TW202132078A - Polarizing film - Google Patents

Polarizing film Download PDF

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TW202132078A
TW202132078A TW110115150A TW110115150A TW202132078A TW 202132078 A TW202132078 A TW 202132078A TW 110115150 A TW110115150 A TW 110115150A TW 110115150 A TW110115150 A TW 110115150A TW 202132078 A TW202132078 A TW 202132078A
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film
bath
polarizing film
electromagnetic wave
polyvinyl alcohol
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TWI764696B (en
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住田幸司
趙天熙
朴重萬
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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
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    • 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

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Abstract

The present invention provides a method for manufacturing polarizing film capable of obtaining a polarizing film having high optical characteristics despite even if the boron content is reduced, and a manufacturing apparatus thereof.
The method for manufacturing a polarizing film having a boron content of 2.0 to 3.5% by weight from a polyvinyl alcohol-based resin film, which comprises: a dyeing step of dyeing the polyvinyl alcohol-based resin film with a dichroic dye; a crosslinking step of immersing the polyvinyl alcohol-based resin film after the dyeing step in a crosslinking bath composed of an aqueous solution of a crosslinking agent containing a boron compound to crosslink the polyvinyl alcohol resin film; an electromagnetic wave irradiation step of irradiating the polyvinyl alcohol-based resin film after the crosslinking step with an electromagnetic wave in which the ratio of radiant energy of infrared radiation with a wavelength of more than 2 μm to 4 μm or less with respect to the total radiant energy is 25% or more; and a washing step of washing the polyvinyl alcohol-based resin film having been irradiated with the electromagnetic wave.

Description

偏光膜 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 of manufacturing a polarizing film from a polyvinyl alcohol-based resin film, and a manufacturing device.

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。 Polarizing plates are widely used as polarizing elements in image display devices such as liquid crystal display devices. As the polarizing plate, a transparent resin film (protective film, etc.) is generally laminated on one side 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 immersing a raw film made of polyvinyl alcohol resin in a dyeing bath containing dichroic pigments such as iodine, and then immersing in a crosslinking bath containing a crosslinking agent such as boric acid. It is produced by uniaxially stretching the film at any stage. Uniaxial stretching includes dry stretching in the air, and wet stretching in the above-mentioned dye bath and crosslinking bath.

經過交聯之偏光膜若加熱則容易收縮,有耐久性不充分之情形。日本特開2013-148806號公報(專利文獻1)中揭示偏光膜的硼含有率低至1至3.5重量%,則可提供耐久性優異之偏光膜。 The cross-linked polarizing film tends to shrink when heated, and the durability may be insufficient. JP 2013-148806 A (Patent Document 1) discloses that the boron content of a polarizing film is as low as 1 to 3.5% by weight, and a polarizing film with excellent durability can be provided.

[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 Laid-Open No. 2013-148806.

但若降低偏光膜中的硼含有率,則有無法獲得充分交聯度且降低光學特性之情形。本發明之目的係提供縱使硼含有率降低卻仍具有高光學特性之偏光膜的製造方法、及其製造裝置。再者,以提供藉由如此之偏光膜的製造方法而獲得之新穎的偏光膜為目的。 However, if the boron content in the polarizing film is lowered, a sufficient degree of crosslinking may not be obtained and the optical characteristics may be lowered. The object of the present invention is to provide a method for manufacturing a polarizing film having high optical properties even if the boron content is reduced, and a manufacturing apparatus thereof. Furthermore, it aims at providing a novel polarizing film obtained by such a manufacturing method of a polarizing film.

本發明提供下述所示偏光膜之製造方法、製造裝置、及偏光膜。 The present invention provides a method of manufacturing a polarizing film, a manufacturing apparatus, and 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硼含有率為2.0至3.5重量%之偏光膜,並含有: [1] A method for manufacturing a polarizing film, which is to produce a polarizing film with a boron content of 2.0 to 3.5% by weight from a polyvinyl alcohol-based resin film, and containing:

染色步驟,係將前述聚乙烯醇系樹脂膜以二色性色素進行染色處理; In the dyeing step, the aforementioned polyvinyl alcohol resin film is dyed with dichroic pigments;

交聯步驟,係將前述染色步驟後之前述聚乙烯醇系樹脂膜浸漬於由包含硼化合物之交聯劑的水溶液所構成之交聯浴而進行交聯處理; In the cross-linking step, the polyvinyl alcohol resin film after the dyeing step is immersed in a cross-linking bath composed of an aqueous solution of a cross-linking agent containing a boron compound for cross-linking treatment;

電磁波照射步驟,係於前述交聯步驟後之前述聚乙烯醇系樹脂膜照射電磁波,該電磁波中超過2μm且4μm以下之波長的紅外線之放射能量的比例為全放射能量的25% 以上;及 In the electromagnetic wave irradiation step, the polyvinyl alcohol resin film after the cross-linking step is irradiated with electromagnetic waves. In the electromagnetic wave, the proportion of the radiated energy of infrared rays with a wavelength exceeding 2 μm and below 4 μm is 25% of the total radiated energy Above; and

洗淨步驟,係將照射前述電磁波後之前述聚乙烯醇系樹脂膜洗淨。 The washing step is to wash the polyvinyl alcohol-based resin film after irradiating the electromagnetic wave.

〔2〕如〔1〕所記載之偏光膜之製造方法,其中,在前述電磁波照射步驟中,前述電磁波的照射能量相對於前述聚乙烯醇系樹脂膜的每單位體積為100J/cm3以上50kJ/cm3以下。 [2] The method for producing a polarizing film as described in [1], wherein in the electromagnetic wave irradiation step, the irradiation energy of the electromagnetic wave is 100 J/cm 3 or more and 50 kJ per unit volume of the polyvinyl alcohol-based resin film /cm 3 or less.

〔3〕如〔1〕或〔2〕所記載之偏光膜之製造方法,更含有除液步驟,該除液步驟係在前述交聯處理後照射前述電磁波前,將附著於前述聚乙烯醇系樹脂膜之表面的前述水溶液去除。 [3] The method for manufacturing a polarizing film as described in [1] or [2] further includes a liquid removal step, which is to adhere to the polyvinyl alcohol before irradiating the electromagnetic wave after the crosslinking treatment. The aforementioned aqueous solution on the surface of the resin film is removed.

〔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5秒內進行。 [4] The method for producing a polarizing film as described in any one of [1] to [3], wherein the electromagnetic wave irradiation step is 5 seconds after the polyvinyl alcohol-based resin film is pulled out of the crosslinking bath Within.

〔5〕如〔1〕至〔4〕中任一項所記載之偏光膜之製造方法,其中,前述交聯步驟中,前述交聯浴係由相對於水100重量份包含1.5重量份以上3重量份以下前述硼化合物之交聯劑的水溶液構成者。 [5] The method for producing a polarizing film as described in any one of [1] to [4], wherein in the cross-linking step, the cross-linking bath contains 1.5 parts by weight or more relative to 100 parts by weight of water. It is composed of an aqueous solution of the crosslinking agent of the above-mentioned boron compound in parts by weight or less.

〔6〕一種偏光膜之製造裝置,係由聚乙烯醇系樹脂膜製造硼含有率為2.0至3.5重量%之偏光膜者,且具備: [6] A manufacturing device for polarizing film, which manufactures a polarizing film with a boron content of 2.0 to 3.5% by weight from a polyvinyl alcohol-based resin film, and has:

染色部,係將前述聚乙烯醇系樹脂膜以二色性色素進行染色處理; In the dyeing part, the aforementioned polyvinyl alcohol resin film is dyed with dichroic pigments;

交聯部,係將前述染色處理後之前述聚乙烯醇系樹脂 膜浸漬於由包含硼化合物之交聯劑的水溶液所構成之交聯浴而進行交聯處理; The cross-linking part is the aforementioned polyvinyl alcohol resin after the aforementioned dyeing treatment The film is immersed in a cross-linking bath composed of an aqueous solution of a cross-linking agent containing a boron compound for cross-linking treatment;

電磁波照射部,係於前述交聯處理後之前述聚乙烯醇系樹脂膜照射電磁波,該電磁波中超過2μm且4μm以下之波長的紅外線之放射能量的比例為全放射能量的25%以上;及 The electromagnetic wave irradiation section irradiates the polyvinyl alcohol-based resin film after the crosslinking treatment with electromagnetic waves, and the ratio of the radiated energy of infrared rays with wavelengths exceeding 2 μm and below 4 μm in the electromagnetic waves is 25% or more of the total radiated energy; and

洗淨部,係將照射前述電磁波後之前述聚乙烯醇系樹脂膜洗淨。 The cleaning part cleans the polyvinyl alcohol-based resin film irradiated with the electromagnetic wave.

〔7〕一種偏光膜,係將聚乙烯醇系樹脂膜以二色性色素染色而成之偏光膜,其中, [7] A polarizing film, which is a polarizing film made by dyeing a polyvinyl alcohol resin film with a dichroic pigment, wherein:

硼含有率為2.0至3.5重量%, The boron content is 2.0 to 3.5% by weight,

視感度修正單體穿透率為42.0%以上, Visual sensitivity correction monomer penetration rate is over 42.0%,

視感度修正偏光度為99.990%以上, The visual sensitivity corrected polarization degree is above 99.990%,

波長480nm中之吸收軸方向的吸光度A480與波長600nm中之吸收軸方向的吸光度A600之比A480/A600為0.75以上1.00以下。 A ratio A 480 absorbance of the 600nm wavelength absorbance A 600 of the absorption axis direction of the absorption axis direction of the wavelength of 480nm 480 / A 600 of 0.75 to 1.00.

根據本發明可提供縱使硼含有率降低卻仍具有高光學特性之偏光膜的製造方法、及製造裝置。而且,根據本發明可提供硼含有率低且光學特性優異的偏光膜。 According to the present invention, it is possible to provide a manufacturing method and a manufacturing apparatus of a polarizing film having high optical characteristics even if the boron content is reduced. Furthermore, according to the present invention, a polarizing film having a low boron content and excellent optical properties can be provided.

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

11:原料卷 11: Raw material roll

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: The second cross-linking bath

19:洗淨浴 19: Wash 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 roller

50至52、53a、53b、54、55:夾輥 50 to 52, 53a, 53b, 54, 55: nip roller

71:電磁波照射部 71: Electromagnetic wave irradiation department

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。 Figure 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左右。 The polarizing film in the present invention is a polyvinyl alcohol resin film that is uniaxially stretched to adsorb and align a dichroic dye (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 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 1,500 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, polyvinyl butyral, etc. 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 the starting material for the polarizing film, unstretched polyvinyl alcohol with a thickness of 65 μm or less (for example, 60 μm or less) is used, preferably 50 μm or less, more preferably 35 μm or less, and even more preferably 30 μm or less. System resin film (raw material film).

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卷(原料卷)。 Thus, a thin-film polarizing film with increasing market requirements can be obtained. The width of the raw film is not particularly limited, and may be, for example, about 400 to 6000 mm. raw material As the 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 one that is laminated on a supporting base film, that is, a laminated film of a base film and a polyvinyl alcohol-based resin film laminated on the base film can be prepared, and As the polyvinyl alcohol-based resin film. In this case, the polyvinyl alcohol-based resin film can be produced by, for example, coating a coating liquid containing a polyvinyl alcohol-based resin on at least one surface 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 composed of a thermoplastic resin can be used. As a specific example, a transparent thermoplastic resin, preferably a film composed of an optically transparent thermoplastic resin, such as a chain polyolefin resin (polypropylene resin, etc.), a cyclic polyolefin resin (Norbornene-based resins, etc.) such as polyolefin-based resins; cellulose-based resins such as cellulose triacetate and cellulose diacetate; 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; poly Chlorine resin; polyether resin; polyarylate resin; polyimide resin; polyimide resin, etc.

偏光膜係邊將上述長條原料膜由原料卷拉出,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 system is continuously conveyed along the film conveying path of the polarizing film manufacturing device while pulling the above-mentioned long raw film from the raw material roll, and is immersed in the processing liquid contained in the processing tank (hereinafter also referred to as "processing bath") Then pull it out, and perform the drying step after the predetermined processing step, so that it can be Continuously manufacture long strips of polarizing film. In addition, the treatment step is not limited to the method of immersing the film in the treatment bath as long as it is a method of contacting the film with the treatment liquid, and may be a method of treating the film by attaching the treatment liquid to the surface of the film by spraying, dripping, dripping, etc. method. When the treatment step is performed by the method of immersing the film in the treatment bath, the treatment bath for performing one treatment step is not limited to one, and the film can be sequentially immersed in two or more treatment baths to complete one treatment 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 above-mentioned treatment liquid include a swelling liquid, a dyeing liquid, a cross-linking liquid, and a cleaning liquid. Next, as the above-mentioned treatment steps, for example, the swelling step of contacting the raw film with a swelling liquid to perform swelling treatment, the dyeing step of contacting the swelling treatment film with the dyeing solution and performing the dyeing treatment, and contacting and crosslinking the dyed film The cross-linking step of the cross-linking treatment is carried out in the liquid, and the cleaning step of the cleaning treatment is carried out by contacting the membrane after the cross-linking treatment with the cleaning solution. Furthermore, the wet or dry uniaxial stretching process may be performed between the series of processing steps (that is, before and 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,在交聯處理後,洗淨處理前,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,即使硼含有率低仍可獲得具有優異光學特性之偏光膜。 In the present invention, after the crosslinking treatment and before the washing treatment, the electromagnetic wave irradiation step described after irradiating the film with electromagnetic waves is performed. By performing the electromagnetic wave irradiation step, a polarizing film with excellent optical properties can be obtained even if the boron content is low.

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藉由原料卷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。 Hereinafter, an example of the manufacturing method of the polarizing film of the present invention will be described in detail with reference to FIG. 1. Fig. 1 is a cross-sectional view schematically showing an example of the manufacturing method of the polarizing film of the present invention and the manufacturing apparatus of the polarizing film used therefor. The polarizing film manufacturing device shown in Figure 1 is as follows Formula: While the raw material (unstretched) film 10 composed of polyvinyl alcohol-based resin is continuously drawn out by the raw material roll 11, it is transported along the film transport path, thereby sequentially passing through the film transport path. Swelling bath (swelling liquid contained in the swelling tank) 13, dyeing bath (dyeing liquid contained in the dyeing tank) 15, the first cross-linking bath (first cross-linking liquid contained in the cross-linking tank) 17a, 2 The cross-linking bath (the second cross-linking liquid contained in the cross-linking tank) 17b, and the washing bath (the washing liquid contained in the washing tank) 19 are finally passed through the drying oven 21. The obtained polarizing film 23 can be directly transported, for example, to the following polarizing plate manufacturing step (a step of attaching a protective film to one or both sides of the polarizing film 23). The arrow in Figure 1 indicates the film transport 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 Figure 1, "treatment tank" is a general term including swelling tank, dyeing tank, cross-linking tank and washing tank, and "treatment liquid" is a general term including swelling liquid, dyeing liquid, cross-linking liquid and washing liquid , "Treatment bath" is a general term including swelling bath, dyeing bath, cross-linking bath and washing bath. The swelling bath, the dyeing bath, the cross-linking bath, and the washing bath constitute the swelling part, the dyeing part, the cross-linking part, and the washing part in the manufacturing apparatus of the present invention, respectively.

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 treatment bath, the film transport path of the polarizing film manufacturing device can be configured as follows: guide rollers 30 to 48, 60, 61 that can support the transported film or further change the film transport direction; can be pressed and clamped The nip rollers 50 to 55 that can hold the conveyed film and can apply driving force to the film through its rotation, or can further change the film conveying direction, are arranged at appropriate positions. Guide rollers or nip rollers can be arranged before and after each treatment bath or in the treatment bath, whereby the film can be introduced and immersed in the treatment bath, and pulled out from the treatment bath [refer to Figure 1]. For example, one or more guide rollers can be installed in each treatment bath The guide roller conveys the film, thereby allowing the film to be immersed in each treatment 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周速差,而進行縱單軸延伸。 The polarizing film manufacturing apparatus shown in Figure 1 is equipped with nip rolls (nip rolls 50 to 54) before and after each treatment bath, so that the roll-to-roll extension can be implemented in any one or more treatment baths. A peripheral speed difference is applied between the nip rolls before and after the treatment bath, and longitudinal uniaxial stretching is performed.

第1圖所示之偏光膜製造裝置中,在第2交聯浴17b下游且洗淨浴19上游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, the electromagnetic wave irradiation part 71 is arrange|positioned in the conveyance path downstream of the 2nd crosslinking bath 17b and the upstream of the washing bath 19, and an electromagnetic wave irradiation step is performed. The steps are explained 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 the swelling step is to remove foreign matter on the surface of the raw film 10, remove the plasticizer in the raw film 10, impart easy dyeability, and plasticize the raw film 10, etc. The processing conditions are determined in a range that can achieve the purpose, and the raw 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藉由原料卷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 implemented by the following method: while the raw film 10 is continuously drawn through the raw material roll 11, it is transported along the film transport path, and the raw film 10 is immersed in the swelling bath 13 for a predetermined time. Then pull it out. In the example of FIG. 1, between the raw film 10 being pulled out and immersed in the swelling bath 13, the raw film 10 is conveyed along the film conveyance path constructed by the guide rollers 60 and 61 and the nip roller 50. As shown in FIG. In the swelling process, it 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 Laid-Open No. 10-153709), chloride (Japanese Patent Laid-Open No. 06-281816), 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, more preferably about 15 to 30°C. The immersion time of the raw film 10 is preferably about 10 to 300 seconds, more preferably about 20 to 200 seconds. In addition, when the raw material film 10 is a polyvinyl alcohol resin film stretched in gas in advance, the temperature of the swelling bath 13 is, for example, about 20 to 70°C, preferably about 30 to 60°C. The immersion time of the raw film 10 is preferably about 30 to 300 seconds, 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之周速差而在膨潤浴13中實施單軸延伸處理。 During the swelling treatment, the raw material film 10 is likely to swell in the width direction to form wrinkles in the film. As one method for removing the wrinkles and transporting the film, the guide rollers 30, 31, and/or 32 use spreading rollers, spiral rollers, crown rolls, and other rollers that have a widening function. Or use other widening devices such as cross guiders, bending bars, tenter clips, etc. Another method for suppressing wrinkles is to implement extension treatment. For example, the difference in peripheral speed between the nip roll 50 and the nip roll 51 can be used to perform uniaxial stretching in the swelling bath 13.

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。 During the swelling treatment, the film also swells and expands in the film conveying direction. Therefore, in order to eliminate film slack in the conveying direction when the film is not actively stretched, it is preferable to control 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 stabilizing the transport of the membrane in the swelling bath 13, the water flow in the swelling bath 13 is controlled by washing in the water, or the EPC device (Edge Position Control device: a device that detects the end of the membrane and prevents the membrane from snake), etc. Department is useful.

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 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 the dyeing step is to adsorb and align the dichroic pigments on the polyvinyl alcohol resin film after the swelling treatment. The treatment conditions are determined in a range that can achieve the purpose without causing problems such as extreme dissolution or devitrification of the film. Referring to Figure 1, the dyeing step can be carried out along the film transport path constructed by the nip roller 51, the guide rollers 33 to 36 and the nip roller 52, and the swollen film is placed in the dyeing bath 15 (the processing of the dyeing tank) (Liquid) immersed for a predetermined time, and then pulled out and implemented. In order to improve the dyeability of the dichroic pigment, the film used in the dyeing step is preferably a film 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 in addition to the one before the dyeing treatment. In addition to the uniaxial stretching treatment, the uniaxial stretching treatment is performed during the dyeing treatment.

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 iodine is used as a dichroic pigment, an aqueous solution having a concentration of iodine/potassium iodide/water=about 0.003 to 0.3/about 0.1 to 10/100 can be used in the dyeing solution of dyeing bath 15, for example. Other iodides such as zinc iodide can be used instead of potassium iodide, or potassium iodide and other iodides can be used in combination. In addition, compounds other than iodide, such as boric acid, zinc chloride, cobalt chloride, etc., may coexist. When boric acid is added, it can be distinguished from the cross-linking treatment described later by the point of containing iodine, and if the aqueous solution contains about 0.003 parts by weight or more of iodine relative to 100 parts by weight of water, it can be regarded as dyeing bath 15. The temperature of the dye bath 15 when the film is dipped 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。 Use water-soluble dichroic dyes as dichroic pigments At this time, an aqueous solution with a concentration of dichroic dye/water=approximately 0.001 to 0.1/100 can be used in the dyeing solution of the dyeing bath 15, for example. The dyeing bath 15 may coexist with a dyeing auxiliary agent, etc., and may also contain, for example, an inorganic salt such as sodium sulfate or a surfactant. Only one type of dichroic dye may be used alone, or two or more types of dichroic dyes may be used in combination. The temperature of the dye bath 15 when the film is immersed is, for example, about 20 to 80°C, preferably 30 to 70°C, and the immersion time of the film is usually about 30 to 600 seconds, preferably about 60 to 300 seconds.

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之間施加周速差等方法而進行。 In the dyeing step as described above, the film can be stretched uniaxially in the dyeing bath 15. The uniaxial stretching of the film can be performed by a method such as applying a peripheral 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使用擴展輥、螺旋輥、凸輥之類之具有擴寬功能之輥,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 treatment, similar to the swelling treatment, in order to remove the wrinkles of the film and to transport the polyvinyl alcohol-based resin film, the guide rollers 33, 34, 35 and/or 36 may use spreading rollers, spiral rollers, convex rollers, etc. For rolls with widening function, other widening devices such as cross guide rollers, bending bars, and tenter clips can also be used. As with the swelling treatment, another method for suppressing the generation of wrinkles is to perform an elongation 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 drawn from the dyeing bath 15 passes through the guide roller 36, the nip roller 52, and the guide roller 37 in this order, and then is introduced into the cross-linking bath 17.

(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 the cross-linking step is to adjust the color tone (to prevent the film from appearing blue, etc.) by the water resistance of the cross-linking. In the example shown in Figure 1, two cross-linking baths are arranged as the cross-linking bath for 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 cross-linking step performed for the purpose is performed in the second cross-linking bath 17b. Refer to In Figure 1, the first cross-linking step can be transported along the film transport path constructed by the nip roller 52, the guide rollers 37 to 40 and the nip roller 53a, and the dyed film is placed in the first cross-linking bath 17a ( The first cross-linking liquid contained in the cross-linking tank) is immersed for a predetermined time, and then pulled out for implementation. In the second cross-linking step, the film after the first cross-linking step can be transported along the film transport path constructed by the nip roller 53a, guide rollers 41 to 44, and nip roller 53b, and the film after the first cross-linking step can be placed in the second cross-linking bath 17b (contained in The second cross-linking liquid in the cross-linking tank is immersed for a predetermined period of time, and then pulled out and implemented. Hereinafter, when referred to as a crosslinking bath, it contains both the first crosslinking bath 17a and the second crosslinking bath 17b, and when referred to as a crosslinking liquid, it also contains both the first crosslinking liquid and the second crosslinking liquid.

作為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。作為溶媒例如可使用水,又,亦可含有與水具有相溶性之有機溶媒。交聯液中之交聯劑之濃度、交聯浴的溫度、膜浸漬時間、浸漬膜的交聯浴個數係沒有特別的限定,可從該等中適當地選擇,藉此獲得硼含有率為2.0至3.5重量%之偏光膜。作為交聯液,例如可使用相對於水100重量份,含有硼酸等硼化合物1至10重量份之水溶液,較佳為使用含有1.5至3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,碘化物之量例如可為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。 As a cross-linking liquid, it can be used in 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. As the solvent, for example, water can be used, and an organic solvent having compatibility with water may also be contained. The concentration of the cross-linking agent in the cross-linking solution, the temperature of the cross-linking bath, the film immersion time, and the number of cross-linking baths in which the film is immersed are not particularly limited, and can be appropriately selected from these to obtain the boron content. The polarizing film is 2.0 to 3.5% by weight. As the crosslinking liquid, for example, an aqueous solution containing 1 to 10 parts by weight of a boron compound such as boric acid can be used with respect to 100 parts by weight of water, and an aqueous solution containing 1.5 to 3 parts by weight is preferably used. When the dichroic dye used in the dyeing treatment is iodine, the crosslinking solution preferably contains iodide in addition to boric acid, and the amount of iodide can be, for example, 1 to 30 parts by weight relative to 100 parts by weight of water. Examples of iodides include potassium iodide and zinc iodide. In addition, compounds other than iodide, such as zinc chloride, cobalt chloride, zirconium chloride, sodium thiosulfate, potassium sulfite, sodium sulfate, etc., may coexist.

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=1至10/1至30/100之水溶液。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 cross-linking treatment, the concentration of boric acid and iodide and the temperature of the cross-linking bath 17 can be appropriately changed according to the purpose. For example, in the case of the first cross-linking liquid whose purpose of cross-linking treatment is to perform hydration resistance by cross-linking, the concentration may be an aqueous solution of boric acid/iodide/water=1 to 10/1 to 30/100 in terms of weight ratio. The temperature of the first crosslinking bath 17a when the film is immersed is usually about 50 to 70°C, preferably 53 to 65°C, and the immersion time of the film is usually about 10 to 600 seconds, preferably 20 to 300 seconds, more preferably For 20 to 200 seconds. In addition, when the polyvinyl alcohol-based resin film stretched before the swelling treatment is sequentially dyed and the first cross-linking treatment is performed, the temperature of the first cross-linking 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 crosslinking liquid for the purpose of adjusting the color tone, for example, when iodine is used as a dichroic dye, the concentration can be used in a weight ratio of boric acid/iodide/water=1 to 5/3 to 30/100. The temperature of the second crosslinking bath 17b when the film is immersed is usually about 10 to 45°C, and the immersion time of the film is usually about 1 to 300 seconds, preferably 2 to 100 seconds.

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 cross-linking treatment can be carried out multiple times, usually 2 to 5 times. At this time, the composition and temperature of each crosslinking bath used can be the same or different. The cross-linking treatment to achieve water resistance through cross-linking and the cross-linking treatment to adjust the color tone can also be performed in plural steps, respectively.

可利用夾輥52與夾輥53a之周速差在第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之周速差在第2交聯浴17b中實施單軸延伸處理。 The difference in peripheral speed between the nip roll 52 and the nip roll 53a can be used to perform uniaxial stretching in the first crosslinking bath 17a. In addition, the difference in peripheral speed between the nip roll 53a and the nip roll 53b may be used to perform uniaxial stretching in the second crosslinking bath 17b.

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使用擴展輥、螺旋輥、凸輥之類之具有擴寬功能的輥,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, similar to the swelling treatment, in order to remove The film is wrinkled and the polyvinyl alcohol resin film is transported. Expanding rolls, spiral rolls, convex rolls, etc. can be used on guide rolls 38, 39, 40, 41, 42, 43, and/or 44 with widening functions. Other widening devices such as cross guide rollers, bending bars, tenter clips, etc. can also be used. As with the swelling treatment, another method for suppressing the generation of wrinkles is to perform 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 crosslinking bath 17b passes through the guide roller 44 and the nip roller 53b in this order and is introduced into the washing bath 19.

(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經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 Figure 1 includes a washing step after the cross-linking step. The purpose of the cleaning treatment is to remove the excess boric acid, iodine and other agents adhering to the polyvinyl alcohol resin film. The washing step is performed, for example, by immersing the crosslinked polyvinyl alcohol-based resin film in the washing bath 19. Also, instead of the step of immersing the membrane in the washing bath 19, the washing step may be performed by spraying the membrane with the washing liquid as a washing bath, or by using both the immersion in the washing bath 19 and the washing liquid. Spray and proceed.

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。洗淨處理的條件,係以使最終獲得之偏光膜的硼含有率為2.0至3.5質量%之方式而適當地選擇即可。 Fig. 1 shows an example in which a polyvinyl alcohol-based resin film is immersed in a washing bath 19 and subjected to washing treatment. In the washing treatment, the temperature of the washing bath 19 is usually about 2 to 40°C, and the immersion time of the film is usually about 2 to 120 seconds. The conditions of the washing treatment may be appropriately selected so that the boron content of the polarizing film finally obtained is 2.0 to 3.5% by mass.

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使用擴展輥、螺旋輥、凸輥之類之具有擴寬功能的輥,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, in the cleaning process, for the purpose of removing wrinkles and conveying the polyvinyl alcohol resin film, spreading rollers, spiral rollers, convex rollers, etc. can be used for guide rollers 45, 46, 47, and/or 48. For functional rolls, other widening devices such as cross guide rolls, bending bars, and tenter clips can also be used. In addition, in the film washing treatment, an elongation treatment to suppress the generation of wrinkles may be performed.

(延伸步驟) (Extension step)

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)間施加周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 wet or dry uniaxial stretching between the series of processing steps (that is, before and after any one or more processing steps and/or during any one or more processing steps). The specific method of uniaxial stretching treatment may be, for example, applying a circumferential speed difference between two nip rollers (for example, two nip rollers arranged before and after the treatment bath) constituting the film conveying path to perform longitudinal uniaxial stretching between the rollers, such as The hot roll stretching, tenter stretching, etc. described in Japanese Patent No. 2731813 are preferably stretching between rolls. The uniaxial stretching step may be performed multiple times between obtaining the polarizing film 23 from the raw film 10. As mentioned above, the stretching treatment is also beneficial to suppress the wrinkles of 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 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 the extension processing is performed in more than two processing steps, 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 drawn from the second crosslinking step 17b and passed through the nip roll 53b, the film is irradiated with electromagnetic waves before being immersed in the washing bath 19 (electromagnetic wave irradiation step). In the device shown in FIG. 1, electromagnetic waves are irradiated by the electromagnetic wave irradiation unit 71. The infrared radiation energy ratio of the electromagnetic wave system used in the electromagnetic wave irradiation step of the present invention with a wavelength exceeding 2 μm and below 4 μm is 25% or more of the total radiation energy, preferably 28% or more, and more preferably 35% or more. By irradiating the film with such electromagnetic waves, the optical properties of the obtained polarizing film can be improved. Also, regarding the electromagnetic wave used in the present invention, it exceeds 2μm The upper limit of the infrared radiation energy ratio with a wavelength of 4 μm or less is not particularly limited, but is, for example, 80% or less. Generally, electromagnetic waves with a wavelength of 0.75 μm to 1000 μm are called infrared rays.

電磁波照射步驟中,藉由照射超過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%以上之電磁波,而可提高偏光膜的光學特性之機制並不明確,但推測為藉由超過2μm且4μm以下波長之紅外線所激發之膜內之分子運動,而促進經交聯處理之膜中之碘等二色性色素之固定化,藉此可提高偏光膜的光學特性。 In the electromagnetic wave irradiation step, by irradiating electromagnetic waves with a wavelength exceeding 2 μm and below 4 μm, the proportion of infrared radiation energy is 25% or more of the total radiation energy. The mechanism by which the optical properties of the polarizing film can be improved is not clear, but it is presumed that The movement of molecules in the film excited by infrared rays with a wavelength of 2μm and below 4μm promotes the immobilization of dichroic pigments such as iodine in the crosslinked film, thereby improving the optical properties 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 domain (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 mid-wavelength infrared heater (heat source temperature 900°C).

[表1]

Figure 110115150-A0101-12-0017-1
[Table 1]
Figure 110115150-A0101-12-0017-1

如表1所示,由於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,故可適用為構成電磁波照射部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,選擇複數台電磁波照射器,以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, due to the short-wavelength infrared heater (heat source temperature 2200℃), the rapid response medium-wavelength infrared heater (heat source temperature 1600°C), carbon heater (heat source temperature 1200°C), carbon heater (heat source temperature 950°C), and mid-wavelength infrared heater (heat source temperature 900°C). The proportion of infrared radiation energy exceeding 2μm and wavelengths below 4μm is all The radiated energy is more than 25%, so it can be applied as an electromagnetic wave irradiator constituting the electromagnetic wave irradiator 71. The electromagnetic wave irradiation unit 71 may be constituted by one electromagnetic wave irradiator, or may be constituted by a plurality of electromagnetic wave irradiators. When it is composed of a plurality of electromagnetic wave irradiators, select a plurality of electromagnetic wave irradiators so that the infrared radiation energy radiated by the multiple electromagnetic wave irradiators with a wavelength exceeding 2 μm and below 4 μm is the total amount of the electromagnetic waves radiated by the multiple electromagnetic wave irradiators More than 25% of the radiated energy. In addition, in Figure 1, the electromagnetic wave irradiator 71 is configured to irradiate electromagnetic waves to only one surface of the film, but it is also possible to arrange multiple electromagnetic wave irradiators to irradiate electromagnetic waves to both surfaces of the film. The electromagnetic wave irradiation section 71 is preferably configured to irradiate electromagnetic waves to the entire width direction of the polyvinyl alcohol-based resin film to be irradiated.

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 part 71, the distance between the electromagnetic wave radiation port of the electromagnetic wave irradiator and the film is preferably 2 to 40 cm, more preferably 5 to 20 cm. However, the distance is preferably selected and performed appropriately in consideration of the radiation energy amount of the electromagnetic wave radiated from the electromagnetic wave irradiator, the temperature of the film surface, and the like. The film surface temperature 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 can usually be 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. In addition, from the viewpoint of suppressing film deterioration due to temperature rise, the radiation heat of electromagnetic waves 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 radiation heat of the electromagnetic wave, but the purpose of the electromagnetic wave irradiation step of the present invention is not to reduce the moisture content of the film, so the radiation heat can be appropriately selected, preferably within the above range. .

在本發明中,藉由在洗淨處理前進行電磁波照射步驟,可使所獲得之偏光膜的光學特性提高。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,可使因浸漬於交聯浴而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, by performing the electromagnetic wave irradiation step before the washing treatment, the optical properties of the obtained polarizing film can be improved. The electromagnetic wave irradiation step may be performed on the film immersed in at least one crosslinking bath, and 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 Figure 1, the film immersed in the first cross-linking bath and before the second cross-linking bath can be irradiated with electromagnetic waves, and the film immersed in the second cross-linking bath can also be irradiated with electromagnetic waves. step. However, the electromagnetic wave irradiation step can crosslink the boric acid that enters the film due to immersion in the crosslinking bath. Therefore, the electromagnetic wave irradiation step for the film immersed in the crosslinking bath can more effectively crosslink the boric acid. Better.

電磁波之照射較佳為從交聯浴拉出膜後在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 irradiation of electromagnetic waves is preferably performed within 10 seconds after the film is drawn from the crosslinking bath, and more preferably within 5 seconds. The shorter the time from the drawing out of the crosslinking bath to the irradiation of electromagnetic waves, the more improved the optical properties of the polarizing film caused by electromagnetic wave irradiation. Furthermore, in the electromagnetic wave irradiation step, it is preferable that there are fewer water molecules attached to the surface of the film. If there are water molecules on the surface of the film, the water molecules on the surface of the film will absorb infrared rays, thus reducing the effect of electromagnetic wave irradiation to stimulate the movement of molecules in the film. After pulling out from the cross-linking bath The cross-linking liquid will adhere to the surface of the film, so it is preferable to set a liquid removal method to remove it before the electromagnetic wave irradiation step. In Fig. 1, the nip roller 53b also has the function of a liquid removing method for removing the cross-linking liquid adhering to the film surface. In addition to the liquid method, in addition to the nip roller, there is also a method of blowing air to the film to remove the liquid, and a doctor blade that contacts the film to remove the liquid can also be used.

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 relatively high, specifically, when the processing speed is 10 to 100 m/min as the faster processing speed, the electromagnetic wave irradiation time may be short and the irradiation heat may be insufficient. The corresponding method is to install a plurality of electromagnetic wave irradiators in parallel, so that sufficient heat can be irradiated.

(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,可以如第1圖所示之例使用乾燥爐21進行。乾燥爐21係例如可使用具備熱風乾燥機者。乾燥溫度例如為約30至100℃,乾燥時間例如為約30至600秒。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 dry the polyvinyl alcohol-based resin film after the washing step. The drying of the film is not particularly limited, and the drying oven 21 can be used as in the example shown in FIG. 1. For the drying furnace 21, for example, one equipped with 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 drying the polyvinyl alcohol-based resin film can be performed with a far-infrared heater. The thickness of the polarizing film 23 obtained by the above method is, for example, about 5 to 30 μm.

所得偏光膜可依序捲繞為捲繞卷並形成卷形態,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 can be wound into a wound roll in sequence and formed into a roll form, or it can be directly used for the polarizing plate manufacturing step (in the step of single-side or two-area layer protective film of the polarizing film) without being wound.

(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 additional treatment include: immersion in a boric-acid-free iodide aqueous solution after the cross-linking step Treatment (complementary color treatment), and treatment (zinc treatment) in which it is immersed in an aqueous solution that does not contain boric acid but contains zinc chloride.

<偏光膜> <Polarizing Film>

以上述方法製造偏光膜藉此可獲得滿足下述之偏光膜: By manufacturing the polarizing film by the above method, a polarizing film satisfying the following can be obtained:

i)硼含有率為2.0至3.5重量%、 i) The boron content is 2.0 to 3.5% by weight,

ii)視感度修正單體穿透率(Ty)為42.0%以上、 ii) Visual sensitivity correction monomer penetration rate (Ty) is above 42.0%,

iii)視感度修正偏光度(Py)為99.990%以上、 iii) The visual sensitivity corrected polarization (Py) is above 99.990%,

iv)波長480nm中之偏光膜之吸收軸方向的吸光度A480與波長600nm中之偏光膜之吸收軸方向的吸光度A600的比A480/A600為0.75以上1.00以下。 iv) the wavelength of 480nm in the absorption axis direction of polarizing film A ratio of absorbance A 480 absorbance and the absorption axis A of the polarizing film in a wavelength of 600nm 600 480 / A 600 of 0.75 to 1.00.

藉由偏光膜之硼含有率為如上述i)所述,可成為收縮力經抑制者。偏光膜的硼含有率,更佳為2.0至3.0重量%。偏光膜之收縮力,較佳為3.8N/2mm以下,更佳為3.5N/2mm以下。此處之偏光膜的硼含有率以及收縮力係依據後述實施例所記載之方式測定。 When the boron content of the polarizing film is as described in i) above, the shrinkage force can be suppressed. The boron content of the polarizing film is more preferably 2.0 to 3.0% by weight. The shrinkage force of the polarizing film is preferably 3.8N/2mm or less, more preferably 3.5N/2mm or less. The boron content and shrinkage force of the polarizing film here are measured in accordance with the method described in the examples described later.

一般而言,藉由使偏光膜的硼含有率成為高至例如3.8重量%以上,而可得到高的光學特性。然而,難以在偏光膜的硼含有率低至如上述i)的同時獲得優異的光學特性。在本發明之製造方法中,藉由具有電磁波照射步驟,可獲得滿足上述i)並且滿足上述ii)以及上述iii)之光學特性優異的偏光膜。此處之偏光膜之視感度修正單體穿透率(Ty)以及視感度修正偏光度(Py)係依據後述實施例所記載之方式測定。 In general, by increasing the boron content of the polarizing film to, for example, 3.8% by weight or more, high optical properties can be obtained. However, it is difficult to obtain excellent optical characteristics while the boron content of the polarizing film is as low as i) above. In the manufacturing method of the present invention, by having an electromagnetic wave irradiation step, a polarizing film that satisfies the above i) and satisfies the above ii) and the above iii) and has excellent optical characteristics can be obtained. The visual sensitivity correction monomer transmittance (Ty) and the visual sensitivity correction polarization (Py) of the polarizing film here are measured according to the method described in the following examples.

再者,在本發明之製造方法中,作為電磁波照射步驟所使用之電磁波者,藉由使用超過2μm且4μm以下之波長的紅外線之放射能量的比例為全放射能量的25%以上之電磁波,可獲得滿足上述iv)之特性,接近中性灰之優異色相的偏光膜。A480/A600未達0.75時藍色強烈,A480/A600超過1.00時紅色強烈。為了抑制紅色,A480/A600較佳為0.90以下。亦即,藉由本發明之製造方法,可得到使偏光膜之硼含有率低至如上述i)而抑制收縮力,並且同時滿足上述ii)至iv)之特性的具有優異的光學特性之偏光膜。 Furthermore, in the manufacturing method of the present invention, as the electromagnetic wave used in the electromagnetic wave irradiation step, by using the electromagnetic wave whose radiation energy ratio of the infrared radiation with a wavelength exceeding 2 μm and below 4 μm is 25% or more of the total radiation energy, A polarizing film that satisfies the characteristics of the above iv) and is close to the excellent hue of neutral gray is obtained. Blue is intense when A 480 /A 600 is less than 0.75, and red is intense when A 480 /A 600 exceeds 1.00. In order to suppress red, A 480 /A 600 is preferably 0.90 or less. That is, by the manufacturing method of the present invention, it is possible to obtain a polarizing film with excellent optical properties that reduces the boron content of the polarizing film as in the above i), suppresses the shrinkage force, and at the same time satisfies the characteristics of the above ii) to iv) .

<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 protective film is attached to at least one side of the polarizing film manufactured by the above method via an adhesive, thereby obtaining a polarizing plate. The protective film may include, for example, a film composed of cellulose acetate resin such as cellulose triacetate or cellulose diacetate; Film composed of polyester resin such as butylene formate; polycarbonate resin film, cycloolefin resin film; acrylic resin film; film composed of chain olefin resin of polypropylene resin.

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、火焰處理、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 adhesion between the polarizing film and the protective film, corona treatment, flame treatment, plasma treatment, ultraviolet radiation, primer coating treatment, saponification treatment, etc. can be applied to the bonding surface of the polarizing film and/or protective film. deal with. The adhesive used for bonding the polarizing film and the protective film may include an active energy ray curable adhesive such as an ultraviolet curable adhesive, an aqueous solution of a polyvinyl alcohol-based resin, or an aqueous solution in which a crosslinking agent is blended, and Carbamate Water-based adhesives such as ethyl ester emulsion adhesives. The ultraviolet curing adhesive may be a mixture of an acrylic compound and a photo-radical polymerization initiator, or a mixture of an epoxy compound and a photo-cationic polymerization initiator, or the like. In addition, a cationic polymerizable epoxy compound and a radical polymerizable acrylic compound may be used in combination, or a photocationic polymerization initiator and a photoradical polymerization initiator as initiators may be used in combination.

[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。 Hereinafter, the present invention will be explained in more detail with 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〕由卷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之膜,於碘化鉀/硼酸/水為11/2.0/100(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11/2.0/100(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5.65倍。 The polarizing film of Example 1 was manufactured from the polyvinyl alcohol-based resin film using the manufacturing apparatus shown in Fig. 1. Specifically, a long strip of polyvinyl alcohol (PVA) raw film with a thickness of 60μm [Kuraray Co., Ltd. product name "Kuraray Vinylon VF-PE#6000", average polymerization degree 2400, saponification degree 99.9 mol% or more] It was continuously transported while being pulled out from the coil, and immersed in a swelling bath containing 30°C pure water for a residence time of 79 seconds (swelling step). After that, the film pulled out from the swelling bath is immersed in a 30°C dyeing bath containing iodine with a potassium iodide/boric acid/water ratio of 1/0.3/100 (weight ratio) for a residence time of 123 seconds (dyeing step). Next, the film drawn from the dyeing bath is immersed in the first cross-linking bath at 53°C at a ratio of 11/2.0/100 (weight ratio) of potassium iodide/boric acid/water with a residence time of 44 seconds, and then immersed in potassium iodide/boric acid/water. The second cross-linking bath at 40°C of 11/2.0/100 (weight ratio) was immersed in a residence time of 6 seconds (cross-linking step). In the dyeing step and the cross-linking step, longitudinal uniaxial stretching is performed by stretching between rolls in the bath. The total stretching ratio based on the raw film is 5.65 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, for the film drawn from the second cross-linking bath 17b and passed through the nip roll 53b, an electromagnetic wave irradiator (medium-wavelength infrared heater (MW heater), product name: Golden 8 Medium-wave twin tube emitter, manufactured by Heraeus) is used , The heat source temperature is 900℃, the maximum energy density is 60kW/m 2 ), the electromagnetic wave radiation port is placed 5cm away from the film surface, and the maximum radiation output of the electromagnetic wave irradiator is to output 50% of the electromagnetic wave. The radiation heat of electromagnetic wave per unit volume of the film is 490J/cm 3 . In addition, the radiation heat of 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) (Electromagnetic wave irradiation heat per unit volume of the film) = ((Maximum energy density) × (heater heating surface area) × 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 output of the actual irradiation 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 from transporting the film to reaching the irradiation position of the electromagnetic wave irradiator and irradiating electromagnetic waves is 5 seconds.

將照射電磁波之膜於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℃、絕對濕度11g/cm3,使膜乾燥,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 residence time of 3 seconds (washing step). Thereafter, the film was dried in the drying oven 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6、比較例3、4> <Examples 2 to 6, Comparative Examples 3, 4>

電磁波照射步驟中,將電磁波照射器之種類、輸出(%)、膜每單位體積之電磁波照射熱量、第1交聯浴及第2交聯浴之相對於水100重量份之硼酸重量份數設為如表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。作為電磁波照射器者,可使用:鹵素加熱器(製品名:直管形鹵素加熱器燈QIR,ushio lighting(股)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)、高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)之任一者。 In the electromagnetic wave irradiation step, the type and output (%) of the electromagnetic wave irradiator, the electromagnetic wave irradiation heat per unit volume of the film, the weight parts of boric acid relative to 100 parts by weight of the water of the first crosslinking bath and the second crosslinking bath are set As shown in Table 2, except for this point, the same operation as in Example 1 was performed to obtain a polarizing film. The thickness of the obtained polarizing film is 23 μm. As an electromagnetic wave irradiator, you can use: halogen heater (product name: straight tube halogen heater 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℃, maximum energy density 200kW/m 2 ), high-speed 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 60kW/m 2 ).

<比較例1、2、5> <Comparative Examples 1, 2, 5>

除了不進行電磁波照射步驟之點、將第1交聯浴及第2交聯浴之相對於水100重量份之硼酸重量份數設為如表2所示之點以外,以與實施例1相同地施作而獲得偏光膜。所得偏光膜之厚度為23μm。 Except that the electromagnetic wave irradiation step is not performed, and the weight parts of boric acid relative to 100 parts by weight of water in the first crosslinking bath and the second crosslinking bath are set as shown in Table 2, the same as in Example 1 Ground application to obtain a polarizing film. The thickness of the obtained polarizing film was 23 μm.

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

(a)單體穿透率及偏光度之測定 (a) Measurement of monomer transmittance and polarization

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。 For the polarizing film obtained in each example and each comparative example, a spectrophotometer with an integrating sphere (manufactured by JASCO Corporation "V7100") was used to measure the MD transmittance and TD transmittance in the wavelength range of 380 to 780 nm , Calculate the monomer transmittance and polarization in each wavelength according to the following formula.

單體穿透率(%)=(MD+TD)/2 Single 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由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,而求出視感度修正單體穿透率(Ty)及視感度修正偏光度(Py)。表2表示視感度修正單體穿透率(Ty)及視感度修正偏光度(Py)之計算結果。 "MD transmittance" refers to the transmittance when the direction of polarized light emitted by Glan Thomson is parallel to the penetration axis of the polarizing film sample. The above formula is expressed as "MD". In addition, "TD transmittance" refers to the transmittance when the direction of polarized light emitted by the Glan-Thomson film is orthogonal to the transmittance axis of the polarizing film sample. The above formula is expressed as "TD". The obtained monomer transmittance and polarization are corrected by the visual sensitivity of 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", and Calculate the single transmittance (Ty) of the visual sensitivity correction and the degree of polarization (Py) of the visual sensitivity correction. Table 2 shows the calculation results of the visual sensitivity correction monomer transmittance (Ty) and the visual sensitivity correction polarization (Py).

(b)偏光膜之吸光度的測定 (b) Measurement of absorbance of polarizing film

使用附積分球之分光光度計〔日本分光(股)製「V7100」〕進行。具體而言,使用波長480nm以及波長600nm中之TD穿透率TD480以及TD600,依據下述式: Use a spectrophotometer with an integrating sphere ("V7100" manufactured by JASCO Corporation). Specifically, using the TD transmittances TD 480 and TD 600 in the wavelength of 480 nm and the wavelength of 600 nm, according to the following formula:

A480=-log10(TD480/100) A 480 =-log 10 (TD 480 /100)

A600=-log10(TD600/100) A 600 =-log 10 (TD 600 /100)

計算出波長480nm之吸光度A480以及波長600nm之吸光度A600。表2表示吸光度A480、吸光度A600、以及依據該等值所計算出之比A480/A600的計算值。 Calculate the absorbance A 480 at the wavelength of 480 nm and the absorbance A 600 at the wavelength of 600 nm. Table 2 shows the calculated values of absorbance A 480 , absorbance A 600 , and the ratio A 480 /A 600 calculated based on these values.

(c)MD收縮力 (c) MD contractility

由所得之偏光膜裁切以吸收軸方向(MD、延伸方向)為長邊之寬度2mm、長度10mm之測定用試料。將該試料設定於SII NanoTechnology股份有限公司製熱機械分析裝置 (TMA)「EXSTAR-6000」,在保持固定尺寸下,測定於80℃保持4小時時所產生長邊方向(吸收軸方向、MD)之收縮力(MD收縮力)。表2表示經測定之收縮力的值。 From the obtained polarizing film, a measurement sample with a width of 2 mm and a length of 10 mm with the absorption axis direction (MD, extension direction) as the long side was cut. Set the sample in the thermal mechanical analysis device manufactured by SII NanoTechnology Co., Ltd. (TMA) "EXSTAR-6000", while maintaining a fixed size, measure the shrinkage force (MD shrinkage force) in the longitudinal direction (absorption axis direction, MD) generated when kept at 80°C for 4 hours. Table 2 shows the values of the measured contractile force.

(d)偏光膜之硼含有率 (d) Boron content of polarizing film

將偏光膜0.2g添加至純水170ml,在95℃完全地溶解後,添加30g甘露醇水溶液(12.5重量%)而作為測定用樣本溶液。在此測定用樣本溶液達到中和點為止,滴下氫氧化鈉水溶液(1mol/l),從滴下量依據下述式計算出聚乙烯醇系樹脂膜中的硼含有率(重量%)。 After adding 0.2 g of the polarizing film to 170 ml of pure water and completely dissolving it at 95°C, 30 g of a mannitol aqueous solution (12.5% by weight) was added as a sample solution for measurement. Here, until the sample solution for measurement reaches the neutralization point, an aqueous sodium hydroxide solution (1 mol/l) is dropped, and the boron content (% by weight) in the polyvinyl alcohol-based resin film is calculated from the dropping amount according to the following formula.

硼含有率(重量%)=1.08×氫氧化鈉水溶液滴下量(ml)/偏光膜之重量(g) Boron content (% by weight) = 1.08 × the amount of sodium hydroxide aqueous solution dripping (ml) / weight of the polarizing film (g)

表2表示所測定之硼含有率的值。 Table 2 shows the values of the measured boron content.

[表2]

Figure 110115150-A0101-12-0028-2
[Table 2]
Figure 110115150-A0101-12-0028-2

如表2所示,實施例1至6偏光膜係滿足: As shown in Table 2, the polarizing film systems of Examples 1 to 6 satisfy:

i)硼含有率為2.0至3.5重量%、 i) The boron content is 2.0 to 3.5% by weight,

ii)視感度修正單體穿透率Ty為42.0%以上、 ii) Visual sensitivity correction monomer penetration rate Ty is above 42.0%,

iii)視感度修正偏光度Py為99.990%以上、 iii) The visual sensitivity corrected polarization Py is above 99.990%,

iv)波長480nm中之偏光膜之吸收軸方向的吸光度A480與波長600nm中之偏光膜之吸收軸方向的吸光度A600的比A480/A600為0.75以上1以下。再者,藉由滿足上述i)而可抑制收縮力,藉由滿足上述iv)則色相亦沒有問題。比較例1之偏光膜沒有實施電磁波照射步驟,而為視感度修正偏光度(Py)之值較低者。 iv) the wavelength of 480nm in the absorption axis direction of polarizing film A ratio of absorbance A 480 absorbance and the absorption axis A of the polarizing film in a wavelength of 600nm 600 480 / A 600 is 0.75 to 1 or less. Furthermore, by satisfying the above i), the contractile force can be suppressed, and by satisfying the above iv), there is no problem with the hue. The polarizing film of Comparative Example 1 did not carry out the electromagnetic wave irradiation step, but was the one with a lower value of the visual sensitivity corrected polarization degree (Py).

比較例2之偏光膜係不滿足上述i)故收縮力較大。比較例3之偏光膜係A480/A600之值超過1故紅色較強烈。比較例4、5係硼含有率不充分,故視感度修正偏光度(Py)之值為較低者。 The polarizing film of Comparative Example 2 does not satisfy the above i), so the shrinkage force is large. The polarizing film of Comparative Example 3 has a value of A 480 /A 600 exceeding 1, so the red color is strong. Comparative Examples 4 and 5 have insufficient boron content, so the value of the visual sensitivity corrected polarization (Py) is lower.

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

11:原料卷 11: Raw material roll

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: The second cross-linking bath

19:洗淨浴 19: Wash 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 roller

50至52、53a、53b、54、55:夾輥 50 to 52, 53a, 53b, 54, 55: nip roller

71:電磁波照射部 71: Electromagnetic wave irradiation department

Claims (1)

一種偏光膜,係將聚乙烯醇系樹脂膜以二色性色素染色而成之偏光膜,其中, A polarizing film, a polarizing film made of polyvinyl alcohol resin film dyed with dichroic pigments, in which, 硼含有率為2.0至3.5重量%, The boron content is 2.0 to 3.5% by weight, 視感度修正單體穿透率為42.0%以上, Visual sensitivity correction monomer penetration rate is over 42.0%, 視感度修正偏光度為99.990%以上, The visual sensitivity corrected polarization degree is above 99.990%, 波長480nm中之吸收軸方向的吸光度A480與波長600nm中之偏光膜的吸光度A600之比A480/A600為0.75以上1.00以下。 480 absorbance A 480nm wavelength of the absorption axis direction of the polarizing film with a wavelength of 600nm in a absorbance of A 600 ratio of A 480 / A 600 of 0.75 to 1.00.
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