TW201605609A - Method for manufacturing polarizing film - Google Patents
Method for manufacturing polarizing film Download PDFInfo
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- TW201605609A TW201605609A TW104122711A TW104122711A TW201605609A TW 201605609 A TW201605609 A TW 201605609A TW 104122711 A TW104122711 A TW 104122711A TW 104122711 A TW104122711 A TW 104122711A TW 201605609 A TW201605609 A TW 201605609A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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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
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- 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
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- Polarising Elements (AREA)
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- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Liquid Crystal (AREA)
Abstract
Description
本發明係關於可使用作為偏光板的構成構件之偏光膜的製造方法。 The present invention relates to a method of producing a polarizing film which can be used as a constituent member of a polarizing plate.
偏光膜，以往係使用將碘或二色性染料般之二色性色素吸附配向於經單軸拉伸之聚乙烯醇系樹脂膜者。偏光膜，通常使用接著劑將保護膜貼合於該單面或雙面而形成偏光板，並使用在以液晶電視、個人電腦用顯示器及行動電話等之液晶顯示裝置為代表之影像顯示裝置。 In the polarizing film, a polyvinyl alcohol-based resin film obtained by uniaxially stretching a dichroic dye such as iodine or a dichroic dye is used. In the polarizing film, a protective film is usually bonded to the one surface or both surfaces to form a polarizing plate, and an image display device typified by a liquid crystal display device such as a liquid crystal television, a personal computer display, or a mobile phone is used.
一般而言，偏光膜係藉由施以使連續地運送之長條狀聚乙烯醇系樹脂膜依序浸漬於膨潤浴、染色浴、交聯浴般的處理浴之處理，並且在此等一連串處理之間施以拉伸處理而製造[例如日本特開2004-070104號公報(專利文獻1)及日本特開2008-250326號公報(專利文獻2)]。專利文獻1及2中揭示為了抑制以1.2倍以上的高倍率對聚乙烯醇系樹脂膜進行濕式拉伸時所造成之薄膜的斷裂(拉伸切斷)，而將在進行該濕式拉伸之浴中所設置之最初薄膜所接觸的導引輥中之薄膜的圍包角，設定在既定範圍之內容。 In general, the polarizing film is immersed in a treatment bath such as a swelling bath, a dye bath, or a cross-linking bath by a long-length polyvinyl alcohol-based resin film that is continuously transported, and is subjected to a series of treatments. The processing is carried out by a stretching process (for example, JP-A-2004-070104 (Patent Document 1) and JP-A-2008-250326 (Patent Document 2)]. Patent Document 1 and 2 disclose that the film is broken (stretched and cut) when the polyvinyl alcohol-based resin film is wet-stretched at a high magnification of 1.2 times or more, and the wet drawing is performed. The wrap angle of the film in the guide rolls that the first film is placed in the bath is set to a predetermined range.
[專利文獻1]日本特開2004-070104號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-070104
[專利文獻2]日本特開2008-250326號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-250326
近年來逐漸要求偏光膜的薄膜化，伴隨於此，當使用厚度較薄者作為屬於原料膜之聚乙烯醇系樹脂膜時，於偏光膜製造步驟中，則容易引起薄膜的寬度方向兩端部往內側圓緩地折彎之翹曲，或是翹曲較強而往內側翹曲之部分形成黏到薄膜內側部分之狀態之內折等缺陷。產生該翹曲或內折之薄膜，之後在通過軋輥時或施以拉伸處理時等，有可能形成折痕，或於折痕處裂開、斷裂。 In recent years, when a thin film of a polarizing film is required to be thinned, it is easy to cause both ends in the width direction of the film in the polarizing film manufacturing step when a thinner polyvinyl alcohol resin film is used. The warp that is gently bent toward the inner side, or the portion that is warped more strongly and warped toward the inner side forms a defect such as a fold in a state of sticking to the inner side portion of the film. The warp or inwardly folded film is produced, and then, when passing through a roll or when subjected to a stretching treatment, it is possible to form a crease or to crack or break at the crease.
翹曲或內折般之缺陷，在將膜浸漬於液中後拉出之任一處理中均可能產生，但本發明特別以抑制浸漬於交聯浴時之上述缺陷為課題。亦即，本發明之目的在於提供一種由薄的聚乙烯醇系樹脂膜來製造偏光膜之方法，其係可抑制因浸漬於交聯浴所造成之薄膜寬度方向兩端部翹曲或內折之製造方法。 The warpage or the indentation-like defect may occur in any treatment in which the film is immersed in the liquid and then pulled out. However, the present invention is particularly intended to suppress the above-mentioned defects when immersed in the crosslinking bath. That is, an object of the present invention is to provide a method for producing a polarizing film from a thin polyvinyl alcohol-based resin film, which can suppress warping or inflection at both end portions in the width direction of the film by immersion in a crosslinking bath. Manufacturing method.
本發明係提供下列所示之偏光膜的製造方法。 The present invention provides a method of producing a polarizing film shown below.
[1]一種製造方法，係一邊運送厚度65μm以下的聚乙烯醇系樹脂膜，一邊至少施以染色處理、以及使該聚乙烯 醇系樹脂膜依序浸漬於容納有含有交聯劑的液體之2個以上的浴中之交聯處理，而製造偏光膜之方法，其中， 於前述2個以上的浴中之至少1個浴中，聚乙烯醇系樹脂膜沿著配置在浴中之2個以上的導引輥而被運送，且於前述2個以上的導引輥中之最後通過的最終導引輥中，以使圍包角成為100°以上且未達180°之方式來通過最終導引輥。 [1] A method of producing a polyvinyl alcohol-based resin film having a thickness of 65 μm or less while applying at least a dyeing treatment and the polyethylene a method of producing a polarizing film by sequentially immersing an alcohol resin film in a bath in which two or more baths containing a liquid containing a crosslinking agent are contained; In at least one of the two or more baths, the polyvinyl alcohol-based resin film is transported along two or more guide rolls disposed in the bath, and is in the two or more guide rolls. The final guide roller passed through finally passes through the final guide roller in such a manner that the wrap angle becomes 100° or more and less than 180°.
[2]如[1]所述之製造方法，其中，於具有以使圍包角成為100°以上且未達180°之方式所配置之前述最終導引輥之前述至少1個浴中，係施以拉伸處理，且於各浴中之該拉伸處理的拉伸倍率為1.14倍以下。 [2] The production method according to [1], wherein the at least one bath having the final guide roller disposed so that the wrap angle is 100° or more and less than 180° is The stretching treatment was applied, and the stretching ratio of the stretching treatment in each bath was 1.14 times or less.
[3]如[1]或[2]所述之製造方法，其中，供應至前述交聯處理之聚乙烯醇系樹脂膜為拉伸膜。 [3] The production method according to the above [1], wherein the polyvinyl alcohol-based resin film supplied to the crosslinking treatment is a stretched film.
[4]如[3]所述之製造方法，其中，以前述厚度65μm以下的聚乙烯醇系樹脂膜為基準之前述偏光膜的累積拉伸倍率為5.9倍以下。 [4] The production method according to the above [3], wherein the polarizing film has a cumulative stretching ratio of 5.9 times or less based on the polyvinyl alcohol resin film having a thickness of 65 μm or less.
[5]如[1]至[4]中任一項所述之製造方法，其中，前述最終導引輥為擴展輥。 [5] The production method according to any one of [1] to [4] wherein the final guide roller is an extension roller.
根據本發明之方法，在由薄的聚乙烯醇系樹 脂膜來製造偏光膜之方法中，可有效地抑制以往所產生之因浸漬於交聯浴所造成之薄膜寬度方向兩端部的翹曲或內折。 According to the method of the present invention, in a thin polyvinyl alcohol tree In the method of producing a polarizing film from a lipid film, it is possible to effectively suppress warpage or inversion which are conventionally caused by immersion in the cross-linking bath at both end portions in the film width direction.
10‧‧‧由聚乙烯醇系樹脂所構成之胚膜 10‧‧‧Making membrane composed of polyvinyl alcohol resin
11‧‧‧拉出輥 11‧‧‧ Pull out the roller
13‧‧‧膨潤浴 13‧‧‧Swelling bath
15‧‧‧染色浴 15‧‧‧dye bath
17a‧‧‧第1交聯浴 17a‧‧‧1st cross-linking bath
17b‧‧‧第2交聯浴 17b‧‧‧2nd cross-linking bath
17c‧‧‧第3交聯浴 17c‧‧‧3rd cross-linking bath
19‧‧‧洗淨浴 19‧‧‧ Washing bath
21‧‧‧乾燥爐 21‧‧‧ drying oven
23‧‧‧偏光膜 23‧‧‧ polarizing film
30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、45、46、47‧‧‧導引輥 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47‧‧ ‧ guide rolls
50、51、52、53、54、55、56、57‧‧‧軋輥 50, 51, 52, 53, 54, 55, 56, 57‧‧ ‧ rolls
第1圖係示意性表示本發明之偏光膜的製造方法及該製造方法所使用之偏光膜製造裝置的一例之剖面圖。 Fig. 1 is a cross-sectional view schematically showing an example of a method for producing a polarizing film of the present invention and a polarizing film producing apparatus used in the method.
本發明中，偏光膜係將二色性色素(碘或二色性染料)吸附配向於經單軸拉伸之聚乙烯醇系樹脂膜之偏光膜者。構成聚乙烯醇系樹脂膜之聚乙烯醇系樹脂，通常可藉由使聚乙酸乙烯酯系樹脂皂化而得。該皂化度通常為約85莫耳%以上，較佳為約90莫耳%以上，更佳為約99莫耳%以上。聚乙酸乙烯酯系樹脂，例如除了乙酸乙烯酯的均聚物之聚乙酸乙烯酯之外，可列舉出乙酸乙烯酯及可與該乙酸乙烯酯共聚合之其他單體的共聚物等。可共聚合之其他單體，例如可列舉出不飽和羧酸類、烯烴類、乙烯醚類、不飽和磺酸類等。聚乙烯醇系樹脂的聚合度，通常為約1000至10000，較佳為約1500至5000左右。 In the present invention, the polarizing film is a polarizing film in which a dichroic dye (iodine or a dichroic dye) is adsorbed to a uniaxially stretched polyvinyl alcohol-based resin film. The polyvinyl alcohol-based resin constituting the polyvinyl alcohol-based resin film can be usually obtained by saponifying a polyvinyl acetate-based resin. The degree of saponification is usually about 85 mol% or more, preferably about 90 mol% or more, more preferably about 99 mol% or more. Examples of the polyvinyl acetate-based resin include, for example, a polyvinyl acetate of a homopolymer of vinyl acetate, and a copolymer of vinyl acetate and another monomer copolymerizable with the vinyl acetate. Examples of the other monomer which can be copolymerized include unsaturated carboxylic acids, olefins, vinyl ethers, and unsaturated sulfonic acids. The degree of polymerization of the polyvinyl alcohol-based resin is usually from about 1,000 to 10,000, preferably from about 1,500 to 5,000.
此等聚乙烯醇系樹脂可經改質，例如亦可使用經醛類改質之聚乙烯甲醛、聚乙烯縮醛(polyvinylacetal)、聚乙烯丁醛等。 These polyvinyl alcohol-based resins may be modified, and for example, aldehyde-modified polyethylene formaldehyde, polyvinylacetal, polyvinyl butyral or the like may be used.
本發明中，偏光膜製造的起始材料，係使用厚度為65μm以下、較佳為約10至50μm、更佳為約10至35μm之未經拉伸的聚乙烯醇系樹脂膜(胚膜)。藉此可得到薄膜的偏光膜。當胚膜的厚度較65μm更厚時，由於薄膜的機械強度相當高，幾乎不會有因將膜浸漬於交聯浴所造成之薄膜寬度方向兩端部的翹曲或內折之問題。 In the present invention, the starting material for producing a polarizing film is an unstretched polyvinyl alcohol-based resin film (sheath film) having a thickness of 65 μm or less, preferably about 10 to 50 μm, more preferably about 10 to 35 μm. . Thereby, a polarizing film of the film can be obtained. When the thickness of the germ film is thicker than 65 μm, since the mechanical strength of the film is relatively high, there is almost no problem of warping or inward folding at both end portions in the film width direction caused by immersing the film in the crosslinking bath.
胚膜的寬度並無特別限定，例如可為400至6000mm左右，但薄膜寬度愈大，愈容易產生翹曲或內折。因此，本發明之製造方法，於胚膜的寬度大時，具體而言，於胚膜的寬度為1000mm以上時特別有效。 The width of the germ film is not particularly limited, and may be, for example, about 400 to 6000 mm, but the larger the film width, the more likely the warpage or the inversion is generated. Therefore, the production method of the present invention is particularly effective when the width of the embryonic membrane is large, specifically, when the width of the embryonic membrane is 1000 mm or more.
胚膜一般係以長條狀之未經拉伸的聚乙烯醇系樹脂膜的輥(捲繞品)來製備。 The embryonic film is generally prepared by a roll (wound product) of a long stretched undrawn polyvinyl alcohol-based resin film.
偏光膜係藉由沿著偏光膜製造裝置的薄膜運送路徑而連續地運送上述胚膜並實施既定的處理步驟，可連續地製造長條狀偏光膜。既定的處理步驟，可包括將胚膜浸漬於膨潤浴之膨潤處理步驟、將膨潤處理步驟後的薄膜浸漬於染色浴之染色處理步驟、以及將染色處理後的薄膜浸漬於交聯浴之交聯處理步驟。此外，在此等一連串處理步驟之間(亦即，任一項以上的處理步驟前後及/或任一項以上的處理步驟中)，藉由濕式或乾式施以單軸拉伸處理。可因應需要附加其他處理步驟。 In the polarizing film, the elongated film is continuously produced by continuously transporting the embryo film along the film transport path of the polarizing film manufacturing apparatus and performing a predetermined processing step. The predetermined treatment step may include a swell treatment step of immersing the embryonic membrane in the swelling bath, a dyeing treatment step of immersing the film after the swelling treatment step in the dyeing bath, and immersing the dyed film in the crosslinking of the crosslinking bath. Processing steps. Further, the uniaxial stretching treatment is performed by wet or dry application between the series of processing steps (that is, before and after any one or more of the processing steps and/or in any one or more of the processing steps). Additional processing steps can be added as needed.
上述各處理步驟，可為將膜浸漬於1個浴中之處理，或是浸漬於2個以上的浴中之處理。本發明之偏光膜中，至少交聯處理步驟係使染色處理步驟後的薄膜依 序浸漬於2個以上的交聯浴中之處理。此為由於使用2個以上的交聯浴來進行交聯處理時，特別容易產生翹曲或內折般的缺陷之故。 Each of the above treatment steps may be a treatment of immersing the membrane in one bath or immersing in two or more baths. In the polarizing film of the present invention, at least the crosslinking treatment step is such that the film after the dyeing treatment step is The process is immersed in two or more crosslinking baths. This is because when two or more crosslinking baths are used for the crosslinking treatment, defects such as warpage or indentation are particularly likely to occur.
以下一邊參考第1圖，一邊更詳細說明本發明之偏光膜的製造方法。第1圖係示意性表示本發明之偏光膜的製造方法及該製造方法所使用之偏光膜製造裝置的一例之剖面圖。第1圖所示之偏光膜製造裝置，係一邊將由聚乙烯醇系樹脂所構成之胚(未拉伸)膜10從抽出輥11連續地捲出，一邊沿著薄膜運送路徑運送，藉此使其依序通過薄膜運送路徑上所設置之膨潤浴13、染色浴15、第1交聯浴17a、第2交聯浴17b、第3交聯浴17c、以及洗淨浴19，最後通過乾燥爐21而構成。所得之偏光膜23，例如可直接運送至下一個偏光板製作步驟(將保護膜貼合於偏光膜23的單面或雙面之步驟)。第1圖中的箭頭，係表示薄膜的運送方向。 Hereinafter, a method of manufacturing the polarizing film of the present invention will be described in more detail with reference to Fig. 1 . Fig. 1 is a cross-sectional view schematically showing an example of a method for producing a polarizing film of the present invention and a polarizing film producing apparatus used in the method. In the polarizing film manufacturing apparatus shown in Fig. 1, the embryo (unstretched) film 10 made of a polyvinyl alcohol-based resin is continuously ejected from the take-up roll 11 and transported along the film transport path. It passes through the swelling bath 13 provided in the film transport path, the dye bath 15, the first cross-linking bath 17a, the second cross-linking bath 17b, the third cross-linking bath 17c, and the washing bath 19, and finally passes through the drying oven. 21 constitutes. The obtained polarizing film 23 can be directly transported, for example, to the next polarizing plate producing step (the step of bonding the protective film to one side or both sides of the polarizing film 23). The arrow in Fig. 1 indicates the direction in which the film is conveyed.
第1圖所示之例子係在交聯處理步驟中使用3個交聯浴，但並不限定於此，只要如上述般設置2個以上的交聯浴即可。此外，不限於第1圖所示之例子，膨潤浴、染色浴、洗淨浴亦可為2個以上。本說明書中，亦將膨潤浴、染色浴、交聯浴、洗淨浴般之用以容納對於聚乙烯醇系樹脂膜施以處理之處理液之浴，通稱為「處理浴」。 In the example shown in Fig. 1, three crosslinking baths are used in the crosslinking treatment step. However, the present invention is not limited thereto, and two or more crosslinking baths may be provided as described above. Further, the present invention is not limited to the example shown in Fig. 1, and the swelling bath, the dye bath, and the washing bath may be two or more. In the present specification, a bath for treating a treatment liquid for treating a polyvinyl alcohol-based resin film, such as a swelling bath, a dye bath, a cross-linking bath, and a washing bath, is also referred to as a "treatment bath".
偏光膜製造裝置的薄膜運送路徑，係除了上述處理浴之外，亦可藉由在適當的位置上配置：可支撐被運送之薄膜或進一步改變薄膜運送方向之導引輥30至 47；按壓/夾持被運送之薄膜，並可將由其旋轉所產生之驅動力賦予至薄膜，或可進一步改變薄膜運送方向之軋輥50至57而建構。例如導引輥可配置在各處理浴的前後或處理浴中，藉此可將膜導入並浸漬於處理浴，以及從處理浴中將膜拉出[參考第1圖]。具體而言，於各處理浴設置2個以上(不限於第1圖之例子，可為3個以上)的導引輥，並沿著此等導引輥來運送膜，藉此可將膜浸漬於各處理浴。 The film transport path of the polarizing film manufacturing apparatus may be disposed at an appropriate position by a suitable position: a guide roller 30 capable of supporting the conveyed film or further changing the film transport direction to 47; pressing/clamping the conveyed film, and imparting a driving force generated by the rotation thereof to the film, or a roll 50 to 57 which can further change the film conveying direction. For example, the guide rolls may be disposed before or after the respective treatment baths or in the treatment bath, whereby the film may be introduced and immersed in the treatment bath, and the film may be pulled out from the treatment bath [refer to Fig. 1]. Specifically, two or more guide rolls (not limited to the first example, three or more) may be provided in each treatment bath, and the film may be transported along the guide rolls, whereby the film may be impregnated. In each treatment bath.
此外，第1圖所示之偏光膜製造裝置，係於各處理浴的前後配置軋輥(軋輥50至56)，藉此於任1個以上的處理浴中，可於配置在其前後之軋輥間形成轉速差，而實施進行縱向單軸拉伸之輥間拉伸。以下說明各處理步驟。 Further, in the polarizing film manufacturing apparatus shown in Fig. 1, the rolls (rolls 50 to 56) are disposed in front of and behind the respective processing baths, so that they can be disposed between the rolls before and after the processing rolls in any one or more of the processing baths. A difference in rotational speed is formed, and stretching between rolls by longitudinal uniaxial stretching is carried out. Each processing step will be described below.
膨潤處理係以去除胚膜10表面的雜質、去除胚膜10中的可塑劑、賦予易染色性、達成胚膜10的可塑化者等為目的而進行。在可達成該目的之範圍且不會產生胚膜10的極端溶解或失透等缺陷之範圍內，來決定處理條件。 The swelling treatment is performed for the purpose of removing impurities on the surface of the germplasm 10, removing the plasticizer in the germplasm 10, imparting dyeability, and achieving plasticization of the membrane 10. The treatment conditions are determined within a range in which the object can be achieved without causing defects such as extreme dissolution or devitrification of the membrane 10.
參考第1圖，膨潤處理可藉由沿著由導引輥30至32及軋輥50所建構之薄膜運送路徑來運送，並將胚膜10浸漬於膨潤浴13(容納於膨潤槽之處理液)既定時間，然後拉出而實施。亦可利用軋輥50與軋輥51之轉速差，而於膨潤浴13中施以單軸拉伸處理。 Referring to Fig. 1, the swelling treatment can be carried by the film transport path constructed by the guide rolls 30 to 32 and the roll 50, and the germ film 10 is immersed in the swelling bath 13 (the treatment liquid contained in the swelling tank) The time is set and then pulled out and implemented. It is also possible to apply a uniaxial stretching treatment to the swelling bath 13 by using the difference in rotational speed between the roll 50 and the roll 51.
最初對胚膜10施以膨潤處理時，膨潤浴13 的溫度例如為10至50℃左右，較佳為10至40℃左右，更佳為15至30℃左右。胚膜10的浸漬時間，較佳為10至300秒左右，更佳為20至200秒左右。此外，在預先於氣體中使經拉伸之聚乙烯醇系樹脂膜膨潤時，膨潤浴13的溫度例如為20至70℃左右，較佳為30至60℃左右。薄膜的浸漬時間，較佳為30至300秒左右，更佳為60至240秒左右。 When the germinal membrane 10 is initially swelled, the swelling bath 13 The temperature is, for example, about 10 to 50 ° C, preferably about 10 to 40 ° C, more preferably about 15 to 30 ° C. The immersion time of the embryo film 10 is preferably from about 10 to 300 seconds, more preferably from about 20 to 200 seconds. Further, when the stretched polyvinyl alcohol-based resin film is swollen in advance in a gas, the temperature of the swelling bath 13 is, for example, about 20 to 70 ° C, preferably about 30 to 60 ° C. The immersion time of the film is preferably from about 30 to 300 seconds, more preferably from about 60 to 240 seconds.
膨潤浴13中，除了純水之外，亦可使用在約0.01至10重量%的範圍內添加硼酸(日本特開平10-153709號公報)、氯化物(日本特開平06-281816號公報)、無機酸、無機鹽、水溶性有機溶劑、醇類等而成之水溶液。 In the swell bath 13, in addition to the pure water, boric acid (Japanese Patent Laid-Open No. Hei 10-153709) and chloride (Japanese Patent Laid-Open No. Hei 06-281816) can be added in the range of about 0.01 to 10% by weight. An aqueous solution of an inorganic acid, an inorganic salt, a water-soluble organic solvent, or an alcohol.
膨潤處理中，容易產生胚膜10往寬度方向膨潤而於薄膜形成皺褶之問題。用以去除該皺褶並同時運送薄膜的手段之一，可列舉於導引輥30、31及/或32中使用擴展輥、螺旋輥、凸面冠輥般之具有擴幅功能之輥，或是使用導布裝置、彎曲棒(bend bar)、拉幅夾鉗般之其他擴幅裝置。用以抑制皺褶產生之另一手段為施以拉伸處理。 In the swelling treatment, the problem that the germ film 10 is swollen in the width direction and wrinkles are formed in the film is likely to occur. One of the means for removing the wrinkles and transporting the film at the same time is exemplified by using a roll having a widening function like a spread roll, a spiral roll or a convex crown roll in the guide rolls 30, 31 and/or 32, or Use a guide device, a bend bar, and a tenter clamp as other expansion devices. Another means for suppressing the generation of wrinkles is to apply a stretching treatment.
膨潤處理中，由於薄膜在薄膜的運送方向上仍會膨潤擴大，在未對膜進行積極的拉伸時，為了消除運送方向上之薄膜的鬆弛，較佳係例如採用控制被配置在膨潤浴13的前後之軋輥50、51的速度等手段。此外，以使膨潤浴13中的薄膜運送達到穩定為目的，以水中沖淋來控制膨潤浴13中的水流，或是併用EPC裝置(Edge Position Control裝置：檢測薄膜的端部並防止薄膜的蛇行之裝置) 等，亦為有效。 In the swelling treatment, since the film is swollen and expanded in the film transport direction, when the film is not actively stretched, in order to eliminate the slack of the film in the transport direction, it is preferably disposed, for example, by the control in the swelling bath 13 The speed of the rolls 50, 51 before and after. Further, in order to stabilize the film transport in the swelling bath 13, the water flow in the swelling bath 13 is controlled by water showering, or an EPC device (Edge Position Control device: detecting the end of the film and preventing the film from being snaked) Device) Etc., also valid.
於第1圖所示之例子中，從膨潤浴13所拉出之薄膜，係依序通過導引輥32、軋輥51而導入至染色浴15。 In the example shown in Fig. 1, the film pulled out from the swelling bath 13 is introduced into the dyeing bath 15 by the guide rolls 32 and the rolls 51 in this order.
染色處理係以使二色性色素吸附、配向於經膨潤處理後的聚乙烯醇系樹脂膜等為目的而進行。在可達成該目的之範圍且不會產生薄膜的極端溶解或失透等缺陷之範圍內，來決定處理條件。參考第1圖，染色處理可藉由沿著由導引輥33至35及軋輥51所建構之薄膜運送路徑來運送，並將膨潤處理後的薄膜浸漬於染色浴15(容納於染色槽之處理液)既定時間，然後拉出而實施。為了提高二色性色素的染色性，提供至染色處理步驟之薄膜，較佳為至少施以某種程度的單軸拉伸處理之薄膜，或者用來取代染色處理前的單軸拉伸處理，較佳係除了染色處理前的單軸拉伸處理之外，亦在染色處理時進行單軸拉伸處理。 The dyeing treatment is carried out for the purpose of adsorbing the dichroic dye, or aligning the polyvinyl alcohol-based resin film after the swelling treatment. The treatment conditions are determined within a range in which the object can be achieved without causing defects such as extreme dissolution or devitrification of the film. Referring to Fig. 1, the dyeing process can be carried by the film transport path constructed by the guide rolls 33 to 35 and the roll 51, and the swollen film is immersed in the dyeing bath 15 (contained in the dyeing tank). The liquid is applied for a given time and then pulled out. In order to improve the dyeability of the dichroic dye, the film provided to the dyeing treatment step is preferably a film which is subjected to at least a certain degree of uniaxial stretching treatment, or is used to replace the uniaxial stretching treatment before the dyeing treatment. Preferably, in addition to the uniaxial stretching treatment before the dyeing treatment, the uniaxial stretching treatment is also performed at the time of the dyeing treatment.
當使用碘作為二色性色素時，染色浴15中，例如可使用濃度以重量比計為碘/碘化鉀/水=約0.003至0.3/約0.1至10/100之水溶液。亦可使用碘化鋅等之其他碘化物來取代碘化鉀，或是併用碘化鉀與其他碘化物。此外，亦可共存碘化物以外的化合物，例如硼酸、氯化鋅、氯化鈷。添加硼酸時，就包含硼之點且與後述交聯處理區分而言，相對於水100重量份，水溶液只要包含約0.003 重量份以上的碘，即可視為染色浴15。浸漬薄膜時之染色浴15的溫度，通常為10至45℃左右，較佳為10至40℃，更佳為20至35℃，薄膜的浸漬時間，通常為30至600秒左右，較佳為60至300秒。 When iodine is used as the dichroic dye, in the dyeing bath 15, for example, an aqueous solution having a concentration by weight of iodine/potassium iodide/water = about 0.003 to 0.3/about 0.1 to 10/100 can be used. Other iodides such as zinc iodide may be used instead of potassium iodide, or potassium iodide and other iodides may be used in combination. Further, a compound other than the iodide such as boric acid, zinc chloride or cobalt chloride may be coexisted. When boric acid is added, the point of boron is included and it is distinguished from the crosslinking treatment described later, and the aqueous solution only needs to contain about 0.003 with respect to 100 parts by weight of water. The iodine in an amount of more than one part by weight can be regarded as the dyeing bath 15. The temperature of the dyeing bath 15 when the film is impregnated is usually about 10 to 45 ° C, preferably 10 to 40 ° C, more preferably 20 to 35 ° C, and the immersion time of the film is usually about 30 to 600 seconds, preferably 60 to 300 seconds.
使用水溶性二色性染料作為二色性色素時，染色浴15中，例如可使用濃度以重量比計為二色性染料/水=約0.001至0.1/100之水溶液。該染色浴15中，可共存染色輔助劑等，例如可含有硫酸鈉等之無機鹽或界面活性劑等。二色性染料可單獨使用1種，或是併用2種以上的二色性染料。浸漬薄膜時之染色浴15的溫度，例如為20至80℃左右，較佳為30至70℃，薄膜的浸漬時間，通常為30至600秒左右，較佳為60至300秒左右。 When a water-soluble dichroic dye is used as the dichroic dye, in the dyeing bath 15, for example, an aqueous solution having a concentration of dichroic dye/water = about 0.001 to 0.1/100 by weight may be used. In the dyeing bath 15, a dyeing auxiliary agent or the like may be present, and for example, an inorganic salt such as sodium sulfate or a surfactant may be contained. The dichroic dye may be used singly or in combination of two or more dichroic dyes. The temperature of the dyeing bath 15 when the film is impregnated is, for example, about 20 to 80 ° C, preferably 30 to 70 ° C, and the immersion time of the film is usually about 30 to 600 seconds, preferably about 60 to 300 seconds.
如上述般，染色處理步驟中，可於染色浴15中進行薄膜的單軸拉伸。薄膜的單軸拉伸，可藉由於配置在染色浴15的前後之軋輥51與軋輥52之間形成轉速差等方法來進行。 As described above, in the dyeing treatment step, the film can be uniaxially stretched in the dyeing bath 15. The uniaxial stretching of the film can be carried out by a method such as forming a difference in rotation speed between the rolls 51 and the rolls 52 arranged before and after the dyeing bath 15.
染色處理中，亦與膨潤處理相同，為了去除薄膜的皺褶並同時運送聚乙烯醇系樹脂膜，可於導引輥33、34及/或35中使用擴展輥、螺旋輥、冠輥般之具有擴幅功能之輥，或是使用導布裝置、彎曲棒、拉幅夾鉗般之其他擴幅裝置。用以抑制皺褶產生之另一手段，與膨潤處理相同，為施以拉伸處理。 In the dyeing treatment, in the same manner as the swelling treatment, in order to remove the wrinkles of the film and simultaneously transport the polyvinyl alcohol-based resin film, the stretching rolls, the spiral rolls, and the crown rolls can be used in the guide rolls 33, 34, and/or 35. Rollers with a widening function, or other expansion devices like a guide device, a bending rod, and a tenter clamp. Another means for suppressing the generation of wrinkles is the same as the swelling treatment, and is subjected to a stretching treatment.
於第1圖所示之例子中，從染色浴15所拉出之薄膜，係依序通過導引輥35、軋輥52而導入至第1交 聯浴17a。 In the example shown in Fig. 1, the film drawn from the dyeing bath 15 is sequentially introduced to the first intersection by the guide roller 35 and the roll 52. Joint bath 17a.
交聯處理係以藉由交聯所達成的耐水化或色相調整(防止膜帶有藍色等)等為目的而進行之處理。參考第1圖，使用第1交聯浴17a之交聯處理，可藉由沿著由導引輥36至38及軋輥52所建構之薄膜運送路徑來運送，並將染色處理後的薄膜浸漬於容納含有交聯劑之液體之第1交聯浴17a(容納於交聯槽之處理液)既定時間，然後拉出而實施。關於使用第2交聯浴17b及第3交聯浴17c之交聯處理亦相同。 The crosslinking treatment is carried out for the purpose of water resistance or hue adjustment (preventing the film with blue or the like) by crosslinking. Referring to Fig. 1, the cross-linking treatment using the first crosslinking bath 17a can be carried by the film transport path constructed by the guide rolls 36 to 38 and the rolls 52, and the dyed film is immersed in The first crosslinking bath 17a (the treatment liquid contained in the crosslinking tank) containing the liquid containing the crosslinking agent is carried out for a predetermined period of time and then pulled out. The crosslinking treatment using the second crosslinking bath 17b and the third crosslinking bath 17c is also the same.
容納於第1交聯浴17a、第2交聯浴17b、第3交聯浴17c之含有交聯劑之液體，相對於水100重量份，例如可為含有約1至10重量份之作為交聯劑的硼酸之水溶液。此等交聯浴，當染色處理所使用之二色性色素為碘時，除了硼酸之外，較佳係含有碘化物，其量相對於水100重量份，例如可為1至30重量份。碘化物可列舉出碘化鉀、碘化鋅等。此外，可共存碘化物以外的化合物，例如氯化鋅、氯化鈷、氯化鋯、硫代硫酸鈉、亞硫酸鉀、硫酸鈉等。 The liquid containing the crosslinking agent contained in the first crosslinking bath 17a, the second crosslinking bath 17b, and the third crosslinking bath 17c may contain, for example, about 1 to 10 parts by weight based on 100 parts by weight of water. An aqueous solution of a boric acid of a binder. In the crosslinking bath, when the dichroic dye used in the dyeing treatment is iodine, it is preferable to contain iodide in addition to boric acid, and the amount thereof may be, for example, 1 to 30 parts by weight based on 100 parts by weight of water. Examples of the iodide include potassium iodide and zinc iodide. Further, a compound other than the iodide such as zinc chloride, cobalt chloride, zirconium chloride, sodium thiosulfate, potassium sulfite, sodium sulfate or the like may be coexisted.
交聯處理中，因應其目的之不同，可適當地改變交聯劑(硼酸)及碘化物的濃度，以及交聯浴的溫度。例如，當交聯處理的目的為藉由交聯所達成之耐水化，且對聚乙烯醇系樹脂膜依序施以膨潤處理、染色處理及交聯處理時，交聯浴之含有交聯劑之液體，可為濃度以重量比 計為硼酸/碘化物/水=3至10/1至20/100之水溶液。可因應需要，使用乙二醛(Glyoxal)或戊二醛(Glutaraldehyde)等之其他交聯劑來取代硼酸，或是併用硼酸與其他交聯劑。浸漬膜時之交聯浴的溫度，通常為50至70℃左右，較佳為53至65℃，薄膜的浸漬時間，通常為10至600秒左右，較佳為20至300秒，更佳為20至200秒。另一方面，當預先對經拉伸後之聚乙烯醇系樹脂膜依序施以染色處理及交聯處理時，交聯浴的溫度通常為50至85℃左右，較佳為55至80℃。 In the crosslinking treatment, the concentration of the crosslinking agent (boric acid) and the iodide, and the temperature of the crosslinking bath can be appropriately changed depending on the purpose. For example, when the purpose of the crosslinking treatment is water resistance by crosslinking, and the polyvinyl alcohol-based resin film is sequentially subjected to swelling treatment, dyeing treatment, and crosslinking treatment, the cross-linking agent contains a crosslinking agent. Liquid, which can be concentration to weight ratio An aqueous solution of boric acid/iodide/water = 3 to 10/1 to 20/100 is considered. Other cross-linking agents such as Glyoxal or Glutaraldehyde may be used instead of boric acid, or boric acid and other cross-linking agents may be used as needed. The temperature of the crosslinking bath when the film is impregnated is usually about 50 to 70 ° C, preferably 53 to 65 ° C, and the immersion time of the film is usually about 10 to 600 seconds, preferably 20 to 300 seconds, more preferably 20 to 200 seconds. On the other hand, when the stretched polyvinyl alcohol-based resin film is subjected to a dyeing treatment and a crosslinking treatment in advance, the temperature of the crosslinking bath is usually about 50 to 85 ° C, preferably 55 to 80 ° C. .
以色相調整為目的之交聯處理中，當例如使用碘作為二色性色素時，可使用濃度以重量比計為硼酸/碘化物/水=1至5/3至30/100之含有交聯劑之液體。浸漬薄膜時之交聯浴的溫度，通常為10至45℃左右，薄膜的浸漬時間，通常為1至300秒左右，較佳為2至100秒。 In the cross-linking treatment for the purpose of hue adjustment, when iodine is used as the dichroic dye, for example, a cross-linking ratio of boric acid/iodide/water=1 to 5/3 to 30/100 in a weight ratio can be used. Liquid of the agent. The temperature of the crosslinking bath when the film is impregnated is usually about 10 to 45 ° C, and the immersion time of the film is usually about 1 to 300 seconds, preferably 2 to 100 seconds.
當實施以耐水化為目的之交聯處理及以色相調整為目的之交聯處理兩者時，可在以耐水化為目的之交聯處理後，進行以色相調整為目的之交聯處理。例如於第1圖所示之例子中，可將使用第1交聯浴17a之交聯處理構當作耐水化目的、將使用第2交聯浴17b之交聯處理構當作耐水化目的或色相調整目的、將使用第3交聯浴17c之交聯處理當作色相調整目的。惟以色相調整為目的之交聯處理為任意處理，故可省略。 When both the cross-linking treatment for the purpose of water resistance and the cross-linking treatment for the purpose of hue adjustment are carried out, the cross-linking treatment for the purpose of hue adjustment can be performed after the cross-linking treatment for the purpose of water resistance. For example, in the example shown in Fig. 1, the cross-linking treatment using the first cross-linking bath 17a can be regarded as the purpose of water resistance, and the cross-linking treatment using the second cross-linking bath 17b can be regarded as a water-resistant purpose or For the purpose of hue adjustment, the crosslinking treatment using the third crosslinking bath 17c is used as the hue adjustment purpose. However, the cross-linking process for the purpose of hue adjustment is arbitrary, so it can be omitted.
染色處理後的聚乙烯醇系樹脂膜往交聯浴之浸漬處理，可藉由沿著配置在該交聯浴中之2個以上的導 引輥來運送該膜而進行。藉由接續的薄膜運送，然後該膜通過配置在交聯浴中之最後(最下游側)的導引輥(最終導引輥)而從交聯浴拉出，此時，本發明中，於2個以上的交聯浴中之至少1個交聯浴中，以使最終導引輥中的圍包角成為100°以上且未達180°之方式使其通過最終導引輥，並從交聯浴中拉出。如此，將最終導引輥中的圍包角調整成較淺(較大)，並使因最終導引輥所造成的薄膜束縛減少，藉此可抑制或防止從該交聯浴拉出膜時可能產生之薄膜寬度方向兩端部的翹曲或內折。 The immersion treatment of the polyvinyl alcohol-based resin film after the dyeing treatment in the crosslinking bath can be carried out along two or more guides arranged in the crosslinking bath The roll is carried to carry the film. The film is transported by the continuous film, and then the film is pulled out from the crosslinking bath through a guide roller (final guide roller) disposed in the last (most downstream side) of the crosslinking bath. In the present invention, At least one of the two or more cross-linking baths is passed through the final guide roll so that the wrap angle in the final guide roll becomes 100° or more and less than 180°. Pull out in the joint bath. Thus, the wrap angle in the final guide roll is adjusted to be shallower (larger), and the film restraint caused by the final guide roll is reduced, whereby the film can be suppressed or prevented from being pulled out from the cross-linking bath. Warpage or inflection at both ends in the width direction of the film may occur.
在此，所謂最終導引輥中的圍包角，係意指第1圖所示之角度θ，為通過最終導引輥前(即將通過前)的薄膜與通過後(剛通過後)的薄膜所形成之角度，且最終導引輥所存在之側的角度。圍包角可採用0至180°之值，但本發明中係將此設為100°以上且未達180°。當角度θ為180°以上時，薄膜已不算是懸掛在最終導引輥之狀態，所以在概念上並不存上180°以上的圍包角。 Here, the wrap angle in the final guide roller means the angle θ shown in Fig. 1, which is a film before passing through the final guide roller (before passing) and a film after passing (just after passing). The angle formed and the angle at which the side of the guide roll is present. The wrap angle may be a value of 0 to 180°, but in the present invention, this is set to 100° or more and less than 180°. When the angle θ is 180° or more, the film is not suspended in the state of the final guide roller, so that the wrap angle of 180° or more is not conceptually present.
從更有效地抑制或防止翹曲或內折之觀點來看，最終導引輥中的圍包角較佳為135至178°，更佳為145至175°。 The wrap angle in the final guide roll is preferably from 135 to 178, more preferably from 145 to 175, from the viewpoint of more effectively suppressing or preventing warpage or inflection.
2個以上的交聯浴中之至少1個，只要是具有以圍包角成為100°以上且未達180°之方式所配置之最終導引輥之交聯浴即可，從更有效地抑制或防止翹曲或內折之觀點來看，在未調整圍包角時特別容易產生此等缺陷之交聯浴中，較佳係將圍包角調整至上述既定範圍內。 At least one of the two or more cross-linking baths can be more effectively suppressed as long as it is a cross-linking bath having a final guide roll disposed so that the wrap angle is 100° or more and less than 180°. In the cross-linking bath which is particularly prone to such defects when the wrap angle is not adjusted, it is preferable to adjust the wrap angle to the above-mentioned predetermined range from the viewpoint of preventing warpage or in-folding.
容易產生翹曲或內折般的缺陷之交聯浴，可列舉出下列交聯浴。 A cross-linking bath which is prone to warpage or intrinsic defects is exemplified by the following cross-linking bath.
(1)交聯浴中之薄膜的張力較其他交聯浴為較小之交聯浴。當薄膜的張力相對較小時，可能因薄膜的寬度方向兩端部鬆緩，而容易產生上述缺陷。 (1) The tension of the film in the cross-linking bath is smaller than that of other cross-linking baths. When the tension of the film is relatively small, the above-mentioned defects may easily occur due to the looseness of both ends in the width direction of the film.
(2)交聯浴(含有交聯劑之液體)之交聯劑(硼酸)的濃度較其他交聯浴為較小之交聯浴。當將膜浸漬於交聯劑濃度相對較小之浴時，膜中的交聯劑濃度亦降低。被認為是由此導致薄膜的寬度方向兩端部容易鬆緩。 (2) The cross-linking agent (boric acid) of the cross-linking bath (liquid containing a cross-linking agent) has a smaller cross-linking bath than other cross-linking baths. When the membrane is immersed in a bath having a relatively small concentration of the crosslinking agent, the concentration of the crosslinking agent in the membrane also decreases. It is considered that the both ends in the width direction of the film are easily relaxed.
(3)交聯浴的溫度較其他交聯浴為較高之交聯浴。當交聯浴的溫度相對較高時，可能因薄膜的寬度方向兩端部鬆緩，而容易產生上述缺陷。 (3) The temperature of the crosslinking bath is higher than that of other crosslinking baths. When the temperature of the crosslinking bath is relatively high, the above-mentioned defects may easily occur due to the looseness of both ends in the width direction of the film.
(4)交聯浴中所實施之拉伸的倍率較其他交聯浴中之拉伸的倍率為較小之交聯浴。為了將期望的累積拉伸倍率賦予至所得之偏光膜以提高該偏光特性，可在2個以上的交聯浴中之複數個交聯浴中進行單軸拉伸處理，但當拉伸倍率相對較小時(例如該交聯浴中的拉伸倍率為1.14倍以下，進一步為1.1倍以下，更進一步為1.05倍以下時)，可能因薄膜的寬度方向兩端部鬆緩，而容易產生上述缺陷。參考第1圖，交聯浴中的單軸拉伸處理，例如為第3交聯 浴17c時，可利用軋輥54與軋輥55之轉速差來進行(關於其他交聯浴亦同)。亦可在2個以上的交聯浴中之1個交聯浴中進行單軸拉伸處理，或是在交聯處理中不進行單軸拉伸處理。交聯浴中所實施之拉伸的倍率，於每1個交聯浴中，通常為1倍以上，典型為超過1倍。 (4) A cross-linking bath in which the stretching ratio in the cross-linking bath is smaller than that in the other cross-linking bath. In order to impart a desired cumulative stretching ratio to the obtained polarizing film to improve the polarizing characteristics, uniaxial stretching treatment may be performed in a plurality of crosslinking baths in two or more crosslinking baths, but when the stretching ratio is relatively When it is small (for example, the draw ratio in the crosslinking bath is 1.14 times or less, further 1.1 times or less, and further 1.05 times or less), the both ends in the width direction of the film may be loose, and the above-mentioned portions are likely to occur. defect. Referring to Figure 1, the uniaxial stretching treatment in the crosslinking bath, for example, the third crosslinking In the case of the bath 17c, the difference in the number of revolutions between the rolls 54 and the rolls 55 can be used (the same applies to other cross-linking baths). The uniaxial stretching treatment may be carried out in one of the two or more crosslinking baths, or the uniaxial stretching treatment may not be performed in the crosslinking treatment. The magnification of the stretching carried out in the crosslinking bath is usually 1 time or more, and typically more than 1 time, per one crosslinking bath.
從膜被浸漬於交聯浴(含有交聯劑之液體)後至到達最終導引輥為止之時間(幾乎相當於浸漬時間)為5秒以上，或較其他交聯浴為較長之交聯浴。當浸漬時間較長時，膜中所含有之交聯劑等的濃度變化容易變大。被認為是由此導致薄膜的寬度方向兩端部容易鬆緩。 The time from when the film is immersed in the crosslinking bath (liquid containing the crosslinking agent) to the time when the final guiding roller is reached (almost equivalent to the immersion time) is 5 seconds or longer, or the crosslinking is longer than other crosslinking baths. bath. When the immersion time is long, the concentration change of the crosslinking agent or the like contained in the film tends to become large. It is considered that the both ends in the width direction of the film are easily relaxed.
使用2個以上的交聯浴來進行交聯處理時，大致上，相較於最初的交聯浴，第2階段以後(包含第2段)的交聯浴較適合於上述(1)至(5)中的至少任一項，最終的交聯浴最適合於上述(1)至(5)中的至少任一項。例如，將最終的交聯浴構當作以色相調整為目的之交聯浴時，硼酸濃度通常較其他交聯浴更小。因此，本發明中，將圍包角調整至上述既定範圍之交聯浴，較佳係包含第2段以後的交聯浴，更佳係包含最終的交聯浴。第1圖係表示於3個交聯浴中之最終的第3交聯浴17c中，將圍包角調整至上述既定範圍之例子。惟針於2個以上的交聯浴之複數個交聯浴或是所有交聯浴，亦可將圍包角調整至上述既定範圍。 When the cross-linking treatment is carried out using two or more cross-linking baths, the cross-linking bath after the second stage (including the second stage) is substantially suitable for the above (1) to (compared to the first cross-linking bath). In at least one of 5), the final crosslinking bath is most suitable for at least any one of the above (1) to (5). For example, when the final crosslinked bath structure is used as a cross-linking bath for hue adjustment, the boric acid concentration is generally smaller than other cross-linking baths. Therefore, in the present invention, the crosslinking bath having the wrap angle adjusted to the above-mentioned predetermined range is preferably a cross-linking bath after the second stage, and more preferably a final cross-linking bath. Fig. 1 shows an example in which the wrap angle is adjusted to the above-described predetermined range in the final third cross-linking bath 17c of the three cross-linking baths. Only in a plurality of cross-linking baths or all cross-linking baths of two or more cross-linking baths, the wrap angle can be adjusted to the above-mentioned predetermined range.
交聯處理中，亦為了去除薄膜的皺褶並同時運送聚乙烯醇系樹脂膜，或是為了更有效地抑制或防止翹曲或內折，可於導引輥中使用擴展輥、螺旋輥、冠輥般之 具有擴幅功能之輥，或是使用導布裝置、彎曲棒、拉幅夾鉗般之其他擴幅裝置。為了更有效地抑制或防止翹曲或內折，特別是於以使圍包角成為100°以上且未達180°之方式所配置之最終導引輥(第1圖中的導引輥43)中使用上述具有擴幅功能之輥為較佳，其中，較佳係使用擴展輥。在交聯處理中進行拉伸處理亦對於抑制皺褶、翹曲及內折為有效。 In the cross-linking treatment, in order to remove wrinkles of the film and simultaneously transport the polyvinyl alcohol-based resin film, or to more effectively suppress or prevent warping or in-folding, an extension roll, a spiral roll, or the like may be used in the guide roll. Crown roll Rollers with a widening function, or other expansion devices like a guide device, a bending rod, and a tenter clamp. In order to more effectively suppress or prevent warpage or inflection, particularly the final guide roller (guide roller 43 in FIG. 1) configured such that the wrap angle becomes 100° or more and less than 180°. It is preferable to use the above-mentioned roller having a widening function, and it is preferable to use an expanding roller. Stretching treatment in the cross-linking treatment is also effective for suppressing wrinkles, warping, and internal folding.
於第1圖所示之例子中，從第3交聯浴17c所拉出之薄膜，係依序通過導引輥44、軋輥55而導入至洗淨浴19。 In the example shown in Fig. 1, the film pulled out from the third crosslinking bath 17c is introduced into the washing bath 19 by the guide rolls 44 and the rolls 55 in this order.
本發明之製造方法，可於交聯處理步驟後包括洗淨處理步驟。洗淨處理係以去除附著於聚乙烯醇系樹脂膜之多餘的硼酸或碘等藥劑者為目的而進行。洗淨處理例如可藉由將經交聯處理後之聚乙烯醇系樹脂膜浸漬於洗淨浴19(水)，或是對該薄膜以淋浴的方式噴霧水，或併用此等方法而進行。 The manufacturing method of the present invention may include a washing treatment step after the crosslinking treatment step. The cleaning treatment is carried out for the purpose of removing excess boric acid or iodine adhering to the polyvinyl alcohol-based resin film. The washing treatment can be carried out, for example, by immersing the crosslinked polyvinyl alcohol resin film in the washing bath 19 (water), or by spraying the film by shower, or by using these methods.
第1圖係表示將聚乙烯醇系樹脂膜浸漬於洗淨浴19來進行洗淨處理時之例子。洗淨處理中之洗淨浴19的溫度，通常為2至40℃左右，薄膜的浸漬時間，通常為2至120秒左右。 Fig. 1 shows an example in which a polyvinyl alcohol-based resin film is immersed in a washing bath 19 to carry out a washing treatment. The temperature of the washing bath 19 in the washing treatment is usually about 2 to 40 ° C, and the immersion time of the film is usually about 2 to 120 seconds.
洗淨處理中，以去除薄膜的皺褶並同時運送聚乙烯醇系樹脂膜者為目的，可於導引輥45、46及/或47 中使用擴展輥、螺旋輥、冠輥般之具有擴幅功能之輥，或是使用導布裝置、彎曲棒、拉幅夾鉗般之其他擴幅裝置。此外，洗淨處理中，為了抑制皺褶的產生，亦可施以拉伸處理。 In the cleaning treatment, for the purpose of removing wrinkles of the film and simultaneously transporting the polyvinyl alcohol resin film, the guide rolls 45, 46, and/or 47 may be used. In the case of a roll having a widening function such as an expanding roll, a spiral roll or a crown roll, or a widening device such as a guide cloth device, a bending rod or a tenter clamp. Further, in the washing treatment, in order to suppress the occurrence of wrinkles, a stretching treatment may be applied.
如上述般，胚膜10係在上述一連串處理步驟之間(亦即，任一項以上的處理步驟前後及/或任一項以上的處理步驟中)，藉由濕式或乾式施進行單軸拉伸處理。單軸拉伸處理的具體方法，例如可為於構成膜運送路徑之2個軋輥(例如配置在處理浴的前後之2個軋輥)之間形成轉速差，而進行縱向單軸拉伸之輥間拉伸；日本特許第2731813號公報所記載之熱輥拉伸；拉幅拉伸等，較佳為輥間拉伸。單軸拉伸處理步驟係可由胚膜10得到偏光膜23為止之間反覆複數次實施。 As described above, the embryonic film 10 is uniaxially coupled by wet or dry application between the above-described series of processing steps (i.e., before or after any one or more of the processing steps and/or in any one or more of the processing steps). Stretching treatment. The specific method of the uniaxial stretching treatment may be, for example, forming a rotation speed difference between two rolls constituting the film conveyance path (for example, two rolls disposed before and after the treatment bath), and performing longitudinal uniaxial stretching between the rolls. Stretching; heat roll stretching as described in Japanese Patent No. 2731813; tenter stretching, etc., preferably stretching between rolls. The uniaxial stretching treatment step can be carried out repeatedly several times until the polarizing film 23 is obtained from the embryo film 10.
以胚膜10(厚度65μm以下的聚乙烯醇系樹脂未拉伸膜)為基準之偏光膜23的最終累積拉伸倍率，雖然取決於胚膜10的厚度，但從所得之偏光膜23的偏光特性之觀點來看，通常為4.5倍以上，較佳為5.0倍以上。另一方面，累積拉伸倍率過高時，膜會過薄而使處理性降低，或是於拉伸處理中容易產生薄膜的破裂或斷裂，因此，當胚膜10的厚度未達35μm時，較佳為5.9倍以下，更佳為5.7倍以下，又更佳為5.5倍以下。胚膜10的厚度為35μm以上且65μm以下時，較佳為6.3倍以下，更佳為6.1 倍以下，又更佳為5.9倍以下。 The final cumulative stretching ratio of the polarizing film 23 based on the embryonic film 10 (polyvinyl alcohol-based resin unstretched film having a thickness of 65 μm or less) depends on the thickness of the germicidal film 10, but is polarized from the obtained polarizing film 23. From the viewpoint of characteristics, it is usually 4.5 times or more, preferably 5.0 times or more. On the other hand, when the cumulative stretching ratio is too high, the film may be too thin to deteriorate the handleability, or the film may be cracked or broken during the stretching treatment, and therefore, when the thickness of the germ film 10 is less than 35 μm, It is preferably 5.9 times or less, more preferably 5.7 times or less, and still more preferably 5.5 times or less. When the thickness of the germ film 10 is 35 μm or more and 65 μm or less, it is preferably 6.3 times or less, more preferably 6.1. Below the fold, it is more preferably 5.9 times or less.
拉伸步驟可於任一處理步驟中進行，於2個以上的處理步驟中進行拉伸處理時，拉伸步驟亦可於任一處理步驟中進行，但從提高二色性色素的染色性之觀點來看，提供至染色處理步驟之薄膜，較佳為至少施以某種程度的單軸拉伸處理之薄膜，或用來取代染色處理前的單軸拉伸處理，較佳係除了染色處理前的單軸拉伸處理之外，亦在染色處理時進行單軸拉伸處理。藉此可將經拉伸處理後之薄膜提供至交聯處理步驟，根據本發明，即使在對因拉伸變薄而容易產生翹曲或內折之薄膜進行交聯時，亦可有效地抑制或防止翹曲或內折。較佳的1項實施形態中，拉伸處理係在膨潤處理步驟及/或染色處理步驟，與交聯處理步驟中實施。 The stretching step can be carried out in any of the processing steps. When the stretching treatment is carried out in two or more processing steps, the stretching step can also be carried out in any of the processing steps, but the dyeing property of the dichroic dye is improved. From the viewpoint, the film provided to the dyeing treatment step is preferably a film which is subjected to at least a certain degree of uniaxial stretching treatment, or is used to replace the uniaxial stretching treatment before the dyeing treatment, preferably in addition to dyeing treatment. In addition to the former uniaxial stretching treatment, uniaxial stretching treatment is also performed at the time of dyeing treatment. Thereby, the stretched film can be provided to the crosslinking treatment step, and according to the present invention, even when the film which is easily warped or inflected due to stretching and thinning is crosslinked, it can be effectively suppressed or Prevent warping or inflection. In a preferred embodiment, the stretching treatment is carried out in the swelling treatment step and/or the dye treatment step, and in the crosslinking treatment step.
如上述般，拉伸處理係有助於抑制被運送之薄膜的皺褶，尤其是在交聯處理中所產生之翹曲及內折。當交聯處理中的拉伸倍率低時，該效果會變小而容易引起翹曲或內折，但根據本發明，即使交聯處理之各交聯浴中的拉伸倍率例如為1.14倍以下、進一步為1.1倍以下，更進一步為1.05倍以下之較低倍率時，亦可有效地抑制或防止翹曲或內折。 As described above, the stretching treatment contributes to suppressing wrinkles of the film to be conveyed, in particular, warpage and inflection generated in the crosslinking treatment. When the stretching ratio in the crosslinking treatment is low, the effect becomes small and warpage or inflection is likely to occur, but according to the present invention, the stretching ratio in each crosslinking bath of the crosslinking treatment is, for example, 1.14 times or less. Further, when it is 1.1 times or less, and further has a lower magnification of 1.05 times or less, warpage or inflection can be effectively suppressed or prevented.
洗淨處理後，較佳係進行使聚乙烯醇系樹脂膜乾燥之處理。薄膜的乾燥並無特別限制，如第1圖所示之例子般， 可使用乾燥爐21來進行。乾燥溫度例如為30至100℃左右，乾燥時間例如為30至600秒左右。以上述方式所得之偏光膜23的厚度，例如為5至30μm左右。 After the washing treatment, it is preferred to carry out a treatment for drying the polyvinyl alcohol-based resin film. The drying of the film is not particularly limited, as in the example shown in Fig. 1, It can be carried out using the drying oven 21. The drying temperature is, for example, about 30 to 100 ° C, and the drying time is, for example, about 30 to 600 seconds. The thickness of the polarizing film 23 obtained in the above manner is, for example, about 5 to 30 μm.
亦可附加上述處理以外之處理。可追加之處理的例子係包括有：於交聯處理後所進行之浸漬於不含硼酸之碘化物水溶液之浸漬處理(補色處理)，以及浸漬於不含硼酸且含有氯化鋅等的水溶液之浸漬處理(鋅處理)。 Processing other than the above processing may be added. Examples of the treatment that can be added include immersion treatment (complementing treatment) immersed in an aqueous solution of iodide containing no boric acid after the crosslinking treatment, and immersion in an aqueous solution containing no boric acid and containing zinc chloride or the like. Dip treatment (zinc treatment).
此外，為了抑制或防止從膨潤浴13及/或染色浴15所拉出之薄膜產生翹曲或內折，可對在雙面附著有處理液之狀態下被拉出之薄膜，進行使該雙面之寬度方向兩端部的液體附著量降低之處理。亦可將降低該液體附著量之處理適用在交聯浴，例如於至少1個交聯浴中，併用降低該液體附著量之處理與將圍包角調整至上述既定範圍內之處理。在此所謂薄膜的寬度方向兩端部，較佳以兩端部合計為膜寬度全體的2至20%。使寬度方向兩端部的液體附著量降低之處理，例如可藉由下列a)至c)的方法來進行。 Further, in order to suppress or prevent warpage or inflection of the film pulled out from the swelling bath 13 and/or the dyeing bath 15, the film which is pulled out in a state in which the treatment liquid is adhered on both sides may be subjected to the double The treatment of lowering the amount of liquid adhering at both end portions in the width direction of the surface. The treatment for lowering the amount of adhesion of the liquid may be applied to a crosslinking bath, for example, in at least one crosslinking bath, and a treatment for reducing the amount of adhesion of the liquid and a process of adjusting the wrap angle to the predetermined range. Here, the both end portions in the width direction of the film are preferably 2 to 20% of the total film width in total at both end portions. The treatment for lowering the amount of liquid adhering at both end portions in the width direction can be carried out, for example, by the following methods a) to c).
a)將氣體吹送至從處理浴所拉出之聚乙烯醇系樹脂膜的雙面，藉此將至少附著於膜寬度方向兩端部的表面之液體去除而使液體附著量降低之方法。該氣體吹送處理，可使用：具有可噴射氣體之1個或複數個噴射孔之導管(配 管)或軟管，或是使用如空氣刀般之氣體吹送裝置。 a) A method in which the gas is blown to both sides of the polyvinyl alcohol-based resin film drawn from the processing bath, thereby removing at least the liquid adhering to the surfaces on both end portions in the film width direction, thereby reducing the amount of liquid adhesion. For the gas blowing treatment, a catheter having one or a plurality of injection holes capable of injecting gas can be used (for Tube) or hose, or use a gas blower like an air knife.
氣體吹送裝置所使用之氣體的種類並無特別限制，通常為空氣、氮氣、氬氣等之對薄膜呈惰性之氣體，較佳為空氣。氣體的噴射壓亦無特別限制，只要可吹走所附著之液體之程度即可。 The type of gas used in the gas blowing device is not particularly limited, and is usually a gas which is inert to a film such as air, nitrogen or argon, and is preferably air. The ejection pressure of the gas is also not particularly limited as long as the attached liquid can be blown away.
為了抑制從處理浴所拉出之薄膜的翹曲或內折，僅對膜雙面的寬度方向兩端部進行氣體吹送處理即足夠，但除了寬度方向兩端部之外，亦可對於其他薄膜表面區域一同實施氣體吹送處理。例如可對膜雙面的全體進行氣體吹送處理。 In order to suppress warpage or inward folding of the film pulled out from the processing bath, it is sufficient to perform gas blowing treatment only on both end portions in the width direction of both sides of the film, but other film layers may be used in addition to both end portions in the width direction. The surface area is subjected to a gas blowing process. For example, a gas blowing treatment can be performed on the entire both sides of the film.
例如參考第1圖，在對從膨潤浴13所拉出之薄膜實施氣體吹送處理時，氣體吹送裝置可設置在：導引輥32與軋輥51之間、膜從膨潤浴13拉出後至到達導引輥32為止之間、或是此等兩者的位置中。氣體吹送處理，較佳係至少對剛從處理浴的液面拉出後之薄膜實施。 For example, referring to Fig. 1, when a gas blowing process is performed on a film drawn from the swelling bath 13, the gas blowing device may be disposed between the guide roller 32 and the roll 51, and after the film is pulled out from the swelling bath 13 to reach The guide rollers 32 are in between or in the position of both. The gas blowing treatment is preferably carried out at least on the film which has just been pulled out from the liquid surface of the treatment bath.
b)使輥或棒接觸(壓抵)於從處理浴所拉出之聚乙烯醇系樹脂膜的雙面，藉此利用輥或棒使至少附著於膜寬度方向兩端部的表面之液體滴落而降低液體附著量之方法。 b) contacting or pressing (contacting) the roller or the rod on both sides of the polyvinyl alcohol-based resin film drawn from the treatment bath, thereby using a roller or a rod to adhere at least a liquid droplet adhering to the surfaces at both end portions in the film width direction A method of falling to reduce the amount of liquid adhering.
接觸於膜寬度方向兩端部的表面之輥，例如可為如導布裝置般之自雙面夾持從處理浴所拉出之聚乙烯醇系樹脂膜之一對輥。通過該一對輥之間之薄膜，在接觸於輥之表面區域中，所附著之液體被擠落。另一方面，接觸於膜寬度方向兩端部的表面之棒，並非如輥般之其本身 會旋轉者，而是自雙面夾持從處理浴所拉出之聚乙烯醇系樹脂膜，或是以每次單面依序與膜接觸之一對棒狀物。使用該棒時，通過棒之間之薄膜，在其接觸於棒之表面區域中，所附著之液體亦會被擠落。 The roller that contacts the surfaces of both end portions in the film width direction may be, for example, a pair of rolls of a polyvinyl alcohol-based resin film that is pulled from the processing bath by double-sided clamping as in a cloth guiding device. Through the film between the pair of rolls, the adhered liquid is squeezed in the surface area in contact with the roll. On the other hand, the rod that contacts the surface at both ends in the width direction of the film is not like a roller itself. The rotator is a polyvinyl alcohol-based resin film which is pulled from the processing bath from both sides, or is in contact with the film one by one on a single side. When the rod is used, the adhered liquid is also squeezed by the film between the rods in the surface area where it contacts the rod.
上述輥及棒中之與膜接觸的表面，例如可由不鏽鋼等金屬所構成，或是橡膠、海綿等所構成。輥及棒的形狀，只要是接觸於薄膜之面呈曲面狀者即可，惟較佳為圓筒形。使用圓筒狀的輥或棒時，其直徑為5至100mm左右，較佳為10至50mm。直徑位於此範圍內即可平順地運送膜。 The surface of the roller and the rod that is in contact with the film may be made of, for example, a metal such as stainless steel, or a rubber or a sponge. The shape of the roll and the rod may be a curved shape as long as it is in contact with the surface of the film, but is preferably cylindrical. When a cylindrical roll or rod is used, it has a diameter of about 5 to 100 mm, preferably 10 to 50 mm. The diameter is within this range to smoothly transport the film.
為了抑制從處理浴所拉出之薄膜的翹曲或內折，只需進行使輥或棒僅接觸於膜雙面的寬度方向兩端部之處理即足夠，但除了寬度方向兩端部之外，亦可對於其他膜表面區域一同實施該接觸處理。例如可對膜雙面的全體進行該接觸處理。輥及棒的設置角度並無特別限制，輥及棒的長度方向可與膜寬度方向平行，或是與膜寬度方向呈傾斜。 In order to suppress the warpage or the inward folding of the film pulled out from the processing bath, it is sufficient to perform the treatment of bringing the roller or the rod into contact only at both end portions in the width direction of both sides of the film, except for the both end portions in the width direction. This contact treatment can also be carried out together with other film surface regions. This contact treatment can be performed, for example, on the entire both sides of the film. The angle at which the roller and the rod are disposed is not particularly limited, and the longitudinal direction of the roller and the rod may be parallel to the film width direction or may be inclined with respect to the film width direction.
例如參考第1圖，在對從膨潤浴13所拉出之薄膜實施與該輥或棒之接觸處理時，該接觸處理可在：導引輥32與軋輥51之間、薄膜從膨潤浴13拉出後至到達導引輥32為止之間、或是此等兩者的位置中實施。與輥或棒之接觸處理，較佳係至少對剛從處理浴的液面拉出後之薄膜實施。 For example, referring to Fig. 1, when the film drawn from the swelling bath 13 is subjected to a contact treatment with the roller or the rod, the contact treatment may be performed between the guide roller 32 and the roll 51, and the film is pulled from the swelling bath 13 It is carried out between the time of reaching the guide roller 32 or the position of both of them. The contact treatment with the roll or the rod is preferably carried out at least on the film which has just been pulled out from the liquid surface of the treatment bath.
c)將從處理浴所拉出之聚乙烯醇系樹脂膜導入於軋輥，並藉由軋輥使附著於膜表面之液體滴落而降低液體附著量之方法。該方法中，通常使附著於膜雙面的全體之液體滴落。 c) A method in which a polyvinyl alcohol-based resin film drawn from a treatment bath is introduced into a roll, and a liquid adhering to the surface of the film is dropped by a roll to reduce the amount of liquid adhesion. In this method, the entire liquid adhering to both surfaces of the film is usually dropped.
使用上述a)或b)的方法而僅對膜寬度方向兩端部進行降低液體附著量之處理時，從處理浴所拉出且已施以降低液體附著量之處理之薄膜，通常是使用直徑涵蓋全寬呈一定的圓筒形導引輥的平輥來運送。亦即，當從處理浴所拉出且已施以降低液體附著量之處理之薄膜首先通過導引輥，然後再通過軋輥時，此1個或2個以上的導引輥較佳為平輥。使用相對於地面呈水平配置之平輥來運送已施以降低液體附著量之處理之薄膜，藉此可防止於薄膜的運送中薄膜之寬度方向中央部的液體流入兩端部，所以更可有效地抑制膜兩端部的翹曲或內折。 When the treatment for reducing the amount of liquid adhesion is applied to both end portions in the film width direction by the method of the above a) or b), the film which is pulled out from the treatment bath and which has been subjected to a treatment for lowering the amount of liquid adhesion is usually a diameter. It covers a flat roller with a full width of a cylindrical guide roller for transport. That is, when the film which is pulled out from the treatment bath and which has been subjected to the treatment for lowering the amount of liquid adhesion first passes through the guide roller and then passes through the roll, the one or more guide rolls are preferably flat rolls. . By using a flat roll that is horizontally disposed with respect to the ground to transport a film that has been subjected to a treatment for reducing the amount of liquid adhering, it is possible to prevent liquid in the central portion in the width direction of the film from flowing into both end portions during transport of the film, so that it is more effective The warpage or the inner fold of both ends of the film is suppressed.
於以上的方式所製造之偏光膜的至少單面上，經介接著劑而貼合保護膜，藉此可得到偏光板。保護膜係例如可列舉出：由三乙酸纖維素或二乙酸纖維素般之乙酸纖維素系樹脂所構成之薄膜；由聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯及聚對苯二甲酸丁二酯般之聚酯系樹脂所構成之薄膜；聚碳酸酯系樹脂膜、環烯烴系樹脂膜；(甲基)丙烯酸系樹脂膜；由聚丙烯系樹脂之鏈狀聚烯烴系樹脂所構成之薄膜。 A polarizing plate can be obtained by bonding a protective film to at least one surface of the polarizing film produced in the above manner via a binder. Examples of the protective film include a film composed of cellulose acetate-like resin such as cellulose triacetate or cellulose diacetate; polyethylene terephthalate, polyethylene naphthalate, and polybutylene. A film composed of a polyester resin such as butyl phthalate; a polycarbonate resin film or a cycloolefin resin film; a (meth)acrylic resin film; and a chain polyolefin system made of a polypropylene resin A film composed of a resin.
本說明書中，所謂「(甲基)丙烯酸」係意指選自丙烯酸及甲基丙烯酸之至少一者。 In the present specification, the term "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid.
為了提升偏光膜與保護膜之接著性，於偏光膜及/或保護膜的貼合面，可施以電暈處理、火焰處理、電漿處理、紫外線照射、底塗塗布處理、皂化處理等之表面處理。偏光膜與保護膜之貼合所使用之接著劑，可列舉出紫外線硬化性接著劑般之活化能射線硬化性接著劑、聚乙烯醇系樹脂的水溶液、或於此調配有交聯劑之水溶液、胺基甲酸乙酯系乳化接著劑般之水系接著劑。紫外線硬化性接著劑可為(甲基)丙烯酸系化合物與光自由基聚合起始劑之混合物，或是環氧化合物與光陽離子聚合起始劑之混合物等。此外，可併用陽離子聚合性環氧化合物與自由基聚合性(甲基)丙烯酸系化合物，亦可併用光陽離子聚合起始劑與光自由基聚合起始劑作為起始劑。 In order to improve the adhesion between the polarizing film and the protective film, corona treatment, flame treatment, plasma treatment, ultraviolet irradiation, primer coating treatment, saponification treatment, etc. may be applied to the bonding surface of the polarizing film and/or the protective film. Surface treatment. The adhesive used for bonding the polarizing film and the protective film may, for example, be an active energy ray-curable adhesive such as an ultraviolet curable adhesive, an aqueous solution of a polyvinyl alcohol-based resin, or an aqueous solution in which a crosslinking agent is formulated. A urethane-based emulsion adhesive-like water-based adhesive. The ultraviolet curable adhesive may be a mixture of a (meth)acrylic compound and a photoradical polymerization initiator, or a mixture of an epoxy compound and a photocationic polymerization initiator. Further, a cationically polymerizable epoxy compound and a radically polymerizable (meth)acrylic compound may be used in combination, and a photocationic polymerization initiator and a photoradical polymerization initiator may be used in combination as a starting agent.
以下，顯示實施例來更具體說明本發明，但本發明並不限定於此等例。 Hereinafter, the present invention will be more specifically described by showing examples, but the present invention is not limited thereto.
使用與第1圖所示之偏光膜製造裝置相同的裝置來製造偏光膜23。導引輥30至41均使用平輥。 The polarizing film 23 is manufactured using the same apparatus as the polarizing film manufacturing apparatus shown in FIG. The guide rolls 30 to 41 each use a flat roll.
連續地運送厚度30μm的聚乙烯醇膜[Kuraray股份有 限公司製之商品名稱「Kuraray Poval Film VF-PE#3000」、聚合度2400、皂化度99.9莫耳%以上]，並浸漬於裝有20℃的純水之膨潤浴13中30秒。該膨潤處理中，係於軋輥50、51之間形成轉速差來進行輥間拉伸(縱向單軸拉伸)，以使剛從膨潤浴13拉出後的膜寬成為浸漬於膨潤浴13前的膜寬以下。以胚膜10為基準之拉伸倍率設為2.5倍。 Continuously transporting a polyvinyl alcohol film with a thickness of 30 μm [Kuraray shares have The product name "Kuraray Poval Film VF-PE #3000", a degree of polymerization 2400, a degree of saponification of 99.9 mol% or more, and immersed in a swelling bath 13 containing pure water at 20 ° C for 30 seconds. In the swelling treatment, a difference in rotation speed is formed between the rolls 50 and 51 to perform inter-roll stretching (longitudinal uniaxial stretching) so that the film width immediately after being pulled out from the swelling bath 13 is immersed in the swelling bath 13 The film width is below. The draw ratio based on the embryo film 10 was set to 2.5 times.
對於從膨潤浴13所拉出之薄膜，使用設置在導引輥32的面前之氣體吹送裝置(空氣噴射噴嘴)以及設置在導引輥32與軋輥51之間之氣體吹送裝置(空氣噴射噴嘴)，對薄膜雙面的寬度方向兩端部噴射空氣，去除附著於此之液體。 For the film pulled out from the swelling bath 13, a gas blowing device (air jet nozzle) provided in front of the guide roller 32 and a gas blowing device (air jet nozzle) provided between the guide roller 32 and the roller 51 are used. Air is sprayed on both ends in the width direction of both sides of the film to remove the liquid adhering thereto.
接著將通過軋輥51之薄膜，浸漬於碘/碘化鉀/水(重量比)為0.05/2/100之30℃的染色浴15中120秒。該染色處理中，亦於軋輥51、52之間形成周速差以進行輥間拉伸(縱向單軸拉伸)，以使剛從染色浴15拉出後的膜寬成為浸漬於染色浴15前的膜寬以下。以胚膜10為基準之膨潤處理與染色處理中的累積拉伸倍率設為2.7倍(染色處理中的拉伸倍率為1.08倍)。 Next, the film passing through the roll 51 was immersed in a dye bath 15 of 30 ° C of iodine/potassium iodide/water (weight ratio) of 0.05/2/100 for 120 seconds. In the dyeing treatment, a peripheral speed difference is also formed between the rolls 51 and 52 to perform inter-roll stretching (longitudinal uniaxial stretching) so that the film width immediately after being pulled out from the dyeing bath 15 is immersed in the dyeing bath 15 The front film width is below. The cumulative stretching ratio in the swelling treatment and the dyeing treatment based on the embryo film 10 was 2.7 times (the stretching ratio in the dyeing treatment was 1.08 times).
為了施行以耐水化為目的之第1交聯處理，將通過軋 輥52之薄膜，浸漬於碘化鉀/硼酸/水(重量比)為12/4.4/100之55℃的第1交聯浴17a中30秒。該第1交聯處理中，亦於軋輥52、與設置在第1交聯浴17a及第2交聯浴17b之間之軋輥53之間形成轉速差來進行輥間拉伸(縱向單軸拉伸)，以使剛從第1交聯浴17a拉出後的膜寬成為浸漬於第1交聯浴17a前的膜寬以下。以胚膜10為基準之膨潤處理、染色處理及第1交聯處理中的累積拉伸倍率設為4.3倍(第1交聯處理中的拉伸倍率為1.6倍)。 In order to perform the first crosslinking treatment for the purpose of water resistance, it will pass through rolling The film of the roll 52 was immersed in the first crosslinking bath 17a at 55 ° C of 12/4.4/100 of potassium iodide/boric acid/water (weight ratio) for 30 seconds. In the first crosslinking treatment, a difference in rotation speed is formed between the rolls 52 and the rolls 53 provided between the first crosslinking bath 17a and the second crosslinking bath 17b to perform stretching between rolls (longitudinal uniaxial drawing) The film width immediately after being pulled out from the first crosslinking bath 17a is equal to or less than the film width before being immersed in the first crosslinking bath 17a. The cumulative stretching ratio in the swelling treatment, the dyeing treatment, and the first crosslinking treatment based on the embryo film 10 was 4.3 times (the stretching ratio in the first crosslinking treatment was 1.6 times).
接著將第1交聯處理後的薄膜，浸漬於與第1交聯浴17a為相同組成之59℃的第2交聯浴17b中30秒(第2交聯處理)，該第2交聯處理中，亦於軋輥53、與設置在第2交聯浴17b及第3交聯浴17c之間之軋輥54之間形成轉速差來進行輥間拉伸(縱向單軸拉伸)，以使剛從第2交聯浴17b拉出後的膜寬成為浸漬於第2交聯浴17b前的膜寬以下。以胚膜10為基準之膨潤處理、染色處理、第1交聯處理及第2交聯處理中的累積拉伸倍率設為5.4倍(第2交聯處理中的拉伸倍率為1.25倍)。 Then, the film after the first crosslinking treatment is immersed in the second crosslinking bath 17b at 59 ° C having the same composition as that of the first crosslinking bath 17a for 30 seconds (second crosslinking treatment), and the second crosslinking treatment is performed. In the middle, the roll 53 is formed between the roll 54 and the roll 54 provided between the second cross-linking bath 17b and the third cross-linking bath 17c to perform stretching between rolls (longitudinal uniaxial stretching) so that The film width after being pulled out from the second crosslinking bath 17b is equal to or less than the film width before being immersed in the second crosslinking bath 17b. The cumulative stretching ratio in the swelling treatment, the dyeing treatment, the first crosslinking treatment, and the second crosslinking treatment based on the embryo film 10 was 5.4 times (the stretching ratio in the second crosslinking treatment was 1.25 times).
接著為了施行以色相調整為目的之交聯處理，將其浸漬於碘化鉀/硼酸/水(重量比)為9/2.9/100之40℃的第3交聯浴17c中15秒(第3交聯處理)。此時，使配置於第3交聯浴17c中的最終導引輥43中之薄膜的圍包角形成160°來進行薄膜運送。該第3交聯處理中，亦於軋輥54與軋輥55之間形成轉速差來進行輥間拉伸(縱向單軸拉伸)，以使剛從第3交聯浴17c拉出後的膜寬成為浸漬於第 3交聯浴17c前的膜寬以下。以胚膜10為基準之膨潤處理、染色處理、第1交聯處理、第2交聯處理及第3交聯處理中的累積拉伸倍率設為5.5倍(第3交聯處理中的拉伸倍率為1.02倍)。 Next, in order to perform the crosslinking treatment for the purpose of hue adjustment, it was immersed in the third crosslinking bath 17c at 40 ° C of potassium iodide/boric acid/water (weight ratio) of 9/2.9/100 for 15 seconds (third crosslinking) deal with). At this time, the film conveyance was carried out by forming the wrap angle of the film in the final guide roll 43 disposed in the third crosslinking bath 17c at 160°. In the third crosslinking treatment, a difference in rotation speed is also formed between the rolls 54 and the rolls 55 to perform inter-roll stretching (longitudinal uniaxial stretching) so that the film width immediately after being pulled out from the third crosslinking bath 17c Become impregnated in the first 3 The film width before the cross-linking bath 17c is below. The cumulative stretching ratio in the swelling treatment, the dyeing treatment, the first crosslinking treatment, the second crosslinking treatment, and the third crosslinking treatment based on the embryonic film 10 is 5.5 times (stretching in the third crosslinking treatment) The magnification is 1.02 times).
然後將第3交聯處理後的薄膜浸漬於裝有5℃的純水之洗淨浴19中，接著通過乾燥爐21，藉此使其在70℃乾燥3分鐘，而製作出偏光膜23。 Then, the film after the third crosslinking treatment was immersed in a washing bath 19 containing pure water at 5 ° C, and then dried in a drying oven 21 at 70 ° C for 3 minutes to prepare a polarizing film 23 .
連續地實施上述偏光膜製造24小時，於24小時的運轉中，於任一處理步驟中薄膜的寬度方向兩端部上均未觀察到翹曲或內折，也未觀察到可能伴隨於此等產生之薄膜的折痕或斷裂。 The polarizing film was continuously produced for 24 hours, and during the 24 hours of operation, no warpage or inflection was observed on both end portions in the width direction of the film in any of the treatment steps, and no accompanying observation was observed. A crease or break in the resulting film.
除了將以胚膜10為基準之膨潤處理、染色處理、第1交聯處理、第2交聯處理及第3交聯處理中的累積拉伸倍率設為6.0倍(第3交聯處理中的拉伸倍率為1.11倍)以外，其他與實施例1同樣，連續地實施偏光膜製造24小時。於24小時的運轉中，於任一處理步驟中雖均未觀察到薄膜的寬度方向兩端部的翹曲或內折，且未觀察到薄膜的折痕，但隨著將累積拉伸倍率設為較大的6.0倍，於24小時的運轉中產生1次薄膜的斷裂。 The cumulative stretching ratio in the swelling treatment, the dyeing treatment, the first crosslinking treatment, the second crosslinking treatment, and the third crosslinking treatment based on the embryonic film 10 was 6.0 times (in the third crosslinking treatment). The polarizing film was continuously produced for 24 hours in the same manner as in Example 1 except that the stretching ratio was 1.11 times. During the 24 hours of operation, warpage or inflection at both end portions in the width direction of the film was not observed in any of the treatment steps, and no crease of the film was observed, but the cumulative stretching ratio was set. For a larger 6.0 times, the film was broken once in 24 hours of operation.
除了將配置在第3交聯浴17c中之最終導引輥43中之 薄膜的圍包角設為135°以外，其他與實施例1同樣，連續地實施偏光膜製造24小時。於24小時的運轉中，於任一處理步驟中薄膜的寬度方向兩端部上均未觀察到翹曲或內折，也未觀察到可能伴隨於此等產生之薄膜的折痕或斷裂。 In addition to the final guide roller 43 to be disposed in the third crosslinking bath 17c The polarizing film was continuously produced for 24 hours in the same manner as in Example 1 except that the wrap angle of the film was 135°. During the 24 hours of operation, no warpage or inflection was observed at both end portions in the width direction of the film in any of the treatment steps, and no crease or breakage of the film which may accompany the film was observed.
除了將配置在第3交聯浴17c中之最終導引輥43中之薄膜的圍包角設為110°以外，其他與實施例1同樣，連續地實施偏光膜製造24小時。在剛從第3交聯浴17c拉出後之位置，大約5小時1次，會於薄膜的寬度方向兩端部上產生1mm寬的內折。但於24小時的運轉中，並未觀察到由此所導致之薄膜的斷裂。 The polarizing film was continuously produced for 24 hours in the same manner as in Example 1 except that the wrap angle of the film in the final guide roll 43 disposed in the third crosslinking bath 17c was 110°. Immediately after the pull-out from the third crosslinking bath 17c, the inner fold of 1 mm width was formed at both end portions in the width direction of the film at about 5 hours. However, during the 24 hours of operation, no breakage of the film caused thereby was observed.
除了將配置在第3交聯浴17c中之最終導引輥43中之薄膜的圍包角設為80°以外，其他與實施例1同樣，連續地實施偏光膜製造24小時。在剛從第3交聯浴17c拉出後之位置，大約2小時1次，會於薄膜的寬度方向兩端部上產生1mm寬的內折，由於在此狀態下通過軋輥55，會於薄膜的端部形成折痕，而產生薄膜的斷裂。薄膜的斷裂於24小時的運轉中產生2次。 The polarizing film was continuously produced for 24 hours in the same manner as in Example 1 except that the wrap angle of the film in the final guide roll 43 disposed in the third crosslinking bath 17c was 80°. At a position immediately after being pulled out from the third crosslinking bath 17c, about 1 hour, an inner fold of 1 mm width is formed at both end portions in the width direction of the film, and in this state, the roll 55 is passed through the film. The ends are creased to cause breakage of the film. The film breakage occurred twice during 24 hours of operation.
除了將配置在第3交聯浴17c中之最終導引輥43中之 薄膜的圍包角設為30°以外，其他與實施例1同樣，連續地實施偏光膜製造24小時。在剛從第3交聯浴17c拉出後之位置，於薄膜的寬度方向兩端部上經常產生2mm寬的內折，由於在此狀態下通過軋輥55，會於薄膜的端部形成折痕，而產生薄膜的斷裂。薄膜的斷裂於24小時的運轉中產生5次。 In addition to the final guide roller 43 to be disposed in the third crosslinking bath 17c The polarizing film was continuously produced for 24 hours in the same manner as in Example 1 except that the wrap angle of the film was 30°. At the position immediately after being pulled out from the third crosslinking bath 17c, an inner fold of 2 mm width is often formed at both end portions in the width direction of the film, and since the roll 55 is passed in this state, creases are formed at the end portions of the film. And the film breaks. The film breakage occurred 5 times during 24 hours of operation.
10‧‧‧由聚乙烯醇系樹脂所構成之胚膜 10‧‧‧Making membrane composed of polyvinyl alcohol resin
11‧‧‧拉出輥 11‧‧‧ Pull out the roller
13‧‧‧膨潤浴 13‧‧‧Swelling bath
15‧‧‧染色浴 15‧‧‧dye bath
17a‧‧‧第1交聯浴 17a‧‧‧1st cross-linking bath
17b‧‧‧第2交聯浴 17b‧‧‧2nd cross-linking bath
17c‧‧‧第3交聯浴 17c‧‧‧3rd cross-linking bath
19‧‧‧洗淨浴 19‧‧‧ Washing bath
21‧‧‧乾燥爐 21‧‧‧ drying oven
23‧‧‧偏光膜 23‧‧‧ polarizing film
30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、45、46、47‧‧‧導引輥 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47‧‧ ‧ guide rolls
50、51、52、53、54、55、56、57‧‧‧軋輥 50, 51, 52, 53, 54, 55, 56, 57‧‧ ‧ rolls
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| JP6910931B2 (en) * | 2016-12-02 | 2021-07-28 | 住友化学株式会社 | Method for manufacturing polarizing film and polarizing laminated film |
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