201206959 六、發明說明： 【發明所屬之技術領域】 醇系 聚乙賴膜製=: 【先前技術】 劑而容液轉於水等之溶 金屬加熱軋議if i(eas+tmg法)而製膜，並使用 素==來：膜展⑼ 前述中，伴隨液晶電視等之書而面要之^^可4生的機器。 需要較習知產品絲雜更佳的偏度化、减細化，而 染料=膜藉=;原=稀等之二色性 即，為了提升絲_需雜高= 料故為了_目容性，亦 者，::該===聚乙烯醇系樹脂而得到偏光膜 0.0W莫耳％選^方=1規If ndl〇咖卿)為55%以上，由含有 基之令之1 ‘上氧伸院基、以及釀胺 偏光膜之原料用聚乙_ 勿所構成的 之均勻性十分重要。，、、〒為句質’4寸別是面内的阻滯值 作為該對策’例如，有人提出：膜寬係為2m以上，離寬度方 201206959 向lcm之兩點間的阻滯值之罢矣5nm以下，n私& 兩關的阻滯值之差為50nm以下的聚乙稀醇向=之 ΐί^ϋίΐ3Γ以上’膜面内之㈣值為3丄以下茶3 見度方向之膜面内的阻滞值之偏差為15ηιη以 取 且臈 (例如，參照專利文獻3。）。 勺水乙烯醇糸膜 專利文獻1 專利文獻2 專利文獻3 [¥知技術文獻] 曰本特開平8-201626號公報 曰本特開2002-28939號公報 曰本特開2007-137042號公報 【發明内容】 [發明所欲解決的問題] 膜稀醇系 進應面高精細化，應更 越來找專4獻的需求 =成孕二供 [=:手:所構成的偏光膜、以及偏光板。 詳。之柄a月之要曰係關於—種聚乙稀醇系膜，係為由含 201206959 酵糸樹脂(A)之膜形成材料製膜而成的聚乙_系膜，且 痄〇^=3〇(：的水5分鐘，令其膨潤時之寬度(TD)方向的臉們 =姻_夠方向的膨潤度(XMD)之比(xtd/xmd)為10= 7 本發明除了該聚⑽醇系膜之製造方法，更提供由今臂 乙烯醇糸膜所構成的偏光膜、右 、由。亥t 構成的偏光板 在偏恤之至少一面設置保護膜而 卜f知於製造聚乙稀縣膜之際，係將聚乙稀醇系樹脂 延成形製膜，並使用複數的熱軋報進行乾燥、執處理。 方向形成某種程度的張力，城時係產 = ^(TD)方向之收縮。得到的聚乙稀醇系膜，令其於水中膨 ’广、寬度(TD)方向之賴度變大，且結果為：其寬度方 二。广偏細之際，寬度方向的膨潤度大時，膜未均勻地膨 Ϊ ΐΐί染色不均或延伸不均。因此，本發明中，如前述，為 申不均之產生，係著眼於聚乙烯醇系膜之膨 潤仃為，而達成較習知膜更小之預定的膨潤度比。 [發明之效果] 本發明之聚乙烯醇祕，延伸性佳，且為具有可得到染色不 光膜之效果者。而且’該聚乙烯醇系膜，作為用於偏 i = i液晶電視等之液晶顯示設備等之偏光膜的原料膜 执供夕丄〈一波·^板或1/4波長板的原料膜片、用於液晶顯示 叹備之相位差胺的原料膜片非常有用。 【實施方式】 以下詳細地說明本發明。 聚乙鱗系膜’係為由含有聚乙騎系樹脂⑷之膜 =成材料製膜而成的聚乙烯耗膜，郫膜浸潰於莉的水5分 鐘，令其膨潤時之寬度⑽方向的膨潤度(Xtd)與機械()方向的 201206959 膨潤度(Xmd)之比(以下有簡稱4「膨潤度比」的情況。）/ ) 在此之機械(MD)方向及寬度(TD)方向的膨潤度传指浸潰於 3〇°C的水5分鐘時之寬度(TD)方向的伸長率及機械方向的伸 長率，且如下述而測定。 詳I之，將膜切割成l〇cmxl0cm的正方形，俾使其與麵(Μ〇) 方向、寬度(TD)方向平行，並放置於平坦的玻璃板上，以游標卡 =別測量MD方向及寬TD方向之尺寸。接著，在調整為航 的離子交換水槽浸潰5分鐘後，取出膜，並立即放置於平坦的玻 璃板上，以游標卡尺分別測量MD方向及寬TD方向之尺機 及ίί㈣方向的制度、及面積膨财，係使用該201206959 VI. Description of the invention: [Technical field of invention] Alcohol-based polyacetal film system: [Prior Art] The liquid is transferred to a molten metal such as water to heat the iron and steel if i (eas + tmg method) Film formation, and using the product == to: Film Exhibition (9) In the above, a machine that is compatible with a book such as a liquid crystal television. It is necessary to have better skewness and thinning than the conventional product, and the dye = film l =; the original = dilute dichroism, that is, for the lifting wire _ need high height = material, so for the purpose , also,:: === polyvinyl alcohol-based resin to obtain a polarizing film 0.0W mol%% ^1 = If ndl〇咖卿) is more than 55%, from the base of the order of 1 ' The uniformity of the composition of the oxygen-extension base and the raw material of the amine-based polarizing film is very important. , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,矣5nm or less, n private & The difference between the retardation values of the two levels is 50nm or less. The distance to the 聚 ϋ ϋ ΐ ΐ ΐ Γ Γ ' ' ' ' 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 四 四 四 四 四 四The deviation of the internal retardation value is 15 ηηη to take 臈 (for example, refer to Patent Document 3). Scoop water vinyl alcohol ruthenium film patent document 1 patent document 2 patent document 3 [ 知 技术 8 8 8 8 8 8 8 8 8 8 2002 2002 2002 2002 2002 2002 2002 2002 2002 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 Contents] [Problems to be Solved by the Invention] The thin film of the film should be highly refined, and the demand for the special 4 should be more and more = the second pregnancy [=: hand: the polarizing film and the polarizer . detailed. The stalk of the month is a polyethylene-based film made of a film-forming material containing 201206959 leaven resin (A), and 痄〇^=3 〇 (: water for 5 minutes, the width of the width (TD) direction of the swelling = the ratio of the degree of swelling (XMD) of the sufficient direction (xtd / xmd) is 10 = 7 in addition to the poly (10) alcohol The method for producing a film is to provide a polarizing film composed of a ruthenium film of the present arm, and a right polarizer. The polarizing plate composed of a hait is provided with a protective film on at least one side of the slanting shirt, and is known to be manufactured in Polyethylene County. At the time of film formation, a polyethylene glycol-based resin is formed into a film, and dried and processed using a plurality of hot-rolled sheets. The direction forms a certain degree of tension, and the city time yields a shrinkage in the direction of ^(TD). The obtained polyethylene glycol film has a large degree of swelling in the water and a width in the width (TD) direction, and as a result, the width is two. When the width is small, the swelling degree in the width direction is large. When the film is not uniformly swelled, the dyeing is uneven or unevenly spread. Therefore, in the present invention, as described above, the occurrence of unevenness is focused on polyethylene. The swelling of the mesial film is a predetermined degree of swelling ratio which is smaller than that of the conventional film. [Effect of the Invention] The polyvinyl alcohol of the present invention is excellent in extensibility and has an effect of obtaining a dyed film. And the "polyvinyl alcohol-based film" is used as a raw material film for a polarizing film such as a liquid crystal display device such as a liquid crystal display device such as a liquid crystal display device, and the raw material film of a wave plate or a quarter wave plate. A raw material film for a phase difference amine for liquid crystal display sighing is very useful. [Embodiment] The present invention will be described in detail below. The polystyrene film is a film containing a polyethylene resin (4). The polyethylene film used for the film formation, the ratio of the swelling degree (Xtd) in the width (10) direction and the 201206959 swelling degree (Xmd) in the machine direction is immersed in the water for 5 minutes. (The following is abbreviated to the case of 4 "swelling ratio".) / ) The degree of swelling in the machine (MD) direction and width (TD) direction refers to the width of the water impregnated at 3 ° C for 5 minutes ( The elongation in the TD direction and the elongation in the machine direction were measured as follows. In detail, the film is cut into a square of l〇cmxl0cm, which is parallel to the direction of the surface (Μ〇) and the width (TD), and placed on a flat glass plate to measure the MD direction and The size of the wide TD direction. Then, after being immersed in the ion exchange tank adjusted for 5 minutes, the film was taken out and immediately placed on a flat glass plate to measure the MD direction and the width TD direction of the ruler and the ίί (4) direction system and area by the vernier caliper. Inflating money, using this
、里、 猎由下式而知之。再者，該操作係於23°C、50%RH 的環境下實施。 機械(MD)方向的膨潤度(ΧΜα)(^ =(浸潰後之MD方向的尺寸/浸潰前之_ 寸)xl〇〇 川八 寬度(TD)方向的膨潤度(Χτ〇)(%) K浸潰後之TD方向的尺寸/浸潰前之TD 面積膨潤度⑺⑽ 方向的膨潤度/勘)X(TD方向的膨潤度力⑻)χΐ〇〇 9 ^ 1.000^1.020 , ίίί 3 UGr.G1i最理想之樣態為讀〜㈣5。該數值未 產^^色二延性會@差’而超過該範圍時’作為偏光膜時會 理相之機械_方向之膨潤度(Χ·)(%)的範圍，較 為11()〜13()% ’特別理想之樣態為U2〜i2s%，最理相 差該範圍過小時，在製作偏光臈時有延伸性i 匕大訏，在作為偏光膜時有偏光性能變差的傾向。 理相膜之寬度㈣方向之_度(xTD)W)的範圍，較 〜樣恶為11G〜13G% ’特別理想之樣態為112〜128%，最理想 201206959 # 114〜126°/°。該範圍過小時，在萝作偏# Γ"蛀女 差，1，而過大時，在作為偏光膜染色生變 較理想之樣態為里^^時之面積膨潤度(γ) 如f ’有偏光·降低的傾向。 脂(a)—M材’係使用含有聚乙稀醇系樹 即’使用«合、樹脂，亦 合的成分之共聚ί物Ι=ϊ=ί耳％以下)的錯酸乙烯醋共聚 、正以=碳 醇鍵、ϊ聚亦可使用在側鏈具有 1，2 —乙二 烯醇‘ ^雜的聚乙 化的方法她酸乙烯醋與甘S5;;= ;;ί=ί ： r丰谢=為99.5莫耳％以上。當平触化度過小時，將〒乙餘 私系純作輕細的纽t，#無法獲得充分的絲 201206959 向。 明的皂化度，係藉由以殘留醋酸乙_旨之水解所 而的驗:粍里（alkali consumption)分析而得之。 水溶卢該聚脂(A)之黏度’作為在机的4重量％ 2“^ P =為〇〇mPa · S較為理想，而更理想之樣態為 20〜400mpa · s ’更加理想之樣態為4〇〜4〇〇mPa · s。 ，液=過i時，有偏光膜製成時之延伸性不夠的 呀，有膜之平面平滑性或透明性降低的傾向。 中，黏 製造 性劑(C)等之公知的摻合劑而製造。j U⑻或界面活 可塑劑(B)，一般而言’係為在製造偏 二 :!·生者乙例7舉出:甘油、二甘油、三甘油等==延 転二一乙一醇、三乙二醇、四乙二醇、聚乙二 ' 。一一 丙二醇等之烷基二醇類或是聚烷基二醇類、三羥 單獨或是組合兩種以上· 油⑼以-與三4 量比)=20/80〜80力〇，而併用甘油甘油/士二甘油(重 甘油Si呈甲基丙炫(重量比)==2L8一〇%==，常為 最理想之樣態為7〜25重量<八^別理想之樣態為3〜30重量份， 成偏光断有延雜§可賴⑻的含量過少時，在製 或捲取為卷狀 餘面之平滑性、 離子系界面活性劑或非離子^面卜 201206959 =子尤以併用陰離子系界面活性劑與 烧’ f如可舉出：脂肪族絲續酸鹽、 絲石瓜酉夂酉曰鹽t乳乙細細硫酸鹽、聚氧 、 高級脂肪酸烷醇醯胺硫酸鹽等，再者，除了 ;工 性劑以外，亦可舉出：炉妒仆、、4 .古'二〜寻陰離子系界面活 硫酸鹽等之硫酸酯鹽、脂y酸4、NH^氧基硫_、單甘油 烯炫基酸鹽、ϋ紐肽等之賴^胺^^及其鹽、聚氧乙 萘磺酸鹽、萘續酸之_ f烷基本％酸鹽、烷基 合物、二院基石黃基琥；if石^：==續酸之鹽甲藤縮 烧基石黃基㈣酸二鹽、絲石黃基乙酉聚氧乙稀 基甲基牛磺酸鹽、二甲基一5—硭^ α —烯烴磺酸鹽、N—醯 聚氧乙烯絲_酸鹽、聚氧乙料之雜鹽型、 等之顧酉旨鹽型等之陰離子系界面活酸鹽、烧基填酸鹽 基_、聚氧乙婦t劑’例如可舉出：聚氧乙烯燒 肪酸酸胺、聚氧乙^基胺或二燒軸安、高級脂 苯基甲駿縮合活性”？以外，亦可舉出：烧基 物、聚氧乙烯甘油脂肪酸§Γ、Τ聚氧乙聚氧丙烯嵌段聚合 氧乙稀.山梨醇軒脂肪酸g|.、.聚氧，=油及硬化藥麻油、聚 非離子系界面活性劑聚乙 ^^=肪酸S旨等之侧旨型 肪酸單甘油酉旨、丙二醇月旨肪:肪t，梨醇酐脂肪酸醋、脂 性劑等。 ·1庶糖知肪醆酯等之酯型界面活 s幻丨面’舌性劑(C)的含量，相斜於取7 1 份，較理想之樣態為〇.〇〗〜〗重=乙烯醇系樹脂(A)l〇〇重量 f份，更加理想之樣態為_〜^重樣態為_〜〇.5重 罝過少時，有難於得到抗 .„刀。每界面活性劑(Q的含 時，有膜之透明性降低的傾向土 111 〇C mg)效果的傾向，而過多 再者，併用陰離子系界面活性劑與非離子系界面活性劑的情 201206959 況中，相對於聚乙烯醇系樹脂( 劑較理想之樣態為0.01〜1重量份，更里知，陰離子系界面活性 份，更加理想之樣態為003〜0 心之樣態為0.02〜0 ^ if2，態為G.GW重量份，更子系界面活性^ 更加理想之樣態為⑽3〜αι 為_〜〇,2重量^ 時，J偏光膜製成時之染料的分“;：離界面活性劑過少 乳泡’無法作為光學用膜而使用二向fjf' ’於膜中易現入 =時，難於得到抗阻塞效果，而過⑧=子系界面活性劑 平/月性降低的傾向。 .有膜之透明性或平面 且本發明中，為了防止膜之普變 而以下示列較理想之齡系抗氧化齊^ 劑亦為有用， 三級丁基2,2,—亞甲基統劑，2,6—二 —亞丁基雙(3—甲基—6— 土 一級丁酚）、4,4, 系左右之對於聚_ 膜形成材=製卿成频。魄，將該 <聚乙烯醇系膜之製造方法> 也說明本雜聚乙烯醇系膜之製造方法。 使用可塑劑 水溶液於滾筒型軋料 3熱她，並予以製膜、 酸鈉本二中：Ί為了去除包含於通常樹脂的錯 法較為ϋ 法需要回收溶劑等，故以水清洗的方 ⑧ 10 201206959 聚乙ϊί季醇系樹脂_餅塊落解，調製 濕餅塊直接溶解於水時f 樹脂(A) 且進行瓶水較為理想。脱水f;，故暫 心力的方法。 …'寸別限疋，但一般為利用離 樣態;⑼以下，較理想之 想。，水率過多時，有難於作為所為理 接著，用於聚乙烯醇系膜之制腹㈣=夜/辰度的傾向。 溶解槽加人水、前叙脫水後^之水溶液，在 、界面__，藉由二、===餅^、 =(=翼解’灌入水蒸氣，令=聚= 在具備上下循環流產生型授拌置的溶 醇系樹脂⑷濕餅塊溶解之際，：:灌入水ίί氣， J，80〇c，較理想之樣態為 =J氣，在 ^ ；ί!：ί 95~i〇〇°c„By^5 9〇-l〇〇°C > 時，樹 其進行溶解。溶解後，進行濃度調整，俾 量‘理:到通常為U),重 當⑽=¾4 向。、’有黏度變躲高而難於㈣地溶解= 201206959 法 接著，得到之膜开, ，可舉出靜置消泡材料的水溶液係予以消泡#理x 造方法中，根據生產；消 理想。 使用多軸擠製機的濟泡方it 進行消泡處理之徭，ώ 苹乂馮 液’ ^蚊量導人τ型縫模之_成材料的水溶 予以表膜、乾燥、熱處理。、咕軋贼是環形帶流延成形， τ型縫模，通常使 的，溫度通常為縫模。T型縫模出口 : Tf縫模出口的樹脂溫度；2之樣態為85, 過咼和，有發泡的傾向。 又、低牯有流動不佳的傾向，而 流延成形時，係以滾筒 — 加長、膜厚之均勻性等 幸貫施，而根據加寬或 以滾筒_昆流延昆實，為理想。 5〜30m/分較為理想，而更理^之蛊二，滾同的旋轉速度為 輥的表面溫度為7〇〜99°c較為相7 〜20m〆分。滾筒型軋 f筒型軋輥的表面溫度過低時；乾^^為75〜97t：。 有發泡的傾向。 秀軚森不锃的傾向，而過高時， 乂/袞同型乾輕製膜的聚乙婦醇系膜之严 ===互地通過複數的熱她群伽 向有乾財佳的傾向，而過高時，有過度乾料 再者，本發明中，乾燥之後係進行熱處理。 ^於，處理，俾使其於作為熱處理為較低之 c Ϊ ΐί^ 7〇"3〇〇C^fe ° ’树水性不足’熱處理斑好，造成光學_傾向，而 ，有偏細製造時之延雜下降_向。再者，熱處理方 /例如可舉出：（1)令膜通過將表面施以鐘祕細j如嶋 P ajng)處理或是鏡面處理之直徑〇.2〜加之軋報(1〜3〇個)的方法、 201206959 ()型乾燥機(長：2〜3〇m)實施的方法等。 因此，可得到聚乙烯醇系膜。 點 ί 51方可:整:為本發明之特徵的膨潤度比之顴 詳言二包含:下ί:包含以下步驟為較為理想^ 於第=輥:=聚乙烯醇系樹脂㈧的膜形成材料之水溶液 輕剝離；及7膜以膜水刀百分率為1G〜25%的狀態自第1熱軋 為互地通過至少5個以上之表面溫度 膜形’第1熱她係指滾筒型軋輕或是環形帶，且將 2材抖之水溶液於第1熱錄(滾筒型她或是帶 百分率ί 瞧上被乾燥，且以膜水分 而過在剝離時易於寬次申的傾向’ 個以=第？==俾蝴離的膜久送至至少5 至少5個以上之第2 ^軋，二正=與反面交互地通過。此時， 較理想之樣態為8〇〜Gc，>理 據抗捲曲性的觀點， 為㈣坨。當該表面’更加理想 生皺摺等之傾向，而過高時 二有乾= 率差’容易產 =捲取膜，此時之延伸比，’經過乾燥、熱處 ，為0·95〜l.G7，更加理想之樣態^⑽〜U ’更理想之 時，在膜搬科有膜鬆弛且容易^生· ^ 5。當該延伸比過低 阻滯變高的傾向。 破抬的傾向，而過高時，有 在此之延耻，触簡之魏錢^減敗旋轉速 13 201206959 度而求得的比。再者，延伸比，習知 向之抑购=== 再者，本發明中，亦根據可調整作為 比之觀點，較理想之樣態為：在將含有之特徵的膨潤度 成，的水溶液流延成形製膜之際，樹脂(Α)之膜形 由端部至總寬的5%以内之區域的膜、之寬度方向， 膜厚ff2)的2〜嶋而製膜，而較為膜寬度中央部之 比過小時，有膨潤度比(Χτό/Χμ〇)變^傾f 厚。該厚度 部之膜厚有容易產生偏差的傾向。 、、向，而過大時，膜端 在控制該膜的端部與中央部的厚 將膜形成材料的水溶液藉由τ型 二列如可舉出：在 延成形時，將τ型缝模之環形帶流 區域的部分)的間央 與膜厚⑽的厚度比之所需的數值而適HI 視膜厚(Τ1) 隙與中央部之間 =的度以住，-邊將寬 輥寬度方向。&相對於軋 (中二之：犧J峨。藉 =更=== 向賦予張力’且有易於得到光;； 輥群(3的膜自之方向賦予張力的觀點，該熱軋 ^击日上二士山礼輕兩端部各別於2〇%以内的任-邦八 之軋幸與中央部之軋輕徑⑻的關係，係滿足下式⑴較^ 14 201206959 心更理想之樣態為下式 綱的關係較該範^)。當乾觀 的傾向。、、向 ，口 時在 0.001 ^(β-α)/·α^〇1 〇·〇〇5-Φ''α)Χα^〇.〇7 η) 〇.010 轉—α)/α$〇.〇5 ⑶ 較理熱她 使其逐漸變大而形成的辦 ^ : 中央部朝兩端部，俾 指自中央部朝兩端部直大^俾使其逐漸變大」，係 該等之組合等。 '、的，交大、或曲線上的變大，且包含 頂部的水找，·τ=__度方向，中央部之 角度⑼為讀侧度較為i線之間的 度(TD)方向賦予之張力有 =；；角度⑼過小恰，對於膜之寬 容易產生蛇行_^有不足賴向，而過大時，在膜通過時有 今理1用相^輥君_的表面溫度通常為4〇〜_較 6^95t 〇 6〇^〇〇〇C ^ 有產生錢;過辦，找料佳賴向，祕大時，, Li, and hunting are known from the following formula. Furthermore, this operation was carried out in an environment of 23 ° C and 50% RH. Swelling degree in the mechanical (MD) direction (ΧΜα) (^ = (size in the MD direction after immersion / _ inch before immersion) xl 膨 八 八 width (TD) direction of swelling (Χτ〇) (% ) TD direction dimension after K impregnation / TD area swelling degree before impregnation (7) (10) Direction of swelling degree / survey) X (Swelling degree force (8) in TD direction) χΐ〇〇 9 ^ 1.000^1.020 , ίίί 3 UGr. The most ideal form of G1i is read ~ (four) 5. If the value is less than the range, the range of the degree of swelling (Χ·) (%) of the machine _ direction when the polarizing film is used is more than 11 () to 13 ( %% is particularly desirable as U2 to i2s%. The most reasonable difference is that the range is too small. When the polarized iridium is produced, the elongation is large, and the polarizing performance tends to be deteriorated when it is used as a polarizing film. The range of the width (4) direction of the phase of the phase-effect film (xTD) W) is 11G~13G%, which is particularly desirable. The most ideal pattern is 112~128%, and the most ideal is 201206959#114~126°/°. When the range is too small, it is in the case of 萝 偏 quot quot quot quot 蛀 蛀 1 1 1 1 1 1 1 1 1 1 1 1 1 萝 萝 萝 萝 萝 萝 萝 萝 萝 萝 萝 萝 萝 萝 萝 萝 萝 萝 萝 萝 萝 萝 萝 面积 面积 面积 面积 面积 面积 面积· The tendency to decrease. The fat (a)-M material is a copolymer of a wrong acid ethylene vinegar containing a polyethylene glycol-based tree, that is, a mixture of a component, a resin, and a component. With the =carbonol bond, the polycondensation can also be used in the side chain with 1,2-acetyldiene's polyacetylation method. Heric acid vinegar and sweet S5;;=;; ί=ί : r Thanks = 99.5% or more. When the degree of flat touch is too small, it will be pure and light, and it will not be able to obtain sufficient silk 201206959. The degree of saponification is obtained by analysis of the residue consumption of residual acetic acid. The solubility of the water-soluble polyester (A) is 4% by weight of the machine 2"^P = 〇〇mPa · S is more desirable, and the more ideal form is 20~400mpa · s 'more ideal form It is 4〇~4〇〇mPa · s. When the liquid = over i, there is a lack of elongation when the polarizing film is made, and the flatness of the film or the transparency tends to decrease. (C) or the like is known to be produced by a known admixture. j U (8) or interfacially active plasticizer (B), generally 'being in the manufacture of two:: · B. B. Example 7: glycerin, diglycerin, three Glycerin, etc. == delayed ethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol. Alkyl glycols such as monopropanediol or polyalkyl glycols, trishydroxyl or Combine two or more types of oil (9) with a ratio of -3 to 4) = 20/80 to 80 〇, and use glycerol glycerol / stearyl glycerol (weight glycerol Si is methyl propylene (weight ratio) == 2L8 〇 %==, often the most ideal form is 7~25 weights<8^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ Winding is smoothing of the roll surface Sexual, ionic surfactants or non-ionic surfactants 201206959 = sub-especially combined with anionic surfactants and burning 'f can be mentioned: aliphatic sucrose, smectite salt t milk B fine sulfate, polyoxygen, higher fatty acid alkanolamine sulfate, etc., in addition to; work agent, can also be mentioned: furnace servant, 4 . ancient 'two ~ seeking anion interface a sulfate salt such as a sulfate, a fat y acid 4, a NH oxy sulphur _, a monoglyceride sulfoate, a ruthenium neodymidine, etc., a salt thereof, a polyoxyethylene naphthalene sulfonate,萘 烷基 本 本 本 本 本 本 本 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 if if if if if if if if if if if if if if if if if if if Polyoxyethylene methyl taurate, dimethyl-5- 硭^ α-olefin sulfonate, N-fluorene polyoxyethylene wire hydride, heteropoly salt of polyoxyethylene, etc. Examples of the anionic interfacial acid salt, the burnt base acid group, and the polyoxymethylene t-agents of the salt type and the like include polyoxyethylene fatty acid amine, polyoxyethylene amine or two Burning shaft, high fat In addition to the base condensate activity, it can also be exemplified by: calcined base, polyoxyethylene glycerol fatty acid § Γ, Τ polyoxyethylene polyoxypropylene block polymerized oxyethylene, sorbitol xanthene fatty acid g|.,. Oxygen, = oil and hardening sesame oil, poly-nonionic surfactants, polyethylene, ^^ = fatty acid, S, etc., the side of the fatty acid monoglyceride, propylene glycol, fat: fat t, pear fatty acid vinegar , fat agent, etc. · 1 庶 知 知 知 醆 等 等 等 等 等 等 等 等 等 ' ' ' ' ' ' ' ' ' ' ' ' ' 舌 舌 舌 舌 舌 舌 舌 舌 舌 舌 舌 舌 舌 舌 舌 舌 舌 舌 舌 舌 舌 舌 舌~〗 〖heavy = vinyl alcohol resin (A) l 〇〇 weight f parts, more ideal form is _ ~ ^ heavy state is _ ~ 〇. 5 when too few 罝 too, it is difficult to get resistance. For each surfactant (the content of Q, there is a tendency for the transparency of the film to decrease, the soil tends to be 111 〇C mg), and too much, and the use of anionic surfactants and nonionic surfactants 201206959 In contrast, the polyvinyl alcohol-based resin (preferably, the agent is preferably 0.01 to 1 part by weight, more preferably, the anionic interface active component, and more preferably, the state is 003 to 0. The state of the heart is 0.02 to 0. ^ if2, the state is G.GW parts by weight, and the more sub-system interface activity ^ is more ideally the state of (10) 3~αι is _~〇, 2 weight ^, when the J polarizer film is made of the dye "; When the surfactant is too small, the emulsion can not be used as an optical film, and when the two-way fjf' is used in the film, it is difficult to obtain an anti-blocking effect, and the tendency to reduce the flat/moon property of the surfactant is too much. There is transparency or flatness of the film. In the present invention, in order to prevent the film from being changed, it is also useful to display a preferred age-based antioxidant agent, a tertiary butyl 2,2,-methylene group. Compound, 2,6-di-butylidene bis(3-methyl-6-first-grade butyl phenol), 4,4, Poly-film forming material = 成 成 魄 魄 魄 & & & & & & & & & & & & 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯Heat her, and make the film, sodium two: Ί In order to remove the wrong method contained in the normal resin, it is necessary to recover the solvent, etc., so the water is washed 8 8 201206959 Polyethylene gluten alcohol resin _ cake The block is dissolved, and the wet cake is directly dissolved in water when the resin (A) is used, and the bottle water is ideal. Dehydration f;, therefore, the method of temporary force. ... 'inch limit, but generally use the off-state; (9) The following is preferable. When the water rate is too high, it is difficult to use it as a reason, and then it is used for the belly (4) = night/time of the polyvinyl alcohol film. The dissolution tank is added with human water, and the former is dehydrated. ^The aqueous solution, at the interface __, by the second, ===cake ^, = (= wing solution 'injection of water vapor, let = poly = in the upper and lower circulation flow to produce a type of dissolved alcohol resin (4) When the wet cake is dissolved, it is: poured into the water, J, 80〇c, the ideal form is = J gas, in ^; !:ί 95~i〇〇°c„By^5 9〇-l〇〇°C > When the tree is dissolved, after concentration, the concentration is adjusted, and the amount is adjusted to: usually U), heavy When (10) = 3⁄44 direction, 'has viscosity becomes high and it is difficult to dissolve (4) = 201206959 method, then the film is opened, and the aqueous solution of the static defoaming material is defoamed. According to the production; eliminate the ideal. Use the multi-axis extrusion machine to do the defoaming treatment, ώ 乂 乂 乂 ' ' ^ Mosquito amount guide τ type slit mold _ into the material of the water soluble film, dry Heat treatment. The rolling thief is a ring-shaped tape casting, a τ-type slitting die, which is usually used, and the temperature is usually a slit die. T-slot die exit: The resin temperature at the exit of the Tf slit die; the state of 2 is 85, which is excessively entangled and tends to foam. In addition, there is a tendency for the flow to be poor, and in the case of casting, it is desirable to carry out the roll-extension, the uniformity of the film thickness, etc., and it is preferable to widen or to roll the cylinder. 5~30m/min is more ideal, and more reasonable, the same rotation speed is the surface temperature of the roller is 7〇~99°c and the phase is 7~20m. When the surface temperature of the drum type roll is too low, the dryness is 75~97t:. There is a tendency to foam. Xiu Yusen's tendency to be unscrupulous, and when it is too high, the 聚/衮 型 干 干 轻 轻 = = = ================================================================= When it is too high, there is excessive dry material. In the present invention, heat treatment is performed after drying. ^,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The time delays the decline _ direction. Further, the heat treatment side may, for example, be: (1) the film is treated by applying the surface to the surface of the key, such as 嶋P ajng) or the diameter of the mirror treatment 〇. 2~ plus the report (1 to 3 〇 Method, 201206959 () type dryer (length: 2~3〇m), etc. Therefore, a polyvinyl alcohol-based film can be obtained. Point ί 51 can be: whole: the swelling ratio of the characteristics of the present invention is more than two: bottom ί: the following steps are more desirable ^ the first roll: = polyvinyl alcohol resin (eight) film forming material The aqueous solution is lightly peeled off; and the 7 film is in a state in which the percentage of the film water jet is 1 G to 25%. From the first hot rolling to the mutual ground, at least 5 or more surface temperatures are formed. It is an endless belt, and the aqueous solution of the two materials is shaken on the first heat record (the drum type is dried on the belt or the percentage ί 瞧, and the film moisture is easy to widen when peeling off) ? == 俾 的 的 久 久 久 久 久 久 久 久 久 久 久 久 久 久 久 久 久 久 久 久 久 久 久 久 久 久 久 久 久 至少 久 久 久 久 久 久 久 久 久 久 久 久 至少 久 久 久 至少 至少 久 至少The curling point of view is (4) 坨. When the surface is more ideal for wrinkles, etc., and too high, there is dry = rate difference 'easy to produce = coiling film, the elongation ratio at this time, 'after drying, The hot part is 0·95~l.G7, and the more ideal form ^(10)~U 'when it is more ideal, there is a film relaxation in the film transfer section and it is easy to ^^·^. The tendency to extend higher than the low block is higher. The tendency to break up, and when it is too high, there is a shame in this, and the Wei Qian, who touches Jane, reduces the rotation speed of 13 201206959 degrees. The extension ratio is conventionally suppressed by the purchase === Furthermore, in the present invention, according to the viewpoint of being adjustable, it is preferable that the aqueous solution is formed by casting an aqueous solution containing the characteristic swelling degree. At the time of film formation, the film shape of the resin (Α) is formed by a film of a region within a range of 5% or less from the end portion to the total width, and a film thickness ff2) is formed to form a film, and the film portion is formed at the center portion of the film width. When the ratio is too small, the swelling ratio (Χτό/Χμ〇) becomes thicker than the inclined f. The thickness of the thickness portion tends to vary. When the film is too large, the film end is controlled by the thickness of the end portion and the central portion of the film. The aqueous solution of the film forming material is represented by the τ type two columns: when the forming is performed, the τ type slitting die is used. The thickness of the intermediate portion and the film thickness (10) of the portion of the annular band flow region is larger than the required value, and the thickness of the film (Τ1) is between the gap and the central portion, and the width of the wide roller is used. . & Relative to rolling (Secondary: Sacrifice J峨. Borrow = more === impart tension to 'and easy to get light';; Roller group (3 film from the direction of the tension, the hot rolling The relationship between the two sides of the two priests and the two sides of the priests of the priests of the two sides is better than that of the central part of the rolling light trail (8), which is more ideal than the following: (1) is better than ^ 14 201206959 The relationship of the state is lower than that of the general formula ^). When the tendency of the observation is, the direction of the mouth is 0.001 ^(β-α)/·α^〇1 〇·〇〇5-Φ''α) Χα^〇.〇7 η) 〇.010 ——α)/α$〇.〇5 (3) It is formed by the fact that she gradually enlarges and becomes larger: the central part faces the two ends, and the 俾 refers to the central part. Straight and large at both ends to make it gradually larger, such as the combination of these. ',, the intersection, or the curve becomes larger, and includes the water at the top, · τ = _ _ direction, the angle of the central portion (9) is the degree of read (1) between the i-line The tension has =;; the angle (9) is too small, the width of the film is prone to snakes _^ has a lack of reliance, and when it is too large, when the film passes, the surface temperature of the phase 1 is usually 4 〇~ _Compared with 6^95t 〇6〇^〇〇〇C ^ There is money; after handling, looking for good optimism, when secret,
It 之乾燥的其他方法，可舉出下述方法。 部的流出宽之敝、麵模之流出寬⑻的寬度方向，自一邊端 产(ίΐΓ、以及自另-03的任一區域(S1)之熱乾親群(Rn)的表面溫 :軋娜)的= -區綱之 沾办存七A w 1开里想之樣態為.較相對於流出寬⑻ 的、哺t3二或及區域(S2)以夕卜的區域(S3)之熱軋輕群⑽） ’表面孤度（3)低之表面溫度。藉由調整該熱軋親群㈣的表面溫 15 201206959 度，而可對於膜之寬度(TD)方向賦 且 向性更少之聚乙烯醇系膜的傾向。 且有易於得到光學異Other methods of drying of It include the following methods. The width of the outflow width of the part, the width direction of the outflow width of the face mold (8), and the surface temperature of the heat-dried relative (Rn) from one side (S1) of any area (S1): The = = area of the section of the work of the seven A w 1 open the way to think about it. Relative to the outflow width (8), feeding t3 two or the area (S2) in the area of the (S3) hot rolling Light group (10)) 'Surface surface degree (3) low surface temperature. By adjusting the surface temperature of the hot-rolled parent group (4) to 15 201206959 degrees, it is possible to impart a less flexible polyvinyl alcohol-based film to the width (TD) direction of the film. And easy to get optically different
特別是根據對於膜之寬度(TD 觀點，熱軋報群(Rn)的表面溫度((f向賦予f力與膜之搬送性的 為··較表面溫度(13)低的表二'皿又(t2)較理想之樣態 1〜18。。的表面溫度’更加理_ ' =二，而$理想之樣態為低 ，溫度差過小時，對於膜之寬度ϋ向溫度。當 向，而過大時，由於對於教軋輕7 ;二3；之張力有不足的傾 搬送，機械(MD)方向的張力變Α，而雜二g二故為了膜 變大的傾向。 為膜的光學異向性有 在此之令區域(S1)之熱軋輕群㈣ ㈣之熱乳幸昆群(蝴表面溫度(t2)，1):以及區域 面溫度⑼紅絲溫度，例何㈣^ 的表 ί 制的熱軋輕，在熱鲍的端部^= 控金單 的端部設置冷卻軋輥等之方法。 人达々風，在熱軋輥 再者’根據膜之搬送性的觀點，該區 模之流出寬⑻的寬度方向，佔有自—邊端m目$自^型縫 流，的寬度方向，佔= 及區域(S2)落於該範圍外時，社當 再者，區域(S3)為該區域(S1)及區域(S2)以外的區^7降的傾向。 ή再Ϊ ^發明，、’關於區域⑽，根據製膜後之面内均句性的 减點’較理4之樣態為：相對於熱軋輥群 方丙上 有中;部分之_3贼，較製職之膜寬(Sf度 對於衣膜後之膜寬⑻’區域⑽的寬為⑽〜心雄為理想，而更 16 201206959 加理想之樣態為100〜110。/。 膜的面=有容易產生不均的傾田向（〕的見過小時，在製膜後之 如刚述，作為聚乙烯醇系膜的乾燥方法， 後之膜見(b)，係指經過該乾燥步驟後_官\曰 在库由步驟後實施熱處理時，經過熱處 、見、或疋 〈聚乙烯醇系膜> 邓设的版見。 如此而得到之本發明的聚乙烯醇系膜，& 度比(Xtb/X-為LOCKM·。再者，本’預定的膨潤 如前述，預定的面積膨潤度⑺為13〇〜17〇0;月^乙稀醇系膜， 又，本發明的聚乙稀醇系膜，根據在寬 觀點，阻滯值為1〇〜4〇nm較為理想，而更理相也延伸的 更加理想之樣態為10〜25nm。 之枚恶為10〜30nm， 在3(ίΪ舌本乂明的聚乙稀醇系膜中’根據染料之毕色性的颧點 在30C的重量膨潤度(W)為19〇〜23 7色ί·生的親點， 為195〜225%，更加理想之樣態為195〜2如^ 樣態 然延===偏光膜的偏光性ί有降低t?向而過大時，難 要將該重置杉潤度(W)控制於該範圍，例 法。將含有聚乙稀醇系樹脂⑷的圍二]二=以下的方 帶流延成形後，較理想之樣能 袞間型軋輥或環形 複數的旋轉加熱幸成形後，藉由 乾燥機或旋轉加熱軋報的溫度、以n i^後’接著’將懸浮 的結晶化速度變慢，故難於得於^稀醇系樹脂⑷ 並進行熱處理時，由於需要⑽。"以ϋ，而水为百分率過低 度變得過低，且易於黃，，财膜的重量膨潤 但是，並非限定於該等方法，口、曰降的傾向。 根據可塑劑的種類或^^加量，亦可:周J是同一熱f理條件，即令 凋正。一般而言，由於只要增 17 201206959 二ίΓ/ΐ，，紐財降低，故有 亦可根據可塑躺種類雖^ 卩^麵的添加量為相同， 乙賴樹脂㈧相溶4:===而與聚 而且，膜製臈時的乾***彼,., J 溫乾燥、高濕乾燥等，令膜中水=焯:=，溫乾燥或低 ==生產性的觀點，其; 率成為5〜30重量％德，茲士盘杏_ 私狀衣联吋之水分百分 想，而可塑劑主要使用甘二，周整重量膨‘潤度(W)較為理 而調整重量膨潤度(W)更為理想。7…、处理溫度於70〜14〇ΐ的範圍 者。 水槽浸潰I5分鐘。接著，取中 ^周整為30C的雜子交換 且，將遽紙(5猶疊於膜之上，胁if 將^開放置， (4.4g/cm2)的 Sus 板 5 秒鐘胺放置1 Wl5Cmx〇.4cm 該膜放入秤量瓶，測定重旦骑、^面的吸附水去除。迅速地將 分之^ :置於1〇5。。的二6小時，進行膜中的太 為乾燥後之膜彳㈣瓶’測定重量，將其i 膜重量B，由下式求得重、膨潤時之膜重量A與麵後的 重量膨潤度(％)=Α/βχΐ()() 40〜60% ’更能系，的間規性較理想之樣態為 間規性過鄉姊; 201206959 有延伸性下降，易於斷裂的傾向。 车樹規性控制於該範圍，例如有將間規性高之聚乙稀醇 二' 生低之聚乙稀醇系樹脂掺合的方法、將改變醋酸乙 St，;:息化的方法、將三甲基酷酸乙稀醋、三氣醋酸 馱乙烯酯等之乙烯酯的聚合物皂化的方法等。 —— 騎一^下*而谢亍普絲，即一間— 劑(〇2〇)中之费7.祕赌金ΗΪ# 丄13。、τι ^ 祕A腚一咖漏广常相如十^一而渐普定者一亦-即一-間-利用咖齡13c—nmr法而測定之 瓣透率為 用，明的聚乙稀醇系膜宜作為光學膜的原料膜片使 用特別疋作為偏光膜的原料膜片使用。 <偏光臈及偏光板> 造方^ 了摘使用本發明之聚乙烯醇縫的本發明之偏光膜的製 處理論:::=:U由通常的染色、延伸，酸交聯及熱 後，予以蝴化合物處理的方法、夜而木色以 魏合物處_方法、藉_或!色以後，予以 的方法等，且可•選*色叹，㈣化合物的溶液中延伸 可分別進行延伸與^以及硼二勿系膜(未延伸膜)， 根據生產性的觀點，在染色=化亦可同時進行’而 的步驟中實施單鶴伸較4理想。。物禮步驟之至少-種 延伸較理想之樣態為在單 樣態為延伸2.8〜7倍。此時，在° ^伸2 10倍’而更理想之 的延伸(防止寬度方向之收角方向亦可進行些許 的溫度選自於20〜17CTC較為理二又$疋八以上的延伸）。延伸時 前述範圍即可，而延伸操作不率，最後設定於 Ν匕奴，且可貫施於製造步驟之 201206959 任意範圍的階段。 而實ί於=用色峨! L ’破化卸的濃度為液’—的濃度為⑽〜2g/ 較為理想。染色時間為3〇〜^秒的重量比為2〇,〇 5〜5〇。(：破為理想。水玄饬由 為只用。處理浴的溫度為 有相溶性的有機溶方，可含有少量與水 任意的方法。 接觸方法’可應用浸潰、塗佈、喷霧等之 合物木=理藉由^f物而予以處理。作為硼化In particular, according to the width of the film (the TD point of view, the surface temperature of the hot-rolled group (Rn) ((f is given to the f-force and the transportability of the film is lower than the surface temperature (13)) (t2) The ideal state 1~18. The surface temperature 'more rational _ ' = two, while the ideal state is low, the temperature difference is too small, for the width of the film ϋ to the temperature. When it is too large, the tension in the machine (MD) direction is reduced due to insufficient tension in the tension of the teaching and rolling, and the tendency in the machine (MD) direction is increased. The hot-rolled light group (4) (4) of the hot zone in the area (S1) (the wind surface temperature (t2), 1): and the surface temperature (9) red wire temperature, for example (4) The hot rolling is light, and the method of cooling the rolls is provided at the end of the hot abalone ^= the end of the gold control sheet. The person reaches the hurricane, and in the hot roll, the model is based on the transportability of the film. The width direction of the outflow width (8) occupies the width direction of the self-edge end m mesh $ self-slot flow, and when the area and the area (S2) fall outside the range, the area (S3) is the Area The tendency of the area other than the domain (S1) and the region (S2) is lowered. ή Ϊ Ϊ ^Invention,, 'About the region (10), according to the in-plane uniformity of the film after the filming It is: relative to the hot roll group, there is a medium; part of the _3 thief, the film width of the work (Sf degree for the film width after the film (8) 'area (10) width is (10) ~ Xinxiong is ideal, and 16 201206959 The ideal state is 100 to 110. The surface of the film = the appearance of the field which is prone to unevenness, and the hour after the film formation, as described later, as a polyvinyl alcohol film The drying method, the film after seeing (b), means that after the drying step, the _ official 曰 曰 曰 曰 实施 由 由 由 由 由 经过 经过 热 热 热 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯The polyvinyl alcohol-based film of the present invention thus obtained has a & degree ratio (Xtb/X- is LOCKM·. Further, the predetermined swelling is as described above, and the predetermined area swelling degree (7) is 13〇. ～ 〇 ; ; ; ; 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚Adding the ideal state is 10~25nm. The abnormity is 10~30nm, in the 3( Ϊ Ϊ 乂 的 的 的 的 的 的 ' ' ' 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据(W) is 19〇~23 7 colors ί·sheng's protagonist, 195~225%, more ideal form is 195~2 such as ^ like state delay === polarizing film polarization ί has reduced t When it is too large, it is difficult to control the replacement degree (W) in this range. For example, a square tape containing the polyethylene resin (4) and two or less squares is cast and formed. It is more desirable to use a rotary roll or a ring-shaped rotary heating for forming, and it is difficult to slow down the crystallization rate by the temperature of the dryer or the rotary heating. When the heat-soluble resin (4) is obtained and heat-treated, (10) is required. "With ϋ, and the percentage of water is too low, and it is easy to yellow, and the weight of the film is swollen. However, it is not limited to these methods, and the tendency of mouth and sputum is lowered. Depending on the type of plasticizer or the amount of addition, it is also possible that: Week J is the same heat condition, that is, it is withered. In general, as long as the increase of 2012 20125925 Γ Γ ΐ , , , , , , , , 纽 纽 纽 纽 纽 纽 纽 纽 2012 2012 2012 2012 2012 2012 2012 2012 纽 纽 2012 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽 纽With the poly and the dry operation of the film, you can dry, high-humidity, etc., so that the water in the film = 焯: =, warm dry or low == productive point of view; ~30wt% De, Zishi Pan Apricot _ private clothing combined with the moisture percentage, and the plasticizer mainly uses Ganji, the whole weight of the expansion 'wetness (W) is more reasonable and adjust the weight swelling degree (W) More ideal. 7..., the processing temperature is in the range of 70~14〇ΐ. The sink was immersed for 1 minute. Next, take the miscellaneous exchange of 30C in the middle and the paper, and put the crepe paper (5 is stacked on the film, the threat if it will be placed, the (4.4g/cm2) Sus plate is placed for 5 seconds, the amine is placed 1 Wl5Cmx 〇.4cm The film is placed in a weighing bottle, and the adsorption water removal of the heavy-duty riding and the surface is measured. The separation is quickly set to 1:5 for 2 hours, and the film is too dry. Membrane 彳 (4) bottle 'measured weight, the i film weight B, from the following formula to obtain the weight, the film weight A and the weight after the surface swelling (%) = Α / β χΐ () () 40 ~ 60% 'More energy, the more ideal pattern is the regularity of the hometown; 201206959 has a tendency to decrease in elongation and is prone to breakage. The vehicle tree is controlled in this range, for example, it will have a high degree of regulation. A method for blending a polyethylene glycol with a lower polyethylene glycol resin, a method for changing the ethyl acetate St, and a method for compounding, a trimethyl succinic acid vinegar, a tris, a vinyl acetate, and the like. The method of saponification of the polymer of vinyl ester, etc. —— riding a ^ lower * and Xie Pu Pusi, that is, a fee in the agent (〇2〇) 7. Secret gambling ΗΪ # 丄13., τι ^ Secret A腚一咖咖漏常相如Ten and one gradually become the first one - that is, one - between - the use of the age of 13c - nmr method to determine the valve permeability, the clear polyethylene film is suitable as a raw material film for the optical film.疋Used as a raw material film for a polarizing film. <Polarized iridium and polarizing plate> Manufacture method of the polarizing film of the present invention using the polyvinyl alcohol sew of the present invention:::=:U is usually The method of dyeing, stretching, acid cross-linking and heat, the method of treating the compound of the butterfly, the method of the night, the color of the wood, the method of using the compound, the method of borrowing _ or the color, the method of giving, etc. (4) The extension of the solution in the compound can be carried out separately and the boron and the bismuth film (unstretched film), and according to the viewpoint of productivity, the step of performing the dyeing can be carried out simultaneously. Ideal. At least the extension of the object-steps is 2.8 to 7 times in the single state. At this time, the extension is 2 10 times and the ideal extension (preventing the width direction) In the direction of the angle of the exit, a certain temperature can be selected from the extension of 20 to 17 CTC and the extension of the second and the second. The above range is sufficient, and the extension operation rate is not set, and finally set to the slave, and can be applied to the stage of the manufacturing process at any range of 201206959. Actually, the color is 用! The concentration of '- is preferably (10) ~ 2g /. The dyeing time is 3〇~^ seconds. The weight ratio is 2〇, 〇5~5〇. (: Breaking is ideal. Water Xuanzang is used only. Treatment bath The temperature is a compatible organic solvent, and may contain a small amount of water and any method. The contact method can be applied to the compound by dipping, coating, spraying, etc. as a boron. Chemical
理想，但當铁亦可用t車if里想。處理法為浸潰法較為 卢二;二佈法、喷霧法。處理時的溫度為2〇〜6(TC =延=：；分左右㈣理想，且縣《可於處理中 箄本發明的偏光膜’在其-面或兩面將光學上 ίϊί用。用於本發明之偏光板的保護臈，例如可舉出 =准^·、二醋酸纖維素、聚碳酸醋、聚ϋ夂 稀、聚啦風、聚亞芳麵、聚—4_曱基本乙 降莰婦系聚雜等謂或薄#。糸乃至 在，將薄膜化作為目的’代替該保護膜，亦可 系樹脂、丙稀酸系樹脂、尿素樹 -2 ΐΐΐί在ΐ少r、面疊層保護膜或是硬化性樹脂者)，視其 劑声，^二每用通t知的方法形成透明的感壓性勒合 ::乙醋:丙烯酸甲醋、丙烯酸2_乙基己醋等之丙:口 烯酸、馬來酸、伊康酸、甲基丙稀酸、巴豆酸等之α—= 之共聚物(亦包含添加_腈、雜乙_旨、苯乙狀類的乙& 20 201206959 體者)作為主體者，由於不會阻 + 但並非限定於此，只要是具有 、=光特性而較為理想， 例如亦可使用聚乙刺系、橡膠㈣。、《雖黏合劑即可使用， 本發明的偏光膜，係用於電子卓 „。 理機、電腦、電視、個人數位助理^ t = #+鐘' 文字處 之液晶顯示刊·借、女陪P> /飞車或機械類的測量器類等 負不5又備、太知眼鏡、暖目眼鏡、立體眼 =)用反射減低層、醫療設備、建築材料、玩具 貫施例 直要實施，具體地說明本發明，但本發明只要不超過 其要曰即可，亚不限定於以下之實施例。 d 列中有「I、:％」者，意指重量基準。 關於各物性’如下述而貫施。 (1) ακ乙細醇糸樹脂之平均息化度(莫耳％) 以殘留醋酸乙_旨單元之水解所需的驗耗量進行分析。 (2) 聚乙烯醇系樹脂之4。/。水溶液黏度(j^pa · s) 20°C > «^*t^|^tt(hoepler viscometer) 而測疋。 (3) % 潤度比(Xtd/Xmd) ★將膜切割成lOcmxlOcm的正方形，俾使其與機械_)方向、 X^(TD)方向平行，並放置於平坦的玻璃板上，以游標卡尺分別 測i MD方向及TD方向之尺寸。接著，在調整為3〇它的離子交 換水槽浸潰5.分鐘後，取出膜，並立即放置於平坦的玻璃板上， 以游標卡尺分別測量MD方向及TD方向之尺寸，並藉由下式而 計算。再者，該操作係於23°C、50%RH的環境下實施。 MD方向的膨潤度 =(浸潰後之MD方向的尺寸/浸潰前之MD方向的尺 寸)xl00 TD方向的膨潤度(xTD)(%) ==(浸潰後之TD方向的尺寸/浸潰前之TD.方向的尺寸)xl〇〇 膨潤度比(Xtd/Xmd) = TD方向的膨潤度(XTO)/MD方向的 21 201206959 膨潤度(Xmd) (4) 面積膨潤度⑺(％) 依據該(3)的方法’算出md方向的膨潤度(Χμ〇;^ TD方向的 膨潤度(Xtd)，並藉由下式而計算。 面積膨潤度(Y)(%) —(MD方向的膨潤度/1〇〇)x(TD方向的膨潤度/1〇〇)χ1〇〇 (5) 阻滞值(mil) 使用阻滯測定設備（王子計測機器(股)製， 測定波長：590mn) ’測定聚乙烯醇系膜之寬度方向之中央部分的 阻滯值。 ⑹重量膨潤度(W)(0/o) 5膜切割? 1Gemxl()em，在調整為3(rc雜子交換水槽浸潰 田接著’取出膜，在遽紙⑽上將膜展開放置，且，將濾 、、氏(2 )重登於膜之上，並於其上方放置15Cmxl5CmxG.4Cm(4.4g/ Γϋsus板5秒鐘，賴表__水去除。迅速地將該膜放 定重量’將其作為膨潤時之膜重量A。該操作係於 23 C、50/oRH的環境下實施。 之本放置於1G5t：的乾賴16小時，進行膜中的水 乾燥Ϊ之膜:迅速地放入㈣瓶’測定重量，將其作為 重量Β由、下，+。然後，基於膨潤時之膜重量Α與乾燥後的膜 重里β，由下式求得重量膨潤度。 重里％ >閏度(％)=Α/Β X1 〇〇 <實施例1> s，平加，聚乙稀醇系樹脂之4%水溶液黏度6411此· 可塑劑(B)之Ϊ油醇系樹脂(A)42kg、水100吆、 聚氧乙嫌+_胶〇. g ·界面活性劑(C)之十二烷基磺酸鈉21g、 止，均勻地>二艇J ’二邊?掉，一邊以加壓加熱升溫至150。〇為 的水溶液。Z合I ’猎由?辰度調整而得到濃度鳩之膜形成材料 接者，將_成材料的水溶液(液溫14Tt)，供給至雙軸播製 22 201206959 機’且予以消泡。將消泡後之膜形成材 岐管型模；straightmanif0ld die)於滾自T型缝模(直 形而製膜。此時，係、使用τ型缝模之熱軋報：叫流延成 置為止)的間隙開度大於中央部之黑部至15〇聰位 該流延成形製膜的條件如下。4度^者。 滾筒型軋報(熱軋親：R1) 直梭：3200mm、寬：4 3m、綠赫、占ώ； 贼、τ猶模出σ簡脂溫度：9；^度：8m/分、表面溫度： ί ΐ 自滾，她剝離之際的膜水分百分率為π%。 親，同時i行乾燥令付到的膜之正面與反面交互地通過乾燥軋 • ^乞燥軋親之第1個〜第5個(熱軋輥：把 94〇c徑：320職、寬：咖、旋轉速度：8111/分、表面溫度： •=軋輪之第6個〜第10個(熱軋輥：R7〜ru) 75t牷：32〇_、寬：4.3m、旋轉速度：8m/分、表面溫度： 丄取樣乾燥後膜’測定膜水分百分率為12%。 懸浮Si機下步驟，藉由自該膜兩面吹送暖空氣的 系膜。 、卩的厗度60叫11、膜鈿部之厚度63μιη的聚乙烯醇 得到的聚乙烤醇系膜之各物性示於表i。 得= 1而件到之本發明的聚乙烯醇系膜，以下述要領而 付到偏^膜’並進行以下之評價。評價結果示於表】。 站灿將㈣的聚乙稀m —邊浸潰於水溫3G°C的水槽，一邊 所細。接著，一邊浸潰於由碘0‘2g，L、碘化鉀❿八 、' '糸色槽(30 C)240秒鐘，一邊延伸至1.3倍，並且浸潰於 ^ 50g/L、碘化鉀3〇g/X之組成的硼酸處理槽(5〇艺），同時一 、早由延伸至3.08倍，一邊花費5分鐘進行爛酸處理。之後，進 23 201206959 行乾無而得到總延伸倍率6倍的偏光膜 <<染色不均之評價>> ' 在由前述而得到之偏光膜的兩面， 黏合劑使用，貼合麟的三^系水溶液作為 乾燥而得到偏光板。該偏光板，自寬产 哉、、隹素膜，並於50°C 樣本，在寬度(TD)方向以2mm節距濟^定刀，成20cmx2〇cm的 與最小値的差，評價染色不均。 父冬透率，求得最大値 再者，正父渗透率，係使用大塚雷 「RBTS-1100A」而測定。 電子⑻製的阻滯測定設備 < <延伸性之評價> > 使用由前述而得到之本發明的聚 =膜的製造中，更進一步提升於二 1 订延巧膜斷裂為止，測定延伸極限料，並二二二'革進 <貫施例2及3、比較例1及2> 、 除^實施例丨之膜製膜的條件改為如表丨所示以外，係與 Λ 相同而實施，得到聚乙騎系膜，且與實施例丨相同而 传到偏光膜。 得到聚乙稀醇系膜以及偏光膜，係進行與實施例1相同的評 仏。評價結果示於表1。 、 製 膜 條 件 實施例1 實施例2 實施例3 比較例1 比較例2 ia對於Τ型縫模之中央部間隙 開度之兩端部的間隙開度之增 抄(％) 5 3 7 0 (平面） 10 滾筒型軋輥(熱軋輥：R1)的表 ^盖度(。〇 · 90 90 90 90 . 90 自滾筒型軋輥(熱軋觀：R1)之 膜剝離時的水分百分率(％) 17 17 17 17 17 知躁軋輥(熱軋輥：R2〜R6)的 表面溫度fC) 94 ' 83 88 75 75 乾燥軋輥(熱軋輥：R7〜R11)的 表面溫度(。〇 75 75 75 75 75 24 201206959 熱處理後之膜水分百分率(％) i乙烯醇系膜之中央苦 (Τ2)(μηι)____ 聚乙烯醇系膜之端部厚度 (Τ1)(μπι) 0.002 0.004Ideal, but when iron can also be used in the car t if. The treatment method is the dip method, the second method, the second method, and the spray method. The temperature at the time of treatment is 2〇~6 (TC=delay=:; the left and right (four) are ideal, and the county “the polarizing film of the present invention which can be processed in the process” is optically used on its side or both sides. The protective 臈 of the polarizing plate of the invention may, for example, be a quasi-^, a cellulose diacetate, a polycarbonate, a polythene, a poly, a poly-aromat, a poly- 4 It is a kind of polystyrene or a thin laminated surface protective film which can be used as a purpose to replace the protective film. Or a hardening resin), depending on the sound of the agent, ^2 each method of using a known method to form a transparent pressure-sensitive pull:: Ethyl vinegar: acrylic acid methyl vinegar, acrylic acid 2-ethyl vinegar, etc. Copolymer of α-= such as enoic acid, maleic acid, itaconic acid, methyl acrylic acid, crotonic acid, etc. (including B-addition of acetonitrile, hetero-ethyl, styrene, and benzene; 20 201206959 As the main body, it is not limited to this, but it is not limited thereto, and it is preferable to have a light characteristic, for example, a polyethylene thorn system or a rubber (four). "Although the adhesive can be used, the polarizing film of the present invention is used for electronic „.. Computer, computer, television, personal digital assistant ^ t = #+钟' The liquid crystal display of the text, borrowed, female accompanying P>/Flight or mechanical measuring instruments, etc., such as negative, too-known glasses, warm eye glasses, and stereoscopic eyes =) implementation of reflection reduction layer, medical equipment, building materials, and toys. The present invention will be specifically described, but the present invention is not limited to the following examples as long as it is not limited to the following examples. The "I, :%" in the column d means the weight basis. The respective physical properties ' are applied as follows. (1) The average degree of recombination of ακ-ethoxylated oxime resin (% by mole) was analyzed by the amount of the test for the hydrolysis of residual acetic acid. (2) 4 of polyvinyl alcohol resin. /. Aqueous solution viscosity (j^pa · s) 20 ° C > «^*t^|^tt(hoepler viscometer) and measure 疋. (3) % Moisture ratio (Xtd/Xmd) ★ Cut the film into a square of lOcmxlOcm, and make it parallel to the mechanical _) direction, X^(TD) direction, and place it on a flat glass plate with vernier calipers Measure the dimensions of the i MD direction and the TD direction. Then, after being immersed for 3 minutes in an ion exchange tank adjusted to 3 Torr, the film was taken out and immediately placed on a flat glass plate, and the dimensions of the MD direction and the TD direction were measured by vernier calipers, respectively, and by the following formula Calculation. Further, this operation was carried out in an environment of 23 ° C and 50% RH. Swelling degree in MD direction = (dimension in MD direction after dipping / size in MD direction before dipping) xl00 Swelling degree in TD direction (xTD) (%) == (dimension in TD direction after dipping / dip Size of TD. direction before collapse) xl〇〇 swelling ratio (Xtd/Xmd) = swelling degree in TD direction (XTO)/MD direction 21 201206959 Swelling degree (Xmd) (4) Area swelling degree (7) (%) According to the method of (3), the degree of swelling in the md direction (Χμ〇; ^ the degree of swelling in the TD direction (Xtd) is calculated and calculated by the following formula. Area swelling degree (Y) (%) - (MD direction Swelling degree / 1 〇〇) x (swelling degree in TD direction / 1 〇〇) χ 1 〇〇 (5) Blocking value (mil) Using a retardation measuring device (manufactured by Oji Scientific Instruments Co., Ltd., measuring wavelength: 590 nm) 'Measure the retardation value of the central portion of the width direction of the polyvinyl alcohol film. (6) Weight swelling degree (W) (0/o) 5 film cutting? 1Gemxl()em, adjusted to 3 (rc hetero-exchange sink dip) After the film was removed, the film was taken out, and the film was placed on the crepe paper (10), and the filter, (2) was placed on the film, and 15 cmxl5CmxG.4Cm was placed thereon (4.4 g/Γϋsus plate for 5 seconds). Clock, Lai table __ water removal. Quickly put the film The fixed weight was taken as the film weight A at the time of swelling. The operation was carried out in an environment of 23 C, 50/oRH. The film was placed in a dry film of 1G5t: for 16 hours, and the film was dried with water in the film: The weight of the (four) bottle was measured rapidly, and the weight was measured as the weight, the bottom, and the weight. Then, based on the film weight 膨 during swelling and the film weight β after drying, the weight swelling degree was obtained from the following formula.闰 degree (%) = Α / Β X1 〇〇 <Example 1> s, flat addition, 4% aqueous solution viscosity of polyvinyl alcohol resin 6411 This plasticizer (B) oleyl alcohol resin ( A) 42kg, water 100吆, polyoxyethylene suspicion +_胶〇. g · surfactant (C) sodium dodecyl sulfate 21g, stop, evenly > two boats J 'two sides, The solution is heated to a temperature of 150 Torr. The Z-I is used to obtain a film forming material having a concentration of 鸠, and the aqueous solution (liquid temperature: 14 Tt) of the material is supplied to the double. Axis sowing 22 201206959 machine 'and defoaming. The film forming material after defoaming is formed by the tube type; straight manif0ld die) is rolled from the T-slot die (straight shape and film formation. At this time, the system The gap opening degree of the hot rolling report using the τ-type slit mold is called the casting, and the gap opening degree is larger than the black portion of the center portion to 15 〇. The conditions for the casting and forming film are as follows: 4 degrees ^. Report (hot rolling pro: R1) straight shuttle: 3200mm, width: 4 3m, green hemp, occupies; thief, τ modulo σ simple fat temperature: 9; ^ degrees: 8m / min, surface temperature: ί ΐ Rolling, the percentage of film moisture at the time of peeling off was π%. Pro, at the same time, i line drying, the front and back sides of the film are passed through the dry rolling. ^ Drying and rolling the first to the fifth (hot roll: 94〇c diameter: 320 positions, width: coffee Rotation speed: 8111/min, surface temperature: •= 6th to 10th of the rolling wheel (hot roll: R7~ru) 75t牷: 32〇_, width: 4.3m, rotation speed: 8m/min, Surface temperature: 丄 After sampling and drying, the film 'measurement film moisture percentage is 12%. The suspension Si machine is the next step, by blowing the warm air film from both sides of the film. The width of the film is called the thickness of the film. The physical properties of the polyb-baked alcohol-based film obtained by the polyvinyl alcohol of 63 μm are shown in Table i. The polyvinyl alcohol-based film of the present invention obtained in the following paragraph was obtained by the following method and was subjected to the following The evaluation results are shown in the table. The station can be immersed in the water tank at a water temperature of 3G ° C while being immersed in the water from the iodine 0'2g, L, Potassium iodide ❿8, ''糸 color trough (30 C) for 240 seconds, one side extended to 1.3 times, and immersed in a boric acid treatment tank of 50 g / L, potassium iodide 3 〇 g / X (5 〇 art At the same time, it was extended to 3.08 times, and it took 5 minutes to carry out rotten acid treatment. After that, 23, 2012,069,059 lines were dried, and a polarizing film having a total stretching ratio of 6 times was obtained. <<Uneven evaluation of dyeing unevenness>>; ' On both sides of the polarizing film obtained as described above, a binder is used, and a polarizing plate obtained by laminating the tri-system aqueous solution is used as a polarizing plate. The polarizing plate is self-producing a bismuth film and a bismuth film at 50°. In the C sample, the knife was fixed at a width of 2 mm in the width (TD) direction, and the difference between the minimum and the 値 is 20 cm x 2 〇 cm. The uneven dyeing was evaluated. The father's winter penetration rate, the maximum 値, the patriarchal permeability In the production of the poly-film obtained by the above-mentioned method, Further, the elongation limit material was measured until the breakage of the film was determined, and the film was formed by the film of the film of Example 2 and 3, and Comparative Examples 1 and 2. The condition was changed to the same as that shown in Table ,, and was carried out in the same manner as Λ, to obtain a poly-Beneze film, and The same procedure was carried out to obtain a polarizing film. The obtained polyethylene film and polarizing film were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1. Example of film formation Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Addition of the gap opening degree at both end portions of the center portion gap opening of the 缝-type slit die (%) 5 3 7 0 (planar) 10 Roller type roll (hot roll: R1 Table cover degree (. 〇· 90 90 90 90 . 90 Moisture percentage (%) of the film peeling from the roll type roll (hot rolling view: R1) 17 17 17 17 17 Known roll (hot roll: R2 ~R6) Surface temperature fC) 94 ' 83 88 75 75 Surface temperature of the drying rolls (hot rolls: R7 to R11). 〇 75 75 75 75 75 24 201206959 Percentage of film moisture after heat treatment (%) i Central bitterness of vinyl alcohol film (Τ2) (μηι) ____ Thickness of end of polyvinyl alcohol film (Τ1)(μπι) 0.002 0.004
0.002 ^^度(XtdX%) 119.0 ^ 潤度(Xmd)(%)___ ^度比(Xtd/Xn®)~~" L005 膨潤度(γ)(%) "~~ !阻滞值(nm) 延伸性(延伸極限倍率)(倍） 根據前述實施例及比較例~ 預^膨潤度比(xtd/Xmd则定範_ :故成之^ 無不均，且未產生染色不均的聚乙_系膜，= =亦為延伸極限倍率7倍以上錢伸_f佳者。 ’可々 較例項’無法得到同時滿足染色不均抑制與延伸性膜。；匕，t 該實施例中，係表示本發明之具體的形態 每° 單純的示列，並不限定於此。再者，屬於施例们 圍的改變’全包含於本發明之範圍内。 庫巳圍之均等| 產業上可利用性 由於本發明之聚乙烯醇系膜，係為由含有 / ==材=膜而成的聚乙烯醇系膜，且 水5为麵，令其膨潤時之寬度(TD)方向的膨潤 有向的膨财(xMD)之比(xtd/xw^丨·⑻ 膜’故延伸性佳，即令為了提高生產性 广乙細醇； 亦具有膜不會_效果。再者亍延伸 抑制效果佳者’作制於電子桌上計算器 不均: ，二視、個人數位助理、汽車或機械類的^量^^ ‘、、、員不讀、太陽眼鏡、護目眼鏡、立體眼鏡、顯示元^^之^ 25 201206959 荨)用反射減低層、醫療設備、建築材料、玩具等之偏 ▲、、 無片、或用於1/2波長板或1/4波長板的原料膜月田:认原料 顯示設備之相位差膜的原料膜片非常有用。 夜晶 【圖式簡單說明】 無 【主要元件符號說明】 無 260.002 ^^度(XtdX%) 119.0 ^ Moisture (Xmd)(%)___^degree ratio (Xtd/Xn®)~~" L005 Swelling degree (γ)(%) "~~ ! Blocking value ( Nm) extensibility (extension limit magnification) (times) According to the foregoing examples and comparative examples ~ pre-expansion ratio (xtd / Xmd is set to _: so that there is no unevenness, and no uneven dyeing _ Membrane, = = is also the extension limit magnification of 7 times or more. The 々 々 々 ' ' ' ' 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 t t t t It is to be understood that the specific embodiment of the present invention is not limited thereto, and the modifications belonging to the embodiment are all included in the scope of the present invention. The polyvinyl alcohol-based film of the present invention is a polyvinyl alcohol-based film containing a film of / == material =, and the water 5 is a surface, and the swelling in the width (TD) direction when swollen is The ratio of the expansion to the rich (xMD) (xtd/xw^丨·(8) film' is excellent in elongation, that is, in order to improve the productivity of the polyethylene glycol; it also has a film that does not have an effect. 'made in Uneven electronic calculator: 2, personal digital assistant, car or mechanical class ^^ ',,, staff not reading, sunglasses, goggles, stereo glasses, display yuan ^^^ 25 201206959 荨)Reducing the thickness of the layer, medical equipment, building materials, toys, etc., no film, or raw material film for 1/wavelength plate or 1⁄4 wavelength plate. The raw film of the poor film is very useful. Night crystal [Simple description of the drawing] No [Main component symbol description] No 26