TW201727266A - Method for manufacturing polarizer - Google Patents
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- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- 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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- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
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- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
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- D06P1/673—Inorganic compounds
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Abstract
Description
本發明係關於偏光片的製造方法。 The present invention relates to a method of producing a polarizer.
以往,偏光板被廣泛使用來作為液晶顯示裝置等顯示裝置中之提供偏光的元件、或作為檢測偏光的元件。偏光板一般係於偏光膜(偏光片)之單面或雙面使用接著劑而貼合保護膜之構成者。 Conventionally, a polarizing plate has been widely used as an element for providing polarization in a display device such as a liquid crystal display device or as an element for detecting polarization. The polarizing plate is generally formed by laminating a protective film on one surface or both surfaces of a polarizing film (polarizing sheet) using an adhesive.
偏光片係藉由對未延伸之聚乙烯醇(PVA)系樹脂膜(胚膜)施以膨潤處理、染色處理、延伸處理、交聯處理、洗淨處理等之後,進行乾燥而製造。 The polarizer is produced by applying a swelling treatment, a dyeing treatment, an elongation treatment, a crosslinking treatment, a washing treatment, and the like to an unstretched polyvinyl alcohol (PVA)-based resin film (embryonic film), followed by drying.
近年來,伴隨液晶顯示裝置之高性能化、薄型化,針對偏光片亦要求薄型化。例如,厚度10μm以下之偏光片,係藉由在熱塑性樹脂基材上塗佈PVA系樹脂溶液,使其乾燥,形成具有PVA系樹脂層之積層體之後,以該積層體作為胚膜,施以上述各處理而製造。 In recent years, with the increase in performance and thickness of liquid crystal display devices, the polarizer is also required to be thinner. For example, a polarizer having a thickness of 10 μm or less is formed by applying a PVA-based resin solution onto a thermoplastic resin substrate and drying it to form a laminate having a PVA-based resin layer, and then applying the laminate as a membrane. It is produced by each of the above processes.
[專利文獻1]日本特開2008-292935號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-292935
又,在將上述PVA系樹脂膜(PVA系樹脂層)染色之染色步驟中,進行將胚膜浸漬於染色浴內之含碘(二色性色素)之染色液中。此時,有時PVA之一部分會從PVA系樹脂膜溶解至染色液中。尤其,被薄膜化至厚度10μm以下之偏光片(PVA系樹脂膜)之溶解性高。 Moreover, in the dyeing step of dyeing the PVA-based resin film (PVA-based resin layer), the embryonic film is immersed in the dyeing liquid containing iodine (dichroic dye) in the dyeing bath. At this time, some of the PVA may be dissolved from the PVA-based resin film into the dyeing liquid. In particular, the polarizer (PVA-based resin film) which is thinned to a thickness of 10 μm or less has high solubility.
在此情況下,若進行偏光片之連續生產,則已溶解的PVA會累積於染色浴中,染色液中之PVA濃度上昇,因而所析出之PVA會附著於PVA系樹脂膜,成為偏光片之染色不均等之原因。又,從染色浴內取出胚膜時,染色液之排液(排水)會變差。結果,會產生使偏光片之產率降低之問題。再者,不只有上述問題,還會因染色液中之PVA濃度上昇,而產生碘對PVA系樹脂膜之吸附速度(染色速度)降低,並損及生產性之問題。 In this case, when the continuous production of the polarizer is performed, the dissolved PVA is accumulated in the dye bath, and the PVA concentration in the dyeing liquid rises, so that the precipitated PVA adheres to the PVA resin film and becomes a polarizer. The reason for uneven dyeing. Moreover, when the embryo film is taken out from the dyeing bath, the drainage (drainage) of the dyeing liquid is deteriorated. As a result, there arises a problem that the yield of the polarizer is lowered. Further, not only the above problem but also the increase in the PVA concentration in the dyeing liquid causes a decrease in the adsorption speed (dyeing speed) of iodine to the PVA-based resin film, which impairs the productivity.
就此對策而言,已揭示一種藉由在交聯浴產生的由PVA所構成之異物與活性碳接觸,而吸附並去除之方法(參照上述專利文獻1)。然而,活性碳亦完全吸附碘,故於必須保持一定的碘濃度之染色浴中,並不佳。 In this regard, a method in which a foreign substance composed of PVA produced by a crosslinking bath is brought into contact with activated carbon and adsorbed and removed is disclosed (refer to Patent Document 1 mentioned above). However, activated carbon also completely adsorbs iodine, so it is not preferable in a dye bath which must maintain a certain iodine concentration.
因此,由於無法將溶解於染色液中之PVA去除,故就對染色浴中之PVA濃度上昇的對策而言,一般係在上述問題發生之前,定期性更新(交換)處理液。然而,在以往的染色步驟中,大多使用碘或碘化鉀等作為染色液。因此,從因鹵素的排出所致之環境問題、成本高等問 題來看,頻繁進行染色液的更新(交換)係屬不佳。 Therefore, since the PVA dissolved in the dyeing liquid cannot be removed, the countermeasure against the increase in the PVA concentration in the dyeing bath is generally periodically updated (exchanged) before the above problem occurs. However, in the conventional dyeing step, iodine or potassium iodide or the like is often used as the dyeing liquid. Therefore, environmental problems due to the discharge of halogens, high cost, etc. In view of the problem, frequent updates (exchanges) of the staining solution are not good.
本發明係有鑑於如此般之以往的情況所提出者,本發明之目的係在於提供一種偏光片的製造方法,其係藉由將溶解於染色液中之PVA去除,而可進一步提升生產性。 The present invention has been made in view of such conventional circumstances, and an object of the present invention is to provide a method for producing a polarizer which can further improve productivity by removing PVA dissolved in a dyeing liquid.
就用以解決上述課題之手段而言,若依本發明之態樣,可提供一種偏光片的製造方法,該製造方法係包含藉由使聚乙烯醇(PVA)系樹脂膜浸漬於含有二色性色素之染色液中,而將前述PVA系樹脂膜染色之染色步驟,其中,前述染色液係含有交聯劑,並且將前述染色液以過濾器過濾。 According to a means for solving the above problems, according to an aspect of the present invention, a method for producing a polarizer comprising immersing a polyvinyl alcohol (PVA) resin film in two colors can be provided. In the dyeing liquid of the dye, the dyeing step of dyeing the PVA-based resin film, wherein the dyeing liquid contains a crosslinking agent, and the dyeing liquid is filtered by a filter.
又,前述態樣之偏光片的製造方法,可為經由前述過濾器而使前述染色液循環之製造方法。 Further, the method for producing a polarizer according to the above aspect may be a method for producing the dye liquid by circulating the filter.
又,前述態樣之偏光片的製造方法,可為攪拌前述染色液之製造方法。 Further, the method for producing a polarizer according to the above aspect may be a method for producing the dyeing liquid by stirring.
又,如前述態樣之偏光片的製造方法,其中,前述交聯劑可為硼化合物。 Further, in the method of producing a polarizer according to the above aspect, the crosslinking agent may be a boron compound.
又,如前述態樣之偏光片的製造方法,其中,前述硼化合物可為硼酸。 Further, in the method of producing a polarizer according to the above aspect, the boron compound may be boric acid.
又,如前述態樣之偏光片的製造方法,其可為:前述PVA系樹脂膜係其厚度為10μm以下,且形成於熱塑性樹脂基材上。 Moreover, in the method of producing a polarizer according to the above aspect, the PVA-based resin film may have a thickness of 10 μm or less and may be formed on a thermoplastic resin substrate.
又,如前述態樣之偏光片的製造方法,其中, 前述交聯劑之濃度可為0.01至0.1重量份。 Moreover, in the method of manufacturing a polarizer according to the above aspect, The concentration of the aforementioned crosslinking agent may be from 0.01 to 0.1 parts by weight.
又,如前述態樣之偏光片的製造方法,其中,前述二色性色素可為碘。 Further, in the method of producing a polarizer according to the above aspect, the dichroic dye may be iodine.
又,如前述態樣之偏光片的製造方法,其中,前述二色性色素之濃度可為0.01至10重量份。 Further, in the method of producing a polarizer according to the above aspect, the concentration of the dichroic dye may be from 0.01 to 10 parts by weight.
又,如前述態樣之偏光片的製造方法,其中,前述染色液可含有碘化鉀。 Further, in the method of producing a polarizer according to the above aspect, the dyeing liquid may contain potassium iodide.
如上所述,若依本發明之態樣,可提供一種偏光片的製造方法,其係藉由將溶解於染色液中之PVA去除,而可進一步提升生產性。 As described above, according to the aspect of the invention, it is possible to provide a method for producing a polarizer which can further improve productivity by removing PVA dissolved in the dyeing liquid.
本實施形態中,列舉下述情況作為例子來說明本發明之偏光片的製造方法:在熱塑性樹脂基材上塗佈PVA系樹脂溶液,使其乾燥,形成具有PVA系樹脂層(膜)之積層體後,以該積層體作為胚膜,並施以各處理,藉此,製造厚度10μm以下之偏光片。 In the present embodiment, a method for producing a polarizer according to the present invention will be described by exemplifying a method in which a PVA-based resin solution is applied onto a thermoplastic resin substrate and dried to form a laminate having a PVA-based resin layer (film). After the body is used, the laminate is used as a germ film, and each treatment is applied to produce a polarizer having a thickness of 10 μm or less.
〈熱塑性樹脂基材〉 <Thermoplastic Resin Substrate>
首先,說明本發明之偏光片的製造方法所使用之熱塑性樹脂基材。就熱塑性樹脂基材而言,可使用以往被使用來作為偏光片之透明保護膜者。 First, a thermoplastic resin substrate used in the method for producing a polarizer of the present invention will be described. As the thermoplastic resin substrate, a transparent protective film which has been conventionally used as a polarizer can be used.
就構成熱塑性樹脂基材之材料而言,例如可使用透明性、機械強度、熱安定性、水分遮蔽性、等向性、延伸性等優異之熱塑性樹脂。就此種熱塑性樹脂之具體例而言,可列舉:三乙醯基纖維素等纖維素樹脂;聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯樹脂;聚醚碸樹脂;聚碸樹脂;聚碳酸酯樹脂;尼龍及芳香族聚醯胺等聚醯胺樹脂;聚醯亞胺樹脂;聚乙烯、聚丙烯、乙烯/丙烯共聚物等聚烯烴樹脂;具有環系乃至於降莰烯結構之環狀聚烯烴樹脂(降莰烯系樹脂);(甲基)丙烯酸樹脂;聚芳酯樹脂;聚苯乙烯樹脂;聚乙烯醇樹脂;以及該等之混合物。又,為了提升與PVA系樹脂層之密著性,熱塑性樹脂基材可施以表面處理(例如電暈處理等),亦可形成底漆(primer)層(底塗層)等薄層。 For the material constituting the thermoplastic resin substrate, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture shielding property, isotropic property, and elongation can be used. Specific examples of such a thermoplastic resin include cellulose resins such as triethylenesulfonyl cellulose; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; and polyether oxime resins; Polyanthene resin; polycarbonate resin; polyamide resin such as nylon and aromatic polyamide; polyimine resin; polyolefin resin such as polyethylene, polypropylene, ethylene/propylene copolymer; a cyclic polyolefin resin (northene-based resin) having a terpene structure; (meth)acrylic resin; polyarylate resin; polystyrene resin; polyvinyl alcohol resin; and a mixture thereof. Moreover, in order to improve the adhesion to the PVA-based resin layer, the thermoplastic resin substrate may be subjected to a surface treatment (for example, corona treatment) or a thin layer such as a primer layer (primer layer).
熱塑性樹脂可大致區分成:高分子規則地排列之結晶狀態者、以及高分子不具規則地排列、或只有一部分之無定形或非晶狀態者。將前者稱為結晶狀態,將後者稱為無定形或非晶狀態。對應上述者,將呈現結晶狀態之性質的熱塑性樹脂稱為結晶性樹脂,將不具有此種性質的熱塑性樹脂稱為非晶性樹脂。 The thermoplastic resin can be roughly classified into those in which the polymer is regularly arranged in a crystalline state, and in which the polymer is not regularly arranged, or only a part of the amorphous or amorphous state. The former is referred to as a crystalline state, and the latter is referred to as an amorphous or amorphous state. Corresponding to the above, a thermoplastic resin exhibiting a property of a crystalline state is referred to as a crystalline resin, and a thermoplastic resin having such a property is referred to as an amorphous resin.
另一方面,無論是結晶性樹脂或非晶性樹脂,皆將未處於結晶狀態之樹脂或未達到結晶狀態之樹脂稱為非晶形或非晶質之樹脂。在此,非晶形或非晶質之樹脂,係與不呈現結晶狀態之性質之非晶性樹脂區別開來使用。 On the other hand, in the case of a crystalline resin or an amorphous resin, a resin which is not in a crystalline state or a resin which does not reach a crystalline state is referred to as an amorphous or amorphous resin. Here, the amorphous or amorphous resin is used in distinction from an amorphous resin which does not exhibit a crystalline state.
就結晶性樹脂而言,例如有:包含聚乙烯 (PE)、聚丙烯(PP)之烯烴系樹脂;及包含聚對苯二甲酸乙二酯(PET)、聚對苯二甲酸丁二酯(PBT)之酯系樹脂。結晶性樹脂的特徵之一係具有一般藉由加熱或延伸定向使高分子排列而進行結晶化之性質。樹脂之物性會依結晶化之程度而有各種變化。 For the crystalline resin, for example, there is: comprising polyethylene (PE), an olefin-based resin of polypropylene (PP); and an ester-based resin containing polyethylene terephthalate (PET) or polybutylene terephthalate (PBT). One of the characteristics of the crystalline resin is a property in which crystallization is generally performed by arranging the polymer by heating or stretching. The physical properties of the resin vary depending on the degree of crystallization.
另一方面,例如,即使為如聚丙烯(PP)、聚對苯二甲酸乙二酯(PET)等結晶性樹脂,藉由阻礙因加熱處理、延伸定向而引起之高分子配列,可抑制結晶化。將結晶化受到抑制之該等聚丙烯(PP)、聚對苯二甲酸乙二酯(PET)稱為非晶性聚丙烯、非晶性聚對苯二甲酸乙二酯,並將該等分別總稱為非晶性烯烴系樹脂、非晶性酯系樹脂。 On the other hand, for example, even a crystalline resin such as polypropylene (PP) or polyethylene terephthalate (PET) can inhibit crystallization by hindering polymer arrangement due to heat treatment and stretching orientation. Chemical. The polypropylene (PP) and polyethylene terephthalate (PET) which are inhibited by crystallization are referred to as amorphous polypropylene and amorphous polyethylene terephthalate, and these are respectively It is collectively referred to as an amorphous olefin resin or an amorphous ester resin.
例如,聚丙烯(PP)的情況,藉由設為無立體規則性之雜排(atactic)結構,可製作結晶化經抑制之非晶性聚丙烯(PP)。又,例如,聚對苯二甲酸乙二酯(PET)的情況,藉由使作為聚合單體之如間苯二甲酸、1,4-環己烷二甲醇等改質基進行共聚合,亦即,使阻礙聚對苯二甲酸乙二酯(PET)的結晶化之分子進行共聚合,可製作結晶化經抑制之非晶性聚對苯二甲酸乙二酯(PET)。 For example, in the case of polypropylene (PP), amorphous polypropylene (PP) which is inhibited by crystallization can be produced by adopting an atactic structure having no stereoregularity. Further, for example, in the case of polyethylene terephthalate (PET), by copolymerizing a modified group such as isophthalic acid or 1,4-cyclohexanedimethanol as a polymerization monomer, In other words, by co-polymerizing a molecule which inhibits crystallization of polyethylene terephthalate (PET), amorphous polyethylene terephthalate (PET) having suppressed crystallization can be produced.
可適當地決定熱塑性樹脂基材(延伸前)之厚度,從強度、操作性等作業性、薄層性等之觀點來看,一般為10至500μm。尤其,較佳係20至300μm,更佳係30至200μm。熱塑性樹脂基材之厚度係以50至150μm之情形為特別適合。 The thickness of the thermoplastic resin substrate (before stretching) can be appropriately determined, and is generally from 10 to 500 μm from the viewpoints of workability such as strength and workability, and thin layer properties. In particular, it is preferably 20 to 300 μm, more preferably 30 to 200 μm. The thickness of the thermoplastic resin substrate is particularly suitable in the case of 50 to 150 μm.
〈聚乙烯醇(PVA)系樹脂層(膜)〉 <Polyvinyl alcohol (PVA) resin layer (film)>
本發明之偏光片的製造方法中,在上述熱塑性樹脂基材上形成包含PVA系樹脂層(膜)之積層體。就PVA系樹脂而言,尤其,可無限制地使用在可見光區域具有透光性,且分散吸附碘、或二色性染料等二色性物質者。 In the method for producing a polarizer of the present invention, a laminate including a PVA-based resin layer (film) is formed on the thermoplastic resin substrate. In particular, the PVA-based resin can be used without limitation in that it has translucency in the visible light region and disperses and adsorbs dichromatic substances such as iodine or a dichroic dye.
就PVA系樹脂而言,可適合使用以往被使用作為偏光片之PVA系樹脂。就PVA系樹脂而言,可列舉PVA或其衍生物。就PVA之衍生物而言,可列舉聚乙烯醇縮甲醛、聚乙烯醇縮乙醛等。其他還可列舉:經乙烯、丙烯等烯烴,丙烯酸、甲基丙烯酸、巴豆酸等不飽和羧酸及其烷基酯、丙烯醯胺等改質者。 As the PVA-based resin, a PVA-based resin which has been conventionally used as a polarizer can be suitably used. The PVA-based resin may, for example, be PVA or a derivative thereof. Examples of the derivative of PVA include polyvinyl formal, polyvinyl acetal and the like. Other examples include an olefin such as ethylene or propylene, an unsaturated carboxylic acid such as acrylic acid, methacrylic acid or crotonic acid, an alkyl ester thereof, and acrylamide.
PVA之聚合度較佳係100至10000,更佳係1000至10000。皂化度一般可使用80至100莫耳%者。 The degree of polymerization of PVA is preferably from 100 to 10,000, more preferably from 1,000 to 10,000. The degree of saponification can generally be from 80 to 100 mol%.
PVA系樹脂中,亦可含有塑化劑、界面活性劑等添加劑。就塑化劑而言,可列舉多元醇及其縮合物等。具體而言,可列舉例如:甘油、二甘油、三甘油、乙二醇、丙二醇、聚乙二醇等。塑化劑等之使用量,雖無特別限制,但宜為:相對於PVA系樹脂100重量份,設為20重量份以下。 The PVA resin may also contain an additive such as a plasticizer or a surfactant. Examples of the plasticizer include a polyhydric alcohol, a condensate thereof, and the like. Specific examples thereof include glycerin, diglycerin, triglycerin, ethylene glycol, propylene glycol, and polyethylene glycol. The amount of the plasticizer to be used is not particularly limited, but is preferably 20 parts by weight or less based on 100 parts by weight of the PVA resin.
〈積層體(胚膜)〉 <Layered layer (embryonic membrane)>
成為胚膜之積層體,可藉由在熱塑性樹脂基材塗佈含有PVA系樹脂之水溶液後,進行乾燥,形成PVA系樹脂層而得。又,積層體可為熱塑性樹脂基材與PVA系樹脂層 隔著底漆層而積層之結構。又,積層體亦可為熱塑性樹脂基材與PVA系樹脂層直接積層之結構、或基材層與親水性高分子層成一體化之狀態之積層體。 The layered body of the embryonic film can be obtained by applying an aqueous solution containing a PVA-based resin to a thermoplastic resin substrate and then drying it to form a PVA-based resin layer. Further, the laminate may be a thermoplastic resin substrate and a PVA resin layer A structure that is laminated with a primer layer. Further, the laminate may be a laminate in which a thermoplastic resin substrate and a PVA-based resin layer are directly laminated, or a laminate in which a base layer and a hydrophilic polymer layer are integrated.
水溶液係可藉由例如將PVA系樹脂之粉末或粉碎物、切割物等溶解於經適當地加熱之水(熱水)中而調製。相對於水100重量份,水溶液之濃度較佳係設為2至20重量份。更佳係4至10重量份。 The aqueous solution can be prepared, for example, by dissolving a powder of a PVA-based resin, a pulverized product, a cut product, or the like in appropriately heated water (hot water). The concentration of the aqueous solution is preferably set to 2 to 20 parts by weight based on 100 parts by weight of water. More preferably, it is 4 to 10 parts by weight.
水溶液於熱塑性樹脂基材上之塗佈,可適當地選擇並使用例如:線棒塗佈法、逆轉式塗佈法、凹版塗佈法等輥塗佈法、旋轉塗佈法、網版塗佈法、噴流式塗佈法(fountain coating)、浸漬法、噴霧法、模具塗佈法、缺角輪塗佈法(comma coating)、唇式塗佈法(lip coating)、旋轉塗佈法等。 The coating of the aqueous solution on the thermoplastic resin substrate can be appropriately selected and used, for example, a roll coating method such as a wire bar coating method, a reverse coating method, or a gravure coating method, a spin coating method, or a screen coating method. Method, fountain coating method, dipping method, spraying method, die coating method, comma coating method, lip coating method, spin coating method, and the like.
熱塑性樹脂基材具有底漆層時,係將水溶液直接塗佈於該底漆層。另一方面,熱塑性樹脂基材不具有底漆層時,係將水溶液直接塗佈於基材層。再者,乾燥溫度較佳係設為50至200℃,更佳係60至150℃。乾燥時間較佳係設為5至30分鐘。 When the thermoplastic resin substrate has a primer layer, an aqueous solution is directly applied to the primer layer. On the other hand, when the thermoplastic resin substrate does not have a primer layer, the aqueous solution is directly applied to the substrate layer. Further, the drying temperature is preferably set to 50 to 200 ° C, more preferably 60 to 150 ° C. The drying time is preferably set to 5 to 30 minutes.
考慮到施加於積層體之延伸處理之延伸倍率,PVA系樹脂層係以使所得之偏光片之厚度成為10μm以下之厚度來形成。未延伸之PVA系樹脂層之厚度較佳係設為3至20μm,更佳係5至15μm。 The PVA-based resin layer is formed to have a thickness of the obtained polarizer of 10 μm or less in consideration of the stretching ratio of the stretching treatment applied to the laminate. The thickness of the unstretched PVA-based resin layer is preferably set to 3 to 20 μm, more preferably 5 to 15 μm.
〈處理步驟〉 <Processing steps>
本發明之偏光片的製造方法中,對於積層體(胚膜)至少施以染色處理及延伸處理。又,本發明之偏光片的製造方法中,可施以交聯處理。染色處理、交聯處理及延伸處理可分別使用染色浴、交聯浴及延伸浴之各處理浴。使用處理浴時,可使用因應各處理之處理液(水溶液等)。 In the method for producing a polarizer of the present invention, at least a dyeing treatment and an elongation treatment are applied to the laminate (primary membrane). Further, in the method for producing a polarizer of the present invention, a crosslinking treatment can be applied. The dyeing treatment, the crosslinking treatment, and the elongation treatment may each be performed using a treatment bath of a dyeing bath, a crosslinking bath, and an extension bath, respectively. When a treatment bath is used, a treatment liquid (aqueous solution or the like) for each treatment can be used.
〈染色步驟〉 <Staining step>
染色步驟中,藉由使碘或二色性染料吸附/定向於積層體中之PVA系樹脂層而進行染色處理。染色步驟中,可與延伸處理一起進行染色處理。 In the dyeing step, the dyeing treatment is carried out by adsorbing/aligning the iodine or the dichroic dye to the PVA-based resin layer in the laminate. In the dyeing step, the dyeing treatment can be carried out together with the stretching treatment.
染色處理係藉由將積層體浸漬於染色浴內之染色液(染色浴)中而進行。就染色液而言,一般為碘溶液。可使用作為碘溶液之碘水溶液,可使用藉由碘及屬於溶解助劑之碘化物而含有碘離子之水溶液等。 The dyeing treatment is carried out by immersing the laminate in a dyeing liquid (dyeing bath) in the dyeing bath. In the case of a staining solution, it is generally an iodine solution. An aqueous solution of iodine as an iodine solution can be used, and an aqueous solution containing iodine and an iodide which is a dissolution aid and containing an iodide ion can be used.
就碘化物而言,可使用例如: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。就碘化物而言,宜為碘化鉀。又,本實施形態所用之碘化物在其他步驟使用時,與上述碘化物相同。 In the case of iodide, for example, potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, cesium iodide, calcium iodide, tin iodide, iodide can be used. Titanium, etc. In the case of iodide, potassium iodide is preferred. Further, when the iodide used in the present embodiment is used in another step, it is the same as the above iodide.
相對於溶劑100重量份,碘溶液中之碘濃度較佳係設為0.01至10重量份,更佳係0.02至5重量份,再更佳係0.1至1.0重量份。相對於溶劑100重量份,碘化物濃度較佳係設為0.1至10重量份,更佳係0.2至8重量份。當碘染色時,碘溶液之溫度較佳係設為20至50℃, 更佳係25至40℃。浸漬時間較佳係設為10至300秒,更佳係20至240秒。再者,染色時間,可以能夠達成指定的偏光度或透射率之方式以任意時間浸漬。 The iodine concentration in the iodine solution is preferably 0.01 to 10 parts by weight, more preferably 0.02 to 5 parts by weight, still more preferably 0.1 to 1.0 part by weight, based on 100 parts by weight of the solvent. The iodide concentration is preferably from 0.1 to 10 parts by weight, more preferably from 0.2 to 8 parts by weight, based on 100 parts by weight of the solvent. When iodine is dyed, the temperature of the iodine solution is preferably set to 20 to 50 ° C. More preferably 25 to 40 ° C. The immersion time is preferably set to 10 to 300 seconds, more preferably 20 to 240 seconds. Further, the dyeing time may be immersed at any time so as to achieve a specified degree of polarization or transmittance.
〈延伸步驟〉 <Extension step>
延伸步驟亦可使用乾式延伸處理及濕潤式延伸處理中之任一種。延伸步驟中,藉由對積層體施以單軸延伸而進行延伸處理。單軸延伸可為對積層體之長度方向進行之縱延伸、及對積層體之寬度方向進行之橫延伸中之任一種。 The stretching step may also use any one of a dry stretching treatment and a wet stretching treatment. In the extending step, the stretching process is performed by applying a uniaxial extension to the laminated body. The uniaxial stretching may be any one of longitudinal extension of the longitudinal direction of the laminated body and lateral extension of the width direction of the laminated body.
在橫延伸中,可在寬度方向進行延伸之同時,於長度方向使其收縮。就橫延伸方式而言,可列舉例如經由拉幅機將一端固定之固定端單軸延伸方法、或未將一端固定之自由端單軸延伸方法等。 In the lateral extension, it is possible to contract in the longitudinal direction while extending in the width direction. Examples of the lateral stretching method include a fixed end uniaxial stretching method in which one end is fixed via a tenter, or a free end uniaxial stretching method in which one end is not fixed.
另一方面,在縱延伸中,可使用例如:輥間延伸方法、壓縮延伸方法、使用拉幅機之延伸方法等。又,延伸處理亦可多階段進行。再者,延伸處理可藉由施、二軸延伸、斜向延伸等而進行。 On the other hand, in the longitudinal extension, for example, an inter-roll stretching method, a compression stretching method, a stretching method using a tenter, or the like can be used. Moreover, the stretching process can also be carried out in multiple stages. Further, the stretching treatment can be performed by application, biaxial stretching, oblique stretching, or the like.
乾式延伸處理,就可將延伸積層體時之溫度範圍廣泛地設定之觀點而言為佳。乾式延伸處理中,以將積層體加熱到50至200℃為較佳,更佳係在加熱至80至180℃之狀態,再更佳係在加熱至100至160℃之狀態,進行延伸處理。延伸步驟中,包含乾式延伸處理時,較佳係在染色步驟前施行該乾式延伸處理。 The dry stretching treatment is preferable from the viewpoint of widely setting the temperature range at which the laminate is stretched. In the dry stretching treatment, it is preferred to heat the laminate to 50 to 200 ° C, more preferably to a temperature of 80 to 180 ° C, and more preferably to a state of heating to 100 to 160 ° C for elongation treatment. In the extending step, including the dry stretching treatment, it is preferred to perform the dry stretching treatment before the dyeing step.
濕潤式延伸處理所使用之處理液中可含有碘 化物。於處理液中含有碘化物時,相對於溶劑100重量份,碘化物濃度較佳係設為0.1至10重量份,更佳係0.2至5重量份。濕潤式延伸方法中之處理溫度較佳係設為25℃以上,更佳係30至85℃,再更佳係50至70℃。浸漬時間較佳係設為10至800秒,更佳係30至500秒。又,可與染色處理、或交聯處理一起施行延伸處理。 The treatment liquid used in the wet extension treatment may contain iodine Compound. When the iodide is contained in the treatment liquid, the iodide concentration is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the solvent. The treatment temperature in the wet stretching method is preferably set to 25 ° C or higher, more preferably 30 to 85 ° C, still more preferably 50 to 70 ° C. The immersion time is preferably set to 10 to 800 seconds, more preferably 30 to 500 seconds. Further, the stretching treatment may be performed together with the dyeing treatment or the crosslinking treatment.
在延伸步驟中,相對於積層體原本的長度,以使總延伸倍率成為4至8倍之方式進行延伸處理。總延伸倍率較佳係5至7倍。再者,總延伸倍率係指當延伸步驟以外之步驟等中伴隨延伸時,包含該等步驟中之延伸之累積之延伸倍率。總延伸倍率係考慮到其他步驟等中之延伸倍率而適當地決定。 In the stretching step, the stretching treatment is performed so that the total stretching ratio is 4 to 8 times with respect to the original length of the laminated body. The total stretching ratio is preferably 5 to 7 times. Further, the total stretch ratio means the cumulative stretch ratio including the extension in the steps when the step is extended in a step other than the stretching step or the like. The total stretching ratio is appropriately determined in consideration of the stretching ratio in other steps and the like.
總延伸倍率較低時,定向不足,難以得到高光學特性(偏光度)之偏光片。另一方面,總延伸倍率過高時,容易產生延伸斷裂。又,偏光片變得過薄,有在後續步驟之加工性降低之虞。 When the total stretching ratio is low, the orientation is insufficient, and it is difficult to obtain a polarizer having high optical characteristics (polarity). On the other hand, when the total stretching ratio is too high, elongation fracture is likely to occur. Further, the polarizer becomes too thin, and the workability in the subsequent step is lowered.
在延伸步驟中,如「日本專利第4751481號公報」所記載,在空中補助延伸處理之後,可施行濕潤式延伸處理。空中補助延伸處理中之延伸溫度係以先設定為60至180℃,甚至於95至150℃之較高溫度為較佳。又,空中補助延伸處理中之延伸倍率較佳係設為1.3至4倍,更佳係設定為1.5至3倍。又,空中補助延伸處理後施行之濕潤式延伸處理中之處理溫度較佳係設為50至80℃,更佳係60至70℃。浸漬時間較佳係設為5至120秒,更 佳係10至60秒。又,濕潤式延伸處理中之延伸倍率,較佳係設成總延伸倍率為4至7倍,更佳係5至6倍。 In the extension step, as described in "Japanese Patent No. 4751481", after the air-assisted extension treatment, a wetting extension treatment can be performed. The extension temperature in the air-subsidy extension treatment is preferably set to 60 to 180 ° C, and even higher temperatures of 95 to 150 ° C are preferred. Further, the stretching ratio in the air-subsidy extension processing is preferably set to 1.3 to 4 times, more preferably 1.5 to 3 times. Further, the treatment temperature in the wetting extension treatment after the air-assisted extension treatment is preferably set to 50 to 80 ° C, more preferably 60 to 70 ° C. The immersion time is preferably set to 5 to 120 seconds, more Good system 10 to 60 seconds. Further, the stretching ratio in the wetting extension treatment is preferably set to a total stretching ratio of 4 to 7 times, more preferably 5 to 6 times.
延伸步驟中,包含空中補助延伸處理及濕潤式延伸處理時,較佳係在染色處理前施行空中補助延伸處理,並在染色處理後施行濕潤式延伸處理。此時,使用於濕潤式延伸處理之處理浴係兼任交聯浴,較佳係與濕潤式延伸處理一起施行交聯處理。 In the extension step, when the air-assisted extension treatment and the wet extension treatment are included, it is preferable to perform the air-assisted extension treatment before the dyeing treatment, and perform the wet extension treatment after the dyeing treatment. In this case, the treatment bath used in the wet stretching treatment also serves as a crosslinking bath, and it is preferred to carry out a crosslinking treatment together with the wet stretching treatment.
〈交聯步驟〉 <Crosslinking step>
在交聯步驟中,使用硼化合物作為交聯劑而進行交聯處理。交聯處理可與染色處理或延伸處理一起進行。又,交聯處理可分成複數次進行。就硼化合物而言,可使用例如硼酸、硼砂等。硼化合物一般能以水溶液或水-有機溶劑混合溶液之形態使用。 In the crosslinking step, a crosslinking treatment is carried out using a boron compound as a crosslinking agent. The crosslinking treatment can be carried out together with the dyeing treatment or the stretching treatment. Further, the crosslinking treatment can be carried out in plural times. As the boron compound, for example, boric acid, borax or the like can be used. The boron compound can be generally used in the form of an aqueous solution or a water-organic solvent mixed solution.
使用硼酸水溶液時,因依交聯度而賦予耐熱性,故相對於溶劑100重量份,硼酸水溶液之硼酸濃度較佳係設為1至10重量份,更佳係2至7重量份。在硼酸水溶液等,係可含有碘化鉀等碘化物。於硼酸水溶液中含有碘化物時,相對於水100重量份,碘化物濃度較佳係設為0.1至10重量份,更佳係0.5至8重量份。 When a boric acid aqueous solution is used, heat resistance is imparted depending on the degree of crosslinking. Therefore, the boric acid concentration of the boric acid aqueous solution is preferably from 1 to 10 parts by weight, more preferably from 2 to 7 parts by weight, per 100 parts by weight of the solvent. The boric acid aqueous solution or the like may contain an iodide such as potassium iodide. When the iodide is contained in the aqueous boric acid solution, the concentration of the iodide is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, per 100 parts by weight of the water.
交聯處理係可藉由將積層體浸漬於硼酸水溶液等而進行。交聯處理中之處理溫度較佳係設為25℃以上,更佳係30至85℃,再更佳係30至60℃。處理時間較佳係設為5至800秒,更佳係8至500秒。 The crosslinking treatment can be carried out by immersing the laminate in a boric acid aqueous solution or the like. The treatment temperature in the crosslinking treatment is preferably set to 25 ° C or higher, more preferably 30 to 85 ° C, still more preferably 30 to 60 ° C. The processing time is preferably set to 5 to 800 seconds, more preferably 8 to 500 seconds.
〈不溶化步驟〉 <insolubilization step>
本發明之偏光片的製造方法中,對積層體施行染色處理或交聯處理之前,可施行不溶化處理。不溶化步驟係以施行用以不使PVA系樹脂層溶解之不溶化處理為目的。 In the method for producing a polarizer of the present invention, the insolubilization treatment may be performed before the layered body is subjected to a dyeing treatment or a crosslinking treatment. The insolubilization step is for the purpose of performing an insolubilization treatment for not dissolving the PVA-based resin layer.
不溶化步驟中,可藉由將積層體中之PVA系樹脂層浸漬於例如含有硼酸或硼砂等硼化合物之溶液中,而進行不溶化處理。溶液一般能以水溶液或水-有機溶劑混合溶液之形態使用。 In the insolubilization step, the insoluble treatment can be carried out by immersing the PVA-based resin layer in the laminate in a solution containing a boron compound such as boric acid or borax. The solution can generally be used in the form of an aqueous solution or a water-organic solvent mixed solution.
使用硼酸水溶液時,相對於溶劑100重量份,硼酸水溶液之硼酸濃度較佳係設為1至4重量份。不溶化步驟中之處理溫度較佳係設為25℃以上,更佳係30至85℃,再更佳係30至60℃。處理時間較佳係設為5至800秒,更佳係8至500秒。 When a boric acid aqueous solution is used, the boric acid concentration of the boric acid aqueous solution is preferably set to 1 to 4 parts by weight based on 100 parts by weight of the solvent. The treatment temperature in the insolubilization step is preferably set to 25 ° C or higher, more preferably 30 to 85 ° C, still more preferably 30 to 60 ° C. The processing time is preferably set to 5 to 800 seconds, more preferably 8 to 500 seconds.
〈洗淨步驟〉 <washing step>
本發明之偏光片的製造方法中,可對積層體施行染色處理、延伸處理,且進一步施行交聯處理,施行該等處理之後,可施行洗淨處理。 In the method for producing a polarizer of the present invention, the layered body may be subjected to a dyeing treatment or an elongation treatment, and further subjected to a crosslinking treatment, and after the treatment, the cleaning treatment may be performed.
在洗淨步驟中,可使用碘化鉀溶液而進行洗淨處理。相對於溶劑100重量份,碘化鉀溶液中之碘化鉀濃度較佳係設為0.5至10重量份,更佳係0.5至8重量份,再更佳係1至6重量份。 In the washing step, the potassium iodide solution can be used for the washing treatment. The potassium iodide concentration in the potassium iodide solution is preferably from 0.5 to 10 parts by weight, more preferably from 0.5 to 8 parts by weight, still more preferably from 1 to 6 parts by weight, based on 100 parts by weight of the solvent.
在以碘化鉀溶液進行之洗淨處理中,其處理 溫度較佳係設為5至60℃,更佳係10至40℃。浸漬時間較佳係設為1至120秒,更佳係3至90秒。以碘化鉀溶液進行之洗淨處理之階段,只要在乾燥處理前即可,無特別限制。 In the washing treatment with potassium iodide solution, the treatment thereof The temperature is preferably set to 5 to 60 ° C, more preferably 10 to 40 ° C. The immersion time is preferably set to 1 to 120 seconds, more preferably 3 to 90 seconds. The stage of the washing treatment with the potassium iodide solution is not particularly limited as long as it is before the drying treatment.
又,就洗淨處理而言,可施行水洗淨處理。水洗淨處理係藉由將PVA系樹脂浸漬於離子交換水、蒸餾水等純水中而進行。水洗淨溫度較佳係設為5至50℃,更佳係10至45℃,再更佳係15至40℃。浸漬時間較佳係設為5至300秒,更佳係10至240秒。 Further, in the case of the washing treatment, a water washing treatment can be performed. The water washing treatment is carried out by immersing the PVA-based resin in pure water such as ion-exchanged water or distilled water. The water washing temperature is preferably set to 5 to 50 ° C, more preferably 10 to 45 ° C, still more preferably 15 to 40 ° C. The immersion time is preferably set to 5 to 300 seconds, more preferably 10 to 240 seconds.
在洗淨步驟中,亦可將以碘化鉀溶液進行之洗淨處理與水洗淨處理組合,亦可使用例如將甲醇、乙醇、異丙醇、丁醇、丙醇等液態醇適當地調配而成之溶液。 In the washing step, the washing treatment with the potassium iodide solution may be combined with the water washing treatment, and for example, a liquid alcohol such as methanol, ethanol, isopropanol, butanol or propanol may be appropriately blended. Solution.
〈乾燥步驟〉 <Drying step>
又,本發明之偏光片的製造方法中,施行上述各處理後,最後施行乾燥處理,製造偏光片。乾燥處理中,因應所得之偏光片(膜)所需之水分率而設定最適宜的乾燥時間及乾燥溫度。具體而言,乾燥溫度較佳係設為20至150℃,更佳係40至100℃。乾燥溫度過低時,乾燥時間變長,無法有效率地製造,故不佳。另一方面,乾燥溫度過高時,所得之偏光片劣化,就光學特性及色相之點變差。加熱乾燥時間較佳係設為1至10分鐘。 Further, in the method for producing a polarizer of the present invention, after the above respective treatments are performed, the drying treatment is finally performed to produce a polarizer. In the drying treatment, an optimum drying time and drying temperature are set in accordance with the moisture content required for the obtained polarizer (film). Specifically, the drying temperature is preferably set to 20 to 150 ° C, more preferably 40 to 100 ° C. When the drying temperature is too low, the drying time becomes long and it cannot be efficiently produced, which is not preferable. On the other hand, when the drying temperature is too high, the obtained polarizer deteriorates, and the point of optical characteristics and hue deteriorates. The heat drying time is preferably set to 1 to 10 minutes.
〈水溶性抗氧化劑〉 <Water Soluble Antioxidant>
本發明之偏光片的製造方法中,自上述染色步驟之後的至少1個步驟中,可進行經由含有至少一種水溶性抗氧化劑之處理液之處理。 In the method for producing a polarizer of the present invention, the treatment via the treatment liquid containing at least one water-soluble antioxidant can be carried out in at least one step after the dyeing step.
經由含有水溶性抗氧化劑之處理液之處理中,對於積層體,使自染色處理之後所施行之各處理所使用之各浴中之至少任一者中含有水溶性抗氧化劑。或者,另外施行經由含有水溶性抗氧化劑之處理液之處理。經由含有水溶性抗氧化劑之處理液之處理較佳係與交聯處理及/或延伸處理一起進行。 In the treatment of the treatment liquid containing the water-soluble antioxidant, at least one of the respective baths used for each treatment performed after the dyeing treatment contains a water-soluble antioxidant for the laminate. Alternatively, treatment with a treatment liquid containing a water-soluble antioxidant is additionally carried out. The treatment via the treatment liquid containing the water-soluble antioxidant is preferably carried out together with the crosslinking treatment and/or the elongation treatment.
再者,交聯處理或延伸處理可藉由與複數個處理同時進行之一併處理而進行。複數個處理同時進行之一併處理中,該一併處理所使用之浴中含有水溶性抗氧化劑。又,交聯處理與延伸處理分別進行之多階段處理中,在交聯處理與延伸處理中之至少任一處理中含有水溶性抗氧化劑。 Further, the cross-linking treatment or the extension processing may be performed by performing one of the processing simultaneously with the plurality of processing. The plurality of treatments are simultaneously performed in one and the treatment, and the bath used in the combined treatment contains a water-soluble antioxidant. Further, in the multi-stage treatment in which the cross-linking treatment and the elongation treatment are respectively performed, at least one of the cross-linking treatment and the elongation treatment contains a water-soluble antioxidant.
就水溶性抗氧化劑而言,可列舉例如:抗壞血酸(維生素C)、異抗壞血酸、硫代硫酸、亞硫酸、綠原酸(chlorogenic acid)、檸檬酸、迷迭香酸(rosmarinic acid)及該等之鹽等。 Examples of the water-soluble antioxidant include ascorbic acid (vitamin C), erythorbic acid, thiosulfuric acid, sulfurous acid, chlorogenic acid, citric acid, rosmarinic acid, and the like. Salt and so on.
就鹽而言,可列舉鈉鹽、鉀鹽等鹼金屬鹽等。 The salt may, for example, be an alkali metal salt such as a sodium salt or a potassium salt.
該等之中,較佳係使用抗壞血酸、異抗壞血酸鹽、硫代硫酸鹽、亞硫酸鹽。該等水溶性抗氧化劑可單獨使用1種或將2種以上組合而使用。 Among these, ascorbic acid, isoascorbate, thiosulfate, and sulfite are preferably used. These water-soluble antioxidants may be used alone or in combination of two or more.
水溶性抗氧化劑之添加量係可依據自染色步 驟之後之各處理液含有之二色性物質(碘或二色性染料)之污染濃度而決定。若經污染之處理液中之二色性物質所致之污染濃度高,則添加之水溶性抗氧化劑之添加量亦變多。 The amount of water-soluble antioxidant can be based on the self-staining step The contamination concentration of the dichroic substance (iodine or dichroic dye) contained in each treatment liquid after the step is determined. If the contamination concentration due to the dichroic substance in the contaminated treatment liquid is high, the added amount of the added water-soluble antioxidant also increases.
各處理液中,較佳係以相對於溶劑100重量份,使水溶性抗氧化劑之濃度成為0.005至1重量份之方式添加水溶性抗氧化劑,更佳係0.005至0.5重量份。水溶性抗氧化劑之濃度未達0.005重量份時,經污染之處理液中之水溶性抗氧化劑之比例變少,變得無法充分抑制所得之偏光片之特性(單體透射率、偏光度)之降低。另一方面,水溶性抗氧化劑之濃度超過1重量份時,浴中之水溶性抗氧化劑之比例變多,故所得之偏光片會脫色且透射率變高。伴隨此情形,擔心染色浴之碘濃度升高之必要性,但在光學特性方面,沒有降低等問題。 In each of the treatment liquids, the water-soluble antioxidant is preferably added in an amount of 0.005 to 1 part by weight based on 100 parts by weight of the solvent, more preferably 0.005 to 0.5 parts by weight. When the concentration of the water-soluble antioxidant is less than 0.005 parts by weight, the proportion of the water-soluble antioxidant in the contaminated treatment liquid is small, and the characteristics (single transmittance and polarization degree) of the obtained polarizer cannot be sufficiently suppressed. reduce. On the other hand, when the concentration of the water-soluble antioxidant exceeds 1 part by weight, the ratio of the water-soluble antioxidant in the bath increases, so that the obtained polarizer is decolored and the transmittance is high. Along with this, there is a fear of an increase in the iodine concentration of the dye bath, but there is no problem in terms of optical characteristics.
〈偏光片〉 <Polarizer>
藉由本發明之偏光片的製造方法所製造之偏光片係形成在熱塑性樹脂基材上,但亦可不使用上述熱塑性樹脂基材,以未延伸之PVA系樹脂層膜作為胚膜,施行上述各處理而製造。此時,偏光片之厚度可為10μm以上,較佳係5至50μm。 The polarizer produced by the method for producing a polarizer of the present invention is formed on a thermoplastic resin substrate, but the above-mentioned respective treatment may be carried out by using the unextended PVA-based resin layer film as a embryonic film without using the above-mentioned thermoplastic resin substrate. And manufacturing. At this time, the thickness of the polarizer may be 10 μm or more, preferably 5 to 50 μm.
熱塑性樹脂基材可直接使用作為後述之偏光板之透明保護膜。又,在偏光片之與熱塑性樹脂基材為相反側之面,可貼合透明保護膜。另一方面,未使用熱塑性樹脂基材時,可在偏光片之兩側貼合透明保護膜。又,將 熱塑性樹脂基材從偏光片剝離後,可在該偏光片之兩側貼合透明保護膜。 As the thermoplastic resin substrate, a transparent protective film which is a polarizing plate to be described later can be used as it is. Further, a transparent protective film can be bonded to the surface of the polarizer opposite to the thermoplastic resin substrate. On the other hand, when a thermoplastic resin substrate is not used, a transparent protective film can be bonded to both sides of the polarizer. Again, After the thermoplastic resin substrate is peeled off from the polarizer, a transparent protective film can be attached to both sides of the polarizer.
就構成透明保護膜之材料而言,可使用例如透明性、機械強度、熱安定性、水分遮蔽性、等向性等優異之熱塑性樹脂。就此種熱塑性樹脂之具體例而言,可列舉:三乙醯基纖維素等纖維素樹脂、聚酯樹脂、聚醚碸樹脂、聚碸樹脂、聚碳酸酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚烯烴樹脂、(甲基)丙烯酸樹脂、環狀聚烯烴樹脂(降莰烯系樹脂)、聚芳酯樹脂、聚苯乙烯樹脂、聚乙烯醇樹脂、及該等之混合物。 As the material constituting the transparent protective film, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture shielding property, isotropic property, and the like can be used. Specific examples of such a thermoplastic resin include cellulose resins such as triethyl fluorenyl cellulose, polyester resins, polyether oxime resins, polyfluorene resins, polycarbonate resins, polyamide resins, and polyfluorene resins. An amine resin, a polyolefin resin, a (meth)acrylic resin, a cyclic polyolefin resin (northene-based resin), a polyarylate resin, a polystyrene resin, a polyvinyl alcohol resin, and a mixture thereof.
〈含有交聯劑之染色液〉 <Staining solution containing cross-linking agent>
上述染色步驟所使用之PVA系樹脂較佳係未染色。又,本發明之偏光片的製造方法中,上述染色步驟所使用之染色液含有交聯劑。就交聯劑而言,例如可從硼酸、硼砂等硼化合物,乙二醛、戊二醛等之中使用至少1種或併用2種類以上。其中,較佳係使用硼化合物,再更佳係使用硼酸。 The PVA-based resin used in the above dyeing step is preferably undyed. Further, in the method for producing a polarizer of the present invention, the dyeing liquid used in the dyeing step contains a crosslinking agent. For the crosslinking agent, for example, at least one of a boron compound such as boric acid or borax, glyoxal or glutaraldehyde, or two or more types may be used in combination. Among them, a boron compound is preferably used, and a boric acid is more preferably used.
上述染色步驟中,藉由使染色液含有微量硼酸(交聯劑),使該硼酸從PVA系樹脂層溶解至染色液中之PVA進行交聯(錯合化)。藉此,生成由溶解於染色液中之PVA與染色液中之碘及硼酸結合而成之凝膠狀碘/PVA/硼酸錯合物(以下,稱為錯合化合物)。 In the dyeing step, the dye liquid contains a trace amount of boric acid (crosslinking agent), and the boric acid is dissolved in the PVA-based resin layer to PVA in the dyeing liquid to carry out crosslinking (coincidation). Thereby, a gelled iodine/PVA/boric acid complex (hereinafter referred to as a "co-compound compound") obtained by combining PVA dissolved in the dyeing liquid with iodine and boric acid in the dyeing liquid is formed.
為了使溶解於染色液中之PVA交聯(錯合 化),相對於溶劑100重量份,染色液中之硼酸(交聯劑)之濃度較佳係設為0.01至0.1重量份,更佳係0.02至0.1重量份。若硼酸之濃度為0.01重量份以上,則可使溶解於染色液中之PVA交聯(錯合化)。另一方面,硼酸之濃度超過0.2重量份時,硼酸會析出至積層體(胚膜)之表面、運送積層體(胚膜)之輥之表面等,有時會成為偏光片之缺陷等之原因。 In order to crosslink the PVA dissolved in the dyeing solution (coincident The concentration of boric acid (crosslinking agent) in the dyeing liquid is preferably 0.01 to 0.1 part by weight, more preferably 0.02 to 0.1 part by weight, based on 100 parts by weight of the solvent. When the concentration of the boric acid is 0.01 parts by weight or more, the PVA dissolved in the dyeing liquid can be crosslinked (missed). On the other hand, when the concentration of boric acid exceeds 0.2 parts by weight, boric acid may precipitate on the surface of the laminate (primary membrane), the surface of the roll on which the laminate (sheath membrane) is conveyed, or the like, which may cause defects such as a polarizer. .
就調整染色液中之硼酸之濃度之方法而言,可為於染色液中添加既定量之硼酸之方法。又,在染色處理之前存在含有硼酸之處理浴時,可使用從該處理浴與積層體一起被帶進去之硼酸。 In the method of adjusting the concentration of boric acid in the dyeing liquid, a method of adding a predetermined amount of boric acid to the dyeing liquid can be used. Further, when a treatment bath containing boric acid is present before the dyeing treatment, boric acid which is carried in together with the laminate from the treatment bath can be used.
本發明之偏光片的製造方法中,上述染色液含有微量硼酸(交聯劑),藉由使該硼酸溶解於染色液中之PVA進行交聯(錯合化),可避免如以往之PVA之附著、染色速度降低等問題。亦即,溶解於染色液中之PVA係因交聯(錯合化)而變得難以附著於PVA系樹脂層(胚膜)。又,將胚膜從染色浴內取出時之染色液之排液(排水)性提升。藉此,可得到沒有染色不均之偏光片。 In the method for producing a polarizer of the present invention, the dyeing liquid contains a trace amount of boric acid (crosslinking agent), and the PVA in which the boric acid is dissolved in the dyeing solution is crosslinked (missed), thereby avoiding the conventional PVA. Problems such as adhesion and dyeing speed reduction. In other words, the PVA dissolved in the dyeing liquid is difficult to adhere to the PVA-based resin layer (the germ film) due to crosslinking (coincidence). Further, the drainage (drainage) of the dyeing liquid when the embryonic membrane is taken out from the dyeing bath is improved. Thereby, a polarizer having no uneven dyeing can be obtained.
〈染色液之過濾〉 <Filtering of staining solution>
再者,本發明之偏光片的製造方法中,係將染色液以過濾器過濾。 Further, in the method for producing a polarizer of the present invention, the dyeing liquid is filtered by a filter.
藉此,可將溶解於染色液中之PVA進行交聯(錯合化)所生成之錯合化合物從染色液分離。例如,調整構成膜之 平膜之製膜條件、或對膜進行分離用之表面處理,可將PVA等有機物與染色液之相異成分分離。就過濾器而言,可使用例如聚丙烯過濾器、聚酯過濾器、尼龍過濾器等。模組雖未特別限制,但較佳係將過濾器收納於可密封之容器,且具有能夠可裝卸地設置在裝置之構造之匣式(cartridge type)。 Thereby, the mismatched compound produced by crosslinking (coinciding) the PVA dissolved in the dyeing liquid can be separated from the dyeing liquid. For example, adjusting the constituent film The film forming conditions of the flat film or the surface treatment for separating the film can separate the organic substances such as PVA from the different components of the dyeing liquid. As the filter, for example, a polypropylene filter, a polyester filter, a nylon filter or the like can be used. Although the module is not particularly limited, it is preferable to store the filter in a sealable container and to have a cartridge type that can be detachably provided in the structure of the device.
更具體而言,藉由調節膜內部之平膜的內部孔徑(例如,以不使分子量300以上之物質通過之方式進行調節)、或在膜上形成可依據離子電荷斥力之差而決定物質可否穿透之機能性塗佈膜或表面處理膜,而可將PVA等有機物與染色液中之其他成分分離。 More specifically, by adjusting the internal pore diameter of the flat membrane inside the membrane (for example, by not passing the substance having a molecular weight of 300 or more), or forming on the membrane, the substance can be determined depending on the difference in ion charge repulsion. By penetrating the functional coating film or the surface treatment film, an organic substance such as PVA can be separated from other components in the dyeing liquid.
就過濾膜而言,可使用例如超過濾(UF)膜、微過濾(MF)膜、奈米過濾(NF)膜、逆滲透(RO)膜等,其中,較佳係使用UF膜、MF膜。又,過濾膜較佳係使用可將PVA等有機物從染色液之相異成分分離之可設定複數種分離基準(例如,分子量和離子電荷斥力)者。 As the filtration membrane, for example, an ultrafiltration (UF) membrane, a microfiltration (MF) membrane, a nanofiltration (NF) membrane, a reverse osmosis (RO) membrane, or the like can be used, and among them, a UF membrane, an MF membrane is preferably used. . Further, it is preferable that the filter membrane is one which can set a plurality of separation standards (for example, molecular weight and ionic charge repulsion) by separating an organic substance such as PVA from a different component of the dyeing liquid.
又,染色浴內之染色液較佳係經由過濾器而循環。藉此,可藉由過濾器而有效率地去除(捕集)染色浴內之錯合化合物。又,可再利用染色液。 Further, the dyeing liquid in the dyeing bath is preferably circulated through the filter. Thereby, the mismatched compound in the dyeing bath can be efficiently removed (captured) by the filter. Also, the staining solution can be reused.
又,染色浴內之染色液較佳係進行攪拌。藉此,可促進溶解於染色液中之PVA之交聯(錯合化)並有效率地將錯合化合物從染色液去除。 Further, the dyeing liquid in the dyeing bath is preferably stirred. Thereby, crosslinking (coincidation) of PVA dissolved in the dyeing liquid can be promoted and the compounded compound can be efficiently removed from the dyeing liquid.
就攪拌染色液之方法而言,可使用於染色浴內設置攪拌葉等攪拌手段,並在染色浴內攪拌染色液之方 法。又,藉由上述染色液之循環,亦可攪拌染色浴內之染色液。再者,藉由在染色浴內搬運(取出放入)之胚膜,可攪拌染色浴內之染色液。 In the method of stirring the dyeing liquid, a stirring means such as a stirring blade may be provided in the dyeing bath, and the dyeing liquid may be stirred in the dyeing bath. law. Further, the dyeing liquid in the dyeing bath can be stirred by the circulation of the dyeing liquid. Further, the dyeing liquid in the dyeing bath can be stirred by carrying (removing and placing) the embryonic film in the dyeing bath.
如上所述,本發明之偏光片的製造方法,可將溶解於染色液中之PVA去除。藉此,由於可避免受到溶解於染色液中之PVA所致之影響,同時亦可延長染色液之更新(交換)時期,故可進一步提升偏光片之生產性。 As described above, in the method for producing a polarizer of the present invention, the PVA dissolved in the dyeing liquid can be removed. Thereby, since the influence of the PVA dissolved in the dyeing liquid can be avoided, and the renewal (exchange) period of the dyeing liquid can be prolonged, the productivity of the polarizer can be further improved.
以下,藉由實施例而可使本發明之效果更明確。再者,本發明並不限於以下之實施例,在不變更本發明要旨之範圍內可適當地變更並實施。 Hereinafter, the effects of the present invention will be made clear by the examples. The present invention is not limited to the embodiments described below, and may be appropriately modified and implemented without departing from the spirit and scope of the invention.
在實施例1中,係使用本發明之偏光片的製造方法,製作在熱塑性樹脂基材上形成有偏光片之偏光性積層膜。 In the first embodiment, a polarizing laminated film in which a polarizing plate is formed on a thermoplastic resin substrate is produced by using the method for producing a polarizer of the present invention.
具體而言,首先,準備非晶質聚對苯二甲酸乙二酯(A-PET)膜(三菱化學股份有限公司製,商品名「NOVACLEAR(註冊商標)」,厚度:200μm)作為熱塑性樹脂基材。 Specifically, an amorphous polyethylene terephthalate (A-PET) film (manufactured by Mitsubishi Chemical Corporation, trade name "NOVACLEAR (registered trademark)", thickness: 200 μm) is prepared as a thermoplastic resin base. material.
繼而,對該熱塑性樹脂基材之單面施以電暈處理(處理條件:90W‧min/m2),將聚合度4000、皂化度99.0莫耳%以上之PVA之水溶液於65℃塗佈在施有該電暈處理之面後,使其乾燥。藉此,得到於熱塑性樹脂基材之單面形成有厚度8.3μm之PVA系樹脂層之積層體作為胚 膜。 Then, a single surface of the thermoplastic resin substrate was subjected to corona treatment (processing conditions: 90 W ‧ min/m 2 ), and an aqueous solution of PVA having a degree of polymerization of 4000 and a degree of saponification of 99.0 mol% or more was applied at 65 ° C. After the surface of the corona treatment was applied, it was dried. Thereby, a laminate having a PVA-based resin layer having a thickness of 8.3 μm formed on one surface of the thermoplastic resin substrate was obtained as a germ film.
繼而,將所得之胚膜於90℃之烘箱內進行單軸延伸至1.8倍(延伸處理)。 Then, the obtained embryonic membrane was uniaxially stretched to 1.8 times (extension treatment) in an oven at 90 °C.
繼而,將延伸後之胚膜浸漬於液溫30℃之不溶化浴(相對於水100重量份,溶解有硼酸3重量份之硼酸水溶液)中30秒(不溶化處理)。 Then, the extended embryo membrane was immersed in an insolubilization bath (3 parts by weight of boric acid solution in which boric acid was dissolved in 100 parts by weight of water) in an insoluble bath at a liquid temperature of 30 ° C (insolubilization treatment).
繼而,一邊以使偏光片之透射率成為約42.0%之方式調整碘濃度、浸漬時間,一邊將胚膜浸漬於染色浴中(染色處理)。 Then, while adjusting the iodine concentration and the immersion time so that the transmittance of the polarizer is about 42.0%, the embryonic membrane is immersed in the dyeing bath (dyeing treatment).
在實施例1中,調製相對於水100重量份,溶解有碘0.18重量份、碘化鉀1.26重量份、硼酸0.02重量份之染色液。然後,將該染色液之液溫設為30℃,將胚膜浸漬13秒。 In Example 1, a dyeing liquid containing 0.18 parts by weight of iodine, 1.26 parts by weight of potassium iodide, and 0.02 parts by weight of boric acid was dissolved in 100 parts by weight of water. Then, the liquid temperature of the staining solution was set to 30 ° C, and the embryo membrane was immersed for 13 seconds.
又,於該染色液中添加0.05重量份之PVA,一邊以磁攪拌器攪拌15分鐘,一邊使經由聚丙烯過濾器所過濾之染色液循環。 Further, 0.05 parts by weight of PVA was added to the dyeing solution, and while stirring with a magnetic stirrer for 15 minutes, the dyeing liquid filtered through the polypropylene filter was circulated.
繼而,將胚膜浸漬於液溫40℃之交聯浴(相對於水100重量份,溶解有碘化鉀3重量份、硼酸3重量份之硼酸水溶液)中30秒(交聯處理)。 Then, the embryonic membrane was immersed in a crosslinking bath having a liquid temperature of 40 ° C (with respect to 100 parts by weight of water, 3 parts by weight of potassium iodide and 3 parts by weight of boric acid in an aqueous solution of boric acid), and 30 seconds (crosslinking treatment).
繼而,一邊將胚膜浸漬於液溫70℃之硼酸水溶液(相對於水100重量份,溶解有硼酸4重量份、碘化鉀5重量份之水溶液)中,一邊於縱方向(長度方向)進行單軸延伸(液中縱延伸)。此時,積層體之最大延伸倍率係5.94倍。 Then, while immersing the embryonic membrane in a boric acid aqueous solution (4 parts by weight of boric acid and 5 parts by weight of potassium iodide dissolved in 100 parts by weight of water) at a liquid temperature of 70 ° C, uniaxially in the longitudinal direction (longitudinal direction) Extension (longitudinal extension in liquid). At this time, the maximum stretching ratio of the laminated body was 5.94 times.
繼而,將胚膜浸漬於液溫30℃之洗淨浴(相對於水100重量份,溶解有碘化鉀4重量份之水溶液)中5秒後,以60℃之溫風乾燥(洗淨處理及乾燥處理)。 Then, the embryo membrane was immersed in a washing bath at a liquid temperature of 30° C. (in an aqueous solution in which 4 parts by weight of potassium iodide was dissolved in 100 parts by weight of water), and then dried at 60° C. (washing treatment and drying) deal with).
經過以上步驟,製作在熱塑性樹脂基材上形成有厚度4.5μm之偏光片之偏光性積層膜。 Through the above procedure, a polarizing laminated film in which a polarizing plate having a thickness of 4.5 μm was formed on a thermoplastic resin substrate was produced.
在實施例2中,除了將硼酸設為0.05重量份以外,調製與實施例1同樣之染色液。然後,使用該染色液,以與實施例1同樣之方法製作偏光片。 In Example 2, a dyeing liquid similar to that of Example 1 was prepared except that boric acid was 0.05 parts by weight. Then, using this dyeing liquid, a polarizer was produced in the same manner as in Example 1.
在實施例3中,除了將硼酸設為0.1重量份以外,調製與實施例1同樣之染色液。然後,使用該染色液,以與實施例1同樣之方法製作偏光片。 In Example 3, the same dyeing liquid as in Example 1 was prepared except that boric acid was used in an amount of 0.1 part by weight. Then, using this dyeing liquid, a polarizer was produced in the same manner as in Example 1.
在實施例4中,除了將硼酸設為0.2重量份以外,調製與實施例1同樣之染色液。然後,使用該染色液,以與實施例1同樣之方法製作偏光片。 In Example 4, the same dyeing liquid as in Example 1 was prepared except that boric acid was 0.2 parts by weight. Then, using this dyeing liquid, a polarizer was produced in the same manner as in Example 1.
在實施例5中,除了將硼酸設為0.01重量份以外,調製與實施例1同樣之染色液。然後,使用該染色液,以與 實施例1同樣之方法進行到染色處理為止。 In Example 5, a dyeing liquid similar to that of Example 1 was prepared except that boric acid was used in an amount of 0.01 part by weight. Then, use the staining solution to The same method as in Example 1 was carried out until the dyeing treatment.
在比較例1中,除了不含硼酸以外,其餘係調製與實施例1同樣之染色液。然後,使用該染色液,以與實施例1同樣之方法製作偏光片。 In Comparative Example 1, the same dyeing liquid as in Example 1 was prepared except that boric acid was not contained. Then, using this dyeing liquid, a polarizer was produced in the same manner as in Example 1.
然後,針對該等實施例1至5及比較例1所製作之各偏光片,以目視觀察有無「染色不均」之產生。又,測定藉由過濾器所捕集到之錯合化合物之殘渣量,評估染色液之「過濾性」。其中,將非常良好設為「◎」,將良好設為「○」,將差設為「×」。再者,以目視觀察染色處理時附著於裝置等之「因硼酸所致之髒污」之有無。將該等彙整於下述表1中。 Then, with respect to each of the polarizers produced in the above Examples 1 to 5 and Comparative Example 1, the presence or absence of "staining unevenness" was visually observed. Further, the amount of the residue of the mixed compound trapped by the filter was measured, and the "filterability" of the dyeing liquid was evaluated. Among them, "Excel" is set to "◎", "Good" is set to "○", and the difference is set to "X". In addition, the presence or absence of "stain due to boric acid" attached to the apparatus or the like during the dyeing treatment was visually observed. These are summarized in Table 1 below.
如表1所示,得知與染色液中含有硼酸之實施例1至5相比,染色液中不含有硼酸之比較例1係過濾性差且產生染色不均。 As shown in Table 1, it was found that Comparative Example 1 which does not contain boric acid in the dyeing liquid has poor filterability and uneven dyeing as compared with Examples 1 to 5 containing boric acid in the dyeing liquid.
另一方面,與實施例1至3、5相比,實施例4係在染色液所含之硼酸量過多,且觀察到因硼酸之析出所致之髒污。 On the other hand, in Example 4, compared with Examples 1 to 3 and 5, the amount of boric acid contained in the dyeing liquid was excessive, and the contamination due to the precipitation of boric acid was observed.
相對於此,實施例1至3、5係過濾性良好、無染色不均、亦未觀察到因硼酸所致之髒污。 On the other hand, in Examples 1 to 3 and 5, the filterability was good, there was no uneven dyeing, and no stain due to boric acid was observed.
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