TWI621533B - Method for manufacturing extended laminate - Google Patents
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Abstract
本發明提供一種延伸積層體，其確保所獲得之偏光膜之光學特性，並且可達成高生產性。 The present invention provides an extended laminate which ensures the optical characteristics of the obtained polarizing film and achieves high productivity.
本發明之延伸積層體之製造方法包括如下步驟：於長條狀之聚酯系樹脂基材(11)上形成聚乙烯醇系樹脂層(12)而製作積層體(10)；將積層體(10)一面於長度方向進行搬送，一面藉由輥間之周速差於100℃以下進行空中延伸；及將該經延伸之積層體加熱至110℃以上。於上述延伸步驟中，延伸間距L1與積層體(10)之寬度W滿足L1/W≧0.3之關係。 The method for producing an extended laminate of the present invention comprises the steps of: forming a polyvinyl alcohol-based resin layer (12) on a long polyester resin substrate (11) to form a laminate (10); 10) Performing the transport in the longitudinal direction while performing air extension by a circumferential speed difference between the rolls of 100 ° C or lower; and heating the stretched laminated body to 110 ° C or higher. In the above extending step, the extending pitch L 1 and the width W of the laminated body (10) satisfy the relationship of L 1 / W ≧ 0.3.
Description
本發明係關於一種延伸積層體之製造方法。 The present invention relates to a method of manufacturing an extended laminate.
代表性之圖像顯示裝置即液晶顯示裝置係由於其圖像形成方式而於液晶單元之兩側配置有偏光膜。近年來，由於期望偏光膜之薄膜化，故而提出有例如如下方法：藉由對特定之熱塑性樹脂基材與聚乙烯醇系樹脂層之積層體進行空中延伸，並進而於硼酸水溶液中進行延伸，而獲得偏光膜(例如專利文獻1)。根據此種方法，可高倍率地延伸積層體，而獲得具有優異光學特性之偏光膜。 A liquid crystal display device which is a typical image display device is provided with a polarizing film on both sides of a liquid crystal cell due to an image forming method. In recent years, since a thin film of a polarizing film is desired, for example, a method in which a laminate of a specific thermoplastic resin substrate and a polyvinyl alcohol-based resin layer is stretched in the air and further extended in an aqueous boric acid solution is proposed. A polarizing film is obtained (for example, Patent Document 1). According to this method, the laminate can be stretched at a high magnification to obtain a polarizing film having excellent optical characteristics.
然而，通常已知，於製造偏光膜時因延伸而於與延伸方向大致垂直方向發生收縮，且已知藉由收縮而可提高光學特性。但，若收縮率過高，則無法獲得具有所需尺寸(製品寬度)之偏光膜，例如有無法充分應對高速生產之問題。 However, it is generally known that when a polarizing film is produced, shrinkage occurs in a direction substantially perpendicular to the extending direction due to stretching, and it is known that optical characteristics can be improved by shrinkage. However, if the shrinkage ratio is too high, a polarizing film having a desired size (product width) cannot be obtained, and for example, there is a problem that it is not possible to sufficiently cope with high-speed production.
[專利文獻1]日本專利特開2012-73580號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-73580
本發明係為了解決上述先前課題而完成者，其主要目的在於提供一種延伸積層體，其確保所獲得之偏光膜之光學特性，並且可達成高生產性。 The present invention has been made to solve the above-mentioned problems, and a main object thereof is to provide an extended laminated body which ensures optical characteristics of the obtained polarizing film and which can achieve high productivity.
本發明之延伸積層體之製造方法包括如下步驟：於長條狀之聚酯系樹脂基材上形成聚乙烯醇系樹脂層而製作積層體；將該積層體一面於長度方向進行搬送，一面藉由輥間之周速差於100℃以下進行空中延伸；及將該經延伸之積層體加熱至110℃以上；且於該延伸步驟中，延伸間距L1與該積層體之寬度W滿足L1/W≧0.3之關係。 The method for producing an extended laminate of the present invention includes the steps of: forming a layered body on a long-length polyester resin substrate to form a layered body; and transferring the layered body in the longitudinal direction while borrowing Performing an air extension by a circumferential speed difference between the rolls below 100 ° C; and heating the extended laminated body to 110 ° C or higher; and in the extending step, the extending pitch L 1 and the width W of the laminated body satisfy L 1 /W≧0.3 relationship.
於較佳之實施形態中，上述空中延伸之延伸倍率為1.4倍以上。 In a preferred embodiment, the extension ratio of the air extension is 1.4 times or more.
於較佳之實施形態中，於上述加熱步驟中於長度方向延伸上述積層體。該延伸較佳為實質上為固定端單軸延伸。 In a preferred embodiment, the laminate is extended in the longitudinal direction in the heating step. The extension is preferably substantially uniaxially extending at a fixed end.
於較佳之實施形態中，於上述加熱步驟中，將上述積層體一面於長度方向進行搬送，一面藉由輥間之周速差進行延伸，且該延伸間距L2與即將進行該延伸前之積層體之寬度W'滿足L2/W'≦0.12之關係。 In a preferred embodiment, in the heating step, the layered body is conveyed in the longitudinal direction, and is extended by the circumferential speed difference between the rolls, and the extending distance L 2 is immediately before the stretching. The width W' of the body satisfies the relationship of L 2 /W' ≦ 0.12.
於較佳之實施形態中，延伸至1.7倍~2.3倍。 In a preferred embodiment, it extends from 1.7 to 2.3 times.
根據本發明之另一態樣，提供一種延伸積層體。該延伸積層體係藉由上述製造方法而製造。 According to another aspect of the present invention, an extended laminate is provided. The extended laminated system is produced by the above manufacturing method.
根據本發明之又一態樣，提供一種偏光膜之製造方法。該偏光膜之製造方法使用上述延伸積層體。 According to still another aspect of the present invention, a method of producing a polarizing film is provided. The method for producing a polarizing film uses the above-mentioned extended laminate.
於較佳之實施形態中，於硼酸水溶液中延伸上述延伸積層體。 In a preferred embodiment, the extended laminate is extended in an aqueous boric acid solution.
根據本發明，將於長條狀之聚酯系樹脂基材上形成聚乙烯醇系樹脂層而獲得之積層體於100℃以下進行自由端延伸之後，於110℃以上進行加熱，藉此可達成高生產性，並製造具有優異光學特性之偏光膜。 According to the present invention, the laminate obtained by forming the polyvinyl alcohol-based resin layer on the long-length polyester resin substrate is subjected to free end stretching at 100 ° C or lower, and then heated at 110 ° C or higher. Highly productive and producing a polarizing film with excellent optical properties.
1‧‧‧輥 1‧‧‧ Roll
2‧‧‧輥 2‧‧‧ Roll
3‧‧‧第1輥 3‧‧‧1st roll
4‧‧‧第2輥 4‧‧‧second roller
5‧‧‧第3輥 5‧‧‧3rd roller
9‧‧‧烘箱 9‧‧‧ oven
10‧‧‧積層體 10‧‧‧Layer
10'‧‧‧延伸積層體 10'‧‧‧Extended laminate
11‧‧‧聚酯系樹脂基材 11‧‧‧ polyester resin substrate
11'‧‧‧樹脂基材 11'‧‧‧Resin substrate
12‧‧‧PVA系樹脂層 12‧‧‧PVA resin layer
12'‧‧‧偏光膜 12'‧‧‧ polarizing film
13‧‧‧黏著劑層 13‧‧‧Adhesive layer
14‧‧‧隔片 14‧‧‧ spacer
15‧‧‧接著劑層 15‧‧‧ adhesive layer
16‧‧‧光學功能膜 16‧‧‧Optical functional film
16'‧‧‧第2光學功能膜 16'‧‧‧2nd optical functional film
100‧‧‧光學膜積層體 100‧‧‧Optical film laminate
101‧‧‧捲出部 101‧‧‧Devolution
110‧‧‧硼酸水溶液之浴 110‧‧‧Bath of boric acid aqueous solution
111‧‧‧輥 111‧‧‧ Roll
112‧‧‧輥 112‧‧‧roll
120‧‧‧二色性物質(碘)及碘化鉀之水溶液之浴 120‧‧‧ bath of aqueous solution of dichromatic substance (iodine) and potassium iodide
121‧‧‧輥 121‧‧‧roll
122‧‧‧輥 122‧‧‧roll
130‧‧‧硼酸及碘化鉀之水溶液之浴 130‧‧‧Bath of aqueous solution of boric acid and potassium iodide
131‧‧‧輥 131‧‧‧roll
132‧‧‧輥 132‧‧‧ Roll
140‧‧‧硼酸水溶液之浴 140‧‧‧Bath of boric acid aqueous solution
141‧‧‧輥 141‧‧‧roll
142‧‧‧輥 142‧‧‧roll
150‧‧‧碘化鉀水溶液之浴 150‧‧‧Bath of potassium iodide solution
151‧‧‧輥 151‧‧‧ Roll
152‧‧‧輥 152‧‧‧roll
160‧‧‧捲取部 160‧‧‧Winding Department
200‧‧‧光學膜積層體 200‧‧‧Optical film laminate
300‧‧‧光學功能膜積層體 300‧‧‧Optical functional film laminate
400‧‧‧光學功能膜積層體 400‧‧‧Optical functional film laminate
L1‧‧‧延伸間距 L 1 ‧‧‧ Extended spacing
L2‧‧‧延伸間距 L 2 ‧‧‧ Extended spacing
W‧‧‧寬度 W‧‧‧Width
W'‧‧‧寬度 W'‧‧‧Width
圖1係本發明之較佳實施形態之積層體之部分剖面圖。 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a partial cross-sectional view showing a laminate of a preferred embodiment of the present invention.
圖2(a)、(b)係表示本發明之空中延伸步驟之一例之概略圖。 2(a) and 2(b) are schematic diagrams showing an example of the air extension step of the present invention.
圖3(a)、(b)係表示本發明之加熱步驟之一例之概略圖。 3(a) and 3(b) are schematic views showing an example of a heating step of the present invention.
圖4係表示本發明之偏光膜之製造方法之一例之概略圖。 Fig. 4 is a schematic view showing an example of a method for producing a polarizing film of the present invention.
圖5(a)、(b)係使用藉由本發明之製造方法獲得之偏光膜的光學膜積層體之概略剖面圖。 5(a) and 5(b) are schematic cross-sectional views showing an optical film laminate using a polarizing film obtained by the production method of the present invention.
圖6(a)、(b)係使用藉由本發明之製造方法獲得之偏光膜的光學功能膜積層體之概略剖面圖。 6(a) and 6(b) are schematic cross-sectional views showing an optical functional film laminate using a polarizing film obtained by the production method of the present invention.
以下，對本發明之較佳實施形態進行說明，但本發明並不限定於該等實施形態。 Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited to the embodiments.
本發明之延伸積層體之製造方法包括如下步驟：於長條狀之聚酯系樹脂基材上形成聚乙烯醇系樹脂層而製作積層體；將該積層體一面於長度方向進行搬送，一面藉由輥間之周速差於100℃以下進行空中延伸；及將該經延伸之積層體加熱至110℃以上。以下，對各個步驟進行說明。 The method for producing an extended laminate of the present invention includes the steps of: forming a layered body on a long-length polyester resin substrate to form a layered body; and transferring the layered body in the longitudinal direction while borrowing The airborne extension is performed by a difference in circumferential speed between the rolls of 100 ° C or less; and the stretched laminated body is heated to 110 ° C or more. Hereinafter, each step will be described.
圖1係本發明之較佳實施形態之積層體之部分剖面圖。積層體10具有聚酯系樹脂基材11及聚乙烯醇系樹脂層12。積層體10係藉由在長條狀之聚酯系樹脂基材上形成聚乙烯醇系樹脂層12而製作。作為聚乙烯醇系樹脂層12之形成方法，可採用任意適合之方法。較佳為，於聚酯系樹脂基材11上塗佈包含聚乙烯醇系樹脂(以下稱為「PVA系樹脂」)之塗佈液，並使其乾燥，藉此形成PVA系樹脂層12。 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a partial cross-sectional view showing a laminate of a preferred embodiment of the present invention. The laminated body 10 has a polyester resin base material 11 and a polyvinyl alcohol-based resin layer 12. The laminated body 10 is produced by forming the polyvinyl alcohol-based resin layer 12 on a long polyester resin substrate. As a method of forming the polyvinyl alcohol-based resin layer 12, any suitable method can be employed. Preferably, a coating liquid containing a polyvinyl alcohol-based resin (hereinafter referred to as "PVA-based resin") is applied onto the polyester-based resin substrate 11 and dried to form a PVA-based resin layer 12.
上述聚酯系樹脂基材之延伸前之厚度較佳為20μm~300μm，更佳為50μm~200μm。若未達20μm，則有PVA系樹脂層之形成變得困難之虞。若超過300μm，則有延伸時需要過大負荷之虞。 The thickness of the polyester resin substrate before stretching is preferably from 20 μm to 300 μm, more preferably from 50 μm to 200 μm. If it is less than 20 μm, the formation of the PVA-based resin layer becomes difficult. If it exceeds 300 μm, there is a need for an excessive load when it is extended.
作為聚酯系樹脂基材之形成材料，可較佳地使用非晶質之(未結晶化之)聚對苯二甲酸乙二酯系樹脂。其中，可尤佳地使用非晶性之(難以結晶化之)聚對苯二甲酸乙二酯系樹脂。作為非晶性之聚對苯二甲酸乙二酯系樹脂之具體例，可列舉進而包含間苯二甲酸作為二羧酸之共聚物、或進而包含環己烷二甲醇作為二醇之共聚物。 As the material for forming the polyester resin substrate, an amorphous (uncrystallized) polyethylene terephthalate resin can be preferably used. Among them, an amorphous (hard to crystallize) polyethylene terephthalate resin can be preferably used. Specific examples of the amorphous polyethylene terephthalate resin include a copolymer containing isophthalic acid as a dicarboxylic acid or a copolymer containing cyclohexanedimethanol as a diol.
聚酯系樹脂基材之玻璃轉移溫度(Tg)較佳為170℃以下，更佳為120℃以下，進而較佳為80℃以下。另一方面，聚酯系樹脂基材之玻璃轉移溫度較佳為60℃以上。再者，玻璃轉移溫度(Tg)係依據JIS K 7121而求出之值。 The glass transition temperature (Tg) of the polyester resin substrate is preferably 170 ° C or lower, more preferably 120 ° C or lower, and still more preferably 80 ° C or lower. On the other hand, the glass transition temperature of the polyester resin substrate is preferably 60 ° C or higher. Further, the glass transition temperature (Tg) is a value obtained in accordance with JIS K 7121.
聚酯系樹脂基材亦可預先(形成PVA系樹脂層之前)經延伸。於一實施形態中，於長條狀之聚酯系樹脂基材之橫向延伸。橫向較佳為與下述積層體之延伸方向正交之方向。再者，於本說明書中，所謂「正交」，亦包含實質上正交之情況。此處，所謂「實質上正交」，包含90°±5.0°之情況，較佳為90°±3.0°，進而較佳為90°±1.0°。 The polyester resin substrate may be extended in advance (before the PVA-based resin layer is formed). In one embodiment, it extends in the lateral direction of the elongated polyester resin substrate. The transverse direction is preferably a direction orthogonal to the extending direction of the laminated body described below. In addition, in this specification, "orthogonal" also includes the case where it is substantially orthogonal. Here, the term "substantially orthogonal" includes 90° ± 5.0°, preferably 90° ± 3.0°, and further preferably 90° ± 1.0°.
聚酯系樹脂基材之延伸溫度係相對於玻璃轉移溫度(Tg)較佳為Tg-10℃~Tg+50℃。聚酯系樹脂基材之延伸倍率較佳為1.5倍~3.0倍。 The elongation temperature of the polyester resin substrate is preferably from Tg to 10 ° C to Tg + 50 ° C with respect to the glass transition temperature (Tg). The stretch ratio of the polyester resin substrate is preferably from 1.5 times to 3.0 times.
作為聚酯系樹脂基材之延伸方法，可採用任意適合之方法。具體而言，可為固定端延伸，亦可為自由端延伸。延伸方式可為乾式，亦可為濕式。聚酯系樹脂基材之延伸可以一階段進行，亦可以多階段進行。於以多階段進行之情形時，上述之延伸倍率為各階段之延伸倍率之積。 As a method of extending the polyester resin substrate, any suitable method can be employed. Specifically, it may be a fixed end extension or a free end extension. The extension can be dry or wet. The extension of the polyester resin substrate can be carried out in one stage or in multiple stages. In the case of performing in multiple stages, the above-described stretching ratio is the product of the stretching ratio of each stage.
作為形成上述PVA系樹脂層之PVA系樹脂，可採用任意適合之樹脂。例如，可列舉聚乙烯醇、乙烯-乙烯醇共聚物。聚乙烯醇係藉由使聚乙酸乙烯酯皂化而獲得。乙烯-乙烯醇共聚物係藉由使乙烯-乙酸乙烯酯共聚物皂化而獲得。PVA系樹脂之皂化度通常為85莫耳%~100 莫耳%，較佳為95.0莫耳%~99.95莫耳%，進而較佳為99.0莫耳%~99.93莫耳%。皂化度可依據JIS K 6726-1994求出。藉由使用此種皂化度之PVA系樹脂，可獲得耐久性優異之偏光膜。於皂化度過高之情形時，有凝膠化之虞。 As the PVA-based resin forming the PVA-based resin layer, any suitable resin can be used. For example, polyvinyl alcohol and ethylene-vinyl alcohol copolymer are mentioned. Polyvinyl alcohol is obtained by saponifying polyvinyl acetate. The ethylene-vinyl alcohol copolymer is obtained by saponifying an ethylene-vinyl acetate copolymer. The saponification degree of the PVA resin is usually 85 mol% to 100 Mohr%, preferably 95.0 mol% to 99.95 mol%, and further preferably 99.0 mol% to 99.93 mol%. The degree of saponification can be determined in accordance with JIS K 6726-1994. By using such a saponification degree PVA-based resin, a polarizing film excellent in durability can be obtained. When the degree of saponification is too high, there is a gelation.
PVA系樹脂之平均聚合度可根據目的適當地選擇。平均聚合度通常為1000~10000，較佳為1200~4500，進而較佳為1500~4300。再者，平均聚合度可依據JIS K 6726-1994求出。 The average degree of polymerization of the PVA-based resin can be appropriately selected depending on the purpose. The average degree of polymerization is usually from 1,000 to 10,000, preferably from 1200 to 4,500, and more preferably from 1,500 to 4,300. Further, the average degree of polymerization can be determined in accordance with JIS K 6726-1994.
代表性情況下，上述塗佈液係使上述PVA系樹脂溶解於溶劑中而成之溶液。作為溶劑，例如可列舉：水、二甲基亞碸、二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯啶酮、各種二醇類、三羥甲基丙烷等多元醇類、乙二胺、二伸乙基三胺等胺類。該等可單獨或組合兩種以上而使用。該等之中，較佳為水。溶液之PVA系樹脂濃度係相對於溶劑100重量份較佳為3重量份~20重量份。若為此種樹脂濃度，則可形成與聚酯系樹脂基材密接之均勻塗佈膜。 In a representative case, the coating liquid is a solution obtained by dissolving the PVA-based resin in a solvent. Examples of the solvent include polyols such as water, dimethyl hydrazine, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, various glycols, and trimethylolpropane. Amines such as ethylenediamine and diethylenetriamine. These may be used alone or in combination of two or more. Among these, water is preferred. The PVA resin concentration of the solution is preferably from 3 parts by weight to 20 parts by weight based on 100 parts by weight of the solvent. When it is such a resin concentration, the uniform coating film which adheres to a polyester-type resin base material can be formed.
亦可於塗佈液中調配添加劑。作為添加劑，例如可列舉塑化劑、界面活性劑等。作為塑化劑，例如可列舉乙二醇或甘油等多元醇。作為界面活性劑，例如可列舉非離子界面活性劑。該等可以更進一步提高所獲得之PVA系樹脂層之均勻性或染色性、延伸性為目的而使用。 It is also possible to formulate an additive in the coating liquid. Examples of the additive include a plasticizer, a surfactant, and the like. Examples of the plasticizer include polyhydric alcohols such as ethylene glycol and glycerin. As a surfactant, a nonionic surfactant is mentioned, for example. These can be used for the purpose of further improving the uniformity, dyeability, and extensibility of the obtained PVA-based resin layer.
作為塗佈液之塗佈方法，可採用任意適合之方法。例如可列舉：輥式塗佈法、旋轉塗佈法、線棒塗佈法、浸漬塗佈法、模具塗佈法、淋幕式塗佈法、噴塗法、刮塗法(刮刀式塗佈法等)等。 As a coating method of a coating liquid, any suitable method can be employ|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, and a knife coating method (blade coating method) and many more.
上述塗佈液之乾燥溫度較佳為50℃以上。 The drying temperature of the coating liquid is preferably 50 ° C or higher.
PVA系樹脂層之延伸前之厚度較佳為3μm~20μm。 The thickness of the PVA-based resin layer before stretching is preferably from 3 μm to 20 μm.
於形成PVA系樹脂層之前，可對聚酯系樹脂基材實施表面處理(例如電暈處理等)，亦可於聚酯系樹脂基材上形成易接著層。藉由進 行此種處理，可提高聚酯系樹脂基材與PVA系樹脂層之密接性。 Before the formation of the PVA-based resin layer, the polyester-based resin substrate may be subjected to a surface treatment (for example, corona treatment or the like), or an easy-adhesion layer may be formed on the polyester-based resin substrate. By entering By such a treatment, the adhesion between the polyester resin substrate and the PVA resin layer can be improved.
雖未圖示，但亦可於聚酯系樹脂基材11之未形成PVA系樹脂層12之側形成任意適合之功能層。於較佳之實施形態中，功能層具有耐熱性。藉由具有耐熱性，例如於對積層體施加聚酯系樹脂基材之玻璃轉移溫度以上之溫度之情形時，亦可防止積層體(樹脂基材)貼附於用於製造之輥，而實現優異之耐黏連性。 Although not shown, any suitable functional layer may be formed on the side of the polyester resin substrate 11 where the PVA-based resin layer 12 is not formed. In a preferred embodiment, the functional layer has heat resistance. When heat resistance is applied, for example, when a temperature higher than the glass transition temperature of the polyester resin substrate is applied to the laminate, the laminate (resin substrate) can be prevented from being attached to the roll for production. Excellent resistance to blocking.
上述功能層例如為包含導電性材料及黏合劑樹脂之防靜電層。根據此種構成，可實現優異之耐黏連性，並提高製造效率。又，可使防靜電性優異。 The functional layer is, for example, an antistatic layer containing a conductive material and a binder resin. According to this configuration, excellent blocking resistance can be achieved and manufacturing efficiency can be improved. Moreover, it is excellent in antistatic property.
作為上述導電性材料，可使用任意適合之導電性材料。較佳為使用導電性聚合物。作為導電性聚合物，例如可列舉：聚噻吩系聚合物、聚乙炔系聚合物、聚二乙炔系聚合物、多炔系聚合物、聚苯系聚合物、聚萘系聚合物、聚茀系聚合物、聚蒽系聚合物、聚芘系聚合物、聚薁系聚合物、聚吡咯系聚合物、聚呋喃系聚合物、聚硒吩系聚合物、聚異苯并噻吩系聚合物、聚二唑系聚合物、聚苯胺系聚合物、聚噻唑系聚合物、聚苯乙炔系聚合物、聚伸噻吩基乙烯系聚合物、多并苯系聚合物、聚菲系聚合物、聚周萘系聚合物等。該等係單獨或組合2種以上而使用。較佳為使用聚噻吩系聚合物。其中，使用可溶解或分散於水性溶劑中之聚噻吩系聚合物。 As the above conductive material, any suitable conductive material can be used. It is preferred to use a conductive polymer. Examples of the conductive polymer include a polythiophene polymer, a polyacetylene polymer, a polydiacetylene polymer, a polyacetylene polymer, a polyphenyl polymer, a polynaphthalene polymer, and a polyfluorene system. Polymer, polyfluorene polymer, polyfluorene polymer, polyfluorene polymer, polypyrrole polymer, polyfuran polymer, poly selenene polymer, polyisobenzothiophene polymer, poly Diazole polymer, polyaniline polymer, polythiazole polymer, polyphenylacetylene polymer, polythiophene vinyl polymer, polyacene polymer, polyphenanthrene polymer, polyhedral naphthalene It is a polymer or the like. These are used alone or in combination of two or more. It is preferred to use a polythiophene-based polymer. Among them, a polythiophene-based polymer which can be dissolved or dispersed in an aqueous solvent is used.
作為構成上述聚噻吩系聚合物之噻吩，例如可列舉聚乙二氧基噻吩等。 Examples of the thiophene constituting the polythiophene-based polymer include polyethylenedioxythiophene and the like.
防靜電層中之導電性材料之含量較佳為1重量%~10重量%，更佳為3重量%~8重量%。又，導電性材料之含量係相對於下述黏合劑樹脂100重量份較佳為1重量份~50重量份，進而較佳為2重量份~20重量份。 The content of the conductive material in the antistatic layer is preferably from 1% by weight to 10% by weight, more preferably from 3% by weight to 8% by weight. Further, the content of the conductive material is preferably from 1 part by weight to 50 parts by weight, more preferably from 2 parts by weight to 20 parts by weight, per 100 parts by weight of the binder resin.
作為上述黏合劑樹脂，可使用任意適合之樹脂。較佳為使用兼 具與上述樹脂基材之密接性與柔軟性、且可溶解或分散於水性溶劑中之樹脂。作為黏合劑樹脂之具體例，可列舉：(甲基)丙烯酸系樹脂、聚胺基甲酸酯系樹脂、聚酯系樹脂(例如聚乳酸系樹脂)、酚樹脂、聚乙烯醇樹脂、乙烯-乙酸乙烯酯樹脂、環氧樹脂、矽樹脂、氰基丙烯酸樹脂、聚醯胺系樹脂(例如尼龍)等。較佳為使用聚胺基甲酸酯系樹脂。黏合劑樹脂較佳為具有羧基。藉由具有羧基，可獲得與樹脂基材之密接性優異之防靜電層。 As the above binder resin, any suitable resin can be used. Better to use A resin having adhesion to the resin substrate and flexibility, and soluble or dispersible in an aqueous solvent. Specific examples of the binder resin include a (meth)acrylic resin, a polyurethane resin, a polyester resin (for example, a polylactic acid resin), a phenol resin, a polyvinyl alcohol resin, and ethylene. Vinyl acetate resin, epoxy resin, enamel resin, cyanoacrylate resin, polyamine resin (for example, nylon), and the like. It is preferred to use a polyurethane resin. The binder resin preferably has a carboxyl group. By having a carboxyl group, an antistatic layer excellent in adhesion to a resin substrate can be obtained.
防靜電層中之黏合劑樹脂之含量較佳為50重量%~99重量%，更佳為70重量%~95重量%。 The content of the binder resin in the antistatic layer is preferably from 50% by weight to 99% by weight, more preferably from 70% by weight to 95% by weight.
代表性情況下，防靜電層係藉由在上述樹脂基材上塗佈包含上述導電性材料及黏合劑樹脂之樹脂組合物並使其乾燥而設置。樹脂組合物較佳為水性。 In a representative case, the antistatic layer is provided by applying a resin composition containing the conductive material and the binder resin to the resin substrate and drying the resin composition. The resin composition is preferably aqueous.
上述樹脂組合物較佳為包含交聯劑。藉由進行交聯，可對所獲得之防靜電層賦予耐水性。其結果為，例如可良好地進行下述之水中延伸。該交聯劑可採用任意適合之交聯劑。例如，作為交聯劑，可較佳地使用具有可與羧基反應之基之聚合物。作為可與羧基反應之基，例如可列舉有機胺基、唑啉基、環氧基、碳二醯亞胺基等。較佳為交聯劑具有唑啉基。 The above resin composition preferably contains a crosslinking agent. Water resistance can be imparted to the obtained antistatic layer by crosslinking. As a result, for example, the following water extension can be favorably performed. The crosslinking agent can be any suitable crosslinking agent. For example, as the crosslinking agent, a polymer having a group reactive with a carboxyl group can be preferably used. Examples of the group reactive with a carboxyl group include an organic amine group. An oxazoline group, an epoxy group, a carbodiimide group or the like. Preferably, the crosslinking agent has Oxazolinyl.
作為上述聚合物，例如可列舉丙烯酸系聚合物、苯乙烯-丙烯酸系聚合物等。較佳為丙烯酸系聚合物。藉由使用丙烯酸系聚合物，可穩定地與水性之樹脂組合物相溶。 Examples of the polymer include an acrylic polymer, a styrene-acrylic polymer, and the like. An acrylic polymer is preferred. By using an acrylic polymer, it can be stably compatible with an aqueous resin composition.
如上所述，樹脂組合物較佳為水性。樹脂組合物中之黏合劑樹脂之濃度較佳為1.5重量%~15重量%，進而較佳為2重量%~10重量%。樹脂組合物之交聯劑(固形物成分)之含量係相對於黏合劑樹脂(固形物成分)100重量份較佳為1重量份~30重量份，進而較佳為3重量份~20重量份。 As described above, the resin composition is preferably aqueous. The concentration of the binder resin in the resin composition is preferably from 1.5% by weight to 15% by weight, and more preferably from 2% by weight to 10% by weight. The content of the crosslinking agent (solid content component) of the resin composition is preferably from 1 part by weight to 30 parts by weight, more preferably from 3 parts by weight to 20 parts by weight, per 100 parts by weight of the binder resin (solid content). .
作為樹脂組合物之塗佈方法，可採用任意適合之方法。例如採用與上述塗佈液之塗佈方法相同之方法。作為乾燥溫度，較佳為50℃以上，進而較佳為60℃以上。另一方面，乾燥溫度較佳為樹脂基材之玻璃轉移溫度(Tg)+30℃以下，進而較佳為Tg以下。 As the coating method of the resin composition, any suitable method can be employed. For example, the same method as the coating method of the above coating liquid is employed. The drying temperature is preferably 50 ° C or higher, and more preferably 60 ° C or higher. On the other hand, the drying temperature is preferably a glass transition temperature (Tg) of the resin substrate + 30 ° C or less, and more preferably Tg or less.
防靜電層之厚度較佳為0.1μm~10μm，進而較佳為0.2μm~2μm。 The thickness of the antistatic layer is preferably from 0.1 μm to 10 μm, more preferably from 0.2 μm to 2 μm.
防靜電層之表面電阻值較佳為未達10×1013Ω/□，更佳為未達10×1011Ω/□，進而較佳為未達10×1010Ω/□。 The surface resistivity of the antistatic layer is preferably less than 10 × 10 13 Ω / □, more preferably less than 10 × 10 11 Ω / □, and still more preferably less than 10 × 10 10 Ω / □.
防靜電層較佳為實施延伸處理。藉由延伸處理，可於防靜電層形成由裂縫形成之凹凸形狀。其結果為，可賦予滑動性，實現更優異之耐黏連性。該延伸處理較佳為於在樹脂基材上形成PVA系樹脂層之前進行(與上述聚酯系樹脂基材之延伸一併)。 The antistatic layer is preferably subjected to an extension process. By the stretching treatment, the uneven shape formed by the crack can be formed in the antistatic layer. As a result, slidability can be imparted, and more excellent blocking resistance can be achieved. This stretching treatment is preferably performed before the formation of the PVA-based resin layer on the resin substrate (together with the extension of the polyester-based resin substrate).
防靜電層之表面之算術平均粗糙度Ra較佳為10nm以上。另一方面，防靜電層之算術平均粗糙度Ra較佳為100nm以下。再者，算術平均粗糙度Ra可依據JIS B0601求出。 The arithmetic mean roughness Ra of the surface of the antistatic layer is preferably 10 nm or more. On the other hand, the arithmetic mean roughness Ra of the antistatic layer is preferably 100 nm or less. Further, the arithmetic mean roughness Ra can be obtained in accordance with JIS B0601.
於上述空中延伸步驟中，將上述積層體一面於其長度方向進行搬送一面藉由輥間之周速差進行延伸。具體而言，藉由輥間之周速差對積層體賦予張力，而於長度方向進行單軸延伸。 In the aerial stretching step, the laminated body is conveyed in the longitudinal direction while extending by the circumferential speed difference between the rolls. Specifically, tension is applied to the laminated body by the circumferential speed difference between the rolls, and uniaxial stretching is performed in the longitudinal direction.
圖2係表示空中延伸步驟之一例之概略圖，(a)係自正面觀察之圖，(b)係自上方觀察之圖。於圖示例中，於積層體之搬送方向(MD)空出特定間隔設置輥對1、1及輥對2、2，藉由各個輥對夾持積層體10。輥1與輥2以不同周速旋轉，下游側之輥2設定為周速大於上游側之輥1。 Fig. 2 is a schematic view showing an example of an air extending step, (a) is a view from the front, and (b) is a view from above. In the example of the drawing, the roller pair 1, 1 and the roller pair 2, 2 are provided at a predetermined interval in the conveyance direction (MD) of the laminated body, and the laminated body 10 is held by each roller pair. The roller 1 and the roller 2 are rotated at different peripheral speeds, and the roller 2 on the downstream side is set to be a roller 1 having a circumferential speed greater than that of the upstream side.
作為加熱至延伸溫度之方法，可採用任意適合之方法。於圖示例中，於輥1與輥2之間設置有烘箱9。延伸溫度為100℃以下，較佳為 95℃以下。另一方面，空中延伸之延伸溫度較佳為70℃以上。再者，空中延伸步驟之延伸溫度(積層體之溫度)例如可使用溫度測定用貼紙或熱電偶進行確認。 As a method of heating to the stretching temperature, any suitable method can be employed. In the illustrated example, an oven 9 is disposed between the roller 1 and the roller 2. The extension temperature is 100 ° C or less, preferably Below 95 °C. On the other hand, the extension temperature of the air extension is preferably 70 ° C or more. Further, the extension temperature (temperature of the laminate) in the air extension step can be confirmed, for example, using a sticker for temperature measurement or a thermocouple.
輥1及輥2係以延伸間距L1與積層體之寬度(即將進行空中延伸前之)W滿足L1/W≧0.3之關係之方式設置，較佳為滿足0.4≦L1/W≦2.0之關係。藉由滿足此種關係，可選擇自由端延伸。自由端延伸通常意指僅於一方向進行延伸之延伸方法。將若對積層體於某一方向進行延伸則積層體可於相對於該延伸方向大致垂直之方向收縮但並未抑制該收縮而進行延伸的方法稱為自由端延伸。再者，於本說明書中，所謂「延伸間距」，係指藉由輥間之周速差附加張力之距離。又，亦為加熱至上述特定延伸溫度之距離。例如，於圖示例中，烘箱9於搬送方向之長度相當於延伸間距L1。 The roller 1 and the roller 2 are disposed such that the extending distance L 1 and the width of the laminated body (before the air is extended) W satisfy the relationship of L 1 / W ≧ 0.3, preferably satisfying 0.4 ≦ L 1 / W ≦ 2.0 Relationship. By satisfying this relationship, free end extension can be selected. Free end extension generally means an extension method that extends only in one direction. A method in which the laminate is stretched in a certain direction so that the laminate can be contracted in a direction substantially perpendicular to the extending direction but does not inhibit the shrinkage is referred to as a free end extension. In the present specification, the term "extended pitch" means the distance by which the tension is added by the circumferential speed difference between the rolls. Also, it is a distance heated to the above specific extension temperature. For example, in the illustrated example, the length of the oven 9 in the transport direction corresponds to the extension pitch L 1 .
代表性情況下，積層體之寬度W為500mm~6000mm，較佳為1000mm~5000mm。 In a representative case, the width W of the laminated body is 500 mm to 6000 mm, preferably 1000 mm to 5000 mm.
空中延伸之延伸倍率係相對於積層體之原長度較佳為1.4倍以上，更佳為1.5倍以上。另一方面，空中延伸之延伸倍率較佳為2.2倍以下，更佳為2.0倍以下。 The stretching ratio in the air extension is preferably 1.4 times or more, more preferably 1.5 times or more, relative to the original length of the laminated body. On the other hand, the stretching ratio in the air extension is preferably 2.2 times or less, more preferably 2.0 times or less.
藉由在上述溫度下進行自由端延伸，可抑制收縮並且提高PVA系樹脂之配向性。藉由提高PVA系樹脂之配向性，於下述之硼酸水中延伸後亦可提高PVA系樹脂之配向性。具體而言，推定：預先利用本步驟提高PVA系樹脂之配向性，藉此於硼酸水中延伸時PVA系樹脂變得容易與硼酸交聯，於硼酸成為結節點之狀態下進行延伸，藉此硼酸水中延伸後PVA系樹脂之配向性亦變高。其結果為，可製作具有優異光學特性之偏光膜。 By performing the free end extension at the above temperature, shrinkage can be suppressed and the alignment of the PVA-based resin can be improved. By improving the alignment of the PVA-based resin, the orientation of the PVA-based resin can be improved by stretching in the following boric acid water. Specifically, it is estimated that the PVA-based resin is easily crosslinked with boric acid when it is extended in boric acid water, and is extended in a state where boric acid is a node, whereby boric acid is used. The orientation of the PVA-based resin after the water is extended also becomes high. As a result, a polarizing film having excellent optical characteristics can be produced.
於加熱步驟中，將上述經空中延伸之積層體加熱至110℃以上。 加熱溫度較佳為120℃以上。另一方面，加熱溫度較佳為160℃以下。藉由在此種溫度下對經空中延伸之積層體進行加熱，可提高PVA系樹脂之結晶性。藉由提高結晶性，於下述之水中延伸中可防止PVA系樹脂層溶解於水中而配向性降低。其結果為，可製作具有優異光學特性之偏光膜。 In the heating step, the above-mentioned airborne laminate is heated to 110 ° C or higher. The heating temperature is preferably 120 ° C or higher. On the other hand, the heating temperature is preferably 160 ° C or lower. The crystallinity of the PVA-based resin can be improved by heating the laminate extending in the air at such a temperature. By increasing the crystallinity, it is possible to prevent the PVA-based resin layer from being dissolved in water and to lower the alignment property in the following water extension. As a result, a polarizing film having excellent optical characteristics can be produced.
作為加熱至上述加熱溫度之方法，可採用任意適合之方法。具體而言，加熱例如可於加熱環境下搬送積層體而進行(熱風乾燥方式)，亦可對搬送輥進行加熱(使用所謂熱輥)而進行(熱輥乾燥方式)，亦可併用該等。較佳為使用熱輥對積層體進行加熱。藉由使用熱輥，可抑制由熱所引起之積層體之收縮。 As a method of heating to the above heating temperature, any suitable method can be employed. Specifically, the heating can be carried out, for example, by transporting the layered body in a heated environment (hot air drying method), or by heating the conveying roller (using a so-called hot roll) (hot roll drying method), or in combination. It is preferred to heat the laminate using a heat roller. By using a heat roller, shrinkage of the laminate due to heat can be suppressed.
圖3係表示加熱步驟之一例之概略圖，(a)係自正面觀察之圖，(b)係自上方觀察之圖。於圖示例中，溫度可控之第1輥3、第2輥4及第3輥5係沿著搬送方向空出特定間隔而設置。該等輥之表面例如以防止積層體貼附為目的而實施有表面處理(例如鍍敷處理)。於圖示例中，積層體10係其一面(例如PVA系樹脂層側)與第1輥3及第3輥5接觸、另一面(例如基材側)與第2輥4接觸而搬送。上游側之第1輥3及第2輥4被加熱至上述加熱溫度而成為熱輥，積層體10自上側、下側均被加熱。第3輥5可設定為任意適合之溫度，例如設定為積層體之玻璃轉移溫度(Tg)以下，而冷卻積層體。藉由如此進行冷卻，可抑制於積層體產生皺褶(例如成為鍍鋅鐵皮狀地形成有表面波紋之狀態)。冷卻輥之溫度例如為30℃~60℃。再者，於圖示例中，使用3根輥，但所使用之輥之數量、熱輥之數量或配置等各種條件當然可適當進行變更。 Fig. 3 is a schematic view showing an example of a heating step, (a) is a view from the front, and (b) is a view from above. In the example of the drawing, the temperature-controllable first roll 3, second roll 4, and third roll 5 are provided at a predetermined interval along the conveyance direction. The surface of the rolls is subjected to a surface treatment (for example, a plating treatment) for the purpose of preventing adhesion of the laminate. In the example of the drawing, the laminated body 10 is brought into contact with the first roller 3 and the third roller 5 on one surface (for example, the PVA-based resin layer side), and the other surface (for example, the substrate side) is brought into contact with the second roller 4 and transported. The first roller 3 and the second roller 4 on the upstream side are heated to the above-described heating temperature to become a heat roller, and the laminated body 10 is heated from both the upper side and the lower side. The third roller 5 can be set to any suitable temperature, for example, set to a glass transition temperature (Tg) or lower of the laminate, and the laminate can be cooled. By cooling in this manner, wrinkles can be suppressed from occurring in the laminated body (for example, a state in which surface corrugations are formed in a galvanized iron sheet shape). The temperature of the cooling roll is, for example, 30 ° C to 60 ° C. Further, in the illustrated example, three rolls are used, but various conditions such as the number of rolls to be used, the number or arrangement of the heat rolls, and the like can be appropriately changed.
於一實施形態中，於加熱步驟中於長度方向延伸積層體。代表性情況下，將積層體一面於其長度方向進行搬送一面藉由輥間之周速差進行延伸。於圖3所示之例中，藉由經加熱之第1輥3與第2輥4對積層體進行延伸。具體而言，第1輥3與第2輥4以不同周速旋轉，下游側 之第2輥4設定為周速大於上游側之第1輥3。 In one embodiment, the laminate is elongated in the longitudinal direction during the heating step. In a typical case, the laminated body is conveyed in the longitudinal direction while extending by the circumferential speed difference between the rolls. In the example shown in FIG. 3, the laminated body is extended by the heated first roll 3 and the second roll 4. Specifically, the first roller 3 and the second roller 4 rotate at different peripheral speeds, and the downstream side The second roller 4 is set to be the first roller 3 whose peripheral speed is larger than the upstream side.
加熱步驟中之延伸較佳為實質上為固定端單軸延伸。具體而言，較佳為一面抑制積層體向相對於延伸方向大致垂直之方向之收縮一面進行延伸。於加熱步驟中，藉由進行固定端單軸延伸，可有助於寬度殘留率之提高。又，例如，可防止寬度方向端部與寬度方向中央部相比因收縮而厚度變厚等不良情況，而使厚度於寬度方向上均勻。於上述圖示例中，例如第1輥3及第2輥4係以其延伸間距L2與即將進行該延伸前之積層體10之寬度W'滿足L2/W'≦0.12之關係之方式設置，較佳為滿足L2/W≦0.06之關係。藉由滿足此種關係，可實現固定端單軸延伸。延伸間距L2係指離開第1輥3直至與第2輥4接觸之距離。再者，於該延伸，於遠離第1輥及第2輥時，積層體實質上亦可保持為上述加熱溫度。 The extension in the heating step is preferably substantially uniaxially extending at the fixed end. Specifically, it is preferable to extend while suppressing the contraction of the laminated body in a direction substantially perpendicular to the extending direction. In the heating step, the uniaxial stretching of the fixed end can contribute to an increase in the residual ratio of the width. Further, for example, it is possible to prevent the thickness direction end portion from being thicker than the center portion in the width direction due to shrinkage, and to make the thickness uniform in the width direction. In the above-described example, for example, the first roller 3 and the second roller 4 have a relationship between the extending distance L 2 and the width W′ of the laminated body 10 immediately before the extension satisfying the relationship of L 2 /W′ ≦ 0.12. The setting preferably satisfies the relationship of L 2 / W ≦ 0.06. By satisfying this relationship, the fixed end uniaxial extension can be achieved. The extension pitch L 2 is a distance from the first roller 3 to the second roller 4 . Further, in the extension, when the first roller and the second roller are separated from each other, the laminated body can be substantially maintained at the heating temperature.
加熱步驟中之延伸之延伸倍率較佳為超過1.0倍且為1.4倍以下。 The stretching ratio in the elongation in the heating step is preferably more than 1.0 times and 1.4 times or less.
本發明之延伸積層體較佳為相對於積層體之原長度經延伸至1.5倍~2.5倍，更佳為1.7倍~2.3倍。該延伸倍率於在加熱步驟中進行延伸之情形時，相當於空中延伸步驟之延伸倍率與加熱步驟之延伸倍率之積，於在加熱步驟中不進行延伸之情形時，相當於空中延伸步驟之延伸倍率。藉由使用由本發明獲得之延伸積層體，例如較僅利用下述之水中延伸對上述積層體進行延伸，最終可達成更高之延伸倍率。具體而言，延伸積層體之聚酯系樹脂基材係一面抑制配向一面進行延伸。配向性越高，延伸張力變得越大，穩定之延伸變得越困難，或樹脂基材斷裂，藉由抑制配向，最終可達成更高之延伸倍率。其結果為，可製作具有優異光學特性(例如偏光度)之偏光膜。 The extended laminate of the present invention preferably extends from 1.5 to 2.5 times, more preferably from 1.7 to 2.3 times, relative to the original length of the laminate. When the stretching ratio is extended in the heating step, it corresponds to the product of the stretching ratio of the air extending step and the stretching ratio of the heating step, and is equivalent to the extension of the air extending step when the stretching step is not performed in the heating step. Magnification. By using the extended laminate obtained by the present invention, for example, the laminate can be extended by using only the water extension described below, and finally a higher stretch ratio can be achieved. Specifically, the polyester-based resin substrate on which the laminate is stretched is stretched while suppressing the alignment. The higher the orientation, the larger the extension tension becomes, the more difficult the stable extension becomes, or the breakage of the resin substrate, and by suppressing the alignment, a higher stretching ratio can be finally achieved. As a result, a polarizing film having excellent optical characteristics (for example, a degree of polarization) can be produced.
代表性情況下，本發明之延伸積層體係供於偏光膜之製造。具 體而言，本發明之延伸積層體適當地實施用以將其PVA系樹脂層製成偏光膜之處理。作為用以製成偏光膜之處理，例如可列舉：延伸處理、染色處理、不溶化處理、交聯處理、清洗處理、乾燥處理等。再者，該等處理之次數、順序等並無特別限定。 Representatively, the extended laminate system of the present invention is used in the manufacture of a polarizing film. With In the body, the extended laminate of the present invention is suitably subjected to a treatment for forming a PVA-based resin layer into a polarizing film. Examples of the treatment for forming the polarizing film include elongation treatment, dyeing treatment, insolubilization treatment, crosslinking treatment, washing treatment, and drying treatment. Further, the number, order, and the like of the processes are not particularly limited.
於較佳之實施形態中，對上述延伸積層體進行水中延伸(硼酸水中延伸)。具體而言，於與上述積層體之延伸方向平行之方向進行水中延伸。藉由水中延伸，可於低於上述樹脂基材或PVA系樹脂層之玻璃轉移溫度(代表性情況下為80℃左右)之溫度下進行延伸，對PVA系樹脂層可抑制其結晶化並且高倍率地進行延伸。其結果為，可製作具有優異光學特性(例如偏光度)之偏光膜。再者，於本說明書中，所謂「平行之方向」，包含0°±5.0°之情況，較佳為0°±3.0°，進而較佳為0°±1.0°。 In a preferred embodiment, the extended laminate is subjected to water extension (boric acid water extension). Specifically, the water is extended in a direction parallel to the extending direction of the laminated body. By extending in water, it can be extended at a temperature lower than the glass transition temperature (typically about 80 ° C) of the resin substrate or the PVA-based resin layer, and the PVA-based resin layer can be prevented from being crystallized and high. Extend in multiples. As a result, a polarizing film having excellent optical characteristics (for example, a degree of polarization) can be produced. Further, in the present specification, the "parallel direction" includes 0 ° ± 5.0 °, preferably 0 ° ± 3.0 °, and more preferably 0 ° ± 1.0 °.
延伸積層體之延伸方法可採用任意適合之方法。具體而言，可為固定端延伸，亦可為自由端延伸。延伸積層體之延伸方向實質上為上述空中延伸之延伸方向(長度方向)。延伸積層體之延伸可以一階段進行，亦可以多階段進行。 The method of extending the extended laminate may employ any suitable method. Specifically, it may be a fixed end extension or a free end extension. The extending direction of the extended laminated body is substantially the extending direction (longitudinal direction) of the above-described aerial extension. The extension of the extended laminate can be carried out in one stage or in multiple stages.
水中延伸較佳為將延伸積層體浸漬於硼酸水溶液中而進行(硼酸水中延伸)。藉由使用硼酸水溶液作為延伸浴，可對PVA系樹脂層賦予承受延伸時之張力之剛性、及不溶解於水中之耐水性。具體而言，硼酸於水溶液中生成四羥基硼酸根陰離子，可與PVA系樹脂藉由氫鍵而交聯。其結果為，對PVA系樹脂層賦予剛性及耐水性而可良好地進行延伸，並可製作具有優異光學特性(例如偏光度)之偏光膜。 The water extension is preferably carried out by immersing the extended laminate in an aqueous boric acid solution (extension in boric acid water). By using an aqueous solution of boric acid as an extension bath, the PVA-based resin layer can be imparted with rigidity to withstand tension at the time of stretching and water resistance which is insoluble in water. Specifically, boric acid forms a tetrahydroxyborate anion in an aqueous solution, and can be crosslinked with a PVA-based resin by hydrogen bonding. As a result, rigidity and water resistance are imparted to the PVA-based resin layer, and elongation can be favorably performed, and a polarizing film having excellent optical characteristics (for example, polarization degree) can be produced.
上述硼酸水溶液較佳為藉由使硼酸及/或硼酸鹽溶解於作為溶劑之水中而獲得。硼酸濃度係相對於水100重量份較佳為1重量份~10重量份。藉由將硼酸濃度設為1重量份以上，可有效地抑制PVA系樹脂 層之溶解，並可製作更高特性之偏光膜。再者，除硼酸或硼酸鹽以外，亦可使用將硼砂等硼化合物、乙二醛、戊二醛等溶解於溶劑中而獲得之水溶液。 The boric acid aqueous solution is preferably obtained by dissolving boric acid and/or borate in water as a solvent. The boric acid concentration is preferably from 1 part by weight to 10 parts by weight per 100 parts by weight of water. By setting the boric acid concentration to 1 part by weight or more, the PVA resin can be effectively suppressed. The layer is dissolved and a polarizing film of higher characteristics can be produced. Further, in addition to boric acid or borate, an aqueous solution obtained by dissolving a boron compound such as borax, glyoxal or glutaraldehyde in a solvent may be used.
於藉由下述染色處理而預先使二色性物質(代表性情況下為碘)吸附於PVA系樹脂層之情形時，較佳為於上述延伸浴(硼酸水溶液)中調配碘化物。藉由調配碘化物，可抑制吸附於PVA系樹脂層之碘之溶出。作為碘化物，例如可列舉：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，較佳為碘化鉀。碘化物之濃度係相對於水100重量份較佳為0.05重量份~15重量份，更佳為0.5重量份~8重量份。 In the case where the dichroic substance (typically, iodine) is adsorbed to the PVA-based resin layer in advance by the dyeing treatment described below, it is preferred to formulate the iodide in the extension bath (aqueous boric acid solution). By dissolving the iodide, the elution of iodine adsorbed to 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, cesium iodide, calcium iodide, tin iodide, titanium iodide, and the like. . Among these, potassium iodide is preferred. The concentration of the iodide is preferably from 0.05 part by weight to 15 parts by weight, more preferably from 0.5 part by weight to 8 parts by weight, per 100 parts by weight of the water.
水中延伸之延伸溫度(延伸浴之液溫)較佳為40℃~85℃，更佳為50℃~85℃。若為此種溫度，則可抑制PVA系樹脂層之溶解並且高倍率地進行延伸。具體而言，如上所述，聚酯系樹脂基材之玻璃轉移溫度(Tg)基於與PVA系樹脂層之形成之關係，較佳為60℃以上。於該情形時，若延伸溫度低於40℃，則有即便考慮由水所引起之聚酯系樹脂基材之可塑化亦無法良好地進行延伸之虞。另一方面，有延伸浴之溫度越高PVA系樹脂層之溶解性越高而無法獲得優異光學特性之虞。延伸積層體向延伸浴之浸漬時間較佳為15秒~5分鐘。 The extension temperature in the water extension (liquid temperature of the stretching bath) is preferably from 40 ° C to 85 ° C, more preferably from 50 ° C to 85 ° C. When it is such a temperature, the dissolution of the PVA-based resin layer can be suppressed and the stretching can be performed at a high rate. Specifically, as described above, the glass transition temperature (Tg) of the polyester resin substrate is preferably 60° C. or more based on the relationship with the formation of the PVA resin layer. In this case, when the elongation temperature is lower than 40° C., even if the plasticization of the polyester resin substrate due to water is considered, the elongation cannot be favorably performed. On the other hand, the higher the temperature of the extension bath, the higher the solubility of the PVA-based resin layer, and the inability to obtain excellent optical characteristics. The immersion time of the extended laminate to the extension bath is preferably from 15 seconds to 5 minutes.
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，可高倍率地進行延伸，可製作具有優異光學特性(例如偏光度)之偏光膜。具體而言，最大延伸倍率係相對於上述積層體之原長度(包含延伸積層體之延伸倍率)較佳為5.0倍以上，更佳為5.5倍以上，進而較佳為6.0倍以上。於本說明書中，所謂「最大延伸倍率」，係指延伸積層體即將斷裂前之延伸倍率，另外，係指確認延伸積層體斷裂之延伸倍率而較該值低0.2之值。再者，使用上述聚酯系樹脂基材之積層體之最大延伸倍率係經過水中延伸時可變得高於僅利用空中延伸進行延 伸。 By combining the above-mentioned polyester-based resin substrate with water extension (boric acid water extension), it is possible to carry out stretching at a high magnification, and it is possible to produce a polarizing film having excellent optical characteristics (for example, a degree of polarization). 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 laminated body (including the stretching ratio of the extended laminated body). In the present specification, the "maximum stretching ratio" refers to the stretching ratio immediately before the elongation of the laminated layer body, and the value of the stretching ratio of the fracture of the extended laminated body is determined to be 0.2 lower than the value. Further, the maximum stretching ratio of the laminate using the above-mentioned polyester-based resin substrate can be made higher than that extending only by air extension when extended in water. Stretch.
代表性情況下，上述染色處理係利用二色性物質對PVA系樹脂層進行染色之處理。較佳為藉由使二色性物質吸附於PVA系樹脂層而進行。作為該吸附方法，例如可列舉如下方法：將PVA系樹脂層(延伸積層體)浸漬於包含二色性物質之染色液中之方法；於PVA系樹脂層塗佈該染色液之方法；將該染色液噴霧於PVA系樹脂層之方法等。較佳為將延伸積層體浸漬於包含二色性物質之染色液中之方法。其原因在於二色性物質可良好地吸附。 In a representative case, the dyeing treatment is a treatment of dyeing a PVA-based resin layer with a dichroic material. It is preferably carried out by adsorbing a dichroic substance to the PVA-based resin layer. Examples of the adsorption method include a method of immersing a PVA-based resin layer (extended laminate) in a dyeing liquid containing a dichroic material, and a method of applying the dyeing liquid to a PVA-based resin layer; A method in which a dyeing liquid is sprayed on a PVA-based resin layer or the like. Preferably, the method of immersing the extended laminated body in the dyeing liquid containing the dichroic substance. The reason for this is that the dichroic substance can be adsorbed well.
作為上述二色性物質，例如可列舉碘、二色性染料。較佳為碘。於使用碘作為二色性物質之情形時，上述染色液為碘水溶液。碘之調配量係相對於水100重量份較佳為0.1重量份~0.5重量份。為了提高碘對水之溶解度，較佳為於碘水溶液中調配碘化物。碘化物之具體例如上所述。碘化物之調配量係相對於水100重量份較佳為0.02重量份~20重量份，更佳為0.1重量份~10重量份，進而較佳為0.7重量份~3.5重量份。為了抑制PVA系樹脂之溶解，染色液於染色時之液溫較佳為20℃~50℃。於將PVA系樹脂層浸漬於染色液中之情形時，為了確保PVA系樹脂層之透過率，浸漬時間較佳為5秒~5分鐘。又，染色條件(濃度、液溫、浸漬時間)可以最終獲得之偏光膜之偏光度或者單體透過率成為特定範圍之方式設定。於一實施形態中，以所獲得之偏光膜之偏光度成為99.98%以上之方式設定浸漬時間。於另一實施形態中，以所獲得之偏光膜之單體透過率成為40%~44%之方式設定浸漬時間。 Examples of the dichroic substance include iodine and a dichroic dye. It is preferably iodine. In the case where iodine is used as the dichroic substance, the above dyeing liquid is an aqueous iodine solution. The amount of iodine is preferably 0.1 part by weight to 0.5 part by weight based on 100 parts by weight of water. In order to increase the solubility of iodine in water, it is preferred to formulate an iodide in an aqueous iodine solution. The specificity of the iodide is as described above. The amount of the iodide compound is preferably from 0.02 part by weight to 20 parts by weight, more preferably from 0.1 part by weight to 10 parts by weight, even more preferably from 0.7 part by weight to 3.5 parts by weight, per 100 parts by weight of water. In order to suppress the dissolution of the PVA-based resin, the liquid temperature of the dyeing liquid at the time of dyeing is preferably from 20 ° C to 50 ° C. When the PVA-based resin layer is immersed in the dyeing liquid, the immersion time is preferably from 5 seconds to 5 minutes in order to secure the transmittance of the PVA-based resin layer. Further, the dyeing conditions (concentration, liquid temperature, immersion time) can be set such that the degree of polarization of the polarizing film finally obtained or the monomer transmittance is in a specific range. In one embodiment, the immersion time is set such that the degree of polarization of the obtained polarizing film is 99.98% or more. In another embodiment, the immersion time is set such that the monomer transmittance of the obtained polarizing film is 40% to 44%.
較佳為，染色處理於上述水中延伸之前進行。 Preferably, the dyeing treatment is carried out before the water is extended.
代表性情況下，上述不溶化處理係藉由將PVA系樹脂層浸漬於硼酸水溶液中而進行。藉由實施不溶化處理，可對PVA系樹脂層賦予耐 水性。該硼酸水溶液之濃度係相對於水100重量份較佳為1重量份~4重量份。不溶化浴(硼酸水溶液)之液溫較佳為20℃~50℃。較佳為不溶化處理於上述水中延伸或上述染色處理之前進行。 In a representative case, the insolubilization treatment is carried out by immersing the PVA-based resin layer in an aqueous boric acid solution. The PVA-based resin layer can be rendered resistant by insolubilization treatment. Water-based. The concentration of the aqueous boric acid solution is preferably from 1 part by weight to 4 parts by weight based on 100 parts by weight of water. The liquid temperature of the insolubilizing bath (aqueous boric acid solution) is preferably from 20 ° C to 50 ° C. It is preferred that the insolubilization treatment be carried out before the above water extension or the above dyeing treatment.
代表性情況下，上述交聯處理係藉由將PVA系樹脂層浸漬於硼酸水溶液中而進行。藉由實施交聯處理，可對PVA系樹脂層賦予耐水性。該硼酸水溶液之濃度係相對於水100重量份較佳為1重量份~4重量份。又，於在上述染色處理後進行交聯處理之情形時，較佳為進而調配碘化物。藉由調配碘化物，可抑制吸附於PVA系樹脂層之碘之溶出。碘化物之調配量係相對於水100重量份較佳為1重量份~5重量份。碘化物之具體例如上所述。交聯浴(硼酸水溶液)之液溫較佳為20℃~50℃。較佳為交聯處理於上述水中延伸之前進行。於較佳之實施形態中，依序進行染色處理、交聯處理及水中延伸。 In a representative case, the crosslinking treatment is carried out by immersing the PVA-based resin layer in an aqueous boric acid solution. Water resistance can be imparted to the PVA-based resin layer by performing the crosslinking treatment. The concentration of the aqueous boric acid solution is preferably from 1 part by weight to 4 parts by weight based on 100 parts by weight of water. Further, in the case where the crosslinking treatment is carried out after the above dyeing treatment, it is preferred to further prepare an iodide. By dissolving the iodide, the elution of iodine adsorbed to the PVA-based resin layer can be suppressed. The amount of the iodide compound is preferably from 1 part by weight to 5 parts by weight per 100 parts by weight of the water. The specificity of the iodide is as described above. The liquid temperature of the crosslinking bath (aqueous boric acid solution) is preferably from 20 ° C to 50 ° C. Preferably, the crosslinking treatment is carried out before the water is extended. In a preferred embodiment, the dyeing treatment, the crosslinking treatment, and the water extension are sequentially performed.
代表性情況下，上述清洗處理係藉由將PVA系樹脂層浸漬於碘化鉀水溶液中而進行。上述乾燥處理之乾燥溫度較佳為30℃~100℃。 In a representative case, the cleaning treatment is performed by immersing the PVA-based resin layer in an aqueous solution of potassium iodide. The drying temperature of the above drying treatment is preferably from 30 ° C to 100 ° C.
圖4係表示偏光膜之製造方法之一例之概略圖。自捲出部101捲出延伸積層體10'，藉由輥111及112將其浸漬於硼酸水溶液之浴110中之後(不溶化處理)，藉由輥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)。繼而，藉由輥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)。其後，將延伸積層體10'一面浸漬於硼酸水溶液之浴140中，一面利用速比不同之輥141及142於縱向(長度方向)賦予張力而進行延伸(水中延伸)。藉由輥151及152將經水中延伸之延伸積層體10'浸漬於碘化鉀水溶液之浴150中(清洗處理)，並供於乾燥處理(未圖示)。其後，將延伸積層體10'捲取於捲取部160。 Fig. 4 is a schematic view showing an example of a method of producing a polarizing film. The extended laminated body 10' is taken up from the unwinding portion 101, and after being immersed in the bath 110 of the boric acid aqueous solution by the rolls 111 and 112 (insolubilization treatment), it is immersed in the dichroic substance by the rolls 121 and 122 ( In bath 120 of an aqueous solution of iodine) and potassium iodide (dyeing treatment). Then, it is immersed in the bath 130 of the aqueous solution of boric acid and potassium iodide by the rolls 131 and 132 (crosslinking process). Then, the stretched laminated body 10' is immersed in the bath 140 of the boric acid aqueous solution, and is stretched (water extending) by applying tension in the longitudinal direction (longitudinal direction) by the rolls 141 and 142 having different speed ratios. The extended laminated body 10' extended in water by the rolls 151 and 152 is immersed in the bath 150 of the potassium iodide aqueous solution (cleaning process), and is supplied to the drying process (not shown). Thereafter, the extended laminated body 10' is taken up by the winding portion 160.
如上所述，藉由對本發明之延伸積層體實施上述各處理，而於 上述樹脂基材上形成偏光膜。該偏光膜實質上為二色性物質吸附配向而成之PVA系樹脂膜。偏光膜之厚度較佳為10μm以下，更佳為7μm以下，進而較佳為5μm以下。另一方面，偏光膜之厚度較佳為0.5μm以上，更佳為1.5μm以上。偏光膜較佳為於波長380nm~780nm中之任一波長顯示吸收二色性。偏光膜之單體透過率較佳為40.0%以上，更佳為41.0%以上，進而較佳為42.0%以上。偏光膜之偏光度較佳為99.8%以上，更佳為99.9%以上，進而較佳為99.95%以上。 As described above, by performing the above respective processes on the extended laminated body of the present invention, A polarizing film is formed on the above resin substrate. The polarizing film is substantially a PVA-based resin film in which a dichroic substance is adsorbed and aligned. The thickness of the polarizing film is preferably 10 μm or less, more preferably 7 μm or less, still more preferably 5 μm or less. On the other hand, the thickness of the polarizing film is preferably 0.5 μm or more, and more preferably 1.5 μm or more. The polarizing film preferably exhibits absorption dichroism at any of wavelengths of 380 nm to 780 nm. The monomer transmittance of the polarizing film is preferably 40.0% or more, more preferably 41.0% or more, still more preferably 42.0% or more. The degree of polarization of the polarizing film is preferably 99.8% or more, more preferably 99.9% or more, still more preferably 99.95% or more.
作為上述偏光膜之使用方法，可採用任意適合之方法。具體而言，可於與上述樹脂基材成為一體之狀態下使用，亦可自上述樹脂基材轉印於其他構件而使用。 As a method of using the above polarizing film, any suitable method can be employed. Specifically, it may be used in a state of being integrated with the resin substrate, or may be used by transferring the resin substrate to another member.
本發明之光學積層體具有上述偏光膜。圖5(a)及(b)係本發明之較佳實施形態之光學膜積層體之概略剖面圖。光學膜積層體100依序具有樹脂基材11'、偏光膜12'、黏著劑層13及隔片14。光學膜積層體200依序具有樹脂基材11'、偏光膜12'、接著劑層15、光學功能膜16、黏著劑層13及隔片14。於本實施形態中，不將上述樹脂基材自所獲得之偏光膜12'剝離而直接用作光學構件。樹脂基材11'例如可作為偏光膜12'之保護膜而發揮作用。 The optical layered body of the present invention has the above polarizing film. 5(a) and 5(b) are schematic cross-sectional views showing an optical film laminate according to a preferred embodiment of the present invention. The optical film laminate 100 sequentially has a resin substrate 11', a polarizing film 12', an adhesive layer 13, and a separator 14. The optical film laminate 200 sequentially includes a resin substrate 11', a polarizing film 12', an adhesive layer 15, an optical functional film 16, an adhesive layer 13, and a separator 14. In the present embodiment, the resin substrate is not directly peeled off from the obtained polarizing film 12' and used as an optical member. The resin substrate 11' functions as, for example, a protective film of the polarizing film 12'.
圖6(a)及(b)係本發明之另一較佳實施形態之光學功能膜積層體之概略剖面圖。光學功能膜積層體300依序具有隔片14、黏著劑層13、偏光膜12'、接著劑層15及光學功能膜16。於光學功能膜積層體400中，除光學功能膜積層體300之構成以外，第2光學功能膜16'介隔黏著劑層13設置於偏光膜12'與隔片14之間。於本實施形態中，去除上述樹脂基材。 6(a) and 6(b) are schematic cross-sectional views showing an optical functional film laminate according to another preferred embodiment of the present invention. The optical functional film laminate 300 has a separator 14 , an adhesive layer 13 , a polarizing film 12 ′, an adhesive layer 15 , and an optical functional film 16 in this order. In the optical functional film laminate 400, in addition to the configuration of the optical functional film laminate 300, the second optical functional film 16' is interposed between the polarizing film 12' and the separator 14 via the adhesive layer 13. In the present embodiment, the above resin substrate is removed.
於構成本發明之光學積層體之各層積層，並不限定於圖示例，可使用任意適合之黏著劑層或接著劑層。代表性情況下，黏著劑層由 丙烯酸系黏著劑形成。作為接著劑層，代表性情況下由乙烯醇系接著劑形成。上述光學功能膜例如可作為偏光膜保護膜、相位差膜等發揮作用。 The respective laminated layers constituting the optical layered body of the present invention are not limited to the illustrated examples, and any suitable adhesive layer or adhesive layer can be used. Representatively, the adhesive layer consists of Acrylic adhesive is formed. The adhesive layer is typically formed of a vinyl alcohol-based adhesive. The optical functional film can function as, for example, a polarizing film protective film, a retardation film, or the like.
以下，藉由實施例具體地說明本發明，但本發明並不限定於該等實施例。再者，各特性之測定方法如下所述。 Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited to the examples. Furthermore, the measurement method of each characteristic is as follows.
使用數位式測微計(Anritsu公司製造，製品名「KC-351C」)進行測定。 The measurement was carried out using a digital micrometer (manufactured by Anritsu Co., Ltd., product name "KC-351C").
依據JIS K 7121進行測定。 The measurement was carried out in accordance with JIS K 7121.
[實施例1] [Example 1]
將水系胺基甲酸酯樹脂(第一工業製藥股份有限公司製造，商品名：Superflex 210R，固形物成分：35%)、唑啉系交聯劑(日本觸媒股份有限公司製造，商品名：Epocros WS700，固形物成分：25%)、導電材料(AGFA製造，商品名：Orgacon LBS，固形物成分：1.2%)、濃度1%之氨水及水以重量比9.03：1.00：18.1：0.060：39.5進行混合，而製備混合液。 Water-based urethane resin (manufactured by Daiichi Kogyo Co., Ltd., trade name: Superflex 210R, solid content: 35%), Oxazoline-based cross-linking agent (manufactured by Nippon Shokubai Co., Ltd., trade name: Epocros WS700, solid content: 25%), conductive material (manufactured by AGFA, trade name: Orgacon LBS, solid content: 1.2%), concentration 1% of aqueous ammonia and water were mixed at a weight ratio of 9.03:1.00:18.1:0.060:39.5 to prepare a mixed solution.
將所獲得之混合液以乾燥後之厚度成為1μm之方式塗佈於厚度200μm且為長條狀之非晶質聚對苯二甲酸乙二酯(A-PET)膜(Tg：70℃，三菱樹脂公司製造，商品名：SH046)之一面。 The obtained mixed liquid was applied to an amorphous polyethylene terephthalate (A-PET) film having a thickness of 200 μm and dried to a thickness of 1 μm (Tg: 70 ° C, Mitsubishi). Made by Resin Company, trade name: SH046).
繼而，將A-PET膜一面於其長度方向進行搬送，一面於115℃下於橫向延伸至2倍。 Then, the A-PET film was conveyed in the longitudinal direction, and was stretched twice in the transverse direction at 115 °C.
繼而，於A-PET膜之另一面塗佈聚乙烯醇(聚合度：4200，皂化度：99.2莫耳%)之水溶液，並於60℃下使其乾燥，而形成厚度10μm之PVA系樹脂層。 Then, an aqueous solution of polyvinyl alcohol (degree of polymerization: 4200, degree of saponification: 99.2 mol%) was applied to the other side of the A-PET film, and dried at 60 ° C to form a PVA-based resin layer having a thickness of 10 μm. .
藉由此種方式，獲得寬度(W)1500mm之積層體。 In this way, a laminate having a width (W) of 1500 mm was obtained.
(延伸積層體之製作) (production of extended laminated body)
如圖2所示，使所獲得之積層體夾持於分別設置於可調溫烘箱(搬送方向之長度L1：900mm，L1/W：0.6)之入口與出口之輥對，並使該等輥間具有周速差，而於長度方向延伸至1.5倍(空中延伸步驟)。此時，適當地調整烘箱之溫度、風量，將延伸時之積層體之最高到達溫度設為88℃。再者，延伸時之積層體之溫度(最高到達溫度)係藉由在積層體之表面貼附熱標籤(Micron股份有限公司製造，商品編號：6R-65或者6R-99)而確認。 As shown in FIG. 2, the obtained laminated body is sandwiched between the pair of inlet and outlet which are respectively disposed in the temperature-adjustable oven (length L 1 of the conveying direction: 900 mm, L 1 / W: 0.6), and the pair is made The rolls have a peripheral speed difference and extend 1.5 times in the length direction (air extension step). At this time, the temperature and the air volume of the oven were appropriately adjusted, and the highest temperature reached by the laminate at the time of extension was set to 88 °C. In addition, the temperature (the highest temperature reached) of the laminate at the time of the extension was confirmed by attaching a thermal label (manufactured by Micron Co., Ltd., product number: 6R-65 or 6R-99) to the surface of the laminate.
繼而，如圖3所示，於表面實施硬質鉻鍍敷，使積層體通過溫度可控之3根鐵輥。此處，使積層體之PVA系樹脂層面與第1輥及第3輥接觸，使另一面(基材側)與第2輥接觸。將第1輥及第2輥之表面溫度設為120℃，將第3輥之表面溫度設為50℃。第1輥與第2輥不具有周速差。即將通過第1輥前之積層體之寬度W'為1220mm，自積層體離開第1輥直至與第2輥接觸之距離L2為37mm，L2/W'為0.03。 Then, as shown in FIG. 3, hard chrome plating was applied to the surface, and the laminated body was passed through three iron rolls whose temperature was controllable. Here, the PVA-based resin layer of the laminate is brought into contact with the first roller and the third roller, and the other surface (substrate side) is brought into contact with the second roller. The surface temperature of the first roll and the second roll was set to 120 ° C, and the surface temperature of the third roll was set to 50 ° C. The first roller and the second roller do not have a peripheral speed difference. The width W' of the laminate before passing through the first roll was 1220 mm, and the distance L 2 from the first roll to the second roll was 37 mm, and L 2 /W' was 0.03.
藉由此種方式，獲得延伸積層體。 In this way, an extended laminate is obtained.
將所獲得之延伸積層體於液溫30℃之硼酸3重量%水溶液(不溶化浴)中浸漬30秒鐘(不溶化處理)。 The obtained extended laminate was immersed in a 3 wt% aqueous solution of boric acid (insolubilization bath) at a liquid temperature of 30 ° C for 30 seconds (insolubilization treatment).
繼而，將積層體以最終獲得之偏光膜之單體透過率(Ts)成為40~44%之方式浸漬於液溫30℃之染色浴(將碘及碘化鉀以重量比1：7調配於水中而獲得之碘水溶液)中(染色處理)。 Then, the laminate was immersed in a dye bath having a liquid temperature of 30 ° C so that the monomer transmittance (Ts) of the finally obtained polarizing film was 40 to 44% (the iodine and potassium iodide were mixed in water at a weight ratio of 1:7). In the obtained aqueous solution of iodine) (dyeing treatment).
繼而，將積層體於液溫30℃之包含硼酸3重量%、碘化鉀3重量%之水溶液(交聯浴)中浸漬30秒鐘(交聯處理)。 Then, the laminate was immersed in an aqueous solution (crosslinking bath) containing 3 wt% of boric acid and 3 wt% of potassium iodide at a liquid temperature of 30 ° C for 30 seconds (crosslinking treatment).
其後，將積層體於液溫70℃且包含硼酸4重量%、碘化鉀5重量%之水溶液中，於周速不同之複數組輥間，於縱向(長度方向)進行單軸延伸直至即將斷裂前(硼酸水中延伸)。 Thereafter, the laminate was placed in an aqueous solution containing 70% by weight of boric acid and 5% by weight of potassium iodide at a liquid temperature of 70 ° C, and uniaxially stretched in the longitudinal direction (longitudinal direction) between the multiple array rolls having different circumferential speeds until immediately before breaking. (Extension in boric acid water).
其後，浸漬於液溫30℃之碘化鉀4重量%水溶液(清洗浴)中後，利用60℃之溫風使其乾燥(清洗、乾燥處理)。 Thereafter, the mixture was immersed in a 4 wt% potassium iodide aqueous solution (cleaning bath) having a liquid temperature of 30 ° C, and then dried by a warm air of 60 ° C (cleaning and drying treatment).
藉由此種方式，獲得厚度4.5μm之偏光膜。 In this manner, a polarizing film having a thickness of 4.5 μm was obtained.
[實施例2-1] [Example 2-1]
於製作延伸積層體時，將延伸倍率設為1.8倍，除此以外，以與實施例1相同之方式獲得偏光膜。所獲得之偏光膜之厚度為4.1μm。 When a stretched laminate was produced, the polarizing film was obtained in the same manner as in Example 1 except that the stretching ratio was 1.8 times. The thickness of the obtained polarizing film was 4.1 μm.
[實施例2-2] [Example 2-2]
藉由下述方式，製作延伸積層體，除此以外，以與實施例1相同之方式獲得偏光膜。所獲得之偏光膜之厚度為4.0μm。 A polarizing film was obtained in the same manner as in Example 1 except that the stretched laminate was produced in the following manner. The thickness of the obtained polarizing film was 4.0 μm.
(延伸積層體之製作) (production of extended laminated body)
如圖2所示，使所獲得之積層體夾持於分別設置於可調溫烘箱(搬送方向之長度L1：900mm，L1/W：0.6)之入口與出口之輥對，並使該等輥間具有周速差，而於長度方向延伸至1.6倍(空中延伸步驟)。此時，適當地調整烘箱之溫度、風量，將延伸時之最高到達溫度設為88℃。 As shown in FIG. 2, the obtained laminated body is sandwiched between the pair of inlet and outlet which are respectively disposed in the temperature-adjustable oven (length L 1 of the conveying direction: 900 mm, L 1 / W: 0.6), and the pair is made The rolls have a peripheral speed difference and extend to 1.6 times in the length direction (air extension step). At this time, the temperature and the air volume of the oven were appropriately adjusted, and the maximum reaching temperature at the time of extension was set to 88 °C.
繼而，如圖3所示，於表面實施硬質鉻鍍敷，使積層體通過溫度可控之3根鐵輥(加熱步驟)。此處，使積層體之PVA系樹脂層面與第1輥及第3輥接觸，使另一面(基材側)與第2輥接觸。將第1輥及第2輥之表面溫度設為120℃，將第3輥之表面溫度設為50℃。使第1輥與第2輥之間具有周速差而延伸至1.13倍。又，即將通過第1輥前之積層體之寬度W'為1160mm，自積層體離開第1輥直至與第2輥接觸之距離L2為35mm，L2/W'為0.03。 Then, as shown in FIG. 3, hard chromium plating was applied to the surface, and the laminated body was passed through three iron rolls (heating step) whose temperature was controllable. Here, the PVA-based resin layer of the laminate is brought into contact with the first roller and the third roller, and the other surface (substrate side) is brought into contact with the second roller. The surface temperature of the first roll and the second roll was set to 120 ° C, and the surface temperature of the third roll was set to 50 ° C. The first roll and the second roll were extended to 1.13 times with a peripheral speed difference. Further, the width W' of the laminate before passing through the first roll was 1160 mm, and the distance L 2 from the first roll to the second roll was 35 mm, and L 2 /W' was 0.03.
[實施例2-3] [Example 2-3]
於製作延伸積層體時，將空中延伸步驟之延伸倍率設為1.4倍，將加熱步驟之延伸倍率設為1.29倍，除此以外，以與實施例2-2相同之方式獲得偏光膜。所獲得之偏光膜之厚度為4.0μm。 When a stretched laminate was produced, a polarizing film was obtained in the same manner as in Example 2-2 except that the stretching ratio of the air extending step was 1.4 times and the stretching ratio of the heating step was 1.29 times. The thickness of the obtained polarizing film was 4.0 μm.
[實施例3-1] [Example 3-1]
於製作延伸積層體時，將延伸倍率設為2.0倍，除此以外，以與實施例1相同之方式獲得偏光膜。所獲得之偏光膜之厚度為4.0μm。 A polarizing film was obtained in the same manner as in Example 1 except that the stretching ratio was 2.0 times in the production of the extended laminated body. The thickness of the obtained polarizing film was 4.0 μm.
[實施例3-2] [Example 3-2]
於製作延伸積層體時，將空中延伸步驟之延伸倍率設為1.8倍，將加熱步驟之延伸倍率設為1.11倍，除此以外，以與實施例2-2相同之方式獲得偏光膜。所獲得之偏光膜之厚度為3.9μm。 When a stretched laminate was produced, a polarizing film was obtained in the same manner as in Example 2-2 except that the stretching ratio of the air extending step was set to 1.8 times and the stretching ratio of the heating step was set to 1.11 times. The thickness of the obtained polarizing film was 3.9 μm.
[實施例3-3] [Example 3-3]
於製作延伸積層體時，將空中延伸步驟之延伸倍率設為1.6倍，將加熱步驟之延伸倍率設為1.25倍，除此以外，以與實施例2-2相同之方式獲得偏光膜。所獲得之偏光膜之厚度為3.9μm。 When a stretched laminate was produced, a polarizing film was obtained in the same manner as in Example 2-2 except that the stretching ratio of the air extending step was 1.6 times and the stretching ratio of the heating step was 1.25 times. The thickness of the obtained polarizing film was 3.9 μm.
[實施例4] [Example 4]
於製作延伸積層體時，將延伸倍率設為2.2倍，除此以外，以與實施例1相同之方式獲得偏光膜。所獲得之偏光膜之厚度為4.1μm。 When a stretched laminate was produced, the polarizing film was obtained in the same manner as in Example 1 except that the stretching ratio was 2.2 times. The thickness of the obtained polarizing film was 4.1 μm.
[實施例5] [Example 5]
於製作延伸積層體時，將延伸倍率設為2.5倍，除此以外，以與實施例1相同之方式獲得偏光膜。所獲得之偏光膜之厚度為4.1μm。 A polarizing film was obtained in the same manner as in Example 1 except that the stretching ratio was 2.5 times in the production of the extended laminated body. The thickness of the obtained polarizing film was 4.1 μm.
[實施例6-1] [Example 6-1]
於製作延伸積層體時，以空中延伸時之最高到達溫度成為99℃之方式進行烘箱之溫度調節，除此以外，以與實施例2-2相同之方式獲得偏光膜。所獲得之偏光膜之厚度為4.2μm。 A polarizing film was obtained in the same manner as in Example 2-2 except that the temperature of the oven was adjusted so that the maximum temperature reached when the air was extended was 99 ° C. The thickness of the obtained polarizing film was 4.2 μm.
[實施例6-2] [Example 6-2]
於製作延伸積層體時，以空中延伸時之最高到達溫度成為71℃之方式進行烘箱之溫度調節，除此以外，以與實施例2-2相同之方式獲得偏光膜。所獲得之偏光膜之厚度為3.6μm。 A polarizing film was obtained in the same manner as in Example 2-2 except that the temperature of the oven was adjusted so that the maximum temperature reached when the air was extended was 71 ° C. The thickness of the obtained polarizing film was 3.6 μm.
[實施例6-3] [Example 6-3]
於製作延伸積層體時，於加熱步驟中，將第1輥及第2輥之表面溫度設為110℃，除此以外，以與實施例2-2相同之方式獲得偏光膜。所獲得之偏光膜之厚度為4.0μm。 In the case of producing the extended laminated body, a polarizing film was obtained in the same manner as in Example 2-2 except that the surface temperature of the first roll and the second roll was set to 110 ° C in the heating step. The thickness of the obtained polarizing film was 4.0 μm.
[實施例6-4] [Example 6-4]
於製作延伸積層體時，於加熱步驟中，將第1輥及第2輥之表面溫度設為130℃，除此以外，以與實施例2-2相同之方式獲得偏光膜。所獲得之偏光膜之厚度為4.0μm。 In the case of producing the extended laminated body, a polarizing film was obtained in the same manner as in Example 2-2 except that the surface temperature of the first roll and the second roll was 130 ° C in the heating step. The thickness of the obtained polarizing film was 4.0 μm.
[實施例6-5] [Examples 6-5]
於製作延伸積層體時，於空中延伸步驟中，將烘箱之搬送方向之長度L1設為600mm(L1/W：0.4)，除此以外，以與實施例2-2相同之方式獲得偏光膜。所獲得之偏光膜之厚度為4.0μm。 When the extended laminate was produced, polarized light was obtained in the same manner as in Example 2-2 except that the length L 1 of the conveyance direction of the oven was set to 600 mm (L 1 / W: 0.4) in the air extending step. membrane. The thickness of the obtained polarizing film was 4.0 μm.
[實施例6-6] [Examples 6-6]
於製作延伸積層體時，於加熱步驟中，將延伸間距L2設為115mm(將L2/W'設為0.1)，除此以外，以與實施例2-2相同之方式獲得偏光膜。所獲得之偏光膜之厚度為3.9μm。 In the case of producing the extended laminated body, a polarizing film was obtained in the same manner as in Example 2-2 except that the stretching pitch L 2 was set to 115 mm (L 2 /W' was set to 0.1) in the heating step. The thickness of the obtained polarizing film was 3.9 μm.
(比較例1) (Comparative Example 1)
於製作延伸積層體時，不進行加熱步驟，除此以外，以與實施例1相同之方式獲得偏光膜。所獲得之偏光膜之厚度為4.5μm。 A polarizing film was obtained in the same manner as in Example 1 except that the heating step was not carried out in the production of the extended laminate. The thickness of the obtained polarizing film was 4.5 μm.
(比較例2) (Comparative Example 2)
於製作延伸積層體時，不進行加熱步驟，除此以外，以與實施例2-1相同之方式獲得偏光膜。所獲得之偏光膜之厚度為4.1μm。 A polarizing film was obtained in the same manner as in Example 2-1 except that the heating step was not carried out in the production of the extended laminate. The thickness of the obtained polarizing film was 4.1 μm.
(比較例3) (Comparative Example 3)
於製作延伸積層體時，不進行加熱步驟，除此以外，以與實施例3-1相同之方式獲得偏光膜。所獲得之偏光膜之厚度為4.0μm。 A polarizing film was obtained in the same manner as in Example 3-1 except that the heating step was not carried out in the production of the extended laminate. The thickness of the obtained polarizing film was 4.0 μm.
(比較例4) (Comparative Example 4)
於製作延伸積層體時，不進行加熱步驟，除此以外，以與實施 例4相同之方式獲得偏光膜。所獲得之偏光膜之厚度為4.1μm。 When the extended laminated body is produced, the heating step is not performed, and other than A polarizing film was obtained in the same manner as in Example 4. The thickness of the obtained polarizing film was 4.1 μm.
(比較例5) (Comparative Example 5)
於製作延伸積層體時，不進行加熱步驟，除此以外，以與實施例5相同之方式獲得偏光膜。所獲得之偏光膜之厚度為4.1μm。 A polarizing film was obtained in the same manner as in Example 5 except that the heating step was not carried out in the production of the extended laminate. The thickness of the obtained polarizing film was 4.1 μm.
(比較例6) (Comparative Example 6)
以空中延伸時之最高到達溫度成為121℃之方式進行烘箱之溫度調節，除此以外，以與比較例1相同之方式獲得偏光膜。所獲得之偏光膜之厚度為4.3μm。 A polarizing film was obtained in the same manner as in Comparative Example 1, except that the temperature of the oven was adjusted so that the highest temperature reached when the air was extended was 121 °C. The thickness of the obtained polarizing film was 4.3 μm.
(比較例7) (Comparative Example 7)
以空中延伸時之最高到達溫度成為121℃之方式進行烘箱之溫度調節，除此以外，以與比較例2相同之方式獲得偏光膜。所獲得之偏光膜之厚度為4.5μm。 A polarizing film was obtained in the same manner as in Comparative Example 2 except that the temperature of the oven was adjusted so that the maximum temperature reached when the air was extended was 121 °C. The thickness of the obtained polarizing film was 4.5 μm.
(比較例8) (Comparative Example 8)
以空中延伸時之最高到達溫度成為121℃之方式進行烘箱之溫度調節，除此以外，以與比較例3相同之方式獲得偏光膜。所獲得之偏光膜之厚度為4.4μm。 A polarizing film was obtained in the same manner as in Comparative Example 3 except that the temperature of the oven was adjusted so that the highest temperature reached when the air was extended was 121 °C. The thickness of the obtained polarizing film was 4.4 μm.
(比較例9) (Comparative Example 9)
以空中延伸時之最高到達溫度成為121℃之方式進行烘箱之溫度調節，除此以外，以與比較例4相同之方式獲得偏光膜。所獲得之偏光膜之厚度為4.6μm。 A polarizing film was obtained in the same manner as in Comparative Example 4 except that the temperature of the oven was adjusted so that the highest temperature reached when the air was extended was 121 °C. The thickness of the obtained polarizing film was 4.6 μm.
(比較例10) (Comparative Example 10)
以空中延伸時之最高到達溫度成為121℃之方式進行烘箱之溫度調節，除此以外，以與比較例5相同之方式獲得偏光膜。所獲得之偏光膜之厚度為4.3μm。 A polarizing film was obtained in the same manner as in Comparative Example 5 except that the temperature of the oven was adjusted so that the maximum temperature reached when the air was extended was 121 °C. The thickness of the obtained polarizing film was 4.3 μm.
(比較例11) (Comparative Example 11)
於製作延伸積層體時，使用拉幅式之延伸機(Bruckner公司製 造，製品名「KARO IV」)，以2.0倍之固定端單軸延伸進行空中延伸，以空中延伸時之最高到達溫度成為121℃之方式進行烘箱之溫度調節，及不進行加熱步驟，除此以外，以與實施例1相同之方式獲得偏光膜。所獲得之偏光膜之厚度為2.8μm。 When making an extended laminate, use a tenter type extension machine (Bruckner) The product name "KARO IV" is air-extended with a fixed-end uniaxial extension of 2.0 times, and the temperature of the oven is adjusted to a temperature of 121 ° C in the air extension, and the heating step is not performed. A polarizing film was obtained in the same manner as in Example 1 except for the above. The thickness of the obtained polarizing film was 2.8 μm.
於各實施例及比較例中，對所獲得之延伸積層體及偏光膜相對於延伸前之積層體之寬度殘留率進行測定。將測定結果與最大延伸倍率(相對於延伸前之積層體)一併示於表1。 In each of the examples and the comparative examples, the width residual ratio of the obtained laminated laminate and the polarizing film with respect to the laminate before stretching was measured. The measurement results are shown in Table 1 together with the maximum stretching ratio (relative to the laminate before stretching).
對各實施例及比較例中獲得之偏光膜之偏光度進行測定。於測定偏光度時，於所獲得之偏光膜之表面塗佈接著劑(日本合成公司製造之GOHSEFIMER Z200之3%水溶液)，貼合厚度80μm之三乙醯纖維素(TAC)膜(Fuji Film公司製造，商品名「TD80UL」，厚度80μm)，並於60℃下加熱5分鐘後，剝離基材(A-PET膜)。如此，將偏光膜轉印於TAC膜，而供於偏光度之測定。 The degree of polarization of the polarizing film obtained in each of the examples and the comparative examples was measured. When measuring the degree of polarization, an adhesive (a 3% aqueous solution of GOHSEFIMER Z200 manufactured by Nippon Synthetic Co., Ltd.) was applied to the surface of the obtained polarizing film, and a film of triethylene terephthalate (TAC) having a thickness of 80 μm was attached (Fuji Film Co., Ltd.) After manufacturing, the product name "TD80UL", thickness 80 μm), and heating at 60 ° C for 5 minutes, the substrate (A-PET film) was peeled off. Thus, the polarizing film was transferred to the TAC film for measurement of the degree of polarization.
偏光度之測定方法如下所述，將偏光度99.99%時之單體透過率之結果示於表1。 The measurement method of the degree of polarization was as follows. The results of the monomer transmittance at a degree of polarization of 99.99% are shown in Table 1.
(偏光度之測定方法) (Method for measuring the degree of polarization)
使用紫外可見分光光度計(日本分光公司製造，製品名「V7100」)對偏光膜之單體透過率(Ts)、平行透過率(Tp)及正交透過率(Tc)進行測定，並藉由下述式求出偏光度(P)。 The monomer transmittance (Ts), the parallel transmittance (Tp), and the orthogonal transmittance (Tc) of the polarizing film were measured by using an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation, product name "V7100"), and by The degree of polarization (P) was obtained by the following formula.
偏光度(P)(%)={(Tp-Tc)/(Tp+Tc)}1/2×100 Polarization (P) (%) = {(Tp-Tc) / (Tp + Tc)} 1/2 × 100
再者，上述Ts、Tp及Tc係藉由JIS Z 8701之2度視野(C光源)進行測定並進行可見度修正而得之Y值。 Further, the above Ts, Tp, and Tc are measured by a 2 degree field of view (C light source) of JIS Z 8701, and the Y value is obtained by performing visibility correction.
各實施例之寬度殘留率、單體透過率均較高，相對於此，比較例1~5、11之單體透過率較低，比較例6~10之寬度殘留率較低。再者，最大延伸倍率為5.4倍之實施例1、比較例1、比較例6及比較例10中，實施例1、比較例1及比較例6之A-PET膜之延伸性不充分，比較例10之PVA系樹脂層之延伸性不充分。 In each of the examples, the width residual ratio and the monomer transmittance were both high. On the other hand, the monomer transmittances of Comparative Examples 1 to 5 and 11 were low, and the width residual ratios of Comparative Examples 6 to 10 were low. Further, in Example 1, Comparative Example 1, Comparative Example 6, and Comparative Example 10 in which the maximum stretching ratio was 5.4 times, the elongation of the A-PET film of Example 1, Comparative Example 1, and Comparative Example 6 was insufficient, and comparison was made. The PVA-based resin layer of Example 10 had insufficient extendability.
本發明之延伸積層體較佳地用於偏光膜之製造。所獲得之偏光膜具有高光學特性，例如可較佳地用於液晶面板或有機 EL(Electroluminescence，電致發光)面板。 The extended laminate of the present invention is preferably used in the production of a polarizing film. The obtained polarizing film has high optical characteristics, and can be preferably used, for example, for a liquid crystal panel or organic EL (Electroluminescence) panel.
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|---|---|---|---|---|
| TW201232065A (en) * | 2010-09-09 | 2012-08-01 | Nitto Denko Corp | Method of producing thin polarizing film |
| TW201231277A (en) * | 2011-01-12 | 2012-08-01 | Sumitomo Chemical Co | Process for manufacture of polarizing laminate film, and process for manufacture of polarizing plate |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201540509A (en) | 2015-11-01 |
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