TWI775958B - Polarizing plate, image display device, and manufacturing method of polarizing plate - Google Patents
Polarizing plate, image display device, and manufacturing method of polarizing plate Download PDFInfo
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- G—PHYSICS
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- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
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Abstract
本發明提供一種偏光板之製造方法,該偏光板與其他光學構件之密著性高且可提升影像顯示裝置之顯示特性。本發明之偏光板之製造方法係一種製造偏光板之方法,該偏光板:具有聚酯系樹脂基材;及,偏光件,其積層於聚酯系樹脂基材之單側且厚度10μm以下;且該製造方法包含:將聚酯系樹脂基材之單側形成有聚乙烯醇系樹脂層的積層體進行染色及延伸,以將聚乙烯醇系樹脂層製成偏光件;及,將聚酯系樹脂基材與偏光件之積層體進行加熱處理;其中,延伸包含延伸倍率為2.55倍以上之水中延伸處理,且加熱處理中之最高加熱溫度為100℃以上。The present invention provides a method for manufacturing a polarizing plate, which has high adhesion to other optical components and can improve the display characteristics of an image display device. The method for producing a polarizing plate of the present invention is a method for producing a polarizing plate, the polarizing plate: having a polyester-based resin substrate; and a polarizer, which is laminated on one side of the polyester-based resin substrate and has a thickness of 10 μm or less; And the manufacturing method includes: dyeing and extending the laminate in which the polyvinyl alcohol-based resin layer is formed on one side of the polyester-based resin substrate to make the polyvinyl-alcohol-based resin layer into a polarizer; The laminated body of the resin substrate and the polarizer is subjected to heat treatment; wherein, the stretching includes an underwater stretching treatment with a stretching ratio of 2.55 times or more, and the maximum heating temperature in the heating treatment is 100°C or more.
Description
本發明涉及一種偏光板、影像顯示裝置及偏光板之製造方法。The present invention relates to a polarizing plate, an image display device and a manufacturing method of the polarizing plate.
發明背景 有文獻提議一種方法,係於聚酯系樹脂基材上形成聚乙烯醇系樹脂層並將該積層體延伸、染色,藉此製得厚度薄的偏光件(例如專利文獻1)。所述偏光件之製造方法,可有助於譬如影像顯示裝置之薄型化而備受矚目。Background of the Invention A document proposes a method of producing a thin polarizer by forming a polyvinyl alcohol-based resin layer on a polyester-based resin substrate, extending and dyeing the laminate (for example, Patent Document 1). The manufacturing method of the polarizer is attracting attention because it can contribute to the thinning of, for example, an image display device.
上述偏光件可在積層於上述聚酯系樹脂基材之狀態下使用,而此時,聚酯系樹脂基材係用來作為偏光件之保護層(專利文獻2)。藉此,可不用於偏光件貼合保護薄膜,即可直接將聚酯系樹脂基材與偏光件之積層體作為偏光板使用,而可有助於譬如影像顯示裝置之低成本化。The above-mentioned polarizer can be used in a state of being laminated on the above-mentioned polyester-based resin substrate, and in this case, the polyester-based resin substrate is used as a protective layer of the polarizer (Patent Document 2). Thereby, the laminated body of the polyester-based resin substrate and the polarizer can be directly used as a polarizer without using a protective film for the polarizer, which can contribute to cost reduction of, for example, an image display device.
先前技術文獻 專利文獻 專利文獻1:日本專利特開2000-338329號公報 專利文獻2:日本專利第4979833號公報prior art literature Patent Literature Patent Document 1: Japanese Patent Laid-Open No. 2000-338329 Patent Document 2: Japanese Patent No. 4979833
發明概要 發明欲解決之課題 然而,如上述之偏光板與其他光學構件之密著性不足,並且在將其用於影像顯示裝置時會有顯示特性不足之問題。Summary of Invention The problem to be solved by the invention However, the above-mentioned polarizing plate has insufficient adhesion with other optical members, and when it is used in an image display device, there is a problem of insufficient display characteristics.
本發明是為了解決上述以往課題而成者,其主要目的在於提供一種偏光板,其與其他光學構件之密著性高且可提升影像顯示裝置之顯示特性;所述偏光板之製造方法、及具備所述偏光板之影像顯示裝置。The present invention is made in order to solve the above-mentioned conventional problems, and its main object is to provide a polarizing plate which has high adhesion to other optical members and can improve the display characteristics of an image display device; a manufacturing method of the polarizing plate, and An image display device provided with the polarizing plate.
用以解決課題之手段 本發明之偏光板之製造方法係一種製造偏光板之方法,該偏光板具有:聚酯系樹脂基材;及,偏光件,其積層於上述聚酯系樹脂基材之單側且厚度10μm以下;且該製造方法包含:將在上述聚酯系樹脂基材之單側形成有聚乙烯醇系樹脂層的積層體進行染色及延伸,以將上述聚乙烯醇系樹脂層製成偏光件;及,將上述聚酯系樹脂基材與上述偏光件之積層體進行加熱處理;其中,上述延伸包含延伸倍率為2.55倍以上之水中延伸處理,且上述加熱處理中之最高加熱溫度為100℃以上。 在一實施形態中,上述加熱處理中之最高加熱溫度為115℃以下。 根據本發明之另一面向係提供一種偏光板。該偏光板具有:聚酯系樹脂基材、與積層於上述聚酯系樹脂基材之單側的偏光件;其中,上述偏光件之厚度為10μm以下,且霧度值小於1.6%;並且,在將上述偏光件側之面透過黏著劑貼合於玻璃並保管於60℃/90%Rh下500小時後,不會從上述玻璃剝落。 根據本發明之另一面向,提供一種影像顯示裝置。該影像顯示裝置具有上述偏光板。means of solving problems The method for producing a polarizing plate of the present invention is a method for producing a polarizing plate comprising: a polyester-based resin substrate; and a polarizer, which is laminated on one side of the polyester-based resin substrate and has a thickness of 10 μm or less ; and the manufacturing method comprises: dyeing and extending a laminate having a polyvinyl alcohol-based resin layer formed on one side of the polyester-based resin substrate to make the polyvinyl-alcohol-based resin layer into a polarizer; and , heat-treating the laminate of the polyester-based resin substrate and the polarizer; wherein the stretching includes an underwater stretching treatment with a stretching ratio of 2.55 times or more, and the maximum heating temperature in the heating treatment is 100°C or more. In one embodiment, the maximum heating temperature in the above-mentioned heat treatment is 115°C or lower. According to another aspect of the present invention, a polarizing plate is provided. The polarizing plate has: a polyester-based resin substrate, and a polarizer laminated on one side of the polyester-based resin substrate; wherein the polarizer has a thickness of 10 μm or less, and a haze value of less than 1.6%; and, The above-mentioned polarizer-side surface was bonded to glass through an adhesive and stored at 60° C./90%Rh for 500 hours, without peeling off from the above-mentioned glass. According to another aspect of the present invention, an image display device is provided. The image display device includes the above-mentioned polarizing plate.
發明效果 根據本發明,可提供一種偏光板,其與其他光學構件之密著性高且可提升影像顯示裝置之顯示特性;所述偏光板之製造方法、及具備所述偏光板之影像顯示裝置。Invention effect According to the present invention, a polarizing plate can be provided, which has high adhesion to other optical components and can improve the display characteristics of an image display device; a manufacturing method of the polarizing plate; and an image display device including the polarizing plate.
用以實施發明之形態 以下說明本發明之實施形態,惟本發明不受該等實施形態限定。Form for carrying out the invention Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.
A.偏光板之製造方法
圖1為本發明之一實施形態之利用偏光板之製造方法製得之偏光板的概略截面圖。偏光板100具有聚酯系樹脂基材20、與積層於聚酯系樹脂基材20之單側的偏光件10。偏光件10之厚度為10μm以下。A. Manufacturing method of polarizing plate
1 is a schematic cross-sectional view of a polarizing plate produced by a method for producing a polarizing plate according to an embodiment of the present invention. The polarizing
偏光板100之製造方法包含:將在聚酯系樹脂基材20之單側形成有聚乙烯醇系樹脂層(PVA系樹脂層)11的積層體200(圖2)進行染色及延伸,以將PVA系樹脂層11製成偏光件10;及,對聚酯系樹脂基材20與偏光件10之積層體進行加熱處理。上述延伸包含延伸倍率為2.55倍以上之水中延伸處理,且上述加熱處理中之最高加熱溫度為100℃以上。上述加熱處理之最高加熱溫度宜為115℃以下。根據上述製造方法可製得一種偏光板,其兼顧了與其他光學構件之密著性及影像顯示裝置之顯示特性。以以往之製造方法,亦即將聚酯系樹脂基材與PVA系樹脂層之積層體進行延伸及染色而製得之偏光板有無法兼顧與其他光學構件之充分密著性及影像顯示裝置之良好顯示特性之情形。具體而言,以如上述的以往之製造方法所製得之偏光板,在將偏光件側之面貼合於其他光學構件並置於高溫高濕環境下時,偏光板之延伸方向上的兩端部可能會發生從光學構件剝落之情形,或者,在將其用於影像顯示裝置時顯示畫面可能會產生眩光。根據本發明之新見解,已知藉由上述製造方法,可將偏光板之聚酯系樹脂基材的結晶化度與結晶尺寸控制在適當範圍內,藉此可兼顧與其他光學構件之密著性及影像顯示裝置之顯示特性(防眩性)。The manufacturing method of the polarizing
圖3為顯示一實施形態之偏光板之製造步驟的概略圖。本實施形態之偏光板之製造步驟在代表上係將聚酯系樹脂基材20與PVA系樹脂層11之積層體200從釋出部101釋出,並以輥件111及112將其浸漬於硼酸水溶液之浴110中之後(不溶解處理),再以輥件121及122將其浸漬於二色性物質(碘)及碘化鉀之水溶液之浴120中(染色處理)。接著,以輥件131及132將其浸漬於硼酸及碘化鉀之水溶液之浴130中(交聯處理)。接著,一邊將積層體200於硼酸水溶液之延伸浴140中,一邊以不同速度比的輥件141及142往縱方向(長邊方向、輸送方向、MD方向)賦予張力而進行延伸(水中延伸處理)。接著,將經水中延伸的積層體200以輥件151及152浸漬於碘化鉀水溶液之浴150中(洗淨處理),再供於乾燥處理(未示於圖式中)。接著,將積層體200放入烘箱160(加熱處理)而藉此製得本實施形態之偏光板100。之後,以捲取部170捲取所製得之偏光板100。雖在圖式中省略,但亦可在對積層體200施行不溶解處理前施行空中延伸處理。另,圖3所示製造步驟僅為一例,上述處理之次數、順序等並無特別限定。FIG. 3 is a schematic diagram showing a manufacturing process of a polarizing plate according to an embodiment. The manufacturing process of the polarizing plate of the present embodiment is represented by releasing the laminated
A-1.聚酯系樹脂基材與PVA系樹脂層之積層體 聚酯系樹脂基材與PVA系樹脂層之積層體可利用任意且適當的方法來製作。較佳為於聚酯系樹脂基材上塗佈含有PVA系樹脂之塗佈液並使其乾燥,藉此可製得於聚酯系樹脂基材之單側形成有PVA系樹脂層的積層體。在一實施形態中,係於聚酯系樹脂基材上塗佈易接著層形成用組成物並使其乾燥而形成易接著層,並於該易接著層上形成PVA系樹脂層。A-1. Laminated product of polyester-based resin base material and PVA-based resin layer The laminate of the polyester-based resin base material and the PVA-based resin layer can be produced by an arbitrary and appropriate method. Preferably, a coating liquid containing a PVA-based resin is coated on a polyester-based resin substrate and dried, whereby a laminate in which a PVA-based resin layer is formed on one side of the polyester-based resin substrate can be obtained . In one embodiment, the composition for forming an easily bonding layer is coated on a polyester-based resin substrate and dried to form an easily bonding layer, and a PVA-based resin layer is formed on the easily bonding layer.
聚酯系樹脂基材之形成材料,舉例而言可使用:聚對苯二甲酸乙二酯(PET)、聚對苯二甲酸丁二酯(PBT)、聚萘二甲酸乙二酯(PEN)、間苯二甲酸、含有含環己烷環等之脂環族二羧酸或脂環族二元醇等的共聚PET(PET-G)、其他聚酯、及該等之共聚物或摻合物等。其中,又以使用非晶質之(未結晶化之)PET或共聚PET為佳。根據該等樹脂在未延伸狀態下為非晶且具有適合高倍率延伸的優異延伸性,而藉由利用延伸、加熱進行結晶化,可賦予耐熱性及尺寸穩定性。此外,可確保在未延伸之狀態下塗佈PVA系樹脂並使其乾燥之可行程度的耐熱性。As the material for forming the polyester resin base material, for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) can be used. , isophthalic acid, copolymerized PET (PET-G) containing cyclohexane ring-containing alicyclic dicarboxylic acids or alicyclic diols, etc., other polyesters, and their copolymers or blends things etc. Among them, amorphous (uncrystallized) PET or copolymerized PET is preferably used. Since these resins are amorphous in an unstretched state and have excellent stretchability suitable for high-rate stretching, heat resistance and dimensional stability can be imparted by crystallization by stretching and heating. In addition, it is possible to secure the heat resistance of a practical level to coat and dry the PVA-based resin in an unstretched state.
聚酯系樹脂基材之玻璃轉移溫度(Tg)宜為170℃以下。藉由使用這類聚酯系樹脂基材,可抑制PVA系樹脂層結晶化的同時又可充分確保延伸性。若考慮以水將聚酯系樹脂基材塑化與順利進行水中延伸等觀點,更宜為120℃以下。在一實施形態中,聚酯系樹脂基材之玻璃轉移溫度宜為60℃以上。藉由使用所述聚酯系樹脂基材,可於塗佈、乾燥後述含有PVA系樹脂之塗佈液時,防止聚酯系樹脂基材變形(譬如,發生凹凸或垂塌、皺摺等)等不良情況。又,可在適宜的溫度(譬如60℃~70℃左右)下將積層體予以延伸。在另一實施形態中,在塗佈、乾燥含有PVA系樹脂之塗佈液時,只要聚酯系樹脂基材不變形,玻璃轉移溫度也可低於60℃。此外,玻璃轉移溫度(Tg)是依據JIS K 7121求出之值。The glass transition temperature (Tg) of the polyester-based resin substrate is preferably 170°C or lower. By using such a polyester-based resin base material, the crystallization of the PVA-based resin layer can be suppressed, and extensibility can be sufficiently ensured. Considering the viewpoints of plasticizing the polyester-based resin base material with water and smooth underwater stretching, the temperature is more preferably 120° C. or lower. In one embodiment, the glass transition temperature of the polyester-based resin substrate is preferably 60°C or higher. By using the polyester-based resin substrate, the polyester-based resin substrate can be prevented from being deformed (for example, uneven, slumped, wrinkled, etc.) during coating and drying of the coating liquid containing the PVA-based resin described later. and other adverse situations. In addition, the laminated body can be stretched at a suitable temperature (for example, about 60° C. to 70° C.). In another embodiment, the glass transition temperature may be lower than 60° C. as long as the polyester-based resin substrate is not deformed when the coating liquid containing the PVA-based resin is applied and dried. In addition, glass transition temperature (Tg) is the value calculated|required based on JISK7121.
在一實施形態中,聚酯系樹脂基材之吸水率宜為0.2%以上,更宜為0.3%以上。這類的聚酯系樹脂基材吸水,水即發揮塑化劑的作用進行塑化。結果,在水中延伸中可大幅減低延伸應力,而有優異的延伸性。另一方面,聚酯系樹脂基材之吸水率宜為3.0%以下,更宜為1.0%以下。藉由使用這類的聚酯系樹脂基材,可防止製造時聚酯系樹脂基材之尺寸穩定性顯著下降造成所得積層體外觀劣化等不良情況。並可防止於水中延伸時斷裂、或PVA系樹脂層從聚酯系樹脂基材剝離之情況。此外,吸水率係按JIS K 7209所求得之值。In one embodiment, the water absorption rate of the polyester-based resin substrate is preferably 0.2% or more, more preferably 0.3% or more. Such polyester-based resin substrates absorb water, and water acts as a plasticizer to plasticize. As a result, the elongation stress can be greatly reduced in water elongation, and the elongation is excellent. On the other hand, the water absorption rate of the polyester-based resin substrate is preferably 3.0% or less, more preferably 1.0% or less. By using such a polyester-based resin base material, it is possible to prevent problems such as deterioration of the appearance of the resulting laminate due to a marked decrease in the dimensional stability of the polyester-based resin base material during production. It is possible to prevent the PVA-based resin layer from being broken or peeled off from the polyester-based resin substrate when extended in water. In addition, the water absorption rate is the value calculated|required based on JISK7209.
聚酯系樹脂基材之厚度(後述延伸前的厚度)宜為20μm~300μm,較宜為50μm~200μm。若小於20μm,恐難以形成PVA系樹脂層。若超過300μm,譬如在水中延伸時聚酯系樹脂基材恐需要較長時間來吸水而對延伸造成過大的負荷。The thickness of the polyester-based resin base material (thickness before extension described later) is preferably 20 μm to 300 μm, more preferably 50 μm to 200 μm. If it is less than 20 μm, it may be difficult to form a PVA-based resin layer. If it exceeds 300 μm, for example, when extending in water, the polyester-based resin substrate may take a long time to absorb water, thereby causing an excessive load on the extending.
形成PVA系樹脂層之PVA系樹脂可採用任意適當之樹脂。可舉例如聚乙烯醇、乙烯-乙烯醇共聚物。聚乙烯醇可藉由將聚乙酸乙烯酯皂化而得。乙烯-乙烯醇共聚物可藉由將乙烯-乙酸乙烯酯共聚物皂化而得。PVA系樹脂之皂化度通常為85莫耳%~100莫耳%,宜為95.0莫耳%~99.95莫耳%,更宜為99.0莫耳%~99.93莫耳%。皂化度係依JIS K 6726-1994而求得。藉由使用所述皂化度的PVA系樹脂,可獲得耐久性優異的偏光件。皂化度太高時,會有膠化之虞。Any appropriate resin can be used as the PVA-based resin forming the PVA-based resin layer. For example, polyvinyl alcohol and an ethylene-vinyl alcohol copolymer are mentioned. Polyvinyl alcohol can be obtained by saponifying polyvinyl acetate. Ethylene-vinyl alcohol copolymers can be obtained by saponifying ethylene-vinyl acetate copolymers. The degree of saponification of the PVA resin is usually 85 mol% to 100 mol%, preferably 95.0 mol% to 99.95 mol%, more preferably 99.0 mol% to 99.93 mol%. The degree of saponification is obtained according to JIS K 6726-1994. By using the PVA-based resin having the above degree of saponification, a polarizer excellent in durability can be obtained. When the degree of saponification is too high, there is a risk of gelation.
PVA系樹脂的平均聚合度可按目的適當選擇。平均聚合度通常為1000~10000,宜為1200~4500,更宜為1500~4300。另,平均聚合度可按JIS K 6726-1994而求得。The average degree of polymerization of the PVA-based resin can be appropriately selected according to the purpose. The average degree of polymerization is usually 1000~10000, preferably 1200~4500, more preferably 1500~4300. In addition, the average degree of polymerization can be calculated|required based on JISK6726-1994.
含有PVA系樹脂之塗佈液代表上係使用已使上述PVA系樹脂溶解在溶劑中之溶液。作為溶劑,可舉例如水、二甲亞碸、二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯啶酮、各種甘醇類、三羥甲丙烷等多元醇類、伸乙二胺、二伸乙三胺等胺類。該等可單獨使用或可將二種以上組合使用。該等中又以水為佳。溶液之PVA系樹脂濃度宜相對於溶劑100重量份為3重量份~20重量份。只要為所述樹脂濃度,便可形成密著於聚酯系樹脂基材且均勻的塗佈膜。在一實施形態中,上述塗佈液含有鹵化物。上述鹵化物可採用任意適當之鹵化物。可舉例如碘化物及氯化鈉。碘化物可舉出例如碘化鉀、碘化鈉及碘化鋰。該等之中又以碘化鉀為佳。塗佈液中之鹵化物量,宜相對於PVA系樹脂100重量份為5重量份~20重量份,更宜相對於PVA系樹脂100重量份為10重量份~15重量份。若鹵化物之量相對於PVA系樹脂100重量份為大於20重量份,則會有鹵化物溢出而使最後製得之偏光件變白濁之情形。將含有鹵化物之PVA系樹脂層與聚酯系樹脂基材之積層體,於在硼酸水中進行延伸前在空氣中進行高溫延伸(輔助延伸),藉此可促進輔助延伸後之PVA系樹脂層中的PVA系樹脂之結晶化。結果,在將PVA系樹脂層浸漬於液體中時,相較於PVA系樹脂層不含鹵化物之情況,更能抑制聚乙烯醇分子之定向紊亂及定向性之降低。藉此,可提升最後所得偏光件之光學特性。The coating liquid containing the PVA-based resin means that a solution obtained by dissolving the above-mentioned PVA-based resin in a solvent is used. Examples of the solvent include water, dimethylsulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, various glycols, polyols such as trimethylolpropane, ethylene glycol Amines such as diamine and ethylene triamine. These may be used alone or in combination of two or more. Among these, water is preferred. The concentration of the PVA-based resin in the solution is preferably 3 to 20 parts by weight relative to 100 parts by weight of the solvent. As long as it is the said resin density|concentration, a uniform coating film which adheres to a polyester-type resin base material can be formed. In one embodiment, the coating liquid contains a halide. Any appropriate halide can be used as the above-mentioned halide. For example, iodide and sodium chloride are mentioned. Examples of the iodide include potassium iodide, sodium iodide, and lithium iodide. Among them, potassium iodide is preferred. The amount of halide in the coating solution is preferably 5 to 20 parts by weight relative to 100 parts by weight of the PVA resin, more preferably 10 to 15 parts by weight relative to 100 parts by weight of the PVA resin. If the amount of the halide is more than 20 parts by weight with respect to 100 parts by weight of the PVA-based resin, the halide may overflow and the polarizer finally produced may become cloudy. The laminate of the halide-containing PVA-based resin layer and the polyester-based resin substrate is stretched at high temperature (assisted stretching) in air before stretching in boric acid water, thereby promoting the PVA-based resin layer after the assisted stretching. Crystallization of PVA-based resins. As a result, when the PVA-based resin layer is immersed in a liquid, the disorder of orientation of the polyvinyl alcohol molecules and the decrease in orientation can be suppressed more than when the PVA-based resin layer does not contain a halide. Thereby, the optical properties of the finally obtained polarizer can be improved.
塗佈液中亦可摻混添加劑。添加劑可舉如塑化劑、界面活性劑等。塑化劑可舉例如乙二醇或丙三醇等多元醇。界面活性劑可舉例如非離子性界面活性劑。該等可為了進一步提升所得PVA系樹脂層的均勻性或染色性、延伸性而使用。又,添加劑可舉如易接著成分。藉由使用易接著成分,可提升聚酯系樹脂基材與PVA系樹脂層之密著性。結果可抑制譬如PVA系樹脂層從聚酯系基材剝落等不良情況,從而良好地進行後述之染色、水中延伸。易接著成分可使用譬如乙醯乙醯基改質PVA等改質PVA。Additives can also be mixed in the coating liquid. Examples of additives include plasticizers, surfactants, and the like. As a plasticizer, polyhydric alcohols, such as ethylene glycol and glycerol, are mentioned, for example. As a surfactant, a nonionic surfactant is mentioned, for example. These can be used in order to further improve the uniformity, dyeability, and extensibility of the obtained PVA-based resin layer. Moreover, as an additive, an easily attachable component is mentioned. The adhesiveness between the polyester-based resin substrate and the PVA-based resin layer can be improved by using the easy-adhesion component. As a result, inconveniences such as peeling of the PVA-based resin layer from the polyester-based base material can be suppressed, and dyeing and underwater stretching, which will be described later, can be performed favorably. As the easy-to-attach component, modified PVA such as acetylacetate modified PVA can be used.
塗佈液之塗佈方法可採用任意且適當的方法。例如可舉出輥塗法、旋塗法、線棒塗佈法、浸塗法、模塗法、淋幕式塗佈法、噴塗法、刮刀式塗佈法(逗號塗佈法等)等。塗佈液之塗佈、乾燥溫度宜為50℃以上。As the coating method of the coating liquid, an arbitrary and appropriate method can be adopted. For example, a roll coating method, a spin coating method, a wire bar coating method, a dip coating method, a die coating method, a curtain coating method, a spray coating method, a blade coating method (comma coating method, etc.) etc. are mentioned. The coating and drying temperature of the coating liquid is preferably 50°C or higher.
上述PVA系樹脂層之厚度(後述延伸前的厚度)宜為3μm~20μm。The thickness of the PVA-based resin layer (thickness before stretching, which will be described later) is preferably 3 μm to 20 μm.
在形成PVA系樹脂層前,可對聚酯系樹脂基材施行表面處理(例如電暈處理等),亦可於聚酯系樹脂基材上塗佈易接著層形成用組成物(塗覆處理)。藉由進行所述處理,可提升聚酯系樹脂基材與PVA系樹脂層之密著性。結果可抑制譬如PVA系樹脂層從聚酯系樹脂基材剝落等不良情況,從而良好地進行後述之染色及延伸。Before forming the PVA-based resin layer, the polyester-based resin substrate may be subjected to surface treatment (eg, corona treatment, etc.), or the composition for forming an easily bonding layer (coating treatment) may be applied to the polyester-based resin substrate. ). The adhesiveness between the polyester-based resin base material and the PVA-based resin layer can be improved by performing the above-mentioned treatment. As a result, inconveniences such as peeling of the PVA-based resin layer from the polyester-based resin base material can be suppressed, and dyeing and stretching, which will be described later, can be performed favorably.
易接著層形成用組成物宜含有聚乙烯醇系成分。聚乙烯醇系成分可使用任意且適當的PVA系樹脂。具體上可舉聚乙烯醇、改質聚乙烯醇。改質聚乙烯醇譬如可舉經以乙醯乙醯基、羧酸基、丙烯醯基及/或胺甲酸酯基改質之聚乙烯醇。該等中以使用乙醯乙醯基改質PVA較為適宜。乙醯乙醯基改質PVA宜使用至少具有下述通式(I)所示重複單元之聚合物。The composition for forming an easily bonding layer preferably contains a polyvinyl alcohol-based component. Arbitrary and appropriate PVA-type resin can be used for a polyvinyl alcohol-type component. Specifically, polyvinyl alcohol and modified polyvinyl alcohol may be mentioned. The modified polyvinyl alcohol includes, for example, polyvinyl alcohol modified with an acetylacetyl group, a carboxylic acid group, an acryl group and/or a urethane group. Among these, PVA modified with an acetyl acetyl group is suitable. A polymer having at least a repeating unit represented by the following general formula (I) is preferably used for the acetylacetate group-modified PVA.
[化學式1] [Chemical formula 1]
上述式(I)中,n相對於l+m+n之比率宜為1%~10%。In the above formula (I), the ratio of n to l+m+n is preferably 1% to 10%.
乙醯乙醯基改質PVA之平均聚合度宜為1000~10000,1200~5000更適宜。乙醯乙醯基改質PVA之皂化度宜為97莫耳%以上。乙醯乙醯基改質PVA之4重量%水溶液的pH宜為3.5~5.5。The average degree of polymerization of the acetylacetate group-modified PVA is preferably 1000-10000, more preferably 1200-5000. The degree of saponification of the acetylacetate-modified PVA should preferably be above 97 mol%. The pH of the 4 wt % aqueous solution of the acetylacetate group-modified PVA is preferably 3.5 to 5.5.
易接著層形成用組成物可因應目的等進一步含有聚烯烴系成分、聚酯系成分、聚丙烯酸系成分等。易接著層形成用組成物宜進一步含有聚烯烴系成分。The composition for forming an easily bonding layer may further contain a polyolefin-based component, a polyester-based component, a polyacrylic-based component, and the like according to the purpose and the like. The composition for forming an easily bonding layer preferably further contains a polyolefin-based component.
上述聚烯烴系成分可使用任意且適當之聚烯烴系樹脂。聚烯烴系樹脂之主成分即烯烴成分譬如可舉乙烯、丙烯、異丁烯、1-丁烯、1-戊烯、1-己烯等碳數2~6之烯烴系烴。該等可單獨使用或可將二種以上組合使用。該等中以使用乙烯、丙烯、異丁烯、1-丁烯等碳數2~4之烯烴系烴為宜,且使用乙烯更適宜。Arbitrary and appropriate polyolefin-type resin can be used for the said polyolefin-type component. The main component of the polyolefin-based resin, that is, the olefin component, includes, for example, olefin-based hydrocarbons having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 1-butene, 1-pentene, and 1-hexene. These may be used alone or in combination of two or more. Among these, olefinic hydrocarbons having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene, and 1-butene are preferably used, and ethylene is more preferably used.
構成上述聚烯烴系樹脂之單體成分中,烯烴成分所佔比率宜為50重量%~95重量%。Among the monomer components constituting the above-mentioned polyolefin-based resin, the proportion of the olefin component is preferably 50% by weight to 95% by weight.
上述聚烯烴系樹脂宜含有羧基及/或其酸酐基。上述聚烯烴系樹脂可分散於水,而可順利形成易接著層。具有所述官能基之單體成分譬如可舉不飽和羧酸及其酸酐、不飽和二羧酸之半酯、半醯胺。該等之具體例可舉丙烯酸、甲基丙烯酸、馬來酸、馬來酸酐、伊康酸、伊康酸酐、延胡索酸、巴豆酸。聚烯烴系樹脂之分子量譬如為5000~80000。The above-mentioned polyolefin-based resin preferably contains a carboxyl group and/or an acid anhydride group thereof. The above-mentioned polyolefin-based resin can be dispersed in water, so that the easy-adhesion layer can be formed smoothly. Examples of the monomer components having the functional group include unsaturated carboxylic acids and their anhydrides, half esters of unsaturated dicarboxylic acids, and half amides. Specific examples of these include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, and crotonic acid. The molecular weight of the polyolefin resin is, for example, 5,000 to 80,000.
在易接著層形成用組成物中,聚乙烯醇系成分與聚烯烴系成分之摻混比(前者:後者(固體成分))宜為5:95~60:40,更宜為20:80~50:50。聚乙烯醇系成分若過多,恐無法獲得足夠的密著性。具體上,恐有從聚酯系樹脂基材剝離偏光件時所需剝離力降低而無法獲得充分的密著性。另一方面,聚乙烯醇系成分若太少,所得偏光板的外觀有損壞之虞。具體上,形成易接著層時恐發生塗佈膜白濁等不良情況而難以獲得外觀優異的偏光板。In the composition for forming an easily bonding layer, the blending ratio of the polyvinyl alcohol-based component and the polyolefin-based component (the former: the latter (solid content)) is preferably 5:95 to 60:40, and more preferably 20:80 to 20:40. 50:50. When there are too many polyvinyl alcohol-type components, sufficient adhesiveness may not be acquired. Specifically, when the polarizer is peeled off from the polyester-based resin base material, the peeling force required for peeling off the polarizer may decrease and sufficient adhesion may not be obtained. On the other hand, when there are too few polyvinyl alcohol-type components, the external appearance of the polarizing plate obtained may be damaged. Specifically, when forming the easy-adhesive layer, there is a fear that problems such as cloudiness of the coating film may occur, and it may be difficult to obtain a polarizing plate excellent in appearance.
易接著層形成用組成物宜為水系。易接著層形成用組成物可含有有機溶劑。有機溶劑可舉乙醇、異丙醇等。易接著層形成用組成物之固體成分濃度宜為1.0重量%~10重量%。The composition for forming an easily bonding layer is preferably an aqueous system. The composition for forming an easily bonding layer may contain an organic solvent. Ethanol, isopropanol, etc. are mentioned as an organic solvent. The solid content concentration of the composition for forming an easily bonding layer is preferably 1.0% by weight to 10% by weight.
易接著層形成用組成物之塗佈方法可採用任意且適當的方法。塗佈易接著層形成用組成物後可將塗佈膜乾燥。乾燥溫度譬如為50℃以上。Arbitrary and appropriate methods can be employ|adopted for the coating method of the composition for easy bonding layer formation. After coating the composition for forming an easily bonding layer, the coating film may be dried. The drying temperature is, for example, 50°C or higher.
A-2.空中延伸處理 空中延伸處理包含熱輥件延伸步驟,該步驟係一邊將上述積層體沿其長邊方向輸送,一邊以熱輥件間之周速差來延伸。空中延伸處理在代表上係包含區域(zone)延伸步驟與熱輥件延伸步驟。另,區域延伸步驟與熱輥件延伸步驟之順序並無限定,可先進行區域延伸步驟,亦可先進行熱輥件延伸步驟。亦可省略區域延伸步驟。在一實施形態中,係依序進行區域延伸步驟及熱輥件延伸步驟。A-2. Air extension processing The air-stretching treatment includes a heat-roller stretching step in which the above-mentioned laminated body is conveyed in the longitudinal direction thereof while being stretched by the difference in peripheral speed between the heat-rollers. The in-air stretching process typically includes a zone stretching step and a thermal roll stretching step. In addition, the sequence of the area extending step and the heating roller extending step is not limited. The area extending step may be performed first, or the heating roller extending step may be performed first. The region extension step can also be omitted. In one embodiment, the area extending step and the heating roller extending step are performed in sequence.
積層體之延伸溫度可因應聚酯系樹脂基材之形成材料、延伸方式等設定成任意且適當之值。空中延伸處理之延伸溫度宜為聚酯系樹脂基材之玻璃轉移溫度(Tg)以上,而聚酯系樹脂基材之玻璃轉移溫度(Tg)+10℃以上更適宜,Tg+15℃以上特別適宜。另一方面,積層體之延伸溫度的上限宜為170℃。在所述溫度下延伸可抑制PVA系樹脂之結晶化快速進展,從而可抑制該結晶化所造成的不良情況(譬如,因延伸而妨礙PVA系樹脂層之定向)。The stretching temperature of the laminate can be set to an arbitrary and appropriate value according to the forming material of the polyester-based resin base material, the stretching method, and the like. The stretching temperature of the air stretching treatment is preferably above the glass transition temperature (Tg) of the polyester resin substrate, and the glass transition temperature (Tg)+10°C or higher of the polyester resin substrate is more suitable, especially Tg+15°C or higher. suitable. On the other hand, the upper limit of the stretching temperature of the laminate is preferably 170°C. Stretching at such a temperature can suppress rapid progress of crystallization of the PVA-based resin, thereby suppressing inconveniences caused by the crystallization (eg, hindering the orientation of the PVA-based resin layer due to elongation).
A-3.不溶解處理 上述不溶解處理代表上係將PVA系樹脂層浸漬於硼酸水溶液中來進行。藉由施行不溶解處理,可賦予PVA系樹脂層耐水性。該硼酸水溶液之濃度宜相對於水100重量份為1重量份~4重量份。不溶解浴(硼酸水溶液)之液溫宜為20℃~50℃。不溶解處理宜於上述水中延伸或上述染色處理前進行。A-3. Insolubility Treatment The above-mentioned insolubilization treatment is performed by immersing the PVA-based resin layer in an aqueous solution of boric acid. Water resistance can be imparted to the PVA-based resin layer by performing the insolubilization treatment. The concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight relative to 100 parts by weight of water. The temperature of the insoluble bath (boric acid aqueous solution) is preferably 20°C to 50°C. The insolubilization treatment is preferably carried out before the above-mentioned stretching in water or the above-mentioned dyeing treatment.
A-4.染色處理 PVA系樹脂層之染色,代表上係藉由使碘吸附於PVA系樹脂層來進行。該吸附方法可舉如:使PVA系樹脂層(積層體)浸漬於含碘之染色液中的方法、將該染色液塗敷於PVA系樹脂層上的方法、及將該染色液噴霧至PVA系樹脂層上的方法等。宜採用使PVA系樹脂層(積層體)浸漬於染色液中的方法。其是因為可良好吸附碘之故。A-4. Dyeing treatment The dyeing of the PVA-based resin layer is typically performed by adsorbing iodine to the PVA-based resin layer. The adsorption method includes, for example, a method of immersing a PVA-based resin layer (layered body) in an iodine-containing dyeing solution, a method of applying the dyeing solution to the PVA-based resin layer, and spraying the dyeing solution to PVA method on the resin layer, etc. A method of immersing the PVA-based resin layer (layered body) in the dyeing solution is preferably employed. This is because it can adsorb iodine well.
上述染色液宜為碘水溶液。碘之摻混量宜相對於水100重量份為0.1重量份~0.5重量份。為了提高碘對水的溶解度,宜於碘水溶液中摻混碘化物。碘化物之具體例如上述。碘化物之摻混量宜相對於水100重量份為0.02重量份~20重量份,較宜為0.1重量份~10重量份。為了抑制PVA系樹脂溶解,染色液於染色時的液溫宜為20℃~50℃。使PVA系樹脂層浸漬於染色液時,為了確保PVA系樹脂層之透射率,浸漬時間宜為5秒~5分鐘。又,染色條件(濃度、液溫、浸漬時間)可以最後所得偏光件之偏光度或單體透射率成為預定範圍內的方式進行設定。在一實施形態中係以使所得偏光件之偏光度成為99.98%以上的方式來設定浸漬時間。在另一實施形態中則以所得偏光件之單體透射率成為40%~44%的方式來設定浸漬時間。The above-mentioned dyeing solution is preferably an aqueous iodine solution. The blending amount of iodine is preferably 0.1 part by weight to 0.5 part by weight with respect to 100 parts by weight of water. In order to improve the solubility of iodine in water, it is suitable to mix iodide in the iodine aqueous solution. Specific examples of the iodide are as described above. The blending amount of the iodide is preferably 0.02 to 20 parts by weight, preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of water. In order to inhibit the dissolution of the PVA resin, the temperature of the dyeing solution during dyeing is preferably 20°C to 50°C. When the PVA-based resin layer is immersed in the dyeing solution, in order to ensure the transmittance of the PVA-based resin layer, the immersion time is preferably 5 seconds to 5 minutes. In addition, dyeing conditions (concentration, liquid temperature, immersion time) can be set so that the polarization degree or the single transmittance of the polarizer finally obtained falls within a predetermined range. In one embodiment, the immersion time is set so that the degree of polarization of the obtained polarizer becomes 99.98% or more. In another embodiment, the immersion time is set so that the single transmittance of the obtained polarizer becomes 40% to 44%.
染色處理可於任意且適當之時機進行。較宜於水中延伸前進行。The dyeing treatment can be performed at an arbitrary and appropriate timing. It is more suitable to carry out before extending in water.
A-5.交聯處理 上述交聯處理,代表上係藉由將PVA系樹脂層(積層體)浸漬於硼酸水溶液中來進行。藉由施行交聯處理,可賦予PVA系樹脂層耐水性。該硼酸水溶液之濃度宜相對於水100重量份為1重量份~5重量份。又,於上述染色處理後進行交聯處理時,宜進一步摻混碘化物。藉由摻混碘化物,可抑制已吸附於PVA系樹脂層之碘的溶出。碘化物之摻混量宜相對於水100重量份為1重量份~5重量份。碘化物之具體例係如上述。交聯浴(硼酸水溶液)之液溫宜為20℃~60℃。交聯處理宜於水中延伸處理前進行。較理想的實施形態係依序進行空中延伸處理、染色處理及交聯處理。A-5. Cross-linking treatment The above-mentioned crosslinking treatment is typically performed by immersing the PVA-based resin layer (layered body) in an aqueous solution of boric acid. By performing the crosslinking treatment, water resistance can be imparted to the PVA-based resin layer. The concentration of the boric acid aqueous solution is preferably 1 to 5 parts by weight relative to 100 parts by weight of water. In addition, when the crosslinking treatment is performed after the above dyeing treatment, it is preferable to further blend iodide. By blending the iodide, the elution of the iodine adsorbed on the PVA-based resin layer can be suppressed. The blending amount of the iodide is preferably 1 to 5 parts by weight relative to 100 parts by weight of water. Specific examples of the iodide are as described above. The liquid temperature of the cross-linking bath (boric acid aqueous solution) is preferably 20°C to 60°C. The cross-linking treatment is preferably carried out before the extension treatment in water. A more ideal embodiment is to carry out in-air extension treatment, dyeing treatment and cross-linking treatment in sequence.
A-6.水中延伸處理 偏光板之製造步驟係如上述,包含:在延伸浴中將積層體進行水中延伸處理。具體而言係往與上述積層體之空中延伸方向平行的方向進行水中延伸。藉由水中延伸,可在比上述聚酯系樹脂基材或PVA系樹脂層之玻璃轉移溫度(代表上為80℃左右)更低的溫度下延伸,而可在抑制PVA系樹脂層結晶化的同時進行高倍率延伸。結果可製作出具有優異光學特性(例如偏光度)之偏光件。另,本說明書中,「平行的方向」包含0°±5.0°之情況,宜為0°±3.0°,更宜為0°±1.0°。A-6. Underwater extension treatment The manufacturing steps of the polarizing plate are as described above, and include: subjecting the laminate to an underwater stretching treatment in a stretching bath. Specifically, underwater extension is performed in a direction parallel to the air extension direction of the above-mentioned laminate. By stretching in water, it can be stretched at a lower temperature than the glass transition temperature of the polyester resin substrate or the PVA resin layer (representatively about 80°C), and the crystallization of the PVA resin layer can be suppressed. Simultaneous high-magnification extension. As a result, a polarizer having excellent optical properties (eg, degree of polarization) can be produced. In addition, in this specification, "parallel direction" includes the case of 0°±5.0°, preferably 0°±3.0°, more preferably 0°±1.0°.
水中延伸處理的延伸倍率如上述為2.55倍以上,較佳為2.65倍以上,更佳為2.75倍以上。另一方面,上述延伸倍率的上限宜為5.0倍,較佳為5.5倍。水中延伸倍率若過高,會有偏光件斷裂之問題。藉由將延伸倍率設定於上述範圍內,並且將後述加熱處理中之最高加熱溫度設於預定之範圍內,可製得一種在高溫高濕環境下從玻璃剝落之情形經抑制且霧度值夠低的偏光板。因此,可製得一種兼顧與其他光學構件之密著性及影像顯示裝置之顯示特性(防眩性)的偏光板。The stretching ratio of the underwater stretching treatment is 2.55 times or more as described above, preferably 2.65 times or more, and more preferably 2.75 times or more. On the other hand, the upper limit of the stretching ratio is preferably 5.0 times, more preferably 5.5 times. If the elongation ratio in water is too high, the polarizer will be broken. By setting the elongation ratio within the above-mentioned range and setting the maximum heating temperature in the heat treatment described later within the predetermined range, it is possible to obtain a glass with a suppressed peeling-off from the glass and a sufficient haze value under a high-temperature and high-humidity environment. Low polarizer. Therefore, it is possible to obtain a polarizing plate which has both the adhesion with other optical members and the display characteristics (anti-glare) of the image display device.
水中延伸處理的延伸溫度宜為40℃~85℃,較宜為50℃~70℃。只要為如上述之溫度,便可抑制PVA系樹脂層溶解,同時又可高倍率地延伸。具體而言,如上所述,若考量由與形成PVA系樹脂層之關係,聚酯系樹脂基材之玻璃轉移溫度(Tg)以60℃以上為宜。此時,延伸溫度若低於40℃,即使考慮利用水使聚酯系樹脂基材塑化,也恐無法良好延伸。另一方面,延伸溫度愈高溫,PVA系樹脂層之溶解性就愈高,而恐無法獲得優異的光學特性。積層體浸漬於延伸浴之浸漬時間宜為15秒~5分鐘。The extension temperature of the water extension treatment is preferably 40°C to 85°C, more preferably 50°C to 70°C. As long as the temperature is as described above, the PVA-based resin layer can be inhibited from being dissolved, and at the same time, it can be stretched at a high rate. Specifically, as described above, in consideration of the relationship with the formation of the PVA-based resin layer, the glass transition temperature (Tg) of the polyester-based resin substrate is preferably 60° C. or higher. At this time, if the stretching temperature is lower than 40° C., even if it is considered to plasticize the polyester-based resin base material with water, it may not be possible to stretch well. On the other hand, the higher the stretching temperature, the higher the solubility of the PVA-based resin layer, and there is a fear that excellent optical properties cannot be obtained. The immersion time for the layered body to be immersed in the stretching bath is preferably 15 seconds to 5 minutes.
水中延伸處理之延伸方法可採用任意且適當的方法。具體而言,可為固定端延伸,亦可為自由端延伸。積層體之延伸方向在實質上為上述空中延伸之延伸方向(長邊方向)。積層體之延伸可在一階段中進行亦可分多階段進行。As the stretching method of the underwater stretching treatment, an arbitrary and appropriate method can be adopted. Specifically, it can be a fixed end extension or a free end extension. The extending direction of the laminated body is substantially the extending direction (longitudinal direction) of the above-mentioned air extending. The extension of the laminate may be performed in one stage or in multiple stages.
水中延伸宜將積層體浸漬於硼酸水溶液中來進行(硼酸水中延伸)。藉由使用硼酸水溶液作為延伸浴,可對PVA系樹脂層賦予得以承受延伸時所受張力的剛性及不溶解於水的耐水性。具體上,硼酸在水溶液中會生成四羥基硼酸陰離子而可藉由氫鍵與PVA系樹脂交聯。結果可賦予PVA系樹脂層剛性與耐水性並良好地延伸,而可製作出具有優異光學特性(例如偏光度)的偏光件。The stretching in water is preferably performed by immersing the layered body in an aqueous solution of boric acid (stretching in water with boric acid). By using the boric acid aqueous solution as the stretching bath, the PVA-based resin layer can be imparted with rigidity capable of withstanding the tension applied during stretching and water resistance insoluble in water. Specifically, boric acid generates tetrahydroxyboronic acid anion in an aqueous solution and can be cross-linked with PVA-based resin by hydrogen bonding. As a result, rigidity and water resistance can be imparted to the PVA-based resin layer and good extension can be obtained, and a polarizer having excellent optical properties (eg, degree of polarization) can be produced.
上述硼酸水溶液宜使硼酸及/或硼酸鹽溶解於溶劑即水而獲得。硼酸濃度宜相對於100重量份的水為1重量份~10重量份。藉由將硼酸濃度設為1重量份以上,可有效抑制PVA系樹脂層之溶解,製造特性更高之偏光件。此外,除硼酸或硼酸鹽外,亦可使用將硼砂等之硼化合物、乙二醛、戊二醛等溶解於溶劑而得之水溶液。The above boric acid aqueous solution is preferably obtained by dissolving boric acid and/or borate in water, which is a solvent. The boric acid concentration is preferably 1 to 10 parts by weight relative to 100 parts by weight of water. By setting the boric acid concentration to 1 part by weight or more, the dissolution of the PVA-based resin layer can be effectively suppressed, and a polarizer with higher characteristics can be produced. In addition to boric acid or borate, an aqueous solution obtained by dissolving boron compounds such as borax, glyoxal, and glutaraldehyde in a solvent can also be used.
若已預先藉由染色處理使二色性物質(以碘為代表)吸附於PVA系樹脂層上時,宜於上述延伸浴(硼酸水溶液)中摻混碘化物。藉由摻混碘化物,可抑制已吸附於PVA系樹脂層之碘的溶出。碘化物可舉出例如:碘化鉀、碘化鋰、碘化鈉、碘化鋅、碘化鋁、碘化鉛、碘化銅、碘化鋇、碘化鈣、碘化錫、碘化鈦等。該等之中又以碘化鉀為佳。碘化物之濃度宜相對於水100重量份為0.05重量份~15重量份,更宜為0.5重量份~8重量份。If a dichroic substance (represented by iodine) has been adsorbed on the PVA-based resin layer by dyeing treatment in advance, it is suitable to mix the iodide in the stretching bath (boric acid aqueous solution). By blending the iodide, the elution of the iodine adsorbed on the PVA-based resin layer can be suppressed. Examples of the iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and titanium iodide. Among them, potassium iodide is preferred. The concentration of iodide is preferably 0.05 parts by weight to 15 parts by weight, more preferably 0.5 parts by weight to 8 parts by weight, relative to 100 parts by weight of water.
藉由將上述聚酯系樹脂基材與水中延伸(硼酸水中延伸)組合,可高倍率延伸,而可製作具有優異光學特性(例如偏光度)之偏光件。具體而言,最大延伸倍率相對於上述積層體之原長(包含空中延伸倍率),宜為5.0倍以上,更宜為5.5倍以上,又更宜為6.0倍以上。本說明書中「最大延伸倍率」意指積層體將要斷裂前的延伸倍率,係另外確認積層體斷裂的延伸倍率後得以比其值低0.2之值。另,以使用有上述聚酯系樹脂基材之積層體的最大延伸倍率來說,相較於僅以空中延伸進行延伸,有經過水中延伸者會更高。By combining the above-mentioned polyester resin base material with water stretching (boric acid water stretching), high-magnification stretching is possible, and a polarizer having excellent optical properties (eg, degree of polarization) can be produced. Specifically, the maximum stretching ratio is preferably 5.0 times or more, more preferably 5.5 times or more, and still more preferably 6.0 times or more with respect to the original length of the laminate (including the aerial stretching ratio). In this specification, the "maximum stretching ratio" means the stretching ratio before the layered body breaks, and is a value lower than the value by 0.2 after confirming the stretching ratio at which the layered body breaks. In addition, the maximum stretching ratio of the laminate using the above-mentioned polyester resin base material is higher when it is stretched in water than when it is stretched only by air stretching.
A-7.洗淨處理 洗淨處理代表上可藉由將PVA系樹脂層浸漬於碘化鉀水溶液中來進行。乾燥處理中之乾燥溫度宜為30℃~100℃。A-7. Cleaning treatment Typically, the cleaning treatment can be performed by immersing the PVA-based resin layer in an aqueous potassium iodide solution. The drying temperature in the drying treatment is preferably 30°C to 100°C.
A-8.加熱處理
加熱處理係在水中延伸後進行。藉由加熱處理可使聚酯系樹脂基材進行結晶化。
加熱處理在代表上係藉由將加熱機構160內所配置的輸送輥件加熱(使用所謂熱滾筒輥件(加熱輥件))來進行(熱滾筒輥件加熱方式)。在一實施形態中,加熱機構160為烘箱,而亦可併用藉由往烘箱內輸送熱風來進行的加熱方式(烘箱加熱方式)。藉由併用熱滾筒滾件加熱方式與烘箱加熱方式,可抑制熱滾筒輥件間之急遽溫度變化,而可易於控制積層體之寬度方向的收縮。烘箱之爐內溫度宜為30℃~100℃。且,烘箱進行之加熱時間宜為1秒~300秒。熱風之風速宜為10m/s~30m/s左右。另,該風速係在烘箱內之風速,可以迷你扇葉型數位風速計來測定。A-8. Heat treatment
The heat treatment is performed after extending in water. The polyester-based resin base material can be crystallized by the heat treatment.
The heat treatment is typically performed by heating the conveyance rollers arranged in the heating mechanism 160 (using a so-called hot roller roller (heat roller)) (heat roller heating method). In one embodiment, the
使用熱滾筒輥件進行加熱,可抑制捲曲而製造出外觀優異的偏光件。具體而言,在使積層體沿於熱滾筒輥件之狀態下進行加熱,可有效率地促進上述聚酯系樹脂基材結晶化而增加結晶化度,而即使是在較低的加熱溫度下,仍可良好地增加聚酯系樹脂基材之結晶化度。結果聚酯系樹脂基材之剛性增加而成為得以承受PVA系樹脂層因加熱而收縮的狀態,從而抑制捲曲。且,藉由使用熱滾筒輥件可在將積層體維持平坦之狀態下進行加熱,因此不只可抑制捲曲,還可抑制皺摺產生。Heating with a hot roller can suppress curling and produce a polarizer with an excellent appearance. Specifically, heating the layered body in a state where the layered body follows the hot roller can effectively promote the crystallization of the polyester-based resin base material and increase the degree of crystallinity, even at a relatively low heating temperature. , the crystallinity of the polyester resin substrate can still be well increased. As a result, the rigidity of the polyester-based resin base material increases, and the PVA-based resin layer is in a state where it can withstand the shrinkage of the PVA-based resin layer due to heating, thereby suppressing curling. Moreover, since the laminated body can be heated while maintaining a flat state by using a hot roller, not only curling but also wrinkle generation can be suppressed.
在加熱機構160內,可配置多個熱滾筒輥件,且各熱滾筒輥件可設定成不同溫度。在加熱機構160內,通常可配置2個~20個熱滾筒輥件,且配置4個~10個更佳。積層體與熱滾筒輥件之接觸時間(總接觸時間)宜為1秒~300秒。藉由調整熱滾筒輥件之溫度、熱滾筒輥件之數量、以及與熱滾筒輥件之接觸時間等,可控制加熱條件。In the
多個熱滾筒輥件之中,在令經設定為最高溫之熱滾筒輥件的溫度為「最高加熱溫度」時,最高加熱溫度為100℃以上,更宜為105℃以上。最高加熱溫度的上限宜為115℃。藉由將加熱處理中之最高加熱溫度設定於上述範圍內,並且將上述水中延伸處理中之延伸倍率設於預定之範圍內,可製得一種在高溫高濕環境下從玻璃剝落之情形經抑制且霧度值夠低的偏光板。因此,可製得一種兼顧與其他光學構件之密著性及影像顯示裝置之顯示特性(防眩性)的偏光板。另,熱滾筒輥件之溫度可以接觸式溫度計來測定。積層體對經保持於最高加熱溫度的熱滾筒輥件之接觸時間(當存在多個最高加熱溫度之熱滾筒輥件時,為合計接觸時間)宜為0.2秒~2秒,更宜為0.5秒~2秒。另,「接觸時間」意指積層體上的任意一點接觸經保持於最高加熱溫度的熱滾筒輥件之外周面後到離開為止之時間。Among the plurality of heat rollers, when the temperature of the heat roller set to the highest temperature is the "maximum heating temperature", the maximum heating temperature is 100°C or higher, more preferably 105°C or higher. The upper limit of the maximum heating temperature is preferably 115°C. By setting the maximum heating temperature in the heat treatment within the above-mentioned range, and setting the stretching ratio in the above-mentioned underwater stretching treatment within the predetermined range, it is possible to obtain a situation where peeling from glass is suppressed in a high temperature and high humidity environment. And the haze value is low enough polarizing plate. Therefore, it is possible to obtain a polarizing plate which has both the adhesion with other optical members and the display characteristics (anti-glare) of the image display device. In addition, the temperature of the hot roller can be measured by a contact thermometer. The contact time of the laminated body to the hot rollers kept at the highest heating temperature (when there are multiple hot rollers with the highest heating temperature, the total contact time) is preferably 0.2 seconds to 2 seconds, more preferably 0.5 seconds ~2 seconds. In addition, "contact time" means the time until it leaves|separates after the arbitrary point on a laminated body contacts the outer peripheral surface of the heat roll roll member which was maintained at the highest heating temperature.
B.偏光板之構成 偏光板如同上述具有:聚酯系樹脂基材、與積層於聚酯系樹脂基材之單側且厚度10μm以下之偏光件。本發明之偏光板的霧度值小於1.6%。偏光板在將偏光件側之面透過丙烯酸系黏著劑貼合於玻璃並保管於60℃/90%Rh下500小時後不會發生從玻璃剝落之情形。聚酯系樹脂基材之厚度宜為10μm~200μm,更宜為20μm~150μm。偏光件宜密著於聚酯系樹脂基材之其中一面(換言之不隔著接著層)而積層。偏光板宜於聚酯系樹脂基材與偏光件之間具有易接著層。偏光板亦可於偏光件之與聚酯系樹脂基材相反之側具有保護薄膜。聚酯系樹脂基材在代表上係作為偏光件之保護層發揮功能。本實施形態之偏光板在將偏光件側之面與其他光學構件貼合時與該光學構件之密著性高,可抑制在高溫高濕環境下剝落,並且可抑制影像顯示裝置之顯示畫面的眩光。因此,本發明之偏光板可兼顧與其他光學構件之密著性、及影像顯示裝置之顯示特性(防眩性)。B. The composition of the polarizing plate The polarizing plate has, as described above, a polyester-based resin substrate, and a polarizer laminated on one side of the polyester-based resin substrate and having a thickness of 10 μm or less. The haze value of the polarizing plate of the present invention is less than 1.6%. The polarizing plate does not peel off from the glass after the polarizer side surface is bonded to the glass through an acrylic adhesive and stored at 60°C/90%Rh for 500 hours. The thickness of the polyester resin base material is preferably 10 μm to 200 μm, more preferably 20 μm to 150 μm. The polarizer is preferably laminated on one side of the polyester resin base material (in other words, without interposing an adhesive layer). The polarizing plate preferably has an easy-bonding layer between the polyester-based resin substrate and the polarizer. The polarizing plate may also have a protective film on the opposite side of the polarizer to the polyester-based resin substrate. The polyester-based resin base material functions as a protective layer of the polarizer. The polarizing plate of the present embodiment has high adhesion to other optical members when the polarizer-side surface is bonded to the optical member, can prevent peeling in a high temperature and high humidity environment, and can prevent the display screen of the image display device from being damaged. glare. Therefore, the polarizing plate of the present invention can achieve both the adhesion with other optical members and the display characteristics (anti-glare) of the image display device.
偏光件實質上係碘經吸附定向之PVA系樹脂層。偏光件之厚度如上述為10μm以下,且宜為7.5μm以下,較宜為5μm以下。另一方面,偏光件之厚度宜為0.5μm以上,較宜為1.5μm以上。厚度若太薄,所得偏光件之光學特性有降低之虞。偏光件宜在波長380nm~780nm的任一波長下顯示吸收二色性。偏光件之單體透射率宜為40.0%以上,較宜為41.0%以上,更宜為42.0%以上。偏光件之偏光度宜為99.8%以上,較宜為99.9%以上,更宜為99.95%以上。The polarizer is essentially a PVA-based resin layer in which iodine is oriented by adsorption. The thickness of the polarizer is 10 μm or less as described above, preferably 7.5 μm or less, and more preferably 5 μm or less. On the other hand, the thickness of the polarizer is preferably 0.5 μm or more, more preferably 1.5 μm or more. If the thickness is too thin, the optical properties of the resulting polarizer may be degraded. The polarizer should exhibit absorption dichroism at any wavelength from 380nm to 780nm. The single transmittance of the polarizer is preferably 40.0% or more, more preferably 41.0% or more, and more preferably 42.0% or more. The degree of polarization of the polarizer should preferably be above 99.8%, preferably above 99.9%, and more preferably above 99.95%.
上述保護薄膜之形成材料譬如可舉(甲基)丙烯酸系樹脂、二乙醯纖維素、三乙醯纖維素等纖維素系樹脂、環烯烴系樹脂、聚丙烯等烯烴系樹脂、聚對苯二甲酸乙二酯系樹脂等酯系樹脂、聚醯胺系樹脂、聚碳酸酯系樹脂、該等之共聚物樹脂等。保護薄膜的厚度宜為10μm~100μm。Examples of materials for forming the protective film include (meth)acrylic resins, cellulose-based resins such as diacetyl cellulose and triacetyl cellulose, cycloolefin-based resins, olefin-based resins such as polypropylene, and polyterephthalene. Ester-based resins such as ethylene formate-based resins, polyamide-based resins, polycarbonate-based resins, copolymer resins of these, and the like. The thickness of the protective film is preferably 10 μm to 100 μm.
易接著層可為實質上僅由易接著層形成用組成物形成之層,亦可為易接著層形成用組成物與偏光件之形成材料混合(含相溶)而成之層或區域。藉由形成有易接著層,可獲得優異的密著性。易接著層之厚度宜設為0.05μm~1μm左右。易接著層譬如可以掃描型電子顯微鏡(SEM)觀察偏光板之截面來確認。The easily bonding layer may be a layer formed substantially only from the composition for forming an easily bonding layer, or may be a layer or region in which the composition for forming an easily bonding layer and a polarizer forming material are mixed (including compatible). By forming the easily adhesive layer, excellent adhesion can be obtained. The thickness of the easy-bonding layer should preferably be set to about 0.05 μm to 1 μm. The easily bonding layer can be confirmed by, for example, observing a cross section of a polarizing plate with a scanning electron microscope (SEM).
C.影像顯示裝置 以上述A項記載之製造方法所製得之上述B項記載之偏光板可應用於液晶顯示裝置等影像顯示裝置。因此,本發明包含使用有上述偏光板之影像顯示裝置。本發明之實施形態之影像顯示裝置具備上述B項所記載之偏光板。 實施例C. Video display device The polarizing plate described in the above item B produced by the manufacturing method described in the above item A can be applied to image display devices such as liquid crystal display devices. Therefore, the present invention includes an image display device using the above-mentioned polarizing plate. An image display device according to an embodiment of the present invention includes the polarizing plate described in the above-mentioned item B. Example
以下,以實施例來具體說明本發明,惟本發明不受該等實施例限定。另,各特性之測定方法及評估方法係如以下所述。 (1)厚度 使用數位測微器(Anritsu公司製,產品名「KC-351C」)測定。 (2)防眩性評估 以JIS 7136所規定之方法,使用霧度計(村上色彩科學研究所公司製,商品名「HN-150」)測定出各實施例及比較例之偏光板的霧度值。偏光板的防眩性之評估中,若霧度值小於1.6%視為良好(○),若霧度值為1.6%以上則視為不良(×)。 (3)密著性評估 將實施例及比較例中所製得之長條狀偏光板裁切成100mm(MD方向)×100mm(TD方向)之尺寸,製成評估用試樣。將上述評估用試樣之偏光件側透過丙烯酸系黏著劑(厚度20μm,日東電工股份有限公司製,製品名「偏光板用泛用黏著劑」)貼合於玻璃,並保管在60℃/90%Rh下500小時後,確認評估用試樣之端部有無從玻璃剝落。且,若評估用試樣有從玻璃剝落,則測定出已剝落部分之長度(剝落長度)。偏光板的密著性之評估中,評估用試樣之端部未從玻璃剝落時視為良好(○),而評估用試樣之端部有從玻璃剝落時視為不良(×)。Hereinafter, the present invention will be specifically described with examples, but the present invention is not limited by these examples. In addition, the measurement method and evaluation method of each characteristic are as follows. (1) Thickness Measured using a digital micrometer (manufactured by Anritsu, product name "KC-351C"). (2) Anti-glare evaluation The haze value of the polarizing plate of each Example and the comparative example was measured by the method prescribed|regulated by JIS 7136 using a haze meter (made by Murakami Color Research Institute, trade name "HN-150"). In the evaluation of the anti-glare property of the polarizing plate, if the haze value was less than 1.6%, it was regarded as good (○), and when the haze value was 1.6% or more, it was regarded as poor (x). (3) Adhesion evaluation The elongated polarizing plates obtained in Examples and Comparative Examples were cut into a size of 100 mm (MD direction)×100 mm (TD direction) to prepare samples for evaluation. The polarizer side of the above-mentioned evaluation sample was pasted with an acrylic adhesive (thickness: 20 μm, manufactured by Nitto Denko Co., Ltd., product name "General-purpose adhesive for polarizers"), and stored at 60°C/90°C. After 500 hours at %Rh, it was confirmed whether or not the edge of the sample for evaluation was peeled off from the glass. Then, when the evaluation sample peeled off from the glass, the length of the peeled portion (peeling length) was measured. In the evaluation of the adhesion of the polarizing plate, when the edge of the sample for evaluation was not peeled off from the glass, it was regarded as good (◯), and when the edge of the sample for evaluation was peeled from the glass, it was regarded as poor (x).
<實施例1> 聚酯系樹脂基材係使用長條狀非晶質間苯二甲酸共聚聚對苯二甲酸乙二酯(IPA共聚PET)薄膜(厚度:100μm,IPA改質度:5mol%)。(改質度=[間苯二甲酸乙二酯單元]/[對苯二甲酸乙二酯單元+間苯二甲酸乙二酯單元]) 對聚酯系樹脂基材之單面施行電暈處理(處理條件:50W・min/m2 )後,將乙醯乙醯基改質聚乙烯醇(PVA)(日本合成化學工業公司製,商品名「GOHSEFIMER Z200」)之改質聚烯烴樹脂水性分散體(Unitika公司製,商品名「ARROW BASE SE1030N」)與純水混合而成之混合液(固體成分濃度4.0%)以使乾燥後之厚度為2000nm之方式塗佈於該電暈處理面,並在65℃下乾燥2分鐘而形成底塗層。於此,混合液中乙醯乙醯基改質PVA與改質聚烯烴之固體成分摻混比為30:70。接著,在25℃下對底塗層面塗佈經將PVA(聚合度4200,皂化度99.2莫耳%)90重量份及乙醯乙醯基改質PVA(日本合成化學工業公司製,商品名「GOHSEFIMER Z410」)10重量份摻混而成之PVA系樹脂、與相對於PVA系樹脂100重量份為13重量份之碘化鉀摻混而成之水溶液並在60℃下乾燥3分鐘,而形成厚度13μm之PVA系樹脂層。依上述而製出積層體。 在140℃之烘箱內,將所得積層體在周速相異的輥件間往縱方向(長邊方向)進行自由端單軸延伸2倍(空中輔助延伸)。 接著,將積層體浸漬於液溫40℃的不溶解浴(相對於水100重量份摻混4重量份之硼酸而得的硼酸水溶液)中30秒(不溶解處理)。 接著,使其浸漬於液溫30℃之染色浴(相對於水100重量份,摻混0.2重量份之碘並摻混1.5重量份之碘化鉀而獲得之碘水溶液)中60秒(染色處理)。 接著,使其浸漬於液溫40℃的交聯浴(相對於水100重量份,摻混3重量份的碘化鉀並摻混5重量份的硼酸而獲得之硼酸水溶液)中30秒(交聯處理)。 之後,將積層體一邊浸漬於硼酸水溶液(相對於水100重量份,摻混3重量份的硼酸並摻混5重量份的碘化鉀而製得之水溶液)之延伸浴(延伸浴溫度:67℃),一邊在不同周速的輥件間往縱方向(長邊方向)進行單軸延伸至2.75倍(總延伸倍率:5.5倍)(水中延伸處理)。 之後,將積層體浸漬於液溫30℃的洗淨浴(相對於水100重量份,摻混3.5重量份的碘化鉀而獲得之水溶液)中(洗淨處理)。 接著,在具有多個經保持於80~100℃之加熱輥件且保持於80℃之烘箱中,以使積層體對經保持於100℃的加熱輥件之接觸時間合計為1秒之方式,使用加熱輥件一邊輸送積層體一邊進行加熱處理。 以上述方式而製得於聚酯系樹脂基材上積層有厚度5μm之偏光件的長條狀偏光板1。將偏光板1供於霧度值與密著性之評估。將結果列於表1。<Example 1> The polyester-based resin base material was a long-length amorphous copolyethylene terephthalate (IPA copolyethylene terephthalate) film (thickness: 100 μm, IPA modification degree: 5 mol%) ). (modification degree=[ethylene isophthalate unit]/[ethylene terephthalate unit+ethylene isophthalate unit]) Corona treatment is performed on one side of the polyester resin base material (Treatment condition: 50W·min/m 2 ), the modified polyolefin resin of acetyl acetyl group modified polyvinyl alcohol (PVA) (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "GOHSEFIMER Z200") was dispersed in water A mixed solution (solid content concentration: 4.0%) obtained by mixing pure water (Unitika Corporation, trade name "ARROW BASE SE1030N") was applied to the corona-treated surface so that the thickness after drying was 2000 nm. The undercoat layer was formed by drying at 65°C for 2 minutes. Here, the mixing ratio of the solid content of the acetylacetate-modified PVA and the modified polyolefin in the mixed solution is 30:70. Next, at 25°C, 90 parts by weight of PVA (polymerization degree 4200, saponification degree 99.2 mol %) and acetylacetate modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "GOHSEFIMER Z410") 10 parts by weight of PVA-based resin, and an aqueous solution of 13 parts by weight of potassium iodide with respect to 100 parts by weight of PVA-based resin, and dried at 60°C for 3 minutes to form a thickness 13μm PVA-based resin layer. A layered body was produced as described above. In an oven at 140° C., the obtained layered body was uniaxially stretched at the free end twice in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds (assisted in-air stretching). Next, the layered body was immersed in an insolubilization bath (a boric acid aqueous solution obtained by blending 4 parts by weight of boric acid with respect to 100 parts by weight of water) at a liquid temperature of 40°C for 30 seconds (insolubility treatment). Next, it was immersed in a dyeing bath (aqueous iodine solution obtained by mixing 0.2 parts by weight of iodine and 1.5 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 30° C. for 60 seconds (dyeing treatment). Next, it was immersed in a crosslinking bath (a boric acid aqueous solution obtained by mixing 3 parts by weight of potassium iodide and 5 parts by weight of boric acid with respect to 100 parts by weight of water) for 30 seconds (crosslinking treatment) at a liquid temperature of 40°C. ). Then, the layered body was immersed in a stretching bath (stretching bath temperature: 67° C.) of a boric acid aqueous solution (an aqueous solution prepared by blending 3 parts by weight of boric acid and 5 parts by weight of potassium iodide with respect to 100 parts by weight of water). , while performing uniaxial stretching to 2.75 times (total stretching ratio: 5.5 times) in the longitudinal direction (longitudinal direction) between rollers with different peripheral speeds (underwater stretching treatment). Then, the layered body was immersed in a cleaning bath (aqueous solution obtained by mixing 3.5 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 30°C (cleaning treatment). Next, in an oven having a plurality of heating rollers kept at 80 to 100°C and kept at 80°C, the contact time of the laminate with the heating rollers kept at 100°C was 1 second in total, The heat treatment is performed while conveying the laminated body using a heating roller. The elongated polarizing plate 1 in which the polarizer of thickness 5 micrometers was laminated|stacked on the polyester resin base material in the above-mentioned way was produced. The polarizing plate 1 was used for evaluation of haze value and adhesion. The results are listed in Table 1.
<實施例2> 將最高加熱溫度設為105℃且將接觸時間之合計設為1秒,除此之外依與實施例1相同方式而製得偏光板2。將偏光板2供於霧度值與密著性之評估。將結果列於表1。<Example 2> Polarizing plate 2 was produced in the same manner as in Example 1, except that the maximum heating temperature was set to 105° C. and the total contact time was set to 1 second. The polarizing plate 2 was used for evaluation of haze value and adhesion. The results are listed in Table 1.
<實施例3> 將最高加熱溫度設為110℃且將接觸時間之合計設為1秒,除此之外依與實施例1相同方式而製得偏光板3。將偏光板3供於霧度值與密著性之評估。將結果列於表1。<Example 3> Polarizing plate 3 was produced in the same manner as in Example 1, except that the maximum heating temperature was set to 110° C. and the total contact time was set to 1 second. The polarizing plate 3 was used for evaluation of haze value and adhesion. The results are listed in Table 1.
<實施例4> 將積層體一邊浸漬於延伸浴中一邊往縱方向延伸2.55倍(總延伸倍率:5.1倍)(水中延伸處理),除此之外依與實施例2相同方式而製得偏光板4。將偏光板4供於霧度值與密著性之評估。將結果列於表1。<Example 4> Polarizing plate 4 was obtained in the same manner as in Example 2, except that the laminate was stretched 2.55 times in the longitudinal direction (total stretching ratio: 5.1 times) while being immersed in a stretching bath (underwater stretching treatment). The polarizing plate 4 was used for evaluation of haze value and adhesion. The results are listed in Table 1.
<比較例1> 將最高加熱溫度設為80℃且將接觸時間之合計設為1秒,除此之外依與實施例1相同方式而製得偏光板5。將偏光板5供於霧度值與密著性之評估。將結果列於表1。<Comparative Example 1> Polarizing plate 5 was produced in the same manner as in Example 1, except that the maximum heating temperature was set to 80° C. and the total contact time was set to 1 second. The polarizing plate 5 was used for evaluation of haze value and adhesion. The results are listed in Table 1.
<比較例2> 將最高加熱溫度設為95℃且將接觸時間之合計設為1秒,除此之外依與實施例1相同方式而製得偏光板6。將偏光板6供於霧度值與密著性之評估。將結果列於表1。<Comparative Example 2> Polarizing plate 6 was produced in the same manner as in Example 1, except that the maximum heating temperature was set to 95° C. and the total contact time was set to 1 second. The polarizing plate 6 was used for evaluation of haze value and adhesion. The results are listed in Table 1.
<比較例3> 使積層體在烘箱內往縱方向延伸2.4倍(空中輔助延伸),再一邊浸漬於延伸浴中一邊往縱方向延伸2.30倍(總延伸倍率:5.5倍)(水中延伸處理),並且將最高加熱溫度設為65℃且將接觸時間之合計設為1秒,除此之外依與實施例1相同方式而製得偏光板7。將偏光板7供於霧度值與密著性之評估。將結果列於表1。<Comparative Example 3> The laminate was stretched 2.4 times in the longitudinal direction in an oven (assisted stretching in the air), and further stretched in the longitudinal direction by 2.30 times (total stretching ratio: 5.5 times) while being immersed in a stretching bath (a water stretching treatment), and the maximum heating A polarizing plate 7 was produced in the same manner as in Example 1, except that the temperature was 65° C. and the total contact time was 1 second. The polarizing plate 7 was used for evaluation of haze value and adhesion. The results are listed in Table 1.
<比較例4> 將最高加熱溫度設為75℃且將接觸時間之合計設為1秒,除此之外依與比較例3相同方式而製得偏光板8。將偏光板8供於霧度值與密著性之評估。將結果列於表1。<Comparative Example 4> Polarizing plate 8 was produced in the same manner as in Comparative Example 3, except that the maximum heating temperature was 75° C. and the total contact time was 1 second. The polarizing plate 8 was used for evaluation of haze value and adhesion. The results are listed in Table 1.
<比較例5> 將最高加熱溫度設為100℃且將接觸時間之合計設為1秒,除此之外依與比較例3相同方式而製得偏光板9。將偏光板9供於霧度值與密著性之評估。將結果列於表1。<Comparative Example 5> Polarizing plate 9 was produced in the same manner as in Comparative Example 3, except that the maximum heating temperature was set to 100° C. and the total contact time was set to 1 second. The polarizing plate 9 was used for evaluation of haze value and adhesion. The results are listed in Table 1.
<比較例6>
將最高加熱溫度設為105℃且將接觸時間之合計設為1秒,除此之外依與比較例3相同方式而製得偏光板10。將偏光板10供於霧度值與密著性之評估。將結果列於表1。<Comparative Example 6>
A
<比較例7>
將最高加熱溫度設為110℃且將接觸時間之合計設為1秒,除此之外依與比較例3相同方式而製得偏光板11。將偏光板11供於霧度值與密著性之評估。將結果列於表1。<Comparative Example 7>
A
<比較例8> 使積層體在烘箱內往縱方向延伸2.6倍(空中輔助延伸),再一邊浸漬於延伸浴中一邊往縱方向延伸2.10倍(總延伸倍率:5.5倍)(水中延伸處理),除此之外依與實施例1相同方式而製得偏光板12。將偏光板12供於霧度值與密著性之評估。將結果列於表1。<Comparative Example 8> The layered body was stretched 2.6 times in the longitudinal direction in an oven (assisted stretching in the air), and further stretched 2.10 times in the longitudinal direction while being immersed in a stretching bath (total stretching ratio: 5.5 times) (underwater stretching treatment), other than that The polarizing plate 12 was produced in the same manner as in Example 1. The polarizing plate 12 was used for evaluation of haze value and adhesion. The results are listed in Table 1.
<比較例9> 使積層體在烘箱內往縱方向延伸2.4倍(空中輔助延伸),再一邊浸漬於延伸浴中一邊往縱方向延伸2.50倍(總延伸倍率:6.0倍)(水中延伸處理),除此之外依與實施例1相同方式而製得偏光板13。將偏光板13供於霧度值與密著性之評估。將結果列於表1。<Comparative Example 9> The layered body was stretched 2.4 times in the longitudinal direction in an oven (assisted stretching in the air), and further stretched 2.50 times in the longitudinal direction while being immersed in a stretching bath (total stretching ratio: 6.0 times) (underwater stretching treatment), other than that In the same manner as in Example 1, a polarizing plate 13 was produced. The polarizing plate 13 was used for evaluation of haze value and adhesion. The results are listed in Table 1.
[表1] [Table 1]
由表1可明顯得知,將水中延伸倍率設為2.55倍以上且將加熱處理中之最高加熱溫度設為100℃以上而製得之偏光板的防眩性及密著性皆良好。As apparent from Table 1, the anti-glare property and the adhesiveness of the polarizing plate obtained by setting the underwater stretching ratio to 2.55 times or more and the maximum heating temperature in the heat treatment to 100° C. or more were favorable.
產業上之可利用性 依本發明之製造方法製出之偏光板可適宜使用在液晶顯示裝置、有機EL顯示裝置等影像顯示裝置。industrial availability The polarizing plate produced by the manufacturing method of the present invention can be suitably used in image display devices such as liquid crystal display devices and organic EL display devices.
10‧‧‧偏光件
11‧‧‧PVA系樹脂層
20‧‧‧聚酯系樹脂基材
100‧‧‧偏光板
101‧‧‧釋出部
110‧‧‧硼酸水溶液之浴
111、112、121、122、131、132、141、142、151、152‧‧‧輥件
120‧‧‧二色性物質(碘)及碘化鉀之水溶液之浴
130‧‧‧硼酸及碘化鉀之水溶液之浴
140‧‧‧硼酸水溶液之延伸浴
150‧‧‧碘化鉀水溶液之浴
160‧‧‧烘箱(加熱機構)
170‧‧‧捲取部
200‧‧‧積層體10‧‧‧
圖1為本發明之一實施形態之偏光板的概略截面圖。 圖2為本發明之一實施形態之偏光板之製造方法中所用聚酯系樹脂基材與PVA系樹脂層之積層體的概略截面圖。 圖3為顯示一實施形態之偏光板之製造步驟的概略圖。FIG. 1 is a schematic cross-sectional view of a polarizing plate according to an embodiment of the present invention. 2 is a schematic cross-sectional view of a laminate of a polyester-based resin substrate and a PVA-based resin layer used in a method for producing a polarizing plate according to an embodiment of the present invention. FIG. 3 is a schematic diagram showing a manufacturing process of a polarizing plate according to an embodiment.
10‧‧‧偏光件 10‧‧‧Polarizer
20‧‧‧聚酯系樹脂基材 20‧‧‧Polyester resin substrate
100‧‧‧偏光板 100‧‧‧Polarizer
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JP2006018089A (en) * | 2004-07-02 | 2006-01-19 | Nippon Zeon Co Ltd | Polarizing plate and liquid crystal display device |
CN104155713A (en) * | 2010-12-16 | 2014-11-19 | 日东电工株式会社 | Polarizing film |
TW201700999A (en) * | 2015-06-18 | 2017-01-01 | 三星Sdi股份有限公司 | Polarizing plate, method of manufacturing the same, and optical display comprising the same |
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JP4979833B1 (en) | 2010-12-02 | 2012-07-18 | 日東電工株式会社 | Manufacturing method of polarizing plate |
JP5616318B2 (en) * | 2011-12-12 | 2014-10-29 | 日東電工株式会社 | Manufacturing method of polarizing film |
JP5615987B2 (en) * | 2013-02-07 | 2014-10-29 | 日東電工株式会社 | Optical laminate having polarizing film |
KR101555782B1 (en) * | 2013-06-18 | 2015-09-24 | 주식회사 엘지화학 | Thin polarizing plate and method for maunfacturing the same |
JPWO2015001980A1 (en) | 2013-07-01 | 2017-02-23 | コニカミノルタ株式会社 | Polarizing plate and liquid crystal display device using the same |
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JP2006018089A (en) * | 2004-07-02 | 2006-01-19 | Nippon Zeon Co Ltd | Polarizing plate and liquid crystal display device |
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TW201700999A (en) * | 2015-06-18 | 2017-01-01 | 三星Sdi股份有限公司 | Polarizing plate, method of manufacturing the same, and optical display comprising the same |
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