TWI771225B - Polyvinyl alcohol film, polarizing film comprising the same as well as a manufacturing method thereof - Google Patents

Polyvinyl alcohol film, polarizing film comprising the same as well as a manufacturing method thereof Download PDF

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TWI771225B
TWI771225B TW110142496A TW110142496A TWI771225B TW I771225 B TWI771225 B TW I771225B TW 110142496 A TW110142496 A TW 110142496A TW 110142496 A TW110142496 A TW 110142496A TW I771225 B TWI771225 B TW I771225B
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polyvinyl alcohol
film
alcohol film
absorbance
wavelength
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TW202321354A (en
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陳家穎
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長春石油化學股份有限公司
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Abstract

The present invention relates to a polyvinyl alcohol (PVA) film, a polarizing film comprising the same as well as the manufacturing method thereof. The IR absorption intensity ratio of the PVA film is 0.85 <A1730 cm -1/ A1710 cm -1< 0.97. The PVA film of the present invention has excellent hue characteristics.

Description

聚乙烯醇薄膜、包含其之偏光薄膜及其製造方法Polyvinyl alcohol film, polarizing film including the same, and manufacturing method thereof

本發明係關於一種聚乙烯醇(polyvinyl alcohol,PVA)薄膜,可用於作為光學薄膜,特別係偏光膜。The present invention relates to a polyvinyl alcohol (PVA) film, which can be used as an optical film, especially a polarizing film.

聚乙烯醇(polyvinyl alcohol,PVA)薄膜是一種親水性聚合物,具有透明性、機械強度、水溶性、可加工性佳等性能,已廣泛用於包裝材料或電子產品的光學膜,特別係偏光膜。Polyvinyl alcohol (PVA) film is a hydrophilic polymer with properties such as transparency, mechanical strength, water solubility, and good processability. It has been widely used in packaging materials or optical films for electronic products, especially polarized light. membrane.

PVA薄膜製備成光學薄膜的製造過程中,可依照所需性能而選擇性地使用官能基改質,隨後再進行拉伸。製造方法可分為乾式及濕式,乾式是在固定的溫濕度下,將PVA薄膜於惰性氣體環境中進行拉伸,隨後進行染色等工序;濕式是將PVA薄膜進行染色,隨後在於溶液中進行拉伸。由於乾式所製備的PVA薄膜常會有表面不平整、或染色不均的問題,而濕式所製造出的PVA薄膜具有較佳性能(例如顏色均勻),因此目前一般係使用濕式方式製造PVA薄膜居多。In the manufacturing process of the PVA film being prepared into an optical film, functional groups can be selectively modified according to the desired properties and then stretched. The manufacturing method can be divided into dry type and wet type. The dry type is to stretch the PVA film in an inert gas environment under a fixed temperature and humidity, followed by dyeing and other processes; the wet type is to dye the PVA film and then put it in a solution. Stretch. Since the PVA film prepared by dry method often has the problem of uneven surface or uneven dyeing, and the PVA film produced by wet method has better properties (such as uniform color), the wet method is generally used to manufacture PVA film at present. Mostly.

製造偏光膜時,拉伸倍率越高,可獲得的光學性能也會隨之提高,因此於拉伸時會盡可能的將PVA薄膜拉伸至接近斷裂的臨界附近,以獲得較佳光學性的PVA薄膜。When manufacturing polarizing films, the higher the stretching ratio, the higher the optical properties that can be obtained. Therefore, when stretching, the PVA film will be stretched as close to the critical point of fracture as possible to obtain better optical properties. PVA film.

良好的偏光膜具有顏色均勻、色斑少及無皺褶等特性,能提供較佳的光學性質。為提高偏光膜的光學性質,先前技術會藉由改變聚乙烯醇結構、或加入官能基(例如陽離子基)等,以改變黏度或皂化度,進而提升光學性質。A good polarizing film has the characteristics of uniform color, less color spots and no wrinkles, and can provide better optical properties. In order to improve the optical properties of the polarizing film, the prior art will change the viscosity or saponification degree by changing the structure of polyvinyl alcohol, or adding functional groups (eg, cationic groups), etc., so as to improve the optical properties.

然而,習知製法殘留的醋酸基分布、對排度(Syndiotacticity)會對於偏光片色相有顯著影響。However, the distribution and syndiotacticity of acetate groups remaining in the conventional manufacturing method have a significant impact on the hue of the polarizer.

發明人發現,造成偏光膜有紅光或藍光洩漏的原因在於膜中I 3 -及 I 5 -的相對含量。 若I 5 -較少,則700 nm吸收度較低,外觀偏紅(Red leak);反之,若I 3 -較少, 則480 nm吸收低,外觀偏藍(Blue leak)。硼酸若能有效與PVA產生交聯,有助於I 5 -錯合物生成、或是避免I 3 -的流失,因此,若硼酸與PVA交聯反應量不足,則有可能造成偏光膜會有色相偏紅或偏藍的現象發生。另一方面,若對排度越高, I 5 -複合物較易形成,容易降低Red leak。除了對排度之外,殘存醋酸基排列形式、硼酸錯合程度等亦會影響相對色相。須同時控制在特定範圍,才能達到色相均勻的效果。 The inventors found that the reason for the leakage of red light or blue light in the polarizing film is the relative content of I 3 - and I 5 - in the film. If I 5 - is less, the absorption at 700 nm is lower, and the appearance is reddish (Red leak); on the contrary, if I 3 - is less, the absorption at 480 nm is low, and the appearance is blue (Blue leak). If boric acid can effectively cross-link with PVA, it will help the formation of I 5 -complex or avoid the loss of I 3 - . Therefore, if the amount of cross-linking reaction between boric acid and PVA is insufficient, it may cause the polarizing film to have A reddish or bluish hue occurs. On the other hand, the higher the degree of alignment , the easier the formation of I 5 -complexes, and the easier the reduction of Red leak. In addition to the alignment degree, the arrangement form of the remaining acetate groups and the degree of boronic acid complexation will also affect the relative hue. It must be controlled in a specific range at the same time to achieve the effect of uniform hue.

是以,為解決上述問題,本發明藉由控制IR吸收光譜中非氫鍵羰基 / 氫鍵羰基的比例,達到色相優異之PVA薄膜,其中非氫鍵羰基之IR吸收強度為A1730 cm -1,氫鍵羰基之IR吸收強度為A1710 cm -1Therefore, in order to solve the above-mentioned problems, the present invention achieves a PVA film with excellent hue by controlling the ratio of the non-hydrogen-bonded carbonyl group/hydrogen-bond carbonyl group in the IR absorption spectrum, wherein the IR absorption intensity of the non-hydrogen-bonded carbonyl group is A1730 cm -1 , The IR absorption intensity of the hydrogen-bonded carbonyl group is A1710 cm -1 .

本發明之目的為提供一種聚乙烯醇(polyvinyl alcohol,PVA)薄膜,其具有IR吸收強度比值為0.85 < A1730 cm -1/A1710 cm -1< 0.97,該IR吸收強度係將該聚乙烯醇薄膜浸泡於純水,攪拌後取出,以 105 ℃/1hr 進行乾燥後,進行分析。 The purpose of the present invention is to provide a polyvinyl alcohol (PVA) film, which has an IR absorption intensity ratio of 0.85 < A1730 cm -1 /A1710 cm -1 < 0.97, and the IR absorption intensity is the value of the PVA film. It was immersed in pure water, stirred, taken out, dried at 105°C/1hr, and analyzed.

於較佳實施例中,該PVA薄膜具有醋酸酯基吸收強度為0.35 < (A1710 cm -1+ A1730 cm -1)/A1425 cm -1< 0.55,該醋酸酯基吸收強度係將該聚乙烯醇薄膜浸泡於純水,攪拌後取出,以 105 ℃/1hr 進行乾燥後,進行分析。 In a preferred embodiment, the PVA film has an acetate-based absorption strength of 0.35 < (A1710 cm -1 + A1730 cm -1 )/A1425 cm -1 < 0.55, and the acetate-based absorption strength is the polyvinyl alcohol The film was immersed in pure water, taken out after stirring, dried at 105°C/1hr, and analyzed.

於較佳實施例中,該PVA薄膜具有對排度為52%至56%。In a preferred embodiment, the PVA film has a parallelism of 52% to 56%.

於較佳實施例中,0.12 g之該PVA薄膜經0.2 wt%硼酸水溶液處理,並以水溶解後該水溶液之硼含量為16至19 ppm。In a preferred embodiment, 0.12 g of the PVA film is treated with a 0.2 wt% aqueous solution of boric acid, and the aqueous solution has a boron content of 16 to 19 ppm after being dissolved in water.

本發明之另一目的為提供一種光學薄膜,其包含如前所述之PVA薄膜。於較佳實施例中,該光學薄膜係偏光薄膜。Another object of the present invention is to provide an optical film comprising the aforementioned PVA film. In a preferred embodiment, the optical film is a polarizing film.

於較佳實施例中,該偏光薄膜在正交尼科耳狀態之波長480 nm之吸光度(A)與波長700 nm之吸光度(B)之比率(A/B)為1.40至1.70。In a preferred embodiment, the ratio (A/B) of the absorbance (A) at a wavelength of 480 nm to the absorbance at a wavelength of 700 nm (B) of the polarizing film in the crossed Nicols state is 1.40 to 1.70.

於較佳實施例中,該偏光薄膜在正交尼科耳狀態之波長480 nm之吸光度(A)與波長700 nm之吸光度(B)之比率(A/B)為1.51至1.65。In a preferred embodiment, the ratio (A/B) of the absorbance (A) at a wavelength of 480 nm to the absorbance at a wavelength of 700 nm (B) of the polarizing film in the crossed Nicols state is 1.51 to 1.65.

本發明之另一目的為提供一種PVA薄膜之製備方法,包含:(a) 將乙烯酯系樹脂單體聚合,形成聚乙烯酯系樹脂後,再進行皂化反應獲得聚乙烯醇樹脂,其中,於聚合反應時添加乙烯基2,2-雙(三氟甲基)丙酸(vinyl 2,2-bis(trifluoromethyl)propionate)共聚物,且該共聚物莫耳量/乙烯酯系樹脂單體莫耳量之添加量比率為1至3 mole %,添加皂化介電常數介於34至36的溶劑;(b) 將該聚乙烯醇樹脂加溫溶解,形成聚乙烯醇澆鑄溶液;(C)將該澆鑄溶液澆鑄至鑄造滾筒;及(d) 經乾燥後形成該PVA薄膜。Another object of the present invention is to provide a preparation method of PVA film, comprising: (a) polymerizing vinyl ester resin monomers to form polyvinyl ester resin, and then performing saponification reaction to obtain polyvinyl alcohol resin, wherein, in During the polymerization reaction, vinyl 2,2-bis(trifluoromethyl)propionate (vinyl 2,2-bis(trifluoromethyl)propionate) copolymer is added, and the copolymer molar amount/vinyl ester resin monomer molar The addition ratio of the amount is 1 to 3 mole %, adding a solvent with a saponification dielectric constant of 34 to 36; (b) heating and dissolving the polyvinyl alcohol resin to form a polyvinyl alcohol casting solution; (c) this The casting solution is cast to a casting drum; and (d) dried to form the PVA film.

於較佳實施例中,該PVA薄膜之製備方法中步驟(a)至(c)係利用外加保溫裝置下進行。In a preferred embodiment, the steps (a) to (c) in the preparation method of the PVA film are carried out by using an external heat preservation device.

於較佳實施例中,該外加保溫裝置為金屬電熱線或內部具液體之夾套。In a preferred embodiment, the external heat preservation device is a metal electric heating wire or a jacket with liquid inside.

於較佳實施例中,該PVA薄膜之製備方法進一步於該步驟(a)中調整pH值,或添加不同介電常數的溶劑,以控制殘存醋酸酯基排列。In a preferred embodiment, the preparation method of the PVA film further adjusts the pH value in the step (a), or adds solvents with different dielectric constants to control the arrangement of the remaining acetate groups.

於較佳實施例中,該PVA薄膜之製備方法進一步於該步驟(a)中,皂化反應獲得之該聚乙烯醇樹脂經過粉碎乾燥,乾燥過程中適時噴進蒸氣,避免樹酯粒過度乾燥,產生結皮。In a preferred embodiment, the preparation method of the PVA film is further in the step (a), the polyvinyl alcohol resin obtained by the saponification reaction is pulverized and dried, and steam is sprayed in a timely manner during the drying process to avoid excessive drying of the resin particles. crust.

本發明之功效在於,不僅改善習知PVA薄膜的製程,並且藉由調控IR吸收光譜中非氫鍵羰基/氫鍵羰基的比例,達到色相優異之PVA薄膜。The effect of the present invention is not only to improve the manufacturing process of the conventional PVA film, but also to achieve a PVA film with excellent hue by adjusting the ratio of non-hydrogen-bonded carbonyl groups/hydrogen-bonded carbonyl groups in the IR absorption spectrum.

以下實施方式不應視為過度地限制本發明。本發明所屬技術領域中具有通常知識者可在不背離本發明之精神或範疇的情況下對本文所討論之實施例進行修改及變化,而仍屬於本發明之範圍。The following embodiments should not be construed to unduly limit the invention. Modifications and variations of the embodiments discussed herein can be made by those of ordinary skill in the art to which this invention pertains without departing from the spirit or scope of the invention, and still fall within the scope of the invention.

本文中術語「一」及「一種」代表於本文中之語法對象有一個或多於一個(即至少一個)。The terms "a" and "an" herein refer to one or more than one (ie, at least one) of the grammatical objects herein.

本發明提供一種PVA薄膜,特別係一種具有特定IR吸收強度比值的PVA薄膜。此外,本發明還提供一種包含該PVA薄膜的一種光學薄膜。The invention provides a PVA film, especially a PVA film with a specific IR absorption intensity ratio. In addition, the present invention also provides an optical film comprising the PVA film.

前述之「IR吸收強度比值」係利用紅外線光譜術(infrared spectroscopy)獲得,其係用來偵測分子的振動能量(或頻率)的技術,利用紅外光和分子作用所產生的分子振動的原理,來記錄分子吸收紅外光之後所呈的振動模式(vibrational modes),記錄吸收光的相對強度對紅外光波長(λ)所得的圖,即稱為紅外光譜,可作為特定分子鑑定之用。所述之IR分析方法例如:參考標準方法JIS k 6726,將 10 cm×10 cm PVA 薄膜浸泡於 2000 ml 的 30 ℃純水,使用磁石攪拌機攪拌 5分鐘後取出。預熱烘箱至 105 ℃,將浸泡後的薄膜鋪平放置托盤中,以 105 ℃/1hr 進行乾燥,之後將該薄膜取出後,進行IR分析。IR吸收值若有產生負值的情況,將數據做適當的平移,所有數據加一固定常數,使全範圍IR光譜吸收值最低點為0。The aforementioned "IR absorption intensity ratio" is obtained by infrared spectroscopy, which is a technique used to detect the vibrational energy (or frequency) of molecules, using the principle of molecular vibrations generated by the interaction of infrared light and molecules, To record the vibrational modes of molecules after absorbing infrared light, and record the relative intensity of absorbed light versus the wavelength of infrared light (λ), which is called infrared spectroscopy, which can be used for specific molecular identification. The IR analysis method described is for example: referring to the standard method JIS k 6726, immerse a 10 cm×10 cm PVA film in 2000 ml of 30 °C pure water, stir it with a magnetic stirrer for 5 minutes, and then take it out. Preheat the oven to 105 °C, place the soaked film flat on a tray, dry at 105 °C/1hr, and then take out the film for IR analysis. If the IR absorption value has a negative value, the data is appropriately shifted, and a fixed constant is added to all the data, so that the lowest point of the full-range IR spectral absorption value is 0.

參照圖1,其為醋酸酯基中的C=0吸收峰分為1710 cm -1(與OH基相連)及1730 cm -1(嵌段內的非氫鍵羰基)。根據至少一實施例,發明人發現,醋酸酯基中的C=0吸收峰分為1710 cm -1(與OH基相連)及1730 cm -1(嵌段內),若1730 cm -1吸收強度(A 1730 cm -1)越高,代表嵌段內C=0較多,對於偏光片色相會有影響。於一較佳實施例中,本發明之聚乙烯醇薄膜具有IR吸收強度比值為0.85 < A1730 cm -1/A1710 cm -1< 0.97。具體以下數值中任意兩者間的範圍但不包含該等數值,例如:0.85、0.86、...、0.97。 Referring to FIG. 1 , the C=0 absorption peak in the acetate group is divided into 1710 cm −1 (connected to the OH group) and 1730 cm −1 (non-hydrogen-bonded carbonyl group in the block). According to at least one embodiment, the inventors found that the C=0 absorption peak in the acetate group is divided into 1710 cm -1 (connected to the OH group) and 1730 cm -1 (in the block), if the 1730 cm -1 absorption intensity The higher the (A 1730 cm -1 ), the more C=0 in the block, which will affect the hue of the polarizer. In a preferred embodiment, the polyvinyl alcohol film of the present invention has an IR absorption intensity ratio of 0.85 < A1730 cm -1 /A1710 cm -1 < 0.97. The range between any two of the following numerical values is specified but not inclusive, for example: 0.85, 0.86, . . . , 0.97.

此外/或者,發明人發現,(A1710 cm -1+A1730 cm -1)/A1425 cm -1代表整體醋酸酯基殘留量,該值越高,偏光度下降,且有紅光洩漏的傾向。於一較佳實施例中,本發明之聚乙烯醇薄膜進一步具有醋酸酯基吸收強度為0.35 < (A1710 cm -1+ A1730 cm -1)/A1425 cm -1< 0.55,具體為以下數值中任意兩者間的範圍但不包含該等數值,例如:0.35、0.36、...、0.55。 A1730 cm -1吸收值越高,嵌段內的醋酸基(OAc基)越多,此可藉由於皂化過程中適當調整pH值,或添加不同介電常數的溶劑,以控制殘存醋酸酯基排列;另外,不同溶劑的鹼化會控制不同殘存醋酸基的排列。 In addition/alternatively, the inventors found that (A1710 cm -1 +A1730 cm -1 )/A1425 cm -1 represents the total residual acetate group, and the higher the value, the lower the degree of polarization and the tendency to leak red light. In a preferred embodiment, the polyvinyl alcohol film of the present invention further has an acetate-based absorption strength of 0.35 < (A1710 cm -1 + A1730 cm -1 )/A1425 cm -1 < 0.55, which is any of the following values Ranges between but not inclusive of such values, eg: 0.35, 0.36, ..., 0.55. The higher the absorption value of A1730 cm -1 , the more acetate groups (OAc groups) in the block. This can be controlled by adjusting the pH value or adding solvents with different dielectric constants during the saponification process to control the arrangement of the remaining acetate groups. ; In addition, the alkalinization of different solvents will control the arrangement of different residual acetate groups.

本發明之PVA薄膜還具有特定的對排度。本文所述之「對排度(Syndiotacticity)」係指分子鏈的立體規整性,指R基團交互出現於鏈的兩側的組態。於較佳實施例中,本發明之PVA薄膜具有對排度為52%至56%。具體為以下數值中任意兩者間的範圍,例如:52%、53%、...、56%。根據至少一實施例,對排度的調控可於聚合反應中,以適當添加特定共聚物來進行調整,會使得立體障礙大,變成高對排,前述共聚物例如但不限於:乙烯基2,2-雙(三氟甲基)丙酸(vinyl 2,2-bis(trifluoromethyl)propionate)、乙烯基5氫-八氟戊酸(vinyl 5H-octafluorovalerate)、三氟化碳(CF 3)等;亦或是稍微調整聚合溫度,若聚合溫度過高,會克服立體障礙,使對排度降低,也容易產生分支(Branch),影響染色性。 The PVA film of the present invention also has a specific alignment. As used herein, "Syndiotacticity" refers to the stereoregularity of the molecular chain, which refers to the configuration in which R groups appear alternately on both sides of the chain. In a preferred embodiment, the PVA film of the present invention has an alignment degree of 52% to 56%. Specifically, it is a range between any two of the following values, for example: 52%, 53%, . . . , 56%. According to at least one embodiment, the regulation of the alignment can be adjusted by appropriately adding a specific copolymer in the polymerization reaction, which will make the steric barrier large and become a high alignment. The aforementioned copolymers are, for example, but not limited to: vinyl 2, 2-bis(trifluoromethyl)propionate (vinyl 2,2-bis(trifluoromethyl)propionate), vinyl 5H-octafluorovalerate (vinyl 5H-octafluorovalerate), carbon trifluoride (CF 3 ), etc.; Or adjust the polymerization temperature slightly, if the polymerization temperature is too high, it will overcome the three-dimensional barrier, reduce the alignment degree, and easily produce branches, which will affect the dyeability.

於較佳實施例中,本發明之PVA薄膜經0.2 wt%硼酸水溶液處理,並以水溶解後該水溶液之硼含量為16至19 ppm,具體為以下數值中任意兩者間的範圍,例如:16ppm、16.5ppm、...、19ppm。本發明中,所述硼含量量測方法包含:裁切約0.12 g的PVA薄膜並放入30 ml玻璃取樣瓶 ,添加20 g純水,使該薄膜完全沒入純水液位之下,添加攪拌石,攪拌速度為250 rpm攪拌1.0小時。接著將瓶內純水倒出,並另添加0.2 wt% 硼酸水溶液,靜置1.0小時,再將硼酸水溶液倒出,使PVA 薄膜在瓶內靜置熟成16.0小時。接著將PVA 薄膜取出,以純水潤洗後,放入30 ml 玻璃取樣瓶,加入純水20 g,待其充分溶解後以感應耦合電漿光學發射光譜儀(ICP-OES)分析溶液中硼濃度。In a preferred embodiment, the PVA film of the present invention is treated with a 0.2 wt% boric acid aqueous solution, and the boron content of the aqueous solution after dissolving with water is 16 to 19 ppm, specifically a range between any two of the following values, for example: 16ppm, 16.5ppm, ..., 19ppm. In the present invention, the method for measuring the boron content comprises: cutting about 0.12 g of PVA film and putting it into a 30 ml glass sampling bottle, adding 20 g of pure water, so that the film is completely submerged under the pure water level, adding Stir the stone at 250 rpm for 1.0 hour. Then, the pure water in the bottle was poured out, and another 0.2 wt% boric acid aqueous solution was added, and the solution was allowed to stand for 1.0 hours. Then, the PVA film was taken out, rinsed with pure water, put into a 30 ml glass sampling bottle, and 20 g of pure water was added. After it was fully dissolved, the concentration of boron in the solution was analyzed by inductively coupled plasma optical emission spectrometer (ICP-OES). .

本文所述之「光學薄膜」係指偏光膜、抗藍光膜、濾光鏡等,且本發明並不限於此等。較佳地,本發明之PVA薄膜是作為偏光薄膜。The "optical film" mentioned herein refers to a polarizing film, an anti-blue light film, an optical filter, etc., and the present invention is not limited to these. Preferably, the PVA film of the present invention is used as a polarizing film.

前述之偏光薄膜具有特定正交尼科耳狀態之波長480 nm之吸光度(A)與波長700 nm之吸光度(B)之比率(A/B)。本文所述之「正交尼柯耳」係指正交尼科耳(Cross Nicol)透射率,為用來分析光學性能的一種方法。測定波長範圍設定為380nm至780nm,將通過格蘭-泰勒偏光鏡而入射至偏光薄膜的偏光的振動方向係與偏光薄膜的透射軸平行時的透射率設為平行透射率,而將與偏光薄膜的透射軸垂直的情況設為正交尼科耳透射率。之後,使用「偏光薄膜評價程式」(日本分光股份有限公司製),以按照JIS Z 8722(物體色的測定方法)的方式,使用前述的平行透射率與正交尼科耳透射率,進行C光源、2°視野的可見光區域的視感度補正,進行偏光薄膜的單體透射率、偏光度的算出,得到這兩個值作為偏光薄膜的光學特性。The aforementioned polarizing film has a ratio (A/B) of absorbance (A) at a wavelength of 480 nm and absorbance (B) at a wavelength of 700 nm in a specific crossed Nicols state. As used herein, "Cross Nicol" refers to Cross Nicol transmittance, a method used to analyze optical performance. The measurement wavelength range was set to 380 nm to 780 nm, and the transmittance when the vibration direction of the polarized light incident on the polarizing film through the Glan-Taylor polarizer was parallel to the transmission axis of the polarizing film was set as the parallel transmittance, and the same as the polarizing film. The case where the transmission axis is perpendicular is set as the crossed Nicols transmittance. Then, using the "Polarizing Film Evaluation Program" (manufactured by JASCO Corporation), in accordance with JIS Z 8722 (Method for Measuring Object Color), using the aforementioned parallel transmittance and crossed Nicol transmittance, C The optical sensitivity of the light source and the visible light region of the 2° visual field was corrected, and the individual transmittance and polarization degree of the polarizing film were calculated, and these two values were obtained as the optical properties of the polarizing film.

於一較佳實施例中,本發明之偏光薄膜在正交尼科耳狀態之波長480 nm之吸光度(A)與波長700 nm之吸光度(B)之比率(A/B)為1.40至1.70,前述比率(A/B)具體為以下數值中任意兩者間的範圍,例如:1.40、1.41、...、1.70。於一更佳實施例中,本發明之偏光薄膜在正交尼科耳狀態之波長480 nm之吸光度(A)與波長700 nm之吸光度(B)之比率(A/B)為1.51至1.65,前述比率(A/B)具體為以下數值中任意兩者間的範圍,例如:1.51、1.52、...、1.65。In a preferred embodiment, the ratio (A/B) of the absorbance (A) at a wavelength of 480 nm to the absorbance at a wavelength of 700 nm (B) of the polarizing film of the present invention in a crossed Nicols state is 1.40 to 1.70, The aforementioned ratio (A/B) is specifically a range between any two of the following values, for example: 1.40, 1.41, . . . , 1.70. In a more preferred embodiment, the ratio (A/B) of the absorbance (A) at a wavelength of 480 nm to the absorbance (B) at a wavelength of 700 nm of the polarizing film of the present invention in the crossed Nicols state is 1.51 to 1.65, The aforementioned ratio (A/B) is specifically a range between any two of the following values, for example: 1.51, 1.52, . . . , 1.65.

另一方面,本發明亦提供該聚乙烯醇薄膜之製造方法,其步驟包含:(a) 將乙烯酯系樹脂單體聚合,形成聚乙烯酯系樹脂後,再進行皂化反應獲得聚乙烯醇樹脂,其中,於聚合反應時添加乙烯基2,2-雙(三氟甲基)丙酸(vinyl 2,2-bis(trifluoromethyl)propionate)共聚物,且該共聚物莫耳量/乙烯酯系樹脂單體莫耳量之添加量比率為1至3 mole %,添加皂化介電常數介於34至36的溶劑;(b) 將該聚乙烯醇樹脂加溫溶解,形成聚乙烯醇澆鑄溶液;(c) 將該澆鑄溶液澆鑄至鑄造滾筒;及(d) 經乾燥後形成該聚乙烯醇薄膜。On the other hand, the present invention also provides a method for producing the polyvinyl alcohol film, the steps comprising: (a) polymerizing a vinyl ester resin monomer to form a polyvinyl ester resin, and then performing a saponification reaction to obtain a polyvinyl alcohol resin , wherein a vinyl 2,2-bis(trifluoromethyl)propionate (vinyl 2,2-bis(trifluoromethyl)propionate) copolymer is added during the polymerization reaction, and the copolymer is molar/vinyl ester resin The addition ratio of the molar amount of the monomer is 1 to 3 mole %, adding a solvent with a saponification dielectric constant between 34 and 36; (b) heating and dissolving the polyvinyl alcohol resin to form a polyvinyl alcohol casting solution; ( c) casting the casting solution onto a casting drum; and (d) drying to form the polyvinyl alcohol film.

於一較佳實施例中,本發明之PVA薄膜之製造方法,該(a)乙烯酯系樹脂單體聚合步驟中,共聚物莫耳量/乙烯酯系樹脂單體莫耳量之添加量比率為1至3 mole %。具體以下數值中任意兩者間的範圍,例如:1、1.2、...、3 mole %,且本發明並不限於此等。於一較佳實施例中,於該步驟(a)中調整pH值,或添加不同介電常數的溶劑,以控制殘存醋酸酯基排列。於另一較佳實施例中,於該步驟(a)中,皂化反應獲得之該聚乙烯醇樹脂經過粉碎乾燥,乾燥過程中適時噴進蒸氣,避免樹酯粒過度乾燥,產生結皮。In a preferred embodiment, in the manufacturing method of the PVA film of the present invention, in the (a) vinyl ester-based resin monomer polymerization step, the ratio of the added amount of copolymer molar amount/vinyl ester-based resin monomer molar amount 1 to 3 mole %. Specifically, the range between any two of the following numerical values, for example: 1, 1.2, . . . , 3 mole %, and the present invention is not limited to these. In a preferred embodiment, in the step (a), the pH value is adjusted, or solvents with different dielectric constants are added to control the arrangement of the remaining acetate groups. In another preferred embodiment, in the step (a), the polyvinyl alcohol resin obtained by the saponification reaction is pulverized and dried, and steam is sprayed in time during the drying process to avoid excessive drying of the resin particles and skin formation.

該步驟(a)中皂化介電常數介於34至36的溶劑例如:甲醇/醋酸甲酯的混合溶劑,醋酸甲酯量越多,皂化介電常數值越低,A1730 cm -1/A1710 cm -1IR吸收強度比值會變高。 In this step (a), a solvent with a saponification permittivity between 34 and 36 is, for example, a mixed solvent of methanol /methyl acetate. The more methyl acetate is, the lower the saponification permittivity value is. -1 IR absorption intensity ratio will be higher.

上開之聚乙烯醇樹脂,係由乙烯酯系樹脂單體聚合,形成聚乙烯酯系樹脂後,再進行皂化反應所獲得;其中,該乙烯酯系樹脂單體包含甲酸乙烯酯、乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、戊酸乙烯酯或辛酸乙烯酯等乙烯酯類,且本發明並不限於此等,較佳為乙酸乙烯酯。此外,烯烴類化合物或丙烯酸酯衍生物,與上述乙烯酯系樹脂單體共聚合形成之共聚合物亦可使用;該烯烴類化合物例如乙烯、丙烯、丁烯等,或烯酸酯衍生物,例如乙酸烯丙酯、丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸異丙酯、丙烯酸正丁酯等,與上述乙烯酯系單體共聚合形成之共聚合物亦可使用。從製造成本及薄膜品質綜合考量下,以乙烯、乙酸烯丙酯、烯丙醇為佳。根據至少一實施例,乙烯、乙酸烯丙酯、烯丙醇單元含有率以5 mole%以內,2至3.5 mole%為佳。The above-mentioned polyvinyl alcohol resin is obtained by polymerizing vinyl ester resin monomers to form polyvinyl ester resins, and then performing saponification reaction; wherein, the vinyl ester resin monomers include vinyl formate, vinyl acetate , vinyl propionate, vinyl butyrate, vinyl valerate, vinyl octoate and other vinyl esters, and the present invention is not limited to these, preferably vinyl acetate. In addition, olefinic compounds or acrylate derivatives, copolymers formed by copolymerization with the above vinyl ester resin monomers can also be used; the olefinic compounds such as ethylene, propylene, butene, etc., or alkenoic acid ester derivatives, For example, allyl acetate, acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, etc., copolymers formed by copolymerizing with the above vinyl ester monomers can also be used. From the comprehensive consideration of manufacturing cost and film quality, ethylene, allyl acetate and allyl alcohol are preferred. According to at least one embodiment, the unit content of ethylene, allyl acetate and allyl alcohol is within 5 mole%, preferably 2 to 3.5 mole%.

聚合中亦可以適當添加特定共聚物以調整對排度,如vinyl 2,2-bis(trifluoromethyl)propionate。亦或是稍微調整聚合溫度。聚合溫度過高,對排度降低,也容易產生分支(Branch),影響染色性。In the polymerization, a specific copolymer can also be appropriately added to adjust the alignment, such as vinyl 2,2-bis(trifluoromethyl)propionate. Alternatively, the polymerization temperature may be slightly adjusted. When the polymerization temperature is too high, the alignment degree is reduced, and branching is also likely to occur, which affects the dyeability.

通常,該聚乙烯醇系樹脂的皂化度係90%以上,較佳係99%以上,以獲得較佳之光學特性,具體為以下數值中任意值,例如:90%、91%、...、99%,或介於前述任二個數值之間。於皂化過程中可適當調整pH值,或添加不同介電常數的溶劑,以控制殘存醋酸酯基排列。Usually, the degree of saponification of the polyvinyl alcohol-based resin is above 90%, preferably above 99%, in order to obtain better optical properties, specifically any of the following values, such as: 90%, 91%, ..., 99%, or between any two of the preceding values. During the saponification process, the pH value can be adjusted appropriately, or solvents with different dielectric constants can be added to control the arrangement of the remaining acetate groups.

該聚乙烯醇的聚合度係介於800至10000之間,且較佳為2200至10000之間,具體例如:800、900、1000、2000、3000、4000、5000、6000、7000、8000、9000、10000或介於前述任二個數值之間,聚合度高於800具有較佳之加工特性,但聚合度若高於10000則不利於溶解。The degree of polymerization of the polyvinyl alcohol is between 800 and 10000, and preferably between 2200 and 10000, for example: 800, 900, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000 , 10000 or between any of the above two values, the degree of polymerization higher than 800 has better processing characteristics, but if the degree of polymerization is higher than 10000, it is not conducive to dissolution.

一般而言,所使用之聚乙烯醇澆鑄溶液中,若聚乙烯醇系樹脂的含量不足,澆鑄溶液黏度過低,乾燥負荷過大,會導致成膜效率差。另一方面,若聚乙烯醇系樹脂的含量過高,聚乙烯醇系樹脂不易溶解,易殘留團簇。因此,本實施例所使用之聚乙烯醇澆鑄溶液中,該聚乙烯醇系樹脂的含量通常係介於10至60重量%,較佳係介於15至40重量%,又更佳係介於20至30重量%,具體例如10、15、20、25、30、35、40、45、50、55、60重量%等。Generally speaking, if the content of polyvinyl alcohol-based resin in the used polyvinyl alcohol casting solution is insufficient, the viscosity of the casting solution will be too low, and the drying load will be too large, resulting in poor film-forming efficiency. On the other hand, when the content of the polyvinyl alcohol-based resin is too high, the polyvinyl alcohol-based resin is not easily dissolved, and clusters are likely to remain. Therefore, in the polyvinyl alcohol casting solution used in this embodiment, the content of the polyvinyl alcohol-based resin is usually between 10 and 60% by weight, preferably between 15 and 40% by weight, and more preferably between 20 to 30% by weight, specifically 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60% by weight and the like.

聚乙烯醇澆鑄溶液之溶解溫度以130至140 ℃為佳,溫度過低易殘留團簇,溫度過高除了耗能,成本也會增加。具體溫度例如為130至140 ℃、133至140 ℃、136至140 ℃、139至140 ℃、130至137 ℃、130至134 ℃ 或 130至131 ℃。The best dissolving temperature of the polyvinyl alcohol casting solution is 130 to 140 °C. If the temperature is too low, clusters may remain, and if the temperature is too high, the cost will increase in addition to energy consumption. The specific temperature is, for example, 130 to 140°C, 133 to 140°C, 136 to 140°C, 139 to 140°C, 130 to 137°C, 130 to 134°C, or 130 to 131°C.

在澆鑄溶液中,除了聚乙烯醇系樹脂,亦可含有塑化劑以增進成膜之加工性,可使用之塑化劑包含多元醇,例如乙二醇、雙乙二醇、三乙二醇、四乙二醇、丙二醇或丙三醇等,且本發明並不限於此等,較佳為乙二醇及丙三醇。該塑化劑的添加量相對於100重量分之聚乙烯醇樹脂,通常係介於3至30重量份,較佳係介於7至20重量份,具體例如:3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30重量份或介於前述任二個數值之間。若該塑化劑含量不足,所形成之PVA薄膜容易產生結晶而影響後續加工之染色效能。相反地,若該塑化劑含量過高,則會破壞PVA薄膜的機械性質。In the casting solution, in addition to the polyvinyl alcohol resin, it can also contain plasticizers to improve the processability of the film. The plasticizers that can be used include polyols, such as ethylene glycol, diethylene glycol, and triethylene glycol. , tetraethylene glycol, propylene glycol or glycerol, etc., and the present invention is not limited to these, preferably ethylene glycol and glycerol. The amount of the plasticizer added is usually 3 to 30 parts by weight, preferably 7 to 20 parts by weight, relative to 100 parts by weight of the polyvinyl alcohol resin, for example: 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 parts by weight or between any of the preceding two values. If the content of the plasticizer is insufficient, the formed PVA film is likely to crystallize and affect the dyeing performance of the subsequent processing. Conversely, if the plasticizer content is too high, the mechanical properties of the PVA film will be destroyed.

該PVA薄膜之製造方法所使用的設備包含溶解槽、過濾器、塗佈機及連接自該溶解槽至該塗佈機前的輸送管線,較佳狀態下該等設備包覆有保溫裝置,該保溫裝置可為金屬電熱線、或為內部裝盛有液體之夾套,該液體例如油或水,藉由加熱金屬導線或夾套內之液體,使該溶解槽、過濾器、塗佈機及連接自溶解槽到塗佈機之管線維持均勻加熱之保溫狀態,特別係設備及管線表面,避免設備或管線因表面喪失溫度而使該聚乙烯醇澆鑄溶液中的聚乙烯醇形成凝膠,而黏附或阻塞過濾器,導致製程無法繼續運轉。另一方面,若加熱溫度過高,會使部分溶液脫水或膠化,而形成焦黃色或黑色的凝膠,亦不利於提升塗佈成型之薄膜表面的品質與均勻性。本發明之方法中,該聚乙烯醇於塗佈成型處係於80至120℃之加熱保溫條件下進行,較佳係於90至110℃之加熱保溫條件下進行,更佳係於90至100 ℃之加熱保溫條件下進行,具體例如:80、85、90、95、100、105、110、115、120 ˚C或介於前述任二個數值之間。於一較佳實施例中,該步驟(a)至(c)係利用外加保溫裝置下進行。The equipment used in the manufacturing method of the PVA film includes a dissolving tank, a filter, a coating machine and a conveying pipeline connected from the dissolving tank to the coating machine. Preferably, the equipment is covered with a heat preservation device. The heat preservation device can be a metal electric heating wire, or a jacket with a liquid inside, such as oil or water, by heating the metal wire or the liquid in the jacket, the dissolving tank, filter, coating machine and The pipeline connected from the dissolving tank to the coating machine maintains a uniformly heated thermal insulation state, especially on the surface of the equipment and pipeline, so as to prevent the polyvinyl alcohol in the polyvinyl alcohol casting solution from forming a gel due to the loss of temperature on the surface of the equipment or pipeline, and Adhesion or clogging of the filter, preventing the process from continuing. On the other hand, if the heating temperature is too high, part of the solution will be dehydrated or gelled to form a scorched yellow or black gel, which is not conducive to improving the quality and uniformity of the coated film surface. In the method of the present invention, the polyvinyl alcohol is carried out in the coating and forming place under the heating and heat preservation condition of 80 to 120°C, preferably under the heating and heat preservation condition of 90 to 110°C, more preferably at 90 to 100°C. It is carried out under the heating and holding conditions of ℃, for example: 80, 85, 90, 95, 100, 105, 110, 115, 120 ℃ or between any two values mentioned above. In a preferred embodiment, the steps (a) to (c) are carried out with an external heat preservation device.

於上揭之方法中,於聚乙烯醇系樹脂及塑化劑溶於溶液中,形成聚乙烯醇澆鑄溶液後,使用過濾器進行過濾,最後再利用齒輪幫浦(gear pump)及T型模頭塗佈機,使該聚乙烯醇澆鑄溶液澆鑄至鑄造滾筒,滾筒速度過慢,則過分乾燥,有位相差、熔點分布不均的傾向;過快,則乾燥不充分,剝離性降低。若提升滾筒溫度,則容易有起泡現象。因此滾筒的旋轉速度宜為3至7公尺/分鐘,較佳為4至6公尺/分鐘,具體可為以下數值中任意兩者間的範圍,例如:2公尺/分鐘、3公尺/分鐘….6公尺/分鐘。溫度設定在85至90 ℃之間,例如為85至90 ℃、86至90 ℃、87至90 ℃、88至90 ℃、89至90 ℃、85至89 ℃、85至88 ℃、85至87 ℃ 或 85至86 ℃。若滾筒溫度過高,於滾筒上的澆鑄溶液容易有起泡現象。In the method disclosed above, the polyvinyl alcohol resin and plasticizer are dissolved in the solution to form a polyvinyl alcohol casting solution, which is filtered with a filter, and finally a gear pump and a T-shaped mold are used. The head coater is used to cast the polyvinyl alcohol casting solution to the casting drum. If the drum speed is too slow, it will be too dry, and there will be a tendency for phase difference and uneven melting point distribution; if it is too fast, the drying will be insufficient and the peelability will be reduced. If the drum temperature is raised, foaming is likely to occur. Therefore, the rotation speed of the drum is preferably 3 to 7 m/min, preferably 4 to 6 m/min, and can be a range between any two of the following values, for example: 2 m/min, 3 m/min /min….6m/min. The temperature is set between 85 and 90°C, such as 85 to 90°C, 86 to 90°C, 87 to 90°C, 88 to 90°C, 89 to 90°C, 85 to 89°C, 85 to 88°C, 85 to 87°C °C or 85 to 86 °C. If the temperature of the drum is too high, the casting solution on the drum is prone to foaming.

自滾筒剝離後經過一系列熱輥進一步乾燥後進行熱處理進而製得聚乙烯醇系薄膜。熱處理方法可列舉如(1)聚乙烯醇系膜在熱輥上或在(2)浮動式乾燥機上進行。熱輥與浮動式乾燥機數目並無特別限制。但以115至130 ℃為佳,例如為115至130 ℃、115至128 ℃、115至126 ℃、115至124 ℃、115至122 ℃、115至120 ℃、115至118 ℃、115至116 ℃、117至130 ℃、119至130 ℃、121至130 ℃、123至130 ℃、125至130 ℃、127至130 ℃ 或 129至130 ℃。溫度過高則膨潤度劣化,影響染色性及硼酸反應性,溫度過低,則PVA會有溶出現象。After being peeled off from the roller, it is further dried by a series of hot rollers, and then heat-treated to obtain a polyvinyl alcohol-based film. As the heat treatment method, (1) the polyvinyl alcohol-based film is carried out on a heated roll or (2) a floating dryer, for example. The number of hot rolls and floating dryers is not particularly limited. But preferably 115 to 130 ℃, for example, 115 to 130 ℃, 115 to 128 ℃, 115 to 126 ℃, 115 to 124 ℃, 115 to 122 ℃, 115 to 120 ℃, 115 to 118 ℃, 115 to 116 ℃ , 117 to 130 °C, 119 to 130 °C, 121 to 130 °C, 123 to 130 °C, 125 to 130 °C, 127 to 130 °C or 129 to 130 °C. If the temperature is too high, the swelling degree will deteriorate, affecting the dyeability and boric acid reactivity. If the temperature is too low, the PVA will be dissolved.

PVA薄膜於製造光學薄膜之時,會進行拉伸及染色,以偏光膜為例,由於偏光膜製程中會使用含有I 3 -、I 5 -碘離子之硼酸水溶液染色PVA薄膜,硼酸可與PVA未定型(amorphous)區域產生交聯作用後,將碘離子固定而避免碘離子溶出。 實施例 PVA film will be stretched and dyed when manufacturing optical film. Taking polarizing film as an example, since the polarizing film manufacturing process will use boric acid aqueous solution containing I 3 - and I 5 -iodide ions to dye PVA film, and boric acid can be combined with PVA. After the cross-linking of the amorphous regions, the iodide ions are immobilized to avoid the dissolution of the iodine ions. Example

在下文中,將進一步以詳細說明與實施例描述本發明。然而,應理解這些實施例僅用於幫助可更加容易理解本發明而非用於限制本發明之範圍。In the following, the invention will be further described with detailed description and examples. However, it should be understood that these examples are only for helping to make the present invention easier to understand and not for limiting the scope of the present invention.

製造 PVA 薄膜:先配製聚乙烯醇澆鑄溶液,再將該聚乙烯醇澆鑄溶液澆鑄至鑄造滾筒,經乾燥後形成聚乙烯醇系聚合物薄膜。具體而言,於上述之聚乙烯醇系聚合物薄膜製法中,聚乙烯醇澆鑄溶液主要包括聚乙烯醇、塑化劑及水,該聚乙烯醇是藉由乙烯酯系樹脂單體聚合得到聚乙烯酯系樹脂,再進行皂化反應而成。 Manufacturing PVA film : firstly prepare a polyvinyl alcohol casting solution, then cast the polyvinyl alcohol casting solution to a casting drum, and form a polyvinyl alcohol-based polymer film after drying. Specifically, in the above-mentioned method for producing a polyvinyl alcohol-based polymer film, the polyvinyl alcohol casting solution mainly includes polyvinyl alcohol, a plasticizer and water, and the polyvinyl alcohol is obtained by polymerizing vinyl ester resin monomers to obtain a polymer Vinyl ester resin, and then saponification reaction.

製造偏光膜:將聚乙烯醇薄膜浸漬於30 ℃水中使其膨潤並朝機械方向(MD)進行單軸延伸至原來長度的2.0倍,接著,一邊浸漬於含有0.03 質量%之碘,及3質量%之碘化鉀的30 ℃水溶液,一邊進行拉伸至原來長度的3.3倍,接著浸入3 質量%之碘化鉀及3 質量%之硼酸的30 ℃水溶液中,並進一步延伸至原先的3.6倍。繼而浸入5 質量%之碘化鉀及4 質量%之硼酸的60 ℃水溶液中,並進一步延伸至原先的6.0倍。後續於3 質量%之碘化鉀水溶液浸泡15秒後,於60 ℃乾燥4分鐘,即可獲得偏光膜。 Production of polarizing film : The polyvinyl alcohol film was immersed in water at 30° C. to swell and uniaxially stretched in the machine direction (MD) to 2.0 times the original length. % potassium iodide in a 30 ℃ aqueous solution, stretched to 3.3 times the original length, then immersed in a 30 ℃ aqueous solution of 3 mass % potassium iodide and 3 mass % boric acid, and further stretched to 3.6 times the original length. Then, it was immersed in a 60° C. aqueous solution of 5 mass % potassium iodide and 4 mass % boric acid, and further extended to 6.0 times the original. After immersing in a 3 mass % potassium iodide aqueous solution for 15 seconds and drying at 60° C. for 4 minutes, a polarizing film can be obtained.

以下請參見表1,係為實施例1至4及比較例1至3之實驗控制變因及色相均勻性測定結果。Please refer to Table 1 below, which are the experimental control variables and the measurement results of hue uniformity of Examples 1 to 4 and Comparative Examples 1 to 3.

表1 項目 實施例1 實施例2 實施例3 實施例4 比較例1 比較例2 比較例3 控制變因 樹脂製程 聚合溫度 (℃) 67 66 65 65 67 65 67 共聚物/乙酸乙烯酯 (mole %) 1 2 3 2 0 5 0 皂化介質界電常數 34 36 36 34 32 36 31 皂化溫度  (℃) 39.5 40.5 41 40 39 41.5 39.5 皂化度 (mole %) 99.92 99.90 99.94 99.96 99.90 99.92 99.90 平均重合度 2510 2550 2560 2485 2535 2490 2500 薄膜製程 溶解溫度 (℃) 130 130 140 140 140 140 140 最高熱處理溫度 (℃) (浮動式乾燥機) 130 120 118 125 140 135 135 技術特徵 A1730 cm -1/ A1710 cm -1 0.965 0.911 0.85 0.96 0.971 0.81 0.975 (A1710 cm -1+A1730 cm -1)/ A1425 cm -1 0.55 0.47 0.35 0.38 0.56 0.33 0.54 對排度 (%) 53.11 54.39 55.61 54.11 51.08 56.69 52.1 硼含量 (ppm) 16 18 19 16 14 15 15 功效 UV-VIS A/B 1.51 1.58 1.62 1.65 1.95 1.33 1.85 Table 1 project Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 control variable Resin process Polymerization temperature (℃) 67 66 65 65 67 65 67 Copolymer/Vinyl Acetate (mole %) 1 2 3 2 0 5 0 Saponification medium boundary electric constant 34 36 36 34 32 36 31 Saponification temperature (℃) 39.5 40.5 41 40 39 41.5 39.5 Saponification degree (mole %) 99.92 99.90 99.94 99.96 99.90 99.92 99.90 average coincidence 2510 2550 2560 2485 2535 2490 2500 Thin film process Melting temperature(℃) 130 130 140 140 140 140 140 Maximum heat treatment temperature (℃) (floating dryer) 130 120 118 125 140 135 135 Technical characteristics A1730 cm -1 / A1710 cm -1 0.965 0.911 0.85 0.96 0.971 0.81 0.975 (A1710 cm -1 +A1730 cm -1 )/ A1425 cm -1 0.55 0.47 0.35 0.38 0.56 0.33 0.54 Alignment (%) 53.11 54.39 55.61 54.11 51.08 56.69 52.1 Boron content (ppm) 16 18 19 16 14 15 15 effect UV-VIS A/B 1.51 1.58 1.62 1.65 1.95 1.33 1.85

本實施例中,IR分析方法包含:將 10 cm×10 cm之PVA薄膜浸泡於 2000 ml的30℃純水,使用磁石攪拌機攪拌5分鐘後取出。預熱烘箱至 105℃,將浸泡後的薄膜鋪平放置托盤中,以 105 ℃/1hr 進行乾燥,將該薄膜取出後,進行分析。IR吸收值若有產生負值的情況,將數據做適當的平移,所有數據加一固定常數,使全範圍IR光譜吸收值最低點為0。In this embodiment, the IR analysis method includes: soaking a 10 cm×10 cm PVA film in 2000 ml of 30°C pure water, stirring with a magnetic stirrer for 5 minutes, and then taking it out. Preheat the oven to 105°C, lay the soaked film flat on a tray, dry at 105°C/1hr, take out the film, and analyze it. If the IR absorption value has a negative value, the data is appropriately shifted, and a fixed constant is added to all the data, so that the lowest point of the full-range IR spectral absorption value is 0.

本實施例中,硼含量量測方法包含:裁切約0.12 g的PVA薄膜並放入30 ml 玻璃取樣瓶,添加20 g 純水,使該薄膜完全沒入純水液位之下,添加攪拌石,攪拌速度為250 rpm,攪拌1.0小時。接著將瓶內純水倒出,並另添加0.2 wt%硼酸水溶液,靜置1.0小時,再將硼酸水溶液倒出,使PVA 薄膜在瓶內封閉(close)靜置熟成16.0小時。接著將PVA 薄膜取出,以純水潤洗後,放入30 ml 玻璃取樣瓶,加入純水20 g,待其充分溶解後以ICP-OES分析溶液中硼濃度。In this embodiment, the method for measuring the boron content includes: cutting a PVA film of about 0.12 g and placing it in a 30 ml glass sampling bottle, adding 20 g of pure water, so that the film is completely submerged under the pure water level, adding stirring Stone, stirring at 250 rpm for 1.0 hours. Then, the pure water in the bottle was poured out, and another 0.2 wt% boric acid aqueous solution was added, and the solution was allowed to stand for 1.0 hours. Then, the PVA film was taken out, rinsed with pure water, put into a 30 ml glass sampling bottle, and 20 g of pure water was added. After it was fully dissolved, the boron concentration in the solution was analyzed by ICP-OES.

本實施例中,ICP-OES分析方法包含:先以外插法製作檢量線,以微量分注器吸取200 ppm之ICP多元素標準液(購自Merck公司)置於100 ml量瓶,再以去離子水稀釋到100 ml,配製成所需濃度(如:100、200、500、2000 ppb)備用;樣品不需前處理,直接上機分析。本方法選擇分析元素為硼(B,249.773 nm)。In this embodiment, the ICP-OES analysis method includes: firstly making a calibration line by extrapolation, drawing 200 ppm of ICP multi-element standard solution (purchased from Merck) with a microdispenser and placing it in a 100 ml volumetric flask, and then adding Dilute it with deionized water to 100 ml, and prepare it to the required concentration (eg: 100, 200, 500, 2000 ppb) for later use; the sample does not need pretreatment, and can be directly analyzed on the machine. The selected analytical element for this method is boron (B, 249.773 nm).

本實施例中,對排度分析方法包含:將 10 cm×10 cm之測試樣品浸泡於2000 ml 的 30℃純水中,使用磁石攪拌機攪拌 5 min 後取出。事先預熱烘箱至 105℃,將浸泡後的薄膜鋪平放置托盤中,以 105 ℃/1hr 進行乾燥。再將薄膜取出後,進行NMR分析。使用的溶劑為氘代二甲基亞碸(dimethyl sulfoxide-d 6);儀器為 1H NMR。該分析方法參考T. Moritani等人1972年於大分子期刊( Macromolecules, 5, 577 )所公開之方法,參照圖2,以NMR求出三元組(triads;mm/mr/rr)百分率(%)後,再經公式:對排度(二元組;dyads) = rr + mr/2計算而得。 In this embodiment, the alignment analysis method includes: immersing a 10 cm×10 cm test sample in 2000 ml of 30°C pure water, stirring with a magnetic stirrer for 5 minutes, and then taking it out. Preheat the oven to 105 °C in advance, lay the soaked film flat on a tray, and dry at 105 °C/1hr. After the film was taken out again, NMR analysis was performed. The solvent used was dimethyl sulfoxide-d 6 ; the instrument was 1 H NMR. The analytical method refers to the method disclosed by T. Moritani et al. in Macromolecules ( Macromolecules, 5, 577 ) in 1972. Referring to Fig. 2, the percentage (%) of triads (triads; mm/mr/rr) is obtained by NMR. ), and then calculated by the formula: Alignment (two-tuple; dyads) = rr + mr/2.

本實施例中,樹脂皂化度、平均重合度是參照JIS 6726試驗方法。In this example, the degree of resin saponification and the average degree of coincidence are based on the test method of JIS 6726.

根據表1,本發明之PVA膜所生產之偏光薄膜,從色相均勻觀點來說,在正交尼科耳狀態中之波長480 nm的吸光度(A)與波長700 nm的吸光度(B)之比率(A/B)係以1.40以上較佳。另一方面,該比率(A/B)過高時,會有紅光洩漏變多之傾向,因此,該比率(A/B)係以2.00以下較佳,更佳係低於1.80。上述吸光度(A)及吸光度(B)可使用分光光度計求得。According to Table 1, the ratio of the absorbance (A) at a wavelength of 480 nm to the absorbance at a wavelength of 700 nm (B) in the crossed Nicols state of the polarizing film produced by the PVA film of the present invention, from the viewpoint of uniformity of hue (A/B) is preferably 1.40 or more. On the other hand, when the ratio (A/B) is too high, the leakage of red light tends to increase. Therefore, the ratio (A/B) is preferably 2.00 or less, more preferably less than 1.80. The said absorbance (A) and absorbance (B) can be calculated|required using a spectrophotometer.

綜上所述,本發明之功效在於,不僅改善習知PVA薄膜的製程,並且藉由調控IR吸收光譜中非氫鍵羰基/氫鍵羰基的比例,達到色相優異之PVA薄膜。To sum up, the effect of the present invention is not only to improve the manufacturing process of conventional PVA films, but also to achieve a PVA film with excellent hue by adjusting the ratio of non-hydrogen-bonded carbonyl groups/hydrogen-bonded carbonyl groups in the IR absorption spectrum.

本文中,所提供的所有範圍旨在包括在給定之範圍內的每個特定範圍以及在該給定範圍之間的子範圍的組合。此外,除非另有說明,否則本文提供的所有範圍皆包括所述範圍的端點。從而,範圍1-5具體包括1、2、3、4和5,以及諸如2-5、3-5、2-3、2-4、1-4等子範圍。All ranges provided herein are intended to include each specific range within the given range and combinations of subranges between the given ranges. Furthermore, all ranges provided herein are inclusive of the endpoints of the stated range unless otherwise indicated. Thus, the range 1-5 specifically includes 1, 2, 3, 4, and 5, as well as subranges such as 2-5, 3-5, 2-3, 2-4, 1-4, and the like.

在本說明書中引用的所有刊物和專利申請案皆透過引用併入本文,並且出於任何及所有目的,每一個別刊物或專利申請案皆明確且個別地指出以透過引用併入本文。在本文與透過引用併入本文的任何刊物或專利申請案之間存在不一致的情況下,以本文為準。All publications and patent applications cited in this specification are incorporated herein by reference, and each individual publication or patent application is expressly and individually indicated to be incorporated by reference for any and all purposes. In the event of inconsistency between this document and any publication or patent application incorporated herein by reference, this document controls.

本文所用之術語「包括」、「具有」和「包含」具有開放、非限制性的意義。術語「一」和「該」應理解為涵蓋複數及單數。術語「一個或多個」係指「至少一個」,因此可包括單一特徵或混合物/組合特徵。The terms "including", "having" and "comprising" as used herein have an open, non-limiting meaning. The terms "a" and "the" should be understood to encompass both the plural and the singular. The term "one or more" means "at least one" and thus may include a single feature or a mixture/combination of features.

除了在操作實施例中或在另外指出的地方,所有表示成分及/或反應條件的量的數字在所有情況下皆可使用術語「約」修飾,意指在所指示的數字的±5%以內。本文所用之術語「基本上不含」或「實質上不含」係指少於約2%的特定特徵。在申請專利範圍中可否定地排除本文中肯定地闡述的所有要素或特徵。Except in the working examples or where otherwise indicated, all numbers indicating amounts of ingredients and/or reaction conditions may in all cases be modified using the term "about", meaning within ±5% of the indicated number . As used herein, the terms "substantially free" or "substantially free" refer to less than about 2% of a particular characteristic. All elements or features expressly stated herein may be negatively excluded from the scope of the claim.

無。none.

圖1為醋酸酯基中的C=0吸收峰分為1710 cm -1(與OH基相連)及1730 cm -1(嵌段內的非氫鍵羰基)之示意圖。 Figure 1 is a schematic diagram showing that the C=0 absorption peak in the acetate group is divided into 1710 cm -1 (connected to OH group) and 1730 cm -1 (non-hydrogen-bonded carbonyl group in the block).

圖2為根據本發明一實施例之對排三元組(Syndiotactic triad)、同排三元組(Isotactic triad)、雜排三元組(Heterotactic triad)之示意圖。2 is a schematic diagram of a syndiotactic triad, an Isotactic triad, and a heterotactic triad according to an embodiment of the present invention.

無。none.

Claims (9)

一種聚乙烯醇薄膜,其具有:IR吸收強度比值為0.85<A1730cm-1/A1710cm-1<0.97,及醋酸酯基吸收強度為0.35<(A1710cm-1+A1730cm-1)/A1425cm-1<0.55;該IR吸收強度及該醋酸酯基吸收強度係將該聚乙烯醇薄膜浸泡於純水,攪拌後取出,以105℃/1hr進行乾燥後,進行分析。 A polyvinyl alcohol film, which has: IR absorption intensity ratio of 0.85<A1730cm -1 /A1710cm -1 <0.97, and acetate-based absorption intensity of 0.35<(A1710cm -1 +A1730cm -1 )/A1425cm -1 <0.55 ; The IR absorption strength and the acetate-based absorption strength are immersed in the polyvinyl alcohol film in pure water, taken out after stirring, dried at 105°C/1hr, and analyzed. 如請求項1之聚乙烯醇薄膜,其進一步具有對排度為52%至56%。 The polyvinyl alcohol film of claim 1, further having an alignment degree of 52% to 56%. 如請求項2之聚乙烯醇薄膜,其中0.12g之該聚乙烯醇薄膜經0.2wt%硼酸水溶液處理,並以水溶解後該水溶液之硼含量為16至19ppm。 The polyvinyl alcohol film of claim 2, wherein 0.12 g of the polyvinyl alcohol film is treated with a 0.2 wt % boric acid aqueous solution, and the boron content of the aqueous solution after dissolving with water is 16-19 ppm. 一種偏光薄膜,其包含如請求項1至3任一項之聚乙烯醇薄膜。 A polarizing film comprising the polyvinyl alcohol film according to any one of claims 1 to 3. 如請求項4之偏光薄膜,其在正交尼科耳狀態之波長480nm之吸光度(A)與波長700nm之吸光度(B)之比率(A/B)為1.40至1.70。 The polarizing film of claim 4, wherein the ratio (A/B) of the absorbance (A) at a wavelength of 480 nm to the absorbance (B) at a wavelength of 700 nm in the crossed Nicols state is 1.40 to 1.70. 如請求項5之偏光薄膜,其在正交尼科耳狀態之波長480nm之吸光度(A)與波長700nm之吸光度(B)之比率(A/B)為1.51至1.65。 The polarizing film of claim 5, wherein the ratio (A/B) of the absorbance (A) at a wavelength of 480 nm to the absorbance at a wavelength of 700 nm (B) in the crossed Nicols state is 1.51 to 1.65. 一種如請求項1至3任一項之聚乙烯醇薄膜之製造方法,包含:(a)將乙烯酯系樹脂單體聚合,形成聚乙烯酯系樹脂後,再進行皂化反應獲得聚乙烯醇樹脂,其中,於聚合反應時添加乙烯基2,2-雙(三氟甲基)丙酸(vinyl 2,2-bis(trifluoromethyl)propionate)共聚物,且該共聚物莫耳量/乙烯 酯系樹脂單體莫耳量之添加量比率為1至3,添加皂化介電常數介於34至36的溶劑;(b)將該聚乙烯醇樹脂加溫溶解,形成聚乙烯醇澆鑄溶液;(c)將該澆鑄溶液澆鑄至鑄造滾筒;及(d)經乾燥後形成該聚乙烯醇薄膜;其中該步驟(a)至(c)係利用外加保溫裝置為金屬電熱線或內部具液體之夾套下進行。 A method for producing a polyvinyl alcohol film as claimed in any one of claims 1 to 3, comprising: (a) polymerizing a vinyl ester resin monomer to form a polyvinyl ester resin, and then performing a saponification reaction to obtain a polyvinyl alcohol resin , wherein, a vinyl 2,2-bis(trifluoromethyl)propionate (vinyl 2,2-bis(trifluoromethyl)propionate) copolymer is added during the polymerization reaction, and the copolymer molar weight/ethylene The molar ratio of the ester resin monomer is 1 to 3, and a solvent with a saponification dielectric constant of 34 to 36 is added; (b) the polyvinyl alcohol resin is heated and dissolved to form a polyvinyl alcohol casting solution; (c) casting the casting solution into a casting drum; and (d) forming the polyvinyl alcohol film after drying; wherein the steps (a) to (c) utilize an external heat preservation device for a metal heating wire or a liquid inside Under the jacket. 如請求項7之製造方法,其中進一步於該步驟(a)中調整pH值,或添加不同介電常數的溶劑,以控制殘存醋酸酯基排列。 The manufacturing method of claim 7, wherein in the step (a), the pH value is further adjusted, or solvents with different dielectric constants are added to control the arrangement of the remaining acetate groups. 如請求項7之製造方法,其中進一步於該步驟(a)中,皂化反應獲得之該聚乙烯醇樹脂經過粉碎乾燥,乾燥過程中適時噴進蒸氣,避免樹酯粒過度乾燥,產生結皮。The manufacturing method of claim 7, wherein further in the step (a), the polyvinyl alcohol resin obtained by the saponification reaction is pulverized and dried, and steam is injected in a timely manner during the drying process to avoid excessive drying of the resin particles and skin formation.
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