TWI389946B - A method for producing a iodine-type polarizing film, a method for producing a polarizer, and a method for producing an optical laminate - Google Patents
A method for producing a iodine-type polarizing film, a method for producing a polarizer, and a method for producing an optical laminate Download PDFInfo
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- TWI389946B TWI389946B TW093135684A TW93135684A TWI389946B TW I389946 B TWI389946 B TW I389946B TW 093135684 A TW093135684 A TW 093135684A TW 93135684 A TW93135684 A TW 93135684A TW I389946 B TWI389946 B TW I389946B
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
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- General Physics & Mathematics (AREA)
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- Engineering & Computer Science (AREA)
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- Polarising Elements (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Description
本發明係關於一種不均勻染色少、又皺紋產生頻率減少或生產性提高之碘系偏光薄膜之製造方法，於所得偏光薄膜的至少一面層合保護薄膜的偏光板之製造方法，以及貼合單獨或複數之相位差薄膜、增亮薄膜、改良視角薄膜以及半透過反射薄膜構成之光學層合體之製造方法。The present invention relates to a method for producing an iodine-based polarizing film having less uneven dyeing, a reduced frequency of wrinkles, and improved productivity, a method for producing a polarizing plate in which a protective film is laminated on at least one side of a polarizing film, and a separate bonding method. Or a method of producing an optical laminate comprising a plurality of retardation films, a brightness enhancing film, a modified viewing angle film, and a semi-transmissive reflective film.
傳統作為偏光薄膜，係使用二向色性(dichroic)色素吸附配向於聚乙烯醇系薄膜者。亦即，已知碘作為二向色性色素之碘元素類偏光薄膜、二向色性染料作為二向色性色素之染料類偏光薄膜等。這些偏光薄膜通常至少一面，較佳為兩面隔著聚乙烯醇系樹脂的水溶液構成的接著劑，貼附三乙醯基纖維素等的保護薄膜，成為偏光板。Conventionally, as a polarizing film, a dichroic dye is used to adsorb a polyvinyl alcohol-based film. In other words, an iodine-based polarizing film in which iodine is used as a dichroic dye, a dye-based polarizing film in which a dichroic dye is used as a dichroic dye, or the like is known. These polarizing films are usually provided with a protective film made of at least one surface, preferably an aqueous solution of a polyvinyl alcohol-based resin on both sides, and a protective film such as triacetyl cellulose is attached thereto to form a polarizing plate.
作為偏光薄膜的製造方法，於專利文獻1中記載將聚乙烯醇系薄膜浸漬於碘以及碘化鉀的水溶液後，將其延伸且以硼酸處理，水洗後再浸漬於碘以及碘化鉀的水溶液，然後乾燥之方法。In the method of producing a polarizing film, Patent Document 1 discloses that a polyvinyl alcohol-based film is immersed in an aqueous solution of iodine and potassium iodide, and then extended, treated with boric acid, washed with water, and then immersed in an aqueous solution of iodine and potassium iodide, and then dried. method.
於專利文獻2中，記載將延伸的薄膜浸漬於含有二向色性色素的水溶液，再浸漬於其他的含有二向色性色素的水溶液後，於硼酸水溶液中延伸，然後乾燥，製造2個吸附配向層設置於厚度方向之偏光薄膜。Patent Document 2 describes that an extended film is immersed in an aqueous solution containing a dichroic dye, and then immersed in another aqueous solution containing a dichroic dye, and then extended in an aqueous boric acid solution, followed by drying to produce two adsorptions. The alignment layer is provided with a polarizing film in the thickness direction.
於專利文獻3中，記載將延伸的聚乙烯醇系薄膜浸漬 於特定的二向色性染料水溶液(染色液A)後，浸漬於碘元素以及碘化鉀的水溶液(染色液B)，然後以硼酸處理、水洗，製造偏光薄膜之方法。Patent Document 3 describes impregnation of an extended polyvinyl alcohol-based film. After a specific dichroic dye aqueous solution (dyeing solution A), it is immersed in an aqueous solution of iodine element and potassium iodide (dyeing liquid B), and then treated with boric acid and washed with water to produce a polarizing film.
這些專利文獻，任一種皆進行2次染色處理。但是，專利文獻1係硼酸處理後，進行2次染色處理，於該情況容易發生皺紋，初期光學特性差。而且，專利文獻2、3係關於使用二向色性色素有機染料的方法。Any of these patent documents is subjected to two dyeing treatments. However, in Patent Document 1, after the boric acid treatment, the dyeing treatment is performed twice, and wrinkles are likely to occur in this case, and the initial optical characteristics are inferior. Further, Patent Documents 2 and 3 relate to a method of using a dichroic dye organic dye.
【專利文獻1】日本公開專利特開平9-133809號公報【專利文獻2】日本公開專利特開昭60-66205號公報【專利文獻3】日本公開專利特開昭62-70802號公報[Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.
本發明的主要課題，在於提供不均勻染色少的碘系偏光薄膜之製造方法、偏光板之製造方法以及光學層合體之製造方法。A main object of the present invention is to provide a method for producing an iodine-based polarizing film having less uneven dyeing, a method for producing a polarizing plate, and a method for producing an optical laminate.
本發明的其他課題，在於提供不均勻染色少、皺紋產生頻率減少或染色處理後的步驟可降低張力之生產性提高之碘系偏光薄膜之製造方法、偏光板之製造方法以及光學層合體之製造方法。Another object of the present invention is to provide a method for producing an iodine-based polarizing film, a method for producing a polarizing plate, and a production of an optical laminate, which have less uneven dyeing, a reduced frequency of wrinkles, and a step of dyeing, which can reduce the productivity of tension. method.
本發明人等，為解決上述課題反覆專心檢討的結果，發現硼酸處理前利用2段以上的染色浴依序進行碘染色， 不均勻染色變少，又於染色浴進行一軸延伸的情況使皺紋產生頻率減少，提高生產性，而完成本發明。In order to solve the above problems, the inventors of the present invention found that the iodine dyeing was performed sequentially by using two or more dye baths before the boric acid treatment. The unevenness of the dyeing is small, and the one-axis stretching in the dyeing bath reduces the frequency of wrinkles generation and improves productivity, and the present invention has been completed.
亦即，關於本發明的偏光薄膜之第1製造方法，係聚乙烯醇系薄膜依序進行膨脹處理、碘染色處理以及硼酸處理之處理步驟前以及/或處理步驟中進行一軸延伸，其特徵為：在硼酸處理步驟前設置2段以上的染色浴進行碘染色。In other words, in the first production method of the polarizing film of the present invention, the polyvinyl alcohol-based film is subjected to one-axis stretching before and/or in the treatment step of the expansion treatment, the iodine dyeing treatment, and the boric acid treatment. : Two or more dye baths were provided for iodine staining before the boric acid treatment step.
關於本發明的偏光薄膜之第2製造方法，其特徵為：在硼酸處理步驟前設置2段以上的染色浴進行碘染色，且至少於其中一染色浴進行一軸延伸。A second method for producing a polarizing film according to the present invention is characterized in that a dye bath having two or more stages is provided before the boric acid treatment step to perform iodine dyeing, and at least one of the dye baths is subjected to one-axis stretching.
關於本發明的偏光薄膜之第3製造方法，其特徵為：在硼酸處理步驟前設置2段以上的染色浴進行碘染色，且於2段以上的染色浴進行一軸延伸，且在最初的染色浴的延伸倍率比第2段以後的染色浴的總延伸倍率高的條件下進行一軸延伸。A third method for producing a polarizing film according to the present invention is characterized in that a dye bath having two or more stages is provided before the boric acid treatment step to perform iodine dyeing, and one-axis stretching is performed in two or more dye baths, and the first dye bath is used. One-axis extension is performed under the condition that the stretching ratio is higher than the total stretching ratio of the dye bath after the second stage.
關於本發明的偏光薄膜之第4製造方法，其特徵為：在硼酸處理步驟前設置2段以上的染色浴進行碘染色，且於2段以上的染色浴進行一軸延伸，且在最後的染色浴的延伸倍率比其之前的染色浴的總延伸倍率高的條件下進行一軸延伸。A fourth method for producing a polarizing film according to the present invention is characterized in that a dye bath having two or more stages is provided before the boric acid treatment step to perform iodine dyeing, and one-axis stretching is performed in two or more dye baths, and the final dye bath is used. The stretching ratio is one-axis extension under conditions higher than the total stretching ratio of the previous dye bath.
上述2段以上的染色浴之複數染色浴，其構成以可單獨分別調整延伸倍率較佳。而且，全部的染色浴包含碘化物，調整該碘化物的含量使其隨處理順序變高較佳。It is preferable that the plurality of dyeing baths of the dyeing baths of the above two stages have a stretching ratio which can be individually adjusted. Further, all the dye baths contain iodide, and the content of the iodide is adjusted to be higher as the processing order becomes higher.
本發明的偏光板之製造方法，其特徵為上述方法得到 的偏光薄膜，至少一面貼合保護薄膜。保護薄膜具備相位差薄膜、增亮薄膜、改良視角薄膜以及半透過反射薄膜中任一功能較佳。或者，本發明的光學層合體之製造方法，其特徵為至少一面貼合保護薄膜的偏光板，與至少1種選自相位差薄膜、增亮薄膜、改良視角薄膜以及半透過反射薄膜所成群的薄膜貼合。The method for producing a polarizing plate of the present invention is characterized in that the above method is obtained The polarizing film is bonded to at least one side of the protective film. The protective film is preferably provided with any one of a retardation film, a brightness enhancement film, a modified viewing angle film, and a semi-transmissive reflection film. Alternatively, the method for producing an optical laminate according to the present invention is characterized in that a polarizing plate having at least one surface bonded to a protective film is combined with at least one selected from the group consisting of a retardation film, a brightness enhancement film, a modified viewing angle film, and a semi-transmissive reflection film. The film fits.
根據本發明，因為硼酸處理步驟前利用2段以上的染色浴進行染色，可得染色不均減少之碘系偏光薄膜。又於染色浴中行一軸延伸，具有使皺紋產生頻率減少，染色處理後的步驟可降低張力，提高生產性的效果。According to the present invention, it is possible to obtain an iodine-based polarizing film having reduced dyeing unevenness by dyeing with a dye bath of two or more stages before the boric acid treatment step. Further, the one-axis stretching in the dyeing bath has a frequency of reducing wrinkles, and the step after the dyeing treatment can reduce the tension and improve the productivity.
具體地，藉由於2段以上的染色浴進行一軸延伸，且在最初的染色浴的延伸倍率比第2段以後的染色浴的總延伸倍率高，特別是乾燥時薄膜寬度的收縮狀態變小(通常稱為乾燥頸(neck-in))，在乾燥爐產生皺紋的頻率變少。Specifically, the one-axis stretching is performed by the dye bath of two or more stages, and the stretching ratio of the first dye bath is higher than the total stretch ratio of the dye bath after the second stage, and in particular, the shrinkage state of the film width during drying becomes small ( Often referred to as a neck-in, the frequency of wrinkles in the drying oven is reduced.
而且，特別是藉由於2段以上的染色浴進行一軸延伸，且在最後的染色浴的延伸倍率比其之前的染色浴的總延伸倍率高，硼酸處理步驟以後的步驟，即使降低附加的張力以防止薄膜收縮，薄膜也難以緩和，提高生產性。而且，張力低時因減少傳送薄膜用的導輪的軸承等的負擔，提高裝置的耐久性，保存管理變得容易。Moreover, in particular, by one-axis stretching by a dye bath of two or more stages, and the stretching ratio of the dye bath in the last dye bath is higher than the total stretch ratio of the dye bath before it, the step after the boric acid treatment step, even if the additional tension is lowered Preventing shrinkage of the film, the film is also difficult to relax, and productivity is improved. Further, when the tension is low, the load on the bearing of the guide roller for transporting the film or the like is reduced, and the durability of the device is improved, and the storage management is facilitated.
藉由將本發明所得偏光板、光學層合體使用於液晶顯 示裝置，可得薄型高品質的液晶顯示。By using the polarizing plate and the optical laminate obtained by the present invention for liquid crystal display The display device can obtain a thin high-quality liquid crystal display.
以下，詳細說明本發明。Hereinafter, the present invention will be described in detail.
形成本發明的聚乙烯醇系薄膜之聚乙烯醇系樹脂，通常為例如聚乙酸乙烯酯類樹脂皂化之物質。皂化度通常約85莫耳%以上，較佳約為90莫耳%以上，更好約為99莫耳%~100莫耳%。作為聚乙酸乙烯酯類樹脂，除乙酸乙烯酯為單聚合物之聚乙酸乙烯酯外，乙酸乙烯酯以及可與其共聚合之其他單量體的共聚合物，例如乙烯-乙酸乙烯酯共聚合物等。作為可與其共聚合之其他單量體，例如不飽和羧酸類、烯烴類、乙烯醚類、不飽和磺酸類等。聚乙烯醇系樹脂的聚合度為1000~10000，較佳為1500~5000的程度。The polyvinyl alcohol-based resin which forms the polyvinyl alcohol-based film of the present invention is usually a material which is saponified by, for example, a polyvinyl acetate-based resin. The degree of saponification is usually about 85 mol% or more, preferably about 90 mol% or more, more preferably about 99 mol% to 100 mol%. As a polyvinyl acetate-based resin, in addition to polyvinyl acetate which is a single polymer of polyvinyl acetate, vinyl acetate and other mono-complex copolymers copolymerizable therewith, such as ethylene-vinyl acetate copolymer Wait. As other monomer types copolymerizable therewith, for example, unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and the like. The degree of polymerization of the polyvinyl alcohol-based resin is from 1,000 to 10,000, preferably from 1,500 to 5,000.
這些聚乙烯醇系樹脂也可為變性而得，例如可使用醛類變性之聚乙烯縮甲醛、聚乙烯縮乙醛、聚乙烯縮丁醛等。通常製造偏光薄膜的起始材料，使用厚度約20μm~100μm、較佳為30μm~80μm的聚乙烯醇系樹脂薄膜之未延伸薄膜。工業上，薄膜的寬度實用上約為1500mm~4000mm。These polyvinyl alcohol-based resins may be obtained by denaturation, and for example, aldehyde-modified polyvinyl formal, polyvinyl acetal, polyvinyl butyral or the like may be used. A starting material for a polarizing film is usually produced, and an unstretched film of a polyvinyl alcohol-based resin film having a thickness of about 20 μm to 100 μm, preferably 30 μm to 80 μm, is used. Industrially, the width of the film is practically about 1500 mm to 4000 mm.
該未延伸薄膜依序進行膨脹處理、碘染色處理、硼酸處理、水洗處理，最後乾燥得到聚乙烯醇系偏光薄膜的厚度，例如約5~50μm的程度。The unstretched film is sequentially subjected to expansion treatment, iodine dyeing treatment, boric acid treatment, water washing treatment, and finally dried to obtain a thickness of the polyvinyl alcohol-based polarizing film, for example, about 5 to 50 μm.
本發明的偏光薄膜的製造方法，大致分為2種製造方 法，第一為聚乙烯醇系薄膜在空氣或不活性氣體中一軸延伸後，依序進行膨脹處理、碘染色處理、硼酸處理、水洗處理之溶液處理，最後進行乾燥的方法。第二為未延伸的聚乙烯醇系薄膜，於水溶液依序進行膨脹處理、碘染色處理、硼酸處理、水洗處理之溶液處理，在硼酸處理步驟以及/或其前一步驟，溼式下進行一軸延伸，最後進行乾燥的方法。The method for producing a polarizing film of the present invention is roughly classified into two types of manufacturers. First, the first method is a method in which a polyvinyl alcohol-based film is stretched in the air or an inert gas, and then subjected to a swelling treatment, an iodine dyeing treatment, a boric acid treatment, a water washing treatment, and finally a drying method. The second is an unstretched polyvinyl alcohol-based film, which is subjected to an expansion treatment in an aqueous solution, an iodine dyeing treatment, a boric acid treatment, and a water-washing treatment, and is subjected to a wet process in a boric acid treatment step and/or a previous step thereof. Extend and finally dry.
在任一種方法，一軸延伸可以由一個步驟進行，也可由2個以上的步驟進行，由複數的步驟進行較佳。延伸方法，可採用習知的方法，例如傳送薄膜的2個夾輪間賦予轉速差進行延伸之滾輪間延伸，如日本專利第2731813號公報記載之熱滾輪延伸法、拉寬機延伸法等。而且，基本上步驟的順序如上述，處理槽的數目、處理條件等並無限制。In either method, the one-axis extension can be performed in one step or in two or more steps, and the plurality of steps are preferably performed. The stretching method can be carried out by a conventional method such as stretching between the two pinch wheels of the transfer film to extend the difference in the number of revolutions, such as the hot roller stretching method and the stretcher stretching method described in Japanese Patent No. 2731813. Further, the order of the basic steps is as described above, and the number of processing tanks, processing conditions, and the like are not limited.
而且，上述步驟中可自由***沒有記載的作為其他目的之步驟。作為該步驟的例子，如硼酸處理後，浸漬於不含硼酸之碘化物水溶液(碘化物處理)或浸漬於不含硼酸之氯化鋅水溶液(鋅處理)的步驟等。Further, in the above steps, steps which are not described as other objects can be freely inserted. As an example of this step, after the boric acid treatment, it is immersed in a boric acid-free iodide aqueous solution (iodide treatment) or a step of immersing in a boric acid-free zinc chloride aqueous solution (zinc treatment).
膨脹步驟之目的在於除去薄膜表面的異物、除去薄膜中的可塑劑、賦予下一步驟易染色的特性、薄膜的可塑化等。處理條件係在可達成這些目的的範圍，且不產生基材薄膜極度溶解、不透明等狀態的範圍內決定。首先氣體中膨脹延伸的薄膜的情況，例如約20℃~70℃，較佳為30℃~60℃的水溶液中浸漬薄膜。薄膜的浸漬時間為30秒~300 秒，更好為60秒~240秒的程度。首先膨脹未延伸的原結構薄膜的情況，例如約10℃~50℃，較佳為20℃~40℃的水溶液中浸漬薄膜。薄膜的浸漬時間為30秒~300秒，更好為60秒~240秒的程度。The purpose of the expansion step is to remove foreign matter on the surface of the film, to remove the plasticizer in the film, to impart dyeability to the next step, to plasticize the film, and the like. The treatment conditions are determined within a range in which these objects can be achieved, and are not determined in a state in which the base film is extremely dissolved or opaque. First, in the case of a film which is expanded and extended in a gas, for example, a film is immersed in an aqueous solution of about 20 ° C to 70 ° C, preferably 30 ° C to 60 ° C. Film immersion time is 30 seconds ~ 300 Seconds, preferably 60 seconds to 240 seconds. When the unstructured original structural film is first expanded, for example, the film is immersed in an aqueous solution of about 10 ° C to 50 ° C, preferably 20 ° C to 40 ° C. The immersion time of the film is from 30 seconds to 300 seconds, more preferably from 60 seconds to 240 seconds.
於膨脹處理步驟，因薄膜的寬度方向膨脹容易產生皺紋等的問題，使用擴張滾輪(expander roll)、螺旋滾輪(spiral roll)、頂輥(crown roll)、交叉導輥(cross guider)、彎曲棒(bend bar)、拉寬夾(tenter crip)等習知拉寬裝置，除去薄膜的皺紋且傳送薄膜較佳。以安定槽中薄膜的傳送為目的，可在膨脹槽中以水中淋浴控制水流，併用EPC裝置(邊緣位置控制裝置：檢查薄膜的端部，防止薄膜蛇行的裝置)等。於本步驟，因在薄膜行走的方向薄膜也膨脹擴大，為使傳送方向的薄膜無鬆弛現象，例如設計控制處理槽前後的傳送滾輪的速度等方式較佳。而且，使用的膨脹處理槽，除純水外，也可使用添加0.01重量%~10重量%範圍之硼酸(記載於日本公開專利特開平10-153709號公報)、氯化物(記載於日本公開專利特開平06-281816號公報)、無機酸、無機鹽、水溶性有機溶劑、醇類等之水溶液。In the expansion treatment step, problems such as wrinkles are likely to occur due to expansion in the width direction of the film, and an expander roll, a spiral roll, a crown roll, a cross guide, and a bending rod are used. A conventional stretching device such as a bend bar or a tenter crip removes wrinkles of the film and preferably transports the film. For the purpose of conveying the film in the stability tank, the water flow can be controlled by showering in the expansion tank, and an EPC device (edge position control device: the end portion of the film is inspected to prevent the film from being meandering) and the like can be used. In this step, the film is also expanded and expanded in the direction in which the film travels, and in order to prevent the film in the transport direction from being slack, for example, it is preferable to design a speed of the transfer roller before and after the control groove. In addition, in the expansion treatment tank to be used, in addition to the pure water, boric acid in the range of 0.01% by weight to 10% by weight (described in Japanese Laid-Open Patent Publication No. Hei 10-153709) and chloride (described in Japanese Laid-Open Patent Publication) can be used. JP-A-06-281816), an aqueous solution of an inorganic acid, an inorganic salt, a water-soluble organic solvent, or an alcohol.
碘的染色處理步驟之目的在薄膜上吸附、配向碘。處理條件係在可達成這些目的的範圍，且不產生基材薄膜極度溶解、不透明等狀態的範圍內決定。於本發明，特別設置2段以上的染色浴依序進行碘染色。2段~4段之染色浴為適當。The purpose of the iodine dyeing treatment step is to adsorb and align iodine on the film. The treatment conditions are determined within a range in which these objects can be achieved, and are not determined in a state in which the base film is extremely dissolved or opaque. In the present invention, in particular, two or more stages of dyeing baths are provided for iodine dyeing. The dye bath for the 2nd to 4th segments is appropriate.
染色浴也可包含硼酸。添加硼酸的情況，因包含碘而與下述的硼酸處理區別。對100重量部的水，包含約0.003重量部以上的碘，溫度約40℃以下之染色浴。The dye bath can also contain boric acid. The case of adding boric acid is distinguished from the following boric acid treatment by containing iodine. For 100 parts by weight of water, a dye bath containing about 0.003 parts by weight or more of iodine and a temperature of about 40 ° C or less is contained.
各染色浴的濃度，以重量比碘/碘化鉀/水=約0.003~0.2/約0.1~10/100，較佳為約0.003~0.1/約0.1~3.0/100。碘元素的含量，各染色浴可相同，或者在上述範圍內依染色處理的順序遞減或遞增。The concentration of each dye bath is iodine/potassium iodide/water = about 0.003 to 0.2/about 0.1 to 10/100, preferably about 0.003 to 0.1/about 0.1 to 3.0/100. The content of the iodine element may be the same for each dye bath or may be decreased or increased in the order of the dyeing treatment within the above range.
各染色浴的碘化鉀濃度，調整使其依染色處理的順序變高較佳。碘化鉀濃度在各染色浴相同或依處理順序變低的情況，長時間運轉時，破壞溶液濃度的平衡，無法安定地保持偏光薄膜的品質。亦即，由於隨處理後段側染色浴的碘化鉀濃度變高，為了減少後段側染色浴碘化鉀濃度，而丟棄溶液，水必然不足夠。這是經濟上的損失，增加環境的負荷。相對地，調整使其從最初開始碘化鉀濃度依處理順序變高，長時間運轉時，即使後段側染色浴的碘化鉀濃度變高，也可防止破壞溶液濃度的平衡。The concentration of potassium iodide in each dye bath is adjusted to be higher in order of dyeing treatment. When the concentration of potassium iodide is the same in each dye bath or in the order of treatment, the balance of the concentration of the solution is broken when the operation is performed for a long period of time, and the quality of the polarizing film cannot be stably maintained. That is, since the concentration of potassium iodide in the dyeing bath at the rear side of the treatment becomes high, in order to reduce the concentration of potassium iodide in the dye bath at the back side, the solution is discarded, and the water is inevitably insufficient. This is an economic loss that increases the load on the environment. In contrast, it is adjusted so that the potassium iodide concentration increases from the beginning to the processing order, and even when the long-time operation is performed, even if the potassium iodide concentration of the dyeing bath in the subsequent stage becomes high, the balance of the concentration of the destruction solution can be prevented.
此外，也可使用其他碘化物代替碘化鉀，例如碘化鋅等。而且，也可其他碘化物與碘化鉀並用。即使是這些情況，碘化物濃度，調整使其依染色處理的順序變高較佳。而且，也可與碘化物以外的化合物共存，例如硼酸、氯化鋅、氯化鈷等。添加硼酸的情況，因包含碘而與下述的硼酸處理區分。對100重量部的水，包含約0.003重量部以上的碘之染色浴。特別是只在最後的染色浴添加硼酸較佳。由此，偏光薄膜的表面狀態良好，染色不均(mura)變 少。添加於最後的染色浴之硼酸濃度，對100重量部的水，為約0.05~2.0重量部。In addition, other iodides may be used instead of potassium iodide, such as zinc iodide. Moreover, other iodides may be used in combination with potassium iodide. Even in these cases, the iodide concentration is adjusted so that the order of the dyeing treatment becomes higher. Further, it may coexist with a compound other than iodide, such as boric acid, zinc chloride, cobalt chloride or the like. The case of adding boric acid is distinguished from the following boric acid treatment by containing iodine. For 100 parts by weight of water, a dye bath containing about 0.003 parts by weight or more of iodine is contained. In particular, it is preferred to add boric acid only in the final dye bath. Thereby, the surface state of the polarizing film is good, and the dyeing unevenness (mura) changes. less. The boric acid concentration added to the final dye bath is about 0.05 to 2.0 parts by weight for 100 parts by weight of water.
各染色浴之染色處理，例如約10℃~40℃、較佳為約20℃~35℃的溫度，進行約30秒~600秒、較佳為約60秒~300秒的浸漬處理。The dyeing treatment of each dye bath is carried out, for example, at a temperature of about 10 ° C to 40 ° C, preferably about 20 ° C to 35 ° C, for about 30 seconds to 600 seconds, preferably about 60 seconds to 300 seconds.
於本發明，在各染色浴進行一軸延伸時，在各染色浴分別單獨調整延伸倍率較佳。因此，例如於各染色浴的入口側以及出口側分別設置夾輪，可改變兩夾輪間的旋轉速度比較好。而且，除可個別調整延伸倍率，也可於染色浴中以及/或槽的出入口處設置擴張滾輪(expander roll)、螺旋滾輪(spiral roll)、頂輥(crown roll)、交叉導輥(cross guider)、彎曲棒(bend bar)等，進行一軸延伸。而且，膨脹處理後、染色處理前聚乙烯醇系薄膜也可進行溼式延伸處理，而且必要時各染色浴之間也可進行一軸延伸，或者各染色浴之間也可設置水洗槽。In the present invention, when the dye bath is subjected to one-axis stretching, it is preferred to separately adjust the stretching ratio in each dye bath. Therefore, for example, a clip wheel is provided on the inlet side and the outlet side of each dye bath, and the rotation speed between the two pinch wheels can be changed. Moreover, in addition to the individual adjustment of the stretching ratio, an expander roll, a spiral roll, a crown roll, a cross guide roller may be provided in the dye bath and/or at the entrance and exit of the tank. ), a bend bar, etc., for one-axis extension. Further, the polyvinyl alcohol-based film may be subjected to a wet stretching treatment after the expansion treatment or before the dyeing treatment, and if necessary, one-axis stretching may be performed between the respective dye baths, or a water washing tank may be provided between the dye baths.
在2段以上的各染色浴進行一軸延伸的情況，延伸倍率無特別限制，但採用以下2個態樣中任一個較佳。In the case where the dyeing baths of two or more stages are subjected to one-axis stretching, the stretching ratio is not particularly limited, but any of the following two aspects is preferable.
(1)在最初的染色浴之延伸倍率比第2段以後的染色浴的總延伸倍率高。因此，因水洗後的乾燥時乾燥頸變小，在乾燥爐產生皺紋的頻率變少。具體地，最初的染色浴之延伸倍率約1.1~3.0倍的範圍內，且第2段以後的染色浴的總延伸倍率的約1.05~2.0倍的程度較佳。(1) The stretching ratio in the first dye bath is higher than the total stretching ratio of the dye bath after the second stage. Therefore, the drying neck is reduced during drying after washing, and the frequency of wrinkles in the drying furnace is reduced. Specifically, the stretching ratio of the first dye bath is in the range of about 1.1 to 3.0 times, and the total stretching ratio of the dye bath after the second stage is preferably about 1.05 to 2.0 times.
(2)在最後的染色浴的延伸倍率比在其之前的染色浴的總延伸倍率高。因此，硼酸處理步驟以後的步驟難以 緩和薄膜，提高生產性。具體地，最後的染色浴之延伸倍率約1.05~2.0倍的範圍內，且在其之前的染色浴的總延伸倍率為約1.1~3.0倍的程度較佳。(2) The stretching ratio in the final dye bath is higher than the total stretching ratio of the dye bath before it. Therefore, the steps after the boric acid treatment step are difficult Relieve the film and improve productivity. Specifically, the stretching ratio of the final dye bath is in the range of about 1.05 to 2.0 times, and the total stretching ratio of the dye bath before it is preferably about 1.1 to 3.0 times.
硼酸處理係碘染色過的聚乙烯醇系薄膜浸漬於水100重量部含有約1~10重量部硼酸的水溶液。於硼酸水溶液包含約1~30重量部的碘化物較佳。作為碘化物，例如碘化鉀、碘化鋅等，而且也可與碘化物以外的化合物例如氯化鋅、氯化鈷、氯化鋯、硫代硫酸鈉、亞硫酸鉀、硫酸鈉等共存。The boric acid-treated iodine-dyed polyvinyl alcohol-based film is immersed in an aqueous solution containing about 1 to 10 parts by weight of boric acid in 100 parts by weight of water. The iodide containing about 1 to 30 parts by weight of the aqueous boric acid solution is preferred. The iodide may be, for example, potassium iodide or zinc iodide, or may be present in combination with a compound other than iodide such as zinc chloride, cobalt chloride, zirconium chloride, sodium thiosulfate, potassium sulfite, sodium sulfate or the like.
該硼酸處理係除為了交鏈的耐水化以外，為調整色調(防止帶藍色等)等而進行。為了交鏈的耐水化的情況，必要時除硼酸外，或與硼酸一起，使用乙二醛、戊二醛等的交鏈劑。This boric acid treatment is carried out in order to adjust the color tone (to prevent bluing, etc.) in addition to the water resistance of the cross-linking. In order to prevent hydration of the cross-linking, a crosslinking agent such as glyoxal or glutaraldehyde may be used in addition to boric acid or with boric acid if necessary.
而且，為了耐水化之硼酸處理，也有稱為交鏈處理、固定化處理等名稱的情況。為了調整色調進行硼酸處理的情況，如此之硼酸處理也有稱為補色處理、再染色處理等名稱。而且以下的說明，為了耐水化之硼酸處理以及為了調整色調之硼酸處理，任一種單獨皆稱為硼酸處理。Further, in the case of boric acid treatment which is resistant to hydration, there are cases where the name is called a cross-linking treatment or an immobilization treatment. In order to adjust the color tone to perform boric acid treatment, such a boric acid treatment may also be referred to as a complementary color treatment or a re-dye treatment. Further, in the following description, any one of them is referred to as a boric acid treatment for the boric acid treatment for hydration resistance and the boric acid treatment for adjusting the color tone.
硼酸處理根據其目的改變硼酸以及碘化物的濃度、處理槽的溫度下進行。沒有特別區分為了耐水化之硼酸處理以及為了調整色調之硼酸處理，依據以下的條件進行。The boric acid treatment is carried out in accordance with the purpose of changing the concentration of boric acid and iodide and the temperature of the treatment tank. There is no particular distinction between boric acid treatment for hydration resistance and boric acid treatment for adjusting the color tone, and the following conditions were carried out.
原結構薄膜在進行膨脹、染色、硼酸處理的情況，硼酸處理以交鏈的耐水化為目的時，使用水100重量部含約3~10重量部的硼酸、約1~20重量部的碘化物之硼酸處理 槽，通常在約50~70℃、較佳為55~65℃的溫度下進行。浸漬時間通常為30~600秒的程度，較佳為約60~420秒，更好為約90~300秒。When the original structure film is subjected to expansion, dyeing, or boric acid treatment, and boric acid treatment is used for the purpose of water resistance of the cross-linking, 100 parts by weight of water contains about 3 to 10 parts by weight of boric acid and about 1 to 20 parts by weight of iodide. Boric acid treatment The tank is usually carried out at a temperature of about 50 to 70 ° C, preferably 55 to 65 ° C. The immersion time is usually from 30 to 600 seconds, preferably from about 60 to 420 seconds, more preferably from about 90 to 300 seconds.
此外，預先延伸的薄膜進行染色、硼酸處理的情況，硼酸處理槽的溫度通常為約50~85℃、較佳為55~80℃的溫度。Further, in the case where the pre-stretched film is subjected to dyeing or boric acid treatment, the temperature of the boric acid treatment tank is usually about 50 to 85 ° C, preferably 55 to 80 ° C.
在為了耐水化之硼酸處理後，也可進行為了調整色調之硼酸處理。為了該目的，使用水100重量部含約1~5重量部的硼酸、約3~30重量部的碘化物之硼酸處理槽，通常在約10~45℃的溫度下進行。浸漬時間通常為3~300秒的程度，較佳為約10~240秒。為了調整色調之硼酸處理，與為了耐水化之硼酸處理比較，通常在較低的硼酸濃度、較高的碘化物濃度、較低的溫度下進行。After the boric acid treatment for water resistance, a boric acid treatment for adjusting the color tone can also be performed. For this purpose, a boric acid treatment tank containing about 1 to 5 parts by weight of boric acid and about 3 to 30 parts by weight of iodide in 100 parts by weight of water is usually used at a temperature of about 10 to 45 °C. The immersion time is usually from 3 to 300 seconds, preferably from about 10 to 240 seconds. The boric acid treatment for adjusting the hue is generally carried out at a lower boric acid concentration, a higher iodide concentration, and a lower temperature than the boric acid treatment for hydration resistance.
這些硼酸處理可以複數個步驟進行，通常2~5個步驟進行較多。於該情況，使用的各硼酸處理槽的水溶液組成、溫度可在上述範圍內相同或相異皆可。上述為了耐水化之硼酸處理、為了調整色調之硼酸處理可分別以複數個步驟進行。於硼酸處理步驟，與染色步驟同樣地，可進行薄膜的延伸。最終的總延伸倍率約為4.5~7.0倍，較佳為5.0~6.5倍。These boric acid treatments can be carried out in a plurality of steps, usually in 2 to 5 steps. In this case, the aqueous solution composition and temperature of each of the boric acid treatment tanks used may be the same or different within the above range. The boric acid treatment for the hydration resistance and the boric acid treatment for adjusting the color tone can be carried out in a plurality of steps. In the boric acid treatment step, as in the dyeing step, the stretching of the film can be performed. The final total stretch ratio is about 4.5 to 7.0 times, preferably 5.0 to 6.5 times.
硼酸處理後，進行水洗處理。水洗處理係例如將硼酸處理過的聚乙烯醇系薄膜浸漬於水中，水成為淋浴式的噴霧或浸漬與噴霧並用。於水洗處理水的溫度通常為2~40℃的程度，浸漬時間為2~120秒的程度。水洗後的乾燥，於 乾燥爐中約40~100℃的溫度下進行約60~600秒。After boric acid treatment, it is washed with water. In the water washing treatment, for example, a boric acid-treated polyvinyl alcohol-based film is immersed in water, and water is used as a shower spray or a combination of dipping and spraying. The temperature of the water to be washed is usually 2 to 40 ° C, and the immersion time is 2 to 120 seconds. Dry after washing, The drying oven is carried out at a temperature of about 40 to 100 ° C for about 60 to 600 seconds.
於本發明，延伸處理後的分別步驟，進行張力控制使薄膜的張力分別實質上一定。在染色處理步驟結束延伸的情況，在其後的硼酸處理步驟以及水洗處理步驟進行張力控制。In the present invention, the respective steps after the extension treatment are performed to control the tension so that the tension of the film is substantially constant. In the case where the dyeing treatment step ends, the tension control is performed in the subsequent boric acid treatment step and the water washing treatment step.
在如此製得的偏光薄膜的至少一面以接著劑貼附保護薄膜，可得偏光板。A protective film is attached to at least one surface of the polarizing film thus obtained by an adhesive to obtain a polarizing plate.
作為保護薄膜，例如三乙醯纖維素、二乙醯纖維素之乙醯纖維素系樹脂構成的薄膜，聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯等聚酯構成的薄膜，聚碳酸酯系樹脂構成的薄膜，環烯烴系樹脂構成的薄膜。作為市售熱塑性環烯烴系樹脂，例如德國Ticona公司販售之「Topas」(註冊商標)、JSR(股)公司販售之「Arton」(註冊商標)、日本Zeon(股)公司販售之「Zeonor」、「Zeonex」(任一皆註冊商標)、三井化學(股)公司販售之「Apel」(註冊商標)等。以如此之環烯烴系樹脂製膜成為保護薄膜，於製膜時可適當使用溶劑鑄膜法、熔融擠出法等的習知方法。製成膜之環烯烴系樹脂薄膜也有販售，例如積水化學工業(股)販售之「Escena」、「SCA40」。As a protective film, for example, a film composed of triacetonitrile cellulose or an ethylene glycol cellulose resin of polyethylene glycol, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate A film made of a polyester such as a diester, a film made of a polycarbonate resin, or a film made of a cycloolefin resin. As a commercially available thermoplastic cycloolefin resin, for example, "Topas" (registered trademark) sold by Ticona, Germany, "Arton" (registered trademark) sold by JSR (share) company, and "Zeon" sold by Japan Zeon Co., Ltd. Zeonor, "Zeonex" (any registered trademark), "Apel" (registered trademark) sold by Mitsui Chemicals Co., Ltd., etc. A film formed of such a cycloolefin resin is used as a protective film, and a conventional method such as a solvent casting method or a melt extrusion method can be suitably used in the film formation. The cycloolefin-based resin film which is formed into a film is also sold, for example, "Escena" and "SCA40" which are sold by Sekisui Chemical Industry Co., Ltd.
保護薄膜的厚度以薄者較佳，太薄的話強度降低，加工性變差，另一方面，太厚的話，透明性降低，層合後產生需要的痊癒時間變長等的問題。因此，保護薄膜適當的厚度為例如5~200μm的程度，較佳為約10~150μm，更好 為約20~100μm。The thickness of the protective film is preferably thin, and if it is too thin, the strength is lowered, and the workability is deteriorated. On the other hand, if it is too thick, the transparency is lowered, and the problem that the required healing time becomes long after lamination is caused. Therefore, the protective film has a suitable thickness of, for example, 5 to 200 μm, preferably about 10 to 150 μm, more preferably It is about 20~100μm.
為了提高接著劑與偏光薄膜以及/或與保護薄膜的接著性，可對偏光薄膜以及/或保護薄膜進行電暈處理、火焰處理、電漿處理、紫外線照射、引子塗佈處理、皂化處理等的表面處理。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 irradiation, primer coating treatment, saponification treatment, or the like. Surface treatment.
於保護薄膜，可進行防眩處理、防反射處理、硬塗處理、防止帶電處理、防污處理等的表面處理之單獨或組合處理。而且，保護薄膜以及/或保護薄膜表面保護層可具有二苯甲酮類化合物、苯***類化合物等的紫外線吸收劑、苯磷酸類化合物、酞酸酯化合物等的可塑劑。The protective film may be subjected to a single or combined treatment of an anti-glare treatment, an anti-reflection treatment, a hard coating treatment, a surface treatment such as a charging treatment, an anti-fouling treatment, or the like. Further, the protective film and/or the protective film surface protective layer may have a plasticizer such as a benzophenone compound or a benzotriazole compound such as an ultraviolet absorber, a benzene phosphate compound or a phthalate compound.
如此的保護薄膜可貼附於偏光薄膜的一面，也可貼附於兩面。Such a protective film can be attached to one side of the polarizing film or attached to both sides.
偏光薄膜與保護薄膜係使用水溶劑類接著劑、有機溶劑類接著劑、熱融類接著劑、無溶劑類接著劑等的接著劑層合。作為水溶劑類接著劑，例如聚乙烯醇系樹脂水溶液、水性二液型胺基甲酸乙酯類乳液接著劑等，作為有機溶劑類接著劑，例如一液型胺基甲酸乙酯類接著劑等。使用與偏光薄膜的接合面以皂化處理等的親水化處理過之乙醯基纖維素類薄膜作為保護薄膜的情況，適合使用聚乙烯醇系樹脂水溶液作為接著劑。用作接著劑之聚乙烯醇系樹脂，除乙酸乙烯酯的單聚合物之聚乙酸乙烯酯進行皂化處理所得之乙烯醇單聚合物外，乙酸乙烯酯以及可與其共聚合之其他單量體的共聚合物進行皂化處理所得之乙烯醇類共聚合物，再者這些氫氧基部分變性之變性聚乙烯醇系聚合 物等。於該接著劑，也可使用多價醛、水溶性環氧化合物、三聚氰胺類化合物等作為添加劑。The polarizing film and the protective film are laminated using an adhesive such as a water solvent-based adhesive, an organic solvent-based adhesive, a hot-melt adhesive, or a solventless adhesive. The water-based solvent-based adhesive agent, for example, a polyvinyl alcohol-based resin aqueous solution, an aqueous two-component urethane-based emulsion adhesive, or the like, and an organic solvent-based adhesive, for example, a one-liquid type urethane-based adhesive or the like . When a hydrophilized treated acetaminocellulose-based film such as a saponification treatment is used as a protective film on the joint surface of the polarizing film, a polyvinyl alcohol-based resin aqueous solution is preferably used as the adhesive. a polyvinyl alcohol-based resin used as an adhesive, a vinyl alcohol single polymer obtained by saponification treatment of polyvinyl acetate of a single polymer of vinyl acetate, vinyl acetate, and other monomeric bodies copolymerizable therewith The vinyl alcohol-based copolymer obtained by the saponification treatment of the copolymer, and the denatured polyvinyl alcohol-based polymerization in which these hydroxyl groups are partially denatured Things and so on. As the binder, a polyvalent aldehyde, a water-soluble epoxy compound, a melamine compound or the like can also be used as an additive.
通常接著劑係於調製後在約15~40℃的溫度下塗佈，貼合溫度通常在15~30℃程度的範圍。貼合後進行乾燥處理，除去接著劑中包含的水等的溶劑，此時乾燥溫度通常約30~85℃，較佳為40~80℃的範圍。然後，在約15~85℃，較佳為約20~50℃，更好為約35~45℃的溫度環境下，通常約1~90天的程度痊癒，使接著劑硬化。因該痊癒時間長則生產性變差，痊癒時間為1~30天的程度，較佳為約1~7天。Usually, the adhesive is applied at a temperature of about 15 to 40 ° C after the preparation, and the bonding temperature is usually in the range of about 15 to 30 ° C. After the bonding, the drying treatment is carried out to remove the solvent such as water contained in the adhesive. The drying temperature is usually about 30 to 85 ° C, preferably 40 to 80 ° C. Then, it is cured at a temperature of about 15 to 85 ° C, preferably about 20 to 50 ° C, more preferably about 35 to 45 ° C, usually about 1 to 90 days to harden the adhesive. Since the recovery time is long, the productivity is deteriorated, and the healing time is 1 to 30 days, preferably about 1 to 7 days.
如此，可得隔著接著劑於偏光薄膜的一面或兩面貼附保護薄膜之偏光板。Thus, a polarizing plate in which a protective film is attached to one or both sides of the polarizing film via an adhesive can be obtained.
於本發明，保護薄膜可具有作為相位差薄膜的功能、作為增亮薄膜的功能、作為反射薄膜的功能、作為半透過反射薄膜的功能、作為擴散薄膜的功能、作為光學補償薄膜的功能等的光學功能。於該情況，除於保護薄膜的表面，藉由層合相位差薄膜、增亮薄膜、反射薄膜、半透過反射薄膜、擴散薄膜、光學補償薄膜等的光學功能性薄膜，可具有如此的功能之外，可賦予保護薄膜本身如此的功能。而且，可使保護薄膜本身具有如增亮薄膜功能之擴散薄膜等之複數功能。In the present invention, the protective film can have a function as a retardation film, a function as a brightness enhancement film, a function as a reflective film, a function as a semi-transmissive reflection film, a function as a diffusion film, a function as an optical compensation film, and the like. Optical function. In this case, in addition to the surface of the protective film, an optical functional film laminated with a retardation film, a brightness enhancement film, a reflective film, a semi-transmissive reflective film, a diffusion film, an optical compensation film, or the like can have such a function. In addition, the protective film itself can be imparted with such a function. Further, the protective film itself can have a plurality of functions such as a diffusion film which enhances the function of the film.
例如藉由於上述的保護薄膜進行記載於日本專利第2841377號公報、專利第3094113號公報等的延伸處理，記載於專利第3168850號公報等的處理，可賦予作為相位 差薄膜的功能。而且，藉由於上述保護薄膜，以記載於日本公開專利特開2002-169025號公報、特開2003-29030號公報的方法形成微細孔，或者選擇反射中心波長相異之2層以上的膽固醇狀液晶層重疊，可賦予作為增亮薄膜的功能。於上述的保護薄膜，藉由蒸鍍、濺鍍等形成金屬薄膜，可賦予作為反射薄膜或半透過反射薄膜的功能。藉由塗佈含微粒子的樹脂於上述保護薄膜，可賦予作為擴散薄膜的功能。而且，藉由塗佈盤狀液晶性化合物等的液晶性化合物於上述保護薄膜使其配向，可賦予作為光學補償薄膜的功能。而且，也可使用適當接著劑，將商品名：DBEF(3M(股)公司製)等的增亮薄膜，商品名：WV薄膜(富士寫真薄膜(股)製)等的改良視角薄膜，商品名：Sumkalight(註冊商標)(住友化學工業(股)製)等的相位差薄膜等的市售的光學功能性薄膜直接貼合於偏光薄膜。For example, the processing described in Japanese Patent No. 2841377 and Japanese Patent No. 3094113 is carried out by the above-mentioned protective film, and the processing described in Japanese Patent No. 3168850 can be given as a phase. The function of the poor film. Further, by the above-mentioned protective film, fine pores are formed by the method described in JP-A-2002-169025, JP-A-2003-29030, or two or more layers of cholesteric liquid crystal having different reflection center wavelengths are selected. The layers overlap to impart a function as a brightness enhancing film. In the above protective film, a metal thin film is formed by vapor deposition, sputtering, or the like, and a function as a reflective film or a semi-transmissive reflective film can be imparted. By applying the fine particle-containing resin to the above protective film, it is possible to impart a function as a diffusion film. In addition, by applying a liquid crystal compound such as a discotic liquid crystalline compound to the protective film to align the film, it is possible to impart a function as an optical compensation film. In addition, a modified viewing film such as a brightening film such as DBEF (made by 3M Co., Ltd.), a product name: WV film (manufactured by Fuji Photo Film Co., Ltd.), or the like, may be used. A commercially available optical functional film such as a phase difference film such as Sumkalight (registered trademark) (manufactured by Sumitomo Chemical Co., Ltd.) is directly bonded to a polarizing film.
以下表示的實施例更具體說明本發明，但本發明不限於這些例子。The examples shown below more specifically illustrate the invention, but the invention is not limited to these examples.
厚度75μm的聚乙烯醇薄膜(Kuraray Vinylon VF-PS # 7500、聚合度2400、皂化度99.9莫耳%以上)於30℃純水，保持薄膜不鬆弛狀態浸漬約130秒，使薄膜充分膨脹。A polyvinyl alcohol film (Kuraray Vinylon VF-PS #7500, polymerization degree 2400, saponification degree: 99.9 mol% or more) having a thickness of 75 μm was immersed in pure water at 30 ° C for about 130 seconds in a state where the film was not slack, and the film was sufficiently expanded.
然後，浸漬於碘元素/碘化鉀/水重量比為 0.02/1.0/100的30℃水溶液，且進行2.50倍之一軸延伸。再者，浸漬於碘元素/碘化鉀/水重量比為0.025/1.5/100的30℃水溶液，且進行1.04倍之一軸延伸。然後，浸漬於碘化鉀/硼酸/水重量比為10/5/100的60℃水溶液，進行硼酸處理且進行一軸延伸直至從原結構的總延伸倍率成為5.9倍為止。硼酸處理後，以10℃純水水洗約10秒。水洗後，於60℃乾燥2分鐘，得到厚度28μm的碘系偏光薄膜。Then, the immersion in iodine/potassium iodide/water weight ratio is A 30 ° C aqueous solution of 0.02 / 1.0 / 100, and a 2.50 times one axis extension. Further, it was immersed in a 30 ° C aqueous solution having an iodine/potassium iodide/water weight ratio of 0.025/1.5/100, and was subjected to 1.04 times of one-axis extension. Then, it was immersed in a 60 ° C aqueous solution having a potassium iodide/boric acid/water weight ratio of 10/5/100, subjected to boric acid treatment, and subjected to one-axis stretching until the total stretching ratio from the original structure was 5.9 times. After boric acid treatment, it was washed with pure water at 10 ° C for about 10 seconds. After washing with water, it was dried at 60 ° C for 2 minutes to obtain an iodine-based polarizing film having a thickness of 28 μm.
由剛水洗後的薄膜寬度(W1)以及乾燥後的薄膜寬度(W2)，求得乾燥頸為13%。From the film width (W1) immediately after washing and the film width (W2) after drying, the dry neck was found to be 13%.
於偏光薄膜的兩面塗佈聚乙烯醇系接著劑，於兩面貼合保護薄膜〔表面施以皂化處理之三乙醯基纖維素薄膜「Fujitac(註冊商標)T80UNL」、富士寫真薄膜(股)製、厚度80μm〕，於60℃乾燥5分鐘，得到偏光板。A polyvinyl alcohol-based adhesive is applied to both surfaces of the polarizing film, and a protective film is bonded to both surfaces (a saponified triethylenesulfonated cellulose film "Fujitac (registered trademark) T80UNL" and a Fuji photo film) The thickness was 80 μm, and dried at 60 ° C for 5 minutes to obtain a polarizing plate.
該偏光薄膜在直交泥科爾(crossed Nicol)狀態下於暗室以目視觀察，幾乎無染色不均。而且，染色不均確認是從偏光板漏光的程度。The polarizing film was visually observed in a dark room in a crossed Nicol state, and there was almost no uneven dyeing. Moreover, the uneven dyeing was confirmed to be the extent of light leakage from the polarizing plate.
厚度75μm的聚乙烯醇薄膜(Kuraray Vinylon VF-PS # 7500、聚合度2400、皂化度99.9莫耳%以上)於30℃純水，保持薄膜不鬆弛狀態浸漬約130秒，使薄膜充分膨脹。A polyvinyl alcohol film (Kuraray Vinylon VF-PS #7500, polymerization degree 2400, saponification degree: 99.9 mol% or more) having a thickness of 75 μm was immersed in pure water at 30 ° C for about 130 seconds in a state where the film was not slack, and the film was sufficiently expanded.
然後，浸漬於碘元素/碘化鉀/水重量比為 0.02/1.0/100的30℃水溶液，且進行1.04倍之一軸延伸。再者，浸漬於碘元素/碘化鉀/水重量比為0.025/1.5/100的30℃水溶液，且進行2.50倍之一軸延伸。然後，浸漬於碘化鉀/硼酸/水重量比為10/5/100的60℃水溶液，進行硼酸處理且進行一軸延伸直至從原結構的總延伸倍率成為5.9倍為止。硼酸處理後，以10℃純水水洗約10秒。水洗後，於60℃乾燥2分鐘，得到厚度28μm的碘系偏光薄膜。Then, the immersion in iodine/potassium iodide/water weight ratio is A 30 ° C aqueous solution of 0.02 / 1.0 / 100, and 1.04 times the axial extension. Further, it was immersed in a 30 ° C aqueous solution having an iodine/potassium iodide/water weight ratio of 0.025/1.5/100, and was subjected to a 2.50-fold axial extension. Then, it was immersed in a 60 ° C aqueous solution having a potassium iodide/boric acid/water weight ratio of 10/5/100, subjected to boric acid treatment, and subjected to one-axis stretching until the total stretching ratio from the original structure was 5.9 times. After boric acid treatment, it was washed with pure water at 10 ° C for about 10 seconds. After washing with water, it was dried at 60 ° C for 2 minutes to obtain an iodine-based polarizing film having a thickness of 28 μm.
乾燥前的純水洗淨時不緩和薄膜之洗淨步驟的張力，以市售差動變壓器方式張力儀於線上測定。其結果，850N/m寬的張力，沒有產生薄膜的緩和。The pure water before drying does not relax the tension of the film washing step, and is measured on a line by a commercially available differential transformer type tension meter. As a result, the tension of 850 N/m width did not cause relaxation of the film.
使用該碘系偏光薄膜，與實施例同樣地得到偏光板。Using this iodine-based polarizing film, a polarizing plate was obtained in the same manner as in the examples.
該偏光薄膜在直交泥科爾(crossed Nicol)狀態下於暗室以目視觀察，幾乎無染色不均。The polarizing film was visually observed in a dark room in a crossed Nicol state, and there was almost no uneven dyeing.
與實施例1相同於厚度75μm的聚乙烯醇薄膜於30℃純水，保持薄膜不鬆弛狀態浸漬約130秒，使薄膜充分膨脹(膨脹約1.2倍)。In the same manner as in Example 1, a polyvinyl alcohol film having a thickness of 75 μm was immersed in pure water at 30 ° C for about 130 seconds in a state where the film was not relaxed, and the film was sufficiently expanded (about 1.2 times in expansion).
然後，浸漬於碘元素/碘化鉀/水重量比為0.025/1.5/100的30℃水溶液，且延伸後的長度與實施例1相同，進行2.60倍之一軸延伸。以下與實施例1央同，進行硼酸處理以及水洗．乾燥，得到厚度28μm的碘系偏光薄膜。Then, it was immersed in a 30 ° C aqueous solution having an iodine/potassium iodide/water weight ratio of 0.025/1.5/100, and the length after stretching was the same as in Example 1, and a 2.60-fold axial extension was performed. The following is the same as in the first embodiment, boric acid treatment and water washing. The film was dried to obtain an iodine-based polarizing film having a thickness of 28 μm.
由剛水洗後的薄膜寬度(W1)以及乾燥後的薄膜寬度(W2)，求得乾燥頸為15%。From the film width (W1) immediately after washing and the film width (W2) after drying, the dry neck was found to be 15%.
使用該碘系偏光薄膜，與實施例同樣地得到偏光板。Using this iodine-based polarizing film, a polarizing plate was obtained in the same manner as in the examples.
該偏光薄膜在直交泥科爾(crossed Nicol)狀態下於暗室以目視觀察，有若干染色不均。The polarizing film was visually observed in a dark room in a crossed Nicol state, and there were some uneven dyeing.
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| JP5667016B2 (en) | 2010-09-03 | 2015-02-12 | 日東電工株式会社 | Thin polarizing film, optical laminate having thin polarizing film, and manufacturing method of thin polarizing film |
| JP5871363B2 (en) | 2010-09-09 | 2016-03-01 | 日東電工株式会社 | Manufacturing method of thin polarizing film |
| CN103725037B (en) * | 2014-01-20 | 2016-05-25 | 云南云天化股份有限公司 | The preparation method of iodine based dye, iodine polarizing film |
| WO2016093277A1 (en) * | 2014-12-12 | 2016-06-16 | 住友化学株式会社 | Method for producing polarizing film, and polarizing film |
| KR20170052991A (en) * | 2015-11-05 | 2017-05-15 | 스미또모 가가꾸 가부시키가이샤 | Polarizer and method of preparing the same |
| TWI620905B (en) * | 2017-06-14 | 2018-04-11 | 住華科技股份有限公司 | Device for removing liquid |
| JP7096700B2 (en) * | 2017-09-13 | 2022-07-06 | 日東電工株式会社 | A method for manufacturing a polarizing film, a polarizing plate, a polarizing plate roll, and a polarizing film. |
| JP7494267B2 (en) | 2022-08-02 | 2024-06-03 | 長春石油化學股▲分▼有限公司 | Polyvinyl alcohol film, optical film and manufacturing method |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0243504A (en) * | 1988-08-03 | 1990-02-14 | Toray Ind Inc | Production of polarizing film |
| JP3264816B2 (en) * | 1995-11-09 | 2002-03-11 | 日本合成化学工業株式会社 | Polarizer |
| JP3448011B2 (en) * | 2000-04-25 | 2003-09-16 | 株式会社クラレ | Manufacturing method of polarizing film |
| TWI230275B (en) * | 2000-05-12 | 2005-04-01 | Kuraray Co | Polyvinyl alcohol film and polarization film |
| JP2001343522A (en) * | 2000-05-31 | 2001-12-14 | Sumitomo Chem Co Ltd | Polarizer film and its manufacturing method |
| JP3976220B2 (en) * | 2000-08-21 | 2007-09-12 | 日本合成化学工業株式会社 | Polyvinyl alcohol film for polarizing film |
| JP2004294808A (en) * | 2003-03-27 | 2004-10-21 | Sumitomo Chem Co Ltd | Iodine-based polarizing film, method for manufacturing the same and polarizing plate |
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2003
- 2003-12-15 JP JP2003416892A patent/JP4421886B2/en not_active Expired - Fee Related
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2004
- 2004-11-19 TW TW093135684A patent/TWI389946B/en active
- 2004-12-07 KR KR1020040102087A patent/KR101137644B1/en active IP Right Grant
- 2004-12-09 CN CNB200410100386XA patent/CN100437162C/en active Active
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|---|---|
| KR20050059993A (en) | 2005-06-21 |
| JP4421886B2 (en) | 2010-02-24 |
| CN1629660A (en) | 2005-06-22 |
| CN100437162C (en) | 2008-11-26 |
| JP2005173495A (en) | 2005-06-30 |
| TW200526715A (en) | 2005-08-16 |
| KR101137644B1 (en) | 2012-04-19 |
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