TW201809759A - Method and apparatus for manufacturing polarizing film - Google Patents

Method and apparatus for manufacturing polarizing film Download PDF

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TW201809759A
TW201809759A TW106127466A TW106127466A TW201809759A TW 201809759 A TW201809759 A TW 201809759A TW 106127466 A TW106127466 A TW 106127466A TW 106127466 A TW106127466 A TW 106127466A TW 201809759 A TW201809759 A TW 201809759A
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film
electromagnetic wave
cross
polyvinyl alcohol
based resin
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TW106127466A
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TWI761361B (en
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住田幸司
趙天熙
崔允碩
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日商住友化學股份有限公司
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29DPRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00Producing optical elements, e.g. lenses or prisms
    • B29D11/00634Production of filters
    • B29D11/00644Production of filters polarizing
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • G02B5/3025Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033Polarisers, 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/06Coating with compositions not containing macromolecular substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12Chemical modification
    • C08J7/123Treatment by wave energy or particle radiation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528Polarisers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Abstract

The present invention is to provide a method and apparatus for manufacturing polarizing film; the method for manufacturing polarizing film is capable of further improving optical characteristics of a polarizing film by performing crosslinking treatment in the manufacturing method of the polarizing film. The method of the present invention is a method for manufacturing a polarizing film from a polyvinyl alcohol-based resin film, comprising: a dyeing step of dyeing the polyvinyl alcohol-based resin film with a dichroic dye; a crosslinking step of subjecting the polyvinyl alcohol-based resin film subjected to the dyeing treatment to a crosslinking treatment with a crosslinking agent; an electromagnetic wave irradiating step of irradiating the polyvinyl alcohol-based resin film after the crosslinking treatment with an electromagnetic wave having a ratio of radiant energy of infrared rays of more than 2 [mu]m to 4 [mu]m or less of 25 % or more; and a washing step of washing the polyvinyl alcohol-based resin film irradiated with the electromagnetic wave.

Description

偏光膜之製造方法及製造裝置 Manufacturing method and manufacturing device of polarizing film

本發明係關於由聚乙烯醇系樹脂膜製造偏光膜之方法、及製造裝置。 The present invention relates to a method for manufacturing a polarizing film from a polyvinyl alcohol-based resin film and a manufacturing apparatus therefor.

偏光板係廣泛使用作為液晶顯示裝置等影像顯示裝置中的偏光元件等。作為偏光板一般為在偏光膜單面或兩面使用接著劑等貼合透明樹脂膜(保護膜等)所構成者。 The polarizing plate is widely used as a polarizing element in an image display device such as a liquid crystal display device. The polarizing plate is generally formed by laminating a transparent resin film (protective film, etc.) on one or both sides of a polarizing film using an adhesive or the like.

偏光膜主要藉由對聚乙烯醇系樹脂所構成原料膜實施浸漬於含有碘等二色性色素之染色浴之處理,接著實施浸漬於含有硼酸等交聯劑之交聯浴之處理等,並在任一階段將膜單軸延伸而製作。單軸延伸有在空氣中進行延伸之乾式延伸、及在上述染色浴及交聯浴等液中進行延伸之濕式延伸。 The polarizing film is mainly processed by dipping a raw material film made of a polyvinyl alcohol resin in a dyeing bath containing a dichroic pigment such as iodine, and then by dipping in a crosslinking bath containing a crosslinking agent such as boric acid. The film was produced by uniaxially stretching the film at any stage. Uniaxial stretching includes dry stretching in air and wet stretching in liquids such as the dyeing bath and cross-linking bath.

以往,偏光膜的製造方法中,係為了提高偏光膜的特性而作出各種努力。日本特開2013-148806號公報(專利文獻1)中係記載,藉由於硼酸處理步驟與水洗步驟之間設有將聚乙烯醇系樹脂膜進行乾燥之一次乾燥步 驟,而可使穿透光成為良好的色相,亦即,可接近中性灰(neutral gray)。 Conventionally, in the manufacturing method of a polarizing film, various efforts have been made to improve the characteristics of the polarizing film. According to Japanese Patent Application Laid-Open No. 2013-148806 (Patent Document 1), a primary drying step for drying a polyvinyl alcohol-based resin film is provided between the boric acid treatment step and the water washing step. This can make the transmitted light a good hue, that is, it can approach neutral gray.

日本特開昭59-094706號公報(專利文獻2)中記載,藉由照射波長為1μm以上之遠紅外線並進行固定化處理,能夠得到收縮率小且具有良好的平板性之偏光膜。 Japanese Patent Application Laid-Open No. 59-094706 (Patent Document 2) describes that by irradiating far-infrared rays having a wavelength of 1 μm or more and performing a fixation treatment, a polarizing film having a small shrinkage and a good flatness can be obtained.

[先前技術文獻] [Prior technical literature] [專利文獻] [Patent Literature]

專利文獻1:日本特開2013-148806號公報。 Patent Document 1: Japanese Patent Application Publication No. 2013-148806.

專利文獻2:日本特開昭59-094706號公報。 Patent Document 2: Japanese Patent Application Laid-Open No. 59-094706.

作為偏光膜所要求的特性,在上述色相、收縮率、平板性以外還有各種特性,重要的特性有將單體穿透率及偏光度作為指標之光學特性。為了使碘等二色性色素固定而使用硼酸等交聯劑之交聯處理,亦為可提升耐水性並提升光學特性的方法之一。 As the characteristics required for the polarizing film, there are various characteristics in addition to the above-mentioned hue, shrinkage, and flatness. The important characteristics are optical characteristics using the monomer transmittance and the degree of polarization as indicators. In order to fix a dichroic dye such as iodine, a cross-linking treatment using a cross-linking agent such as boric acid is also one of the methods that can improve water resistance and optical properties.

專利文獻1所記載的方法中,雖進行交聯處理,但藉由進行一次乾燥步驟是否可進一步提升偏光膜的光學特性之點仍未明朗。專利文獻2所記載的方法中,並未進行交聯處理,且由於進行照射遠紅外線之步驟而顯示偏光度降低之結果(專利文獻2的表1所示之固定化處理法為比較「處理前」與「遠紅外線」之實施例的偏光度)。 In the method described in Patent Document 1, although a crosslinking treatment is performed, it is not clear whether the optical characteristics of the polarizing film can be further improved by performing a single drying step. In the method described in Patent Document 2, a cross-linking treatment is not performed, and the result of reducing the degree of polarization due to the step of irradiating far-infrared rays is shown. "And the far-infrared embodiment of polarization).

本發明之目的在於提供一種偏光膜之製造 方法及其製造裝置,前述偏光膜之製造方法,係在進行交聯處理之偏光膜的製造方法中,可使偏光膜的光學特性更為提升。 An object of the present invention is to provide a polarizing film. The method and the manufacturing device thereof, and the aforementioned method for manufacturing a polarizing film are in a method for manufacturing a polarizing film subjected to a cross-linking treatment, which can further improve the optical characteristics of the polarizing film.

本發明提供以下所示偏光膜之製造方法、及製造裝置。 The present invention provides a manufacturing method and a manufacturing apparatus of a polarizing film shown below.

〔1〕一種偏光膜之製造方法,係由聚乙烯醇系樹脂膜製造偏光膜,並含有:將前述聚乙烯醇系樹脂膜以二色性色素進行染色處理之染色步驟、將前述染色處理後之前述聚乙烯醇系樹脂膜以交聯劑進行交聯處理之交聯步驟、於前述交聯步驟後之前述聚乙烯醇系樹脂膜照射全放射能量中超過2μm且4μm以下的波長之紅外線之放射能量比例為全放射能量的25%以上之電磁波之電磁波照射步驟、將前述電磁波照射後之前述聚乙烯醇系樹脂膜進行洗淨之洗淨步驟。 [1] A method for producing a polarizing film, which is a method of producing a polarizing film from a polyvinyl alcohol resin film, and comprising: a dyeing step of dyeing the polyvinyl alcohol resin film with a dichroic dye; The above-mentioned polyvinyl alcohol-based resin film is subjected to a cross-linking step of a cross-linking treatment with a cross-linking agent. An electromagnetic wave irradiation step of an electromagnetic wave having a radiation energy ratio of 25% or more of the total radiation energy, and a cleaning step of washing the polyvinyl alcohol-based resin film after the electromagnetic wave is irradiated.

〔2〕如〔1〕所記載之偏光膜之製造方法,其在前述電磁波照射步驟中,前述電磁波的照射熱量是每單位體積前述聚乙烯醇系樹脂膜為100J/cm3以上50kJ/cm3以下。 [2] The method for producing a polarizing film according to [1], wherein in the aforementioned electromagnetic wave irradiation step, the irradiation heat of the electromagnetic wave is 100 J / cm 3 or more and 50 kJ / cm 3 or more per unit volume of the polyvinyl alcohol-based resin film. the following.

〔3〕如〔1〕或〔2〕所記載之偏光膜之製造方法,其中,前述交聯劑包含硼化合物。 [3] The method for producing a polarizing film according to [1] or [2], wherein the crosslinking agent contains a boron compound.

〔4〕如〔1〕至〔3〕中任一項所記載之偏光膜之製造方法,其中,前述交聯步驟為將前述聚乙烯醇系樹脂膜浸漬於由前述交聯劑的水溶液所成之交聯浴之步驟。 [4] The method for producing a polarizing film according to any one of [1] to [3], wherein the cross-linking step is obtained by immersing the polyvinyl alcohol-based resin film in an aqueous solution of the cross-linking agent. Steps of the crosslinking bath.

〔5〕如〔4〕所記載之偏光膜之製造方法,其在前述交聯處理之後、前述照射電磁波之前,進一步包含將附著於前述聚乙烯醇系樹脂膜的表面之前述水溶液去除之除液步驟。 [5] The method for producing a polarizing film according to [4], further comprising removing the aqueous solution attached to the surface of the polyvinyl alcohol-based resin film after the cross-linking treatment and before the electromagnetic wave is irradiated. step.

〔6〕如〔4〕或〔5〕所記載之偏光膜之製造方法,其中,前述電磁波照射步驟係在將前述聚乙烯醇系樹脂膜從前述交聯浴拉出後的5秒以內進行。 [6] The method for producing a polarizing film according to [4] or [5], wherein the electromagnetic wave irradiation step is performed within 5 seconds after the polyvinyl alcohol-based resin film is pulled out of the crosslinking bath.

〔7〕一種偏光膜之製造裝置,係由聚乙烯醇系樹脂膜製造偏光膜,並具備:將前述聚乙烯醇系樹脂膜以二色性色素進行染色處理之染色部、將前述染色處理後之前述聚乙烯醇系樹脂膜以交聯劑進行交聯處理之交聯部、於前述交聯步驟後之前述聚乙烯醇系樹脂膜,進行照射超過2μm且4μm以下的波長之紅外線之放射能量比例為全放射能量的25%以上的電磁波之電磁波照射部、將前述電磁波照射後之前述聚乙烯醇系樹脂膜進行洗淨之洗淨部。 [7] An apparatus for producing a polarizing film, which is a polarizing film made of a polyvinyl alcohol resin film, and includes a dyeing section for dyeing the polyvinyl alcohol resin film with a dichroic dye, and after the dyeing treatment, The polyvinyl alcohol-based resin film is cross-linked with a cross-linking agent, and the polyvinyl alcohol-based resin film after the cross-linking step is irradiated with infrared rays having a wavelength exceeding 2 μm and 4 μm or less. An electromagnetic wave irradiating portion having an electromagnetic wave whose proportion is 25% or more of the total radiant energy, and a washing portion that cleans the polyvinyl alcohol-based resin film after the electromagnetic wave is irradiated.

根據本發明,可提供可使偏光膜的光學特 性提升之偏光膜的製造方法及製造装置。 According to the present invention, it is possible to provide an optical feature capable of making a polarizing film Manufacturing method and manufacturing device of improved polarizing film.

10‧‧‧聚乙烯醇系樹脂所構成之原料膜 10‧‧‧ Raw material film made of polyvinyl alcohol resin

11‧‧‧原料輥 11‧‧‧ raw material roller

13‧‧‧膨潤浴 13‧‧‧Swelling bath

15‧‧‧染色浴 15‧‧‧ Dyeing bath

17a‧‧‧第1交聯浴 17a‧‧‧The first cross-linking bath

17b‧‧‧第2交聯浴 17b‧‧‧ 2nd Crosslinking Bath

19‧‧‧洗淨浴 19‧‧‧washing bath

21‧‧‧乾燥爐 21‧‧‧ drying furnace

23‧‧‧偏光膜 23‧‧‧Polarizing Film

30至48、60、61‧‧‧導輥 30 to 48, 60, 61‧‧‧ guide rollers

50至52、53a、53b、54、55‧‧‧夾輥 50 to 52, 53a, 53b, 54, 55 ...

71‧‧‧電磁波照射部 71‧‧‧ electromagnetic wave irradiation section

第1圖係概略地表示本發明之偏光膜之製造方法及其所使用的偏光膜製造裝置之一例之剖面圖。 FIG. 1 is a cross-sectional view schematically showing an example of a method for manufacturing a polarizing film of the present invention and a polarizing film manufacturing apparatus used therefor.

第2圖係表示各種電磁波照射器的種類之放射能量光譜。 Fig. 2 shows the radiation energy spectrum of various types of electromagnetic wave irradiators.

<偏光膜之製造方法> <Manufacturing method of polarizing film>

本發明中之偏光膜係於經單軸延伸的聚乙烯醇系樹脂膜吸附配向有二色性色素(碘或二色性染料)者。構成聚乙烯醇系樹脂膜之聚乙烯醇系樹脂通常係藉由皂化聚乙酸乙烯酯系樹脂而獲得。其皂化度通常為約85莫耳%以上,較佳為約90莫耳%以上,更佳為約99莫耳%以上。聚乙酸乙烯酯系樹脂例如除了乙酸乙烯酯均聚物之聚乙酸乙烯酯以外,也可為乙酸乙烯酯與可與其共聚之其他單體的共聚物等。作為可共聚之其他單體可舉例如:不飽和羧酸類、烯烴類、乙烯基醚類、不飽和磺酸類等。聚乙烯醇系樹脂之聚合度通常為約1000至10000,較佳為約1500至5000程度。 The polarizing film in the present invention is a polyvinyl alcohol-based resin film that is uniaxially stretched, and is adsorbed and aligned with a dichroic pigment (iodine or dichroic dye). The polyvinyl alcohol-based resin constituting the polyvinyl alcohol-based resin film is usually obtained by saponifying a polyvinyl acetate-based resin. The degree of saponification is usually about 85 mol% or more, preferably about 90 mol% or more, and more preferably about 99 mol% or more. The polyvinyl acetate-based resin may be, for example, a copolymer of vinyl acetate and other monomers copolymerizable therewith, in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate. Examples of other copolymerizable monomers include unsaturated carboxylic acids, olefins, vinyl ethers, and unsaturated sulfonic acids. The degree of polymerization of the polyvinyl alcohol-based resin is usually about 1,000 to 10,000, preferably about 1500 to 5,000.

該等聚乙烯醇系樹脂可進行改質,亦可使用例如以醛類改質之聚乙烯醇縮甲醛、聚乙烯醇縮乙醛、聚乙烯醇縮丁醛等。 These polyvinyl alcohol-based resins can be modified, and for example, polyvinyl formal, polyvinyl acetal, and polyvinyl butyral modified with aldehydes can also be used.

本發明中,作為製造偏光膜之起始材料, 係使用厚度為65μm以下(例如60μm以下),較佳為50μm以下,更佳為35μm以下,又更佳為30μm以下之未延伸的聚乙烯醇系樹脂膜(原料膜)。 In the present invention, as a starting material for manufacturing a polarizing film, An unstretched polyvinyl alcohol-based resin film (raw material film) having a thickness of 65 μm or less (for example, 60 μm or less), preferably 50 μm or less, more preferably 35 μm or less, and even more preferably 30 μm or less is used.

藉此可獲得市場要求日漸提高之薄膜偏光膜。原料膜之寬度並無特別限制,例如可為約400至6000mm。原料膜例如可準備長條未延伸的聚乙烯醇系樹脂膜之輥(原料輥)。 In this way, a thin film polarizing film that is increasingly required by the market can be obtained. The width of the raw material film is not particularly limited, and may be, for example, about 400 to 6000 mm. As the raw material film, for example, a roll (raw material roll) of a long unstretched polyvinyl alcohol-based resin film can be prepared.

又,本發明所使用聚乙烯醇系樹脂膜可為將其積層於支持之基材膜者,亦即,可準備基材膜與積層於其上之聚乙烯醇系樹脂膜的積層膜,而作為該聚乙烯醇系樹脂膜。此時,聚乙烯醇系樹脂膜例如可藉由在基材膜的至少一面塗佈含有聚乙烯醇系樹脂之塗佈液後進行乾燥而製造。 In addition, the polyvinyl alcohol-based resin film used in the present invention may be a substrate film laminated on a supporting substrate film, that is, a laminated film of a substrate film and a polyvinyl alcohol-based resin film laminated thereon may be prepared, and As this polyvinyl alcohol-based resin film. In this case, the polyvinyl alcohol-based resin film can be produced, for example, by applying a coating solution containing a polyvinyl alcohol-based resin to at least one side of the base film and then drying it.

基材膜例如可使用熱塑性樹脂所構成之膜。作為具體例係具有透光性之熱塑性樹脂,較佳為以光學性透明之熱塑性樹脂所構成之膜,例如可為鏈狀聚烯烴系樹脂(聚丙烯系樹脂等)、環狀聚烯烴系樹脂(降莰烯系樹脂等)之類之聚烯烴系樹脂;三乙酸纖維素、二乙酸纖維素之類之纖維素系樹脂;聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯之類之聚酯系樹脂;聚碳酸酯系樹脂;甲基丙烯酸甲酯系樹脂之類之(甲基)丙烯酸系樹脂;聚苯乙烯系樹脂;聚氯乙烯系樹脂;丙烯腈/丁二烯/苯乙烯系樹脂;丙烯腈/苯乙烯系樹脂;聚乙酸乙烯酯系樹脂;聚偏二氯乙烯系樹脂;聚醯胺系樹脂;聚縮醛系樹脂;改質聚苯醚系樹脂;聚碸系樹脂;聚醚碸系樹脂;聚芳酯系樹脂;聚醯胺醯亞胺系樹脂; 聚醯亞胺系樹脂等。 As the base film, for example, a film made of a thermoplastic resin can be used. As a specific example, a light-transmitting thermoplastic resin is preferably a film made of an optically transparent thermoplastic resin, and may be, for example, a chain polyolefin resin (such as a polypropylene resin) or a cyclic polyolefin resin. (Norbornene-based resins) and other polyolefin-based resins; cellulose triacetate and cellulose diacetate-based cellulose resins; polyethylene terephthalate, polybutylene terephthalate Polyester resins such as; polycarbonate resins; (meth) acrylic resins such as methyl methacrylate resins; polystyrene resins; polyvinyl chloride resins; acrylonitrile / butadiene / Styrene resin; acrylonitrile / styrene resin; polyvinyl acetate resin; polyvinylidene chloride resin; polyamide resin; polyacetal resin; modified polyphenylene ether resin;碸 resin; polyether 碸 resin; polyarylate resin; polyamidamine 醯 imine resin; Polyimide-based resins and the like.

偏光膜係邊將上述長條原料膜由原料輥拉出,邊沿著偏光膜製造裝置之膜搬送路徑連續地搬送,並且浸漬於收容於處理槽之處理液(以下亦稱為「處理浴」)後拉出,在實施預定之處理步驟後實施乾燥步驟,藉此可連續製造長條偏光膜。此外,處理步驟只要是使膜接觸處理液並處理之方法,則不限定於將膜浸漬於處理浴之方法,可為藉由噴霧、流下、滴下等將處理液附著於膜表面而處理膜之方法。以藉由將膜浸漬於處理浴之方法進行處理步驟時,進行一個處理步驟之處理浴並不限定於一個,可將膜依序浸漬於二個以上處理浴而完成一個處理步驟。 The polarizing film is continuously conveyed along the film conveying path of the polarizing film manufacturing device while the long raw film is pulled out from the raw material roll, and is immersed in a processing liquid (hereinafter also referred to as a "processing bath") stored in a processing tank. It is then pulled out, and a drying step is performed after performing a predetermined processing step, whereby a long polarizing film can be continuously manufactured. In addition, the processing step is not limited to a method of immersing a film in a processing bath as long as the film is brought into contact with a processing solution, and may be a method of processing the film by attaching the processing liquid to the surface of the film by spraying, flowing down, or dropping. method. When the processing step is performed by immersing the film in a processing bath, the processing bath performing one processing step is not limited to one, and the film may be sequentially immersed in two or more processing baths to complete one processing step.

作為上述處理液可舉例如:膨潤液、染色液、交聯液、洗淨液等。接著,作為上述處理步驟可舉例如:使原料膜接觸膨潤液而進行膨潤處理之膨潤步驟、使膨潤處理後之膜接觸染色液而進行染色處理之染色步驟、使染色處理後之膜接觸交聯液而進行交聯處理之交聯步驟、及使交聯處理後之膜接觸洗淨液而進行洗淨處理之洗淨步驟。再者,可在該等一連串處理步驟之間(亦即,在任1個以上處理步驟之前後及/或任1個以上處理步驟中)實施濕式或乾式單軸延伸處理。因應所需可加入其他處理步驟。 Examples of the treatment liquid include a swelling liquid, a dyeing liquid, a crosslinking liquid, and a cleaning liquid. Next, as the above-mentioned treatment steps, for example, a swelling step in which a raw film is brought into contact with a swelling solution to perform a swelling treatment, a dyeing step in which a swelling-treated film is brought into contact with a dyeing liquid to perform a dyeing treatment, and a film after the dyeing treatment is brought into contact with cross-linking A cross-linking step for performing a cross-linking treatment with liquid, and a washing step for subjecting the film after the cross-linking treatment to a cleaning solution to perform a washing treatment. Furthermore, a wet or dry uniaxial stretching process may be performed between such a series of processing steps (that is, before or after any one or more processing steps and / or during any one or more processing steps). Other processing steps can be added as needed.

本發明中,是在交聯處理後、洗淨處理之前進行對膜照射電磁波之後述電磁波照射步驟。藉由進行電磁波照射步驟而可使所得偏光膜之光學特性提升。 In the present invention, the electromagnetic wave irradiation step is performed after the film is irradiated with electromagnetic waves after the crosslinking treatment and before the washing treatment. By performing the electromagnetic wave irradiation step, the optical characteristics of the obtained polarizing film can be improved.

以下邊參照第1圖邊詳細係說明本發明之偏光膜之製造方法之一例。第1圖係概略地示意表示本發明之偏光膜之製造方法及其所使用偏光膜製造裝置之一例之剖面圖。第1圖所示之偏光膜製造裝置係如以下述之方式構成:一邊將聚乙烯醇系樹脂所構成之原料(未延伸)膜10藉由原料輥11連續地拉出,一邊沿著膜搬送路徑搬送,藉此依序通過設置於膜搬送路徑上之膨潤浴(收容於膨潤槽內之膨潤液)13、染色浴(收容於染色槽內之染色液)15、第1交聯浴(收容於交聯槽內之第1交聯液)17a、第2交聯浴(收容於交聯槽內之第2交聯液)17b、及洗淨浴(收容於洗淨槽內之洗淨液)19,最後通過乾燥爐21。所得之偏光膜23例如可直接搬送至下述偏光板製作步驟(於偏光膜23之單面或兩面貼合保護膜之步驟)。第1圖中的箭頭表示膜搬送方向。 An example of a method for manufacturing the polarizing film of the present invention will be described in detail below with reference to FIG. 1. FIG. 1 is a cross-sectional view schematically showing an example of a method for producing a polarizing film of the present invention and an apparatus for producing a polarizing film used therefor. The polarizing film manufacturing apparatus shown in FIG. 1 is configured as follows: The raw material (unstretched) film 10 made of a polyvinyl alcohol resin is continuously drawn along the film while being pulled out by a raw material roll 11. Path transfer, so as to sequentially pass through the swelling bath (swelling solution stored in the swelling tank) provided on the film transfer path 13, the dyeing bath (staining solution stored in the dyeing tank) 15, the first cross-linking bath (storage The first cross-linking liquid in the cross-linking tank) 17a, the second cross-linking bath (the second cross-linking liquid contained in the cross-linking tank) 17b, and the washing bath (the cleansing liquid contained in the wash tank) ) 19, and finally pass through the drying furnace 21. The obtained polarizing film 23 can be directly transported, for example, to the following polarizing plate manufacturing step (a step of laminating a protective film on one or both sides of the polarizing film 23). The arrow in FIG. 1 shows the film conveyance direction.

第1圖之說明中,「處理槽」係包括膨潤槽、染色槽、交聯槽及洗淨槽之總稱,「處理液」係包括膨潤液、染色液、交聯液及洗淨液之總稱,「處理浴」係包括膨潤浴、染色浴、交聯浴及洗淨浴之總稱。膨潤浴、染色浴、交聯浴及洗淨浴係分別構成本發明之製造裝置中的膨潤部、染色部、交聯部及洗淨部。 In the description of Fig. 1, "treatment tank" is a general term including a swelling tank, a dyeing tank, a cross-linking tank, and a cleaning tank, and "treatment liquid" is a general term including a swelling liquid, a dyeing liquid, a cross-linking liquid, and a cleaning liquid "Processing bath" is a general term that includes a swelling bath, a dyeing bath, a crosslinking bath, and a washing bath. The swelling bath, the dyeing bath, the crosslinking bath, and the washing bath each constitute a swelling part, a dyeing part, a crosslinking part, and a washing part in the manufacturing apparatus of the present invention.

偏光膜製造裝置之膜搬送路徑除了上述處理浴以外可藉由如下述方式構成:將可支持所搬送之膜或進一步變更膜搬送方向之導輥30至48、60、61;可壓押、夾持所搬送之膜並可經由其旋轉對膜賦予驅動力、或進一 步可變更膜搬送方向之夾輥50至55配置於適當的位置。導輥或夾輥可配置於各處理浴前後或處理浴中,藉此可進行將膜導入及浸漬於處理浴、以及從處理浴拉出〔參照第1圖〕。例如可在各處理浴中設置1個以上導輥並沿著該等導輥搬送膜,藉此可將膜浸漬於各處理浴。 In addition to the above-mentioned processing bath, the film transfer path of the polarizing film manufacturing device can be configured as follows: guide rollers 30 to 48, 60, and 61 that can support the film to be transferred or further change the film transfer direction; can be pressed, clamped Hold the transported film and give driving force to the film through its rotation, or further The nip rollers 50 to 55 that can change the film conveying direction are arranged at appropriate positions in steps. The guide rollers or nip rollers can be arranged before and after each processing bath or in the processing baths, whereby the film can be introduced and immersed in the processing bath, and pulled out from the processing bath [see FIG. 1]. For example, one or more guide rollers may be provided in each processing bath, and a film may be conveyed along these guide rollers, whereby a film may be immersed in each processing bath.

第1圖所示之偏光膜製造裝置係在各處理浴前後配置有夾輥(夾輥50至54),藉此可在任1個以上處理浴中實施輥間延伸,該輥間延伸係在配置於該處理浴前後之夾輥間施加轉速差,而進行縱單軸延伸。 The polarizing film manufacturing apparatus shown in FIG. 1 is provided with nip rollers (nip rollers 50 to 54) before and after each processing bath, so that roll extension can be performed in any one or more treatment baths. A rotational speed difference is applied between the nip rolls before and after the treatment bath, and longitudinal uniaxial extension is performed.

第1圖所示之偏光膜製造裝置中,在第2交聯浴17b下流且洗淨浴19上流之搬送路徑上配置有電磁波照射部71,並進行電磁波照射步驟。以下說明各步驟。 In the polarizing film manufacturing apparatus shown in FIG. 1, an electromagnetic wave irradiation section 71 is disposed on a transport path downstream of the second crosslinking bath 17 b and upstream of the cleaning bath 19, and performs an electromagnetic wave irradiation step. Each step is described below.

(膨潤步驟) (Swelling step)

進行膨潤步驟之目的係去除原料膜10表面之異物、去除原料膜10中之塑化劑、賦予易染色性、及原料膜10之可塑化等。處理條件係以可達成該目的之範圍,且原料膜10不會產生極端溶解或失透等不良之範圍而決定。 The purpose of performing the swelling step is to remove foreign matter on the surface of the raw material film 10, remove plasticizers in the raw material film 10, impart easy dyeability, and plasticize the raw material film 10. The processing conditions are determined within a range in which the object can be achieved, and a range in which the raw material film 10 does not cause defects such as extreme dissolution or devitrification.

參照第1圖,膨潤步驟可藉由下述方式實施:一邊將原料膜10藉由原料輥11連續地拉出,一邊沿著膜搬送路徑搬送,將原料膜10於膨潤浴13浸漬預定時間,接著拉出。第1圖之例中,在拉出原料膜10至浸漬於膨潤浴13之間,原料膜10係沿著導輥60、61及夾輥50所構築之膜搬送路徑而搬送。膨潤處理中,係沿著導輥30至32及夾輥51所構築之膜搬送路徑而搬送。 Referring to FIG. 1, the swelling step can be performed by continuously pulling the raw material film 10 through the raw material roller 11 while carrying the raw material film 10 along the film conveying path, soaking the raw material film 10 in the swelling bath 13 for a predetermined time, Then pull it out. In the example of FIG. 1, the raw material film 10 is conveyed along the film conveyance path constructed by the guide rollers 60 and 61 and the nip roller 50 between the raw material film 10 being pulled out and immersed in the swelling bath 13. In the swelling process, the film is transported along the film transport path constructed by the guide rollers 30 to 32 and the nip roller 51.

作為膨潤浴13之膨潤液除了純水以外,可使用以約0.01至10重量%之範圍添加有硼酸(日本特開平10-153709號公報)、氯化物(日本特開平06-281816號公報)、無機酸、無機鹽、水溶性有機溶媒、醇類等之水溶液。 As the swelling liquid of the swelling bath 13, in addition to pure water, boric acid (Japanese Patent Application Laid-Open No. 10-153709), chloride (Japanese Patent Application Laid-Open No. 06-281816) added in a range of about 0.01 to 10% by weight, Aqueous solutions of inorganic acids, inorganic salts, water-soluble organic solvents, alcohols, etc.

膨潤浴13之溫度例如為約10至50℃,較佳為約10至40℃,更佳為約15至30℃。原料膜10之浸漬時間較佳為約10至300秒,更佳為約20至200秒。又,原料膜10為預先在氣體中延伸之聚乙烯醇系樹脂膜時,膨潤浴13之溫度例如為約20至70℃,較佳為約30至60℃。原料膜10之浸漬時間較佳為約30至300秒,更佳為約60至240秒。 The temperature of the swelling bath 13 is, for example, about 10 to 50 ° C, preferably about 10 to 40 ° C, and more preferably about 15 to 30 ° C. The immersion time of the raw film 10 is preferably about 10 to 300 seconds, and more preferably about 20 to 200 seconds. When the raw material film 10 is a polyvinyl alcohol-based resin film previously stretched in a gas, the temperature of the swelling bath 13 is, for example, about 20 to 70 ° C, and preferably about 30 to 60 ° C. The immersion time of the raw film 10 is preferably about 30 to 300 seconds, and more preferably about 60 to 240 seconds.

膨潤處理中容易產生原料膜10於寬度方向膨潤而在膜形成皺紋之問題。作為用以去除該皺紋並搬送膜之1個方法,可舉出於導輥30、31及/或32使用擴展輥、螺旋輥、凸輥(crown roll)之類之具有擴寬功能之輥,或使用交叉導輥(cross guider)、彎曲棒、拉幅機夾之類之其他擴寬裝置。用以抑制皺紋產生之另1個方法係實施延伸處理。例如可利用夾輥50與夾輥51之轉速差而在膨潤浴13中實施單軸延伸處理。 In the swelling treatment, a problem that the raw material film 10 swells in the width direction and wrinkles are formed in the film easily occurs. As a method for removing the wrinkles and transporting the film, a roll having a widening function such as an expansion roll, a spiral roll, or a crown roll may be used for the guide rolls 30, 31, and / or 32. Or use other widening devices such as cross guides, bending rods, and tenter clips. Another method to suppress the occurrence of wrinkles is to perform an extension treatment. For example, a uniaxial stretching process can be performed in the swelling bath 13 using the difference in the rotation speed of the nip roll 50 and the nip roll 51.

膨潤處理中,膜亦在膜搬送方向膨潤擴大,故在未積極地對膜進行延伸之形況,為了消去搬送方向之膜鬆弛,較佳為採取例如控制配置於膨潤浴13前後之夾輥50、51之速度等方法。又,以安定化膨潤浴13中之膜搬送為目的,以水中沖浴控制膨潤浴13中之水流、或併 用EPC裝置(Edge Position Control裝置:檢測膜之端部並防止膜蛇行之裝置)等係有用的。 In the swelling process, the film also swells and expands in the film conveying direction. Therefore, in the case where the film is not actively stretched, in order to eliminate the film slack in the conveying direction, it is preferable to take control of the nip rollers 50 arranged before and after the swelling bath 13, for example. , 51 speed and other methods. In addition, for the purpose of transporting the film in the stabilizing swelling bath 13, the water flow in the swelling bath 13 is controlled by a flush bath in water, or It is useful to use an EPC device (Edge Position Control device: a device that detects the end of the film and prevents the film from meandering).

第1圖所示例中,由膨潤浴13拉出之膜係依序通過導輥32、夾輥51、導輥33而導入於染色浴15。 In the example shown in FIG. 1, the film system drawn from the swelling bath 13 is introduced into the dyeing bath 15 through the guide roller 32, the nip roller 51, and the guide roller 33 in this order.

(染色步驟) (Dyeing step)

進行染色步驟之目的係使經膨潤處理後之聚乙烯醇系樹脂膜吸附、配向二色性色素等。處理條件係以可達成該目的之範圍,且不會產生膜極端溶解或失透等不良之範圍而決定。參照第1圖,染色步驟可藉由沿著夾輥51、導輥33至36及夾輥52所構築之膜搬送路徑搬送,將膨潤處理後之膜於染色浴15(收容於染色槽之處理液)浸漬預定時間,接著拉出而實施。為了提高二色性色素之染色性,供於染色步驟之膜較佳為實施至少一定程度單軸延伸處理的膜,或較佳為取代染色處理前之單軸延伸處理、或除了染色處理前之單軸延伸處理以外,在染色處理時進行單軸延伸處理。 The purpose of performing the dyeing step is to adsorb the polyvinyl alcohol-based resin film after swelling treatment, and to align the dichroic pigment. The processing conditions are determined within a range in which the object can be achieved without causing defects such as extreme dissolution or devitrification of the membrane. Referring to FIG. 1, the dyeing step can be carried along the film conveying path constructed by the nip rollers 51, guide rollers 33 to 36, and nip rollers 52, and the swelled film is processed in the dyeing bath 15 (the treatment stored in the dyeing tank) Liquid) is immersed for a predetermined time and then pulled out. In order to improve the dyeability of the dichroic pigment, the film used in the dyeing step is preferably a film that is subjected to at least a certain degree of uniaxial stretching treatment, or it is preferable to replace the uniaxial stretching treatment before the dyeing treatment, or otherwise. In addition to the uniaxial stretching process, the uniaxial stretching process is performed during the dyeing process.

使用碘作為二色性色素時,於染色浴15之染色液中可使用例如濃度為重量比碘/碘化鉀/水=約0.003至0.3/約0.1至10/100之水溶液。可使用碘化鋅等其他碘化物取代碘化鉀,也可併用碘化鉀與其他碘化物。又,可共存有碘化物以外之化合物,例如硼酸、氯化鋅、氯化鈷等。添加硼酸時,可藉由含有碘之點而與後述之交聯處理區別,且相對於水100重量份,水溶液只要為含有碘約0.003重量份以上者則可視為染色浴15。浸漬膜時之染色 浴15之溫度通常為約10至45℃,較佳為10至40℃,更佳為20至35℃,膜之浸漬時間通常為約30至600秒,較佳為60至300秒。 When using iodine as a dichroic pigment, an aqueous solution having a concentration of, for example, a weight ratio of iodine / potassium iodide / water = about 0.003 to 0.3 / about 0.1 to 10/100 can be used in the dyeing liquid of the dyeing bath 15. Instead of potassium iodide, other iodides such as zinc iodide may be used, or potassium iodide may be used in combination with other iodides. In addition, compounds other than iodide may be coexisted, such as boric acid, zinc chloride, and cobalt chloride. When boric acid is added, it can be distinguished from the crosslinking treatment described later by the point containing iodine, and it can be regarded as dyeing bath 15 as long as the aqueous solution contains about 0.003 parts by weight or more of iodine. Dyeing when dipping the film The temperature of the bath 15 is usually about 10 to 45 ° C, preferably 10 to 40 ° C, more preferably 20 to 35 ° C, and the immersion time of the film is usually about 30 to 600 seconds, preferably 60 to 300 seconds.

使用水溶性二色性染料作為二色性色素時,在染色浴15之染色液中可使用例如濃度為重量比二色性染料/水=約0.001至0.1/100之水溶液。該染色浴15中可共存有染色助劑等,也可含有例如硫酸鈉等無機鹽或界面活性劑等。二色性染料可僅單獨使用1種,也可併用2種類以上的二色性染料。浸漬膜時染色浴15之溫度例如為約20至80℃,較佳為30至70℃,膜之浸漬時間通常為約30至600秒,較佳為約60至300秒。 When a water-soluble dichroic dye is used as the dichroic dye, for example, an aqueous solution having a concentration of dichroic dye / water = about 0.001 to 0.1 / 100 in a weight ratio can be used in the dyeing liquid of the dyeing bath 15. The dyeing bath 15 may coexist with a dyeing aid and the like, and may contain an inorganic salt such as sodium sulfate, a surfactant, and the like. The dichroic dye may be used alone, or two or more kinds of dichroic dyes may be used in combination. The temperature of the dyeing bath 15 when the film is immersed is, for example, about 20 to 80 ° C, preferably 30 to 70 ° C. The immersion time of the film is usually about 30 to 600 seconds, preferably about 60 to 300 seconds.

在如上述染色步驟中,可在染色浴15進行膜之單軸延伸。膜之單軸延伸可藉由在配置於染色浴15前後之夾輥51與夾輥52之間施加轉速差等方法而進行。 In the dyeing step as described above, uniaxial stretching of the film can be performed in the dyeing bath 15. The uniaxial stretching of the film can be performed by a method such as applying a rotational speed difference between the nip roller 51 and the nip roller 52 arranged before and after the dyeing bath 15.

染色處理中,亦可與膨潤處理同樣地為了去除膜之皺紋並搬送聚乙烯醇系樹脂膜,而在導輥33、34、35及/或36使用具有擴展輥、螺旋輥、凸輥之類之擴寬功能之輥,也可使用交叉導輥、彎曲棒、拉幅機夾之類之其他擴寬裝置。與膨潤處理同樣地,用以抑制皺紋產生之另1個方法係實施延伸處理。 In the dyeing process, in order to remove the wrinkles of the film and convey the polyvinyl alcohol-based resin film in the same manner as the swelling process, the guide rollers 33, 34, 35, and / or 36 may be provided with an expansion roller, a spiral roller, a convex roller, or the like. For the roller with widening function, other widening devices such as cross guide rollers, bending rods, and tenter clips can also be used. As with the swelling treatment, another method for suppressing the occurrence of wrinkles is the extension treatment.

第1圖所示例中,由染色浴15拉出之膜係依序通過導輥36、夾輥52、及導輥37而導入交聯浴17。 In the example shown in FIG. 1, the film system drawn out from the dyeing bath 15 is introduced into the crosslinking bath 17 through the guide roller 36, the nip roller 52, and the guide roller 37 in this order.

(交聯步驟) (Crosslinking step)

進行交聯步驟之目的係藉由交聯之耐水化或調整色調 (防止膜出現藍色等)等。第1圖所示例中係配置二個交聯浴作為進行交聯步驟之交聯浴,以耐水化為目的所進行之第1交聯步驟係於第1交聯浴17a進行,以調整色調為目的所進行之第2交聯步驟係於第2交聯浴17b進行。參照第1圖,第1交聯步驟可藉由沿著夾輥52、導輥37至40及夾輥53a所構築之膜搬送路徑而搬送,將染色處理後之膜於第1交聯浴17a(收容於交聯槽之第1交聯液)浸漬預定時間,接著拉出而實施。第2交聯步驟可藉由沿著夾輥53a、導輥41至44及夾輥53b所構築之膜搬送路徑搬送,將第1交聯步驟後之膜於第2交聯浴17b(收容於交聯槽之第2交聯液)浸漬預定時間,接著拉出而實施。以下,稱為交聯浴時係含有第1交聯浴17a及第2交聯浴17b兩者,稱為交聯液時亦含有第1交聯液及第2交聯液兩者。 The purpose of performing the cross-linking step is to adjust the color tone by cross-linking (To prevent the film from appearing blue, etc.). In the example shown in FIG. 1, two cross-linking baths are used as cross-linking baths for performing the cross-linking step. The first cross-linking step performed for the purpose of water resistance is performed in the first cross-linking bath 17a to adjust the color tone as The second crosslinking step performed for the purpose is performed in the second crosslinking bath 17b. Referring to FIG. 1, the first cross-linking step can be carried along the film conveying path constructed by the nip roller 52, the guide rollers 37 to 40 and the nip roller 53 a, and the dyed film is transferred to the first cross-linking bath 17 a. (The first cross-linking solution contained in the cross-linking tank) is immersed for a predetermined time, and then pulled out for implementation. The second cross-linking step can be carried along the film transport path constructed by the nip rollers 53a, guide rollers 41 to 44 and nip rollers 53b. The film after the first cross-linking step is placed in the second cross-linking bath 17b (contained in The second crosslinking liquid in the crosslinking tank) is immersed for a predetermined time, and then pulled out for implementation. Hereinafter, when the cross-linking bath is referred to, it includes both the first cross-linking bath 17a and the second cross-linking bath 17b. When it is referred to as the cross-linking liquid, both the first cross-linking liquid and the second cross-linking liquid are included.

交聯液可使用於溶媒溶解有交聯劑之溶液。作為交聯劑可舉例如:硼酸、硼砂等硼化合物、乙二醛、戊二醛等。該等可為一種類也可併用二種類以上。溶媒例如可使用水,又,亦可含有與水具有相溶性之有機溶媒。交聯溶液中交聯劑之濃度較佳為1至20重量%之範圍,更佳為6至15重量%,但並不限定於此。 The cross-linking solution can be used for a solution in which a cross-linking agent is dissolved in a solvent. Examples of the crosslinking agent include boron compounds such as boric acid and borax, glyoxal, and glutaraldehyde. These may be one type or two or more types may be used in combination. The solvent may be, for example, water, or may contain an organic solvent compatible with water. The concentration of the crosslinking agent in the crosslinking solution is preferably in the range of 1 to 20% by weight, more preferably 6 to 15% by weight, but is not limited thereto.

相對水100重量份,交聯液可為含有硼酸例如約1至10重量份之水溶液。染色處理所使用之二色性色素為碘時,交聯液除了硼酸以外較佳為含有碘化物,相對於水100重量份,其量例如可為1至30重量份。碘化物可舉出碘化鉀、碘化鋅等。又,亦可共存碘化物以外之化 合物,例如氯化鋅、氯化鈷、氯化鋯、硫代硫酸鈉、亞硫酸鉀、硫酸鈉等。 The crosslinking solution may be an aqueous solution containing boric acid, for example, about 1 to 10 parts by weight with respect to 100 parts by weight of water. When the dichroic dye used for the dyeing treatment is iodine, the crosslinking solution preferably contains iodide in addition to boric acid, and its amount may be, for example, 1 to 30 parts by weight relative to 100 parts by weight of water. Examples of the iodide include potassium iodide and zinc iodide. It is also possible to coexist other than iodide Compounds such as zinc chloride, cobalt chloride, zirconium chloride, sodium thiosulfate, potassium sulfite, sodium sulfate, and the like.

交聯處理中,可因應其目的適當地變更硼酸及碘化物之濃度、以及交聯浴17之溫度。例如屬於交聯處理目的為藉由交聯進行耐水化之第1交聯液時,濃度以重量比計可為硼酸/碘化物/水=3至10/1至20/100之水溶液。因應所需可取代硼酸而使用其他交聯劑,也可併用硼酸與其他交聯劑。浸漬膜時之第1交聯浴17a之溫度通常為約50至70℃,較佳為53至65℃,膜之浸漬時間通常為約10至600秒,較佳為20至300秒,更佳為20至200秒。又,對在膨潤處理前預先延伸之聚乙烯醇系樹脂膜依序實施染色處理及第1交聯處理時,第1交聯浴17a之溫度通常為約50至85℃,較佳為55至80℃。 In the crosslinking treatment, the concentrations of boric acid and iodide, and the temperature of the crosslinking bath 17 can be appropriately changed according to the purpose. For example, when the first cross-linking solution whose cross-linking treatment purpose is to be water resistant by cross-linking, the concentration may be an aqueous solution of boric acid / iodide / water = 3 to 10/1 to 20/100 by weight ratio. Other cross-linking agents may be used instead of boric acid as needed, and boric acid may be used in combination with other cross-linking agents. The temperature of the first crosslinking bath 17a when the film is impregnated is usually about 50 to 70 ° C, preferably 53 to 65 ° C. The immersion time of the film is usually about 10 to 600 seconds, preferably 20 to 300 seconds, more preferably For 20 to 200 seconds. In addition, when the polyvinyl alcohol-based resin film stretched in advance before the swelling treatment is sequentially subjected to a dyeing treatment and a first crosslinking treatment, the temperature of the first crosslinking bath 17a is usually about 50 to 85 ° C, preferably 55 to 80 ° C.

在以調整色調為目的之第2交聯液中,例如使用碘作為二色性色素時,可使用濃度以重量比計為硼酸/碘化物/水=1至5/3至30/100。浸漬膜時之第2交聯浴17b之溫度通常為約10至45℃,膜之浸漬時間通常為約1至300秒,較佳為2至100秒。 In the second cross-linking liquid for the purpose of adjusting color tone, for example, when iodine is used as a dichroic dye, the concentration in terms of weight ratio may be boric acid / iodide / water = 1 to 5/3 to 30/100. The temperature of the second crosslinking bath 17b when the film is impregnated is usually about 10 to 45 ° C, and the impregnation time of the film is usually about 1 to 300 seconds, preferably 2 to 100 seconds.

交聯處理可進行複數次,通常進行2至5次。此時,所使用之各交聯浴之組成及溫度只要為上述範圍內,則可相同或相異。用以經由交聯而達成耐水化之交聯處理、及用以調整色調之交聯處理亦可分別以複數步驟進行。 The crosslinking treatment may be performed a plurality of times, usually 2 to 5 times. At this time, as long as the composition and temperature of each crosslinking bath used are within the above ranges, they may be the same or different. The cross-linking treatment for achieving water resistance through cross-linking and the cross-linking treatment for adjusting color tone may be performed in a plurality of steps, respectively.

可利用夾輥52與夾輥53a之轉速差在第1 交聯浴17a中實施單軸延伸處理。又,亦可利用夾輥53a與夾輥53b之轉速差在第2交聯浴17b中實施單軸延伸處理。 The difference between the rotation speed of the nip roller 52 and the nip roller 53a is the first The cross-linking bath 17a is uniaxially stretched. In addition, a uniaxial stretching process may be performed in the second cross-linking bath 17b by utilizing the difference in the rotational speed of the nip rollers 53a and 53b.

交聯處理中,與膨潤處理同樣地,為了去除膜之皺紋並搬送聚乙烯醇系樹脂膜,可於導輥38、39、40、41、42、43及/或44使用具有擴展輥、螺旋輥、凸輥之類之擴寬功能的輥,也可使用交叉導輥、彎曲棒、拉幅機夾之類之其他擴寬裝置。與膨潤處理同樣地,為了抑制皺紋產生之另1個方法係實施延伸處理。 In the cross-linking treatment, in the same manner as the swelling treatment, in order to remove the wrinkles of the film and convey the polyvinyl alcohol-based resin film, the guide rollers 38, 39, 40, 41, 42, 43 and / or 44 can be used with an extension roller, a spiral Rollers with widening functions such as rollers and convex rollers can also use other widening devices such as cross guide rollers, bending rods, and tenter clips. As with the swelling treatment, another method for suppressing the occurrence of wrinkles is a stretching treatment.

第1圖所示例中,由第2交聯浴17b拉出之膜係依序通過導輥44、夾輥53b而導入洗淨浴19。 In the example shown in FIG. 1, the film drawn from the second cross-linking bath 17 b is sequentially introduced into the washing bath 19 through the guide roller 44 and the nip roller 53 b.

(洗淨步驟) (Washing step)

第1圖所示例中係含有交聯步驟後之洗淨步驟。進行洗淨處理之目的係去除附著於聚乙烯醇系樹脂膜之多餘硼酸、碘等藥劑。洗淨步驟係例如藉由將交聯處理之聚乙烯醇系樹脂膜浸漬於洗淨浴19而進行。又,取代將膜浸漬於洗淨浴19之步驟,洗淨步驟亦可藉由將洗淨液作為沖浴而對膜噴霧而進行,或藉由併用洗淨浴19之浸漬及洗淨液之噴霧而進行。 The example shown in Fig. 1 includes a washing step after the crosslinking step. The purpose of the cleaning treatment is to remove excess boric acid, iodine, and other agents attached to the polyvinyl alcohol resin film. The washing step is performed, for example, by immersing a cross-linked polyvinyl alcohol-based resin film in the washing bath 19. In addition, instead of the step of dipping the film in the washing bath 19, the washing step may be performed by spraying the film with the washing liquid as a rinsing bath, or by using the dipping and washing liquid of the washing bath 19 in combination. Spraying.

第1圖中表示將聚乙烯醇系樹脂膜浸漬於洗淨浴19並進行洗淨處理之例。洗淨處理中洗淨浴19之溫度通常為約2至40℃,膜之浸漬時間通常為約2至120秒。 FIG. 1 shows an example in which a polyvinyl alcohol-based resin film is immersed in a washing bath 19 and subjected to a washing treatment. The temperature of the washing bath 19 in the washing treatment is usually about 2 to 40 ° C, and the immersion time of the film is usually about 2 to 120 seconds.

此外,洗淨處理中,以去除皺紋並搬送聚 乙烯醇系樹脂膜為目的下,可於導輥45、46、47及/或48使用具有擴展輥、螺旋輥、凸輥之類之擴寬功能的輥,也可使用交叉導輥、彎曲棒、拉幅機夾之類之其他擴寬裝置。又,在膜洗淨處理中可實施為了抑制皺紋產生之延伸處理。 In addition, during the washing process, wrinkles are removed and For the purpose of vinyl alcohol-based resin film, rollers with widening functions such as expansion rollers, spiral rollers, and convex rollers can be used for guide rollers 45, 46, 47, and / or 48. Cross guide rollers and curved rods can also be used. And other widening devices such as tenter clips. In addition, the film washing process may be extended to suppress the occurrence of wrinkles.

(延伸步驟) (Extended steps)

如上述,原料膜10係在上述一連串處理步驟之間(亦即任1個以上處理步驟之前後及/或任1個以上處理步驟中)實施濕式或乾式之單軸延伸處理。單軸延伸處理之具體方法例如可為在構成膜搬送路徑之2個夾輥(例如配置於處理浴前後之2個夾輥)間施加轉速差而進行縱單軸延伸之輥間延伸,如日本專利第2731813號公報所記載之熱輥延伸、拉幅機延伸等,較佳為輥間延伸。單軸延伸步驟可在由原料膜10獲得偏光膜23之間實施複數次。如上述,延伸處理對抑制膜之皺紋產生亦有利。 As described above, the raw film 10 is subjected to a wet or dry uniaxial stretching process between the above-mentioned series of processing steps (that is, before or after any one or more processing steps and / or during any one or more processing steps). A specific method of uniaxial stretching may be, for example, applying a speed difference between two nip rollers (for example, two nip rollers arranged before and after the processing bath) constituting the film conveying path to perform longitudinal uniaxial stretching between rollers, such as Japan The hot roll stretching, tenter stretching, and the like described in Patent No. 2731813 are preferably extended between rolls. The uniaxial stretching step may be performed a plurality of times between obtaining the polarizing film 23 from the raw film 10. As described above, the stretching treatment is also advantageous for suppressing the occurrence of wrinkles in the film.

以原料膜10為基準,偏光膜23之最終累積延伸倍率通常為約4.5至7倍,較佳為5至6.5倍。延伸步驟可在任一處理步驟進行,在2個以上處理步驟進行延伸處理時,延伸處理可在任一處理步驟進行。 Based on the raw material film 10, the final cumulative extension ratio of the polarizing film 23 is usually about 4.5 to 7 times, preferably 5 to 6.5 times. The extension step can be performed in any processing step. When two or more processing steps are performed in the extension processing, the extension processing can be performed in any processing step.

(電磁波照射步驟) (Electromagnetic wave irradiation step)

第1圖所示之裝置中,膜從第2交聯步驟17b拉出並通過夾輥53b後,在浸漬於洗淨浴19前對膜進行電磁波之照射(電磁波照射步驟)。第1圖所示裝置中,藉由電磁波照射部71照射電磁波。本發明之電磁波照射步驟所使用電磁波係超過2μm且4μm以下波長之紅外線放射能量比例為 全放射能量之25%以上,較佳為28%以上,更佳為35%以上。藉由對膜照射如此電磁波而可提高所獲得偏光膜之光學特性。又,關於本發明所使用電磁波,超過2μm且4μm以下波長之紅外線放射能量比例之上限值並無特別限定,但例如為80%以下。通常波長0.75μm至1000μm之電磁波係稱為紅外線。 In the apparatus shown in FIG. 1, after the film is pulled out from the second crosslinking step 17b and passed through the nip roller 53b, the film is irradiated with electromagnetic waves before being immersed in the washing bath 19 (electromagnetic wave irradiation step). In the apparatus shown in FIG. 1, an electromagnetic wave is irradiated by the electromagnetic wave irradiation section 71. In the electromagnetic wave irradiation step of the present invention, the ratio of the infrared radiation energy of the electromagnetic wave system with a wavelength exceeding 2 μm and less than 4 μm is 25% or more of total radiation energy, preferably 28% or more, and more preferably 35% or more. By irradiating the film with such an electromagnetic wave, the optical characteristics of the obtained polarizing film can be improved. The upper limit of the ratio of the infrared radiation energy exceeding a wavelength of 2 μm to 4 μm is not particularly limited for the electromagnetic wave used in the present invention, but it is, for example, 80% or less. Generally, electromagnetic waves with a wavelength of 0.75 μm to 1000 μm are called infrared rays.

於電磁波照射步驟中,藉由照射波長超過2μm且4μm以下的紅外線之放射能量比例為全放射能量的25%以上之電磁波,而可提高偏光膜之光學特性之機制並不明確,但推測為藉由超過2μm且4μm以下的波長之紅外線激發膜內之分子運動,可促進經交聯處理之膜中碘等二色性色素之固定化,使偏光膜之光學特性提升。 In the electromagnetic wave irradiation step, the mechanism of improving the optical characteristics of the polarizing film is not clear by irradiating an electromagnetic wave having an infrared radiation ratio of more than 2 μm and less than 4 μm with a radiation energy ratio of 25% or more of the total radiation energy. Molecules in the film are excited by infrared rays with a wavelength of more than 2 μm and less than 4 μm, which can promote the fixation of dichroic pigments such as iodine in the cross-linked film, and improve the optical characteristics of the polarizing film.

第2圖表示各種類電磁波照射器之放射能量光譜。又,表1表示各種類電磁波照射器之各波長域(以波長xμm之範圍表示)之電磁波放射能量占全放射能量之比例。第2圖及表1所示之電磁波照射器係鹵素加熱器(熱源溫度2600℃)、短波長紅外線加熱器(熱源溫度2200℃)、快速反應中波長紅外線加熱器(熱源溫度1600℃)、碳加熱器(熱源溫度1200℃)、碳加熱器(熱源溫度950℃)、及中波長紅外線加熱器(熱源溫度900℃)。 Figure 2 shows the radiation energy spectrum of various types of electromagnetic wave irradiators. In addition, Table 1 shows the ratio of the electromagnetic wave radiation energy to the total radiation energy in each wavelength region (expressed in the range of wavelength x μm) of various types of electromagnetic wave irradiators. The electromagnetic wave irradiators shown in Figure 2 and Table 1 are halogen heaters (heat source temperature 2600 ° C), short-wavelength infrared heaters (heat source temperature 2200 ° C), fast-response medium-wavelength infrared heaters (heat source temperature 1600 ° C), carbon Heater (heat source temperature 1200 ° C), carbon heater (heat source temperature 950 ° C), and medium wavelength infrared heater (heat source temperature 900 ° C).

如表1所示,短波長紅外線加熱器(熱源溫度2200℃)、快速反應中波長紅外線加熱器(熱源溫度1600℃)、碳加熱器(熱源溫度1200℃)、碳加熱器(熱源溫度950℃)、及中波長紅外線加熱器(熱源溫度900℃)係超過2μm且4μm以下波長之紅外線放射能量比例為全放射能量之25%以上,故可適合使用於構成電磁波照射部71之電磁波照射器。電磁波照射部71可藉由1台電磁波照射器構成,也可藉由複數台電磁波照射器構成。藉由複數台電磁波照射器來構成時,係選擇複數台電磁波照射器,使由複數台電磁波照射器放射之超過2μm且4μm以下波長之紅外線放射能量為由複數台電磁波照射器放射之電磁波之全放射能量的25%以上。又,第1圖中係以僅對膜之一面照射電磁波之方式構成電磁波照射部71,但亦可以對膜兩面照射電磁波之方式配置複數電磁波照射器。電磁波照射部71較佳為以對照射對象之聚乙烯醇系樹脂膜之寬度方向全域照射電磁波之方式構成。 As shown in Table 1, short-wavelength infrared heaters (heat source temperature 2200 ° C), fast-response medium-wavelength infrared heaters (heat source temperature 1600 ° C), carbon heaters (heat source temperature 1200 ° C), carbon heaters (heat source temperature 950 ° C) ), And medium-wavelength infrared heaters (heat source temperature of 900 ° C) are infrared radiation energy ratios of wavelengths exceeding 2 μm and less than 4 μm which are more than 25% of the total radiation energy, so they can be suitably used for the electromagnetic wave irradiator constituting the electromagnetic wave irradiation section 71. The electromagnetic wave irradiation section 71 may be configured by one electromagnetic wave irradiator, or may be configured by a plurality of electromagnetic wave irradiators. In the case of a plurality of electromagnetic wave irradiators, the plurality of electromagnetic wave irradiators are selected so that the infrared radiation energy of a wavelength exceeding 2 μm and less than 4 μm emitted by the plurality of electromagnetic wave irradiators is the total of the electromagnetic waves emitted by the plurality of electromagnetic wave irradiators. More than 25% of the radiated energy. In the first figure, the electromagnetic wave irradiating unit 71 is configured to irradiate electromagnetic waves to only one side of the film, but a plurality of electromagnetic wave irradiators may be arranged to irradiate electromagnetic waves to both sides of the film. The electromagnetic wave irradiation section 71 is preferably configured to irradiate the entire area in the width direction of the polyvinyl alcohol-based resin film to be irradiated with electromagnetic waves.

電磁波照射步驟中,電磁波較佳為自相對於膜表面之垂直方向上側照射。又,電磁波照射部71中,電磁波照射器之電磁波放射口與膜之間之距離較佳為2至40cm,更佳為5至20cm。但是,該距離較佳為考慮自電磁波照射器放射之電磁波之放射能量量、或膜表面之溫度等而適當地選擇並進行。電磁波照射時之膜表面溫度較佳為維持於30至90℃,更佳為維持於40至80℃。 In the electromagnetic wave irradiation step, the electromagnetic wave is preferably irradiated from the upper side in the vertical direction with respect to the film surface. In addition, in the electromagnetic wave irradiating section 71, the distance between the electromagnetic wave emitting port of the electromagnetic wave irradiator and the film is preferably 2 to 40 cm, and more preferably 5 to 20 cm. However, the distance is preferably appropriately selected and performed in consideration of the amount of radiated energy of electromagnetic waves radiated from the electromagnetic wave irradiator, the temperature of the film surface, and the like. The temperature of the film surface during electromagnetic wave irradiation is preferably maintained at 30 to 90 ° C, and more preferably maintained at 40 to 80 ° C.

電磁波照射步驟中,膜之每單位體積之電 磁波照射熱量通常可為100J/cm3以上50kJ/cm3以下。以提高偏光膜之光學特性之觀點而言,較佳為100J/cm3以上,更佳為500J/cm3以上,又更佳為1000J/cm3以上。又,以抑制因溫度上升造成膜劣化之觀點而言,膜之每單位體積之電磁波之照射熱量較佳為10kJ/cm3以下,更佳為5000J/cm3以下,又更佳為3000J/cm3以下。通常,膜的水分量減少與電磁波之照射熱量成比例,但本發明之電磁波照射步驟的目的並非為減少膜的水分量,故可適當地選擇照射熱量,較佳為在上述範圍內適當地選擇。 In the electromagnetic wave irradiation step, the electromagnetic wave irradiation heat per unit volume of the film may be generally 100 J / cm 3 or more and 50 kJ / cm 3 or less. In the viewpoint of improving the optical characteristics of the polarizing film, it is preferably 100J / cm 3 or more, more preferably 500J / cm 3 or more, and more preferably 1000J / cm 3 or more. From the viewpoint of suppressing the deterioration of the film due to temperature rise, the radiation heat of the electromagnetic wave per unit volume of the film is preferably 10 kJ / cm 3 or less, more preferably 5000 J / cm 3 or less, and still more preferably 3000 J / cm. 3 or less. Generally, the reduction of the moisture content of the film is proportional to the amount of heat irradiated by the electromagnetic waves. However, the purpose of the electromagnetic wave irradiation step of the present invention is not to reduce the amount of moisture of the film. Therefore, the amount of heat radiated can be appropriately selected, and it is preferable to appropriately select within the above range .

於本發明,係在洗淨步驟前進行電磁波照射步驟,藉此可使所得到的偏光膜的光學特性提升。電磁波照射步驟只要對浸漬於至少一個交聯浴後之膜進行即可,如第1圖所示,並不限定於對浸漬於所有交聯浴後之膜進行。亦即,第1圖所示例中,可對浸漬於第1交聯浴後且浸漬於第2交聯浴前之膜進行電磁波照射步驟,亦可對浸漬於第2交聯浴後之膜進行電磁波照射步驟。但藉由電磁波照射步驟並浸漬於交聯浴,而可使進入膜內之硼酸進行交聯,故對完成所有交聯浴浸漬之膜進行電磁波照射步驟係可更有效地進行硼酸之交聯而較佳。 In the present invention, the electromagnetic wave irradiation step is performed before the washing step, thereby improving the optical characteristics of the obtained polarizing film. The electromagnetic wave irradiation step may be performed on the film immersed in at least one crosslinking bath. As shown in FIG. 1, it is not limited to the film immersed in all the crosslinking baths. That is, in the example shown in FIG. 1, an electromagnetic wave irradiation step may be performed on the film immersed in the first cross-linking bath and before the second cross-linking bath, or the film immersed in the second cross-linking bath may be subjected to electromagnetic wave irradiation. step. However, through the electromagnetic wave irradiation step and immersion in the cross-linking bath, the boric acid entering the film can be cross-linked. Therefore, the electromagnetic wave irradiation step on the film that has completed all the cross-linking bath immersion can more effectively perform the cross-linking of boric acid Better.

電磁波之照射較佳為從交聯浴拉出膜後再10秒以內進行,又更佳為在5秒以內進行。從交聯浴拉出至照射電磁波為止的時間越短,則可進一步提高經由電磁波照射所致之偏光膜之光學特性。又,電磁波照射步驟中,較佳為附著於膜表面的水分子較少。若在膜表面存在有水 分子,則膜表面之水分子會吸收紅外線,因此會降低藉由電磁波照射激發膜內分子運動之效果。從交聯浴拉出之後交聯液會附著於膜表面,故較佳為在電磁波照射步驟前設置將其去除之除液方法。第1圖中,夾輥53b亦具有去除附著於膜表面之交聯液之除液方法的功能。除液方法除了夾輥以外亦有對膜吹以空氣而進行除液之方法,也可使用接觸膜而進行除液之刮刀等。 The electromagnetic wave irradiation is preferably performed within 10 seconds after the film is pulled out from the crosslinking bath, and more preferably within 5 seconds. The shorter the time from when the cross-linking bath is drawn until the electromagnetic wave is irradiated, the further the optical characteristics of the polarizing film caused by the electromagnetic wave irradiation can be further improved. In the electromagnetic wave irradiation step, it is preferable that there are fewer water molecules attached to the surface of the film. If water is present on the membrane surface Molecules, water molecules on the surface of the film will absorb infrared rays, so the effect of stimulating the movement of molecules in the film by electromagnetic wave irradiation will be reduced. The cross-linking liquid will adhere to the film surface after being pulled out from the cross-linking bath, so it is preferable to set a liquid removing method to remove it before the electromagnetic wave irradiation step. In Fig. 1, the nip roller 53b also has a function of a liquid removal method for removing the cross-linking liquid adhered to the film surface. In addition to the nip roller, there is a method for removing liquid by blowing air on the film, and a doctor blade or the like may be used to remove the liquid by contacting the film.

以經濟性觀點而言,若膜加工速度為較高速,具體而言係以加工速度為10至100m/min作為較快加工速度時,有電磁波照射時間較短且照射熱量不足之情形。該對應方式係並行地設置複數台電磁波照射器,藉此可獲得充分照射熱量。 From an economic point of view, if the film processing speed is high, specifically when the processing speed is 10 to 100 m / min as the faster processing speed, there may be cases where the electromagnetic wave irradiation time is short and the irradiation heat is insufficient. In this correspondence method, a plurality of electromagnetic wave irradiators are provided in parallel, whereby sufficient irradiation heat can be obtained.

(乾燥步驟) (Drying step)

較佳為在洗淨步驟後進行乾燥聚乙烯醇系樹脂膜之處理。膜之乾燥並無特別限制,可使用如第1圖所示之例中的乾燥爐21來進行。乾燥爐21,例如可使用具備熱風乾燥機者。乾燥溫度例如為30至100℃左右,乾燥時間例如為30至600秒左右。乾燥聚乙烯醇系樹脂膜之處理可使用遠紅外線加熱器進行。由上述方式所獲得偏光膜23之厚度例如約5至30μm左右。 It is preferable to perform a process of drying a polyvinyl alcohol-type resin film after a washing process. The drying of the film is not particularly limited, and can be performed using a drying furnace 21 in the example shown in FIG. 1. As the drying furnace 21, for example, a person having a hot air dryer can be used. The drying temperature is, for example, about 30 to 100 ° C, and the drying time is, for example, about 30 to 600 seconds. The treatment of the dried polyvinyl alcohol-based resin film can be performed using a far-infrared heater. The thickness of the polarizing film 23 obtained in the above manner is, for example, about 5 to 30 μm.

考量與視感度修正偏光度Py之平衡,所得偏光膜之視感度修正單體穿透率Ty較佳為40至47%,更佳為41至45%。視感度修正偏光度Py較佳為99.9%以上,更佳為99.95%以上,值為大則越佳。偏光膜之視感度修正 單體穿透率Ty越大,則由本發明所獲得之光學特性提高效果越大。因此,製造視感度修正單體穿透率Ty為41%以上,進一步為42%以上,又進一步為43%以上之偏光膜時,在本發明係特別有利。藉由本發明可獲得例如Ty為43%以上且Py為99.994%以上之偏光膜。Ty及Py係可根據後述實施例之記載而測定。 In consideration of the balance with the visual sensitivity correction polarization degree Py, the visual sensitivity correction monomer transmittance Ty of the obtained polarizing film is preferably 40 to 47%, more preferably 41 to 45%. The visual sensitivity correction polarization Py is preferably 99.9% or more, more preferably 99.95% or more, and the larger the value, the better. Visual sensitivity correction of polarizing film The greater the monomer transmittance Ty, the greater the optical property improvement effect obtained by the present invention. Therefore, it is particularly advantageous in the present invention to manufacture a polarizing film having a transmittance Ty of 41% or more, 42% or more, and 43% or more. According to the present invention, for example, a polarizing film having a Ty of 43% or more and a Py of 99.994% or more can be obtained. Ty and Py can be measured according to the description in the examples described later.

所得偏光膜可依序捲繞為捲繞輥並形成輥形態,也可不捲繞而直接供於偏光板製作步驟(於偏光膜之單面或兩面積層保護膜等步驟)。 The obtained polarizing film may be sequentially wound into a winding roll to form a roll shape, or may be directly supplied to a polarizing plate manufacturing step (such as a single-sided or two-area layer protective film step of the polarizing film) without winding.

(對聚乙烯醇系樹脂膜之其他處理步驟) (Other processing steps for polyvinyl alcohol resin film)

可追加上述處理以外之處理。所追加處理之例包括:在交聯步驟後進行之浸漬於不含硼酸之碘化物水溶液之處理(補色處理)、及浸漬於不含有硼酸而含有氯化鋅等水溶液之處理(鋅處理)。 Processing other than the above processing can be added. Examples of the additional treatment include a treatment (dip color treatment) immersed in an aqueous iodide solution containing no boric acid and a treatment (zinc treatment) immersed in an aqueous solution containing no boric acid and containing zinc chloride and the like after the crosslinking step.

<偏光板> <Polarizer>

在由上述方式製造之偏光膜之至少單面經由接著劑貼合保護膜,藉此可獲得偏光板。保護膜可舉例如由三乙酸纖維素或二乙酸纖維素之類之乙酸纖維素系樹脂所構成之膜;由聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯及聚對苯二甲酸丁二酯之類之聚酯系樹脂所構成之膜;聚碳酸酯系樹脂膜、環烯烴系樹脂膜;丙烯酸系樹脂膜;聚丙烯系樹脂之鏈狀烯烴系樹脂所構成之膜。 A polarizing plate can be obtained by bonding a protective film on at least one side of the polarizing film manufactured by the above method via an adhesive. The protective film may be, for example, a film composed of a cellulose acetate resin such as cellulose triacetate or cellulose diacetate; polyethylene terephthalate, polyethylene naphthalate, and polyethylene terephthalate. Films made of polyester resins such as butyl formate; polycarbonate resin films, cycloolefin resin films; acrylic resin films; polypropylene resin resin chain olefin resin films.

為了提高偏光膜與保護膜之接著性,故可在偏光膜及/或保護膜之貼合面實施電暈處理、火炎處理、 電漿處理、紫外線照射、底漆塗佈處理、皂化處理等表面處理。貼合偏光膜與保護膜所使用之接著劑可舉出紫外線硬化性接著劑之類之活性能量線硬化性接著劑、聚乙烯醇系樹脂之水溶液或於其中摻配交聯劑之水溶液、及胺甲酸乙酯系乳液接著劑之類之水系接著劑。紫外線硬化型接著劑可為丙烯酸系化合物與光自由基聚合起始劑之混合物、或環氧化合物與光陽離子聚合起始劑之混合物等。又,可併用陽離子聚合性環氧化合物與自由基聚合性丙烯酸系化合物,也可併用作為起始劑之光陽離子聚合起始劑與光自由基聚合起始劑。 In order to improve the adhesiveness between the polarizing film and the protective film, a corona treatment, a flame treatment, Surface treatments such as plasma treatment, ultraviolet irradiation, primer coating treatment, saponification treatment, etc. Examples of the adhesive used for bonding the polarizing film and the protective film include an active energy ray-curable adhesive such as a UV-curable adhesive, an aqueous solution of a polyvinyl alcohol resin or an aqueous solution in which a crosslinking agent is blended, and Water-based adhesives such as urethane-based emulsion adhesives. The ultraviolet curing type adhesive may be a mixture of an acrylic compound and a photoradical polymerization initiator, or a mixture of an epoxy compound and a photocationic polymerization initiator. Moreover, a cationic polymerizable epoxy compound and a radical polymerizable acrylic compound may be used in combination, and a photocationic polymerization initiator and a photoradical polymerization initiator may be used in combination as an initiator.

[實施例] [Example]

以下以實施例進一步具體地說明本發明,但本發明並不限定於該等例。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

<實施例1> <Example 1>

使用第1圖所示之製造裝置,從聚乙烯醇系樹脂膜製造實施例1之偏光膜。具體而言係一邊將厚度60μm之長條聚乙烯醇(PVA)原料膜〔Kuraray股份有限公司製商品名「Kuraray Vinylon VF-PE#6000」、平均聚合度2400、皂化度99.9莫耳%以上〕由輥拉出一邊連續地搬送,並於包含30℃純水之膨潤浴中以滯留時間79秒進行浸漬(膨潤步驟)。其後將從膨潤浴拉出之膜,於3碘化鉀/硼酸/水為1/0.3/100(重量比)之含碘30℃染色浴以滯留時間123秒進行浸漬(染色步驟)。接著將從染色浴拉出膜,於碘化鉀/硼酸/水為11/3.8/100(重量比)之53℃第1交聯浴以滯留時間 44秒進行浸漬,接著於碘化鉀/硼酸/水為11/3.8/100(重量比)之40℃第2交聯浴以滯留時間6秒進行浸漬(交聯步驟)。在染色步驟及交聯步驟中,藉由浴中之輥間延伸而進行縱單軸延伸。以原料膜為基準之總延伸倍率為65倍。 The polarizing film of Example 1 was manufactured from a polyvinyl alcohol-based resin film using the manufacturing apparatus shown in FIG. 1. Specifically, a long polyvinyl alcohol (PVA) raw material film with a thickness of 60 μm [Kuraray Co., Ltd.'s trade name "Kuraray Vinylon VF-PE # 6000", an average degree of polymerization of 2400, and a degree of saponification of 99.9 mole% or more] It was continuously conveyed while being pulled out by a roller, and immersed in a swelling bath containing pure water at 30 ° C. for a residence time of 79 seconds (swelling step). Thereafter, the film pulled out from the swelling bath was immersed in a iodine-containing 30 ° C dyeing bath having a potassium iodide / boric acid / water ratio of 1 / 0.3 / 100 (weight ratio) for a retention time of 123 seconds (dyeing step). Next, the film was pulled out from the dyeing bath, and the retention time was in a 53 ° C first crosslinking bath with potassium iodide / boric acid / water 11 / 3.8 / 100 (weight ratio). The impregnation was performed for 44 seconds, followed by impregnation in a second crosslinking bath at 40 ° C with potassium iodide / boric acid / water of 11 / 3.8 / 100 (weight ratio) at a retention time of 6 seconds (crosslinking step). In the dyeing step and the crosslinking step, longitudinal uniaxial stretching is performed by stretching between the rolls in the bath. The total stretching ratio based on the raw film is 65 times.

接著,對於從第2交聯浴17b拉出並通過夾輥53b之膜,使用電磁波照射器(中波長紅外線加熱器(MW加熱器)、製品名:Golden 8 Medium-wave twin tube emitter、Heraeus公司製、熱源溫度900℃、最大能量密度60kW/m2),將電磁波放射口配置於離開膜表面5cm之位置,相對於電磁波照射器之最大照射輸出以輸出50%照射電磁波。膜每單位體積之電磁波之照射熱量為490J/cm3。此外,膜每單位體積之電磁波之照射熱量係由下式計算。 Next, an electromagnetic wave irradiator (medium-wavelength infrared heater (MW heater), product name: Golden 8 Medium-wave twin tube emitter, Heraeus Co., Ltd.) was used for the film drawn from the second crosslinking bath 17b and passed through the nip roller 53b. The heating and heating source temperature is 900 ° C and the maximum energy density is 60kW / m 2 ). The electromagnetic wave radiation port is arranged 5cm away from the film surface, and the maximum irradiation output of the electromagnetic wave irradiator is to output 50% of the electromagnetic wave. The irradiation heat of the electromagnetic wave per unit volume of the film was 490 J / cm 3 . In addition, the amount of heat radiated by electromagnetic waves per unit volume of the film is calculated by the following formula.

(膜每單位體積之電磁波之照射熱量)={(最大能量密度)×(加熱器加熱部表面積)×輸出(%)/(電磁波照射面積)}×(電磁波照射時間)÷(膜厚度) (Irradiation heat of the electromagnetic wave per unit volume of the film) = ((maximum energy density) × (surface area of the heater heating section) × output (%) / (electromagnetic wave irradiation area)) × (electromagnetic wave irradiation time) ÷ (film thickness)

輸出(%)是指實際照射之輸出相對於電磁波照射器之最大照射輸出之比例(%)。 Output (%) refers to the ratio (%) of the actual irradiation output to the maximum irradiation output of the electromagnetic wave irradiator.

由第2交聯浴17b拉出後,從搬送膜至到達電磁波照射器之照射位置並照射電磁波為止之所需時間為5秒。 After being pulled out from the second cross-linking bath 17b, the time required to transport the film to the irradiation position of the electromagnetic wave irradiator and irradiate the electromagnetic wave was 5 seconds.

將經照射電磁波之膜於5℃之包含純水之洗淨浴19以滯留時間3秒進行浸漬(洗淨步驟)。其後在乾燥爐21內以溫度60℃、絶對濕度為11g/cm3,將膜乾燥膜而獲得偏光膜。所得偏光膜之厚度為23μm。 The film irradiated with electromagnetic waves was immersed in a washing bath 19 containing pure water at 5 ° C for a retention time of 3 seconds (washing step). Thereafter, the film was dried in a drying furnace 21 at a temperature of 60 ° C. and an absolute humidity of 11 g / cm 3 to obtain a polarizing film. The thickness of the obtained polarizing film was 23 μm.

<實施例2至4、比較例2> <Examples 2 to 4, Comparative Example 2>

電磁波照射步驟中,電磁波照射器之種類、輸出(%)、及膜每單位體積之電磁波照射熱量如表2所示,除此點以外以與實施例1相同地施作而獲得偏光膜。所得偏光膜之厚度皆為23μm。作為電磁波照射器,係使用下述之任一者:鹵素加熱器(製品名:直管形鹵素加熱燈QIR、USHIO LIGHTING股份有限公司製,熱源溫度2600℃、最大能量密度300kW/m2)、短波長紅外線加熱器(SW加熱器)(製品名:Golden 8 Short-wave twin tube emitter,Heraeus公司製,熱源溫度2200℃、最大能量密度200kW/m2)、快速反應中波長紅外線加熱器(FRMW加熱器)(製品名:Golden 8 Medium-wave fast response twin tubu emitter,Heraeus公司製,熱源溫度1600℃、最大能量密度150kW/m2)、中波長紅外線加熱器(Mw加熱器)(製品名:Golden 8 Medium-wave twin tube emitter,Heraeus公司製,熱源溫度900℃、最大能量密度60kW/m2)。 In the electromagnetic wave irradiation step, the type, output (%) of the electromagnetic wave irradiator, and the electromagnetic wave irradiation heat per unit volume of the film are shown in Table 2. Except for this point, a polarizing film was obtained in the same manner as in Example 1. The thickness of the obtained polarizing films was 23 μm. As the electromagnetic wave irradiator, any one of the following: a halogen heater (product name: straight-tube halogen heating lamp QIR, manufactured by USHIO LIGHTING Co., Ltd., heat source temperature 2600 ° C, maximum energy density 300kW / m 2 ), Short-wavelength infrared heater (SW heater) (product name: Golden 8 Short-wave twin tube emitter, manufactured by Heraeus, heat source temperature 2200 ° C, maximum energy density 200kW / m 2 ), fast-response medium-wavelength infrared heater (FRMW Heater) (product name: Golden 8 Medium-wave fast response twin tubu emitter, manufactured by Heraeus, heat source temperature 1600 ° C, maximum energy density 150kW / m 2 ), medium wavelength infrared heater (Mw heater) (product name: Golden 8 Medium-wave twin tube emitter, manufactured by Heraeus, with a heat source temperature of 900 ° C and a maximum energy density of 60 kW / m 2 ).

<比較例1> <Comparative example 1>

除了不進行電磁波照射步驟以外,以與實施例1相同地施作而獲得偏光膜。 A polarizing film was obtained in the same manner as in Example 1 except that the electromagnetic wave irradiation step was not performed.

所得偏光膜之厚度為23μm。 The thickness of the obtained polarizing film was 23 μm.

<實施例5> <Example 5>

一邊將厚度20μm的長條聚乙烯醇(PVA)原料膜〔Kuraray股份有限公司製之商品名「Kuraray poval膜VF-PE # 2000」、平均聚合度2400、皂化度99.9莫耳%以上〕由輥拉出一邊連續地搬送,以乾式進行4.1倍之單軸 延伸,在保持於緊繃狀態下,於包含30℃純水之膨潤浴中以滯留時間40秒進行浸漬(膨潤步驟)。其後將從膨潤浴拉出之膜,於碘化鉀/水為6/100(重量比)之含碘28℃染色浴以滯留時間30秒進行浸漬(染色步驟)。其後將從染色浴拉出之膜,於碘化鉀/硼酸/水為15/5.5/100(重量比)之67℃交聯浴以滯留時間120秒進行浸漬(交聯步驟)。在染色步驟及交聯步驟中,藉由浴中之輥間延伸而進一步進行縱單軸延伸。以原料膜為基準之總延伸倍率為4.59倍。 On the one side, a long polyvinyl alcohol (PVA) raw material film with a thickness of 20 μm [trade name “Kuraray poval film VF-PE # 2000” manufactured by Kuraray Co., Ltd., an average degree of polymerization of 2400, and a degree of saponification of 99.9 mol% or more] were roll Conveying continuously while pulling out, dry-type single-shaft 4.1 times Stretching, and immersing in a swelling bath containing pure water at 30 ° C. with a retention time of 40 seconds while keeping in a tight state (swelling step). Thereafter, the film pulled out from the swelling bath was immersed in a iodine-containing 28 ° C dyeing bath with potassium iodide / water 6/100 (weight ratio) for a retention time of 30 seconds (dyeing step). Thereafter, the film pulled out from the dyeing bath was immersed in a 67 ° C crosslinking bath with potassium iodide / boric acid / water 15 / 5.5 / 100 (weight ratio) for a retention time of 120 seconds (crosslinking step). In the dyeing step and the cross-linking step, longitudinal uniaxial stretching is further performed by stretching between rolls in a bath. The total stretching ratio based on the raw film was 4.59 times.

接著,對於從交聯浴拉出並通過夾輥之膜,使用電磁波照射器(中波長紅外線加熱器(MW加熱器)、製品名:Golden 8 Medium-wave twin tube emitter、Heraeus公司製、熱源溫度900℃、最大能量密度60kW/m2),將電磁波放射口配置於離開膜表面4cm之位置,以輸出30%照射電磁波。膜每單位體積之電磁波之照射熱量為960J/cm3。從交聯浴拉出後,至搬送膜到達電磁波照射器之照射位置並照射電磁波為止之所需時間為5秒。 Next, for the film drawn from the cross-linking bath and passing through the nip roller, an electromagnetic wave irradiator (medium-wavelength infrared heater (MW heater), product name: Golden 8 Medium-wave twin tube emitter, manufactured by Heraeus, heat source temperature was used). 900 ° C, maximum energy density 60kW / m 2 ), the electromagnetic wave radiation port is arranged 4cm away from the surface of the film to output 30% of the electromagnetic wave. The irradiation heat of the electromagnetic wave per unit volume of the film was 960 J / cm 3 . The time required for the transfer film to reach the irradiation position of the electromagnetic wave irradiator and irradiate the electromagnetic wave after being pulled out from the crosslinking bath was 5 seconds.

將經照射電磁波之膜以滯留時間3秒浸漬於包含15℃純水之洗淨浴(洗淨步驟)。之後,將乾燥爐內設為溫度40℃、絕對濕度11g/cm3,使膜乾燥而得到偏光膜。所得之偏光膜的厚度為8μm。 The film irradiated with electromagnetic waves was immersed in a washing bath containing pure water at 15 ° C. for a retention time of 3 seconds (washing step). Thereafter, the temperature in the drying furnace was set to 40 ° C. and the absolute humidity was 11 g / cm 3 , and the film was dried to obtain a polarizing film. The thickness of the obtained polarizing film was 8 μm.

<實施例6> <Example 6>

除了電磁波照射步驟中,電磁波照射器之輸出(%)及膜每單位體積之電磁波照射熱量如表3所示以外,以與實施例5相同地施作而獲得偏光膜。所得偏光膜之厚度為8μm。 A polarizing film was obtained in the same manner as in Example 5 except that the output (%) of the electromagnetic wave irradiator and the electromagnetic wave irradiation heat per unit volume of the film were as shown in Table 3. The thickness of the obtained polarizing film was 8 μm.

<比較例3> <Comparative example 3>

除了不進行電磁波照射步驟之點以外,以與實施例5相同地施作而獲得偏光膜。所得偏光膜之厚度為8μm。 A polarizing film was obtained in the same manner as in Example 5 except that the electromagnetic wave irradiation step was not performed. The thickness of the obtained polarizing film was 8 μm.

〔偏光膜之評估〕 [Evaluation of Polarizing Film]

(a)單體穿透率、偏光度及直交色相之b值之測定對於各實施例及各比較例所得偏光膜使用附有積分球之分光光度計〔日本分光股份有限公司製「V7100」〕,測定波長380至780nm之範圍中的MD穿透率及TD穿透率,根據下式計算各波長中的單體穿透率及偏光度。 (a) Measurement of b value of monomer transmittance, polarization, and orthogonal hue. For the polarizing films obtained in each of the Examples and Comparative Examples, a spectrophotometer with an integrating sphere was used [V7100, manufactured by JASCO Corporation] , Measure the MD transmittance and TD transmittance in the range of 380 to 780 nm, and calculate the monomer transmittance and polarization at each wavelength according to the following formula.

單體穿透率(%)=(MD+TD)/2 Cell penetration rate (%) = (MD + TD) / 2

偏光度(%)={(MD-TD)/(MD+TD)}×100 Polarization (%) = ((MD-TD) / (MD + TD)) × 100

「MD穿透率」是指格蘭-湯姆森稜鏡射出之偏光方向與偏光膜試料之穿透軸平行時之穿透率,上述式中表示為「MD」。又,「TD穿透率」是指格蘭-湯姆森稜鏡射出之偏光方向與偏光膜試料之穿透軸直交時之穿透率,上述式中表示為「TD」。所得單體穿透率及偏光度係穿透JIS Z 8701:1999「色表示方法-XYZ表色系及X10Y10Z10表色系」之2度視野(C光源)進行視感度修正,而求視感度修正單體穿透率(Ty)、視感度修正偏光度(Py)及直交色相之b值。於表2及表3表示視感度修正單體穿透率(Ty)、視感度修正偏光度(Py)及直交色相之b值,和於波長480nm及波長600nm之偏光度之計算結果。 "MD transmittance" refers to the transmittance when the polarization direction of the polarized light emitted by Gran-Thomson is parallel to the transmission axis of the polarizing film sample, and it is expressed as "MD" in the above formula. The "TD transmittance" refers to the transmittance when the direction of polarization of the polarized light emitted by Glan-Thomson is perpendicular to the transmission axis of the polarizing film sample, and is expressed as "TD" in the above formula. The obtained monomer transmittance and polarization degree are corrected for visual sensitivity by passing through the 2-degree field of view (C light source) of JIS Z 8701: 1999 "color representation method-XYZ color system and X 10 Y 10 Z 10 color system", Obtain the b-values of visual sensitivity correction monomer transmission (Ty), visual sensitivity correction polarization (Py), and orthogonal hue. Tables 2 and 3 show the calculation results of the visual acuity correction monomer transmittance (Ty), visual acuity correction polarization (Py), and orthogonal hue, and the polarization values at the wavelengths of 480 nm and 600 nm.

如表2所示,相較於比較例1至4之偏光膜,實施例1、2之偏光膜係視感度修正單體穿透率(Ty)幾乎相同,但偏光度較高,具有更優異之光學特性。又,如表3所示,相較於比較例3之偏光膜,實施例5及6之偏光膜雖然視感度修正單體穿透率(Ty)幾乎相同,但偏光度較高,具有更優異之光學特性。 As shown in Table 2, compared to the polarizing films of Comparative Examples 1 to 4, the polarizing films of Examples 1 and 2 have almost the same transmittance correction (Ty), but have a higher degree of polarization and are more excellent. Optical characteristics. As shown in Table 3, compared with the polarizing film of Comparative Example 3, although the polarizing films of Examples 5 and 6 had almost the same visual sensitivity correction unit transmittance (Ty), they had a higher degree of polarization and were more excellent. Optical characteristics.

10‧‧‧聚乙烯醇系樹脂所構成之原料膜 10‧‧‧ Raw material film made of polyvinyl alcohol resin

11‧‧‧原料輥 11‧‧‧ raw material roller

13‧‧‧膨潤浴 13‧‧‧Swelling bath

15‧‧‧染色浴 15‧‧‧ Dyeing bath

17a‧‧‧第1交聯浴 17a‧‧‧The first cross-linking bath

17b‧‧‧第2交聯浴 17b‧‧‧ 2nd Crosslinking Bath

19‧‧‧洗淨浴 19‧‧‧washing bath

21‧‧‧乾燥爐 21‧‧‧ drying furnace

23‧‧‧偏光膜 23‧‧‧Polarizing Film

30至48、60、61‧‧‧導輥 30 to 48, 60, 61‧‧‧ guide rollers

50至52、53a、53b、54、55‧‧‧夾輥 50 to 52, 53a, 53b, 54, 55 ...

71‧‧‧電磁波照射部 71‧‧‧ electromagnetic wave irradiation section

Claims (7)

一種偏光膜之製造方法,係由聚乙烯醇系樹脂膜製造偏光膜,並含有:將前述聚乙烯醇系樹脂膜以二色性色素進行染色處理之染色步驟、將前述染色處理後之前述聚乙烯醇系樹脂膜以交聯劑進行交聯處理之交聯步驟、於前述交聯處理後之前述聚乙烯醇系樹脂膜照射超過2μm且4μm以下的波長之紅外線之放射能量比例為全放射能量的25%以上之電磁波之電磁波照射步驟、及將前述照射電磁波後之前述聚乙烯醇系樹脂膜進行洗淨之洗淨步驟。 A method for manufacturing a polarizing film is a polarizing film made of a polyvinyl alcohol-based resin film, and includes: a dyeing step of dyeing the polyvinyl alcohol-based resin film with a dichroic dye; and The cross-linking step of the vinyl alcohol-based resin film using a cross-linking agent to perform a cross-linking treatment. After the cross-linking treatment, the radiation energy ratio of the polyvinyl alcohol-based resin film irradiated with infrared rays having a wavelength exceeding 2 μm and less than 4 μm is the total radiation energy An electromagnetic wave irradiation step of 25% or more of electromagnetic waves, and a washing step of washing the polyvinyl alcohol-based resin film after the electromagnetic wave is irradiated. 如申請專利範圍第1項所述之偏光膜之製造方法,其在前述電磁波照射步驟中,前述電磁波的照射熱量是前述聚乙烯醇系樹脂膜每單位體積為100J/cm3以上50kJ/cm3以下。 According to the method for manufacturing a polarizing film according to item 1 of the scope of the patent application, in the aforementioned electromagnetic wave irradiation step, the irradiation heat of the electromagnetic wave is 100 J / cm 3 or more and 50 kJ / cm 3 or more per unit volume of the polyvinyl alcohol resin film. the following. 如申請專利範圍第1或2項所述之偏光膜之製造方法,其中,前述交聯劑包含硼化合物。 The method for manufacturing a polarizing film according to item 1 or 2 of the scope of the patent application, wherein the crosslinking agent contains a boron compound. 如申請專利範圍第1至3項中任一項所述之偏光膜之製造方法,其中,前述交聯步驟為將前述聚乙烯醇系樹脂膜浸漬於由前述交聯劑的水溶液所成之交聯浴之步驟。 The method for manufacturing a polarizing film according to any one of claims 1 to 3, wherein the cross-linking step is a process in which the polyvinyl alcohol-based resin film is dipped in an aqueous solution of the cross-linking agent. Steps of the combined bath. 如申請專利範圍第4項所述之偏光膜之製造方法,其 在前述交聯處理之後、前述電磁波照射之前,進一步包含將附著於前述聚乙烯醇系樹脂膜的表面之前述水溶液去除之除液步驟。 The method for manufacturing a polarizing film as described in item 4 of the scope of patent application, which After the cross-linking treatment and before the electromagnetic wave irradiation, the liquid-removing step of removing the aqueous solution attached to the surface of the polyvinyl alcohol-based resin film is further included. 如申請專利範圍第4或5項所述之偏光膜之製造方法,其中,前述電磁波照射步驟係在將前述聚乙烯醇系樹脂膜從前述交聯浴拉出後的5秒以內進行。 The method for manufacturing a polarizing film according to item 4 or 5 of the scope of the patent application, wherein the electromagnetic wave irradiation step is performed within 5 seconds after the polyvinyl alcohol-based resin film is pulled out of the crosslinking bath. 一種偏光膜之製造裝置,係由聚乙烯醇系樹脂膜製造偏光膜,並具備:將前述聚乙烯醇系樹脂膜以二色性色素進行染色處理之染色部、將前述染色處理後之前述聚乙烯醇系樹脂膜以交聯劑進行交聯處理之交聯部、於前述交聯處理後之前述聚乙烯醇系樹脂膜,照射超過2μm且4μm以下的波長之紅外線之放射能量比例為全放射能量的25%以上之電磁波之電磁波照射部、及將前述照射電磁波後之前述聚乙烯醇系樹脂膜進行洗淨之洗淨部。 An apparatus for producing a polarizing film is a polarizing film produced from a polyvinyl alcohol resin film, and includes a dyeing section for dyeing the polyvinyl alcohol resin film with a dichroic dye, and a polymerizing agent for the polymer after the dyeing treatment. The ratio of the radiation energy of the cross-linked part of the vinyl alcohol-based resin film to a cross-linking treatment with a cross-linking agent and the aforementioned polyvinyl alcohol-based resin film after the cross-linking treatment is irradiated to a wavelength exceeding 2 μm and 4 μm is total radiation An electromagnetic wave irradiating section for electromagnetic waves having an energy of 25% or more, and a washing section for washing the polyvinyl alcohol-based resin film after the electromagnetic wave is irradiated.
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