201219214 鼻 六、發明說明：201219214 nose six, invention description:
c發明所屬技術領域I 發明領域 本發明係有關於一種薄型偏光膜的製造方法。 L· ittr 發明背景 代表性的顯示裝置亦即液晶顯示裝置係起因於其影像 形成方式而在液晶胞的兩側配置有具有偏光膜之光學積層 體。近年來’因為具有偏光膜之光學積層體係被期待薄膜 化，有提案揭示一種方法(例如專利文獻丨），其係將熱塑性 樹脂基材與聚乙料純脂層（以下齡「PVA純脂層」） 的積層體’進打空中延伸，隨後使其浸潰在染色液而得到 薄型偏光膜之料。但是，此種方法健在有所得到的薄 型偏光膜的光學特性(例如偏光度)不充分之問題。 先前技術文獻 專利文獻 [專利文獻1]日本專利特開2001-343521號公報 【發明内象j 發明概要 發明欲解決之課題 本發明係為了解決上述課題而進行，其主要目的係提 供-種製造具有優良的絲雜之_偏光膜。 用以欲解決課題之手段 本發明的薄型偏光膜的製造方法係包含下列步驟：在 3 201219214 吸水率為0.2%以上且3.0%以下、且玻璃轉移溫度(丁§)為6〇 °C以上的熱塑性樹脂基材上形成聚乙烯醇系樹脂層而製造 積層體之步驟；及將積層體在硼酸水溶液中進行水中延伸 之步驟。 在較佳實施態樣，上述熱塑性樹脂基材係由非晶質的 聚對酞酸乙二酯系樹脂所構成。 在較佳實施態樣’係在上述硼酸水中延伸之前，包含 將上述積層體於95°C以上進行空中延伸之步驟。 在較佳實施態樣，相較於只有將上述積層體進行空中 延伸時的最大延伸倍率，經過上述水中延伸步驟之上述積 層體的最大延伸倍率係較高。 在較佳實施態樣，上述該積層體的最大延伸倍率為5 〇 倍以上。 依照本發明的另外態樣，係提供一種薄型偏光膜。該 薄型偏光膜係使用上述製造方法而得到。 依照本發明的又另外態樣，係提供一種具有上述薄型 偏光膜之光學積層體。 依照本發明的又另外態樣，係提供一種積層體。該積 層體係具有：吸水率為〇_2%以上、3 G%以下且玻璃轉移溫 度(Tg)為6G°〇X上的熱紐職基材；及形成於該熱塑性 樹脂基材上之PVA系樹脂層。 發明效果 依照本發明，藉由使用吸水率為0.2¼以上、3·0%以下 且玻璃轉移溫度(Tg)為贼以上的熱塑性樹脂基材，而且 201219214 使用侧酸水溶液作為延伸浴，能夠將形成有PVA系樹脂層 之積層體南倍率良好地延伸。具體上，此種熱塑性樹脂 基材係在水中延伸而吸收水，水產生塑化劑的作用而能夠 可塑化。其結果’能夠大幅度地使延伸應力降低，使得高 倍率地延伸成為可能，相較於空中延伸時，熱塑性樹脂基 材的延伸性能夠較優良。因此，此種使用熱塑性樹脂基材 的積層體之最大延伸倍率，相較於只有空中延伸，係經過 水中延伸步驟者能夠較高。又，藉由使用硼酸水溶液，能 夠對PVA系樹脂層賦予經得起延伸時施加的張力之剛性及 不溶於水之耐水性。如此進行，能夠使積層體良好地進行 水中延伸而能夠製造光學特性(例如偏光度）非常優良的薄 型偏光膜。 圖式簡單說明 第1圖係本發明的較佳實施形態之積層體之概略剖面 圖0 第2圖係顯示本發明的薄型偏光膜的製造方法之一個 例子之概略圖。 第3(a)〜3(b)圖係本發明的較佳實施形態之光學薄膜學 積層體之概略剖面圖。 第4(a)〜4(b)圖係本發明的另外較佳實施形態之光學薄 膜學積層體之概略剖面圖。 第5圖係顯示在實施例1所使用之熱塑性樹脂基材的延 伸倍率與延伸應力的關於之圖表。 第6圖係顯示在實施例1所使用之熱塑性樹脂基材的延 5 201219214 伸倍率與延伸應力的_之圖表。 【實施冷式】 用以實施發明之形態 以下說明本發明的較佳形態’但是本發明不被該等 實施例限定。 A.製造方法 本毛月的薄型偏光膜之製造方法，係包含下列步驟： 在吸水率為G.2%以上、3⑽以下且玻璃轉移溫度(τ幻為6〇 c以上、1〇〇 c以下的熱塑性樹脂基材上形成pVA系樹脂層 而製造積層體之步驟(步驟A);及將該積層體在魏水溶液 中進行水中延伸之步驟（步驟B)(棚酸水中延伸卜以下說明 各自的步驟。TECHNICAL FIELD OF THE INVENTION The present invention relates to a method of manufacturing a thin polarizing film. BACKGROUND OF THE INVENTION A typical display device, that is, a liquid crystal display device, has an optical layered body having a polarizing film disposed on both sides of a liquid crystal cell due to an image forming method. In recent years, "because the optical laminated system having a polarizing film is expected to be thinned, there is a proposal to disclose a method (for example, Patent Document) which is a thermoplastic resin substrate and a polyethylene pure fat layer (PVA pure fat layer of the following age) The layered body of the "" is stretched in the air, and then it is immersed in the dyeing liquid to obtain a thin polarizing film. However, this method is advantageous in that the optical characteristics (e.g., the degree of polarization) of the obtained thin polarizing film are insufficient. CITATION LIST Patent Literature [Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-343521A SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The present invention has been made to solve the above problems, and its main object is to provide Excellent silky _ polarizing film. Means for Solving the Problem The method for producing a thin polarizing film of the present invention comprises the following steps: at 3 201219214, the water absorption rate is 0.2% or more and 3.0% or less, and the glass transition temperature (D) is 6 〇 ° C or more. a step of forming a layered body on a thermoplastic resin substrate to form a polyvinyl alcohol-based resin layer; and a step of extending the layered body in water in an aqueous boric acid solution. In a preferred embodiment, the thermoplastic resin substrate is composed of an amorphous polyethylene terephthalate resin. In a preferred embodiment, prior to extending in the boric acid water, the step of extending the laminate at 95 ° C or higher in the air is included. In a preferred embodiment, the maximum stretching magnification of the laminate passing through the water extending step is higher than the maximum stretching ratio when the laminate is extended in the air. In a preferred embodiment, the laminate has a maximum stretch ratio of 5 〇 or more. According to another aspect of the present invention, a thin polarizing film is provided. This thin polarizing film is obtained by the above production method. According to still another aspect of the present invention, an optical laminate having the above-described thin polarizing film is provided. According to still another aspect of the present invention, a laminate is provided. The laminated system has a heat-resistant base material having a water absorption ratio of 〇_2% or more and 3 G% or less and a glass transition temperature (Tg) of 6 G°〇X; and a PVA system formed on the thermoplastic resin substrate Resin layer. Advantageous Effects of Invention According to the present invention, a thermoplastic resin substrate having a water absorption ratio of 0.21⁄4 or more and 3.0% or less and a glass transition temperature (Tg) of thief or more is used, and 201219214 can be formed by using an aqueous acid solution as an extension bath. The laminate having the PVA-based resin layer has a good south magnification. Specifically, such a thermoplastic resin substrate is extended in water to absorb water, and water acts as a plasticizer to be plasticizable. As a result, the elongation stress can be greatly reduced, making it possible to extend at a high magnification, and the elongation of the thermoplastic resin substrate can be excellent as compared with the air stretching. Therefore, the maximum stretching ratio of such a laminate using a thermoplastic resin substrate can be higher than that in the water extending step as compared with the case of only extending in the air. Further, by using a boric acid aqueous solution, it is possible to impart rigidity to the PVA-based resin layer which can withstand the tension applied during stretching and water-insoluble water resistance. By doing so, the laminate can be easily extended in water, and a thin polarizing film having excellent optical characteristics (e.g., degree of polarization) can be produced. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a laminate of a preferred embodiment of the present invention. Fig. 0 is a schematic view showing an example of a method for producing a thin polarizing film of the present invention. 3(a) to 3(b) are schematic cross-sectional views showing an optical thin film laminate of a preferred embodiment of the present invention. 4(a) to 4(b) are schematic cross-sectional views showing an optical film laminate of another preferred embodiment of the present invention. Fig. 5 is a graph showing the elongation ratio and the extension stress of the thermoplastic resin substrate used in Example 1. Fig. 6 is a graph showing the elongation and elongation stress of the extension of the thermoplastic resin substrate used in Example 1 in 2012. [Embodiment of the Invention] Mode for Carrying Out the Invention Hereinafter, preferred embodiments of the present invention will be described. However, the present invention is not limited by the embodiments. A. Manufacturing Method The method for producing a thin polarizing film of the present invention includes the following steps: The water absorption rate is G. 2% or more, 3 (10) or less, and the glass transition temperature (τ illusion is 6 〇 c or more and 1 〇〇 c or less). a step of forming a pVA-based resin layer on a thermoplastic resin substrate to produce a laminate (step A); and a step of extending the laminate in water in a Wei aqueous solution (step B) step.
A-1.步驟A 第1圖係本發明的較佳實施形態之積層體的概略構成 圖。積層體10係具有熱塑性樹脂基材11及PVA系樹脂層 12 ’且能夠藉由在熱塑性樹脂基材形成pvA系樹脂層丨2來 製造。PVA系樹脂層12的形成方法係能夠採用任意適當的 方法。較佳是在熱塑性樹脂基材丨丨上，藉由塗布含有pvA 系樹脂層的塗布液且乾燥，來形成pvA系樹脂層12。 上述熱塑性樹脂基材，其吸水率為0.2%以上，以〇3% 以上為佳。此種熱塑性樹脂基材係在後述的步驟B吸收水， 水產生塑化劑的作用而能夠可塑化。其結果，能夠使延伸 應力大幅度地降低，使得高倍率地延伸成為可能，相較於 空中延伸時，熱塑性樹脂基材的延伸性能夠較優良。其妹 201219214 果’能夠製造具有優良的光學特性(例如偏光度)之薄型偏光 膜。另一方面，熱塑性樹脂基材的吸水率係以3 〇%以下為 佳，以ι·ο°/。以下為更佳。藉由使用此種熱塑性樹脂基材， 在製造時能夠防止熱塑性樹脂基材的尺寸安定性顯著低落 致使所得到的薄型偏光膜的外觀變差的不良。又，在水中 延伸時能夠防止基材產生斷裂、或PVA系樹脂層從熱塑性 樹脂基材剝離。又，吸水率係依據JISK72〇9而求得之值。 熱塑性樹脂基材的玻璃轉移溫度(Tg)係以170°c以下 為佳。藉由使用此種熱塑性樹脂基材，能夠邊抑制pVA系 樹脂層的結晶化、邊充分地確保積層體的延伸性。而且， 考慮利用水之熱塑性樹脂基材的可塑化及良好地進行水中 延伸時’以12GX：以下為更佳。另__方面’熱塑性樹脂基材 的玻璃轉移溫度(Tg)係、靖。c以上為佳。藉由使用此種熱 塑性樹脂基材’在將含有上述PVA系樹脂的塗布液進行塗 布.乾燥時，能夠防止熱塑性樹脂基材產生變形(例如產生 凹凸和下垂、皺紋等）等之不良而良好地製造積層體。又， 能夠以適當的溫度(例如60t左右）而良好地進行pvA系樹 脂層的延伸。又’玻璃轉移溫度(Tg)係依據;isk7i2i而求 得之值。 熱塑性樹脂基材的構成材料係只要熱塑性樹脂基材的 吸水率及__溫度為上述範_，㈣採躲意適當 的材料。在此，吸水率係例如能夠藉由在構成材料導入改 性基來調整。玻璃轉移溫度係例如能夠藉由在構成材料使 用導入改性基之結晶化㈣且加絲調整。作為熱塑性樹 201219214 脂基材的構成材料，非晶質的（不結晶化）聚對酞酸乙二酯系 樹脂係適合使用。其中非晶性的（難以結晶化）聚對酞酸乙二 醋系樹脂係特別適合使用。作為非晶性的聚對酞酸乙二酯 系樹脂的具體例，可舉出進而含有異酞酸作為二羧酸之共 聚物、進而含有環己烷二曱醇作為二醇之共聚物。 熱塑性樹脂基材之延伸前的厚度係以20μιη〜3 00μιη為 佳’以50μηι〜200μιη為更佳。小於20μιη時，PVA系樹脂層 的形成有變為困難之可能性。大於3〇〇μηι時，在步驟Β，有 熱塑性樹脂基材需要長時間來吸收水，同時在延伸時有需 要過大的負荷之可能性。 上述PVA系樹脂係能夠採用任意適當的樹脂。例如可 舉出聚乙烯醇、乙烯-乙烯醇共聚物。聚乙烯係能夠藉由將 聚乙酸乙烯酯皂化而得到。乙烯·乙烯醇共聚物係能夠藉由 將乙烯-乙酸乙酯共聚物皂化而得到。pVA系樹脂的爸化度 係通常為 85mol%〜lOOmol%，以 95.〇m〇l%〜99.95mol% 為 佳，以99.0mol°/〇〜99.93mol%為更佳。皂化度係能夠依據JIS K 6726-1994來求得。藉由使用此種皂化度的PVA系樹脂， 能夠得到耐久性優良的薄型偏光膜。皂化度太高時，有凝 膠化掉之可能性。 PVA系樹脂的平均聚合度，係能夠按照目的而適當地 選擇。平均聚合度係通常為1200〜4500 ’以1500〜4300為更 佳。又’平均聚合度係能夠依據JISK 6726-1994而求得。 上述塗布液，代表性係使上述PVA系樹脂溶解於溶劑 而成之溶液。作為溶劑，例如可舉出水、二曱基亞砜、二 201219214 甲基甲酿胺、二甲基乙醯祕甲基各咬酮、各種二醇類、 =甲基狀料元_、乙二胺、二伸乙三胺料麵。 «係可單獨使用或組合2種以上而使用。該等之中，以水 為佳。溶液的PVA系樹脂濃度係相對於⑽重量份之溶劑， 以3重量份〜2〇重量份為佳。如此的樹脂濃度時，能夠形成 在熱塑性樹脂基材密著而成之均勻的塗布膜。 亦可以在塗布液調配添加劑，作為添加劑，例如可舉 出塑化劑、界面活性劑等。作為塑化劑，例如可舉出乙二 醇和甘油等的多讀。作為界岐_，例何舉出非離 子界面活_。該等能夠為了進—步提升所得到的pvA系 樹脂層之均勻性、染色性、延伸性之目的而使用。 作為塗布液的塗布方法，係能夠制任意適當的方 法。例如輥塗布法、旋轉塗布法、繞線棒塗布法、浸潰塗 布法、模頭塗布法、簾流塗布法、喷霧塗布法、刮刀塗布 法(comma coating ;刮刀式塗布法等）等。 上述塗布液的塗布·乾燥溫度係以5〇〇c以上為佳。 PVA系樹脂層延伸前的厚度以3μπι〜2〇μιη為佳。 在形成PVA系樹脂層之前，亦可以在熱塑性樹脂基材 施行表面處理(例如電暈處理等），且亦可以在熱塑性樹脂基 材形成易接著層。藉由進行如此的處理，能夠使熱塑性樹 脂基材與PVA系樹脂層的密著性提升。 Α-2.步驟ΒA-1. Step A Fig. 1 is a schematic configuration diagram of a laminated body according to a preferred embodiment of the present invention. The laminate 10 has a thermoplastic resin substrate 11 and a PVA-based resin layer 12', and can be produced by forming a pvA-based resin layer 在2 on a thermoplastic resin substrate. The method of forming the PVA-based resin layer 12 can be any appropriate method. The pvA-based resin layer 12 is preferably formed by applying a coating liquid containing a pvA-based resin layer on a thermoplastic resin substrate and drying it. The thermoplastic resin substrate preferably has a water absorption ratio of 0.2% or more and more preferably 3% or more. Such a thermoplastic resin substrate absorbs water in the step B described later, and the water can be plasticized by the action of a plasticizer. As a result, the elongation stress can be greatly lowered to make it possible to extend at a high magnification, and the elongation of the thermoplastic resin substrate can be excellent as compared with the air stretching. Its sister 201219214 is able to manufacture thin polarizing films with excellent optical properties such as polarization. On the other hand, the water absorption of the thermoplastic resin substrate is preferably 3% or less, and is ι·ο°/. The following is better. By using such a thermoplastic resin substrate, it is possible to prevent the dimensional stability of the thermoplastic resin substrate from being significantly lowered during production, resulting in deterioration of the appearance of the obtained thin polarizing film. Further, when the water is extended, it is possible to prevent the substrate from being broken or the PVA-based resin layer from being peeled off from the thermoplastic resin substrate. Further, the water absorption rate is a value obtained in accordance with JIS K72〇9. The glass transition temperature (Tg) of the thermoplastic resin substrate is preferably 170 ° C or less. By using such a thermoplastic resin substrate, it is possible to sufficiently ensure the elongation of the laminate while suppressing the crystallization of the pVA-based resin layer. Further, in consideration of plasticization of a thermoplastic resin substrate using water and good water extension, it is more preferable to be 12 GX: or less. In addition, the glass transition temperature (Tg) of the thermoplastic resin substrate is jing. Above c is better. When the coating liquid containing the PVA-based resin is applied and dried by using such a thermoplastic resin substrate, it is possible to prevent the thermoplastic resin substrate from being deformed (for example, unevenness, sag, wrinkles, etc.). Make a laminate. Further, the pvA-based resin layer can be favorably extended at an appropriate temperature (e.g., about 60 t). Further, the glass transition temperature (Tg) is a value obtained based on isk7i2i. The constituent material of the thermoplastic resin substrate is such that the water absorption rate and the __temperature of the thermoplastic resin substrate are the above-mentioned specifications, and (4) materials which are suitable for hiding. Here, the water absorption rate can be adjusted, for example, by introducing a modifying group into a constituent material. The glass transition temperature can be adjusted, for example, by crystallization (IV) of introducing a modifying group into a constituent material. As a constituent material of the thermoplastic resin 201219214, a non-crystalline (non-crystallized) polyethylene terephthalate resin is suitably used. Among them, amorphous (difficult to crystallize) polyethylene terephthalate resin is particularly suitable for use. Specific examples of the amorphous polyethylene terephthalate resin include a copolymer containing isophthalic acid as a copolymer of a dicarboxylic acid and further containing cyclohexanedonol as a diol. The thickness of the thermoplastic resin substrate before stretching is preferably from 20 μm to 300 μm, and more preferably from 50 μm to 200 μm. When it is less than 20 μm, the formation of the PVA-based resin layer may become difficult. When it is more than 3 〇〇μηι, in the step Β, the thermoplastic resin substrate takes a long time to absorb water, and at the same time, there is a possibility that an excessive load is required at the time of stretching. Any suitable resin can be used for the PVA resin. For example, polyvinyl alcohol or ethylene-vinyl alcohol copolymer can be mentioned. Polyethylene can be obtained by saponifying polyvinyl acetate. The ethylene-vinyl alcohol copolymer can be obtained by saponifying an ethylene-ethyl acetate copolymer. The degree of doping of the pVA-based resin is usually from 85 mol% to 100 mol%, more preferably from 95. 〇m〇l% to 99.95 mol%, still more preferably from 99.0 mol/〇 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 thin polarizing film excellent in durability can be obtained. When the degree of saponification is too high, there is a possibility that the gelation will be lost. 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 1200 to 4,500 Å, preferably from 1,500 to 4,300. Further, the average degree of polymerization can be obtained in accordance with JIS K 6726-1994. The coating liquid is typically a solution obtained by dissolving the PVA-based resin in a solvent. Examples of the solvent include water, dimercaptosulfoxide, bis 201219214 methyl amide, dimethyl acetamyl methyl ketone, various diols, = methyl material _, and ethylene Amine, diethylene glycol triamide surface. The «series can be used alone or in combination of two or more. Among these, water is preferred. The PVA-based resin concentration of the solution is preferably 3 parts by weight to 2 parts by weight based on the (10) parts by weight of the solvent. When such a resin concentration is obtained, a uniform coating film formed by adhering a thermoplastic resin substrate can be formed. The additive may be added to the coating liquid, and examples of the additive include a plasticizer, a surfactant, and the like. The plasticizer may, for example, be a multi-read such as ethylene glycol or glycerin. As a boundary _, how to cite a non-ionic interface _. These can be used for the purpose of further improving the uniformity, dyeability, and extensibility of the obtained pvA-based resin layer. As a coating method of the coating liquid, any appropriate method can be produced. For example, a roll coating method, a spin coating method, a wire bar coating method, a dipping coating method, a die coating method, a curtain flow coating method, a spray coating method, a knife coating method (comma coating, a doctor blade coating method, etc.). The coating/drying temperature of the coating liquid is preferably 5 〇〇c or more. The thickness of the PVA-based resin layer before stretching is preferably 3 μm to 2 μm. Before the PVA-based resin layer is formed, a surface treatment (e.g., corona treatment) may be applied to the thermoplastic resin substrate, and an easy-adhesion layer may be formed on the thermoplastic resin substrate. By performing such a treatment, the adhesion between the thermoplastic resin substrate and the PVA-based resin layer can be improved. Α-2. Step Β
上述步驟Β係將上述積層體進行水中延伸（硼酸水中延 伸）。藉由水中延伸，能夠在比上述熱塑性樹脂基材和PVA 201219214 系樹脂層的玻璃轉移溫度（代表性係8 〇七卢右 行延伸，且能夠將PVA系樹脂層邊抑制其：曰)低的溫度進 率地進行延伸。錢果，高倍 如偏光度）之薄型偏光膜。 +特性(例 積層體的延伸方法係能夠採用任意適當的方法。 上，可以m定端延伸，亦可以自由端延伸 ” 過不同周速的輥之_進行單Φ , a體通 ^ 甲之方法）。積層體的延 ^可使用-階段進行，亦可使用多階段進行。使用多= 又進仃時’後相積層體的延伸倍率（最大延伸 段的延伸倍率之積。 水中延伸係純是使積層體浸潰於《水溶液中而途 行(删λ水巾延伸）。藉由使㈣酸水溶麟歧伸浴，能詞 .VA系餘層料轉起㈣時施加賴力之剛性及不 冷於水之财水性。具體上，餐係藉由在水溶液中生成四 經基删酸陰離子而能夠與ρνΑ系樹脂藉由氫鍵來進行交 聯其、1果’此夠對1>从系樹脂層賦予剛性及对水性而良 好地進灯水巾延伸，且㈣製造具有優良的光學特性(例如 偏光度)之薄型偏光膜。 上述翊酸水溶液係較佳是藉由使硼酸及/或硼酸鹽溶 解於冷劑亦即水中來得到。爛酸濃度係相對於⑽重量份之 水，以1重里伤至10重量份為佳。藉由使硼酸濃度為i重量 份以上’能夠有效地抑制pvA^脂成形體的溶解，且能 夠製造更南特性的薄型偏光膜。X，除了棚酸或硼酸鹽以 外’亦能夠使用將蝴砂等_化合物、乙二酸、戊二搭等 10 201219214 溶解於溶劑而得到的水溶液。 藉由後述的染色步驟，預先在PVA系樹脂層吸附二色 性物質（代表性係峨）的情、、牙，P杜a μ、+ /、）的m父佳疋在上述延伸浴(侧酸水 t液)調配錢物。藉由調配魏物，能夠抑制使Μ系樹 月曰層吸附之礙產生溶出。作為峨化物，例如可舉出換化卸、 峨化經、魏鈉' 峨化鋅、魏ls、㈣錯、蛾化銅 '埃 化鎖、碟化㉖、社錫、峨化鈦等。該等之中，以蛾化鉀 為佳。峨化物的濃度係相對於⑽重量份之水以 重置份為佳，以〇·5重量份〜8重量份為更佳。 在步驟B之延伸溫度（延伸浴的液溫）係以4〇。匸〜85它為 佳’以5(TC〜机為更佳。如此的溫度時，能夠邊抑制pvA 系樹脂的溶解邊高倍率地進行延伸。具體上，如上述，熱 塑性樹脂基材的㈣轉移溫度(τ g)係與㈣P VA系樹脂層 有關，以60C以上為佳。此時，延伸溫度低於4〇()(：時，考 慮利用水之熱塑性樹脂基材的可塑化，亦有無法良好地延 伸之可能性。另-方面，延伸浴的溫度越高，pvA系樹脂 層的溶解性變為越高，有無法得到優良的光學特性之可能 性。積層體在延伸浴的浸潰時間係以15秒〜5分鐘為佳。 藉由組合上述熱塑性樹脂基材及水中延伸（硼酸水中 延伸），能夠高倍率地延伸，且能夠製造具有優良的光學特 性(例如偏光度）之薄型偏光膜。具體上，相對於積層體的原 來長度，最大延伸倍率係以5 〇倍以上為佳。在本說明書所 謂「最大延伸倍率」係指積層體即將斷裂時之延伸倍率， 且係指另外確認積層體斷裂之延伸倍率，比該值低〇2之 201219214 步驟者較高 A-3.其他步驟 值。又，使用上述熱㈣樹脂基材之積層義最大延伸倍 率，相較料有_空中延伸進行延伸，係'經過水中料 本發明的薄型偏光膜之製造方法係除了上述步驟A及 步驟⑽外，亦可包含其他步驟。作為其他步驟例如可舉 出不溶化步驟、染色步驟、交聯步驟、與上述步驟B另外的 延伸步驟、洗淨步驟、錢(調節水分率）步料。其他步驟 係能夠在任意適當的時序進行。 上述染色步驟，代表性係使用二色性物質將pvA系樹 月曰層染色之步驟。較佳是藉由使PVA系樹脂層吸附二色性 物資來進行n玄吸附方法，例如可舉出使系樹脂 層（積層體)浸潰於含二色性物質的染色液之方法；在PVA系 樹脂層塗布該染色液之方法；及將該染色液對PVA系樹脂 層進行喷霧之方法等。較佳是使積層體浸潰於含二色性物 質的染色液之方法，因為二色性物質能夠良好地吸附。 作為上述二色性物質，例如可舉出峨、二色性染料。 較佳是碘。使用碘作為二色性物質時，上述染色液係碘水 溶液。碘的調配量係相對於100重量份之水，以01重量份 〜0·5重量份為佳。為了提高碘對水的溶解度，以在碘水溶 液調配碘化物為佳。碘化物的具體例係如上述。碘化物的 調配量係相對於100重量份之水，以〇_〇2重量份〜20重量份 為佳’以0.1重量份〜10重量份為更佳。為了抑制PVA系樹脂 的溶解，染色液的染色時之液溫係以20°C〜50°C為佳。使染 12 201219214 色液浸潰PVA系樹脂層時，為了確保PVA系樹脂層的透射 率，浸潰時間係以5秒~5分鐘為佳。又，染色條件（濃度、 液溫、浸潰時間）能夠以最後所得到的偏光膜之偏光度或單 體透射率為在預定範圍的方式設定。在一實施形態，係以 所得到的偏光膜之偏光度為99.98%以上的方式來設定浸潰 時間。在另外一實施形態，係以所得到的偏光膜之單體透 射率為40%〜44%的的方式來設定浸潰時間。 較佳是在上述步驟B之前進行染色步驟。 上述不溶化步驟，代表性係使爛酸水溶液浸潰pVA系 樹脂層來進行。藉由施行不溶化，能夠賦予pVA系樹脂層 耐水性。该硼酸水溶液的濃度係相對於1〇〇重量份之水。以 1重量份〜4重#份為佳。不溶化浴(爾水溶液）的液溫係以 2〇 C〜50 C為佳。較佳是在積層體製造後、染色步驟和步驟 B之前進行不溶化步驟。In the above step, the above-mentioned laminated body is stretched in water (extension in boric acid water). By extending in water, it is possible to lower the glass transition temperature (representatively extending 8 to 7 liters in the right line and suppressing the PVA-based resin layer side: 曰) from the thermoplastic resin substrate and the PVA 201219214-based resin layer. The temperature is advanced to extend. A thin polarizing film of money, high magnification such as polarized light. +Characteristics (for example, the method of extending the laminated body can adopt any appropriate method. On the top, it can be extended at m end, or it can be extended at the free end.) The method of performing single Φ and a body through a roller with different peripheral speeds The extension of the laminate can be carried out in stages or in multiple stages. When using more = when entering the crucible, the extension ratio of the post-phase layer (the extension of the maximum extension). The layered body is immersed in the "aqueous solution" (by deleting the λ water towel). By making the (four) acid water-soluble skeletal stretch bath, the rigidity of the VA-based residual material is increased and the pressure is not applied. It is colder than the water of the water. Specifically, the meal can be cross-linked with the ρν-based resin by hydrogen bonding by forming a tetra-based acid-anion in an aqueous solution, and the result is '1'. The resin layer imparts rigidity and water to the water towel to extend well, and (4) produces a thin polarizing film having excellent optical properties (for example, a degree of polarization). The above aqueous solution of citric acid is preferably made of boric acid and/or boric acid. The salt is dissolved in a cold agent, that is, water. The degree is preferably from 1 to 10 parts by weight with respect to (10) parts by weight of water. By allowing the concentration of boric acid to be more than 1 part by weight, the dissolution of the pvA^lip formed body can be effectively suppressed, and the southerness characteristic can be produced. A thin polarizing film, X, in addition to linic acid or borate, can also be used as an aqueous solution obtained by dissolving a compound such as a butterfly, oxalic acid or pentane pentoxide, 10 201219214 in a solvent, by a dyeing step described later. In the PVA-based resin layer, a dichroic substance (representative 峨), a tooth, a P-a μ, a +/- a m-parent are mixed in the above-mentioned extension bath (side acid water t liquid). By blending the Weiwu, it is possible to suppress the dissolution of the ruthenium layer of the lanthanide tree. As the ruthenium compound, for example, the chemical conversion, the sulphurization, the Wei sodium, the zinc bismuth, the Wei ls, (4) Wrong, moth-copper 'Aihua lock, disc 26, tin, titanium telluride, etc. Among them, potassium moth is preferred. The concentration of telluride is relative to (10) parts by weight of water. Preferably, it is more preferably 5 parts by weight to 8 parts by weight. The extension temperature in step B (extension bath liquid) The temperature is 4 〇. 匸 85 is better than 5 (TC ~ machine is better. At such a temperature, it can be extended at a high magnification while suppressing the dissolution of the pvA resin. Specifically, as described above, The (four) transfer temperature (τ g) of the thermoplastic resin substrate is related to the (IV) P VA-based resin layer, preferably 60 C or more. In this case, when the elongation temperature is lower than 4 〇 (), a thermoplastic resin substrate using water is considered. In addition, the higher the temperature of the stretching bath, the higher the solubility of the pvA-based resin layer, and the possibility that excellent optical properties are not obtained. The impregnation time in the stretching bath is preferably 15 seconds to 5 minutes. By combining the above thermoplastic resin substrate and water extension (boric acid water extension), it is possible to extend at a high magnification and to produce excellent optical characteristics (for example). Thin polarizing film of polarized light). Specifically, the maximum stretching ratio is preferably 5 〇 or more with respect to the original length of the laminated body. In the present specification, the "maximum stretching ratio" refers to the stretching ratio when the laminate is about to be broken, and refers to the extension ratio of the laminate fracture, which is lower than the value of 201219214. The step is higher. A-3. Other steps value. Further, the method of manufacturing the thin polarizing film of the present invention is the method of manufacturing the thin polarizing film of the present invention, except that the above steps A and (10) are used, in addition to the above-mentioned steps (10), Other steps can also be included. As another step, for example, an insolubilization step, a dyeing step, a crosslinking step, an additional stretching step in the above step B, a washing step, and a money (adjusting moisture content) step are mentioned. Other steps can be performed at any suitable timing. The above dyeing step is representative of a step of dyeing the pvA system of the ruthenium layer using a dichroic substance. Preferably, the n-type adsorption method is carried out by adsorbing a dichroic material in the PVA-based resin layer, and for example, a method of impregnating a resin layer (layered body) with a dyeing liquid containing a dichroic substance; A method of applying the dyeing liquid to the resin layer; and a method of spraying the dyeing liquid on the PVA-based resin layer. Preferably, the layered body is impregnated into the dyeing liquid containing the dichroic substance because the dichroic substance can be adsorbed well. Examples of the dichroic substance include an anthracene or a dichroic dye. Preferably it is iodine. When iodine is used as the dichroic substance, the above dyeing liquid is an aqueous iodine solution. The amount of iodine to be added is preferably from 0.1 part by weight to 0.5 parts 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 iodide in an aqueous solution of iodine. Specific examples of the iodide are as described above. The amount of the iodide compounded is preferably from 2,000 parts by weight to 20 parts by weight, more preferably from 0.1 part by weight to 10 parts by weight, per 100 parts by weight of water. In order to suppress the dissolution of the PVA-based resin, the liquid temperature at the time of dyeing the dyeing liquid is preferably 20 ° C to 50 ° C. When the PVA-based resin layer is impregnated with the dyeing liquid 2012 201214, the impregnation time is preferably 5 seconds to 5 minutes in order to secure the transmittance of the PVA-based resin layer. Further, the dyeing conditions (concentration, liquid temperature, and immersion time) can be set such that the degree of polarization or the single transmittance of the polarizing film finally obtained is within a predetermined range. In one embodiment, the impregnation time is set such that the degree of polarization of the obtained polarizing film is 99.98% or more. In another embodiment, the impregnation time is set such that the obtained polarizing film has a monomer transmittance of 40% to 44%. Preferably, the dyeing step is carried out before step B above. The above insolubilization step is typically carried out by impregnating a pVA-based resin layer with a rotten acid aqueous solution. By performing insolubilization, it is possible to impart water resistance to the pVA-based resin layer. The concentration of the aqueous boric acid solution is relative to 1 part by weight of water. It is preferred to use 1 part by weight to 4 parts by weight. The liquid temperature of the insolubilizing bath (aqueous solution) is preferably 2 〇 C 50 50 C. Preferably, the insolubilization step is carried out after the production of the laminate, the dyeing step and the step B.
上述乂聯步驟，代表性係使石朋酸水溶液浸潰pvA系樹 月曰層來進4。藉由施仃交聯處理，㈣賦予·樹脂層 耐水性。制酸水溶㈣濃度係㈣㈣0重量份之水，以 1重量伤〜4重讀為佳’又，在上述染色步驟後進行交聯步 驟時’以更調配蛾化物為佳。藉由調配蛾化物，能夠抑制 已使其吸附於p爾樹脂層之衫生溶出。魏物的調配 量係相對於刚重量份之水，以1量份〜5重量份為佳。蛾 化物的具體例’係如上述。交聯浴㈣酸水溶液)的液溫係以 2〇 5〇c為佳。紹圭是交聯步驟係在上述步獅之前進行。 在較佳的實施形態，能夠依《色步驟、交聯步驟及步驟B 13 201219214 的順序而進行。 作為與上述步驟B另外的延伸步驟，例如可舉出將上述 積層體於高溫(例如95°C以上）進行空中延伸之步驟。此種空 中延伸步驟較佳是在步驟B(硼酸水中延伸）及染色步驟之 前進行。因為此種空中延伸步驟係能夠定位作為對硼酸水 中延伸之預備或輔助性的延伸，以下稱為「空中輔助延 伸」）。 藉由組合空中輔助延伸，有能夠更高倍率延伸積層體 之情況。其結果，能夠製造具有更優良的光學特性(例如偏 光度）之薄型偏光膜。例如使用聚對酞酸乙二酯作為上述熱 塑性樹脂基材時，相較於只有使用硼酸水中延伸進行延 伸，組合空中輔助延伸與硼酸水中延伸能夠邊抑制熱塑性 樹脂基材的配向邊進行延伸。該熱塑性樹脂基材係隨著其 配向性提升，延伸張力變大，致使安定的延伸變為困難， 或熱塑性樹脂基材產生斷裂。因此，藉由邊抑制熱塑性樹 脂基材的配向邊延伸，能將積層體更高倍率地延伸。 又，藉由組合空中輔助延伸而使PVA系樹脂的配向性 提升，藉此，即便在硼酸水中延伸後亦能夠使PVA系樹脂 的配向性提升。具體上，藉由預先空中輔助延伸使PVA系 樹脂的配向性提升，在硼酸水中延伸時PVA系樹脂與硼酸 變為容易進行交聯，推定藉由以硼酸成為結點(node)的狀態 被延伸，硼酸水中延伸後，PVA系樹脂的配向性亦會變高。 其結果，能夠製造具有優良的光學特性(例如偏光度)之薄型 偏光膜。 14 201219214 空中輔助延伸的延伸方法係與上述步驟B同樣，可以固 定端延伸，亦可以自由端延伸（例如將積聽通過不同周速 的輥之間而進行單軸延伸之方法）。延伸係可使用__階段進 行’亦可使用多階段進行。使用多階段進行時，後述的延 伸倍率係各階段的延伸倍率之積。在本步驟之延伸方向係 以與上述步驟B的延伸方向大略相同為佳。 在空中輔助延伸之延伸倍率係以35倍以下為佳。空中 輔助延伸的延伸溫度係以PVA系樹脂的麵轉移溫度以上 為佳。延伸溫度係⑽為佳。又，組合空中輔助 延伸及上述魏水巾延㈣，4目祕積㈣的原來長度， 最大延伸倍率係以5.G倍以上為佳，以5 5倍以上為較佳，以 6.0倍以上為更佳。 上述洗淨步驟，代表性係藉由使峨化水溶液浸潰PVA 系樹脂層來以卜上述乾燥步驟之賴溫度係錢t〜i〇〇 °C為佳。 第2圖係顯示本發明的薄型偏光膜的製造方法之一個 例子之概略圖。將積層體職捲放部i轉放而丨，且藉由 親111及112使其浸潰於侧酸水溶液的浴u〇中之後（不溶化 步驟）’藉由輥m及122使其浸潰於二色性物質(峨)及硬化 狎的水溶液的浴120中（染色步驟）。隨後，藉由報131及132 使其浸潰㈣酸及德鉀的水麵的別对（交聯步驟）。 隨後，使積層_邊浸潰於魏切㈣別辦邊在不同 速比的輥⑷及丨懈縱向（長度方向）賦予張力而進行延伸 (步㈣延伸處理之積層體1G藉由輥⑸及152使其浸 15 201219214 潰於碘化鉀水溶液的浴150中（洗淨步驟）且供給至乾燥步驟 (未圖示）。隨後，藉由捲取部160捲取。 B. 薄型偏光膜 本發明的薄型偏光膜能夠藉由上述的製造方法來得 到。本發明的薄型偏光膜，實質上係二色性物質被吸附配 向而成之PVA系樹脂膜。薄型偏光膜的厚度係以1〇μιη以下 為佳’以7μηι以下為較佳，以5μηι以下為更佳。另一方面， 溥型偏光膜的厚度係以〇·5μπι以上為佳，以ι.5μηια上為更 佳。薄型偏光膜係在波長380nm〜780nm的任一波長顯示吸 收二色性為佳。薄型偏光膜的單體透射率係以4〇 〇%以上為 佳，以41.0%以上為較佳，以42〇%以上為更佳。薄型偏光 膜的偏光度係以99.8%以上為佳，以99.9%以上為較佳，以 99.95%以上為更佳。 上述薄型偏光膜的使用方法係能夠採用任意適當的方 去。具體上，可以與上述熱塑性樹脂成為整體的狀態而使 用，亦可以從上述熱塑性樹脂基材轉印至其他構件而使用。 C. 光學積層體 本發明的光學積層體係具有上述薄型偏光膜。第3(a) 及3(b)圖係本發明的較佳實施形態之光學薄膜學積層體之 概略剖面圖。光學薄膜積層體10〇係依照以下的順序而具有 熱塑性樹脂基材u，、薄型偏光犋12,、黏著劑層13及分離片 14光學薄膜積層體2〇〇係依照以下的順序而具有熱塑性樹 脂基材11’、薄型偏光膜12，、接著劑層15、光學功能偏光膜 16、黏著劑層13及分離片14。本實施形態係不將上述的熱 16 201219214 塑性樹脂基材從所得到的薄型偏光膜12’剝離而直接使用 作為光學構件。熱塑性樹脂基材11’係能夠具有作為薄型偏 光膜12’的保護薄膜之功能。 第4(a)及4(b)圖係本發明的另外較佳實施形態之光學 薄膜學積層體之概略剖面圖。光學薄膜積層體300係依照以 下的順序而具有分離片14、黏著劑層13、薄型偏光膜12’、 接著劑層15及光學功能偏光膜16。光學薄膜積層體400係除 了光學薄膜積層體300的結構以外，第2光學功能偏光膜16’ 係在薄型偏光膜12’與分離片14之間透過黏著劑層13而設 置。本實施形態係將上述熱塑性樹脂基材除去。 積層構成本發明的光學積層體之各層係不被圖示例限 定，能夠使用任意適當的黏著劑層或接著劑層。黏著劑層 的代表性係使用丙稀酸系黏著劑形成。作為接著劑層，代 表性係使用乙烯醇系接著劑形成。上述光學功能薄膜係例 如能夠具有與作為偏光膜保護薄膜、相位差薄膜同等之功 能。 [實施例] 以下藉由實施例來說明本發明，但是本發明係不被該 等實施例限定。又，各特性的測定方法係如以下。 1. 厚度 使用數位微計量器（Anritsu公司製、製品名「KC-351C」 進行測定。 2. 熱塑性樹脂基材的吸水率 依據JISK 7209進行測定。 17 201219214 3.熱塑性樹脂基材的破㈣移溫度⑽ 依據JISK7121進行測定。 [實施例1-1] (步驟Α) 作為熱塑性樹脂基材’係使用吸水率〇 6〇%、Tg8〇〇c的 非晶質聚對酞酸乙二酯（A_pET)薄膜（三菱樹脂公司製 '商 品名「NOVACLEAR」、厚度：1〇〇μιη)。 在熱塑性樹脂基材的一面，將聚合度2600、皂化度 99.9%的聚乙烯醇(PVA)樹脂（日本合成化學工業公司製、商 品名「Gohsenol (註冊商標）ΝΗ-26」）的水溶液於6〇。(：塗布 及乾無而形成厚度為7μηι的PVA系樹脂層。如此進行而製造 積層體。 使所得到的積層體在液溫30°C的不溶化浴（相對於1〇〇 重量份之水，調配4重量份硼酸而得到的硼酸水溶液）浸潰 3〇秒(不溶化步驟）。 隨後，在液溫30°C的染色浴（相對於100重量份之水， 調配0.2重量份碘且調配2重量份碘化鉀而得到的碘水溶液) 使其浸潰60秒（染色步驟）。 隨後，在液溫30°C的交聯浴(相對於1〇〇重量份之水， 調配3重量份碘化鉀且調配3重量份硼酸而得到的硼酸水溶 液)使其浸潰3〇秒（交聯步驟）。 隨後，使積層體在液溫6〇°C的硼酸水溶液（相對於1〇〇 重量份之水，調配4重量份硼酸且調配5重量份峨化卸而得 到的水溶液)邊浸潰、邊通過不同周速的輥之間而在縱向（長 201219214 度方向）進行單軸延伸（步_。在砸水溶液之浸漬時間係 I,且延伸至積層體即將斷裂為止。 ^後’使積層體浸潰於洗淨浴（相躲1GG重量份之 X »周配3重量份峨化鉀而得到的水溶液於 風使其乾⑽成(洗淨•絲料）。 士此進仃而得到在熱塑性樹脂基材上形成有薄型偏光 膜之光學薄膜積層體。 [實施例1-2] 將與實施例M同樣地進行而製造之積層體，於un； 供_在不同周速的輥之間而在縱向（長度方向）進行單軸 延伸至2倍(空中輔助延伸步驟）。隨後與實施例Μ同樣地進 二而且進行不溶化步驟、染色步驟、交聯步驟'步驟Β及洗 淨•乾燥步驟’來得到光學薄膜積層體。 (比較例1) 將與實把例1-1同樣地進行而製造之積層體，於⑽。C 的烘箱内進行空中延伸至積層體即將斷裂為止。 隨後，與實施例Μ同樣地依照以下的順序進行染色步 驟、交聯步驟及洗淨•乾燥步驟，來得到薄型偏光膜。 [實施例2-1] 除了作為熱塑性樹脂基材’係使用吸水率〇.75%、Tg75 C的非晶質異敵酸共聚合聚對酞酸乙二酯(jpA共聚合ρΕτ) 薄膜(厚度：ΙΟΟμηι)以外，與實施例M同樣地進行而得到 薄型偏光膜。 [實施例2-2] 19 201219214 除了作為熱塑性樹脂基材，係使用上述IPA共聚合PET 薄膜以外，與實施例1-2同樣地進行而得到薄型偏光膜。 (比較例2) 除了作為熱塑性樹脂基材，係使用上述IPA共聚合pet 薄膜以外，與比較例1同樣地進行而得到薄型偏光膜。 (比較例3-1) 除了作為熱塑性树脂基材，係使用吸水率〇. 1 %、Tgl 1 〇 °C的聚對酞酸乙二酯（PET)薄膜（帝人DUPONT公司製、商 品名「Teijin Tetoron」、厚度：i〇〇pm)及在步驟b將硼酸水 溶液的溫度設作80°C以外’與實施例1-1同樣地進行而嘗試 積層體的延伸’但是完全無法延伸。 (比較例3-2) 除了作為熱塑性Μ脂基材’係使用上述ΡΕτ薄膜及於 130°C進行空中延伸以外，與比較例i同樣地進行而得到薄 型偏光膜。 (比較例4-1) 除了作為熱塑性樹脂基材，係使用吸水率〇 〇3%、Tg8〇 °(：的未延伸聚苯乙烯薄膜(厚度：1〇〇μΓη)及在步驟8將硼酸 水溶液的溫度設作8〇t以外，與實施例μ同樣地進行而得 到薄型偏光膜。 (比較例4-2) 除了作為熱塑性樹脂基材，係使用上述聚笨乙烯薄膜 及於9(rc進行空中延伸以外，與比較例1同樣地進行而得到 薄型偏光膜。 20 201219214 (比較例5-1) 除了作為熱塑性樹脂基材’係使用吸水率〇 03%、Tg °C的未延伸聚丙烯薄膜(T〇hcell〇股份公司製、RX(：系列、 厚度：7〇μηι)以外，與實施例1-1同樣地進行而嘗試製造薄 型偏光膜。 (比較例5-2) 除了作為熱塑性樹脂基材’係使用上述聚丙烯薄膜及 於6〇°C進行空中延伸以外’與比較例1同樣地進行而嘗試製 造薄型偏光膜。 (比較例6-1) 除了作為熱塑性樹脂基材’係使用吸水率3 5%、丁吕65 °C的耐綸6薄膜（無延伸耐綸薄膜、三菱樹脂公司製、商品 名「DAIAMILON C」、厚度：ΙΟΟμιη)以外，與實施例μ 同樣地進行而嘗試製造薄型偏光膜。 (比較例6-2) 除了作為熱塑性樹脂基材’係使用上述耐綸6薄膜以 外’與比較例1同樣地進行而嘗試製造薄型偏光膜。 (實施例3-1) 除了作為熱塑性樹脂基材’係使用吸水率3.5%、Tg75 C的非晶質環己烧二甲醇共聚合對駄酸乙二酯 (CHDM-PET)薄膜（三菱樹脂公司製、商品名「novaCLEAR SH046」、厚度：150μιη)及在步驟B將硼酸水溶液的溫度設 作70°C以外，以外，與實施例1-1同樣地進行而得到薄型偏 光膜。 21 201219214 (實施例3-2) 除了作為熱塑性樹脂基材，係使用上述CHDM-PET薄 膜及在步驟B將硼酸水溶液的溫度設作70°c以外，與實施例 1-2同樣地進行而得到薄型偏光膜。 (比較例7) 除了作為熱塑性樹脂基材，係使用上述CHDM-PET薄 膜以外，與比較例1同樣地進行而得到薄型偏光膜。 在各實施例及比較例，藉由目視觀察延伸後的積層體 之外觀。將評價結果與最大延伸倍率同時顯示在表1。又， 實施例1-2、實施例2-2及實施例3-2的最大延伸倍率係包含 空中輔助延伸之總延伸倍率。 (外觀的評價基準） 〇：良好。 X :由於產生凹凸和下垂、變形•尺寸變化致使外觀不良。 測定在各實施例及比較例所得到之薄型偏光臈的偏光 度。測定偏光度時’在所得到的光學薄膜積層體的薄型偏 光膜侧邊塗布接著劑邊貼合厚度為8 0 μηι的三乙酸纖維素 薄膜(TAC薄膜)之後’將熱塑性樹脂基材剝離。如此進行， 將薄型偏光膜轉印至TAC薄膜而提供偏光度的測定。偏光 度的測定方法係如以下。將測定結果與所得到薄型偏光膜 的厚度同時顯示在表1。 (偏光度的測定方法） 使用紫外可見分光光度計（日本分光公司製、製品名 「V7100」）而測定薄型偏光膜的單體透射率(Ts)'平行透射 22 201219214 率（Τρ)及正交透射率(Tc)，且依照下式求取偏光度(p)。 偏光度(P) (%)={ (Tp-Tc)/(Tp+Tc) } 1/2x 100 又，上述(Τρ)及(Tc)係依據JIS Z 8701的2度視野(C光源) 測定且進行視感度修正而成之Y值。 [表1] 熱塑性 樹脂基材 延伸條件 積層體 -¾¾丨偏光膜 構成材料 吸水率 (%/23,24h) Tg CC) 方式 溫度 CC) 最大延 伸倍率 (倍） 外覲 Ts (%) P (%) 厚度 (μηι) 實施例1-1 Α-ΡΕΤ 0.60 80 水中 60 5.0 〇 42.2 99.96 3 實施例1-2 Α-ΡΕΤ 0.60 80 空中 水中 120 60 6.5 〇 42.8 99.98 3 比較例1 Α-ΡΕΤ 0.60 80 空中 100 4.0 〇 40.6 99.93 3 實施例2-1 ΙΡΑ共聚合PET 0.75 75 水中 80 5.5 〇 42.5 99.99 3 货施例2-2 IPA共聚合PET 0.75 75 空中 水中 120 60 6.5 〇 42.9 99.99 3 比较例2 IPA共聚合PET 0.75 75 空中 100 4.5 〇 41.6 99.88 3 比較例3·1 PET 0.10 110 水中 80 - • - - - 比較例3-2 PET 0.10 110 空中 130 2.0 〇 6.0 99.30 5 比較例4-1 PS 0.03 80 水中 80 3.5 〇 38.8 99.94 4 比较例4-2 PS 0.03 80 空中 90 3.5 〇 38.3 99.93 4 比較例5-1 PP 0.03 -10 水中 60 7.0 X - - - 比較例5-2 PP 0.03 •10 空中 60 7.0 X - - 比較例6*1 耐綸6 3.5 65 水中 60 3.0 X - - 比較例6-2 耐綸6 3.5 65 空中 100 1.5 X - - 實施例3-1 CHDM-PET 0.35 75 水中 70 5.0 0 42.1 99.97 3 實施例3-2 CHDM-PHT 0.35 75 空中 水中 120 70 6.0 〇 42.9 99.99 3 比較例7 CHDM-PET 0.35 75 空中 100 4.0 〇 40.7 99.90 3 使用滿足預定的吸水率及玻璃轉移溫度之熱塑性樹脂 之實施例係能夠良好地進行水中延伸，最大延伸倍率亦非 常高且外觀及光學特性亦非常優良。各自比較實施例1-1、 1-2與比較例1、實施例2-卜2-2與比較例2、實施例3-1、3-2 與比較例7時’相較於只有藉由空中延伸進行延伸，經過水 中延伸步驟者係最大延伸倍率較高。 比較例3-1係無法進行水中延伸。雖然比較例3-2、比較 23 201219214 例4-1及4-2的外觀優良，但是無法得到充分的光學特性。 使用玻璃轉移溫度較低的熱塑性樹脂基材之比較例 5-1及比較例5-2，雖然能夠高倍率地進行延伸，但是pvA系 樹月θ層的形成（塗布.乾燥）時在熱塑性樹脂基材產生皺紋， 而且依照延伸時的溫度而在積層體產生凹凸和下垂而無法 得到經得起光學用途之外觀。 使用吸水率高的熱塑性樹脂基材之比較例6 _丨及比較 例6-2,係在塗布PVA樹脂的水溶液時，容易產生尺寸變化， 而且，比較例6-1在水中延伸時產生皺紋而無法到優良的外 觀。 將實施例1所使用的熱塑性樹脂基材（APET)K 60〇c及 80°C進行延伸（水中、空中）β將此時的延伸倍率及延伸應力 之關係顯示在第5圖及第6圖。又，第5圖係—併顯示在贼 空中輔助延伸2倍之後，於60<t進行水中延伸至總倍率為6 倍為止時之延伸倍率與延伸應力之關係。 從第5圖及6圖，得知相較於空中延伸，水中延伸係熱 塑性樹脂基材的延伸應力大幅度地降低。由此，水可以說 是作為塑化劑的作用而熱塑性樹脂基材產生可塑化。 產業上之可利用性 相較於先前的薄型偏光膜，本發明的薄型偏光膜係具 有較高的偏光性能。因此，依照本發明，能夠使薄型偏光 膜應用在液晶電視、液晶顯示器、行動電話、數位相機、 攝錄影機、可攜式遊戲機、汽車導航器、影印機、印表機、 傳真機、鐘錶、電爐等的液晶面板。 24 201219214 【圓式簡單説明3 第1圖係本發明的較佳實施形態之積層體之概略剖面 圖。 第2圖係顯示本發明的薄型偏光膜的製造方法之一個 例子之概略圖。 第3 (a)〜3 (b)圖係本發明的較佳實施形態之光學薄膜學 積層體之概略剖面圖。 第4(a)〜4(b)圖係本發明的另外較佳實施形態之光學薄 膜學積層體之概略剖面圖。 第5圖係顯示在實施例1所使用之熱塑性樹脂基材的延 伸倍率與延伸應力的關於之圖表。 第6圖係顯示在實施例1所使用之熱塑性樹脂基材的延 伸倍率與延伸應力的關於之圖表。 【主要元件符號說明】 10.. .積層體 11、11’…熱塑性樹脂基材 12.. .PVA系樹脂層 12’...薄型偏光膜 13.. .黏著劑層 14.. .分離片 15…接著劑層 16.. .光學功能薄膜 16’…第2光學功能薄膜 100.. .捲放部 110.··硼酸水溶液的浴 111Ί12Ί21Ί22Ί31Ί32' 141 > 142' 151 ' 152...1¾ 120.. .二色性物質及破化鉀的 水溶液的浴 130…磁酸及峨化卸的水溶液 的浴 140.. .硼酸水溶液的浴 150···碘化鉀水溶液的浴 160·.·捲取部 2〇〇…光學薄膜積層體 300、400...光學功能薄膜積層體 25In the above-mentioned coupling step, the representative is such that the aqueous solution of the piponic acid is impregnated into the pvA system tree layer to enter 4. (4) The water resistance of the resin layer is imparted by the cross-linking treatment. Acid-soluble water (4) Concentration system (4) (4) 0 parts by weight of water, preferably 1 weight loss ~ 4 re-reading 'again, when the crosslinking step is carried out after the above dyeing step' is more preferably formulated with moth compounds. By disposing the moth compound, it is possible to suppress the dissolution of the shirt which has been adsorbed to the p-resin layer. The amount of the preparation is preferably from 1 part by weight to 5 parts by weight relative to the water of the part by weight. A specific example of the moth compound is as described above. The liquid temperature of the crosslinking bath (tetra) aqueous solution is preferably 2 〇 5 〇 c. Shaogui is the cross-linking step before the above-mentioned step lion. In a preferred embodiment, it can be carried out in the order of the color step, the crosslinking step, and the step B 13 201219214. As a further extension step to the above step B, for example, a step of stretching the laminate at a high temperature (e.g., 95 ° C or higher) in the air may be mentioned. This aerial extension step is preferably carried out in step B (extension of boric acid water) and before the dyeing step. This aerial extension step is capable of positioning as a preliminary or auxiliary extension to the extension of boric acid water, hereinafter referred to as "airborne extension". By combining the air-assisted extension, there is a case where the laminated body can be extended at a higher magnification. As a result, a thin polarizing film having more excellent optical characteristics (e.g., degree of polarization) can be produced. For example, when polyethylene terephthalate is used as the thermoplastic resin substrate, the extension in the airborne auxiliary extension and the boric acid water can be extended while suppressing the alignment of the thermoplastic resin substrate as compared with the extension using only boric acid water. As the thermoplastic resin substrate is improved in the orientation, the elongation tension becomes large, which makes it difficult to extend the stability, or the thermoplastic resin substrate is broken. Therefore, the laminate can be stretched more at a higher rate by suppressing the elongation of the alignment of the thermoplastic resin substrate. Further, by combining the air-assisted stretching, the alignment of the PVA-based resin is improved, whereby the alignment of the PVA-based resin can be improved even after stretching in boric acid water. Specifically, the orientation of the PVA-based resin is improved by the advance of the air-assisted extension, and the PVA-based resin and the boric acid are easily crosslinked when extended in boric acid water, and it is estimated that the state is extended by the state in which boric acid is a node. After extending in boric acid water, the alignment of the PVA resin is also increased. As a result, a thin polarizing film having excellent optical characteristics (e.g., degree of polarization) can be produced. 14 201219214 The extension method of the air-assisted extension is the same as the above-mentioned step B, and it is possible to fix the end extension or extend the free end (for example, a method of uniaxially extending the stack between rollers of different peripheral speeds). Extensions can be performed using the __ phase or multiple phases. When the multistage is used, the elongation ratio described later is the product of the stretching ratio at each stage. It is preferable that the extending direction of this step is substantially the same as the extending direction of the above step B. The extension ratio in the air-assisted extension is preferably 35 times or less. The extension temperature of the air-assisted extension is preferably at least the surface transfer temperature of the PVA-based resin. The extension temperature system (10) is preferred. In addition, combined with the air-assisted extension and the original length of the above-mentioned Weishui towel extension (4), 4 mesh secret product (4), the maximum extension magnification is preferably 5.G times or more, more preferably 5 5 times or more, and 6.0 times or more. Better. The washing step is preferably carried out by dipping the PVA-based resin layer with the aqueous deuteration solution, preferably by the temperature of the drying step, t to i〇〇 °C. Fig. 2 is a schematic view showing an example of a method for producing a thin polarizing film of the present invention. The laminated body roll portion i is transferred and immersed, and after being immersed in the bath u〇 of the aqueous acid solution by the pro 111 and 112 (insolubilization step), it is immersed in the rolls m and 122. In a bath 120 of a dichroic substance (峨) and an aqueous solution of hardened hydrazine (dyeing step). Subsequently, by referring to 131 and 132, the water surface of (tetra) acid and potassium is impregnated (crosslinking step). Subsequently, the laminate layer is immersed in the Wei cut (4), and the tension is applied to the rolls (4) of different speed ratios and the longitudinal direction (longitudinal direction) of the stretch (the step (4) is extended by the step (4) by the rolls (5) and 152. The immersion 15 201219214 is immersed in the bath 150 of the potassium iodide aqueous solution (washing step) and supplied to a drying step (not shown). Then, it is taken up by the winding portion 160. B. Thin polarizing film The thin polarizing film of the present invention The thin polarizing film of the present invention is substantially a PVA-based resin film in which a dichroic substance is adsorbed and aligned. The thickness of the thin polarizing film is preferably 1 μm or less. It is preferably 7 μηι or less, more preferably 5 μηι or less. On the other hand, the thickness of the 溥-type polarizing film is preferably 〇·5 μπι or more, more preferably ι.5 μηια. The thin polarizing film is at a wavelength of 380 nm. Any wavelength of 780 nm exhibits absorption dichroism. The transmittance of the thin polarizing film is preferably 4% or more, more preferably 41.0% or more, and more preferably 42% or more. The degree of polarization of the film is 99.8% or more. Preferably, 99.9% or more is preferable, and 99.95% or more is more preferable. The method of using the above-mentioned thin polarizing film can be any appropriate one. Specifically, it can be used in the same state as the thermoplastic resin. The optical resin substrate may be transferred to another member and used. C. Optical laminate The optical laminate system of the present invention has the above-mentioned thin polarizing film. Figs. 3(a) and 3(b) are preferred embodiments of the present invention. A schematic cross-sectional view of the optical thin film laminate of the form. The optical film laminate 10 has a thermoplastic resin substrate u, a thin polarizing film 12, an adhesive layer 13, and an optical film laminate of the separator 14 in the following order. The bismuth system has a thermoplastic resin substrate 11', a thin polarizing film 12, an adhesive layer 15, an optical function polarizing film 16, an adhesive layer 13, and a separator 14 in the following order. Heat 16 201219214 The plastic resin substrate is directly used as an optical member from the obtained thin polarizing film 12'. The thermoplastic resin substrate 11' can have a thin polarized light. 4(a) and 4(b) are schematic cross-sectional views of an optical thin film laminate according to another preferred embodiment of the present invention. The optical thin film laminate 300 is in the following order. The separation sheet 14, the adhesive layer 13, the thin polarizing film 12', the adhesive layer 15, and the optical function polarizing film 16. The optical thin film laminated body 400 is a second optical functional polarizing film 16 in addition to the structure of the optical thin film laminated body 300. The adhesive layer 13 is provided between the thin polarizing film 12' and the separator 14. The thermoplastic resin substrate is removed in the present embodiment. The layers of the optical laminate of the present invention are not laminated. By definition, any suitable adhesive or adhesive layer can be used. Representative of the adhesive layer is formed using an acrylic adhesive. As the adhesive layer, a representative one is formed using a vinyl alcohol-based adhesive. The optical functional film can have, for example, the same function as a polarizing film protective film or a retardation film. [Examples] The present invention is illustrated by the following examples, but the present invention is not limited by the examples. Moreover, the measuring method of each characteristic is as follows. 1. The thickness is measured using a digital micrometer (manufactured by Anritsu Co., Ltd., product name "KC-351C". 2. The water absorption rate of the thermoplastic resin substrate is measured in accordance with JIS K 7209. 17 201219214 3. Breaking of the thermoplastic resin substrate (4) The temperature (10) was measured in accordance with JIS K7121. [Example 1-1] (Step Α) As the thermoplastic resin substrate, amorphous polyparaphthalic acid ethylene ester (A_pET) having a water absorption of 〇6〇% and Tg8〇〇c was used. Film (product name "NOVACLEAR" manufactured by Mitsubishi Plastics Co., Ltd., thickness: 1〇〇μηη). Polyvinyl alcohol (PVA) resin having a polymerization degree of 2600 and a saponification degree of 99.9% on one side of the thermoplastic resin substrate (Japanese synthesis) An aqueous solution of the product name "Gohsenol (registered trademark) ΝΗ-26" manufactured by Chemical Industry Co., Ltd. was placed at 6 〇. (: A PVA-based resin layer having a thickness of 7 μm was formed by coating and drying.) The laminate was produced in this manner. The obtained laminate was impregnated for 3 sec (insolubilization step) in an insolubilizing bath at a liquid temperature of 30 ° C (a boric acid aqueous solution obtained by dispersing 4 parts by weight of boric acid with respect to 1 part by weight of water). Subsequently, at a liquid temperature 30 ° C dyeing (Iodine aqueous solution obtained by formulating 0.2 part by weight of iodine and mixing 2 parts by weight of potassium iodide with respect to 100 parts by weight of water) was immersed for 60 seconds (dyeing step). Subsequently, a crosslinking bath at a liquid temperature of 30 ° C ( The aqueous solution of boric acid obtained by dispersing 3 parts by weight of potassium iodide and 3 parts by weight of boric acid was added to the water for 1 Torr (crosslinking step) with respect to 1 part by weight of water. Subsequently, the layered body was allowed to stand at a liquid temperature of 6 〇. The aqueous solution of boric acid at °C (with respect to 1 part by weight of water, 4 parts by weight of boric acid and 5 parts by weight of an aqueous solution obtained by deuteration) are impregnated while passing between rolls of different peripheral speeds in the longitudinal direction. (long 201219214 degree direction) uniaxially stretched (step _. in the immersion time of the hydrazine aqueous solution I, and extended until the laminated body is about to break. ^ After 'throwing the laminated body in the washing bath (to hide 1 GG parts by weight) X » The aqueous solution obtained by dispersing 3 parts by weight of potassium telluride in the air is dried (10) into (washed and silk). The optical film having a thin polarizing film formed on the thermoplastic resin substrate is obtained. [Launch 1-2] The same as in the embodiment M The laminate produced by the line is uniaxially stretched to 2 times in the longitudinal direction (longitudinal direction) between the rolls of different peripheral speeds (air-assisted extension step). Then proceeds in the same manner as the embodiment Μ Furthermore, the optical film laminate was obtained by performing an insolubilization step, a dyeing step, a crosslinking step, a step, and a washing and drying step. (Comparative Example 1) A laminate produced in the same manner as in Example 1-1 was used. In the oven of (10) C, the film was stretched in the air until the laminate was about to be broken. Then, the dyeing step, the crosslinking step, and the washing and drying step were carried out in the same manner as in Example , to obtain a thin polarizing film. [Example 2-1] In addition to the thermoplastic resin substrate', a mixture of amorphous isocyanate copolymerized polyethylene terephthalate (jpA copolymerized ρΕτ) film having a water absorption ratio of 75.75% and Tg75 C was used. A thin polarizing film was obtained in the same manner as in Example M except that ΙΟΟμηι). [Example 2-2] 19 201219214 A thin polarizing film was obtained in the same manner as in Example 1-2 except that the above-mentioned IPA copolymerized PET film was used as the thermoplastic resin substrate. (Comparative Example 2) A thin polarizing film was obtained in the same manner as in Comparative Example 1, except that the above-mentioned IPA copolymerized PET film was used as the thermoplastic resin substrate. (Comparative Example 3-1) A polyethylene terephthalate (PET) film having a water absorption of 0.1% and Tgl 1 〇 ° C was used as a thermoplastic resin substrate (manufactured by Teijin DuPont Co., Ltd., trade name "Teijin"). "Tetoron", thickness: i pm), and the temperature of the boric acid aqueous solution was set to 80 ° C in the step b, and the extension of the laminate was attempted in the same manner as in Example 1-1, but it was not extended at all. (Comparative Example 3-2) A thin polarizing film was obtained in the same manner as in Comparative Example i except that the above-mentioned ΡΕτ film was used as a thermoplastic resin substrate and air-dried at 130 °C. (Comparative Example 4-1) In addition to the thermoplastic resin substrate, an unstretched polystyrene film (thickness: 1 〇〇μΓη) having a water absorption ratio of 3%, Tg8 〇 (:: and an aqueous solution of boric acid in the step 8) was used. A thin polarizing film was obtained in the same manner as in Example μ except that the temperature was set to 8 Torr. (Comparative Example 4-2) In addition to the thermoplastic resin substrate, the above-mentioned polystyrene film was used and 9 (rc was airborne). In the same manner as in Comparative Example 1, a thin polarizing film was obtained in the same manner as in Comparative Example 1. 20 201219214 (Comparative Example 5-1) An unstretched polypropylene film having a water absorption ratio of %03% and Tg °C was used as the thermoplastic resin substrate. An attempt was made to produce a thin polarizing film in the same manner as in Example 1-1 except that RX (: series, thickness: 7 〇μηι), manufactured by T〇hcell Co., Ltd. (Comparative Example 5-2) except as a thermoplastic resin substrate. A thin polarizing film was produced in the same manner as in Comparative Example 1 except that the above-mentioned polypropylene film was used and air-extended at 6 ° C. (Comparative Example 6-1) Water absorption rate was used as a thermoplastic resin substrate. 3 5%, Ding Lu 65 °C nylon 6 thin A thin polarizing film was produced in the same manner as in Example μ except that the film was not stretched, and the product name was "DAIAMILON C" (manufactured by Mitsubishi Plastics Co., Ltd., product name "DAIAMILON C", thickness: ΙΟΟμηη). (Comparative Example 6-2) Except as a thermoplastic resin In the same manner as in Comparative Example 1, except that the above-mentioned nylon 6 film was used, an attempt was made to produce a thin polarizing film. (Example 3-1) In addition to the thermoplastic resin substrate, a water absorption ratio of 3.5% and Tg75 C was used. Amorphous cyclohexene dimethanol copolymerization of ethylene phthalate (CHDM-PET) film (manufactured by Mitsubishi Plastics Co., Ltd., trade name "novaCLEAR SH046", thickness: 150 μm) and temperature of boric acid aqueous solution in step B A thin polarizing film was obtained in the same manner as in Example 1-1 except for the temperature of 70 ° C. 21 201219214 (Example 3-2) In addition to the thermoplastic resin substrate, the above-mentioned CHDM-PET film was used and in the step B A thin polarizing film was obtained in the same manner as in Example 1-2 except that the temperature of the boric acid aqueous solution was changed to 70 ° C. (Comparative Example 7) In addition to the above-mentioned CHDM-PET film, the ratio was used as the thermoplastic resin substrate. In the same manner as in Example 1, a thin polarizing film was obtained in the same manner. In each of the examples and the comparative examples, the appearance of the laminated body after stretching was visually observed. The evaluation results and the maximum stretching ratio were simultaneously shown in Table 1. Further, Example 1 2. The maximum stretching ratio of Example 2-2 and Example 3-2 is the total stretching ratio including the air-assisted extension. (Evaluation criteria of appearance) 〇: Good. X: Due to unevenness and sagging, deformation, dimensional change The appearance was poor. The degree of polarization of the thin polarized enamel obtained in each of the examples and the comparative examples was measured. When the degree of polarization is measured, a thermoplastic cellulose substrate is peeled off by applying a film of a cellulose triacetate (TAC film) having a thickness of 80 μm to the side of the thin polarizing film of the obtained optical film laminate. In this manner, the thin polarizing film was transferred to the TAC film to provide measurement of the degree of polarization. The method of measuring the degree of polarization is as follows. The measurement results are shown in Table 1 together with the thickness of the obtained thin polarizing film. (Measurement method of the degree of polarization) The transmittance (Ts) of the thin polarizing film was measured by an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation, product name "V7100"). Parallel transmission 22 201219214 Rate (Τρ) and orthogonal Transmittance (Tc), and the degree of polarization (p) was obtained according to the following formula. Polarization degree (P) (%)={ (Tp-Tc)/(Tp+Tc) } 1/2x 100 Further, the above (Τρ) and (Tc) are measured according to the 2D field of view (C light source) of JIS Z 8701. And the Y value of the visual sensitivity is corrected. [Table 1] Thermoplastic Resin Substrate Extended Condition Laminate - ⁄ ⁄ ⁄ 丨 丨 丨 丨 构成 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 吸水 吸水 吸水 吸水 吸水 吸水 吸水 吸水 吸水 吸水 吸水 吸水 吸水 吸水 吸水 吸水 吸水 吸水 吸水) Thickness (μηι) Example 1-1 Α-ΡΕΤ 0.60 80 Water 60 5.0 〇42.2 99.96 3 Example 1-2 Α-ΡΕΤ 0.60 80 Airborne water 120 60 6.5 〇42.8 99.98 3 Comparative Example 1 Α-ΡΕΤ 0.60 80 Airborne 100 4.0 〇40.6 99.93 3 Example 2-1 ΙΡΑCopolymerized PET 0.75 75 Water 80 5.5 〇42.5 99.99 3 Goods Example 2-2 IPA copolymerized PET 0.75 75 Aerial water 120 60 6.5 〇42.9 99.99 3 Comparative Example 2 IPA Polymerized PET 0.75 75 Air 100 4.5 〇41.6 99.88 3 Comparative Example 3·1 PET 0.10 110 Water 80 - • - - - Comparative Example 3-2 PET 0.10 110 Aerial 130 2.0 〇6.0 99.30 5 Comparative Example 4-1 PS 0.03 80 Water 80 3.5 〇38.8 99.94 4 Comparative Example 4-2 PS 0.03 80 Air 90 3.5 〇38.3 99.93 4 Comparative Example 5-1 PP 0.03 -10 Water 60 7.0 X - - - Comparative Example 5-2 PP 0.03 •10 Air 60 7.0 X - - Comparative Example 6*1 Nylon 6 3.5 65 Water 60 3.0 X - - Comparative Example 6-2 6 3.5 65 Air 100 1.5 X - - Example 3-1 CHDM-PET 0.35 75 Water 70 5.0 0 42.1 99.97 3 Example 3-2 CHDM-PHT 0.35 75 Aerial water 120 70 6.0 〇42.9 99.99 3 Comparative Example 7 CHDM- PET 0.35 75 Air 100 4.0 〇40.7 99.90 3 The embodiment using a thermoplastic resin which satisfies a predetermined water absorption rate and glass transition temperature enables good water extension, a maximum stretching ratio, and an excellent appearance and optical characteristics. Comparing Examples 1-1, 1-2 and Comparative Example 1, Example 2 - 2-2, and Comparative Example 2, and Examples 3-1, 3-2 and Comparative Example 7 respectively The air extension extends, and the maximum extension ratio is higher in the water extension step. Comparative Example 3-1 was not capable of extending in water. Although Comparative Example 3-2 and Comparative 23 201219214 Examples 4-1 and 4-2 were excellent in appearance, sufficient optical characteristics could not be obtained. In Comparative Example 5-1 and Comparative Example 5-2 in which a thermoplastic resin substrate having a low glass transition temperature was used, the stretching was possible at a high magnification, but the formation of a pvA tree θ layer (coating and drying) was carried out at a thermoplastic resin. The substrate is wrinkled, and unevenness and sag occur in the laminate in accordance with the temperature at the time of stretching, so that the appearance which can withstand optical use cannot be obtained. In Comparative Example 6 _ 丨 and Comparative Example 6-2 using a thermoplastic resin substrate having a high water absorption rate, dimensional change was likely to occur when an aqueous solution of a PVA resin was applied, and wrinkles were generated when Comparative Example 6-1 was extended in water. Unable to get a good look. The thermoplastic resin substrate (APET) K 60〇c used in Example 1 and 80 ° C were extended (in water, air) β, and the relationship between the stretching ratio and the elongation stress at this time is shown in Fig. 5 and Fig. 6 . . Further, Fig. 5 is a graph showing the relationship between the stretching ratio and the extension stress when the water is extended to a total magnification of 6 times after 60 times in the thief. From Figs. 5 and 6, it is found that the elongation stress of the water-extended thermoplastic resin substrate is drastically lowered as compared with the air extension. Thus, water can be said to function as a plasticizer and the thermoplastic resin substrate can be plasticized. Industrial Applicability The thin polarizing film of the present invention has higher polarizing performance than the conventional thin polarizing film. Therefore, according to the present invention, a thin polarizing film can be applied to a liquid crystal television, a liquid crystal display, a mobile phone, a digital camera, a video camera, a portable game machine, a car navigator, a photocopying machine, a printer, a facsimile machine, A liquid crystal panel such as a clock or an electric furnace. 24 201219214 [Circular Simple Description 3] Fig. 1 is a schematic cross-sectional view showing a laminated body of a preferred embodiment of the present invention. Fig. 2 is a schematic view showing an example of a method for producing a thin polarizing film of the present invention. 3(a) to 3(b) are schematic cross-sectional views showing an optical thin film laminate of a preferred embodiment of the present invention. 4(a) to 4(b) are schematic cross-sectional views showing an optical film laminate of another preferred embodiment of the present invention. Fig. 5 is a graph showing the elongation ratio and the extension stress of the thermoplastic resin substrate used in Example 1. Fig. 6 is a graph showing the elongation ratio and the extension stress of the thermoplastic resin substrate used in Example 1. [Description of main component symbols] 10.. Laminate 11, 11'... thermoplastic resin substrate 12. PVA resin layer 12'... Thin polarizing film 13. Adhesive layer 14: Separator 15...Binder layer 16: Optical functional film 16'... 2nd optical functional film 100.. Reeling part 110.·Boil solution of boric acid solution 111Ί12Ί21Ί22Ί31Ί32' 141 > 142' 151 ' 152...13⁄4 120 .. . bath of dichroic substance and aqueous solution of decomposing potassium... bath of magnetic acid and deuterated aqueous solution 140.. bath of boric acid aqueous solution 150··· bath of potassium iodide aqueous solution 160·. 2〇〇...Optical film laminates 300, 400... Optical functional film laminates 25