TWI618620B - Polarizing film and method for manufacturing - Google Patents

Polarizing film and method for manufacturing Download PDF

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Publication number
TWI618620B
TWI618620B TW102144136A TW102144136A TWI618620B TW I618620 B TWI618620 B TW I618620B TW 102144136 A TW102144136 A TW 102144136A TW 102144136 A TW102144136 A TW 102144136A TW I618620 B TWI618620 B TW I618620B
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film
treatment
air
moisture
blown
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TW102144136A
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TW201422410A (en
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網谷圭二
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住友化學股份有限公司
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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
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
    • B29C55/026—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets of preformed plates or sheets coated with a solution, a dispersion or a melt of thermoplastic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00634—Production of filters
    • B29D11/00644—Production of filters polarizing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
    • B29K2029/04—PVOH, i.e. polyvinyl alcohol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0034—Polarising
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Ophthalmology & Optometry (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Polarising Elements (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Laminated Bodies (AREA)

Abstract

在洗淨處理之後，進行水分去除處理，其係一邊對偏光薄膜施加200~1500N/m之張力且將薄膜捲附在設置於其單面之第一輥上，一邊對第一輥之相反側的薄膜表面吹送空氣以除去水分；接著，一邊將被空氣吹送的面捲附在第二輥上，一邊對第二輥之相反側的薄膜表面吹送空氣以除去水分，並藉由設置在各個空氣吹送位置附近之第一排出容器及第二排出容器，來回收被空氣所除去的水分。 After the washing treatment, a moisture removal treatment is performed by applying a tension of 200 to 1500 N/m to the polarizing film and attaching the film to the first roller provided on one side thereof while facing the opposite side of the first roller. The surface of the film is blown with air to remove moisture; then, while the surface of the film blown by the air is attached to the second roll, air is blown to the surface of the film on the opposite side of the second roll to remove moisture, and is disposed in each air. The first discharge container and the second discharge container near the blowing position recover the moisture removed by the air.

Description

偏光薄膜及偏光板之製造方法 Polarizing film and method for manufacturing polarizing plate

本發明係關於一種製造偏光薄膜之方法及在藉由此方法得到之偏光薄膜上貼合保護薄膜之偏光板之製造方法。 The present invention relates to a method for producing a polarizing film and a method for producing a polarizing plate in which a protective film is bonded to a polarizing film obtained by the method.

從過往以來，在偏光薄膜方面，一直使用於聚乙烯醇系樹脂薄膜吸附配向有碘等之二色性色素而成之物。該偏光薄膜通常是至少在單面、一般是在兩面透過黏著劑，貼合三醋酸纖維素等之保護薄膜來做為偏光板，可被使用於液晶電視、個人電腦用顯示器、行動電話等之液晶顯示裝置。 In the past, a polarizing film has been used in a polyvinyl alcohol-based resin film to adsorb a dichroic dye having an iodine or the like. The polarizing film is generally used as a polarizing plate by adhering a protective film such as cellulose triacetate to a single surface, usually on both sides, and is applied to a liquid crystal television, a display for a personal computer, a mobile phone, or the like. Liquid crystal display device.

偏光薄膜係藉由對於聚乙烯醇系樹脂薄膜進行膨潤處理、染色處理、拉伸處理、交聯處理(硼酸處理)及洗淨處理，最後藉由進行乾燥所製造而得。在像這樣的製造步驟中，聚乙烯醇系樹脂薄膜，在從各處理浴被拉出來而傳送至下一步驟之際，通常會使用軋輥等來進行薄膜表面的水分去除處理。 The polarizing film is obtained by subjecting a polyvinyl alcohol-based resin film to swelling treatment, dyeing treatment, stretching treatment, crosslinking treatment (boric acid treatment), and washing treatment, and finally drying. In the manufacturing process as described above, the polyvinyl alcohol-based resin film is usually subjected to moisture removal treatment on the surface of the film by using a roll or the like when it is taken out from the respective treatment baths and transported to the next step.

此水分去除處理之方法，例如，在特開2011-180576號公報(專利文獻1)段落〔0034〕已記載著一種水分除去方法，其係為了防止在製造偏光薄膜之時發生液體滴落，因而在從各處理浴拉出薄膜之際，使用夾輥等之除液輥，藉由氣刀來削落液滴，以從薄膜表面除去多餘的水分之方法。又，在特開2011-232016號公報(專利文獻2)揭示了一種水分去除處理裝置，其係用以對於在洗淨處理後輸送到乾燥爐之長尺狀薄片進行水分去除處理，並具備：供張開放置長尺狀薄片用之導引輥；從斜方向對著該已被張開放置於導引輥的長尺狀薄片吹送空氣的氣刀；以及回收因所吹送的空氣而飛濺的水分之排 氣室，專利文獻2也例示了將水分去除處理裝置使用於偏光薄膜之製造的例子。 In the method of removing moisture, a method of removing moisture is disclosed in paragraph [0034] of JP-A-2011-180576 (Patent Document 1), in order to prevent liquid dripping during the production of a polarizing film. When the film is pulled out from each of the processing baths, a liquid removing blade is used to remove the liquid droplets by using a liquid removing blade such as a nip roll to remove excess water from the surface of the film. Japanese Laid-Open Patent Publication No. 2011-232016 (Patent Document 2) discloses a moisture removal treatment device for performing a moisture removal treatment on a long-sized sheet conveyed to a drying furnace after a washing treatment, and comprising: a guide roller for opening a long-length sheet; an air knife that blows air from an obliquely facing long-length sheet that has been opened to the guide roller; and recovering a splash due to the blown air Water row In the gas chamber, Patent Document 2 also exemplifies an example in which a moisture removal treatment device is used for the production of a polarizing film.

如專利文獻1所示，因為當使用氣刀來進行水分去除處理時，可以有效地去除附著於薄膜表面的水分，又也可以除去塵埃等之異物，所以能夠製造缺陷少的薄膜。但是，在以氣刀吹落而除去薄膜表面的水滴之情況，有時會有飛散的水污染製造設備的情形。對於此點，如專利文獻2所示，可藉由設置回收水分之排氣室來防止因水之飛散所引起之污染。 As shown in Patent Document 1, when moisture removal treatment is performed using an air knife, moisture adhering to the surface of the film can be effectively removed, and foreign matter such as dust can be removed, so that a film having few defects can be produced. However, in the case where the water droplets on the surface of the film are removed by blowing with an air knife, there may be cases where scattered water contaminates the manufacturing equipment. In this regard, as shown in Patent Document 2, it is possible to prevent contamination due to scattering of water by providing an exhaust chamber for recovering moisture.

另一方面，偏光薄膜及偏光板被要求比以往更加薄片化，例如，以往係使用75μm厚的聚乙烯醇系樹脂薄膜來做為偏光薄膜之原始薄膜；近年則也有以厚度為60μm以下之原始薄膜來製造偏光薄膜。使用薄的原始薄膜，在被實施染色處理、拉伸處理、交聯處理及洗淨處理所得到的水濡濕的狀態下，當從氣刀將空氣吹送至薄的偏光薄膜以去除水分時，則會發生薄膜破裂，薄膜表面上一部分的水去除不良、附著有殘留的異物等，以致發生偏光薄膜外觀不佳的問題。 On the other hand, the polarizing film and the polarizing plate are required to be more flaky than in the related art. For example, a 75 μm thick polyvinyl alcohol resin film is conventionally used as a polarizing film. In recent years, the original film has a thickness of 60 μm or less. The film is used to manufacture a polarizing film. When a thin original film is used, in the state where the water obtained by the dyeing treatment, the stretching treatment, the crosslinking treatment, and the cleaning treatment is wet, when air is blown from the air knife to the thin polarizing film to remove moisture, The film breakage occurs, and a part of the surface of the film is poorly removed by water, and residual foreign matter adheres to the film, so that the appearance of the polarizing film is poor.

本發明係為解決上述之課題所完成者，其目的係在於：提供一種生產效率優異，且外觀良好的偏光薄膜之製造方法。本發明之另外一個課題係在於提供一種生產效率優異，且外觀良好的偏光板之製造方法。 The present invention has been made to solve the above problems, and an object of the invention is to provide a method for producing a polarizing film which is excellent in production efficiency and has a good appearance. Another object of the present invention is to provide a method for producing a polarizing plate which is excellent in production efficiency and has a good appearance.

本發明人發現：由薄片的聚乙烯醇系樹脂薄膜(原始薄膜)製造偏光薄膜時，藉由一邊如上述專利文獻2所揭示者那樣地將薄膜捲附在導引輥上，一邊對著該輥的相反側之薄膜表面吹送空氣，以排出容器回收被吹落的水來除去水分之方法，藉由對薄膜提供特定範圍的張力，可以外觀良好且生產效率良好地製造出相較於習知還要薄的偏光薄膜，並進一步地加入各種的檢討 研究，至此乃完成本發明。 The present inventors have found that when a polarizing film is produced from a polyvinyl alcohol-based resin film (original film) of a sheet, the film is wound on a guide roller as disclosed in Patent Document 2, and is opposed to the film. The method of blowing air from the opposite side of the roll to remove the water by discharging the blown water to the container, by providing a specific range of tension to the film, can be manufactured with good appearance and production efficiency. Also need a thin polarizing film and further add various reviews The research thus completes the present invention.

即，本發明係提供一種偏光薄膜的製造方法，其係在對於厚度為1~60μm之聚乙烯醇系樹脂薄膜，依序進行膨潤處理、染色處理、交聯處理及洗淨處理，且實施拉伸處理直到交聯處理結束為止；並且，於上述洗淨處理之後，進行水分去除處理之方法，其係一邊對薄膜提供200~1500N/m的張力且將薄膜捲附在其設置於其單面之第一輥上，一邊對第一輥之相反側的薄膜表面吹送空氣以去除水分；接著，一邊將被吹送空氣的面捲附在第二輥上，一邊對第二輥之相反側的薄膜表面吹送空氣以去除水分，並藉由設置於各個空氣吹送位置附近的第一排出容器及第二排出容器，來回收被空氣所除去的水分。 In other words, the present invention provides a method for producing a polarizing film which is subjected to swelling treatment, dyeing treatment, cross-linking treatment, and washing treatment for a polyvinyl alcohol-based resin film having a thickness of 1 to 60 μm. Stretching treatment until the end of the cross-linking treatment; and, after the above-described washing treatment, a method of removing moisture by applying a tension of 200 to 1500 N/m to the film and attaching the film to the one side thereof On the first roll, air is blown to the surface of the film on the opposite side of the first roll to remove moisture; then, the surface of the air blown is attached to the second roll while the film on the opposite side of the second roll The surface is blown with air to remove moisture, and the moisture removed by the air is recovered by the first discharge container and the second discharge container provided near the respective air blowing positions.

在此製造方法中，吹送到薄膜之空氣的風量可以是2~20m3/分。空氣係由氣刀前端的噴嘴對薄膜吹送，該噴嘴係可以按照：使得通過其吹出口前端的中心線相對於薄膜表面呈30~80°的角度，且使該吹出口前端至薄膜表面的距離成為1.5mm以下的方式配置而成。 In this manufacturing method, the amount of air blown into the film may be 2 to 20 m 3 /min. The air is blown to the film by a nozzle at the front end of the air knife, and the nozzle can be such that the center line passing through the front end of the air outlet is at an angle of 30 to 80° with respect to the surface of the film, and the distance from the front end of the air outlet to the surface of the film It is configured to be 1.5 mm or less.

回收所去除的水分之排出容器，可以具有開口部，且可按照使得該開口部至薄膜表面距離成為2mm以下的方式被配置而成。 The discharge container for recovering the removed moisture may have an opening, and may be disposed such that the distance from the opening to the surface of the film is 2 mm or less.

在本發明之製造方法中，可於在如上述實施水分去除處理之後，再進行乾燥處理。在此情況，除了在水分去除處理之前所設置的軋輥之外，乾燥爐的內部或乾燥爐之後方設置軋輥也是有效的，在此形態中之水分去除處理及乾燥處理，可以是藉由以設置在此等處理之前後的一組軋輥，於對薄膜施加200~800N/m的張力之狀態下進行。 In the production method of the present invention, the drying treatment may be carried out after the moisture removal treatment as described above. In this case, in addition to the rolls provided before the moisture removal treatment, it is also effective to set the rolls inside the drying furnace or after the drying furnace, and the moisture removal treatment and the drying treatment in this form may be set by The set of rolls before and after the treatment were carried out while applying a tension of 200 to 800 N/m to the film.

又，本發明也提供一種偏光板之製造方法，其係使用紫外線硬化型之黏著劑，將保護薄膜貼合於藉由包含乾燥處理之上述方法所製造的偏光薄膜上。 Moreover, the present invention also provides a method for producing a polarizing plate which is bonded to a polarizing film produced by the above-described method including drying treatment using an ultraviolet curable adhesive.

根據本發明，因為即使在原始薄膜為薄的情況下，也不會發生 薄膜之破裂、除水不良等，可以製造外觀良好的偏光薄膜，所以採用此偏光薄膜之偏光板為生產效率優異、缺陷少、並且能成為良好品質之物。 According to the present invention, it does not occur even in the case where the original film is thin. A polarizing film having a good appearance can be produced by rupturing a film or removing water, and the polarizing plate using the polarizing film is excellent in production efficiency, has few defects, and can be a good quality.

10‧‧‧原始薄膜 10‧‧‧Original film

11‧‧‧輸送輥 11‧‧‧Conveying roller

13‧‧‧膨潤槽 13‧‧‧Swelling trough

15‧‧‧染色槽 15‧‧‧Dyeing tank

17‧‧‧交聯槽 17‧‧‧ Crosslinking slot

19‧‧‧洗淨槽 19‧‧‧cleaning trough

21‧‧‧軋輥 21‧‧‧ Rolls

23‧‧‧水分去除裝置 23‧‧‧Water removal device

25‧‧‧乾燥爐 25‧‧‧ drying oven

27‧‧‧軋輥 27‧‧‧ Rolls

30‧‧‧偏光薄膜 30‧‧‧Polarized film

40‧‧‧第一輥 40‧‧‧First roll

42‧‧‧第一氣刀 42‧‧‧First air knife

44‧‧‧第一排出容器 44‧‧‧First discharge container

46‧‧‧第二輥 46‧‧‧second roll

48‧‧‧第二氣刀 48‧‧‧second air knife

50‧‧‧第二排出容器 50‧‧‧Second discharge container

第1圖係顯示偏光薄膜的製造方法中，裝置的合適配置例之截面示意圖。 Fig. 1 is a schematic cross-sectional view showing a suitable arrangement example of the device in the method for producing a polarizing film.

第2圖係顯示水分去除裝置23內的配置例之截面示意圖。 Fig. 2 is a schematic cross-sectional view showing an arrangement example in the moisture removing device 23.

第3圖係顯示水分去除裝置23內合適的配置條件之截面示意圖。 Fig. 3 is a schematic cross-sectional view showing suitable arrangement conditions in the moisture removing device 23.

本發明係對聚乙烯醇系樹脂薄膜依序進行膨潤處理、染色處理、交聯處理及洗淨處理，且實施拉伸處理直到交聯處理結束為止，從而製造偏光薄膜。又，於洗淨處理之後，再實施水分去除處理。根據本發明實施水分去除處理來製造偏光薄膜之方法，適合使用在水分去除處理之後，實施乾燥處理所得到的偏光薄膜上，透過紫外線硬化型的黏著劑，貼合保護薄膜以製造偏光板之方法中。以下、參照適當圖式來詳細地說明本發明。 In the present invention, the polyvinyl alcohol-based resin film is sequentially subjected to a swelling treatment, a dyeing treatment, a crosslinking treatment, and a washing treatment, and the stretching treatment is performed until the crosslinking treatment is completed, thereby producing a polarizing film. Further, after the washing treatment, the moisture removal treatment is performed. According to the method of the present invention for producing a polarizing film by performing a moisture removal treatment, it is preferable to use a method of manufacturing a polarizing plate by applying a protective film to a polarizing film obtained by performing a drying treatment after a moisture removal treatment, and by adhering a UV-curable adhesive. in. Hereinafter, the present invention will be described in detail with reference to the appropriate drawings.

〔偏光薄膜之製造方法〕 [Method of Manufacturing Polarized Film]

具體而言，偏光薄膜為在聚乙烯醇系樹脂薄膜吸附配向有二色性色素之物。作為原料之聚乙烯醇系樹脂通常是藉由將聚乙酸乙烯酯系樹脂予以皂化而得。該皂化度通常是85莫耳%以上，較佳為90莫耳%以上，更佳為99莫耳%以上。聚乙酸乙烯酯系樹脂，例如，除了乙酸乙烯酯的單獨聚合物之聚乙酸乙烯酯之外，舉例來說，其可以是乙酸乙烯酯、與能和它共聚合之其他的單體之共聚物等。能與乙酸乙烯酯共聚合之其他的單體，舉例來說，其可以是不飽和羧酸類、烯烴類、不飽和磺酸類、乙烯基醚類等。聚乙烯醇系樹脂之 聚合度通常是1000~10000左右，較佳者為1500~5000左右。 Specifically, the polarizing film is a material in which a dichroic dye is adsorbed and aligned in a polyvinyl alcohol-based resin film. The polyvinyl alcohol-based resin as a raw material is usually obtained by saponifying a polyvinyl acetate-based resin. The degree of saponification is usually 85 mol% or more, preferably 90 mol% or more, more preferably 99 mol% or more. A polyvinyl acetate-based resin, for example, in addition to polyvinyl acetate of a single polymer of vinyl acetate, for example, it may be a copolymer of vinyl acetate and other monomers copolymerizable therewith. Wait. Other monomers which can be copolymerized with vinyl acetate may be, for example, unsaturated carboxylic acids, olefins, unsaturated sulfonic acids, vinyl ethers and the like. Polyvinyl alcohol resin The degree of polymerization is usually about 1000 to 10,000, preferably about 1500 to 5,000.

聚乙烯醇系樹脂可以是被改質，例如，可使用經以醛類改質的聚乙烯基甲醛、聚乙烯基縮醛、聚乙烯基縮丁醛等。 The polyvinyl alcohol-based resin may be modified. For example, polyvinyl formaldehyde modified with an aldehyde, polyvinyl acetal, polyvinyl butyral or the like may be used.

在本發明中係使用厚度為1~60μm的聚乙烯醇系樹脂薄膜做為偏光薄膜的原始薄膜。薄膜的厚度較佳為約20~60μm，更佳者為約30~60μm。在工業上，實際上有時也使用薄膜的寬度為約1500~6000mm之物。 In the present invention, a polyvinyl alcohol-based resin film having a thickness of 1 to 60 μm is used as an original film of a polarizing film. The thickness of the film is preferably from about 20 to 60 μm, more preferably from about 30 to 60 μm. In the industry, the width of the film is sometimes about 1500 to 6000 mm.

偏光薄膜係藉由對於上述的由聚乙烯醇系樹脂構成的原始薄膜，依序進行膨潤處理、染色處理、交聯處理及洗淨處理之溶液處理，並於交聯處理中及視需要而定在交聯處理之前，進行薄膜之單軸拉伸，最後再加以乾燥而得到者。交聯處理中進行的單軸拉伸為濕式拉伸，雖然在那之前的膨潤處理及染色處理時進行單軸拉伸的情況也是濕式拉伸，然而在膨潤處理之前也可以乾式來進行單軸拉伸。 The polarizing film is subjected to a solution treatment of swelling, dyeing, cross-linking, and washing treatment on the original film made of the above polyvinyl alcohol-based resin, and is subjected to crosslinking treatment and optionally. Before the cross-linking treatment, the film is uniaxially stretched and finally dried to obtain. The uniaxial stretching performed in the crosslinking treatment is wet stretching, and although the uniaxial stretching at the time of the swelling treatment and the dyeing treatment before that is also wet stretching, it may be carried out dry before the swelling treatment. Uniaxial stretching.

如這種的單軸拉伸可以是只以一個步驟來進行，也可以二個以上的步驟來進行；可以採用眾所皆知的拉伸方法。拉伸方法的具體例子，舉例來說，有在搬運薄膜的二個軋輥之間，使其具有轉速差地進行拉伸之輥間拉伸，如日本專利第2731813號公報上所記載的熱輥拉伸、拉幅機拉伸等。步驟的順序，基本上係如上述，對於處理浴的數量或處理條件等沒有限制。 Such uniaxial stretching may be carried out in only one step, or may be carried out in two or more steps; a well-known stretching method may be employed. Specific examples of the stretching method include, for example, stretching between rolls between the two rolls for conveying the film so as to have a difference in rotation speed, as described in Japanese Patent No. 2731813. Stretching, tenter stretching, etc. The order of the steps is basically as described above, and there is no limitation on the number of processing baths, processing conditions, and the like.

又，可以為了別的目的而追加上述以外的處理。可追加的處理之例子，舉例來說，有可於交聯處理後進行的不含硼酸之碘化物水溶液之浸漬處理(碘化物處理)，不含硼酸但含有氯化鋅等之水溶液的浸漬處理(鋅處理)。 Further, processing other than the above may be added for another purpose. Examples of the additional treatment include, for example, immersion treatment (iodide treatment) of an aqueous solution of boric acid-free iodide which can be carried out after the crosslinking treatment, and immersion treatment of an aqueous solution containing no boric acid but containing zinc chloride or the like. (Zinc treatment).

第1圖為顯示關於本發明偏光薄膜之製造方法中所使用的製造裝置之較佳的配置例之截面示意圖。該製造裝置係按照使得：由聚乙烯醇系樹脂構成的原始薄膜10從輸送輥11被捲出來，依序通過膨潤槽13、染色槽15、交聯槽17及洗淨槽19，接著輸送到水分去除裝置23，最後通過乾燥爐25 的方式所構成的。在第1圖中雖然未明示，然而在交聯槽17或在它之前可實施單軸拉伸。又，在第1圖中，雖然分別例示了膨潤槽13、染色槽15、交聯槽17及洗淨槽19之每一槽的設計例；然而視需要而定，也可以對於某一個處理設計複數個處理槽。所製造的偏光薄膜30就這樣直接輸送到貼合下個保護薄膜之步驟中。以下，針對本發明中所實施的處理進行說明。 Fig. 1 is a schematic cross-sectional view showing a preferred arrangement example of a manufacturing apparatus used in the method for producing a polarizing film of the present invention. The manufacturing apparatus is such that the original film 10 made of a polyvinyl alcohol-based resin is taken up from the conveying roller 11, sequentially passes through the swelling tank 13, the dyeing tank 15, the crosslinking tank 17, and the washing tank 19, and then conveyed to Moisture removal device 23, finally passed through drying oven 25 The way it is composed. Although not explicitly shown in Fig. 1, uniaxial stretching can be carried out before or before the crosslinking groove 17. Moreover, in the first drawing, a design example of each of the swelling tank 13, the dyeing tank 15, the crosslinking tank 17, and the washing tank 19 is exemplified; however, it may be designed for a certain treatment as needed. Multiple processing slots. The polarized film 30 thus produced is directly conveyed to the step of bonding the next protective film. Hereinafter, the processing performed in the present invention will be described.

(膨潤處理) (swelling treatment)

膨潤處理係進行：除去聚乙烯醇系樹脂薄膜表面之異物，除去薄膜中之可塑劑，提供後續染色處理之易染色性，為了薄膜之可塑化等之目的而使其與水接觸。膨潤處理的條件係按照在可以達成該等目的的範圍，且不發生薄膜之喪失透明度與極端溶解等之不良現象的範圍來決定的。 The swelling treatment is carried out by removing foreign matter on the surface of the polyvinyl alcohol-based resin film, removing the plasticizer in the film, providing easy dyeing property for subsequent dyeing treatment, and bringing it into contact with water for the purpose of plasticization of the film or the like. The conditions of the swelling treatment are determined in such a range that the purpose can be achieved, and the extent of the loss of transparency, extreme dissolution, and the like of the film does not occur.

在對於聚乙烯醇系樹脂構成的原始薄膜實施最初的膨潤處理之情況，例如，可藉由將薄膜浸漬於溫度10~50℃左右、較佳為20~40℃左右之處理浴中來進行。薄膜的浸漬時間，較佳者為30~300秒左右，更佳者為60~240秒左右。對於已預先在大氣中拉伸的聚乙烯醇系樹脂薄膜實施膨潤處理的情況，例如，可以藉由將薄膜浸漬於溫度20~70℃左右、較佳為30~60℃左右的處理浴中來進行。薄膜的浸漬時間，較佳者為30~300秒左右，更佳者為60~240秒左右。 The first swelling treatment of the original film composed of the polyvinyl alcohol-based resin can be carried out, for example, by immersing the film in a treatment bath having a temperature of about 10 to 50 ° C, preferably about 20 to 40 ° C. The immersion time of the film is preferably about 30 to 300 seconds, and more preferably about 60 to 240 seconds. When the polyvinyl alcohol-based resin film which has been previously stretched in the air is subjected to a swelling treatment, for example, the film may be immersed in a treatment bath having a temperature of about 20 to 70 ° C, preferably about 30 to 60 ° C. get on. The immersion time of the film is preferably about 30 to 300 seconds, and more preferably about 60 to 240 seconds.

在膨潤處理中，由於聚乙烯醇系樹脂薄膜會在寬度方向膨潤，致使容易發生薄膜形成皺褶等之問題，因而較佳者為使用開幅輥(擴展輥)、螺旋輥、中凸輥、導布器、彎曲桿、拉幅機拑具等之眾所皆知的寬度擴展裝置，藉以消除薄膜之皺褶且一併輸送薄膜。又，為了使浴中輸送薄膜達到安定化之目的，可以使用水中灑水器來制控膨潤槽13中之水流，與EPC裝置(Edge Position Control裝置：偵測薄膜的端部，以防止薄膜扭曲的裝置)等一起併用是有用的。 In the swelling treatment, since the polyvinyl alcohol-based resin film swells in the width direction, the problem of wrinkles such as film formation is likely to occur, and therefore, it is preferable to use an opening roll (expansion roll), a spiral roll, a center roll, A width expansion device known as a guide, a bending rod, a tenter, and the like, thereby eliminating the wrinkles of the film and transporting the film together. Moreover, in order to achieve the purpose of stabilization of the transport film in the bath, an aqueous sprinkler can be used to control the flow of water in the swelling tank 13, and an EPC device (Edge Position Control device: detecting the end of the film to prevent film distortion It is useful to use together.

在膨潤處理中，即使是在薄膜的輸送方向上，薄膜也是會膨潤擴大，所以在不對薄膜積極進行拉伸的情況，由於輸送方向上之薄膜未放鬆，所以較佳者為：例如，在膨潤槽13的前後設置有控制輸送輥的轉速度等之構件。又，在依序對於原始薄膜實施膨潤處理、染色處理及交聯處理的情況，可以在膨潤處理中進行單軸拉伸，該情況的拉伸倍率通常是1.2~3倍，較佳為1.3~2.5倍。 In the swelling treatment, even if the film is swollen and expanded in the conveying direction of the film, the film is not stretched actively, and since the film in the conveying direction is not relaxed, it is preferably: for example, in swelling The front and rear of the groove 13 are provided with members for controlling the rotation speed of the conveying roller and the like. Further, in the case where the original film is sequentially subjected to swelling treatment, dyeing treatment, and crosslinking treatment, uniaxial stretching may be performed in the swelling treatment, and the stretching ratio in this case is usually 1.2 to 3 times, preferably 1.3 to 2.5 times.

在膨潤槽13所使用的處理浴中，除了純水之外，可以使用添加有約0.01~10重量%的範圍之硼酸(特開平10-153709號公報)、氯化物(特開平06-281816號公報)、無機酸、無機鹽、水溶性有機溶媒、醇類等而成的水溶液。 In the treatment bath used in the swell tank 13, in addition to pure water, boric acid (Japanese Laid-Open Patent Publication No. Hei 10-153709) and chloride (Japanese Patent Laid-Open No. Hei 06-281816) can be used in an amount of about 0.01 to 10% by weight. An aqueous solution of a mineral acid, an inorganic salt, a water-soluble organic solvent, an alcohol, or the like.

(染色處理) (dyeing treatment)

染色處理係以讓聚乙烯醇系樹脂薄膜吸附二色性色素為目的；例如，可以將薄膜浸漬於含有碘及水溶性二色性染料等之二色性色素的處理浴中來進行。染色處理的條件係按照在可以達成該等目的的範圍、且不會使聚乙烯醇系樹脂薄膜發生極端的溶解、或喪失透明度等之不合適現象的範圍內來決定的。 The dyeing treatment is carried out for the purpose of adsorbing a dichroic dye on a polyvinyl alcohol-based resin film; for example, the film may be immersed in a treatment bath containing a dichroic dye such as iodine or a water-soluble dichroic dye. The conditions of the dyeing treatment are determined within a range in which the above-described objects can be achieved without causing extreme dissolution of the polyvinyl alcohol-based resin film or loss of transparency or the like.

於使用碘來做為二色性色素的情況，在處理浴(染色浴)中，例如，可以使用重量比濃度：碘/碘化鉀/水=約0.003~0.2/約0.1~10/100的水溶液。也可以使用碘化鋅等之其他的碘化物來代替碘化鉀，也可以將碘化鉀與其他的碘化物一起併用。又，碘化物以外的化合物，例如，也可以共存有硼酸、氯化鋅、鹽化鈷等。於添加硼酸的情況，在含有碘的特點上係與後述的交聯處理有所區別，只要是水溶液中相對於100重量份的水計為含有約0.003重量份以上的碘，即可以視為染色浴了。於浸漬薄膜時之染色浴的溫度宜為10~45℃左右，較佳為20~35℃；薄膜的浸漬時間宜為30~600秒左右較佳為60~300 秒。 In the case where iodine is used as the dichroic dye, in the treatment bath (dye bath), for example, an aqueous solution having a weight ratio of iodine/potassium iodide/water = about 0.003 to 0.2/about 0.1 to 10/100 can be used. Instead of potassium iodide, other iodides such as zinc iodide may be used, and potassium iodide may be used in combination with other iodides. Further, for example, boric acid, zinc chloride, cobaltated cobalt or the like may be present in the compound other than the iodide. In the case of adding boric acid, the iodine-containing property is different from the crosslinking treatment described later, and it can be regarded as dyeing as long as it contains about 0.003 parts by weight or more of iodine in an aqueous solution with respect to 100 parts by weight of water. Bathed. The temperature of the dye bath when immersing the film is preferably about 10 to 45 ° C, preferably 20 to 35 ° C; the immersion time of the film is preferably about 30 to 600 seconds, preferably 60 to 300. second.

使用水溶性二色性染料做為二色性色素的情況，在處理浴中，可以使用重量比濃度：二色性染料/水=約0.001~0.1/100的水溶液。在該處理浴中，也可以共存有染色助劑等；例如，可以含有硫酸鈉等之無機鹽或界面活性劑等。又，二色性染料，可以是單獨使用，也可以二種類以上的二色性染料一起併用。浸漬薄膜時之染色浴的溫度宜為20~80℃左右，較佳為30~70℃；薄膜的浸漬時間宜為30~600秒左右，較佳為60~300秒。 When a water-soluble dichroic dye is used as the dichroic dye, an aqueous solution having a weight ratio of dichroic dye/water = about 0.001 to 0.1/100 can be used in the treatment bath. In the treatment bath, a dyeing assistant or the like may be coexisted; for example, an inorganic salt such as sodium sulfate or a surfactant may be contained. Further, the dichroic dye may be used singly or in combination of two or more kinds of dichroic dyes. The temperature of the dye bath when immersing the film is preferably about 20 to 80 ° C, preferably 30 to 70 ° C; the immersion time of the film is preferably about 30 to 600 seconds, preferably 60 to 300 seconds.

對聚乙烯醇系樹脂薄膜依序進行膨潤處理、染色處理、交聯處理時，通常是在染色槽進行薄膜的拉伸。薄膜的拉伸係以使設置於染色槽前後之軋輥產生轉速差等方法來進行。到染色處理為止之累積拉伸倍率(在染色處理以前沒有拉伸步驟的情況則為染色處理的拉伸倍率)，通常係1.6~4.5倍，較佳為1.8~4倍。拉伸倍率為小於1.6倍時，則就會有薄膜的破裂頻率變多，產率惡化的傾向。 When the polyvinyl alcohol-based resin film is sequentially subjected to swelling treatment, dyeing treatment, or cross-linking treatment, the film is usually stretched in a dyeing bath. The stretching of the film is carried out by a method such as a difference in the number of rotations of the rolls provided before and after the dyeing tank. The cumulative stretching ratio until the dyeing treatment (the stretching ratio of the dyeing treatment in the case where there is no stretching step before the dyeing treatment) is usually 1.6 to 4.5 times, preferably 1.8 to 4 times. When the draw ratio is less than 1.6 times, the cracking frequency of the film increases, and the yield tends to deteriorate.

此外，於染色處理中，為了與膨潤處理同樣地消除薄膜之皺褶並且輸送聚乙烯醇系樹脂薄膜，則可以在染色槽15的內部及/或其出入口設置開幅輥(擴展輥)、螺旋輥、中凸輥、導布器、彎曲桿等。 Further, in the dyeing treatment, in order to eliminate the wrinkles of the film and transport the polyvinyl alcohol-based resin film in the same manner as the swelling treatment, an opening roller (expansion roller) or a spiral may be provided inside the dyeing tank 15 and/or its inlet and outlet. Rollers, centering rolls, guides, bending rods, etc.

(交聯處理) (cross-linking processing)

交聯處理係以藉由交聯來達成耐水化及色相調整(防止薄膜染上藍色等)等為目的；相對於100重量份的水而言，可以藉由在含有1~10重量份的硼酸之處理浴中，浸漬該已為二色性色素所染色的聚乙烯醇系樹脂薄膜來進行。在染色處理中使用二色性色素為碘的情況，處理浴較佳為除了硼酸以外尚含有碘化物；相對於100重量份的水而言，它的量可以設定為1~30重量份。碘化物，舉例來說，其可以是碘化鉀、碘化鋅等。又，碘化物以外的化合物，例如，可以共存有氯化鋅、鹽化鈷、鹽化鋯、硫代硫酸鈉、亜硫酸鉀、硫酸鈉 等。另外，用以耐水化之交聯處理，有時也被稱呼為耐水化處理、交聯處理、固定化處理等名稱。又，用以色相調整之交聯處理，有的情況也被稱為補色處理、再染色處理等名稱。 The crosslinking treatment is carried out by crosslinking to achieve water resistance and hue adjustment (preventing the film from being dyed with blue, etc.), and may be contained in an amount of 1 to 10 parts by weight per 100 parts by weight of water. In the treatment bath of boric acid, the polyvinyl alcohol-based resin film dyed with the dichroic dye is impregnated. In the case where the dichroic dye is used as the iodine in the dyeing treatment, the treatment bath preferably contains iodide in addition to boric acid; and the amount thereof may be set to 1 to 30 parts by weight based on 100 parts by weight of water. The iodide may be, for example, potassium iodide, zinc iodide or the like. Further, compounds other than the iodide may, for example, coexist with zinc chloride, cobaltated cobalt, zirconium salt, sodium thiosulfate, potassium sulfonate, sodium sulfate. Wait. Further, the crosslinking treatment for hydration resistance may be referred to as a name such as a water resistance treatment, a crosslinking treatment, or an immobilization treatment. Further, the cross-linking process for adjusting the hue is also referred to as a term such as a complementary color process or a re-staining process.

交聯處理可以隨著該目的而適當地變更硼酸及碘化物的濃度、以及處理浴的溫度。用以耐水化之交聯處理、及用以色相調整之交聯處理，沒有什麼特別區別，可於以下之條件下實施。交聯處理的目的是以交聯致使耐水化，在對於聚乙烯醇系樹脂構成的原始薄膜，依序實施膨潤處理、染色處理及交聯處理的情況，處理浴可以是重量比濃度：硼酸/碘化物/水=3~10/1~20/100的水溶液。視需要而定，也能以使用乙二醛及戊二醛等之交聯劑來代替硼酸，也能以硼酸與交聯劑一起併用。處理浴的溫度通常是50~70℃左右，較佳為53~65℃，薄膜的浸漬時間通常是10~600秒左右，較佳為20~300秒，更佳為20~200秒。又，在對於已預先拉伸的聚乙烯醇系樹脂薄膜依序實施染色處理及交聯處理的情況下，交聯處理浴的溫度通常是50~85℃左右，較佳為55~80℃。 The crosslinking treatment can appropriately change the concentration of boric acid and iodide and the temperature of the treatment bath in accordance with the purpose. The cross-linking treatment for hydration resistance and the cross-linking treatment for hue adjustment are not particularly different and can be carried out under the following conditions. The purpose of the cross-linking treatment is to achieve water resistance by crosslinking, and in the case of the original film composed of the polyvinyl alcohol-based resin, the swelling treatment, the dyeing treatment, and the crosslinking treatment are sequentially performed, and the treatment bath may be a weight ratio: boric acid/ Iodide/water = 3~10/1~20/100 aqueous solution. It is also possible to use a crosslinking agent such as glyoxal or glutaraldehyde instead of boric acid as needed, or to use boric acid together with a crosslinking agent. The temperature of the treatment bath 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. In the case where the dyeing treatment and the crosslinking treatment are sequentially performed on the polyvinyl alcohol-based resin film which has been stretched in advance, the temperature of the crosslinking treatment bath is usually about 50 to 85 ° C, preferably 55 to 80 ° C.

在進行以耐水化為目的之交聯處理後，也可以進行以色相調整為目的之交聯處理。以該色相調整為目的之交聯處理的條件，例如，在染色處理中使用的二色性染料為碘的情況，可以使用重量比濃度：硼酸/碘化物/水=1~5/3~30/100的處理浴。處理浴的溫度通常是10~45℃左右；薄膜的浸漬時間通常是1~300秒左右，較佳為2~100秒。 After the crosslinking treatment for the purpose of water resistance, a crosslinking treatment for the purpose of color adjustment can also be performed. The conditions of the crosslinking treatment for the purpose of the hue adjustment, for example, when the dichroic dye used in the dyeing treatment is iodine, the weight ratio concentration: boric acid/iodide/water = 1 to 5/3 to 30 can be used. /100 treatment bath. The temperature of the treatment bath is usually about 10 to 45 ° C; the immersion time of the film is usually about 1 to 300 seconds, preferably 2 to 100 seconds.

此等之交聯處理可以進行複數次，通常是進行2~5次。在此情況，所使用的各交聯處理浴之組成及溫度，只要是在上述的範圍內，可以是相同的，也可以是不同的。在以交聯致使耐水化用的交聯處理及色相調整用的交聯處理，也可以分別以複數個步驟來進行。 These cross-linking treatments can be performed multiple times, usually 2 to 5 times. In this case, the composition and temperature of each of the crosslinking treatment baths used may be the same or different as long as they are within the above range. The crosslinking treatment for crosslinking treatment and the phase adjustment for coloring by crosslinking may be carried out in a plurality of steps.

(洗淨處理) (washing treatment)

洗淨處理係在交聯處理之後，為了達成去除附著在聚乙烯醇系樹脂薄膜上之多餘的硼酸及碘等之藥劑的目的而進行的。洗淨處理，例如，為了耐水化及/或色調調整，可藉由將已交聯處理的聚乙烯醇系樹脂薄膜浸漬於水中，或以灑水器把水噴霧於薄膜上，或者將該等一起併用來進行。 The washing treatment is carried out for the purpose of removing excess boric acid and iodine adhering to the polyvinyl alcohol-based resin film after the crosslinking treatment. For the washing treatment, for example, in order to prevent hydration and/or color tone adjustment, the polyvinyl alcohol-based resin film which has been cross-linked may be immersed in water, or water may be sprayed onto the film by a sprinkler, or the like. Together and used to carry out.

在第1圖中係顯示將聚乙烯醇系樹脂薄膜浸漬於水中來進行洗淨處理的情況之例子。洗淨處理中之水的溫度通常是2~40℃左右；浸漬時間為2~120秒左右。另外，即使在交聯處理及洗淨處理中，為了達成去除皺褶並且輸送聚乙烯醇系樹脂薄膜之目的，也可以使用開幅輥。 In the first drawing, an example in which a polyvinyl alcohol-based resin film is immersed in water to perform a washing treatment is shown. The temperature of the water in the washing treatment is usually about 2 to 40 ° C; the immersion time is about 2 to 120 seconds. Further, even in the cross-linking treatment and the washing treatment, an opening roller can be used for the purpose of removing wrinkles and transporting the polyvinyl alcohol-based resin film.

(水分去除處理) (water removal treatment)

本發明所進行的聚乙烯醇系樹脂薄膜之水分去除處理，為了達成去除薄膜表面的水及異物等之附著物的目的，可以藉由使用氣刀吹送空氣到薄膜表面來進行。具體而言，經過洗淨處理的聚乙烯醇系樹脂薄膜，係在施加預定的張力之狀態下被輸送至水分去除裝置23，藉由設置於裝置內的氣刀吹送空氣至薄膜表面來實施水分去除處理的。以下，針對本發明所進行的水分去除處理，一邊適當地參照第2圖及第3圖，一邊依序進行說明。 The water removal treatment of the polyvinyl alcohol-based resin film according to the present invention can be carried out by blowing air to the surface of the film by using an air knife for the purpose of removing deposits of water and foreign matter on the surface of the film. Specifically, the polyvinyl alcohol-based resin film which has been subjected to the cleaning treatment is transported to the moisture removing device 23 while applying a predetermined tension, and the air is blown to the surface of the film by the air knife provided in the device to carry out the moisture. Removed from the treatment. Hereinafter, the water removal treatment performed by the present invention will be sequentially described with reference to FIGS. 2 and 3 as appropriate.

第2圖為顯示水分去除裝置23內之裝置的配置例之截面示意圖。參照第2圖，在水分去除裝置23內配置有二組的輥、氣刀及排出容器之套組，藉以對於薄膜的每一單面進行水分去除。輸送至水分去除裝置23內的聚乙烯醇系樹脂薄膜，一邊將薄膜捲附在設置於其單面的第一輥40，一邊將來自第一氣刀42的空氣吹送至第一輥之相反側的薄膜表面；接著，一邊將被空氣吹送的面捲附在設置於輸送方向下游的第二輥46，一邊將來自第二氣刀48的空氣吹送至第二輥之相反側的薄膜表面來進行。經由空氣所除去的水係藉由設置在空氣吹送位置附近的第一排出容器44及第二排出容器50來分別回收。 Fig. 2 is a schematic cross-sectional view showing an arrangement example of the apparatus in the moisture removing device 23. Referring to Fig. 2, a set of two sets of rolls, an air knife, and a discharge container are disposed in the moisture removing device 23, whereby moisture removal is performed on each of the single faces of the film. The polyvinyl alcohol-based resin film that has been transported to the moisture removing device 23 is blown to the first roller 40 provided on one surface thereof, and the air from the first air knife 42 is blown to the opposite side of the first roller. Then, the surface of the film is blown by the second roller 46 disposed downstream of the conveying direction, and the air from the second air knife 48 is blown to the surface of the film on the opposite side of the second roller. . The water removed by the air is separately recovered by the first discharge container 44 and the second discharge container 50 provided near the air blowing position.

第3圖係顯示適合於進行上述的水分去除處理之水分去除裝置 內的配置條件之截面示意圖。以下，參照第3圖來說明。第一氣刀42係被配置在薄膜接觸第一輥40前的薄膜輸送方向之下游側空間上，而從薄膜輸送方向的下游側向上游側吹送空氣。第一氣刀42是從位於前端的噴嘴將空氣吹送出來之物；上述的噴嘴係按照使得：通過該吹出口前端的中心線(第3圖之點線)成為從第一輥40的切線起30~80°的角度(第3圖之∠θ)的方式來配置。又，配置成使得：上述的吹出口前端到薄膜表面的距離成為1.5mm以下。當氣刀被設置的角度、及到薄膜表面的距離為在上述的範圍時，可以抑制由於空氣而產生的薄膜破裂，又能夠以良好的效率來進行水分去除。 Fig. 3 shows a moisture removing device suitable for performing the above-described moisture removal treatment A schematic cross-sectional view of the configuration conditions within. Hereinafter, it will be described with reference to FIG. The first air knife 42 is disposed on the downstream side space in the film transport direction before the film contacts the first roller 40, and blows air from the downstream side to the upstream side in the film transport direction. The first air knife 42 is a material that blows air from a nozzle located at the front end; the nozzle is such that the center line (the dotted line of FIG. 3) passing through the front end of the air outlet is from the tangent of the first roller 40. The angle is 30~80° (第 θ in Figure 3). Further, the distance from the end of the above-mentioned outlet to the surface of the film is set to be 1.5 mm or less. When the angle at which the air knife is set and the distance to the surface of the film are within the above range, the film breakage due to the air can be suppressed, and the moisture can be removed with good efficiency.

上述的第一排出容器44係按照使得：在通過第一輥40上的薄膜之中，被空氣吹到的位置之附近，排出容器的開口部為向著氣刀側的形態加以配置而成的。此時，可以按照使得：從排出容器的開口部至輥上的薄膜表面為止之距離成為0.3~2mm的方式加以配置。當排出容器與薄膜的距離為2mm以下時，由氣刀吹出的空氣到達薄膜之後，附著在薄膜的水同時圓滑地排出而進入容器內，因而可以效率良好地除去水並加以回收。又，當排出容器與薄膜的距離為0.3mm以上，可以藉由排出容器與薄膜之接觸來防止薄膜破裂。排出容器內所回收的水係經由排出容器內的吸引，而從內壁被收集、通過廢液溝而被排出到廢液管路。 The first discharge container 44 described above is disposed such that the opening of the discharge container is disposed toward the air knife side in the vicinity of the position where the air is blown through the film on the first roller 40. In this case, the distance from the opening of the discharge container to the surface of the film on the roll may be set to be 0.3 to 2 mm. When the distance between the discharge container and the film is 2 mm or less, the air blown by the air knife reaches the film, and the water adhering to the film is smoothly discharged into the container, so that the water can be efficiently removed and recovered. Further, when the distance between the discharge container and the film is 0.3 mm or more, the film can be prevented from being broken by the contact of the discharge container with the film. The water recovered in the discharge container is collected from the inner wall through the suction in the discharge container, and is discharged to the waste liquid pipe through the waste liquid groove.

第二輥46、第二氣刀48及第二排出容器50係可以分別與上述第一輥40、第一氣刀42及第一排出容器44相同地配置。 The second roller 46, the second air knife 48, and the second discharge container 50 may be disposed in the same manner as the first roller 40, the first air knife 42, and the first discharge container 44, respectively.

本發明中一邊對於洗淨處理後的聚乙烯醇系樹脂薄膜施加200~1500N/m的張力，一邊進行水分去除處理。張力為在該範圍內時，於經由氣刀實施水分去除處理之際，由於能夠抑制因空氣所導致的薄膜擺動，所以薄膜就不會接觸排出容器而破裂，因而就能夠提高薄膜的生產性。又，軋輥除了設置於洗淨槽19之後方以外，可以設置在水分去除裝置23或乾燥爐25之後 方，藉此能夠對於薄膜施加張力。當考慮有無因不能被水分去除裝置23除去的水滴而引起軋輥的污染時，如第2圖所示，較佳者為將軋輥設置在乾燥爐25的內部或乾燥爐25之後方；在此情況的軋輥間之張力(水分去除處理及乾燥處理中的張力)係設定在200~800N/m之範圍。 In the present invention, the water removal treatment is performed while applying a tension of 200 to 1500 N/m to the polyvinyl alcohol-based resin film after the cleaning treatment. When the tension is within this range, when the moisture removal treatment is performed via the air knife, since the film swing due to the air can be suppressed, the film does not come into contact with the discharge container and is broken, so that the productivity of the film can be improved. Further, the rolls may be disposed after the moisture removing device 23 or the drying furnace 25, except for being disposed behind the washing tank 19. In this way, tension can be applied to the film. When considering whether or not there is contamination of the roll due to water droplets that cannot be removed by the moisture removing device 23, as shown in Fig. 2, it is preferable to arrange the roll inside the drying furnace 25 or after the drying furnace 25; in this case The tension between the rolls (the tension in the moisture removal treatment and the drying treatment) is set in the range of 200 to 800 N/m.

上述的張力係可以藉由設置組裝有使用市售的荷重單元、或應變規的張力輥感測器等之導引輥，來進行測定。張力之測定可藉由使聚乙烯醇系樹脂薄膜接觸導引輥來進行。另外，張力測定用之荷重單元或張力感測器輥為僅於測定上使用，通常是被配置成不會與薄膜接觸。 The tension system described above can be measured by providing a guide roller in which a commercially available load cell or a tension gauge sensor such as a strain gauge is assembled. The measurement of the tension can be carried out by bringing the polyvinyl alcohol-based resin film into contact with the guide rolls. Further, the load cell for tension measurement or the tension sensor roller is used only for measurement, and is usually arranged so as not to come into contact with the film.

由氣刀所吹出的空氣之風量可以設定為2~20m3/分。當風量小於2m3/分的時候，因風壓過弱以致不能充分進行水分去除；在不能去除附著薄膜表面的水分或異物而就這樣地製造偏光薄膜時，將它應用於偏光板時就有形成缺陷的可能性。又，當風量大於20m3/分的時候，因風壓過強以致薄膜就會有發生破裂的可能性。 The air volume blown by the air knife can be set to 2~20m 3 /min. When the air volume is less than 2 m 3 /min, the wind pressure is too weak to sufficiently remove the moisture; when the polarizing film is not removed by removing the moisture or foreign matter adhering to the surface of the film, it is applied to the polarizing plate. The possibility of forming defects. Moreover, when the air volume is more than 20 m 3 /min, the film may be broken due to excessive wind pressure.

以上說明的水分去除處理係可以按照配置條件及處理條件而在該範圍內適當地調整。在上述的範圍內時，即使是在聚乙烯醇系樹脂的原始薄膜之厚度為60μm的情況下，亦能夠進行水分去除處理而不會發生部分的水分去除不良的情形。因此，能夠抑制在薄膜表面發生結晶的異物，於製造應用偏光薄膜的偏光板之際，特別是在使用紫外線硬化型黏著劑等之活性能量線硬化型黏著劑來製造偏光板的情況，亦能夠有效地抑制上述之異物所引起的缺陷。 The moisture removal treatment described above can be appropriately adjusted within this range in accordance with the arrangement conditions and processing conditions. In the case of the above range, even when the thickness of the original film of the polyvinyl alcohol-based resin is 60 μm, the moisture removal treatment can be performed without causing partial moisture removal failure. Therefore, it is possible to suppress the occurrence of foreign matter which crystallizes on the surface of the film, and in the case of producing a polarizing plate to which a polarizing film is applied, in particular, when a polarizing plate is produced using an active energy ray-curable adhesive such as an ultraviolet curable adhesive, The defects caused by the above foreign matter are effectively suppressed.

(乾燥處理) (drying treatment)

在水分去除處理之後，可以藉由將聚乙烯醇系樹脂薄膜予以乾燥來製作偏光薄膜。薄膜之乾燥，在乾燥爐25內，例如，可以設定在溫度30~100℃左右、30~600秒左右。 After the moisture removal treatment, a polarizing film can be produced by drying a polyvinyl alcohol resin film. The drying of the film is set in the drying furnace 25, for example, at a temperature of about 30 to 100 ° C for about 30 to 600 seconds.

如此作法所製造的偏光薄膜之最終累積拉伸倍率，通常是 4.5~7倍，較佳為5~6.5倍。 The final cumulative stretching ratio of the polarizing film produced by such a method is usually 4.5 to 7 times, preferably 5 to 6.5 times.

〔偏光板之製造方法〕 [Method of Manufacturing Polarizing Plate]

本發明的偏光板之製造方法係透過黏著劑將保護薄膜，貼合在如上述所製造的偏光薄膜之至少一面而成之物。 The method for producing a polarizing plate of the present invention is a method in which a protective film is bonded to at least one surface of a polarizing film manufactured as described above through an adhesive.

(保護薄膜) (protective film)

構成上述的保護薄膜之材料，舉例來說，其可以是如環烯烴系樹脂及乙酸纖維素系樹脂、聚對苯二甲酸乙二酯及聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯之類的聚酯系樹脂、聚碳酸酯系樹脂、丙烯酸系樹脂、聚丙烯系樹脂等在該領域中過往以來所廣泛使用的薄膜材料。在偏光薄膜的兩面貼合有保護薄膜的情況，可以是各個保護薄膜皆相同，也可以是不同種類的薄膜。 The material constituting the protective film described above may be, for example, a cycloolefin resin and a cellulose acetate resin, polyethylene terephthalate, polyethylene naphthalate, or polybutylene terephthalate. A film material such as a polyester resin such as a diester, a polycarbonate resin, an acrylic resin, or a polypropylene resin which has been widely used in the field. In the case where a protective film is bonded to both surfaces of the polarizing film, each of the protective films may be the same or different types of films.

所謂環烯烴系樹脂，例如，其係指具有由如降冰片烯及多環降冰片烯系單體之類的環狀烯烴(環烯烴)構成的單體之單位的熱可塑性樹脂，也稱為熱可塑性環烯烴系樹脂。環烯烴系樹脂，可以是如上述的環烯烴之開環聚合物、或使用二種以上的環烯烴之開環共聚物的加氫物，也可以是環烯烴、與鏈狀烯烴類、及具有如乙烯基之類的聚合性雙鍵的芳香族化合物等之加成聚合物。又，在環烯烴系樹脂導入有極性基之物也是有效的。 The cycloolefin-based resin is, for example, a thermoplastic resin having a unit composed of a cyclic olefin (cycloolefin) such as norbornene and a polycyclic norbornene-based monomer, and is also called a thermoplastic resin. Thermoplastic cyclic olefin resin. The cycloolefin resin may be a ring-opening polymer of the above cycloolefin or a hydrogenated product of a ring-opening copolymer of two or more kinds of cyclic olefins, or may be a cyclic olefin, a chain olefin, or the like. An addition polymer such as a polymerizable double bond aromatic compound such as a vinyl group. Further, it is also effective to introduce a polar group into the cycloolefin resin.

在使用環烯烴、與鏈狀烯烴及/或具有乙烯基的芳香族化合物之共聚物來構成第一保護薄膜的情況，鏈狀烯烴，舉例來說，其可以是乙烯、丙烯等；又，具有乙烯基的芳香族化合物，舉例來說，其可以是苯乙烯、α-甲基苯乙烯、核烷基取代苯乙烯等。在像這類的共聚物中，由環烯烴構成的單體之單位可以是50莫耳%以下，然而較佳者為15~50莫耳%左右。特別是在使用環烯烴與鎖狀烯烴及具有乙烯基的芳香族化合物之三元共聚物來構成第一保護薄膜的情況，由環烯烴構成的單體之單位，如上述，其可以是比較少的量。在此種三元共聚物中，由鏈狀烯烴構成的單體之單位通常是5~80莫耳%，而由具有 乙烯基的芳香族化合物構成的單體之單位，通常是5~80莫耳%。 In the case of using a copolymer of a cyclic olefin, a chain olefin, and/or an aromatic compound having a vinyl group to constitute a first protective film, the chain olefin may be, for example, ethylene, propylene or the like; The aromatic compound of a vinyl group may, for example, be styrene, α-methylstyrene, a core alkyl-substituted styrene or the like. In the copolymer of this type, the unit of the monomer composed of the cyclic olefin may be 50 mol% or less, preferably 15 to 50 mol%. In particular, in the case of using a terpolymer of a cyclic olefin and a lock olefin and an aromatic compound having a vinyl group to constitute the first protective film, the unit of the monomer composed of the cyclic olefin may be relatively small as described above. The amount. In such a terpolymer, the unit of the monomer composed of a chain olefin is usually 5 to 80 mol%, and The unit of the monomer composed of the vinyl aromatic compound is usually 5 to 80 mol%.

在使用環烯烴與鎖狀烯烴及/或具有乙烯基的芳香族化合物之共聚物的情況，鏈狀烯烴，舉例來說，其可以是乙烯、丙烯等；又，具有乙烯基的芳香族化合物，舉例來說，其可以是苯乙烯、α-甲基苯乙烯、核烷基取代苯乙烯等。在像這類的共聚物中，由環烯烴構成的單體之單位可以是50莫耳%以下(較佳為15~50莫耳%)。特別是在使用環烯烴與鎖狀烯烴及具有乙烯基的芳香族化合物之三元共聚物的情況，由環烯烴構成的單體之單位，如上述，其可以是比較少的量。在此種三元共聚物中，鏈狀烯烴構成的單體之單位通常是5~80莫耳%；具有乙烯基的芳香族化合物構成的單體之單位，通常是5~80莫耳%。 In the case of using a copolymer of a cyclic olefin and a lock olefin and/or an aromatic compound having a vinyl group, the chain olefin may be, for example, ethylene, propylene or the like; and an aromatic compound having a vinyl group, For example, it may be styrene, α-methylstyrene, a core alkyl-substituted styrene, or the like. In the copolymer of this type, the unit of the monomer composed of the cyclic olefin may be 50 mol% or less (preferably 15 to 50 mol%). In particular, in the case of using a terpolymer of a cyclic olefin, a lock olefin, and an aromatic compound having a vinyl group, the unit of the monomer composed of a cyclic olefin may be a relatively small amount as described above. In such a terpolymer, a unit of a monomer composed of a chain olefin is usually 5 to 80 mol%; and a unit of a monomer having a vinyl aromatic compound is usually 5 to 80 mol%.

環烯烴系樹脂可以使用適合的市售品，例如，分別適合使用商品名之“TOPAS”〔Topas Advanced Polymers GmbH社製〕、“阿通”〔JSR股份有限公司製〕、“傑歐諾阿(ZEONOR)”及“傑歐諾克斯(ZEONEX)”〔以上為日本傑恩股份有限公司製〕、“阿貝魯”〔三井化學股份有限公司製〕、“歐克西斯(OXIS)”〔大倉工業股份有限公司製〕等。將像這類的環烯烴系樹脂予以製膜而形成薄膜之際，可適合使用溶劑流延法、溶融擠壓法等之眾所皆知的方法。又，例如，也可以使用“S西納”及“SCA40”〔以上為積水化學工業股份有限公司製〕、“傑歐諾阿薄膜”〔日本傑恩股份有限公司製〕等之預先製膜的環烯烴系樹脂製薄膜之市售品。 For the cycloolefin-based resin, a commercially available product can be used. For example, "TOPAS" (manufactured by Topas Advanced Polymers GmbH), "Atong" (manufactured by JSR Co., Ltd.), and "Jenonoa" are suitable for use. ZEONOR)" and "ZEONEX" (above is made by Japan Jain Co., Ltd.), "Aberu" (manufactured by Mitsui Chemicals Co., Ltd.), "Oxis (OXIS)" [ Okura Industrial Co., Ltd.] and so on. When a cycloolefin-based resin of this type is formed into a film to form a film, a well-known method such as a solvent casting method or a melt extrusion method can be suitably used. In addition, for example, a pre-formed ring such as "S Sina" and "SCA40" (above is Sekisui Chemical Co., Ltd.), "Jenonoa Film" (made by Japan Jayne Co., Ltd.), or the like may be used. A commercially available product of a film made of an olefin resin.

環烯烴系樹脂薄膜可以是經單軸拉伸之物，也可以是經雙軸拉伸之物。藉由實施拉伸，可以賦予環烯烴系樹脂薄膜任何的相位差值。拉伸通常是一邊捲出薄膜圓筒，一邊在加熱爐中向輥的進行方向(薄膜的長軸方向)、向垂直於其進行方向之方向(薄膜的寬度方向)、或向其兩方向連續地進行拉伸。加熱爐的溫度通常是採用環烯烴系樹脂的玻璃轉移溫度附近至大於玻璃轉 移溫度100℃的範圍。拉伸的倍率通常是1.1~6倍，較佳者為1.1~3.5倍。 The cycloolefin-based resin film may be uniaxially stretched or may be biaxially stretched. By performing stretching, any phase difference value of the cycloolefin-based resin film can be imparted. The stretching is usually carried out in a direction in which the roll is rolled up in the heating furnace (the long axis direction of the film), in a direction perpendicular to the direction of the film (the width direction of the film), or in both directions. Stretching the ground. The temperature of the heating furnace is usually near the glass transition temperature of the cycloolefin resin to be larger than the glass rotation. The temperature is shifted to a range of 100 °C. The stretching ratio is usually 1.1 to 6 times, preferably 1.1 to 3.5 times.

當環烯烴系樹脂薄膜為處於圓筒卷狀態時，由於薄膜彼此接合而有容易產生黏結的傾向，所以通常是在貼合保護薄膜之後再形成圓筒卷。又，一般而言，環烯烴系樹脂薄膜的表面活性差，因而較佳者為對於和偏光薄膜接合的表面進行電漿處理、電暈處理、皂化處理、紫外線照射處理及燒成(火焰)處理等之表面處理。其中，比較容易能夠實施的是電漿處理，特別適合的是大氣壓電漿處理及電暈處理。 When the cycloolefin-based resin film is in the state of a roll, the film tends to be bonded due to the bonding of the films. Therefore, the roll is usually formed after the protective film is bonded. Further, in general, since the surface activity of the cycloolefin-based resin film is poor, it is preferred to subject the surface to be bonded to the polarizing film to plasma treatment, corona treatment, saponification treatment, ultraviolet irradiation treatment, and firing (flame) treatment. Wait for the surface treatment. Among them, it is relatively easy to implement plasma treatment, and particularly suitable for atmospheric piezoelectric slurry treatment and corona treatment.

乙酸纖維素系樹脂係指纖維素的一部分或完全酯化物，舉例來說，其可以是由纖維素的乙酸酯、丙酸酯、丁酸酯、此等之混合酯等所構成的薄膜。比較具體地舉例來說，其可以是三醋酸纖維素薄膜、二乙醯基纖維素薄膜、乙酸纖維素丙酸酯薄膜、乙酸纖維素丁酸酯薄膜等。像這類的纖維素酯系樹脂薄膜，可以適合使用適當的市售品，舉例來說，其可以是分別為商品名之“富士特克TD80”、“富士特克TD80UF”、“富士特克TD80UZ”及“富士特克TD60UL”〔以上為富士薄膜股份有限公司製〕；“KC8UX2M”、“KC8UY”、“KC4UYW”及“KC6UAW”〔以上為柯尼卡照明股份有限公司製〕等。 The cellulose acetate-based resin refers to a part or a complete esterified product of cellulose, and may be, for example, a film composed of cellulose acetate, propionate, butyrate, mixed esters or the like. More specifically, for example, it may be a cellulose triacetate film, a diethyl cellulose film, a cellulose acetate propionate film, a cellulose acetate butyrate film, or the like. A cellulose ester-based resin film of this type may be suitably used as a commercially available product, and may be, for example, "Fujitec TD80", "Fujitec TD80UF", and "Fujitec", respectively. TD80UZ" and "Fujitec TD60UL" (above is made by Fuji Film Co., Ltd.); "KC8UX2M", "KC8UY", "KC4UYW" and "KC6UAW" (above is Konica Lighting Co., Ltd.).

又，保護薄膜也適合使用已賦予相位差特性的乙酸纖維素系樹脂薄膜。此種已賦予相位差特性的乙酸纖維素系樹脂薄膜的市售品，舉例來說，其可以是分別為商品名之“WV BZ 438”〔富士薄膜股份有限公司製〕、“KC4FR-1”、“KC4CR-1”及“KC4AR-1”〔以上為柯尼卡照明股份有限公司製〕等。乙酸纖維素有時也稱為乙醯纖維素、纖維素乙酸酯。 Further, as the protective film, a cellulose acetate resin film to which phase difference characteristics have been imparted is also suitably used. For example, the commercially available product of the cellulose acetate-based resin film to which the phase difference property is imparted may be "WV BZ 438" (manufactured by Fuji Film Co., Ltd.) and "KC4FR-1", respectively. "KC4CR-1" and "KC4AR-1" (above, manufactured by Konica Lighting Co., Ltd.). Cellulose acetate is sometimes also referred to as acetaminophen, cellulose acetate.

本發明之偏光板之製造方法所用的保護薄膜之厚度，雖然較佳者是薄的，然而過薄時，強度就會變低、加工性變差。另一方面，過厚時，則會有透明性降低，積層後需要長的熟成時間等之問題。因此，保護薄膜之適當的厚度，例如，可以是5~200μm，較佳者為10~150μm，更佳者為10~100μm。 The thickness of the protective film used in the method for producing a polarizing plate of the present invention is preferably thin, but when it is too thin, the strength is lowered and the workability is deteriorated. On the other hand, when it is too thick, there is a problem that transparency is lowered, and a long ripening time is required after lamination. Therefore, the appropriate thickness of the protective film may be, for example, 5 to 200 μm, preferably 10 to 150 μm, and more preferably 10 to 100 μm.

為了提高黏著劑與偏光薄膜及/或保護薄膜之接合性，也可以對於偏光薄膜及/或保護薄膜實施電暈處理、火焰處理、電漿處理、紫外線處理、底劑塗佈處理及皂化處理等之表面處理。 In order to improve the adhesion between the adhesive and the polarizing film and/or the protective film, the polarizing film and/or the protective film may be subjected to corona treatment, flame treatment, plasma treatment, ultraviolet treatment, primer coating treatment, saponification treatment, etc. Surface treatment.

又，對於保護薄膜亦可以實施防眩處理、抗反射處理、硬被覆處理、抗靜電處理及防污處理等之表面處理，此等可以分別單獨實施，或者組合二種以上一起實施。又，保護薄膜也可以含有二苯甲酮系化合物及苯并***系化合物等之紫外線吸收劑，以及苯基膦系化合物及酞酸酯化合物等之可塑劑。 Further, the protective film may be subjected to a surface treatment such as an anti-glare treatment, an anti-reflection treatment, a hard coating treatment, an antistatic treatment, or an antifouling treatment, and these may be used alone or in combination of two or more. Further, the protective film may contain a UV absorber such as a benzophenone compound or a benzotriazole compound, and a plasticizer such as a phenylphosphine compound or a phthalate compound.

另外，保護薄膜可以具有做為相位差薄膜之功能、做為增加亮度薄膜之功能、做為反射薄膜之功能、做為半穿透反射薄膜之功能、做為擴散薄膜之功能、及做為光學補償薄膜之功能等之光學功能。在此種情況，例如，除了藉由在保護薄膜的表面積層相位差薄膜、增加亮度薄膜、反射薄膜、半穿透反射薄膜、擴散薄膜及光學補償薄膜等之光學功能性薄膜，以使其具有這類的功能以外，也可對保護薄膜本身賦予這類的功能。又，也可以是使保護薄膜持有：如具有增加亮度薄膜之功能的擴散薄膜等這樣的複數種功能。 In addition, the protective film may have a function as a retardation film, a function of increasing a brightness film, a function as a reflective film, a function as a transflective film, a function as a diffusion film, and an optical function. An optical function that compensates for the function of the film. In this case, for example, an optical functional film such as a phase difference film, a brightness film, a reflective film, a transflective film, a diffusion film, and an optical compensation film on the surface layer of the protective film is provided to have In addition to this type of function, it is also possible to impart such a function to the protective film itself. Further, the protective film may have a plurality of functions such as a diffusion film having a function of increasing the brightness of the film.

做為相位差薄膜之功能，例如，其係可以對於上述的保護薄膜實施於日本專利第2841377號公報、日本專利第3094113號公報等之上所記載的拉伸處理，也可以藉由實施於日本專利第3168850號公報所記載的處理來提供。 As a function of the retardation film, for example, the above-mentioned protective film may be subjected to the stretching treatment described in Japanese Patent No. 2841377, Japanese Patent No. 3094113, or the like, or may be implemented in Japan. The process described in Japanese Patent No. 3168850 is provided.

相位差薄膜中之相位差特性，例如，可以在正面相位差值為5~100nm、厚度方向相位差值為40~300nm的範圍等而加以適當地選擇。又，做為增加亮度薄膜之功能係可以對於上述的保護薄膜，藉由以如特開2002-169025號公報或特開2003-29030號公報所記載這類的方法形成微細孔，或者藉由選擇反射的中心波長不同的二層以上之膽固醇型(cholesteric)液晶層、並加 以重疊來提供。 The phase difference characteristic in the retardation film can be appropriately selected, for example, in a range in which the front phase difference value is 5 to 100 nm, and the thickness direction retardation value is 40 to 300 nm. Further, as a function of increasing the brightness of the film, the above-mentioned protective film can be formed by a method such as that described in JP-A-2002-169025 or JP-A-2003-29030, or by selection. Two or more layers of cholesteric liquid crystal layers with different center wavelengths of reflection Provided by overlapping.

做為反射薄膜或半穿透反射薄膜之功能係可以藉由對於保護薄膜以蒸鍍或濺鍍等來形成金屬薄膜而賦予；做為擴散薄膜之功能係可以藉由於保護薄膜上塗佈含有微粒子的樹脂溶液來賦予；此等之功能可以分別地賦予。又，做為光學補償薄膜之功能係可以藉由在保護薄膜上塗佈碟狀液晶性化合物等之液晶性化合物並進行配向來賦予。保護薄膜可以含有表現相位差的化合物；再者，也可以使用適當的黏著劑而直接將各種的光學功能性薄膜貼合於偏光薄膜上。光學功能性薄膜之市售品的例子，舉例來說，分別為商品名“DBEF”〔3M社製，在日本可從住友3M股份有限公司取得〕等之增加亮度薄膜；“WV薄膜”〔富士薄膜股份有限公司製〕等之視野角改良薄膜、“阿通薄膜”〔JSR股份有限公司製〕、“傑歐諾阿薄膜”〔日本傑恩股份有限公司製〕、“S西納”〔積水化學工業股份有限公司製〕、“VA-TAC薄膜”〔柯尼卡照明股份有限公司製〕及“斯密卡萊特”〔住友化學股份有限公司製〕等之相位差薄膜等。 The function as a reflective film or a semi-transmissive reflective film can be imparted by forming a metal thin film by vapor deposition or sputtering of the protective film; the function as a diffusion film can be achieved by coating the protective film with fine particles. The resin solution is given; these functions can be imparted separately. Further, the function as an optical compensation film can be imparted by applying a liquid crystal compound such as a liquid crystal compound to a protective film and performing alignment. The protective film may contain a compound exhibiting a phase difference; in addition, various optical functional films may be directly bonded to the polarizing film by using an appropriate adhesive. Examples of commercially available optical functional films are, for example, a brightness-increasing film such as "DBEF" (available from 3M Corporation, available from Sumitomo 3M Co., Ltd. in Japan); "WV film" [Fuji Vision Film Improvement Film, etc., "Atong Film" (manufactured by JSR Co., Ltd.), "Jionoa Film" (made by Japan Jayne Co., Ltd.), "S Sina" (Shuishui Chemical Co., Ltd.) Industrial Co., Ltd., "VA-TAC film" (manufactured by Konica Lighting Co., Ltd.) and "Smecta" (manufactured by Sumitomo Chemical Co., Ltd.) and other retardation films.

(黏著劑層) (adhesive layer)

構成黏著劑層的黏著劑，舉例來說，其可以是水系黏著劑及活性能量線硬化型之黏著劑等。 The adhesive constituting the adhesive layer may be, for example, a water-based adhesive or an active energy ray-curable adhesive.

水系黏著劑，舉例來說，其可以是聚乙烯醇系樹脂水溶液、水系二液型胺基甲酸酯系乳化液黏著劑等。做為黏著劑使用的聚乙烯醇系樹脂，除了由對乙酸乙烯酯的單獨聚合物之聚乙酸乙烯酯實施皂化處理而得到的乙烯基醇同元聚合物以外，也有對乙酸乙烯酯與能和它共聚合之其他的單體之共聚物進行皂化處理而得到的乙烯基醇系共聚物，更進一步地對此等之羥基進行部分改質而得之改質聚乙烯醇系聚合物等。在水系黏著劑中也可以添加多價醛、水溶性環氧化合物、蜜胺系化合物、氧化鋯化合物、鋅化合物等之添加劑。在 使用像這樣的水系之黏著劑的情況，由此等所得到黏著劑層通常是遠比1μm還要更薄。水系黏著劑係在其調製後於15~40℃的溫度下被塗佈；貼合溫度通常是15~30℃的範圍。 The water-based adhesive may be, for example, a polyvinyl alcohol-based resin aqueous solution or an aqueous two-liquid urethane-based emulsion adhesive. As the polyvinyl alcohol-based resin used as an adhesive, in addition to the vinyl alcohol homopolymer obtained by saponifying the polyvinyl acetate of the individual polymer of vinyl acetate, there is also a compatibility with vinyl acetate and The vinyl alcohol-based copolymer obtained by saponifying the copolymer of another monomer copolymerized, and the modified polyvinyl alcohol-based polymer obtained by partially modifying the hydroxyl group. An additive such as a polyvalent aldehyde, a water-soluble epoxy compound, a melamine compound, a zirconia compound, or a zinc compound may be added to the aqueous adhesive. in In the case of using an aqueous adhesive such as this, the adhesive layer thus obtained is usually much thinner than 1 μm. The water-based adhesive is applied at a temperature of 15 to 40 ° C after the preparation thereof; the bonding temperature is usually in the range of 15 to 30 ° C.

活性能量線硬化型之黏著劑，從耐候性及折射率、陽離子聚合性等之觀點來看，較佳者為黏著劑中有使用在分子內不含芳香環之環氧基化合物者。像這樣的環氧基化合物的例子，例如，可以是具有脂環式環的多元醇之縮水甘油醚、脂肪族環氧基化合物、脂環式環氧基化合物等。可適合使用於像這類的活性能量線硬化性黏著劑中之環氧基化合物，例如，雖然在日本專利第4306270號公報(即特開2004-245925號)中已詳細說明了，然而在此則概略地說明。 The active energy ray-curing type adhesive is preferably one in which an epoxy group having no aromatic ring in the molecule is used in the adhesive from the viewpoints of weather resistance, refractive index, cationic polymerizability and the like. Examples of the epoxy compound as described above may be, for example, a glycidyl ether of a polyhydric alcohol having an alicyclic ring, an aliphatic epoxy compound, an alicyclic epoxy compound, or the like. An epoxy compound which can be suitably used in an active energy ray-curable adhesive such as this one is described in detail in Japanese Patent No. 4,306, 270 (Japanese Patent Application No. 2004-245925). Then explain it roughly.

具有脂環式環的多元醇之縮水甘油醚，可以是對於在觸媒之存在下、加壓下，選擇性地將芳香族多元醇予以氫化反應而得到的核加氫多羥基化合物，將它予以縮水甘油醚化而成之物。芳香族多元醇，舉例來說，其可以是如雙酚A、雙酚F及雙酚S之類的雙酚型化合物；如苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂及羥基苯并醛苯酚酚醛清漆樹脂之類的酚醛清漆型樹脂；四羥基二苯基甲烷、四羥基二苯甲酮及聚乙烯基苯酚之類的多官能型之化合物等。藉由讓對於使此等之芳香族多元醇的芳香環進行氫化反應而得到的脂環式多元醇、與表氯醇起反應，可以形成縮水甘油醚。在具有像這類的脂環式環之多元醇的縮水甘油醚之中，較佳者為使用經氫化的雙酚A之二縮水甘油醚。 The glycidyl ether of the polyhydric alcohol having an alicyclic ring may be a nuclear hydrogenated polyhydroxy compound obtained by selectively hydrogenating an aromatic polyol in the presence of a catalyst under pressure. An etherified product of glycidol. The aromatic polyol may, for example, be a bisphenol type compound such as bisphenol A, bisphenol F or bisphenol S; such as a phenol novolak resin, a cresol novolak resin, and a hydroxybenzoaldehyde phenol novolac A novolac type resin such as a varnish resin; a polyfunctional compound such as tetrahydroxydiphenylmethane, tetrahydroxybenzophenone or polyvinylphenol. A glycidyl ether can be formed by reacting an alicyclic polyol obtained by hydrogenating an aromatic ring of such an aromatic polyol with epichlorohydrin. Among the glycidyl ethers of the polyol having an alicyclic ring like this, it is preferred to use a hydrogenated bisphenol A diglycidyl ether.

脂肪族環氧基化合物可以是脂肪族多價醇或其環氧烷加成物之聚縮水甘油醚。較具體而言，舉例來說，其可以是1,4-丁烷二醇之二縮水甘油醚；1,6-己烷二醇之二縮水甘油醚；甘油之三縮水甘油醚；三羥甲基丙烷之三縮水甘油醚；聚乙二醇之二縮水甘油醚；丙二醇之二縮水甘油醚；藉由在乙二醇、丙二醇或甘油之類的脂肪族多價醇中，加成一種或二種以上的環氧烷(環氧 乙烷、環氧丙烷)所得到的聚醚多元醇的聚縮水甘油醚等。 The aliphatic epoxy compound may be a polyglycidyl ether of an aliphatic polyvalent alcohol or an alkylene oxide adduct thereof. More specifically, for example, it may be a diglycidyl ether of 1,4-butanediol; a diglycidyl ether of 1,6-hexanediol; a triglycidyl ether of glycerol; Triglycidyl ether of propane; diglycidyl ether of polyethylene glycol; diglycidyl ether of propylene glycol; by adding one or two in an aliphatic polyvalent alcohol such as ethylene glycol, propylene glycol or glycerin More than one type of alkylene oxide (epoxy A polyglycidyl ether of a polyether polyol obtained by ethane or propylene oxide.

脂環式環氧基化合物係指在分子內具有一個以上的鍵結於脂環式環的環氧基之環氧基化合物的意思。「鍵結於脂環式環的環氧基」係指下式(I)所示的構造中之橋接的氧原子-O-之意。下式(I)中，m為2~5的整數。 The alicyclic epoxy compound means an epoxy compound having one or more epoxy groups bonded to an alicyclic ring in the molecule. The "epoxy group bonded to the alicyclic ring" means the bridged oxygen atom -O- in the structure represented by the following formula (I). In the following formula (I), m is an integer of 2 to 5.

上述式(I)中之(CH2)m中的一個或複數個氫原子已除去的形式之基為鍵結於其他的化學構造之化合物，係可以用來做為脂環式環氧基化合物。(CH2)m中的一個或複數個氫原子也可以被甲基或乙基等之直鏈狀烷基適當地取代。在脂環式環氧基化合物之中，較佳為使用具有氧雜聯環己烷環〔上述式(I)中m=3之物〕及氧雜聯環庚烷環〔上述式(I)中m=4之物〕的環氧基化合物，因為它顯示出偏光薄膜與保護薄膜間之優異的接合性。以下，具體地例示該較佳使用的脂環式環氧基化合物，然而未限定於此等之化合物。 The group in which one or a plurality of hydrogen atoms in (CH 2 ) m in the above formula (I) has been removed is a compound bonded to another chemical structure, and can be used as an alicyclic epoxy compound. . One or a plurality of hydrogen atoms in (CH 2 ) m may be appropriately substituted with a linear alkyl group such as a methyl group or an ethyl group. Among the alicyclic epoxy compounds, those having an oxaheterocyclohexane ring (m=3 in the above formula (I)) and an oxabicycloheptane ring are preferred (the above formula (I) The epoxy compound of m=4 is because it exhibits excellent bonding property between the polarizing film and the protective film. Hereinafter, the alicyclic epoxy compound which is preferably used is specifically exemplified, but the compound is not limited thereto.

(a)環氧基環六甲基 環氧基環己烷羧酸酯類：以下式(II)所示，式中的R1及R2係表示互相獨立之氫原子或碳數1~5的直鏈狀烷基。 (a) Epoxycyclohexamethylepoxycyclohexanecarboxylate: represented by the following formula (II), wherein R 1 and R 2 represent a mutually independent hydrogen atom or a carbon number of 1 to 5 Linear alkyl group.

(b)鏈烷二醇之環氧基環己烷羧酸酯類：以下式(III)所示，式中的R3及R4表示相互獨立之氫原子或碳數1~5的直鏈狀烷基；n表示2~20之整數。 (b) an epoxy-cyclohexanecarboxylic acid ester of an alkanediol: represented by the following formula (III), wherein R 3 and R 4 represent mutually independent hydrogen atoms or a linear chain having 1 to 5 carbon atoms; An alkyl group; n represents an integer from 2 to 20.

(c)二羧酸之環氧基環六甲基酯類：以下式(IV)所示，式中的R5及R6表示相互獨立的氫原子或碳數1~5之直鏈狀烷基；p表示2~20之整數。 (c) Epoxycyclohexamethyl ester of a dicarboxylic acid: represented by the following formula (IV), wherein R 5 and R 6 represent mutually independent hydrogen atoms or linear alkyl groups having 1 to 5 carbon atoms; Base; p represents an integer from 2 to 20.

(d)聚乙二醇之環氧基環六甲基醚類：以下式(V)所示，式中的R7及R8表示相互獨立的氫原子或碳數1~5之直鏈狀烷基；q表示2~10之整數。 (d) Epoxycyclohexamethyl ether of polyethylene glycol: represented by the following formula (V), wherein R 7 and R 8 in the formula represent mutually independent hydrogen atoms or linear chains having a carbon number of 1 to 5 Alkyl; q represents an integer from 2 to 10.

(e)鏈烷二醇之環氧基環六甲基醚類：以下式(VI)所示，式中的R9及R10表示相互獨立的氫原子或碳數1~5之直鏈狀烷基；r表示2~20之整數。 (e) Epoxycyclohexamethyl ether of an alkanediol: represented by the following formula (VI), wherein R 9 and R 10 represent a mutually independent hydrogen atom or a linear chain having a carbon number of 1 to 5 Alkyl; r represents an integer from 2 to 20.

(f)二環氧基三螺旋化合物：以下式(VII)所示，式中的R11及R12表示相互獨立的氫原子或碳數1~5之直鏈狀烷基。 (f) The di-epoxy-helix compound: represented by the following formula (VII), wherein R 11 and R 12 in the formula represent a mutually independent hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms.

(g)二環氧基單螺旋化合物：以下式(VIII)所示，式中的R13及R14表示相互獨立的氫原子或碳數1~5之直鏈狀烷基。 (g) The diepoxy single helix compound is represented by the following formula (VIII): R 13 and R 14 in the formula represent a mutually independent hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms.

(h)乙烯基環己烷二環氧化物類：以下式(IX)所示，式中的R15表示氫原子或碳數1~5之直鏈狀烷基。 (h) Vinylcyclohexane diepoxide: represented by the following formula (IX), wherein R 15 in the formula represents a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms.

(i)環氧基環戊醚類：以下式(X)所示，式中的R16及R17表示相互獨立的氫原子或碳數1~5之直鏈狀烷基。 (i) Epoxycyclopentane ether: represented by the following formula (X), wherein R 16 and R 17 in the formula represent a mutually independent hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms.

(j)二環氧基三環癸烷類：以下式(XI)所示，式中的R18表示氫原子或碳數1~5之直鏈狀烷基。 (j) Dicyclooxytricyclodecane: represented by the following formula (XI), wherein R 18 in the formula represents a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms.

在以上所例示的脂環式環氧基化合物之中，從有市售或其類似物為比較容易得到等之理由來看，較佳為使用：例如3,4-環氧基環六甲基3,4-環氧基環己烷羧酸酯〔式(II)中R1=R2=H之化合物〕、3,4-環氧基-6-甲基環六甲基3,4-環氧基-6-甲基環己烷羧酸酯〔式(II)中，R1=4-CH3、R2=4-CH3之化合物〕、乙烯雙(3,4-環氧基環己烷羧酸酯)〔式(III)中，R3=R4=H、n=2之化合物〕、雙(3,4-環氧基環六甲基)己二酸酯、〔式(IV)中，R5=R6=H、p=4之化合物〕、雙(3,4-環氧基-6-甲基環六甲基)己二酸酯〔式(IV)中，R5=4-CH3、R6=4-CH3、p=4之化合物〕、乙二醇雙(3,4-環氧基環六甲基醚)〔式(VI)中，R9=R10=H、r=2之化合物〕。 Among the alicyclic epoxy compounds exemplified above, it is preferred to use, for example, 3,4-epoxycyclohexylmethyl from the viewpoint of being commercially available or the like, which is relatively easy to obtain, and the like. 3,4-epoxycyclohexanecarboxylate [Compound of R 1 =R 2 =H in the formula (II)], 3,4-epoxy-6-methylcyclohexylmethyl 3,4- Epoxy-6-methylcyclohexanecarboxylate [in the formula (II), a compound of R 1 =4-CH 3 , R 2 =4-CH 3 ], ethylene bis(3,4-epoxy group) Cyclohexane carboxylate) [in the formula (III), a compound of R 3 =R 4 =H, n=2], bis(3,4-epoxycyclohexyl)adipate, (IV), a compound wherein R 5 = R 6 = H, p = 4), bis (3,4-epoxy-6-methylcyclohexamethyl) adipate (in the formula (IV), R 5 =4-CH 3 , R 6 =4-CH 3 , p=4 compound], ethylene glycol bis(3,4-epoxycyclohexamethyl ether) [in formula (VI), R 9 =R 10 =H, compound of r=2].

在活性能量線硬化性黏著劑中，環氧基化合物可以是只單獨使用一種，也可以併用二種以上。該組成物中所用的環氧基化合物之環氧基當量通常是30~3000g/當量，較佳者為在50~1500g/當量之範圍。當環氧基當量下降到30g/當量時，就會有硬化後之保護膜的可撓性降低、接合強度減低的可能 性。另一方面，當超過3000g/當量時，就會有與其他的成分間之相溶性降低的可能性。 In the active energy ray-curable adhesive, the epoxy compound may be used alone or in combination of two or more. The epoxy group equivalent of the epoxy compound used in the composition is usually from 30 to 3,000 g/equivalent, preferably from 50 to 1,500 g/equivalent. When the epoxy equivalent is lowered to 30 g/eq, there is a possibility that the flexibility of the cured protective film is lowered and the joint strength is lowered. Sex. On the other hand, when it exceeds 3000 g/eq, there is a possibility that the compatibility with other components is lowered.

又，活性能量線硬化性黏著劑，除了上述之環氧基化合物之外，也可以具有氧雜環丁烷化合物。藉由添加氧雜環丁烷化合物，可以降低上述的黏著劑之黏度，並且可以加快硬化速度。 Further, the active energy ray-curable adhesive may have an oxetane compound in addition to the above epoxy group-containing compound. By adding an oxetane compound, the viscosity of the above-mentioned adhesive can be lowered, and the hardening speed can be accelerated.

氧雜環丁烷化合物為在分子內具有至少一個氧雜環丁烷環(四員環醚)之化合物，舉例來說，其可以是3-乙基-3-羥基甲基氧雜環丁烷、1,4-雙[(3-乙基-3-氧雜環丁基)甲氧基甲基]苯、3-乙基-3-(苯氧基甲基)氧雜環丁烷、二[(3-乙基-3-氧雜環丁基)甲基]醚、3-乙基-3-(2-乙基己氧基甲基)氧雜環丁烷、苯酚酚醛清漆氧雜環丁烷等。氧雜環丁烷化合物之摻混量，以活性能量線硬化性化合物全體為基準時，通常是50重量%以下，較佳者為10~40重量%。氧雜環丁烷化合物的市售品係能夠容易購得的，舉例來說，其可以是由東亞合成股份有限公司所販賣的商品名為“阿龍氧雜環丁烷OXT-101”、“阿龍氧雜環丁烷OXT-121”、“阿龍氧雜環丁烷OXT-211”、“阿龍氧雜環丁烷OXT-221”、“阿龍氧雜環丁烷OXT-212”等之任何一者。 The oxetane compound is a compound having at least one oxetane ring (four-membered cyclic ether) in the molecule, and for example, it may be 3-ethyl-3-hydroxymethyl oxetane , 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 3-ethyl-3-(phenoxymethyl)oxetane, two [(3-Ethyl-3-oxetanyl)methyl]ether, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, phenol novolac oxirane Butane and so on. The blending amount of the oxetane compound is usually 50% by weight or less, preferably 10% to 40% by weight based on the total of the active energy ray-curable compound. Commercially available products of oxetane compounds are readily available, for example, which may be sold under the trade name "Alon oxetane OXT-101" by East Asia Synthetic Co., Ltd., Aaron oxetane OXT-121", "Alon oxetane OXT-211", "Alon oxetane OXT-221", "Alon oxetane OXT-212" Any one of them.

在該黏著劑中，從反應性的觀點來看，較佳者為使用陽離子聚合來做為環氧基化合物的硬化反應劑；該組成物中較佳為摻混有陽離子聚合啟始劑。陽離子聚合啟始劑為可藉由照射可見光線、紫外線、X線、電子線等之活性能量線而產生陽離子種或路易士酸，進而使得環氧基之聚合開始反應。以下，將藉由活性能量線之照射而產生陽離子種或路易士酸、使環氧基之聚合開始反應的陽離子聚合啟始劑稱為「光陽離子聚合啟始劑」。 Among the binders, from the viewpoint of reactivity, it is preferred to use cationic polymerization as a hardening reactant for the epoxy compound; it is preferred to incorporate a cationic polymerization initiator in the composition. The cationic polymerization initiator is a cationic species or a Lewis acid which can be generated by irradiation of visible light rays, ultraviolet rays, X-rays, electron beams and the like, thereby causing polymerization of the epoxy groups to start the reaction. Hereinafter, a cationic polymerization initiator which generates a cationic species or a Lewis acid by irradiation with an active energy ray and initiates polymerization of an epoxy group is referred to as a "photocationic polymerization initiator".

使用光陽離子聚合啟始劑，藉由活性能量線之照射來進行黏著劑之硬化的方法，由於能夠在常溫下進行硬化，可減少考慮因偏光薄膜之耐熱性或膨脹所引起的不均之必要性，並能夠使偏光薄膜與保護薄膜良好地接合的 特點上是有利的。又，光陽離子聚合啟始劑由於是以光促動觸媒作用，所以即使混合於黏著劑中保存安定性及作業性也是優異的。 The photo-cationic polymerization initiator is used to cure the adhesive by irradiation with an active energy ray, and since it can be hardened at normal temperature, it is necessary to reduce the necessity of considering unevenness due to heat resistance or expansion of the polarizing film. And capable of bonding the polarizing film and the protective film well. It is advantageous in terms of features. Further, since the photocationic polymerization initiator is acted by a photo-actuator, it is excellent in storage stability and workability even when it is mixed in an adhesive.

上述的光陽離子聚合啟始劑，可以是任何的形式之物；其具體例，舉例來說，有芳香族重氮鎓鹽；芳香族錪鹽或芳香族鋶鹽之類的鎓鹽；鐵-芳烴錯合物等。 The photocationic polymerization initiator described above may be in any form; specific examples thereof include, for example, an aromatic diazonium salt; an onium salt such as an aromatic onium salt or an aromatic onium salt; and iron- An aromatic hydrocarbon complex or the like.

芳香族重氮鎓鹽，舉例來說，其可以是苯重氮鎓六氟銻酸鹽、苯重氮鎓六氟膦、苯重氮鎓六氟硼酸鹽等。又，芳香族錪鹽，舉例來說，其可以是二苯基錪四(五氟苯基)硼酸鹽、二苯基錪六氟膦、二苯基錪六氟銻酸鹽、二(4-壬基苯基)錪六氟膦等。 The aromatic diazonium salt may, for example, be benzenediazonium hexafluoroantimonate, benzenediazepine hexafluorophosphine or benzenediazonium hexafluoroborate. Further, the aromatic onium salt may, for example, be diphenylphosphonium tetrakis(pentafluorophenyl)borate, diphenylphosphonium hexafluorophosphine, diphenylphosphonium hexafluoroantimonate or di(4-) Nonylphenyl) hexafluorophosphine and the like.

芳香族重氮鎓鹽，舉例來說，其可以是苯重氮鎓六氟銻酸鹽、苯重氮鎓六氟膦、苯重氮鎓六氟硼酸鹽等。 The aromatic diazonium salt may, for example, be benzenediazonium hexafluoroantimonate, benzenediazepine hexafluorophosphine or benzenediazonium hexafluoroborate.

芳香族錪鹽，舉例來說，其可以是二苯基錪四(五氟苯基)硼酸鹽、二苯基錪六氟膦、二苯基錪六氟銻酸鹽、二(4-壬基苯基)錪六氟膦等。 The aromatic onium salt may, for example, be diphenylphosphonium tetrakis(pentafluorophenyl)borate, diphenylphosphonium hexafluorophosphine, diphenylphosphonium hexafluoroantimonate or bis(4-fluorenyl) Phenyl) hexafluorophosphine.

芳香族鋶鹽，舉例來說，其可以是三苯基鋶六氟膦、三苯基鋶六氟銻酸鹽、三苯基鋶四(五氟苯基)硼酸鹽、4,4’-雙(二苯基鋶基)二苯基硫化物雙六氟膦、4,4’-雙[二(β-羥基乙氧基)苯基鋶基]二苯基硫化物雙六氟銻酸鹽、4,4’-雙[二(β-羥基乙氧基)苯基鋶基]二苯基硫化物雙六氟膦、7-[二(p-甲苯基)鋶基]-2-異丙基硫代己酮六氟銻酸鹽、7-[二(p-甲苯基)鋶基]-2-異丙基硫代己酮四(五氟苯基)硼酸鹽、4-苯基羰基-4’-二苯基鋶基-二苯基硫化物六氟膦、4-(p-三級丁基苯基羰基)-4’-二苯基鋶基-二苯基硫化物六氟銻酸鹽、4-(p-三級丁基苯基羰基)-4’-二(p-甲苯基)鋶基-二苯基硫化物四(五氟苯基)硼酸鹽等。 The aromatic onium salt, for example, may be triphenylsulfonium hexafluorophosphine, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, 4,4'-double (diphenylindenyl)diphenyl sulfide dihexafluorophosphine, 4,4'-bis[bis(β-hydroxyethoxy)phenylindenyl]diphenyl sulfide dihexafluoroantimonate, 4,4'-bis[bis(β-hydroxyethoxy)phenylindenyl]diphenyl sulfide dihexafluorophosphine, 7-[bis(p-methylphenyl)indolyl]-2-isopropyl Thiohexanone hexafluoroantimonate, 7-[bis(p-methylphenyl)indenyl]-2-isopropylthiohexanone tetrakis(pentafluorophenyl)borate, 4-phenylcarbonyl-4 '-Diphenylfluorenyl-diphenyl sulfide hexafluorophosphine, 4-(p-tris-butylphenylcarbonyl)-4'-diphenylfluorenyl-diphenyl sulfide hexafluoroantimonate 4-(p-tris-butylphenylcarbonyl)-4'-di(p-methylphenyl)indenyl-diphenyl sulfide tetrakis(pentafluorophenyl)borate.

又，鐵-芳烴錯合物，舉例來說，其可以是二甲苯-環戊二烯基鐵(II)六氟銻酸鹽、異丙苯-環戊二烯基鐵(II)六氟膦、二甲苯-環戊二烯基鐵(II)參(三氟甲基磺醯基)甲烷化物等。 Further, the iron-aromatic complex, for example, may be xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphine. , xylene-cyclopentadienyl iron (II) gin (trifluoromethylsulfonyl) methanide, and the like.

此等之光陽離子聚合啟始劑的市售品係能夠容易購得的，例如，分別為商品名“卡亞拉得PCI-220”及“卡亞拉得PCI-620”〔以上為日本化藥股份有限公司製〕、“UVI-6990”〔大宇化學社製〕、“ADEKA歐普特瑪SP-150”及“ADEKA歐普特瑪SP-170”〔以上為ADEKA股份有限公司製〕、“CI-5102”、“CIT-1370”、“CIT-1682”、“CIP-1866S”、“CIP-2048S”及“CIP-2064S”〔以上為日本曹達股份有限公司製〕、“DPI-101”、“DPI-102”、“DPI-103”、“DPI-105”、“MPI-103”、“MPI-105”、“BBI-101”、“BBI-102”、“BBI-103”、“BBI-105”、“TPS-101”、“TPS-102”、“TPS-103”、“TPS-105”、“MDS-103”、“MDS-105”、“DTS-102”及“DTS-103”〔以上為綠化學股份有限公司製〕、“PI-2074”〔諾迪亞社製〕等。 Commercially available products of such photocationic polymerization initiators are readily available, for example, under the trade names "Kayarad PCI-220" and "Kayarad PCI-620" (above is Japanese) Pharmaceutical Co., Ltd.], "UVI-6990" [manufactured by Daewoo Chemical Co., Ltd.], "ADEKA OPTema SP-150" and "ADEKA OPTema SP-170" (above ADEKA Co., Ltd.), "CI -5102", "CIT-1370", "CIT-1682", "CIP-1866S", "CIP-2048S" and "CIP-2064S" (above is made by Japan Soda Co., Ltd.), "DPI-101", "DPI-102", "DPI-103", "DPI-105", "MPI-103", "MPI-105", "BBI-101", "BBI-102", "BBI-103", "BBI" -105", "TPS-101", "TPS-102", "TPS-103", "TPS-105", "MDS-103", "MDS-105", "DTS-102" and "DTS-103" "[The above is manufactured by Green Chemical Co., Ltd.], "PI-2074" (manufactured by Nordia Corporation), and the like.

此等之光陽離子聚合啟始劑可以是分別單獨使用，也可以由二種以上混合來使用。在此等之中，特佳者為使用芳香族鋶鹽，因為它即使是在300nm以上的波長領域中亦具有紫外線吸收特性，所以硬化性優異、並能夠提供良好的機械強度，又能夠提供在偏光薄膜與保護薄膜之間具有良好的密合性之硬化物。 These photocationic polymerization initiators may be used singly or in combination of two or more. Among these, it is particularly preferable to use an aromatic sulfonium salt because it has ultraviolet absorbing properties even in a wavelength region of 300 nm or more, so that it has excellent hardenability and can provide good mechanical strength, and can provide A cured product having good adhesion between the polarizing film and the protective film.

光陽離子聚合啟始劑的摻混量，相對於包含有環氧基化合物或氧雜環丁烷化合物的陽離子聚合性化合物之合計100重量份而言，通常是0.5~20重量份，較佳者為1~6重量份。光陽離子聚合啟始劑的摻混量少時，則硬化會變得不夠充分，而有使得機械強度降低、及在偏光薄膜與保護薄膜間之接合性降低的傾向。另一方面，當光陽離子聚合啟始劑的摻混量過多時，則硬化物中的離子性物質會增加而致使硬化物的吸濕性變高，所得到的黏著劑層之耐久性能就會有降低的可能性。 The blending amount of the photocationic polymerization initiator is usually 0.5 to 20 parts by weight, based on 100 parts by weight of the total of the cationically polymerizable compound containing the epoxy compound or the oxetane compound. It is 1 to 6 parts by weight. When the blending amount of the photocationic polymerization initiator is small, the curing tends to be insufficient, and the mechanical strength is lowered and the bondability between the polarizing film and the protective film tends to be lowered. On the other hand, when the amount of the photocationic polymerization initiator is too large, the ionic substance in the hardened material increases, so that the hygroscopicity of the cured product becomes high, and the durability of the obtained adhesive layer is high. There is a possibility of reduction.

在活性能量線硬化型的黏著劑中，可以更進一步地摻混離子捕捉劑、抗氧化劑、連鎖移動劑、黏合賦予劑、熱可塑性樹脂、填充劑、流動調 整劑、整平劑、可塑劑、消泡劑等之添加劑。離子捕捉劑，舉例來說，其可以是銻系、粉末狀之鉍系、鎂系、鋁系、鈣系、鈦系及此等之混合系等之無機化合物；抗氧化劑，舉例來說，其可以是受阻酚系抗氧化劑等。 In the active energy ray-curable adhesive, ion trapping agent, antioxidant, chain shifting agent, adhesion-imparting agent, thermoplastic resin, filler, and flow adjustment can be further blended. Additives such as bulking agents, leveling agents, plasticizers, defoamers, and the like. The ion scavenger may be, for example, an inorganic compound such as a lanthanoid, a powdery lanthanide, a magnesium system, an aluminum system, a calcium system, a titanium system, or the like; and an antioxidant, for example, It may be a hindered phenol-based antioxidant or the like.

活性能量線硬化型的黏著劑，可以使用實質上不含溶劑成分的無溶劑型黏著劑，然而由於各塗佈方式各有其最適合的黏度範圍，所以也可以含有黏度調整用之溶劑。溶劑較佳者為使用不會降低偏光薄膜之光學性能、而且可良好地溶解構成黏著劑的環氧基化合物等之物，舉例來說，其可以是以甲苯為代表的烴類、乙酸乙酯為代表的酯類等之有機溶劑。本發明所用的活性能量線硬化型之黏著劑的黏度，例如為在5~1000mPa．s左右的範圍，較佳者為10~200mPa．s，更佳者為20~100mPa．s。活性能量線硬化型的黏著劑之塗佈方法沒有特別的限定，例如可以藉由刮刀、線條、模塗機、點塗佈機、印刷塗佈機等之各種的塗佈方式，來塗佈於保護薄膜或偏光薄膜之貼合面。 As the active energy ray-curable adhesive, a solvent-free adhesive which does not substantially contain a solvent component can be used. However, since each coating method has its most suitable viscosity range, it may contain a solvent for viscosity adjustment. The solvent is preferably one which does not lower the optical properties of the polarizing film, and which can dissolve the epoxy compound or the like which constitutes the adhesive well. For example, it may be a hydrocarbon represented by toluene or ethyl acetate. It is an organic solvent such as an ester. The viscosity of the active energy ray-curable adhesive used in the present invention is, for example, 5 to 1000 mPa. The range around s, preferably 10~200mPa. s, the better is 20~100mPa. s. The application method of the active energy ray-curing type adhesive is not particularly limited, and for example, it can be applied by various coating methods such as a doctor blade, a line, a die coater, a dot coater, and a printing coater. The bonding surface of the protective film or the polarizing film.

在如此作法而被形成於偏光薄膜的黏著劑層之上，可貼合上述的保護薄膜。在偏光薄膜的兩面貼合保護薄膜的情況，可以分階段地於每單面貼合二片保護薄膜，也可以一階段來貼合兩面。對於該偏光薄膜與保護薄膜的積層體，照射活性能量線而使黏著劑硬化。活性能量線之照射上所用的光源，並未特別地限定，可具有波長400nm以下之發光分佈；例如可以使用由低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈、黑光燈、微波激發水銀燈、金屬鹵化物燈等。光照射強度係按照各目標組成物來決定的，仍然是沒有特別限定，然而較佳者是對啟始劑之活性化有效的波長領域之照射強度為10~5000mW/cm2。當光照射強度為小於10mW/cm2時，反應時間會變得過長；當超過5000mW/cm2時，則會有因從燈所輻射的熱及組成物之聚合時的發熱，而致使產生黏著劑層之黄變及偏光子之劣化的可能性。 The protective film described above can be bonded to the adhesive layer formed on the polarizing film in such a manner. In the case where the protective film is bonded to both surfaces of the polarizing film, two protective films may be bonded to each side in a stepwise manner, or both surfaces may be bonded in one stage. The layered body of the polarizing film and the protective film is irradiated with an active energy ray to cure the adhesive. The light source used for the irradiation of the active energy ray is not particularly limited, and may have a light-emitting distribution with a wavelength of 400 nm or less; for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, a black lamp, a microwave may be used. Excite mercury lamps, metal halide lamps, and the like. The light irradiation intensity is determined according to each target composition, and is not particularly limited. However, it is preferable that the irradiation intensity in the wavelength region effective for activation of the initiator is 10 to 5000 mW/cm 2 . When the light irradiation intensity is less than 10 mW/cm 2 , the reaction time becomes too long; when it exceeds 5000 mW/cm 2 , there is heat generated by the lamp and heat generated during polymerization of the composition, resulting in generation The yellowing of the adhesive layer and the possibility of deterioration of the polarizer.

活性能量線的照射時間為按照各硬化的組成物來控制的，仍然 是沒有特別限定，然而由照射強度與照射時間之乘積所表示的積算光量較佳為設定成10~5000mJ/cm2。上述之積算光量為小於10mJ/cm2時，由啟始劑而來的活性種之發生就會不夠充分，所得到的保護薄膜之硬化就會有變成不足夠的可能性，另一方面，當其積算光量超過5000mJ/cm2時，則照射時間會變成非常地長，而變成不利於提高生產性。硬化後的黏著劑層之厚度通常是0.1~10μm，更佳為0.2~4μm。 The irradiation time of the active energy ray is controlled according to each hardened composition, and is not particularly limited. However, the amount of integrated light represented by the product of the irradiation intensity and the irradiation time is preferably set to 10 to 5000 mJ/cm 2 . When the integrated light amount is less than 10 mJ/cm 2 , the occurrence of the active species by the initiator is insufficient, and the hardening of the obtained protective film may become insufficient. On the other hand, when When the integrated light amount exceeds 5000 mJ/cm 2 , the irradiation time becomes extremely long, which is unfavorable for improving productivity. The thickness of the cured adhesive layer is usually 0.1 to 10 μm, more preferably 0.2 to 4 μm.

如以上作法所製造的偏光板為具備偏光薄膜、與貼合在偏光薄膜的至少一面之保護薄膜，偏光板可以使用來做為構成液晶顯示裝置之構件。 The polarizing plate manufactured by the above method is a protective film including a polarizing film and bonded to at least one surface of the polarizing film, and the polarizing plate can be used as a member constituting the liquid crystal display device.

《實施例》 "Embodiment"

接著，列舉本發明之實施例來具體地說明，但本發明並不限定於此等實施例。又，偏光薄膜之穿透檢查係以如下之方法來進行。 Hereinafter, the embodiments of the present invention will be specifically described, but the present invention is not limited to the embodiments. Further, the penetration inspection of the polarizing film was carried out in the following manner.

偏光薄膜之穿透檢查係藉由將所製作的偏光薄膜切割出寬度1m、長度(薄膜的輸送方向)20m之薄膜切片，透過背光等之光源以目視觀察該切片，計算所檢測出的100μm以上之異物的個數，計算出每1m2的偏光薄膜之異物個數。 The penetration test of the polarizing film is performed by cutting a film of a width of 1 m and a length (transport direction of the film) by 20 m, and visually observing the slice through a light source such as a backlight to calculate the detected thickness of 100 μm or more. The number of foreign matters was calculated, and the number of foreign matter per 1 m 2 of the polarizing film was calculated.

〔實施例1〕 [Example 1]

將厚度60μm的聚乙烯基醇薄膜〔可樂麗股份有限公司製之商品名“可樂麗畢尼龍VF-PE#6000”、聚合度2400、皂化度99.9莫耳%以上〕浸漬於已放入30℃之純水的膨潤槽中，使薄膜保持於不鬆放之緊張狀態下浸漬100秒鐘，使薄膜充分地膨潤。其次，在碘/碘化鉀/水的重量比為0.02/1.5/100之30℃的染色槽中浸漬90秒鐘並且進行單軸拉伸之後，再於碘化鉀/硼酸/水的重量比為12/4.4/100之55℃的交聯槽中浸漬60秒鐘，進行耐水化處理並進行單軸拉伸直到從原始所積算的拉伸倍率成為5.5倍為止。繼續於硼酸/碘化鉀/水的重量比為9.0/2.9/100之40℃的硼酸水溶液中浸漬10秒鐘之後，再於已放入12℃的 純水之洗淨槽中浸漬2秒鐘。對於完成上述的各處理之聚乙烯基醇薄膜，使用如第2圖這樣的水分去除裝置，對於薄膜的表面，於每個單面吹送風量10m3/分的空氣，來進行薄膜之兩面的水分去除。此時，各別的水分去除處理之條件：薄膜的張力為600N/m(第1圖之軋輥21與軋輥27間之張力)，空氣的噴嘴與薄膜的角度為40°，空氣的噴嘴與薄膜之距離為0.6mm，排出容器與薄膜的距離為1mm。水分去除處理之後，於70℃乾燥3分鐘而製作成偏光薄膜。對於此偏光薄膜進行穿透檢查的結果，100μm以上之缺陷數為0.05個/m2。 A polyvinyl alcohol film having a thickness of 60 μm (trade name "Keleli Nylon VF-PE #6000" manufactured by Kuraray Co., Ltd., degree of polymerization 2400, saponification degree: 99.9 mol% or more) was immersed in 30 ° C In the swell tank of the pure water, the film was immersed for 100 seconds while being kept in a relaxed state, and the film was sufficiently swollen. Next, after immersing in a dyeing tank of 30 ° C of iodine/potassium iodide/water at a weight ratio of 0.02/1.5/100 for 90 seconds and performing uniaxial stretching, the weight ratio of potassium iodide/boric acid/water was 12/4.4. The mixture was immersed in a cross-linking tank of 55 ° C for 100 seconds, subjected to hydration treatment, and uniaxially stretched until the draw ratio calculated from the original was 5.5 times. The mixture was immersed in a 40 ° C boric acid aqueous solution having a boric acid/potassium iodide/water weight ratio of 9.0/2.9/100 for 10 seconds, and then immersed in a washing tank of pure water at 12 ° C for 2 seconds. For the polyvinyl alcohol film which completed each of the above-mentioned processes, the moisture removal apparatus of FIG. 2 was used, and air of 10 m 3 /min of air was blown on each surface of the film to carry out moisture on both sides of the film. Remove. At this time, the conditions of the respective moisture removal treatments are: the tension of the film is 600 N/m (the tension between the rolls 21 and the rolls 27 in Fig. 1), the angle of the nozzle of the air and the film is 40, and the nozzle and film of the air The distance is 0.6 mm and the distance between the discharge container and the film is 1 mm. After the moisture removal treatment, it was dried at 70 ° C for 3 minutes to prepare a polarizing film. As a result of the penetration inspection of the polarizing film, the number of defects of 100 μm or more was 0.05/m 2 .

〔實施例2〕 [Example 2]

除了使用厚度50μm的聚乙烯基醇薄膜〔可樂麗股份有限公司製之商品名“可樂麗畢尼龍VF-PE#5000”、聚合度2400、皂化度99.9莫耳%以上〕，在水分去除處理中施加於薄膜的張力變更為500N/m以外，與實施例1同樣地製作成偏光薄膜。對於所得到的偏光薄膜進行穿透檢查的結果，100μm以上的缺陷數為0.05個/m2。 In addition to the use of a polyvinyl alcohol film having a thickness of 50 μm (trade name "Keleli Nylon VF-PE #5000" manufactured by Kuraray Co., Ltd., degree of polymerization 2400, saponification degree of 99.9 mol% or more], in the moisture removal treatment A polarizing film was produced in the same manner as in Example 1 except that the tension applied to the film was changed to 500 N/m. As a result of performing the penetration inspection on the obtained polarizing film, the number of defects of 100 μm or more was 0.05/m 2 .

〔實施例3〕 [Example 3]

除了使用厚度30μm的聚乙烯基醇薄膜〔可樂麗股份有限公司製之商品名“可樂麗畢尼龍VF-PE#3000”、聚合度2400、皂化度99.9莫耳%以上〕，在水分去除處理中施加於薄膜的張力變更為450N/m以外，與實施例1同樣地製作偏光薄膜。對於所得到的偏光薄膜進行穿透檢查的結果，100μm以上的缺陷數為0.10個/m2。 In addition to the use of a polyvinyl alcohol film having a thickness of 30 μm (trade name "Keleli Nylon VF-PE #3000" manufactured by Kuraray Co., Ltd., degree of polymerization 2400, saponification degree of 99.9 mol% or more], in the moisture removal treatment A polarizing film was produced in the same manner as in Example 1 except that the tension applied to the film was changed to 450 N/m. As a result of performing the penetration inspection on the obtained polarizing film, the number of defects of 100 μm or more was 0.10 / m 2 .

〔實施例4〕 [Example 4]

除了在水分去除處理中，將氣刀前端的噴嘴與薄膜之角度變更為20°以外，與實施例1同樣製作偏光薄膜。對於所得到的偏光薄膜進行穿透檢查的結果，100μm以上的缺陷數為0.8個/m2。 A polarizing film was produced in the same manner as in Example 1 except that the angle between the nozzle at the tip end of the air knife and the film was changed to 20° in the moisture removal treatment. As a result of performing the penetration inspection on the obtained polarizing film, the number of defects of 100 μm or more was 0.8/m 2 .

〔實施例5〕 [Example 5]

除了在水分去除處理中，將氣刀前端的噴嘴與薄膜之角度變更為90°以外，與實施例1同樣地製作偏光薄膜。對於所得到的偏光薄膜進行穿透檢查的結果，100μm以上的缺陷數為1.2個/m2。 A polarizing film was produced in the same manner as in Example 1 except that the angle between the nozzle and the film at the tip end of the air knife was changed to 90° in the moisture removal treatment. As a result of performing the penetration inspection on the obtained polarizing film, the number of defects of 100 μm or more was 1.2 / m 2 .

〔實施例6〕 [Example 6]

除了在水分去除處理中，將氣刀前端的噴嘴與薄膜之距離變更為2mm以外，與實施例1同樣地製作偏光薄膜。對於所得到的偏光薄膜進行穿透檢查的結果，100μm以上的缺陷數為2.1個/m2。 A polarizing film was produced in the same manner as in Example 1 except that the distance between the nozzle at the tip end of the air knife and the film was changed to 2 mm in the moisture removal treatment. As a result of performing the penetration inspection on the obtained polarizing film, the number of defects of 100 μm or more was 2.1 / m 2 .

〔實施例7〕 [Example 7]

除了在水分去除處理中，將排出容器與薄膜之距離變更為3mm以外，與實施例1同樣地製作偏光薄膜。對於所得到的偏光薄膜進行穿透檢查的結果，100μm以上的缺陷數為2.3個/m2。 A polarizing film was produced in the same manner as in Example 1 except that the distance between the discharge container and the film was changed to 3 mm in the moisture removal treatment. As a result of performing the penetration inspection on the obtained polarizing film, the number of defects of 100 μm or more was 2.3 / m 2 .

〔比較例1〕 [Comparative Example 1]

除了不以水分去除裝置進行水分去除，而是只以洗淨槽之後的軋輥來對於聚乙烯基醇薄膜進行水分去除以外，與實施例1同樣地製作偏光薄膜。對於所得到的偏光薄膜進行穿透檢查的結果，100μm以上的缺陷數為5.2個/m2。 A polarizing film was produced in the same manner as in Example 1 except that the polyvinyl alcohol film was removed by a roll after the washing tank, without removing the water by the moisture removing device. As a result of performing the penetration inspection on the obtained polarizing film, the number of defects of 100 μm or more was 5.2/m 2 .

〔比較例2〕 [Comparative Example 2]

除了在水分去除處理中，將施加於薄膜的張力變更為150N/m以外，雖然與實施例1同樣地製作偏光薄膜，然而由於薄膜產生擺動，與排出容器接觸的薄膜產生破裂，不能製作成偏光薄膜。 In the water removal treatment, the polarizing film was produced in the same manner as in Example 1 except that the tension applied to the film was changed to 150 N/m. However, since the film was oscillated, the film in contact with the discharge container was broken, and polarization could not be produced. film.

上述實施例1~7及比較例1,2的製造條件及穿透檢查的結果表示於以下之表1中。 The production conditions and the results of the penetration inspection of the above Examples 1 to 7 and Comparative Examples 1 and 2 are shown in Table 1 below.

由根據本發明之製造方法製造出偏光薄膜之實施例1及4~7、與使用和實施例1相同的聚乙烯基醇薄膜(原始薄膜)以不屬於本發明之製造方法的方法作成偏光薄膜的比較例1及2之比較結果來看，可知於偏光薄膜產生的缺陷，在滿足水分去除處理的條件之狀態下製作時，可以有效地被抑制。又，由使用膜厚比實施例1薄的原始薄膜之實施例2及3的結果來看，可知本發明所規定的水分去除處理之條件，即使在製造厚度是薄的偏光薄膜之際也是很有效的。 Examples 1 and 4 to 7 in which a polarizing film was produced according to the production method of the present invention, and a polyvinyl alcohol film (original film) which was the same as in Example 1 were used as a polarizing film in a method not belonging to the production method of the present invention. As a result of the comparison between Comparative Examples 1 and 2, it is understood that the defects generated in the polarizing film can be effectively suppressed when they are produced in a state in which the conditions of the moisture removal treatment are satisfied. Further, from the results of Examples 2 and 3 in which the film thickness was thinner than that of the original film of Example 1, it was found that the conditions of the moisture removal treatment prescribed by the present invention are very high even when a polarizing film having a small thickness is produced. Effective.

《產業利用之可能性》 "The possibility of industrial utilization"

根據本發明，即使原始薄膜是薄的情況，也不會發生薄膜之破裂及水分去除不良等，可以製造出外觀良好的偏光薄膜，因而採用它的偏光板，其生產效率是優異的、缺陷少、並且能成為良好品質之物。 According to the present invention, even if the original film is thin, cracking of the film, poor moisture removal, and the like do not occur, and a polarizing film having a good appearance can be produced. Therefore, the polarizing plate using the polarizing plate has excellent production efficiency and few defects. And can be a good quality thing.

Claims (5)

一種偏光薄膜之製造方法，其係藉由對於厚度為1~60μm的聚乙烯醇系樹脂薄膜，依序進行膨潤處理、染色處理、交聯處理及洗淨處理，且進行拉伸處理直到交聯處理結束為止；而且在該洗淨處理之後，進行水分去除處理之方法，其係一邊對薄膜施加200~1500N/m之張力且將薄膜捲附在設置於其單面之第一輥上，一邊對該第一輥之相反側的薄膜表面吹送空氣以除去水分；接著，一邊將被空氣吹送的面捲附在第二輥上，一邊對前述第二輥之相反側的薄膜表面吹送空氣以除去水分，並藉由設置在各個空氣吹送位置附近之第一排出容器及第二排出容器，來回收被空氣所除去的水分；其中，排出容器係具有開口部，且按照使得該開口部至薄膜表面距離成為0.3mm以上且2mm以下的方式配置而成；及空氣係由噴嘴對薄膜吹送；該噴嘴係按照：使得通過其吹出口前端的中心線相對於薄膜表面呈30~80°的角度，且使該吹出口前端至薄膜表面的距離成為1.5mm以下的方式配置而成。 A method for producing a polarizing film by sequentially performing swelling treatment, dyeing treatment, cross-linking treatment, and washing treatment on a polyvinyl alcohol-based resin film having a thickness of 1 to 60 μm, and performing stretching treatment until crosslinking After the completion of the treatment, and after the cleaning treatment, a method of removing moisture is applied to the film while applying a tension of 200 to 1500 N/m to the film and attaching the film to the first roll provided on one side thereof. Air is blown to the surface of the film on the opposite side of the first roller to remove moisture; and then, while the surface of the film blown by the air is wound on the second roller, air is blown to the surface of the film on the opposite side of the second roller to remove Moisture, and recovering moisture removed by the air by the first discharge container and the second discharge container disposed near the respective air blowing positions; wherein the discharge container has an opening portion, and the opening portion is formed to the film surface The distance is set to be 0.3 mm or more and 2 mm or less; and the air is blown by the nozzle to the film; the nozzle is arranged such that the center of the front end of the outlet is passed through With respect to the film surface at an angle of 30 ~ 80 °, and that the outlet from the front end surface of the film to be disposed from 1.5mm or less. 如請求項1所述之製造方法，其中所吹送的空氣之風量係為2~20m3/分。 The manufacturing method according to claim 1, wherein the air volume of the air to be blown is 2 to 20 m 3 /min. 如請求項1或2所述之製造方法，其係於水分去除處理之後，再進行乾燥處理。 The manufacturing method according to claim 1 or 2, which is subjected to a drying treatment after the moisture removal treatment. 如請求項3所述之製造方法，其係藉由設置於水分去除處理前的軋輥、與設置於乾燥處理的內部或乾燥處理的後方之軋輥，一邊對薄膜施加200~800N/m之張力一邊進行水分去除處理及乾燥處理。 The manufacturing method according to claim 3, wherein a tension of 200 to 800 N/m is applied to the film by a roll provided before the moisture removal process and a roll provided inside the drying process or after the drying process. The moisture removal treatment and the drying treatment are performed. 一種偏光板之製造方法，其為使用紫外線硬化型黏著劑，將保護薄 膜貼合在如請求項3或4所述之製造方法所製造而成之偏光薄膜上。 A method for producing a polarizing plate, which uses an ultraviolet curing adhesive to protect the thin film The film is bonded to a polarizing film manufactured by the manufacturing method according to claim 3 or 4.
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