TWI712620B - Polyvinyl alcohol-based film, manufacturing method of polyvinyl alcohol-based film, polarizing film and polarizing plate - Google Patents
Polyvinyl alcohol-based film, manufacturing method of polyvinyl alcohol-based film, polarizing film and polarizing plate Download PDFInfo
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Abstract
本發明提供一種可獲得厚度變動少、偏光特性優異之偏光薄膜的聚乙烯醇系薄膜，並提供一種偏光薄膜。該聚乙烯醇系薄膜，係厚度5～60μm、寬度2m以上、長度2km以上之聚乙烯醇系薄膜；其特徵為：薄膜整面之厚度之變動係數為1%以下。The present invention provides a polyvinyl alcohol-based film that can obtain a polarizing film with less thickness variation and excellent polarization characteristics, and provides a polarizing film. The polyvinyl alcohol-based film is a polyvinyl alcohol-based film with a thickness of 5-60 μm, a width of 2 m or more, and a length of 2 km or more; it is characterized in that the coefficient of variation of the thickness of the entire film is 1% or less.
Description
本發明關於一種聚乙烯醇系薄膜。更詳細而言，係關於一種可獲得厚度變動少、偏光特性優異之偏光薄膜的聚乙烯醇系薄膜，及該聚乙烯醇系薄膜之製造方法、與偏光薄膜、偏光板。The present invention relates to a polyvinyl alcohol film. More specifically, it relates to a polyvinyl alcohol-based film that can obtain a polarizing film with less thickness variation and excellent polarization characteristics, and a method for producing the polyvinyl alcohol-based film, a polarizing film, and a polarizing plate.
以往，聚乙烯醇系薄膜係藉由將聚乙烯醇系樹脂溶解於水等溶劑而製備原液後，利用溶液流延法(澆鑄法)製膜，並使用金屬加熱輥等進行乾燥而製造。如此獲得之聚乙烯醇系薄膜，作為透明性、染色性優異之薄膜被利用在多種用途，其有用的用途之一可列舉偏光薄膜。該偏光薄膜作為液晶顯示器之基本構成要素使用，近年要求高等級且高可靠性之機器及其使用正擴大中。Conventionally, a polyvinyl alcohol-based film is produced by dissolving a polyvinyl alcohol-based resin in a solvent such as water to prepare a stock solution, forming a film by a solution casting method (casting method), and drying it using a metal heating roller or the like. The polyvinyl alcohol-based film obtained in this manner is used in various applications as a film having excellent transparency and dyeability, and one of its useful applications includes a polarizing film. The polarizing film is used as a basic component of a liquid crystal display. In recent years, machines requiring high-level and high reliability and their use are expanding.
該等中，伴隨液晶電視等的畫面大型化，需要比起以往產品更上一層之平坦性優異，且寬幅長條薄型之偏光薄膜及成為其原捲之聚乙烯醇系薄膜。聚乙烯醇系薄膜由於厚度變動而不平坦時，偏光薄膜的厚度變動亦變大，偏光性能之面內均勻性不充分，於組裝成之液晶胞產生應力而引起液晶胞本身的變形、耐久性的降低。就針對此類問題的對策而言，例如，有人提出了將TD方向(寬度方向)之厚度變動為0.5μm/mm以下之聚乙烯醇系薄膜用於偏光薄膜的製造(例如，參照專利文獻1。)。又，為了抑制厚度變動，有人提出了將聚乙烯醇系薄膜使用處於特定位置關係之模具與金屬輥進行製膜的方法(例如，參照專利文獻2。)。 [專利文獻]Among these, as the screens of liquid crystal televisions and the like become larger, it is necessary to have a higher level of flatness than conventional products, a wide, long and thin polarizing film, and a polyvinyl alcohol-based film that becomes the original roll. When the polyvinyl alcohol film is not flat due to the thickness variation, the thickness variation of the polarizing film also becomes larger, and the in-plane uniformity of the polarization performance is insufficient, and the assembled liquid crystal cell generates stress, which causes the deformation and durability of the liquid crystal cell itself. The reduction. As for countermeasures against such problems, for example, it has been proposed to use a polyvinyl alcohol-based film with a thickness variation in the TD direction (width direction) of 0.5 μm/mm or less for the production of polarizing films (for example, refer to
[專利文獻1]日本特開2002－31720號公報 [專利文獻2]日本特開2002－144355號公報[Patent Document 1] Japanese Patent Application Publication No. 2002-31720 [Patent Document 2] Japanese Patent Application Publication No. 2002-144355
[發明所欲解決之課題] 但，吾人等認為上述專利文獻1中，雖然TD方向之厚度變動為每長度lmm 0.5μm以下，但至多為長度lmm中之變動值，於特別是如全寬為2m以上之寬幅薄膜的情況下，該變動值會大幅增加。進一步於如全長2km以上之長條薄膜的情況下，該TD方向之厚度變動會進一步變大。 又，若只減小TD方向之厚度變動，在從聚乙烯醇系薄膜輥將薄膜捲出而製造偏光薄膜時，由於MD方向(流動方向：長邊方向)之厚度變動，當進行諸如染色、延伸、硼酸處理之各步驟時難以均勻地處理，會有於偏光薄膜之面內偏光度變得不均勻的問題。[Problem to be Solved by the Invention] However, we believe that although the thickness variation in the TD direction in the
上述專利文獻2之實施例中，雖然薄膜之TD方向之厚度變動為1.5μm，但薄膜的厚度為75μm之厚，難以因應偏光薄膜的薄型化，為60μm以下之薄型化時，會有不能確保足夠的厚度精度的問題。此外，薄膜的厚度為30μm時，若薄膜之厚度變動為1.5μm的話，厚度變動係數為0.8%左右。 又，與上述專利文獻1的情況相同，若只減小TD方向之厚度變動，在從聚乙烯醇系薄膜輥將薄膜捲出而製造偏光薄膜時，由於MD方向之厚度變動，當進行諸如染色、延伸、硼酸處理之各步驟時難以均勻地處理，會有於偏光薄膜之面內偏光度變得不均勻的問題。In the example of
又，聚乙烯醇系薄膜之厚度變動大而不平坦時，會難以捲取於輥，在保存及輸送中薄膜吸濕時，起伏增大，而會有不得不在偏光薄膜製造前毀掉大部分薄膜的問題。In addition, when the thickness of the polyvinyl alcohol-based film varies greatly and is uneven, it will be difficult to wind up on a roll. When the film absorbs moisture during storage and transportation, the fluctuations will increase, and most of it will have to be destroyed before the polarizing film is manufactured. The problem with the film.
因此，本發明於該等背景下，旨在提供一種可獲得厚度變動少、偏光特性優異之偏光薄膜的聚乙烯醇系薄膜，及該聚乙烯醇系薄膜之製造方法、與偏光薄膜、偏光板。 [解決課題之手段]Therefore, under these backgrounds, the present invention aims to provide a polyvinyl alcohol-based film that can obtain a polarizing film with less thickness variation and excellent polarization characteristics, and a method for manufacturing the polyvinyl alcohol-based film, and polarizing films and polarizing plates. . [Means to solve the problem]
本案發明人們鑒於該等情況而進行努力研究的結果，著眼於聚乙烯醇系薄膜的膜厚，發現藉由控制其變動係數使其變小，可獲得偏光特性優異之偏光薄膜，而完成了本發明。As a result of diligent research by the inventors in view of these circumstances, they focused on the film thickness of the polyvinyl alcohol-based film, and found that by controlling the coefficient of variation to make it smaller, a polarizing film with excellent polarization characteristics can be obtained. invention.
亦即，本發明之第1要旨關於一種聚乙烯醇系薄膜，係厚度5～60μm、寬度2m以上、長度2km以上之聚乙烯醇系薄膜；其特徵為：薄膜整面之厚度之變動係數為1%以下。That is, the first gist of the present invention relates to a polyvinyl alcohol-based film, which is a polyvinyl alcohol-based film having a thickness of 5 to 60 μm, a width of 2 m or more, and a length of 2 km or more; it is characterized in that the coefficient of variation of the thickness of the entire film is 1% or less.
又，本發明之第2要旨關於一種聚乙烯醇系薄膜之製造方法，係將聚乙烯醇系樹脂之水溶液從T型狹縫模(slit die)吐出至旋轉的澆鑄滾筒(cast drum)上而製膜，並連續地乾燥而獲得聚乙烯醇系薄膜；其特徵為：薄膜整面之厚度之變動係數為1%以下。 進一步，本發明之第3要旨關於一種偏光薄膜，係由該聚乙烯醇系薄膜構成。 且，本發明之第4要旨關於一種偏光板，係於該偏光薄膜之至少單面設置保護薄膜而成。 [發明之效果]In addition, the second gist of the present invention relates to a method for producing a polyvinyl alcohol-based film, which is to discharge an aqueous solution of a polyvinyl alcohol-based resin from a T-shaped slit die onto a rotating cast drum. A film is formed and continuously dried to obtain a polyvinyl alcohol-based film; it is characterized in that the coefficient of variation of the thickness of the entire film is 1% or less. Furthermore, the third gist of the present invention relates to a polarizing film composed of the polyvinyl alcohol-based film. Furthermore, the fourth gist of the present invention relates to a polarizing plate, which is formed by providing a protective film on at least one side of the polarizing film. [Effects of Invention]
本發明之聚乙烯醇系薄膜，由於具有優異的厚度精度，可獲得偏光特性優異之偏光薄膜，尤其作為薄型且長條之偏光薄膜的原捲使用較佳，可獲得偏光度在面內均勻之偏光薄膜。The polyvinyl alcohol film of the present invention can obtain a polarizing film with excellent polarization characteristics due to its excellent thickness accuracy, and is particularly suitable for use as the original roll of a thin and long polarizing film, and the degree of polarization can be uniform in the plane. Polarizing film.
本發明之聚乙烯醇系薄膜，係厚度5～60μm、寬度2m以上、長度2km以上之聚乙烯醇系薄膜，其特徵為：薄膜整面之厚度之變動係數為1%以下。The polyvinyl alcohol film of the present invention is a polyvinyl alcohol film having a thickness of 5-60 μm, a width of 2 m or more, and a length of 2 km or more, and is characterized in that the coefficient of variation of the thickness of the entire film is 1% or less.
此處，上述變動係數係藉由以下的方法而求得。 ＜測定方法＞ 首先，測定聚乙烯醇系薄膜之任意處的厚度。 ・流動方向(MD方向)的測定係使用KEYENCE公司製「光譜干涉型膜厚計SI－T80」以0.3mm級距針對寬度方向(TD方向)之中央部與兩端部的3個地方分別測定6萬點。 ・TD方向的測定係使用山文電氣公司製「連續膜厚計TOF－5R01」，針對MD方向之前端部、中央部、終端部的3個地方分別測定4000點。 然後，針對上述厚度之測定值，根據下列公式計算標準偏差。Here, the above-mentioned coefficient of variation is obtained by the following method. <Measurement method> First, the thickness of the polyvinyl alcohol-based film is measured at any point.・The flow direction (MD direction) is measured using the "Spectral Interference Film Thickness Gauge SI-T80" manufactured by KEYENCE at 0.3mm steps at the center and both ends in the width direction (TD direction). 60,000 points.・The measurement in the TD direction uses the "Continuous Film Thickness Gauge TOF-5R01" manufactured by Sanbun Electric Co., and measures 4000 points at three locations at the front end, center, and end in the MD direction. Then, for the measured value of the above thickness, calculate the standard deviation according to the following formula.
[數1] 標準偏差(S.D.)=√ (Σ (xi-x)2 /(n-1)) x ：平均值 xi：第i點的值 n：樣品數[Number 1] Standard deviation (SD)=√ (Σ (xi-x) 2 /(n-1)) x: average value xi: value at the i-th point n: number of samples
最後根據以下的公式計算變動係數。 變動係數(C.V.)=100×S.D./xFinally, calculate the coefficient of variation according to the following formula. Coefficient of Variation (C.V.)=100×S.D./x
此外，本發明中「薄膜整面」係指針對全長、全寬的測定，具體而言，在MD方向係指中央部與兩端部之最少3個地方，在TD方向也是中央部與兩端部之最少3個地方。In addition, in the present invention, "the entire surface of the film" refers to the measurement of the full length and the full width. Specifically, in the MD direction, it refers to at least three places between the center and both ends. In the TD direction, it is also the center and both ends. At least 3 places in the department.
本發明之聚乙烯醇系薄膜，根據上述方法而得之厚度之變動係數為1%以下係必要，0.7%以下較佳，0.5%以下特佳，0.4%以下更佳。厚度之變動係數大於1%的話，偏光薄膜的性能惡化，不能達成本發明之目的。 又，上述厚度之變動係數的下限值通常為0.01%，0.05%較佳，0.1%特佳。For the polyvinyl alcohol film of the present invention, it is necessary that the coefficient of variation of the thickness obtained by the above method is 1% or less, preferably 0.7% or less, particularly preferably 0.5% or less, and more preferably 0.4% or less. If the coefficient of variation of the thickness is greater than 1%, the performance of the polarizing film will deteriorate and the purpose of the invention will not be achieved. In addition, the lower limit of the coefficient of variation of the thickness is usually 0.01%, preferably 0.05%, and particularly preferably 0.1%.
如上述之本發明之聚乙烯醇系薄膜，宜為將聚乙烯醇系樹脂之水溶液從T型狹縫模吐出至旋轉的澆鑄滾筒上而製膜，並連續地乾燥而製得者較佳。The above-mentioned polyvinyl alcohol-based film of the present invention is preferably prepared by discharging an aqueous solution of a polyvinyl alcohol-based resin from a T-shaped slot die onto a rotating casting drum to form a film, and then drying it continuously.
就該聚乙烯醇系樹脂而言，通常使用未改性的聚乙烯醇系樹脂，亦即，將使乙酸乙烯酯聚合而獲得之聚乙酸乙烯酯皂化而製得的樹脂。必要時，亦可使用將乙酸乙烯酯和少量(例如10莫耳%以下，5莫耳%以下較佳)可與乙酸乙烯酯共聚之成分的共聚物皂化而獲得的樹脂。可與乙酸乙烯酯共聚之成分，例如，可列舉不飽和羧酸(例如，包括鹽、酯、醯胺、腈等)、碳數2～30之烯烴類(例如，乙烯、丙烯、 正丁烯、異丁烯等)、乙烯醚類、不飽和磺酸鹽等。又，亦可使用將皂化後之羥基進行化學修飾而獲得的改性聚乙烯醇系樹脂。As for the polyvinyl alcohol-based resin, an unmodified polyvinyl alcohol-based resin is usually used, that is, a resin obtained by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate. If necessary, a resin obtained by saponifying a copolymer of vinyl acetate and a small amount (for example, 10 mol% or less, 5 mol% or less) of a component copolymerizable with vinyl acetate can also be used. Components that can be copolymerized with vinyl acetate, for example, unsaturated carboxylic acids (for example, including salts, esters, amides, nitriles, etc.), olefins with 2 to 30 carbon atoms (for example, ethylene, propylene, n-butene) , Isobutylene, etc.), vinyl ethers, unsaturated sulfonates, etc. In addition, modified polyvinyl alcohol-based resins obtained by chemically modifying saponified hydroxyl groups can also be used.
又，作為聚乙烯醇系樹脂，亦可使用於側鏈具有1,2－二醇結構之聚乙烯醇系樹脂。該於側鏈具有1,2－二醇結構之聚乙烯醇系樹脂，例如，可藉由(i)將乙酸乙烯酯與3,4－二乙醯氧基－1－丁烯之共聚物皂化的方法、(ii)將乙酸乙烯酯與碳酸乙烯基亞乙酯之共聚物皂化及脫羧的方法、(iii)將乙酸乙烯酯與2,2－二烷基－4－乙烯基－1,3－二氧環戊烷之共聚物皂化及脫縮酮化的方法、(iv)將乙酸乙烯酯與甘油單烯丙醚之共聚物皂化的方法等而獲得。In addition, as a polyvinyl alcohol-based resin, it can also be used for a polyvinyl alcohol-based resin having a 1,2-diol structure in the side chain. The polyvinyl alcohol resin having a 1,2-diol structure in the side chain, for example, can be saponified by (i) a copolymer of vinyl acetate and 3,4-diethoxy-1-butene The method of (ii) saponification and decarboxylation of the copolymer of vinyl acetate and vinyl ethylene carbonate, (iii) the method of combining vinyl acetate with 2,2-dialkyl-4-vinyl-1,3 -The method of saponification and deketalization of the copolymer of dioxolane, (iv) the method of saponifying the copolymer of vinyl acetate and glycerol monoallyl ether, etc.
聚乙烯醇系樹脂之重量平均分子量宜為10萬～30萬較佳，11萬～28萬特佳，12萬～26萬更佳。該重量平均分子量過小的話，會有將聚乙烯醇系樹脂形成光學薄膜時難以獲得充分的光學性能的傾向；過大的話，會有將聚乙烯醇系薄膜製成偏光薄膜時的延伸變得困難的傾向。此外，上述聚乙烯醇系樹脂之重量平均分子量係利用GPC－MALS法而測得的重量平均分子量。The weight average molecular weight of the polyvinyl alcohol resin is preferably 100,000 to 300,000, particularly preferably 110,000 to 280,000, and more preferably 120,000 to 260,000. If the weight average molecular weight is too small, it will tend to be difficult to obtain sufficient optical performance when the polyvinyl alcohol-based resin is formed into an optical film; if it is too large, it may become difficult to stretch when the polyvinyl alcohol-based film is made into a polarizing film. tendency. In addition, the weight average molecular weight of the said polyvinyl alcohol-type resin is the weight average molecular weight measured by GPC-MALS method.
本發明所使用之聚乙烯醇系樹脂之平均皂化度，通常宜為98莫耳%以上較佳，99莫耳%以上特佳，99.5莫耳%以上更佳，99.8莫耳%以上尤佳。該平均皂化度過小的話，會有將聚乙烯醇系薄膜形成偏光薄膜時不能獲得充分的光學性能的傾向。 此處，本發明中之平均皂化度係依照JIS K 6726而測定。The average saponification degree of the polyvinyl alcohol resin used in the present invention is generally preferably 98 mol% or more, 99 mol% or more is particularly preferred, 99.5 mol% or more is more preferred, and 99.8 mol% or more is particularly preferred. If the average saponification is too small, there is a tendency that sufficient optical performance cannot be obtained when the polyvinyl alcohol-based film is formed into a polarizing film. Here, the average degree of saponification in the present invention is measured in accordance with JIS K 6726.
本發明所使用之聚乙烯醇系樹脂，亦可倂用改性物質、重量平均分子量、平均皂化度等不同之2種以上。The polyvinyl alcohol-based resin used in the present invention may also be used with two or more different modified substances, weight average molecular weight, average saponification degree, and the like.
使用上述聚乙烯醇系樹脂製備聚乙烯醇系樹脂水溶液，並將該水溶液流延至旋轉的澆鑄滾筒(滾筒型輥)，利用澆鑄法製膜並乾燥，可藉此連續地製造本發明之聚乙烯醇系薄膜，例如，可藉由以下的步驟而製造。 (A)利用澆鑄法將薄膜製膜。 (B)將已製膜之薄膜加熱並乾燥。 (C)將乾燥後的薄膜切開後，捲取於輥。The polyvinyl alcohol-based resin aqueous solution is prepared using the above-mentioned polyvinyl alcohol-based resin, and the aqueous solution is cast on a rotating casting drum (roller type roll), and a film is formed by a casting method and dried, thereby continuously manufacturing the polyvinyl alcohol of the present invention The thin film can be produced by the following steps, for example. (A) The thin film is formed by a casting method. (B) Heat and dry the formed film. (C) After cutting the dried film, it is wound on a roll.
以下，對上述步驟(A)進行說明。 步驟(A)中，宜將上述聚乙烯醇系樹脂利用水等溶劑予以洗淨，並使用離心分離機等進行脫水，而形成含水率50重量%以下之聚乙烯醇系樹脂濕餅塊較佳。含水率過大的話，會有難以形成所期望之水溶液濃度的傾向。 將該聚乙烯醇系樹脂濕餅塊溶解於溫水或熱水而製備聚乙烯醇系樹脂水溶液。Hereinafter, the above-mentioned step (A) will be described. In step (A), it is preferable to wash the above-mentioned polyvinyl alcohol-based resin with a solvent such as water, and use a centrifugal separator for dehydration to form a polyvinyl alcohol-based resin wet cake with a moisture content of 50% by weight or less. . If the water content is too large, it will tend to be difficult to achieve the desired concentration of the aqueous solution. This polyvinyl alcohol-based resin wet cake is dissolved in warm water or hot water to prepare a polyvinyl alcohol-based resin aqueous solution.
聚乙烯醇系樹脂水溶液之製備方法並無特別限定，例如，可使用已加熱之多軸擠壓機製備，又，亦可於具備上下循環流產生型攪拌翼之溶解槽加入上述聚乙烯醇系樹脂濕餅塊，並於槽中吹入水蒸氣，溶解並製備所期望濃度之水溶液。The preparation method of the polyvinyl alcohol-based resin aqueous solution is not particularly limited. For example, it can be prepared using a heated multi-axis extruder, and the polyvinyl alcohol-based resin solution can also be added to a dissolving tank equipped with a vertical circulation flow generating type stirring blade. Wet the resin cake and blow water vapor into the tank to dissolve and prepare an aqueous solution of the desired concentration.
聚乙烯醇系樹脂水溶液中，除聚乙烯醇系樹脂以外，視需要含有甘油、二甘油、 三甘油、乙二醇、 三乙二醇、聚乙二醇、 三羥甲基丙烷等一般所使用之塑化劑；非離子性、陰離子性、或陽離子性界面活性劑的話，在聚乙烯醇系薄膜之製膜性的方面為較佳。In addition to the polyvinyl alcohol resin, the aqueous solution of polyvinyl alcohol resin contains glycerin, diglycerin, triglycerin, ethylene glycol, triethylene glycol, polyethylene glycol, trimethylolpropane, etc. as necessary. Generally used The plasticizer; nonionic, anionic, or cationic surfactants are preferred in terms of film-forming properties of polyvinyl alcohol-based films.
如此獲得之聚乙烯醇系樹脂水溶液的樹脂濃度宜為15～60重量%較佳，17～55重量%特佳，20～50重量%更佳。該樹脂濃度過低的話，由於乾燥負荷變大而會有生產能力降低的傾向，過高的話，黏度變得過高而會有難以均勻地溶解的傾向。The resin concentration of the polyvinyl alcohol-based resin aqueous solution thus obtained is preferably 15 to 60% by weight, particularly preferably 17 to 55% by weight, and more preferably 20 to 50% by weight. If the resin concentration is too low, the drying load will increase and the productivity will tend to decrease. If it is too high, the viscosity will become too high and it will tend to be difficult to dissolve uniformly.
然後，將所獲得之聚乙烯醇系樹脂水溶液進行消泡處理。就消泡方法而言，可列舉靜置消泡、利用多軸擠壓機所為之消泡等方法。多軸擠壓機只要是具有通氣孔之多軸擠壓機即可，並無特別限定，通常使用具有通氣孔之雙軸擠壓機。Then, the obtained polyvinyl alcohol-based resin aqueous solution is subjected to defoaming treatment. As far as defoaming methods are concerned, methods such as static defoaming and defoaming using a multi-axis extruder can be cited. The multi-screw extruder is not particularly limited as long as it is a multi-screw extruder with vent holes, and a twin-screw extruder with vent holes is generally used.
消泡處理後，將聚乙烯醇系樹脂水溶液逐次定量地導入T型狹縫模，並吐出及流延至旋轉的澆鑄滾筒上，利用澆鑄法製膜。After the defoaming treatment, the polyvinyl alcohol-based resin aqueous solution is quantitatively introduced into the T-shaped slit die successively, and discharged and cast onto a rotating casting drum, and a film is formed by a casting method.
T型狹縫模出口之聚乙烯醇系樹脂水溶液的溫度宜為80～100℃較佳，85～98℃特佳。 該聚乙烯醇系樹脂水溶液的溫度過低的話會有流動不良的傾向，過高的話會有起泡的傾向。The temperature of the polyvinyl alcohol resin aqueous solution at the exit of the T-shaped slit die is preferably 80-100°C, and 85-98°C is particularly preferred. If the temperature of the polyvinyl alcohol-based resin aqueous solution is too low, the flow will tend to be poor, and if it is too high, there will be a tendency to foam.
該聚乙烯醇系樹脂水溶液的黏度，在吐出時宜為50～200Pa·s較佳，70～150Pa·s特佳。 該水溶液的黏度過低的話會有流動不良的傾向，過高的話會有流延變得困難的傾向。The viscosity of the polyvinyl alcohol-based resin aqueous solution is preferably 50 to 200 Pa·s during discharge, and particularly preferably 70 to 150 Pa·s. If the viscosity of the aqueous solution is too low, the flow will tend to be poor, and if it is too high, the casting will tend to become difficult.
從T型狹縫模吐出至澆鑄滾筒之聚乙烯醇系樹脂水溶液的吐出速度宜為0.5～5m/分較佳，0.8～4m/分特佳，1～3m/分更佳。 該吐出速度過慢的話會有生產性降低的傾向，過快的話會有流延變得困難的傾向。The discharge speed of the polyvinyl alcohol resin aqueous solution discharged from the T-shaped slit die to the casting drum is preferably 0.5-5 m/min, 0.8-4 m/min is particularly preferable, and 1-3 m/min is more preferable. If the discharge rate is too slow, productivity tends to decrease, and if it is too fast, casting tends to become difficult.
又，聚乙烯醇系樹脂水溶液從T型狹縫模吐出口直至到達澆鑄滾筒表面的飛行時間宜為0.1～0.7秒較佳，考量後述拉伸應力及壓縮應力的緩和的方面，為0.2～0.6秒特佳，考量可避免後述起因於環境之形狀變形的方面，為0.2～0.4秒更佳。 該飛行時間過短或過長都會有厚度變動增大的傾向。In addition, the flight time of the polyvinyl alcohol-based resin aqueous solution from the T-slot die outlet to reaching the surface of the casting drum is preferably 0.1 to 0.7 seconds, and considering the relaxation of tensile stress and compressive stress described later, it is 0.2 to 0.6 The second is particularly good, considering that it can avoid the shape deformation caused by the environment described later, 0.2 to 0.4 seconds is more preferable. If the flight time is too short or too long, the thickness variation tends to increase.
該飛行時間可藉由調節從T型狹縫模1的吐出速度、從T型狹縫模1之吐出口1a至澆鑄滾筒2之表面(接地點P)的距離A、T型狹縫模1的唇部開度、聚乙烯醇系樹脂水溶液的黏度等而調節(參照圖1)。The flight time can be adjusted by adjusting the discharge speed from the T-shaped
本發明中，為了減小所獲得之聚乙烯醇系薄膜之厚度變動，宜設定使伴隨應力釋放之形狀變形緩和的時間、及極力避免起因於環境之形狀變形的時間較佳。In the present invention, in order to reduce the thickness variation of the obtained polyvinyl alcohol-based film, it is preferable to set the time to relax the shape deformation accompanying stress release and the time to avoid the shape deformation caused by the environment as much as possible.
關於前者，例如，當聚乙烯醇系樹脂水溶液3從上方垂直吐出至旋轉的澆鑄滾筒2的頂點時，剛吐出之聚乙烯醇系樹脂水溶液3在澆鑄滾筒側R產生拉伸應力，在自由面側S產生壓縮應力(參照圖2)。水溶液於短時間內接地至澆鑄滾筒2的話，兩應力差會造成厚度變動，但即使是黏度相對較高之聚乙烯醇系樹脂水溶液3，若設定適當的應力緩和時間，便可減小對於厚度變動的影響。本發明之飛行時間的下限值，可考慮該應力緩和的時間而進行設定。Regarding the former, for example, when the polyvinyl alcohol-based resin
該澆鑄滾筒的直徑宜為2～5m較佳，2.4～4.5m特佳，2.8～4m更佳。 該直徑過小的話會有乾燥長不足而難以達到速度的傾向，過大的話會有輸送性降低的傾向。The diameter of the casting drum is preferably 2-5m, particularly preferably 2.4-4.5m, and even more preferably 2.8-4m. If the diameter is too small, the drying length will be insufficient and the speed will tend to be difficult to achieve, and if the diameter is too large, the transportability will tend to decrease.
該澆鑄滾筒的寬度宜為2m以上較佳，3m以上特佳，4m以上更佳，5～6m尤佳。 澆鑄滾筒的寬度過小的話會有生產性降低的傾向。The width of the casting drum is preferably at least 2m, particularly preferably at least 3m, more preferably at least 4m, and particularly preferably 5-6m. If the width of the casting drum is too small, the productivity tends to decrease.
該澆鑄滾筒的旋轉速度宜為3～50m/分較佳，4～40m/分特佳，5～35m/分更佳。 該旋轉速度過慢的話會有生產性降低的傾向，過快的話會有乾燥不充分的傾向。The rotation speed of the casting drum is preferably 3-50m/min, 4-40m/min is particularly preferred, and 5~35m/min is more preferred. If the rotation speed is too slow, the productivity will tend to decrease, and if it is too fast, the drying will tend to be insufficient.
該澆鑄滾筒的表面溫度宜為40～99℃較佳，60～97℃特佳。 該表面溫度過低的話會有乾燥不良的傾向，過高的話會有起泡的傾向。The surface temperature of the casting drum is preferably 40-99°C, particularly preferably 60-97°C. If the surface temperature is too low, there will be a tendency for poor drying, and if it is too high, there will be a tendency for foaming.
然後，對上述步驟(B)進行說明。步驟(B)係將已製膜之薄膜進行加熱並乾燥的步驟。Next, the above step (B) will be described. Step (B) is a step of heating and drying the formed film.
澆鑄滾筒中已製膜之薄膜的乾燥，係藉由使膜的表面與背面交替接觸多個熱輥而進行。熱輥的表面溫度通常為40～150℃，50～140℃較佳。該表面溫度過低的話會有乾燥不良的傾向，過高的話會有乾燥過度而導致起伏等外觀不良的傾向。 又，關於熱輥，例如，宜為已對表面進行硬鉻鍍敷處理或鏡面處理之直徑0.2～2m的輥，且通常使用2～30根、較佳10～25根而進行乾燥較佳。The drying of the film formed in the casting drum is performed by alternately contacting the surface and back of the film with a plurality of hot rollers. The surface temperature of the heat roller is usually 40 to 150°C, preferably 50 to 140°C. If the surface temperature is too low, there will be a tendency for poor drying, and if it is too high, there will be a tendency for excessive drying to cause poor appearance such as undulation. In addition, as for the heat roller, for example, a roller having a diameter of 0.2 to 2 m on which a hard chromium plating treatment or a mirror surface treatment has been applied to the surface is preferable, and usually 2 to 30, preferably 10 to 25, are used for drying.
本發明中，利用熱輥之乾燥後，宜對薄膜進行熱處理較佳。熱處理溫度宜為60～150℃較佳，70～140℃特佳。熱處理溫度過低的話，會有聚乙烯醇系薄膜的耐水性降低等，而成為相位差擺盪的原因的傾向，過高的話會有偏光薄膜製造時的延伸性降低的傾向。該熱處理方法，例如，可列舉接觸高溫熱輥的方法、利用浮動式乾燥機而進行的方法等。In the present invention, it is preferable to heat-treat the film after drying by a heat roller. The heat treatment temperature is preferably 60-150°C, particularly preferably 70-140°C. If the heat treatment temperature is too low, the water resistance of the polyvinyl alcohol-based film may decrease, which may cause retardation oscillations. If the heat treatment temperature is too high, the extensibility during the production of the polarizing film may decrease. The heat treatment method includes, for example, a method of contacting a high-temperature heat roller, a method of using a floating dryer, and the like.
進行乾燥、視需要之熱處理後之薄膜，經過上述步驟(C)而成為產品(本發明之聚乙烯醇系薄膜)。步驟(C)係將薄膜的兩端切開而捲取於輥的步驟。The film after drying and optionally heat treatment undergoes the above step (C) to become a product (the polyvinyl alcohol film of the present invention). Step (C) is a step of cutting both ends of the film and winding it up on a roll.
此外，到此為止，對製備聚乙烯醇系樹脂水溶液，並將該水溶液流延至旋轉的澆鑄滾筒(滾筒型輥)，利用澆鑄法製膜並乾燥，而製造聚乙烯醇系薄膜的方法進行了說明，亦可將聚乙烯醇系樹脂水溶液流延至樹脂薄膜上、或金屬帶上，並製膜、乾燥。In addition, up to this point, the method of preparing a polyvinyl alcohol-based resin aqueous solution, casting the aqueous solution on a rotating casting drum (roller type roll), forming a film by a casting method, and drying to produce a polyvinyl alcohol-based film has been described. It is also possible to cast the polyvinyl alcohol-based resin aqueous solution onto a resin film or metal belt, and form a film and dry it.
如此可獲得本發明之聚乙烯醇系薄膜。In this way, the polyvinyl alcohol-based film of the present invention can be obtained.
本發明之聚乙烯醇系薄膜，厚度為5～60μm係必要，考量薄型化的方面，為5～50μm特佳，5～30μm更佳，考量避免破裂的方面，為10～30μm尤佳。The polyvinyl alcohol-based film of the present invention must have a thickness of 5-60 μm. Considering thinness, 5-50 μm is particularly preferred, and 5-30 μm is more preferred, and 10-30 μm is particularly preferred for avoiding cracking.
本發明之聚乙烯醇系薄膜，寬度為2m以上係必要，考量大面積化的方面，為3m以上特佳，考量避免破裂的方面，為4～6m更佳。It is necessary for the polyvinyl alcohol film of the present invention to have a width of 2 m or more. Considering a larger area, it is particularly preferably 3 m or more, and considering avoiding breakage, it is more preferably 4-6 m.
本發明之聚乙烯醇系薄膜，長度為2km以上係必要，考量大面積化的方面，為3km以上特佳，4km以上更佳。 此外，薄膜之長度的上限，考量避免破裂的方面，宜為50km以下較佳，40km以下特佳，30km以下更佳。It is necessary for the polyvinyl alcohol film of the present invention to have a length of 2 km or more. Considering a larger area, 3 km or more is particularly preferable, and 4 km or more is more preferable. In addition, the upper limit of the length of the film, considering the avoidance of breakage, is preferably 50km or less, 40km or less is particularly preferred, and 30km or less is more preferred.
如上述般，本發明之聚乙烯醇系薄膜，薄膜整面之厚度之變動係數為1%以下，而薄膜之流動方向(MD方向)之厚度之變動係數，考量偏光薄膜之偏光性能的方面，宜為0.7%以下較佳，0.6%以下特佳，0.5%以下更佳。 又，寬度方向(TD方向)之厚度之變動係數，考量偏光薄膜之偏光性能的方面，宜為0.7%以下較佳，0.6%以下特佳，0.5%以下更佳。 此處，聚乙烯醇系薄膜的厚度薄時，於偏光薄膜製造中在流動方向偏光度容易變得不均勻，原捲之流動方向(MD方向)之厚度精度變得重要。As described above, in the polyvinyl alcohol film of the present invention, the coefficient of variation of the thickness of the entire film is less than 1%, and the coefficient of variation of the thickness of the film in the direction of flow (MD direction) takes into account the polarization performance of the polarizing film. It is preferably 0.7% or less, particularly preferably 0.6% or less, and more preferably 0.5% or less. In addition, the coefficient of variation of the thickness in the width direction (TD direction), considering the polarization performance of the polarizing film, is preferably 0.7% or less, 0.6% or less is particularly preferred, and 0.5% or less is more preferred. Here, when the thickness of the polyvinyl alcohol-based film is thin, the degree of polarization in the flow direction tends to become uneven in the production of the polarizing film, and the thickness accuracy in the flow direction (MD direction) of the original roll becomes important.
對本發明之厚度變動係數進行詳細說明。The thickness variation coefficient of the present invention will be described in detail.
薄膜之厚度變動係數，取決於澆鑄滾筒的平滑性、澆鑄滾筒的均勻旋轉、T型狹縫模狹縫之開口部的均勻性、聚乙烯醇系樹脂水溶液的吐出精度、聚乙烯醇系樹脂水溶液之朝向澆鑄滾筒的吐出角度、直至聚乙烯醇系樹脂水溶液接地至澆鑄滾筒的時間與距離、聚乙烯醇系樹脂水溶液與澆鑄滾筒的穩定接觸、澆鑄滾筒或之後之熱輥中的乾燥條件等。 其中，聚乙烯醇系樹脂水溶液與澆鑄滾筒的穩定接觸係重要，若接觸線(觸線)在MD方向前後移動的話，會在薄膜的MD方向產生厚度變動。又，若接觸線在TD方向晃動的話，會在薄膜的TD方向產生厚度變動。為了使該觸線穩定化，調整以下之[I]～[V]的方法係有效且較佳。The coefficient of variation of film thickness depends on the smoothness of the casting drum, the uniform rotation of the casting drum, the uniformity of the opening of the T-slot die, the discharge accuracy of the polyvinyl alcohol resin aqueous solution, and the polyvinyl alcohol resin aqueous solution The discharge angle toward the casting drum, the time and distance until the polyvinyl alcohol-based resin aqueous solution is grounded to the casting drum, the stable contact between the polyvinyl alcohol-based resin aqueous solution and the casting drum, the drying conditions in the casting drum or the subsequent hot roller, etc. Among them, stable contact between the polyvinyl alcohol-based resin aqueous solution and the casting roll is important, and if the contact line (contact line) moves back and forth in the MD direction, the thickness of the film will vary in the MD direction. In addition, if the contact line wobbles in the TD direction, the thickness of the film will fluctuate in the TD direction. In order to stabilize the antenna, the method of adjusting the following [I] to [V] is effective and preferable.
[I]「聚乙烯醇系樹脂水溶液從T型狹縫模1之吐出口1a至澆鑄滾筒2之表面(接地點P)的飛行距離A(參照圖1)。」 該飛行距離A越長，聚乙烯醇系樹脂水溶液越容易受到澆鑄滾筒2之旋轉或環境氣流的影響，故從吐出口1a至澆鑄滾筒2的距離盡可能接近為較理想。 本發明中，從T型狹縫模1之吐出口1a至澆鑄滾筒2之表面(接地點P)的最短距離B宜為2mm以下較佳，1.5mm以下特佳，lmm以下更佳。該最短距離B過大的話，會有薄膜之厚度變動增大的傾向。[I] "The flying distance A (refer to Fig. 1) of the polyvinyl alcohol-based resin aqueous solution from the discharge port 1a of the T-shaped
[II]「聚乙烯醇系樹脂水溶液從T型狹縫模1朝向澆鑄滾筒2之吐出方向D(參照圖3)。」 聚乙烯醇系樹脂水溶液從上方吐出直至接地至澆鑄滾筒2，由於重力產生滴液的話，觸線容易混亂。例如，澆鑄滾筒2在接地點P處的切線與吐出方向D平行時，吐出液(聚乙烯醇系樹脂水溶液)由於重力下滴而難以順暢地接地。 本發明中，從T型狹縫模1朝向澆鑄滾筒2之吐出方向(面向T型狹縫模內部之唇面的方向)D、和連接T型狹縫模1之吐出口1a與澆鑄滾筒2之中心軸C之平面E形成的角度θ宜為40°以下較佳，1～30°特佳，2～20°更佳，3～10°尤佳。該角度θ過大的話，會有薄膜之厚度變動增大的傾向。[II] "The discharging direction D of the polyvinyl alcohol-based resin aqueous solution from the T-shaped
[III]「氣刀及/或氣室。」 係樹脂之擠壓成形中用於使觸線強制穩定化的一般方法。就氣刀或氣室而言，可使用公知的方法。[III] "Air knife and/or air chamber." A general method used to forcibly stabilize the contact wire in resin extrusion molding. As for the air knife or air chamber, a known method can be used.
[IV]「T型狹縫模的水平度。」 由於製膜而得之薄膜的寬度為2m以上，故T型狹縫模的寬度亦為2m以上。該等情況下不能無視重力的影響， T型狹縫模使用高剛性的材質，同時為了使於寬度方向之T型狹縫模中央部不發生彎曲，將其吊起的方法係有效。 本發明中，宜以1根以上之懸吊件將T型狹縫模吊起較佳，具體而言，T型狹縫模之寬度方向中央部之由於重力所致之彎曲宜為0.3mm以下較佳，0.2mm以下特佳，0.lmm以下更佳。為了減小該彎曲量，可列舉增加懸吊件的根數，變更吊起位置等方法。[IV] "The levelness of the T-shaped slit die." Since the width of the film formed by the film is 2m or more, the width of the T-shaped slit die is also 2m or more. In this case, the influence of gravity cannot be ignored. The T-shaped slit die uses a high-rigidity material. At the same time, in order to prevent the central part of the T-shaped slit die from bending in the width direction, the method of lifting it is effective. In the present invention, it is better to lift the T-shaped slit die with one or more suspension parts. Specifically, the bending of the central part of the T-shaped slit die in the width direction due to gravity should be 0.3mm or less Preferably, 0.2 mm or less is particularly preferable, and 0.1 mm or less is more preferable. In order to reduce the amount of bending, methods such as increasing the number of suspensions and changing the hanging position can be cited.
[V]「澆鑄滾筒之空間上的位移量。」 當然，澆鑄滾筒似在空間上搖晃時，來自T型狹縫模之吐出液不能穩定地接地。本發明中，旋轉的澆鑄滾筒之向上下、前後(MD方向)、左右(TD方向)的搖晃分別宜為±50μm以下較佳，±40μm以下特佳，±30μm以下更佳。該搖晃過大的話，會有薄膜之厚度變動增大的傾向。為了減小澆鑄滾筒的搖晃，可列舉諸如減小澆鑄滾筒的重量，提高馬達旋轉精度的方法。[V] "The amount of displacement in the space of the casting drum." Of course, when the casting drum seems to sway in space, the spit from the T-shaped slot mold cannot be grounded stably. In the present invention, the shaking of the rotating casting drum up and down, front and back (MD direction), and left and right (TD direction) are preferably ±50 μm or less, preferably ±40 μm or less, and more preferably ±30 μm or less. If the shaking is too large, the thickness variation of the film tends to increase. In order to reduce the shaking of the casting drum, methods such as reducing the weight of the casting drum and improving the rotation accuracy of the motor can be cited.
本發明之聚乙烯醇系薄膜，厚度精度優異，可適當用作光學用之聚乙烯醇系薄膜，進一步用作偏光膜用之原捲特佳。The polyvinyl alcohol-based film of the present invention has excellent thickness accuracy, and can be suitably used as a polyvinyl alcohol-based film for optics, and is particularly preferably used as a raw roll for a polarizing film.
以下，對使用本發明之聚乙烯醇系薄膜而獲得之偏光膜的製造方法進行說明。Hereinafter, the manufacturing method of the polarizing film obtained using the polyvinyl alcohol film of this invention is demonstrated.
本發明之偏光膜，係將上述聚乙烯醇系薄膜從輥捲出並於水平方向移送，經由膨潤、染色、硼酸交聯、延伸、洗淨、乾燥等步驟而製造。The polarizing film of the present invention is produced by unwinding the above-mentioned polyvinyl alcohol-based film from a roll and transporting it in a horizontal direction, and is manufactured through steps such as swelling, dyeing, boric acid crosslinking, stretching, washing, and drying.
膨潤步驟係於染色步驟之前實施。藉由膨潤步驟，除可將聚乙烯醇系薄膜表面的污漬洗淨外，藉由使聚乙烯醇系薄膜膨潤，還具有防止染色不均等的效果。膨潤步驟中，就處理液而言，通常使用水。該處理液只要主成分是水即可，亦可加入少量碘化合物、界面活性劑等添加物、醇等。膨潤浴的溫度通常為10～45℃左右，於膨潤浴的浸漬時間通常為0.1～10分鐘左右。The swelling step is implemented before the dyeing step. The swelling step not only cleans the stains on the surface of the polyvinyl alcohol-based film, but also has the effect of preventing uneven dyeing by swelling the polyvinyl alcohol-based film. In the swelling step, water is usually used as the treatment liquid. As long as the main component of the treatment liquid is water, a small amount of additives such as iodine compounds and surfactants, alcohol, etc. may be added. The temperature of the swelling bath is usually about 10 to 45°C, and the immersion time in the swelling bath is usually about 0.1 to 10 minutes.
染色步驟係藉由使薄膜接觸含有碘或二色性染料之液體而進行。通常使用碘－碘化鉀之水溶液，且碘的濃度為0.1～2g/L，碘化鉀的濃度為1～100g/L較適宜。染色時間為30～500秒左右較實用。處理浴的溫度宜為5～50℃較佳。水溶液中除水溶劑以外，亦可含有少量與水相溶之有機溶劑。The dyeing step is performed by contacting the film with a liquid containing iodine or a dichroic dye. Usually, an aqueous solution of iodine-potassium iodide is used, and the concentration of iodine is 0.1-2g/L, and the concentration of potassium iodide is 1-100g/L. The dyeing time is about 30 to 500 seconds, which is more practical. The temperature of the treatment bath is preferably 5-50°C. In addition to water solvents, the aqueous solution may also contain a small amount of organic solvents that are compatible with water.
硼酸交聯步驟係使用硼酸或硼砂等硼化合物而進行。硼化合物，以水溶液或水－有機溶劑混合液的形態及10～100g/L左右的濃度使用，使碘化鉀共存於液體中的話，在偏光性能的穩定化的方面為較佳。處理時的溫度宜為30～70℃左右，處理時間宜為0.1～20分鐘左右較佳，又，必要時亦可於處理中進行延伸操作。The boric acid crosslinking step is performed using boron compounds such as boric acid or borax. The boron compound is used in the form of an aqueous solution or a water-organic solvent mixture and a concentration of about 10 to 100 g/L. When potassium iodide is coexisted in the liquid, it is preferable to stabilize the polarization performance. The temperature during the treatment is preferably about 30 to 70°C, and the treatment time is preferably about 0.1 to 20 minutes. Moreover, the stretching operation may be performed during the treatment when necessary.
延伸步驟宜在單軸方向延伸3～10倍，3.5～6倍較佳。此時，即使在延伸方向之直角方向進行些許的延伸(防止寬度方向之收縮的程度、或該程度以上的延伸)亦無妨。延伸時的溫度宜為40～170℃較佳。進一步，只要將延伸倍率最終設定為上述範圍即可，延伸操作不僅在單一階段實施，在製造步驟之任意範圍的階段中實施即可。The extension step should preferably extend 3-10 times in the uniaxial direction, preferably 3.5-6 times. At this time, even if a slight extension is performed in the direction at right angles to the extension direction (the degree of preventing shrinkage in the width direction, or the extension of more than this degree). The temperature during stretching is preferably 40 to 170°C. Furthermore, as long as the stretching magnification is finally set to the above-mentioned range, the stretching operation is not only performed in a single stage, but may be performed in a stage within an arbitrary range of the manufacturing process.
洗淨步驟，例如，藉由將聚乙烯醇系薄膜浸漬於水或碘化鉀等碘化物水溶液而進行，可除去薄膜表面所產生的析出物。使用碘化鉀水溶液時的碘化鉀濃度可為1～80g/L左右。洗淨處理時的溫度通常為 5～50℃，10～45℃較佳。處理時間通常為 1～300秒，10～240秒較佳。此外，水洗淨與利用碘化鉀水溶液之洗淨，宜可適當組合進行。The washing step is performed by, for example, immersing the polyvinyl alcohol-based film in water or an iodide aqueous solution such as potassium iodide to remove precipitates generated on the surface of the film. The potassium iodide concentration when using the potassium iodide aqueous solution can be about 1 to 80 g/L. The temperature during the washing treatment is usually 5 to 50°C, preferably 10 to 45°C. The treatment time is usually 1 to 300 seconds, preferably 10 to 240 seconds. In addition, washing with water and washing with potassium iodide aqueous solution may be suitably combined.
乾燥步驟，只要是在大氣中於40～80℃進行1～10分鐘即可。The drying step may be performed in the air at 40 to 80°C for 1 to 10 minutes.
又，偏光薄膜之偏光度宜為99.5%以上較佳，99.8%以上更佳。偏光度過低的話，會有不能確保液晶顯示器之對比度的傾向。 此外，偏光度一般係由在將2片偏光薄膜重合以使其配向方向成為同一方向的狀態下於波長λ所測得之光線透射率(H11 )、及在將2片偏光薄膜重合以使配向方向成為相互垂直之方向的狀態下於波長λ所測得之光線透射率(H1 )，根據下式算出。 [(H11 -H1 )/(H11 +H1 )]1/2 In addition, the degree of polarization of the polarizing film is preferably 99.5% or more, more preferably 99.8% or more. If the polarization is too low, there is a tendency that the contrast of the liquid crystal display cannot be ensured. In addition, the degree of polarization is generally determined by the light transmittance (H 11 ) measured at the wavelength λ in a state where two polarizing films are superimposed so that their alignment directions become the same direction, and when the two polarizing films are superimposed to make The light transmittance (H 1 ) measured at the wavelength λ in the state where the alignment directions are perpendicular to each other is calculated according to the following formula. [(H 11 -H 1 )/(H 11 +H 1 )] 1/2
進一步，本發明之偏光薄膜之單體透射率宜為42%以上較佳。該單體透射率過低的話，會有不能達成液晶顯示器之高亮度化的傾向。 單體透射率，係使用分光光度計測定偏光薄膜單體之光線透射率而獲得的值。Furthermore, the monomer transmittance of the polarizing film of the present invention is preferably 42% or more. If the transmittance of the monomer is too low, there is a tendency that high brightness of the liquid crystal display cannot be achieved. The monomer transmittance is a value obtained by measuring the light transmittance of the polarizing film monomer using a spectrophotometer.
如此，可獲得本發明之偏光薄膜，而本發明之偏光薄膜適合於染色不均較少之偏光板的製造。 以下，對本發明之偏光板的製造方法進行說明。In this way, the polarizing film of the present invention can be obtained, and the polarizing film of the present invention is suitable for manufacturing a polarizing plate with less uneven dyeing. Hereinafter, the manufacturing method of the polarizing plate of the present invention will be described.
本發明之偏光薄膜，在其單面或雙面介由黏接劑貼合光學上等向性之樹脂薄膜作為保護薄膜而形成偏光板。作為保護薄膜，例如，可列舉三乙酸纖維素、二乙酸纖維素、聚碳酸酯、聚甲基丙烯酸甲酯、環烯烴聚合物、環烯烴共聚物、聚苯乙烯、聚醚碸、聚伸芳基酯、聚－4－甲基戊烯、聚伸苯醚等的薄膜或片材。The polarizing film of the present invention is formed by bonding an optically isotropic resin film as a protective film to one or both sides of the polarizing plate via an adhesive. As the protective film, for example, cellulose triacetate, cellulose diacetate, polycarbonate, polymethyl methacrylate, cyclic olefin polymer, cyclic olefin copolymer, polystyrene, polyether block, polyarylene Films or sheets of base ester, poly-4-methylpentene, polyphenylene ether, etc.
貼合方法可利用公知的手法進行，例如，將液狀的黏接劑組成物均勻地塗布於偏光膜、保護薄膜、或該兩者後，使兩者貼合並壓接，藉由加熱或照射活性能量射線而進行。The bonding method can be performed by a known technique. For example, a liquid adhesive composition is uniformly coated on a polarizing film, a protective film, or both, and then the two are bonded and press-bonded by heating or irradiation. Active energy rays.
又，為了薄膜化，亦可在偏光薄膜之單面或雙面塗布胺甲酸乙酯系樹脂、丙烯酸系樹脂、尿素樹脂等硬化性樹脂以替代上述保護薄膜，並進行硬化而形成偏光板。In order to make the film into a thin film, a curable resin such as urethane resin, acrylic resin, or urea resin may be applied to one or both sides of the polarizing film instead of the protective film, and then cured to form a polarizing plate.
根據本發明所獲得之偏光薄膜、偏光板，厚度變動係數優異，無染色不均且偏光性能之面內均勻性亦優異，可理想地使用於攜帶式資訊終端機、個人電腦、電視、投影機、標示牌、電子桌上計算機、電子時鐘、文字處理機、電子紙、遊戲機、攝影機、照相機、相簿、溫度計、音響、汽車或機械類之測量儀器類等的液晶顯示裝置、太陽眼鏡、防眩眼鏡、立體眼鏡、穿戴式顯示器、顯示元件(CRT、LCD、有機EL、電子紙等)用反射減少層、光通信設備、醫療設備、建築材料、玩具等。 [實施例]The polarizing film and polarizing plate obtained according to the present invention have excellent thickness variation coefficient, no dyeing unevenness and excellent in-plane uniformity of polarization performance, and can be ideally used in portable information terminals, personal computers, televisions, and projectors , Sign boards, electronic desktop computers, electronic clocks, word processors, electronic paper, game consoles, video cameras, cameras, photo albums, thermometers, audio, automotive or mechanical measuring instruments such as liquid crystal display devices, sunglasses, Anti-glare glasses, stereo glasses, wearable displays, display elements (CRT, LCD, organic EL, electronic paper, etc.) with reflection reduction layer, optical communication equipment, medical equipment, construction materials, toys, etc. [Example]
以下，列舉實施例對本發明進行更具體地說明，但只要不超出其要旨本發明並不限定於以下的實施例。 此外，示例中「份」、「%」意指重量基準。 各物性係如下述般求得。Hereinafter, the present invention will be explained more specifically with examples, but the present invention is not limited to the following examples as long as it does not exceed the gist. In addition, "parts" and "%" in the examples mean weight basis. The various physical properties are obtained as follows.
(1)厚度 測定聚乙烯醇系薄膜之MD方向與TD方向的厚度。 ・流動方向(MD方向)的測定係使用KEYENCE公司製「光譜干涉型膜厚計SI－T80」以0.3mm級距針對寬度方向(TD方向)之中央部與兩端部(距兩端20cm內側)的3個地方分別測定6萬點。 ・TD方向的測定係使用山文電氣公司製「連續膜厚計TOF－5R01」，針對MD方向之前端部、中央部、終端部的3個地方分別測定4000點。(1) Thickness The thickness of the MD and TD directions of the polyvinyl alcohol-based film is measured.・The flow direction (MD direction) is measured using the "Spectral Interference Film Thickness Gauge SI-T80" manufactured by KEYENCE, with a 0.3mm step on the center and both ends of the width direction (TD direction) (inside 20 cm from both ends) ) Measure 60,000 points at 3 places.・The measurement in the TD direction uses the "Continuous Film Thickness Gauge TOF-5R01" manufactured by Sanbun Electric Co., and measures 4000 points at three locations at the front end, center, and end in the MD direction.
(2)厚度變動係數 利用上述厚度之測定值，根據下列公式算出。(2) Thickness variation coefficient Use the measured value of the above thickness to calculate according to the following formula.
[數2] 變動係數(C.V.)=100×S.D./x 「標準偏差(S.D.)=√(Σ(xi-x)2 /(n-1)) x ：平均值 xi：第i點的值 n：樣品數」[Number 2] Coefficient of Variation (CV)=100×SD/x "Standard Deviation (SD)=√(Σ(xi-x) 2 /(n-1)) x: mean value xi: value n at the i-th point ：Number of samples"
(3)偏光度(%) 從所獲得之偏光薄膜之寬度方向的中央部，切出延伸方向200mm×寬度方向40mm的條形樣品，並使用大塚電子公司製「RETS－1100A」在延伸方向以10mm節距測定10點的偏光度。(3) Polarization degree (%) From the center part of the obtained polarizing film in the width direction, a strip sample with an extension direction of 200 mm × a width direction of 40 mm was cut out, and "RETS-1100A" manufactured by Otsuka Electronics Co., Ltd. was used in the extension direction. The degree of polarization at 10 points is measured with a pitch of 10 mm.
＜實施例1＞ (聚乙烯醇系薄膜的製造) 加入重量平均分子量142,000、皂化度99.8莫耳%之聚乙烯醇系樹脂1000kg、水2000kg、作為塑化劑之甘油100kg，邊攪拌邊升溫至150℃，進行濃度調整至樹脂濃度25%，獲得溶解均勻之聚乙烯醇系樹脂水溶液。然後，將該聚乙烯醇系樹脂水溶液供給雙軸擠壓機並消泡後，使水溶液溫度成為95℃，以吐出速度2.5m/分從T型狹縫模吐出口流延至旋轉的澆鑄滾筒而製膜。從T型狹縫模吐出口至澆鑄滾筒表面的最短距離為2mm，從T型狹縫模朝向澆鑄滾筒之吐出方向(面向T型狹縫模內部之唇面的方向)、和連接T型狹縫模吐出口與澆鑄滾筒中心軸之平面形成的角度為15°(參照表1。)。 然後，將獲得之薄膜從澆鑄滾筒剝離，進行利用熱輥之乾燥與利用浮動式乾燥機之熱處理。然後，將兩端部切開以使寬度成為4m，獲得聚乙烯醇系薄膜。 獲得之聚乙烯醇系薄膜的特性顯示於表2中。<Example 1> (Production of polyvinyl alcohol-based film) 1000kg of polyvinyl alcohol-based resin with a weight average molecular weight of 142,000 and a saponification degree of 99.8 mol%, 2000kg of water, and 100kg of glycerin as a plasticizer were added, and the temperature was raised while stirring. At 150°C, the concentration was adjusted to 25% of the resin concentration to obtain a uniformly dissolved aqueous solution of polyvinyl alcohol resin. Then, the polyvinyl alcohol-based resin aqueous solution was supplied to a biaxial extruder and defoamed, and the temperature of the aqueous solution was set to 95°C, and the solution was cast from the T-slot die outlet to the rotating casting drum at a discharge speed of 2.5 m/min. Film making. The shortest distance from the outlet of the T-shaped slit die to the surface of the casting drum is 2mm, from the T-shaped slit die toward the ejection direction of the casting drum (the direction facing the lip surface inside the T-shaped slit die), and the connecting T-shaped slit The angle formed by the slot die outlet and the plane of the central axis of the casting drum is 15° (refer to Table 1). Then, the obtained film is peeled from the casting drum, and dried with a hot roll and heat treatment with a floating dryer. Then, both ends were cut so that the width became 4 m, and a polyvinyl alcohol-based film was obtained. The properties of the obtained polyvinyl alcohol-based film are shown in Table 2.
然後，使用上述所獲得之聚乙烯醇系薄膜，依以下之要領得到偏光薄膜，並進行下列評價。評價結果顯示於表3中。Then, using the polyvinyl alcohol-based film obtained above, a polarizing film was obtained according to the following procedures, and the following evaluation was performed. The evaluation results are shown in Table 3.
(偏光薄膜的製造) 將獲得之聚乙烯醇系薄膜邊浸漬於水溫25℃之水槽中邊延伸至1.7倍。然後邊浸漬於由碘0.5g/L、碘化鉀30 g /L組成之28℃水溶液中邊延伸至1.6倍，之後浸漬於硼酸40g/L、碘化鉀30g/L之組成之水溶液中(55℃)，同時邊進行單軸延伸至2.1倍邊進行硼酸處理。然後，以碘化鉀水溶液進行洗淨，並乾燥得到總延伸倍率5.8倍之偏光薄膜。獲得之偏光薄膜的偏光特性顯示於表3中。(Production of polarizing film) The obtained polyvinyl alcohol-based film was stretched to 1.7 times while being immersed in a water tank with a water temperature of 25°C. Then it was immersed in a 28°C aqueous solution composed of 0.5g/L of iodine and 30 g/L of potassium iodide while extending to 1.6 times, and then immersed in an aqueous solution (55°C) of 40g/L of boric acid and 30g/L of potassium iodide, At the same time, the boric acid treatment was performed while uniaxially stretched to 2.1 times. Then, it was washed with a potassium iodide aqueous solution and dried to obtain a polarizing film with a total stretching ratio of 5.8 times. The polarization characteristics of the obtained polarizing film are shown in Table 3.
＜實施例2、3、5～7、比較例1～4＞ 除將實施例1中之薄膜製膜的條件如表1所示般進行變更以外，與實施例1同樣進行，得到聚乙烯醇系薄膜，進一步，與實施例1同樣得到偏光薄膜。 針對獲得之聚乙烯醇系薄膜、及偏光薄膜，進行與實施例1同樣的評價。評價結果顯示於表2及表3中。<Examples 2, 3, 5 to 7, Comparative Examples 1 to 4> Except that the film forming conditions in Example 1 were changed as shown in Table 1, the same procedure as in Example 1 was carried out to obtain polyvinyl alcohol A thin film, and further, a polarizing film was obtained in the same manner as in Example 1. The same evaluations as in Example 1 were performed for the obtained polyvinyl alcohol-based film and polarizing film. The evaluation results are shown in Table 2 and Table 3.
＜實施例4＞ 將實施例1中之薄膜製膜的條件如表1所示般進行變更，進一步於水溶液吐出時在水溶液之觸線上部設置氣刀(高度5mm、角度90°)，以空氣壓力10kPa從氣刀吐出空氣而使觸線穩定化，除此以外，與實施例1同樣進行，得到聚乙烯醇系薄膜，進一步，與實施例1同樣得到偏光薄膜。 針對獲得之聚乙烯醇系薄膜、及偏光薄膜，進行與實施例1同樣的評價。評價結果顯示於表2及表3中。<Example 4> The film forming conditions in Example 1 were changed as shown in Table 1, and an air knife (height 5mm, angle 90°) was installed on the top of the aqueous solution when the aqueous solution was discharged. Except that air was discharged from an air knife at a pressure of 10 kPa to stabilize the antenna, the same procedure as in Example 1 was carried out to obtain a polyvinyl alcohol-based film, and further, a polarizing film was obtained in the same manner as in Example 1. About the obtained polyvinyl alcohol-based film and the polarizing film, the same evaluation as Example 1 was performed. The evaluation results are shown in Table 2 and Table 3.
【表1】
【表2】
【表3】
實施例1～7之聚乙烯醇系薄膜，儘管為薄型寬幅長條，MD方向、TD方向之任一者的厚度變動係數皆為1%以下，因而所獲得之偏光薄膜的偏光度在面內均勻，反觀比較例1～4之聚乙烯醇系薄膜，厚度之變動係數大，所獲得之偏光薄膜的偏光度在面內不均勻。 又，發現藉由調節從T型狹縫模吐出口至澆鑄滾筒表面的最短距離(mm)、從T型狹縫模朝向澆鑄滾筒之吐出方向(面向T型狹縫模內部之唇面的方向)和連接T型狹縫模吐出口與澆鑄滾筒中心軸之平面形成的角度(°)、及氣刀的使用等，可製造厚度變動係數小的聚乙烯醇系薄膜。Although the polyvinyl alcohol-based films of Examples 1 to 7 are thin, wide and long, the thickness variation coefficient of either the MD direction or the TD direction is 1% or less. Therefore, the degree of polarization of the obtained polarizing film is In contrast, the polyvinyl alcohol-based films of Comparative Examples 1 to 4 have a large variation coefficient of thickness, and the degree of polarization of the obtained polarizing film is not uniform in the plane. In addition, it was found that by adjusting the shortest distance (mm) from the discharge port of the T-shaped slit die to the surface of the casting drum, the direction from the T-shaped slit die to the ejection direction of the casting drum (the direction facing the lip surface inside the T-shaped slit die) ) And the angle (°) formed by the plane connecting the outlet of the T-shaped slit die and the central axis of the casting drum, and the use of an air knife, etc., to produce a polyvinyl alcohol film with a small thickness variation coefficient.
上述實施例中顯示了本發明之具體形態，但上述實施例僅限於例示，並非作限定性解釋。對於該技術領域中具有通常知識者而言各種明顯的變形仍意欲包括於本發明之範圍內。 [產業上利用性]The above-mentioned embodiment shows the specific form of the present invention, but the above-mentioned embodiment is only an illustration, and is not a limited interpretation. For those with ordinary knowledge in this technical field, various obvious modifications are still intended to be included in the scope of the present invention. [Industrial availability]
根據本發明所獲得之偏光薄膜、偏光板，厚度變動係數優異，偏光性能之面內均勻性亦優異，可理想地使用於攜帶式資訊終端機、個人電腦、電視、投影機、標示牌、電子桌上計算機、電子時鐘、文字處理機、電子紙、遊戲機、攝影機、照相機、相簿、溫度計、音響、汽車或機械類之測量儀器類等的液晶顯示裝置、太陽眼鏡、防眩眼鏡、立體眼鏡、穿戴式顯示器、顯示元件(CRT、LCD、有機EL、電子紙等)用反射減少層、光通信設備、醫療設備、建築材料、玩具等。The polarizing film and polarizing plate obtained according to the present invention have excellent thickness variation coefficient and excellent in-plane uniformity of polarization performance. They can be ideally used in portable information terminals, personal computers, televisions, projectors, sign boards, and electronics. Desktop computers, electronic clocks, word processors, electronic paper, game consoles, video cameras, cameras, photo albums, thermometers, stereos, automotive or mechanical measuring instruments such as liquid crystal display devices, sunglasses, anti-glare glasses, stereo Reflection reduction layers for glasses, wearable displays, display elements (CRT, LCD, organic EL, electronic paper, etc.), optical communication equipment, medical equipment, building materials, toys, etc.
1‧‧‧T型狹縫模 1a‧‧‧T型狹縫模之吐出口 2‧‧‧澆鑄滾筒 3‧‧‧聚乙烯醇系樹脂水溶液 A‧‧‧聚乙烯醇系樹脂水溶液從T型狹縫模1之吐出口1a至澆鑄滾筒2之表面(接地點P)的飛行距離 B‧‧‧從T型狹縫模1之吐出口1a至澆鑄滾筒2之表面(接地點P)的最短距離 C‧‧‧澆鑄滾筒2之中心軸 D‧‧‧從T型狹縫模1朝向澆鑄滾筒2之吐出方向(面向T型狹縫模內部之唇面的方向) E‧‧‧連接T型狹縫模1之吐出口1a與澆鑄滾筒2之中心軸C之平面 P‧‧‧接地點 R‧‧‧澆鑄滾筒側 S‧‧‧自由面側 θ‧‧‧從T型狹縫模1朝向澆鑄滾筒2之吐出方向(面向T型狹縫模內部之唇面的方向)D、和連接T型狹縫模1之吐出口1a與澆鑄滾筒2之中心軸C之平面E形成的角度1‧‧‧T-shaped slit die 1a‧‧‧T-shaped slit die outlet 2‧‧‧Casting drum 3‧‧‧Polyvinyl alcohol resin aqueous solution A‧‧‧The flying distance of the polyvinyl alcohol resin aqueous solution from the outlet 1a of the T-shaped slit die 1 to the surface of the casting drum 2 (grounding point P) B‧‧‧The shortest distance from the outlet 1a of the T-shaped slot die 1 to the surface of the casting drum 2 (grounding point P) C‧‧‧Central axis of casting drum 2 D‧‧‧From the T-shaped slit mold 1 to the direction of the casting drum 2 (the direction facing the lip surface of the T-shaped slit mold) E‧‧‧The plane connecting the outlet 1a of the T-shaped slit die 1 and the central axis C of the casting drum 2 P‧‧‧Ground point R‧‧‧Casting drum side S‧‧‧free side θ‧‧‧The discharge direction from the T-shaped slit die 1 to the casting drum 2 (the direction facing the lip surface of the T-shaped slit die) D, and the outlet 1a connecting the T-shaped slit die 1 and the casting drum 2 The angle formed by the plane E of the central axis C
[圖1]係表示聚乙烯醇系樹脂水溶液從T型狹縫模吐出口朝向澆鑄滾筒表面之吐出狀態(飛行時間)的說明圖。 [圖2]係表示聚乙烯醇系樹脂水溶液之朝向澆鑄滾筒表面之著陸狀態的說明圖。 [圖3]係表示聚乙烯醇系樹脂水溶液從T型狹縫模朝向澆鑄滾筒之吐出方向的說明圖。Fig. 1 is an explanatory diagram showing the state (flight time) of the polyvinyl alcohol-based resin aqueous solution discharged from the T-slot die discharge port toward the surface of the casting drum. Fig. 2 is an explanatory diagram showing the landed state of the polyvinyl alcohol-based resin aqueous solution toward the surface of the casting drum. Fig. 3 is an explanatory diagram showing the direction in which the polyvinyl alcohol-based resin aqueous solution is discharged from the T-shaped slot die toward the casting drum.
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