201141882 六、發明說明： 【發明所屬之技術領域】 本發明關於聚乙烯醇（以下亦將「聚乙烯醇」簡稱 「PVA」）系聚合物薄膜、其製造方法及該PVA系聚合物 薄膜的保管方法。 【先前技術】 使用PVA系聚合物所形成的PVA系聚合物薄膜，係 活用水溶性單元的特徵與其它各式各樣的優異物性，而使 用於偏光薄膜製造原料等的光學用途、農業.洗劑等的化 學藥品之包裝用途、纖維製品的包裝用途等各種的用途。 而且’使用T模頭等來製造PVA系聚合物薄膜時， 作爲抑制模頭線的發生或異物的發生，改善製膜性的方 法’有提案摻合非離子系界面活性劑之方法（參照專利文 獻1)。又，作爲提供一種沒有光學條紋或光學顏色不均等 而具有優異的光學特性’可在耐黏結性發揮優異的效果之 PVA系聚合物薄膜的方法’有提案摻合複數種的特定界面 活性劑之方法（參照專利文獻2)。 [先前技術文獻] [專利文獻] [專利文獻1]特開200 1 -253 993號公報 [專利文獻2]特開20〇5_206809號公報 【發明內容】 [發明所欲解決的問題] -4- 201141882 然而，近年來已知將摻合界面活性劑所！ 系聚合物薄膜捲繞成捲筒狀，在溫度經控制於 倉庫內保管數個月左右時，捲筒的顏色會有顯 的問題。此黃變雖然對於PVA系聚合物薄 度·延伸性•霧度等物性幾乎沒有造成影響， 材料使用時，內容物的顏色帶有黃色調，或作 製造時的原料使用時，穿透所得之偏光薄膜的 色調，而對消費者或使用者有給予不良印象的 本發明之目的爲提供一種PVA系聚合物 使在溫度經控制於常溫附近的倉庫內等保管 後，薄膜的顏色也不易帶有黃色調。 [用以解決問題的手段] 本發明者爲了達成上述目的，重複專心致 結果發現藉由一種PVA系聚合物薄膜達成上 係含有PVA系聚合物及界面活性劑的PVA 膜，溶解於水時的pH係在一定範圍，以該知 進一步重複地檢討，而完成本發明。 即，本發明關於： [1] 一種PVA系聚合物薄膜，其係含有PVA 及相對於該PVA系聚合物（A) 100質量份而言 量份的界面活性劑（B)之PVA系聚合物薄膜， %的濃度溶解於水時在2(TC的pH爲2.0〜8.0 [2] 如上述[1]的PVA系聚合物薄膜，其中 物（A)的皂化度爲90莫耳％以上； 契造的 PVA 常溫附近的 著帶黃色調 膜的機械強 但作爲包裝 爲偏光薄膜 光線帶有黃 可能性。 薄膜，其即 數個月左右 力的檢討， 述目的，其 系聚合物薄 識爲基礎， 系聚合物（A) 0 · 0 0 1〜1質 其以7質量 PVA系聚合 201141882 [3] 如上述[1]或[2]的PVA系聚合物薄膜，其係使用酸 性物質（C)而得者； [4] 如上述[3]的PVA系聚合物薄膜，其中酸性物質（C) 在25°C的pKa(酸解離常數）爲3.5以上，而且該酸性物質 (C)在常壓下的沸點係超過120°C ; [5] 如上述[1]〜[4]中任一項之PVA系聚合物薄膜，其 中界面活性劑（B)係非離子系界面活性劑； [6] 如上述[5]的PVA系聚合物薄膜，其中非離子系界面 活性劑係烷醇醯胺型的界面活性劑； [7] 如上述[1]〜[6]中任一項之PVA系聚合物薄膜，其 中相對於界面活性劑（B)而言，含有〇·〇ι〜3質量％的抗氧 化劑（D); [8] —種如上述[1]〜[7]中任一項之pvA系聚合物薄膜 的製造方法’其含有：調製含有PVA系聚合物（A)及相對 於該PVA系聚合物（A)100質量份而言〇·001〜ι質量份的 界面活性劑（Β)之製膜原液的步驟，與將該製膜原液製膜 的步驟，其中上述製膜原液係使用含有70質量％以上的 界面活性劑（Β)之混合物所得者； [9] 如上述[8]的製造方法’其中上述製膜原液係使用酸 性物質（C)所得者； [10] 如上述[8]或[9]的製造方法，其中上述混合物以〇1 質量％的濃度溶解於水時在20°C的pH爲8.0以上； 201141882 [11]—種PVA系聚合物薄膜之保管方法，其特徵爲將 如上述[1]〜[7]中任一項之PVA系聚合物薄膜在溫度〇 〜4(TC及濕度75%RH以下的條件下保管。 [發明的效果] 本發明的PVA系聚合物薄’即使在倉庫內等長期間 保管，薄膜的顏色也不易帶有黃色調。因此，即使將該 PVA系聚合物薄膜當作包裝材料或偏光薄膜製造時的原料 使用，也不易對消費者或使用者造成不良的印象。又，若 依照本發明的製造方法，可容易且便宜地製造上述PVA 系聚合物薄膜。 再者’若藉由本發明的保管方法來保管PVA系聚合 物薄膜，則可更有效地抑制薄膜的黃變。 【實施方式】 [實施發明的形態] 以下更詳細說明本發明。 本發明的PVA系聚合物薄膜含有PVA系聚合物（A)與 界面活性劑（B)。 作爲PVA系聚合物（A)’可舉出將乙烯酯系單體聚合 而得之乙烯酯系聚合物皂化而製造者。作爲乙烯酯系單 體，例如可舉出甲酸乙烯酯、醋酸乙烯酯、丙酸乙烯酯、 戊酸乙烯酯 '月桂酸乙烯酯、硬脂酸乙烯酯、苯甲酸乙燦 基、三甲基乙酸乙烯酯、維沙酸乙烯酯等，此等之中較佳 爲醋酸乙烯酯° 201141882 上述乙烯酯系聚合物，較佳爲僅使用1種或2種以上 的乙稀醋系單體當作單體而得者，更佳爲僅使用1種的乙 嫌醋系單體當作單體而得者，亦可爲1種或2種以上的乙 烯醋系單體與可和其共聚合的其它單體之共聚物。 作爲如此之可和乙烯酯系單體共聚合的其它單體，例 如可舉出乙烯；丙烯、1-丁烯、異丁烯等之碳數3〜30的 烯烴；丙烯酸或其鹽；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、丙烯酸異丁酯、 丙烯酸第三丁酯、丙烯酸2-乙基己酯、丙烯酸十二酯、丙 烯酸十八酯等的丙烯酸酯；甲基丙烯酸或其鹽；甲基丙烯 酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯 酸異丙酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基 丙烯酸第三丁酯、甲基丙烯酸2_乙基己酯、甲基丙烯酸十 二酯、甲基丙烯酸十八酯的甲基丙烯酸酯；丙烯醯胺、N-甲基丙烯醯胺、N -乙基丙烯醯胺、N，N’-二甲基丙烯醯 胺、二丙酮丙烯醯胺、丙烯醯胺丙磺酸或其鹽、丙烯醯胺 丙基二甲基胺或其鹽、N-羥甲基丙烯醯胺或其衍生物等的 丙烯醯胺衍生物；甲基丙烯醯胺、N-甲基甲基丙烯醯胺、 N -乙基甲基丙烯醯胺、甲基丙烯醯胺丙磺酸或其鹽、甲基 丙烯醯胺丙基二甲基胺或其鹽、N-羥甲基甲基丙烯醯胺或 其衍生物等的甲基丙烯醯胺衍生物；N-乙烯基甲醯胺、N-乙烯基乙醯胺、N-乙烯基吡咯啶酮等的N-乙烯基醯胺； 甲基乙烯基醚、乙基乙烯基醚、正丙基乙烯基醚、異丙基 201141882 乙烯基醚、正丁基乙烯基醚、異丁基乙烯基醚、第 乙烯基醚、十二基乙烯基醚、十八基乙烯基醚等的 醚：丙烯腈、甲基丙烯腈等的丙烯腈；氯乙烯、偏 稀、氟(乙嫌、偏一氟乙嫌等的鹵乙嫌；醋酸稀丙醋 基氯等的烯丙基化合物；馬來酸或其鹽、酯或酸酐 酸或其鹽、酯或酸酐：乙烯基三甲氧基矽烷等的乙 烷基化合物；醋酸異丙烯酯等，上述乙烯酯系聚合 具有來自此等其它單體中的1種或2種以上之構造 來自上述其它單體的構造單位佔上述乙烯酯系 的比例’以構成乙烯酯系聚合物的全部構造單位之 爲基礎’較佳爲1 5莫耳％以下，更佳爲5莫耳。/。以 pVA系聚合物（A)的聚合度係沒有特別的限制 膜強度等之點來看，較佳爲200以上，更佳爲 15,000的範圍內，尤佳爲3〇〇~5〇〇〇的範圍內。 謂的聚合度，就是意味根據jIS K6726-1994的記 定的平均聚合度，於將PVA系聚合物再皂化、精 由在3〇°C的水中所測定的極限黏度[η](單位：分 用下式求得： Ρο = ([η]χ 1 0 3 / 8.2 9 )( 1 / 0 6 2 )[Technical Field] The present invention relates to a polyvinyl alcohol (hereinafter referred to as "PVA") polymer film, a method for producing the same, and a storage of the PVA polymer film. method. [Prior Art] A PVA-based polymer film formed using a PVA-based polymer is used for optical applications such as polarizing film production materials, agricultural use, etc., by utilizing the characteristics of a water-soluble unit and various other excellent physical properties. Various uses such as packaging of chemicals such as agents, packaging applications of fiber products, and the like. In addition, when a PVA-based polymer film is produced by using a T-die or the like, a method of suppressing the occurrence of a die line or the generation of foreign matter and improving the film formability is proposed as a method of blending a nonionic surfactant (see Patent). Document 1). In addition, as a method of providing a PVA-based polymer film which has excellent optical properties and has excellent optical properties without adhesion to optical streaks or optical color unevenness, it is proposed to incorporate a plurality of specific surfactants. Method (refer to Patent Document 2). [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-200-253993 [Patent Document 2] JP-A-20-206809 (Summary of the Invention) [Problems to be Solved by the Invention] -4- 201141882 However, in recent years it has been known to blend surfactants! The polymer film is wound into a roll shape, and the color of the roll may be a problem when the temperature is controlled in the warehouse for several months. Although the yellowing has little effect on the physical properties such as PVA-based polymer thinness, elongation, and haze, when the material is used, the color of the content has a yellow color, or when used as a raw material at the time of manufacture, the penetration is obtained. The object of the present invention is to provide a PVA-based polymer for the color tone of the polarizing film, and to provide a poor impression to the consumer or the user. The color of the film is not easily carried out after the temperature is controlled in a warehouse near normal temperature. Yellow tone. [Means for Solving the Problem] In order to achieve the above object, the inventors of the present invention have found that a PVA film having a PVA-based polymer and a surfactant is obtained by a PVA-based polymer film, and is dissolved in water. The pH system is in a certain range, and the present invention is completed by repeating the review in this knowledge. In other words, the present invention relates to: [1] A PVA-based polymer film containing PVA and a PVA-based polymer of a surfactant (B) in an amount of 100 parts by mass based on 100 parts by mass of the PVA-based polymer (A). When the concentration of the film is dissolved in water at 2 (the pH of the TC is 2.0 to 8.0 [2], the PVA-based polymer film of the above [1], wherein the degree of saponification of the substance (A) is 90 mol% or more; The PVA produced near the normal temperature is strong with a yellow film, but as a package, the light of the polarizing film is yellow. The film, which is a review of the force for several months, is based on the polymer thin knowledge. , polymer (A) 0 · 0 0 1~1, which is polymerized with 7 mass PVA 201141882 [3] A PVA-based polymer film of the above [1] or [2], which uses an acidic substance (C) [4] The PVA-based polymer film of the above [3], wherein the acidic substance (C) has a pKa (acid dissociation constant) at 25 ° C of 3.5 or more, and the acidic substance (C) is at atmospheric pressure. The PVA-based polymer film according to any one of the above [1] to [4], wherein the surfactant (B) is a non-ionic boundary [6] A PVA-based polymer film according to the above [5], wherein the nonionic surfactant is a surfactant of an alkanolamine type; [7] as in the above [1] to [6] Any one of PVA-based polymer films, wherein the antioxidant (D) is contained in an amount of 〇·〇ι 3 to 3 mass% with respect to the surfactant (B); [8] is as described above [1]~[ (7) The method for producing a pvA-based polymer film according to any one of the preceding claims, which comprises: preparing a PVA-based polymer (A) and a mass of 100 parts by mass relative to the PVA-based polymer (A) And a step of forming a film forming stock solution of the surfactant; and the film forming raw liquid is obtained by using a mixture containing 70% by mass or more of a surfactant; [9] The production method according to the above [8], wherein the above-mentioned film-forming stock solution is obtained by using the acidic substance (C); [10] The production method according to [8] or [9] above, wherein the mixture is a mass of 〇1 When the concentration of % is dissolved in water, the pH at 20 ° C is 8.0 or more; 201141882 [11] - a method for storing a PVA-based polymer film, which is characterized by The PVA-based polymer film according to any one of the above [1] to [7] is stored at a temperature of 〇4 to 4 (TC and a humidity of 75% RH or less. [Effect of the Invention] The PVA-based polymer of the present invention is thin. Even if it is stored in the warehouse for the same period of time, the color of the film is not easily yellowish. Therefore, even if the PVA-based polymer film is used as a packaging material or a raw material for the production of a polarizing film, it is not easy for consumers or users. Caused a bad impression. Further, according to the production method of the present invention, the PVA-based polymer film can be easily and inexpensively produced. In addition, when the PVA-based polymer film is stored by the storage method of the present invention, yellowing of the film can be more effectively suppressed. [Embodiment] [Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in more detail. The PVA-based polymer film of the present invention contains a PVA-based polymer (A) and a surfactant (B). The PVA-based polymer (A) is produced by saponifying a vinyl ester-based polymer obtained by polymerizing a vinyl ester-based monomer. Examples of the vinyl ester monomer include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl laurate, vinyl stearate, ethyl benzoate, and trimethylacetic acid. Vinyl acetate, vinyl methacrylate, etc., among which vinyl acetate is preferred. 201141882 The vinyl ester polymer is preferably used alone or in combination of two or more kinds of ethylene vinegar monomers. It is preferable that one type of B vinegar type monomer is used as a monomer, and one type or two or more types of ethylene vine type monomer may be used together with other copolymerizable monomers. a copolymer of monomers. Examples of the other monomer copolymerizable with the vinyl ester monomer include ethylene; an olefin having 3 to 30 carbon atoms such as propylene, 1-butene or isobutylene; acrylic acid or a salt thereof; methyl acrylate, Acrylic acid, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, etc. Ester; methacrylic acid or a salt thereof; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, A Tert-butyl acrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, methacrylate of octadecyl methacrylate; acrylamide, N-methyl acrylamide, N- Ethyl acrylamide, N,N'-dimethyl decylamine, diacetone acrylamide, acrylamide sulfonic acid or a salt thereof, acrylamide propyl dimethylamine or a salt thereof, N-hydroxyl A acrylamide derivative such as methacrylamide or a derivative thereof; methyl Acrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamide or its salt, methacrylamide dimethylamine or a salt thereof a methacrylamide derivative such as N-methylol methacrylamide or a derivative thereof; N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone or the like N-vinyl decylamine; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl 201141882 vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, ethylene Ethers such as ketone, decyl vinyl ether, octyl vinyl ether, etc.: acrylonitrile such as acrylonitrile or methacrylonitrile; vinyl chloride, partial dilute, fluorine (such as B, PF, etc.) An allyl compound such as diacetate chloride; maleic acid or a salt, ester or anhydride acid thereof or a salt, ester or anhydride thereof; an ethane compound such as vinyltrimethoxydecane; acetic acid The isopropenyl ester or the like, wherein the vinyl ester-based polymerization has one or more of the other monomers, and the structural unit derived from the other monomer The ratio of the vinyl ester type 'based on all structural units constituting the vinyl ester polymer' is preferably 15 mol% or less, more preferably 5 mol%. The pVA polymer (A) is used. The degree of polymerization is preferably in the range of 200 or more, more preferably 15,000, and particularly preferably in the range of 3 Å to 5 Å, without particularly restricting the film strength and the like. It means that the PVA-based polymer is resaponified according to the average degree of polymerization specified in JIS K6726-1994, and the ultimate viscosity [η] measured in water at 3 ° C (unit: divided into the following formula: Ρο = ([η]χ 1 0 3 / 8.2 9 )( 1 / 0 6 2 )
又’ PVA系聚合物（Α)的皂化度較佳爲 90 1 上’更佳爲9 3莫耳％以上。皂化度低於9 0莫] PVA系聚合物薄膜的耐水性.耐久性會有變不充夕 此處’ PVA系聚合物的皂化度，係指相對於PVA 三丁基 乙烯基 二氯乙 、烯丙 :伊康 烯基矽 物係可 單位。 聚合物 莫耳數 下。 ，從薄 200〜 此處所 載所測 製後， 升 /g)， I耳％以 f %時， •之虞。 系聚合 201141882 物所具有的可藉由皂化轉換成乙烯醇單位之構造單{ 型地乙烯酯系單體單位）與乙烯醇單位的合計莫耳 言，該乙烯醇單位的莫耳數所佔有的比例（莫耳％)。 系聚合物的皂化度係可依據JIS K6726-1994的記載 定。 於製造本發明的PVA系聚合物薄膜之際，作爲 系聚合物（A)，可單獨使用1種類的PVA系聚合物， 摻合聚合度或皂化度或改性度等互相不同的2種以 PVA系聚合物而使用。惟’本發明的PVA系聚合物 若含有具羧基、磺酸基等的酸性官能基之PVA系 物’具酸酐基的PVA系聚合物，具胺基等的鹼性官 之PVA系聚合物’此等的中和物等之具有促進交聯 的官能基之PVA系聚合物，則由於pva系聚合物分 的交聯反應’ PVA系聚合物薄膜的二次加工性會降低 此，尤其在光學用途所代表的要求優異二次加工性之 等中，PVA系聚合物薄膜較佳爲不含有具酸性官能 PVA系聚合物、具酸酐基的PVA系聚合物、具鹼性 基的PVA系聚合物及此等的中和物中之任—者； PVA系聚合物（A)’較佳爲只含有將在單體僅使用乙 系單體而得之乙稀醋系聚合物官化所製造之PVA系 物’及/或將在單體僅使用乙烯酯系單體與乙烯及/或 3〜30的烯烴而得之乙烯酯聚合物皂化所製造之Pva 合物；作爲PVA系聚合物（A)，更佳爲只含有將在單 U典 數而 P VA 來測 P VA 亦可 上之 薄膜 聚合 能基 反應 子間 。因 情況 基的 官能 作爲 烯酯 聚合 碳數 系聚 體僅 -10- 201141882 使用乙烯酯系系單體而得之乙烯酯系聚合物皂化所製造之 P VA系聚合物。 本發明中所使用的界面活性劑（B)之種類係沒有特別 的限制，例如可舉出陰離子系界面活性劑、非離子系界面 活性劑。 作爲陰離子系界面活性劑，例如可舉出月桂酸鉀等的 竣酸型；硫酸辛酯等的硫酸酯型；十二基苯磺酸鹽等的磺 酸型等。 作爲非離子系界面活性劑，例如可舉出聚氧化乙烯油 基醚等的烷基醚型；聚氧化乙烯辛基苯基醚等的烷基苯基 酸型；聚氧化乙烯月桂酸酯等的烷基酯型；聚氧化乙烯月 桂基胺基醚等的烷基胺型；聚氧化乙烯月桂醯胺等的烷基 醯胺型；聚氧化乙烯聚氧化丙烯醚等的聚丙二醇醚型；月 桂酸二乙醇醯胺、油基二乙醇醯胺等的烷醇醯胺型；聚氧 化烯烯丙基苯基醚等的烯丙基苯基醚型等。 界面活性劑係可使用單獨1種，也可倂用2種以上。 於此等界面活性劑之中，從製膜時的膜面異常之減低效果 優異來看，較佳爲非離子系界面活性劑，而且從更顯著地 達成本發明的效果來看’較佳爲烷醇醯胺型的界面活性 劑，更佳爲脂肪族羧酸（例如碳數8〜3 0的飽和或不飽和 脂肪族羧酸等）的二烷醇醯胺（例如二乙醇醯胺等）。 從取得容易且亦便宜來看，界面活性劑（B)較佳爲以 含有界面活性劑（B)的混合物之形態來使用。該混合物中 -11 - 201141882 的界面活性劑（B)之含有率較佳爲70質量％以上’更佳爲 80質量％以上，尤佳爲90質量。/。以上。又’作爲該混合物 中的界面活性劑（B)之含有率的上限’例如可舉出99.99 質量％。於該混合物所含有的界面活性劑（B)以外之成分’ 並沒有特別的限制，例如可舉出在製造界面活性劑（B )之 際所使用的原料、觸媒、溶劑；界面活性劑（B)分解而產 生的分解物；爲了使界面活性劑（B)的安定性提高而添加 之安定劑等。更具.體而言，當界面活性劑（B)爲烷醇醯胺 型的非離子系界面活性劑之情形，可舉出對應的烷醇胺。 含有上述界面活性劑（B)的混合物，從更顯著地達成 本發明的效果來看，以 〇. 1質量％的濃度溶解於水時在 20°C的pH(所得之水溶液的pH)較佳爲8.0以上，更佳爲 8.5〜12.0的範圍內。再者，將含有界面活性劑（B)的混合 物以成爲〇. 1質量％的方式加到水中攪拌（視需要亦可更加 熱及/或冷卻），然後於溫度維持在20t之際，即使含該界 面活性劑（B)的混合物中所含有的成分之一部分係不完全 溶解於而成爲分散液的形態時，也可藉由測定該分散液的 pH，將所得之値視爲上述pH。 PVA系聚合物薄膜中的界面活性劑（B)之含有率，必 須相對於PVA系聚合物1〇〇質量份而言在0.001〜1質量 份的範圍內，更佳在0.01〜0.7質量份的範圍內，尤佳在 0.05〜0.5質量份的範圍內。上述含有率若少於0.001質 量份’則製膜時的膜面異常之減低效果係不易出現，若多 -12- 201141882 於1質量份，則在薄膜表面溶出’成爲黏結的原因而操作 性降低。 本發明的PVA系聚合物薄膜，以7質量％的濃度溶解 於水時在20°C的pH(所得之水溶液的pH)爲2.0〜8.0的範 圍內’此在長期保管時的抑制薄膜之黃變上係極重要。當 上述pH低於2.0時’由於PVA系聚合物本身的劣化而容 易發生黃變。又’上述pH低於2.0的薄膜，係在製膜時 需要施予防腐加工的特殊製殊設備。由此觀點來看，上述 pH較佳爲2.5以上’更佳爲3.0以上。另一方面，上述pH 超過8.0時’係得不到充分的黃變抑制效果。由此觀點來 看’上述pH較佳爲7.5以下，更佳爲7.0以下，尤佳爲 以下’特佳爲6.5以下，最佳爲6.0以下。再者，將 P V A系聚合物薄膜以成爲7質量％的方式加到水中攪拌（視 需要亦可更加熱及/或冷卻），然後於溫度維持在2(TC之 際，即使含有該PVA系聚合物薄膜的混合物中所含有的成 分之一部分係不完全溶解於而成爲分散液的形態時，也可 藉由測定該分散液的pH，將所得之値視爲上述PH。 對於本發明的PVA系聚合物薄膜，將以7質量％的濃 度使溶解於水時在20 °C的pH控制在2.0〜8.0的範圍內之 方法，係未必要限定，但從控制容易來看，於PVA系聚 合物薄膜的製程中適量摻合酸性物質（C)的方法係合宜。 酸性物質（C)的種類係沒有特別的限制，但在25〇c的 pKa(酸解離常數）爲3.5以上的酸性物質係較佳。若使用 -13- 201141882 上述pKa低於3 · 5的強酸性物質，則由於酸性物質的使用 量之稍微變動，使所得之PVA系聚合物薄膜溶解於水 時，上述pH係有大幅變化的可能性，得到目的之PVA系 聚合物薄膜會變困難，_而且於PVA系聚合物薄膜中，當 如此強的酸性物質之濃度發生偏差時，在濃度高的部位亦 有發生黃變等的問題之可能性。 又，酸性物質（C)在常壓下（絕對壓力的latm)的沸點較 佳爲超過120°C。常壓下的沸點爲120t以下時，長期保 管中酸性物質係自PVA系聚合物薄膜緩慢地揮發，黃變的 抑制效果有降低之虞。再者，於本說明書中，將酸性物質 在常壓下1 20 °C時實質上不具有揮發性者亦視爲常壓下的 沸點超過120°C者。作爲此處實質上不具有揮發性的酸性 物質，例如可舉出於蒸發皿上載置約1 g經精秤的該酸性 物質，將此在常壓下於12CTC保持1〇分鐘後，該酸性物質 的質量減少量也爲1 〇質量％以下的酸性物質等。酸性物質 (C)的沸點更佳爲125°C以上，尤佳爲130°C以上。 作爲在25°C的pKa爲3.5以上且常壓下的沸點超過 1 2 0 °C之酸性物質，例如可舉出乳酸、琥珀酸、己二酸、 苯甲酸、癸酸、檸檬酸、月桂酸等的有機酸；硼酸、磷酸 二氫鉀、磷酸二氫鈉等的無機酸性物質；天冬胺酸、麩胺 酸等的胺基酸等，但未必受此等所限定。此等酸性物質可 使用單獨1種，也可倂用2種以上。於此等之中，從可實 質上忽視揮發所致的散逸來看，較佳爲無機酸性物質。 -14- 201141882 於本發明的PVA系聚合物薄膜的製程中，較宜使用 的酸性物質（C )之量，係使最終所得之P V A系聚合物薄膜 以7質量％的濃度溶解於水時在20°C的pH成爲2.0〜8.0 的範圍內。PVA系聚合物薄膜中所使用的酸性物質（C)之 含有率（惟，對於成爲共軛鹼之形態者，亦考慮含有與該 共軛鹼相同莫耳數的酸性物質（C ))，係取決於所使用的酸 性物質（C)之種類等而無法一槪地決定，例如可舉出相對 於PVA系聚合物（A)100g而言，成爲0.000 1〜0.05莫耳的 比例。 本發明的PVA系聚合物薄膜係如上述，以7質量％的 濃度溶解於水時在20°C的pH爲在2.0〜8.0的範圍內，溶 解於水時顯示如此pH的本發明之PVA系聚合物薄膜若更 含有抗氧化劑（D)，雖然理由未確定，但可使黃變的抑制 效果更長時間持續。以7質量％的濃度溶解於水時在20°C 的pH爲上述範圍以外的pVA系聚合物薄膜之情況中，如 此的抗氧化劑（D)之效果係幾乎沒有看到。 抗氧化劑（D)的種類係沒有特別的限制，可例示酚 系、亞磷酸酯系、硫酯系、苯并三唑系、受阻胺系等的有 機系抗氧化劑當作合適物。 本發明的PVA系聚合物薄膜中之抗氧化劑（D)的含有 率’以界面活性劑（B)的質量爲基礎，較佳爲〇.〇1〜3質 量％的範圍內’更佳爲0.05〜1質量％的範圍內。該含有 率以界面活性劑（B)的質量爲基礎，若低於〇.〇1質量％， -15- 201141882 則會無法使黃變的抑制效果更長期間持續；若超過3質量 %，則抗氧化劑（D )凝聚，當作P V A系聚合物薄膜上的缺 點表現，有損害外觀之虞。 於不含有塑化劑的狀態下，與其它塑膠薄膜相比， PVA系聚合物薄膜係剛直，衝撃強度等的機械物性或二次 加工時的製程通過性等會成爲問題。爲了防止該等的問 題，本發明的PVA系聚合物薄膜較佳爲含有塑化劑（E)。 作爲較佳的塑化劑，可舉出多元醇，具體地例如可舉出乙 二醇、甘油、丙二醇、二乙二醇、三乙二醇、四乙二醇、 三羥甲基丙烷等。此等塑化劑（E)可單獨使用1種，也可 倂用2種以上。於此等塑化劑之中，從將本發明的PVA 系聚合物薄膜延伸而使用時的延伸性提高效果等的觀點來 看，較佳爲乙二醇或甘油。PVA系聚合物薄膜中的塑化劑 (E)之含有率，相對於PVA系聚合物薄膜中所含有的PVA 系聚合物100質量份而言，較佳爲1〜30質量份的範圍 內，更佳爲3〜25質量份的範圍內，尤佳爲5〜20質量份 的範圍內。上述含有率若低於1質量份，則有容易發生上 述問題的傾向，若超過3 0質量份，則薄膜變過度柔軟， 操作性會降低。 本發明的PVA系聚合物薄膜係可僅由PVA系聚合物 (A)及界面活性劑（B)所組成，也可由PVA系聚合物（A)及 界面活性劑（B)與上述酸性物質（C)(惟，成爲共軛鹼的形態 時，包含含有該共軛鹼的鹽）、抗氧化劑（D)及塑化劑（E)中 -16- 201141882 的至少一種所組成’按照需要在不妨礙本發明的效果之範 圍內，也可更含有 PVA(A)、界面活性劑（B)、酸性物質 (C)(惟，成爲共軛鹼的形態時，包含含有該共鞭鹼·的鹽）、 抗氧化劑（D)及塑化劑（E)以外的其它成分。作爲如此的其 它成分，例如可舉出水分、紫外線吸收劑、滑劑、著色 劑、塡充劑、防腐劑、防黴劑、上述成分以外的其它高分 子化合物等。惟，含有多羧酸、多胺所代表的螯合化劑或 在其上配位有金屬而成的螯合化合物之PVA系聚合物薄 膜，由於在其製過中容易發生凝膠，視用途而定，該凝膠 會降低最終製品的品質，故PVA系聚合物薄膜較佳爲不 含有螯合化劑及螯合化合物中的任一者。 PVA系聚合物（A)、界面活性劑（B)、酸性物質 (C)(惟，成爲共輕驗的形態時，包含含有該共輞驗的鹽）、 抗氧化劑（D)及塑化劑（E)的各質量之合計値，佔本發明的 PVA系聚合物薄膜之全質量之比例，較佳爲60〜1〇〇質量 %的範圍內，更佳爲80〜100質量％的範圍內，尤佳爲90 〜100質量％的範圍內。 本發明的PVA系聚合物薄膜，係可藉由將含有PVA 系聚合物（A)及相對於該PVA系聚合物（A)100質量份而言 0.001〜1質量份（較佳爲0.01〜0.7質量份，更佳爲〇.05 〜〇.5質量份）的界面活性劑（B)之製膜原液製膜而製造。 作爲該製膜原液的具體例，例如可舉出將PVA系聚合物 (A)溶解於溶劑中所成，同時以上述比例含有界面活性劑 -17- 201141882 (B)的PVA系聚合物溶液，或將含水狀態的PVA系聚合物 (A)(亦可更含有有機溶劑等）熔融所成，同時以上述比例 含有界面活性劑（B )的熔融物等。 作爲用於製造PVA系聚合物薄膜的具體方法，例如 可採用使用上述PVA系聚合物溶液，藉由流延製膜法、 濕式製膜法（吐出到貧溶劑中）' 乾濕式製膜法、凝膠製膜 法（一旦將PVA系聚合物溶液冷卻膠化後，萃取去除溶 劑，而得到PVA系聚合物薄膜之方法）或此等的組合來製 膜之方法、或將使用擠壓機等以得到上述熔融物由T模頭 等壓出而製膜之熔融壓出製膜法等任意的方法。於此等之 中，較佳爲流延製膜法及熔融壓出製膜法，因爲可得到透 明性高、著色少的PVA系聚合物薄膜。 上述製膜原液的揮發份濃度（製膜時因揮發或蒸發而 去除的溶劑等之揮發性成分的濃度）較佳爲5 0〜9 0質量％ 的範圍內’更佳爲55〜80質量％的範圍內。揮發份濃度 若低於50質量％’則黏度變高而製膜會變困難。另—方 面，揮發份濃度若超過9 0質量％，則黏度變低而容易損 害所得之薄膜的厚度均性，故不宜。 上述製膜原液的調製方法係沒有特別的限制，例如可 舉出在水中溶解有PVA系聚合物（A)者中，添加界面活性 劑（B) ’與視需要更且酸性物質、抗氧化劑、塑化 劑（E)及上述其它成分中的至少1種之方法，或使用擠壓 機將含水狀態的PVA系聚合物（A)熔融混煉時，同時熔融 -18 - 201141882 混煉界面活性劑（B ) ’與視需要更且酸性物質（c)、抗氧化 劑（D)、塑化劑（E)及上述其它成分中的至少1種之方法 等。於此等之中’以流延製膜法來製造PVA系聚合物薄 膜時，較佳爲在水中溶解有PVA系聚合物（A)者中，添加 界面活性劑（B) ’與視需要更且酸性物質（C)、抗氧化劑 (D)、塑化劑（E)及上述其它成分中的至少1種之方法。 又，於製膜原液的調製時摻合界面活性劑（B)時，若 以含有上述界面活性劑（B )的混合物之形態使用，則由於 不需要界面活性劑（B)的繁雜精製作業，而且不需要使用 更高價的高純度界面活性劑（B)，可容易且便宜地調製製 膜原液而較佳。再者，當上述製膜原液使用酸性物質（c) 獲得時，由於可在酸性物質（C)的摻合時藉由調整其摻合 量，將所得之PVA系聚合物薄膜溶解於水時的PH容易地 P整至上述範圍而較佳。 本發明的PVA系聚合物薄膜之厚度係沒有特別的限 制’可按照用途來設定恰當的厚度。具體地，例如於包裝 材料用途中，平均厚度較佳爲5〜500 μιη的範圍內；於作 爲偏光薄膜的原料使用時，平均厚度較佳爲5〜150 μιη的 範厪I內。再者’ PVA系聚合物薄膜的平均厚度係可測定任 意的10個地方（例如，在PVA系聚合物薄膜的寬度方向 中所畫的直線上之任意10個地方）之厚度，以該等的平均 値求得。 -19- 201141882 又’本發明包含將上述本發明的PVA系聚合物 在溫度0〜40°C及濕度75%RH以下的條件下保管之 系聚合物薄膜的保管方法。本發明的PVA系聚合物 之特徵爲與以往的PVA系聚合物薄膜比較下，長期 管時的黃變係少，由於若保管時的溫度愈高則有愈容 變的傾向’故較佳爲在4 0 °C以下的溫度保管。又， 時的溫度若過低’則由保管場所取出而使用時，薄膜 會發生結露，因此有發生薄膜的黏結或鬆弛等的異 虞。由此觀點來看，保管時的溫度較佳爲〇°C以上》 地’若在濕度超過75%RH的條件下保管，則由PVA 合物薄膜的吸濕，而有發生薄膜的黏結或鬆弛等的異 虞。保管PVA系聚合物薄膜時的保管期間係沒有特 限定，但若太長，尤其在高溫下保管時等，有緩慢地 黃變的可能性，故較佳爲1星期以上2年以內，更佳 個月以上1.5年以內，尤佳爲3個月以上1年以內。 本發明的PVA系聚合物薄膜之用途係沒有特別 制，例如可作爲包裝材料；製造偏光薄膜、相位差薄 的光學薄膜用之原料；洗衣袋等的水溶性薄膜；製造 大理石時的脫模薄膜等使用；惟本發明的PVA系聚 薄膜即使在倉庫內等長期間保管，薄膜的顔色也不易 黃色調，不易對消費者或使用者造成不良的印象，故 爲使用作爲製造包裝材料、偏光薄膜或相位差薄膜用 料。又’以上述比例含有界面活性劑（B)而且以7質遍 薄膜 P VA 薄膜 間保 易黃 保管 表面 常之 同樣 系聚 常之 別的 進行 爲1 的限 膜等 人造 合物 帶有 較佳 的原 t %的 -20- 201141882 濃度溶解於水時在20 °C的pH爲在上述範圍內的本發明之 PVA系聚合物薄膜，即使在長時間（較佳爲72小時以上， 更佳爲1 2 0小時以上，尤佳爲丨8 〇小時以上）連續製造 時’也可高度地抑制推測因界面活性劑（B)的凝聚物所造 成的條紋狀之缺點（在與薄膜的流動方向呈平行地連續或 斷續地發生之薄膜的微細凹凸之缺點）之發生，故在如偏 光薄膜或相位差薄膜之最終製品要求高品質的情況中，可 特佳地使用作爲製造它們用的原料。 [實施例] 以下藉由實施例等來具體說明本發明，惟本發明完全 不受此等實施例所限定。 再者’以下顯不下述實施例及比較例中所採用的使 PVA薄膜溶解於水時的pH及PVA薄膜之黃色度（YI値）的 各測定方法。 [使PVA薄膜溶解於水時的pH之測定] 將7g PVA薄膜置入室溫的93g去離子水中，於攪拌 下加熱至約9 0 °C而使薄膜完全溶解後，將所得之水溶液 冷卻至 20 °C ，使用 pH計（METTLER TOLEDO公司製 「MP230」）來測定該水溶液的pH» [PVA薄膜的黃色度（ΥΙ値）之測定] 重疊8片樣品的薄膜，使用色差計（日本電色工業股 份有限公司製Model「NF-902」）測定薄膜的YI値，當作 8片全體的値。 -21 - 201141882 [實施例1 ] 將皂化度99.9莫耳％、聚合度2400、醋酸鈉含量2.4 質量％的PVA(聚醋酸乙烯酯的皂化物）之碎片10〇質量 份，浸漬於35°C的蒸餾水2500質量份中24小時後’進 行離心脫水而得到PVA含水碎片。所得之PVA含水碎片 中的醋酸鈉含量係相對於PVA的 〇.1質量％，而且 PVA 含水碎片中的揮發份濃度爲70質量％ ° 對333質量份（以乾燥狀態PVA換算爲100質量份）的 該PVA含水碎片，添加12質量份的甘油、〇·3質量份含 界面活性劑的混合物（以95質量％的比例含有月桂酸二乙 醇醯胺，而且含有二乙醇胺當作雜質的混合物。使該混合 物以0.1質量％的濃度溶解於水時在20°C的pH(關於PVA 薄膜的情況，藉由與上述同樣的方法來測定）爲 9.64)、 0.003質量份的 4,4’-亞丁基雙（·6-第三丁基-3-甲基苯 酚）（酚系抗氧化劑），再以對100g PVA而言成爲i〇mi的 比例添加1 m ο 1 /1的磷酸二氫鉀水溶液後，充分混合而成 爲混合物，用最高溫度1 30°C的二軸擠壓機將此加熱熔 融。用熱交換機冷卻至l〇〇°C後，在95°C的金屬滾筒上熔 融壓出製膜，進行乾燥而得到薄膜寬度1.2m、平均厚度 60pm的PVA薄膜。在所得的PVA薄膜上沒有看到條紋等 的缺陷而外觀良好。使用所得之PVA薄膜，以上述方法 來測定溶解於水時的ρ Η，結果爲6.0。 -22- 201141882 又’將所得之PVA薄膜切成A4大小，首先以上 法測定初期狀態的黃色度（γ I値），結果爲4.6。將此 薄膜吊掛放置在已調整至801的熱風乾燥機中。而 上述方法測定自放置起3日後、5日後及10日後的 之黃色度（YI値），各自爲7.6、9_〇、10.1。因此，黃 (YI値）之由初期値的增加量，即黃變度（△ YI)各自計 3.0 、 4.4 、 5.5 。 表1中顯示以上的各種評價之結果。再者，240 連續進行上述的製膜，沒有看到條紋狀的缺點之發生 [實施例2] 除了於實施例1中，代替以對100g PVA而言 1 0ml的比例添加lmo 1/1的磷酸二氫鉀水溶液，以對 P V A而言成爲 5 m 1的比例添加1 m ο 1 /1的乳酸水溶 外，與實施例1同樣地，得到PVA薄膜。在所得的 薄膜上沒有看到條紋等的缺陷而外觀良好。 使用所得之PVA薄膜，與實施例1同樣地進行 測定。表1中顯示結果。 [實施例3 ] 除了於實施例1中，代替以對l〇〇g PVA而言 10ml的比例添加lmo 1/1的磷酸二氫鉀水溶液，以對 PVA而言成爲 l〇ml的比例添加 lmol/1的醋酸水溶 外，與實施例1同樣地，得到PVA薄膜。在所得的 薄膜上沒有看到條紋等的缺陷而外觀良好。Further, the degree of saponification of the PVA-based polymer (Α) is preferably 90 1 or more, more preferably 9 3 mol% or more. The degree of saponification is lower than that of the 90%] PVA-based polymer film. The durability of the PVA-based polymer film may not change. The degree of saponification of the PVA-based polymer means that it is relative to PVA, tributylvinyldichloroethane. Allyl: Ikonic alkenyl is a unit. The polymer has a molar number. From the thin 200~ measured here, liter / g), I ear % with f %, • 虞. The total amount of the structural unit {the vinyl ester monomer unit which can be converted into a vinyl alcohol unit by saponification 201141882 and the vinyl alcohol unit, the mole number of the vinyl alcohol unit Proportion (% by mole). The degree of saponification of the polymer can be determined in accordance with JIS K6726-1994. When the PVA-based polymer film of the present invention is produced, as the polymer (A), one type of PVA-based polymer can be used alone, and two kinds of different degrees of polymerization degree, saponification degree, and degree of modification are blended. PVA is used as a polymer. When the PVA-based polymer of the present invention contains a PVA-based polymer having an acidic functional group such as a carboxyl group or a sulfonic acid group, a PVA-based polymer having an acid anhydride group, and an alkali-based PVA-based polymer having an amine group or the like In the PVA-based polymer having a functional group which promotes crosslinking, such as a neutralized substance, the cross-linking reaction of the pva-based polymer component, the secondary processability of the PVA-based polymer film is lowered, especially in the optical In the case of demanding excellent secondary workability, the PVA-based polymer film preferably does not contain an acidic functional PVA-based polymer, a PVA-based polymer having an acid anhydride group, or a PVA-based polymer having a basic group. And any of the neutralizing substances of the above; the PVA-based polymer (A)' is preferably produced by only officially converting the ethylene vinegar-based polymer obtained by using only the ethylenic monomer in the monomer. a PVA compound' and/or a Pva compound produced by saponifying a vinyl ester polymer obtained by using only a vinyl ester monomer and ethylene and/or an olefin of 3 to 30 in a monomer; as a PVA-based polymer (A) ), more preferably, it only contains a film polymerization energy base which will be measured on a single U number and P VA to measure P VA Between the reactions. The functional group-based functional group is an olefin-polymerized carbon number-based polymer. Only -10-201141882 A P-VA-based polymer produced by saponification of a vinyl ester-based polymer obtained by using a vinyl ester-based monomer. The type of the surfactant (B) used in the present invention is not particularly limited, and examples thereof include an anionic surfactant and a nonionic surfactant. Examples of the anionic surfactant include a citric acid type such as potassium laurate; a sulfate type such as octyl sulfate; and a sulfonic acid type such as dodecylbenzenesulfonate. Examples of the nonionic surfactant include an alkyl ether type such as polyoxyethylene oleyl ether, an alkylphenyl acid type such as polyoxyethylene octylphenyl ether, and a polyoxyethylene laurate. Alkyl ester type; alkylamine type such as polyoxyethylene lauryl amine ether; alkylguanamine type such as polyoxyethylene laurylamine; polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether; lauric acid An alkanolamine type such as diethanolamine or oleyldiethanolamine; an allylphenyl ether type such as a polyoxyalkylene allyl ether or the like. The surfactant may be used singly or in combination of two or more. Among these surfactants, from the viewpoint of excellent effect of reducing the film surface abnormality at the time of film formation, a nonionic surfactant is preferred, and from the viewpoint of more remarkable achievement of the present invention, it is preferable. The alkanoguanamine type surfactant is more preferably an aliphatic carboxylic acid (for example, a saturated or unsaturated aliphatic carboxylic acid having a carbon number of 8 to 30), or a dialkanolamine (for example, diethanolamine or the like). . The surfactant (B) is preferably used in the form of a mixture containing the surfactant (B) in view of ease of availability and low cost. The content of the surfactant (B) in the mixture of -11 - 201141882 is preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass. /. the above. Further, the upper limit of the content ratio of the surfactant (B) in the mixture is, for example, 99.99% by mass. The component other than the surfactant (B) contained in the mixture is not particularly limited, and examples thereof include a raw material, a catalyst, and a solvent used in the production of the surfactant (B); and a surfactant ( B) a decomposition product produced by decomposition; a stabilizer or the like added to improve the stability of the surfactant (B). More specifically, when the surfactant (B) is a nonionic surfactant of the alkanolamine type, the corresponding alkanolamine can be mentioned. The mixture containing the above surfactant (B) is more preferably at a pH of 20 ° C (pH of the obtained aqueous solution) when dissolved in water at a concentration of 0.1% by mass. It is 8.0 or more, more preferably 8.5 to 12.0. Further, the mixture containing the surfactant (B) is added to water in a manner of being 1% by mass or more (further and/or cooled if necessary), and then maintained at a temperature of 20 t, even if it is contained. When a part of the component contained in the mixture of the surfactant (B) is not completely dissolved and becomes a dispersion, the pH of the dispersion may be measured, and the obtained hydrazine may be regarded as the above pH. The content of the surfactant (B) in the PVA-based polymer film must be in the range of 0.001 to 1 part by mass, more preferably 0.01 to 0.7 part by mass, per part by mass of the PVA-based polymer. In the range, it is particularly preferably in the range of 0.05 to 0.5 part by mass. When the content is less than 0.001 part by mass, the effect of reducing the film surface abnormality at the time of film formation is less likely to occur, and if the amount is more than 1 to 201141882, the film is eluted on the surface of the film to cause adhesion and the workability is lowered. . When the PVA-based polymer film of the present invention is dissolved in water at a concentration of 7 mass% at a pH of 20 ° C (the pH of the obtained aqueous solution) is in the range of 2.0 to 8.0, the yellow of the film is inhibited during long-term storage. It is extremely important to change the system. When the above pH is lower than 2.0, yellowing is liable to occur due to deterioration of the PVA-based polymer itself. Further, the above-mentioned film having a pH lower than 2.0 is a special type of equipment which requires anti-corrosion processing at the time of film formation. From this point of view, the pH is preferably 2.5 or more', more preferably 3.0 or more. On the other hand, when the pH exceeds 8.0, a sufficient yellowing suppression effect is not obtained. From this point of view, the pH is preferably 7.5 or less, more preferably 7.0 or less, and particularly preferably hereinafter 6.5 or less, and most preferably 6.0 or less. In addition, the PVA-based polymer film is added to water to be stirred at 7% by mass (and may be heated and/or cooled if necessary), and then maintained at a temperature of 2 (TC) even if the PVA-based polymerization is contained. When a part of the component contained in the mixture of the film is not completely dissolved and becomes a dispersion, the pH of the dispersion may be measured, and the obtained ruthenium may be regarded as the above PH. The polymer film is a method in which the pH at 20 ° C is controlled to be in the range of 2.0 to 8.0 when dissolved in water at a concentration of 7 mass%, which is not necessarily limited, but is easily controlled from the PVA polymer. The method of blending an appropriate amount of the acidic substance (C) in the process of the film is suitable. The type of the acidic substance (C) is not particularly limited, but an acidic substance having a pKa (acid dissociation constant) of 25 or more at 25 〇c is more preferable. If the above-mentioned strong acid substance having a pKa of less than 3.5 is used, the above-mentioned pH system greatly changes when the obtained PVA-based polymer film is dissolved in water due to a slight change in the amount of the acidic substance used. Possibility The PVA-based polymer film of the purpose becomes difficult, and in the PVA-based polymer film, when the concentration of such a strong acid substance varies, there is a possibility that yellowing or the like may occur in a portion having a high concentration. Further, the acidic substance (C) preferably has a boiling point of more than 120 ° C at normal pressure (latm of absolute pressure). When the boiling point at normal pressure is 120 t or less, the acidic substance in the long-term storage is slow from the PVA-based polymer film. The volatilization of the earth and the suppression effect of the yellowing are reduced. Further, in the present specification, the acidic substance is substantially not volatile at a normal pressure of 1 20 ° C, and the boiling point of the acidic substance is more than 120 under normal pressure. For example, as the acidic substance which is substantially nonvolatile at this time, for example, about 1 g of the acidic substance of the fine scale is placed on the evaporating dish, and this is kept at 12 CTC for 1 minute after the normal pressure. The amount of the acid substance to be reduced is also 1% by mass or less of an acidic substance, etc. The boiling point of the acidic substance (C) is more preferably 125 ° C or higher, and particularly preferably 130 ° C or higher. As a pKa at 25 ° C It is 3.5 or more and the boiling point under normal pressure exceeds 1 2 0 °C Examples of the acidic substance include organic acids such as lactic acid, succinic acid, adipic acid, benzoic acid, citric acid, citric acid, and lauric acid; inorganic acidic substances such as boric acid, potassium dihydrogen phosphate, and sodium dihydrogen phosphate; An amino acid such as amylin or glutamic acid, but not limited thereto. These acidic substances may be used alone or in combination of two or more. In view of dissipating the volatilization due to volatilization, it is preferably an inorganic acidic substance. -14- 201141882 In the process of the PVA-based polymer film of the present invention, the amount of the acidic substance (C) which is preferably used is the final result. When the PVA-based polymer film was dissolved in water at a concentration of 7 mass%, the pH at 20 ° C was in the range of 2.0 to 8.0. The content of the acidic substance (C) used in the PVA-based polymer film (except for the form of the conjugate base, the acidic substance (C) containing the same molar number as the conjugate base) is also considered. Depending on the type of the acidic substance (C) to be used, etc., it is not possible to determine the ratio of, for example, 100 g of the PVA-based polymer (A) to 0.000 1 to 0.05 mol. The PVA-based polymer film of the present invention is a PVA system of the present invention which exhibits such a pH when dissolved in water at a pH of 20 ° C in a range of 2.0 to 8.0 when dissolved in water at a concentration of 7 mass% as described above. If the polymer film further contains an antioxidant (D), although the reason is not determined, the effect of suppressing yellowing can be continued for a longer period of time. When the pVA-based polymer film having a pH of 20 ° C outside the above range was dissolved in water at a concentration of 7 mass%, the effect of the antioxidant (D) was hardly observed. The type of the antioxidant (D) is not particularly limited, and an organic antioxidant such as a phenol type, a phosphite type, a thioester type, a benzotriazole type or a hindered amine type can be exemplified as a suitable product. The content rate of the antioxidant (D) in the PVA-based polymer film of the present invention is based on the mass of the surfactant (B), preferably in the range of 〜1 to 3 mass%, more preferably 0.05. ~1% by mass range. The content rate is based on the mass of the surfactant (B). If it is less than 〇.〇1% by mass, -15-201141882 may not cause the yellowing inhibition effect to continue for a longer period; if it exceeds 3% by mass, The antioxidant (D) aggregates and appears as a defect on the PVA-based polymer film, which is detrimental to the appearance. In the state where the plasticizer is not contained, the PVA-based polymer film is straight as compared with other plastic films, and mechanical properties such as punching strength or processability at the time of secondary processing may become a problem. In order to prevent such problems, the PVA-based polymer film of the present invention preferably contains a plasticizer (E). The preferred plasticizer may, for example, be a polyhydric alcohol, and specific examples thereof include ethylene glycol, glycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and trimethylolpropane. These plasticizers (E) may be used singly or in combination of two or more. Among these plasticizers, ethylene glycol or glycerin is preferred from the viewpoint of the effect of improving the elongation when the PVA-based polymer film of the present invention is extended and used. The content of the plasticizer (E) in the PVA-based polymer film is preferably in the range of 1 to 30 parts by mass based on 100 parts by mass of the PVA-based polymer contained in the PVA-based polymer film. More preferably, it is in the range of 3 to 25 parts by mass, and more preferably in the range of 5 to 20 parts by mass. When the content is less than 1 part by mass, the above-mentioned problem tends to occur. When the content is more than 30 parts by mass, the film becomes excessively soft and the workability is lowered. The PVA-based polymer film of the present invention may be composed only of the PVA-based polymer (A) and the surfactant (B), and may also be a PVA-based polymer (A) and a surfactant (B) and the above-mentioned acidic substance ( C) (except that when the form of the conjugate base is included, the salt containing the conjugate base), the antioxidant (D), and at least one of the plasticizer (E)-16-201141882 are formed as needed The PVA (A), the surfactant (B), and the acidic substance (C) may be further contained in the range of the effect of the present invention. (When the form is a conjugate base, the salt containing the cokalkiate is contained. ), other components than antioxidant (D) and plasticizer (E). Examples of such other components include water, an ultraviolet absorber, a lubricant, a colorant, a chelating agent, a preservative, an antifungal agent, and other high molecular compounds other than the above components. However, a PVA-based polymer film containing a chelating agent represented by a polycarboxylic acid or a polyamine or a chelating compound having a metal coordinated thereto is likely to be gelled during its production, depending on the use. However, the gel lowers the quality of the final product, so the PVA-based polymer film preferably does not contain any of a chelating agent and a chelating compound. PVA-based polymer (A), surfactant (B), and acidic substance (C) (except when it is in a form of a total test, including a salt containing the test), an antioxidant (D), and a plasticizer The total mass of (E) is preferably in the range of 60 to 1% by mass, more preferably 80 to 100% by mass, based on the total mass of the PVA-based polymer film of the present invention. , especially good for the range of 90 to 100% by mass. The PVA-based polymer film of the present invention is 0.001 to 1 part by mass (preferably 0.01 to 0.7) per 100 parts by mass of the PVA-based polymer (A) and the PVA-based polymer (A). The mass fraction, more preferably 〇.05 〇.5 parts by mass, of the surfactant (B) is formed into a film-forming stock solution. Specific examples of the film-forming raw material solution include a PVA-based polymer solution in which a PVA-based polymer (A) is dissolved in a solvent and a surfactant -17-201141882 (B) is contained in the above ratio. Further, a PVA-based polymer (A) in a water-containing state (which may further contain an organic solvent or the like) is melted, and a melt of the surfactant (B) or the like is contained in the above ratio. As a specific method for producing a PVA-based polymer film, for example, a PVA-based polymer solution can be used, and a wet-film formation method can be employed by a cast film formation method or a wet film formation method (discharged into a poor solvent). Method, gel film forming method (when a PVA-based polymer solution is cooled and gelatinized, and a solvent is removed to obtain a PVA-based polymer film) or a combination thereof to form a film, or an extrusion method is used. The machine or the like obtains any method such as a melt extrusion film forming method in which the melt is extruded by a T die or the like to form a film. Among these, a cast film forming method and a melt-pressing film forming method are preferred because a PVA-based polymer film having high transparency and little coloration can be obtained. The concentration of the volatile matter of the film-forming raw material solution (concentration of a volatile component such as a solvent which is removed by volatilization or evaporation at the time of film formation) is preferably in the range of from 50 to 90% by mass, more preferably from 55 to 80% by mass. In the range. When the concentration of the volatile matter is less than 50% by mass, the viscosity becomes high and film formation becomes difficult. On the other hand, if the concentration of the volatile matter exceeds 90% by mass, the viscosity becomes low and the thickness of the obtained film is easily damaged, which is not preferable. The preparation method of the film-forming raw material solution is not particularly limited, and examples thereof include a surfactant (B) in which a PVA-based polymer (A) is dissolved in water, and an acidic substance or an antioxidant, if necessary. When at least one of the plasticizer (E) and the above other components is used, or when the PVA-based polymer (A) in a hydrated state is melt-kneaded by using an extruder, the -18 - 201141882 kneading surfactant is simultaneously melted. (B) 'A method of at least one of an acidic substance (c), an antioxidant (D), a plasticizer (E), and the other components as needed. In the case of producing a PVA-based polymer film by a cast film forming method, it is preferred to add a surfactant (B) in a PVA-based polymer (A) dissolved in water. Further, at least one of the acidic substance (C), the antioxidant (D), the plasticizer (E), and the other components described above. Further, when the surfactant (B) is blended in the preparation of the film forming solution, when it is used in the form of a mixture containing the above surfactant (B), the complicated refining operation of the surfactant (B) is not required. Further, it is not necessary to use a higher-priced high-purity surfactant (B), and it is preferable to prepare the film forming solution easily and inexpensively. Further, when the above-mentioned film-forming stock solution is obtained using the acidic substance (c), the PVA-based polymer film obtained by dissolving the obtained PVA-based polymer film in water can be adjusted by adjusting the blending amount at the time of blending the acidic substance (C). It is preferable that the pH is easily P to the above range. The thickness of the PVA-based polymer film of the present invention is not particularly limited, and an appropriate thickness can be set according to the use. Specifically, for example, in the use of the packaging material, the average thickness is preferably in the range of 5 to 500 μm; and when used as a raw material of the polarizing film, the average thickness is preferably in the range of 5 to 150 μm. Further, the average thickness of the 'PVA-based polymer film can be measured in any 10 places (for example, any 10 places on a straight line drawn in the width direction of the PVA-based polymer film), and the like. Average pleading. -19-201141882 Further, the present invention includes a method of storing a polymer film in which the PVA polymer of the present invention is stored under the conditions of a temperature of 0 to 40 ° C and a humidity of 75% RH or less. The PVA-based polymer of the present invention is characterized in that the yellowing of the long-term tube is less than that of the conventional PVA-based polymer film, and the higher the temperature during storage, the more prone to change. Store at a temperature below 40 °C. Further, if the temperature is too low, the film will be dew condensation when it is taken out from the storage place, and thus the film may be stuck or loosened. From this point of view, the temperature at the time of storage is preferably 〇 ° C or more. If the humidity is more than 75% RH, the PVA compound film absorbs moisture and the film is stuck or loosened. Waiting for the difference. The storage period of the PVA-based polymer film is not particularly limited. However, if it is too long, especially when stored at a high temperature, there is a possibility of slow yellowing. Therefore, it is preferably one week or longer and two years or less. Within 1.5 months or more, it is more than 3 months and less than 1 year. The use of the PVA-based polymer film of the present invention is not particularly suitable, and can be used, for example, as a packaging material; a polarizing film, a raw material for an optical film having a small retardation; a water-soluble film such as a laundry bag; and a release film for producing marble. However, the PVA-based polyfilm of the present invention is not easily yellowish in color even when stored in the warehouse for the same length of time, and it is difficult to cause a bad impression to consumers or users, so it is used as a packaging material and a polarizing film. Or a phase difference film material. Further, it is preferable to contain the surfactant (B) in the above ratio and to use a 7-pass film P VA film to keep the yellow storage surface, which is often the same as that of the film. The original t% of -20-201141882 concentration of the PVA-based polymer film of the present invention at a pH of 20 ° C at a concentration of 20 ° C in the above range, even for a long time (preferably 72 hours or more, more preferably More than 1 to 20 hours, especially preferably 丨8 〇 or more) When continuously manufactured, the disadvantage of speckle caused by the surfactant (B) is also highly suppressed (in the direction of flow of the film) The occurrence of the defects of the fine concavities and convexities of the film which occur continuously or intermittently in parallel occurs. Therefore, in the case where the final product such as the polarizing film or the retardation film requires high quality, the raw material for the production thereof can be particularly preferably used. [Examples] Hereinafter, the present invention will be specifically described by examples and the like, but the present invention is not limited by the examples. Further, the following methods for measuring the pH of the PVA film dissolved in water and the yellowness (YI値) of the PVA film used in the following examples and comparative examples are shown. [Measurement of pH when PVA film was dissolved in water] 7 g of the PVA film was placed in 93 g of deionized water at room temperature, and heated to about 90 ° C under stirring to completely dissolve the film, and then the obtained aqueous solution was cooled to The pH of the aqueous solution was measured using a pH meter ("MP230" manufactured by METTLER TOLEDO Co., Ltd.) at 20 °C. [Measurement of yellowness (ΥΙ値) of PVA film] Films of 8 samples were superposed, using a color difference meter (Japan Electric Color) Model "NF-902" manufactured by Industrial Co., Ltd.) measures the YI of the film and treats it as a total of 8 pieces. -21 - 201141882 [Example 1] 10 parts by mass of PVA (sodium succinate saponified product) having a degree of saponification of 99.9 mol%, a degree of polymerization of 2400, and a sodium acetate content of 2.4% by mass, immersed in 35 ° C After 2 hours in 2500 parts by mass of distilled water, 'centrifugal dehydration was performed to obtain PVA aqueous chips. The content of sodium acetate in the obtained PVA aqueous chips is 〇1% by mass relative to PVA, and the volatile concentration in the PVA aqueous chips is 70% by mass to 333 parts by mass (100 parts by mass in dry PVA) The PVA aqueous granules were added with 12 parts by mass of glycerin, 〇·3 parts by mass of a surfactant-containing mixture (containing octaethanol laurate in a ratio of 95% by mass, and containing diethanolamine as a mixture of impurities. When the mixture was dissolved in water at a concentration of 0.1% by mass, the pH at 20 ° C (measured by the same method as described above for the PVA film) was 9.64), 0.003 parts by mass of 4,4'-butylene. Bis(·6-t-butyl-3-methylphenol) (phenolic antioxidant), after adding 1 m ο 1 /1 of potassium dihydrogen phosphate solution in a ratio of i〇mi to 100 g of PVA The mixture was thoroughly mixed to form a mixture, which was melted by a two-axis extruder at a maximum temperature of 1 30 °C. After cooling to 1 °C with a heat exchanger, the film was melted and extruded on a metal cylinder of 95 ° C, and dried to obtain a PVA film having a film width of 1.2 m and an average thickness of 60 pm. No defects such as streaks were observed on the obtained PVA film, and the appearance was good. Using the obtained PVA film, ρ 溶解 dissolved in water was measured by the above method, and it was 6.0. -22- 201141882 Further, the obtained PVA film was cut into an A4 size, and the yellowness (γ I 初期) of the initial state was measured by the above method, and it was 4.6. The film was hung in a hot air dryer adjusted to 801. On the other hand, the yellowness (YI値) after 3 days, 5 days, and 10 days from the standstill was measured, and each was 7.6, 9_〇, and 10.1. Therefore, the increase in the initial enthalpy of yellow (YI値), that is, the yellowing degree (ΔYI), is 3.0, 4.4, and 5.5, respectively. The results of the above various evaluations are shown in Table 1. Further, 240 was continuously subjected to the above-described film formation, and no occurrence of streaky defects was observed. [Example 2] In addition to Example 1, instead of adding 1 mol of 1/ml of phosphoric acid to 100 g of PVA, A PVA film was obtained in the same manner as in Example 1 except that an aqueous solution of potassium dihydrogenate was added in an amount of 5 m 1 for PVA to be dissolved in 1 m ο 1 /1 of lactic acid. No defects such as streaks were observed on the obtained film, and the appearance was good. The obtained PVA film was used for measurement in the same manner as in Example 1. The results are shown in Table 1. [Example 3] Except that in Example 1, instead of adding 1 mol of a potassium dihydrogen phosphate aqueous solution in a ratio of 10 ml to 10 g of PVA, 1 mol was added in a ratio of 10 μm to PVA. A PVA film was obtained in the same manner as in Example 1 except that the acetic acid was dissolved in water of /1. No defects such as streaks were observed on the obtained film, and the appearance was good.
述方 P VA 且以 薄膜 色度 算爲 小時 〇 成爲 l〇〇g 液以 P V A 各種 成爲 l〇〇g 液以 P VA -23- 201141882 使用所得之PVA薄膜，與實施例1同樣地進行各種 測定。表1中顯示結果。 [實施例4] 除了於實施例2中，將乳酸水溶液的添加量由以對 lOOgPVA而言成爲5ml的比例變更爲以對l〇〇gPVA而言 成爲2ml的比例以外，與實施例2同樣地，得到PVA薄 膜。在所得的PVA薄膜上沒有看到條紋等的缺陷而外觀 良好。 使用所得之PVA薄膜，與實施例1同樣地進行各種 測定。表1中顯示結果。 [實施例5 ] 作爲PVA的碎片，使用皂化度88.0莫耳％、聚合度 2400、醋酸鈉含量2.0質量％的PVA(聚醋酸乙烯酯的皂化 物）之碎片’與實施例1同樣地得到P V A含水碎片。所得 之PVA含水碎片中的醋酸鈉含量係相對於PVA的〇.〇8質 量％ ’而且PV A含水碎片中的揮發份濃度爲8 6質量％。 將此PVA含水碎片在201減壓乾燥，以將揮發份濃度調 整至7 0質量％。 除了使用所得之P V A含水碎片代替實施例1中所使 用的揮發份濃度爲70質量％的PVA含水碎片以外，與實 施例1同樣地得到P V A薄膜。在所得的p V A薄膜上沒有 看到條紋等的缺陷而外觀良好。 使用所得之PVA薄膜，與實施例1同樣地進行各種 測定。表1中顯示結果。 -24- 201141882 [實施例6] 除了於實施例1中，不添加4,4’-亞丁基雙（6-第 基-3 -甲基苯酚）以外，與實施例1同樣地得到P V A薄 在所得的P V A薄膜上沒有看到條紋等的缺陷而外 好》 使用所得之PVA薄膜，與實施例1同樣地進行 測定。表1中顯示結果。 [實施例7] 除了於實施例1中，對3 3 3質量份（以乾燥狀態 換算爲100質量份）的該PVA含水碎片，將4,4’-亞丁 (6-第三丁基-3-甲基苯酚）的添加量由0.003質量份變 0.018質量份以外，與實施例1同樣地，得到PVA薄 所得之PVA薄膜雖然並無成爲實用上的妨礙，但若 光等的強光下觀察，則可略爲看到推測因4，4 ’ -亞丁 (6-第三丁基-3-甲基苯酚）所發生的凝聚物狀之缺點。 使用所得之P V A薄膜，與實施例1同樣地進行 測定。表1中顯示結果。 [實施例8] 除了於實施例1中，將磷酸二氫鉀水溶液的添加 以對l〇〇g PVA而言成爲10ml的比例變更爲以對 PVA而言成爲5ml的比例以外，與實施例1同樣地， P V A薄膜。在所得的P V A薄膜上沒有看到條紋等的 而外觀良好。 三丁 觀良 各種 P V A 基雙 更爲 膜。 在曰 基雙 各種 量由 l〇〇g 得到 缺陷 -25- 201141882 使用所得之PVA薄膜，與實施例1同樣地進行各種 測定。表1中顯示結果。再者，24〇小時連續進行上述的 製膜，結果稍微看到條紋狀的缺點之發生。 [實施例9 ] 除了於實施例8中，不添加4,4’-亞丁基雙（6-第三丁 基-3-甲基苯酚）以外，與實施例8同樣地，得到PVA薄 膜。在所得的PVA薄膜上沒有看到條紋等的缺陷而外觀 良好。 使用所得之PVA薄膜，與實施例1同樣地進行各種 測定。表1中顯示結果。 [比較例1 ] 除了於實施例1中，不添加甘油、含界面活性劑的混 合物、4,4’-亞丁基雙（6-第三丁基-3-甲基苯酚）、磷酸二氫 鉀水溶液的任一者以外，與實施例1同樣地，得到PVA 薄膜。在所得的 PVA薄膜上，條紋等的缺陷多而外觀 差。 使用所得之P V A薄膜，與實施例1同樣地進行各種 測定。表1中顯示結果。 [比較例2] 除了於實施例1中，不添加4,4，-亞丁基雙（6-第三丁 基-3 -甲基苯酚）及磷酸二氫鉀水溶液的任一者以外’與實 施例1同樣地，得到P V A薄膜。在所得的P V A薄膜上沒 有看到條紋等的缺陷而外觀良好。 -26- 201141882 使用所得之P V A薄膜，與實施例1同樣地進行各種 測定。表1中顯示結果。 [比較例3 ] 除了於實施例1中，不添加磷酸二氫鉀水溶液以外， 與實施例1同樣地，得到PVA薄膜。在所得的PVA薄膜 上沒有看到條紋等的缺陷而外觀良好。 使用所得之PVA薄膜，與實施例1同樣地進行各種 測定。表1中顯示結果。再者，2 4 0小時連續進行上述的 製膜，結果看到條紋狀的缺點之發生 [比較例4 ] 除了於實施例2中，代替以對l〇〇g PVA而言成爲 5 m.l的比例添加1 mo 1 /1的乳酸水溶液，不將乳酸稀釋在水 中而直接使用，以對100g PVA而言成爲〇.lm〇l的比例添 加以外，與實施例1同樣地，得到P V A含水碎片與各種 添加物的混合物。藉由將水加到此混合物中以製作固體成 分濃度7質量％的水溶液。藉由與PVA薄膜之情況的上述 同樣方法，判斷所得之水溶液的pH，結果爲1 .7。使用擠 壓機將此混合物熔融製膜時，由於施予熔融樹膜路徑的鍍 敷係有腐蝕的可能性，而放棄製膜。 [比較例5 ] 除了於實施例1中，將含界面活性劑的混合物之添加 量，由以對3 3 3質量份（以乾燥狀態PVA換算爲100質量 份）的PVA而言之0.3質量份變更爲3質量份以外，與實 -27- 201141882 施例1同樣地’得到PVA薄膜。所得的PVA薄膜 紋等的缺陷多而外觀差。 使用所得之P V A薄膜，與實施例！同樣地進 測定。表1中顯示結果。 [實施例10] 將實施例1所得之PVA薄膜以50m捲繞在直 的紙管上而成爲捲筒狀，在經調整至溫度30°C 5 0 % RH的恆溫恆濕機內保管。6個月後取出，以上 測定PVA薄膜的黃色度（YI値），結果相對於保管 的4.6而言爲5.4，黃變度（ΛΥΙ)爲小到〇.8，又， 與保管前沒有特別的改變而良好。表2中顯示評價 [比較例6 ] 除了於實施例1 0中，不使用實施例1所得的 膜，而使用比較例3所得的PVA薄膜以外，與實 同樣地保管PVA薄膜。表2中顯示6個月後取出 薄膜之評價結果。In the same manner as in Example 1, the measurement was carried out in the same manner as in Example 1 except that the PVA film obtained by using PVA was used as the PVA film of PVA VA-201141882. . The results are shown in Table 1. [Example 4] In the same manner as in Example 2 except that the amount of the lactic acid aqueous solution was changed to a ratio of 5 ml to 100 g of PVA to 2 ml of l〇〇gPVA. , a PVA film was obtained. No defects such as streaks were observed on the obtained PVA film, and the appearance was good. Various measurements were carried out in the same manner as in Example 1 using the obtained PVA film. The results are shown in Table 1. [Example 5] As a fragment of PVA, a PVA having a degree of saponification of 88.0 mol%, a degree of polymerization of 2400, and a sodium acetate content of 2.0% by mass of PVA (saponified polyvinyl acetate) was obtained in the same manner as in Example 1. Aqueous debris. The sodium acetate content in the obtained PVA aqueous chips was 〇.〇8 mass%' relative to PVA and the volatile concentration in the PV A aqueous chips was 86% by mass. This PVA aqueous cake was dried under reduced pressure at 201 to adjust the volatile concentration to 70% by mass. A P V A film was obtained in the same manner as in Example 1 except that the obtained P V A aqueous chips were used instead of the PVA aqueous chips having a volatile concentration of 70% by mass used in Example 1. No defects such as streaks were observed on the obtained p V A film, and the appearance was good. Various measurements were carried out in the same manner as in Example 1 using the obtained PVA film. The results are shown in Table 1. -24-201141882 [Example 6] In the same manner as in Example 1, except that 4,4'-butylene bis(6-diyl-3-methylphenol) was not added, PVA was obtained in the same manner as in Example 1. No defects such as streaks were observed on the obtained PVA film, and the measurement was carried out in the same manner as in Example 1 using the obtained PVA film. The results are shown in Table 1. [Example 7] Except that in Example 1, 3,3 parts by mass (100 parts by mass in dry state) of the PVA aqueous fragment, 4,4'-butylene (6-tert-butyl-3) In the same manner as in the first embodiment, the PVA film obtained by thinning the PVA was not practically hindered, but was observed under strong light such as light, except that the amount of the methylphenol was changed from 0.003 parts by mass to 0.018 parts by mass. However, the shortcomings of the agglomerate shape which is presumed to be caused by 4,4 '-butylene (6-tert-butyl-3-methylphenol) can be slightly observed. The obtained P V A film was measured in the same manner as in Example 1. The results are shown in Table 1. [Example 8] Except that in Example 1, the addition of the aqueous potassium dihydrogen phosphate solution was changed to a ratio of 10 ml to 10 g of PVA to a ratio of 5 ml to PVA, and Example 1 Similarly, a PVA film. No streaks or the like were observed on the obtained P V A film, and the appearance was good. Sanding Guanliang Various P V A base pairs are more membranes. Defects were obtained from 〇〇 双 各种 各种 - - - 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 The results are shown in Table 1. Further, the film formation described above was continuously carried out for 24 hours, and as a result, the occurrence of the streaky defect was slightly observed. [Example 9] A PVA film was obtained in the same manner as in Example 8 except that in Example 8, except that 4,4'-butylenebis(6-tributyl-3-methylphenol) was not added. No defects such as streaks were observed on the obtained PVA film, and the appearance was good. Various measurements were carried out in the same manner as in Example 1 using the obtained PVA film. The results are shown in Table 1. [Comparative Example 1] Except that in Example 1, no glycerin, a surfactant-containing mixture, 4,4'-butylene bis(6-tert-butyl-3-methylphenol) or potassium dihydrogen phosphate was added. A PVA film was obtained in the same manner as in Example 1 except for any of the aqueous solutions. On the obtained PVA film, streaks and the like have many defects and are inferior in appearance. Various measurements were carried out in the same manner as in Example 1 using the obtained P V A film. The results are shown in Table 1. [Comparative Example 2] Except that in Example 1, no addition of 4,4,-butylene bis(6-tert-butyl-3-methylphenol) or potassium dihydrogen phosphate aqueous solution was carried out. In the same manner as in Example 1, a PVA film was obtained. No defects such as streaks were observed on the obtained P V A film, and the appearance was good. -26-201141882 Various measurements were carried out in the same manner as in Example 1 using the obtained P V A film. The results are shown in Table 1. [Comparative Example 3] A PVA film was obtained in the same manner as in Example 1 except that in Example 1, the potassium dihydrogen phosphate aqueous solution was not added. No defects such as streaks were observed on the obtained PVA film, and the appearance was good. Various measurements were carried out in the same manner as in Example 1 using the obtained PVA film. The results are shown in Table 1. Further, the film formation described above was continuously carried out for 240 hours, and as a result, the occurrence of the streaky defect was observed [Comparative Example 4] In addition to the case of Example 2, instead of 5 ml for l〇〇g PVA An aqueous solution of lactic acid of 1 mol / 1 was added, and the lactic acid was diluted and used in water, and the PVA water-containing chips and various kinds were obtained in the same manner as in Example 1 except that 100 g of PVA was added in a ratio of 〇.lm〇l. A mixture of additives. An aqueous solution having a solid component concentration of 7 mass% was prepared by adding water to the mixture. The pH of the obtained aqueous solution was judged by the same method as above in the case of the PVA film, and it was 1.7. When the mixture was melt-formed by using an extruder, the plating applied to the path of the molten tree film was corroded, and the film formation was abandoned. [Comparative Example 5] In addition to the amount of the surfactant-containing mixture added in Example 1, 0.3 parts by mass of PVA for 33 parts by mass (100 parts by mass in dry state PVA) The PVA film was obtained in the same manner as in Example 1 of the actual -27-201141882, except that the amount was changed to 3 parts by mass. The obtained PVA film has many defects and poor appearance. Use the resulting P V A film, and the examples! The same is measured. The results are shown in Table 1. [Example 10] The PVA film obtained in Example 1 was wound up on a straight paper tube at 50 m to form a roll, and stored in a constant temperature and humidity machine adjusted to a temperature of 30 ° C and 50% RH. After 6 months, the yellowness (YI値) of the PVA film was measured, and the result was 5.4 with respect to 4.6, and the yellowing degree (ΛΥΙ) was as small as 〇.8, and there was no special before storage. Change is good. Evaluation is shown in Table 2 [Comparative Example 6] A PVA film was stored in the same manner as in the case of Example 10 except that the film obtained in Example 1 was not used, and the PVA film obtained in Comparative Example 3 was used. Table 2 shows the evaluation results of the film taken out after 6 months.
上’條 行各種 徑3时 及濕度 .述方法 開始前 膜面係 結果。 PVA薄 施例10 的Ρ V A -28- 201141882 【I撇】 比較例 in 〇\ α\ 〇\ ΓΟ < 〇 〇 Ο 〇〇 〇〇 o 10.5 19.2 寸 Ον 〇\ 〇\ cn d PQ ο 1 卜 S—✓ 1 1 1 m Os crs α\ m d 1 1 CN 〇〇 σ\ 卜 as 1-H (N 〇\ 〇\ 〇\ d 1 I 1 m oo in o oo (N Os 〇\ 〇\ 1 1 I 1 寸 vd 寸 卜 t—H CN 實施例 ON OS 〇\ 〇\ ro 〇 < 0.005 1 π^ ο Ι> o V〇 m vd (N 00 〇\ α\ Ον m d < 0.005 00 CN vd On Os 卜 〇\ 〇\ Os d < ο ο 薄的 缺點 Os (N σ\ m 卜 ^t* Ό σ\ Ον Ον m 〇 < Ο ο 1 σ\ »n m CS in ο 00 00 d ο ο τ-Η 賦 CN v〇 as CN 〇 oo r-H m 寸 σ\ 〇\ 〇\ m o PQ 0.002 ” H 〇 v〇 oo 〇 r—^ ΡΊ σ\ 〇\ ον m d U ι—Η Ο ο 1—^ v〇 ro 寸 卜 寸 (Ν Os α\ Os CO d CQ 0.005 •π^ v〇 m m 寸 — o T—H 〇\ 〇\ σ\ ΓΟ d < τ-^ Ο -0¾ 〇 vd 〇 cn 寸 in PVA 皂化度 莫耳％ 界面活性劑 添加量~ 質量份 酸性物質 種類t2 添加量Μ 莫耳 抗氧化劑 添加量~ 質量％ m 嫩鼸 > Pm w-> « ffi a f m <1 ^ w 1 U 〇 M °g m »n 1 P o oo 80°C_ 10 日後 。鐮 WMSllllnE<>」&0001炱諒要 ε * 氍魎：υ< 氍忒：a -siliu 氍湛：ν(N* -ca -61- 。Hd spofN坩驼毖键鹋 Z- K1S酿 v>d 赵 s* ^qq-hJ_m_MSgiH、姐陌虼迄萷要 寸 * 201141882 [表2 ] 實施例10 比較例6 所使用的PVA薄膜 實施例1 比較例3 保管條件~~ " 溫度 °c 30 30 福度 °/〇RH 50 50 6個月保管而取出後 黃變度(ΔΥΙ) 0.8 7.2 1面肤態 良好 5薛 [產業上的可利用性] 若依照本發明，由於即使在倉庫內等長期間保管，也 可得到薄膜的顏色不易帶黃色調的PVA系聚合物薄膜， 該PVA系聚合物例如可較佳地使用作爲包裝材料^ 偏光薄膜、相位差薄膜等的光學薄膜用之原料：洗衣袋胃 的水溶性薄膜；製造人造大理石時的脫模薄膜等。 【圖式簡單說明】 那。 【主要元件符號說明】 ίΕ 。The top of the line is 3 hours and the humidity. The method before the start of the film surface results. PVA thin example 10 Ρ VA -28- 201141882 [I撇] Comparative example in 〇\α\ 〇\ ΓΟ < 〇〇Ο 〇〇〇〇o 10.5 19.2 inch Ον 〇\ 〇\ cn d PQ ο 1 S—✓ 1 1 1 m Os crs α\ md 1 1 CN 〇〇σ\ 卜 as 1-H (N 〇\ 〇\ 〇\ d 1 I 1 m oo in o oo (N Os 〇\ 〇\ 1 1 I 1 inch vd inch t t-H CN Example ON OS 〇\ 〇\ ro 〇< 0.005 1 π^ ο Ι> o V〇m vd (N 00 〇\ α\ Ον md < 0.005 00 CN vd On Os 〇 〇 \ 〇 \ Os d < ο ο thin shortcomings Os (N σ \ m 卜 ^t* Ό σ \ Ον Ον m 〇 < Ο ο 1 σ\ » nm CS in ο 00 00 d ο ο τ -Η CN CN v〇as CN 〇oo rH m inch σ\ 〇\ 〇\ mo PQ 0.002 ” H 〇v〇oo 〇r—^ ΡΊ σ\ 〇\ ον md U ι—Η Ο ο 1—^ v〇 Ro 寸 inch inch (Ν Os α\ Os CO d CQ 0.005 •π^ v〇mm inch - o T-H 〇\ 〇\ σ\ ΓΟ d < τ-^ Ο -03⁄4 〇vd 〇cn inch in PVA saponification Molex% % of surfactant added ~ Part by mass of acidic substance t2 Addition amount 莫 Moore antioxidant Quantity ~ mass % m tenderness > Pm w-> « ffi afm <1 ^ w 1 U 〇M °gm »n 1 P o oo 80°C_ 10 days later.镰WMSllllnE<>&0001炱Forgiveness ε * 氍魉: υ < 氍忒: a -siliu 氍湛: ν (N* -ca -61-. Hd spofN坩 camel key 鹋Z- K1S brewing v>d Zhao s* ^qq-hJ_m_MSgiH, Sister 虼 虼 萷 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 Yellowness (ΔΥΙ) after storage and removal of 0.8 7.2 1 good skin condition 5 industrial [Availability] According to the present invention, the color of the film can be obtained even if it is stored for a long period of time in the warehouse. A PVA-based polymer film which is less likely to have a yellow hue. For the PVA-based polymer, for example, a raw material for an optical film such as a polarizing film or a retardation film can be preferably used: a water-soluble film of a laundry bag stomach; Release film for marble, etc. [Simple diagram of the diagram] That. [Main component symbol description] ίΕ.
/VW -30-/VW -30-