合物，除此之外以與實施例2相同操作而製出偏光膜及偏光薄膜。所得偏光膜以逸出氣分析法檢測出之水的最大強度之峰值溫度為197℃，偏光膜中的上述通式(9)所示化合物之含量為0重量%，偏光膜之厚度為12μm。<Comparative example 1> <Production of polarizing film and polarizing film> When making the polarizing film, the compound represented by the above general formula (9) was not added as a compound with a free radical trapping function in the washing bath, except that the same operation as in Example 2 was used to prepare the polarizing film and the polarizing film . The peak temperature of the maximum intensity of water detected by the outgas analysis method of the obtained polarizing film was 197°C, the content of the compound represented by the general formula (9) in the polarizing film was 0% by weight, and the thickness of the polarizing film was 12 μm.
＜比較例2＞ ＜製作偏光膜、偏光薄膜＞ 在製作偏光膜時，將染色浴之碘濃度調整成使最後獲得之偏光膜的碘濃度成為2.5重量%，且未於洗淨浴中添加上述通式(9)所示化合物作為具有自由基捕捉功能之化合物，除此之外以與實施例1相同操作而製出偏光膜及偏光薄膜。所得偏光膜以逸出氣分析法檢測出之水的最大強度之峰值溫度為206℃，偏光膜中的上述通式(9)所示化合物之含量為0重量%，偏光膜之厚度為12μm。＜Comparative example 2＞ <Production of polarizing film and polarizing film> When making the polarizing film, the iodine concentration of the dyeing bath is adjusted so that the iodine concentration of the polarizing film finally obtained becomes 2.5% by weight, and the compound represented by the above general formula (9) is not added to the washing bath as a free radical trap The functional compound, except that the polarizing film and the polarizing film were prepared by the same operation as in Example 1. The peak temperature of the maximum intensity of water detected by the outgassing analysis method of the obtained polarizing film was 206°C, the content of the compound represented by the general formula (9) in the polarizing film was 0% by weight, and the thickness of the polarizing film was 12 μm.
＜比較例3＞ ＜製作偏光膜、偏光薄膜＞ 除了於第1透明保護薄膜使用厚度20μm且透濕度1270g/(m2 ・24h)之三醋酸纖維素薄膜(Konica Minolta製，商品名「KC2CT」)外，以與實施例1相同方法而製作出偏光薄膜。<Comparative example 3><Preparation of polarizing film and polarizing film> Except for the first transparent protective film, a tri-cellulose acetate film (manufactured by Konica Minolta, trade name "KC2CT" with a thickness of 20 μm and a moisture permeability of 1270 g/(m 2 · 24h)) was used ), using the same method as in Example 1 to produce a polarizing film.
＜比較例4＞ ＜製作偏光膜、偏光薄膜＞ 於製作偏光膜時，一邊於周速比相異之輥間將厚度為75μm之聚乙烯醇薄膜浸漬於35℃之膨潤浴(水浴)中30秒進行膨潤，一邊沿輸送方向延伸成2.2倍(膨潤步驟)，並將染色浴的碘濃度調整成最後獲得之偏光膜的碘濃度成為3.1重量%，且於洗淨浴中添加3重量%之氯化鈉，並於第1透明保護薄膜使用厚度20μm且透濕度1270g/m2 ・24hr之三醋酸纖維素薄膜(Konica Minolta製，商品名「KC2CT」)，除此以外以與比較例1相同操作方法而製出偏光膜及偏光薄膜。所得偏光膜以逸出氣分析法檢測出之水的最大強度之峰值溫度為209℃，偏光膜中的氯離子之含量為1.1重量%，偏光膜之厚度為28μm。<Comparative example 4><Preparation of polarizing film and polarizing film> When preparing a polarizing film, a polyvinyl alcohol film with a thickness of 75μm was immersed in a swelling bath (water bath) at 35°C between rolls with different peripheral speed ratios. 30 It swells in seconds and stretches 2.2 times in the conveying direction (swelling step). The iodine concentration of the dyeing bath is adjusted so that the iodine concentration of the polarizing film obtained finally becomes 3.1% by weight, and 3% by weight is added to the washing bath. Sodium chloride, and a tri-cellulose acetate film (manufactured by Konica Minolta, trade name "KC2CT") with a thickness of 20μm and a moisture permeability of 1270g/m 2·24hr is used as the first transparent protective film. Other than that, the same as Comparative Example 1 Operation method to produce polarizing film and polarizing film. The peak temperature of the maximum intensity of water detected by the outgas analysis method of the obtained polarizing film was 209°C, the content of chloride ions in the polarizing film was 1.1% by weight, and the thickness of the polarizing film was 28 μm.
使用上述所得各實施例及各比較例之偏光薄膜，進行上述[在高溫環境下之單體透射率的測定方法]、[評估偏光度]、[評估加濕耐久性]及[評估加熱剝落]。將結果列於表1。Using the polarizing films of the respective Examples and Comparative Examples obtained above, the above-mentioned [Method for Measuring Monomer Transmittance in High-Temperature Environment], [Evaluation of Polarization Degree], [Evaluation of Humidification Durability], and [Evaluation of Heat Peeling] . The results are listed in Table 1.
[表1]
(無)(no)
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