TWI670314B - Polyvinyl alcohol film, optical film and manufacturing method thereof - Google Patents
Polyvinyl alcohol film, optical film and manufacturing method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
- B29C41/26—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on a rotating drum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
- B29C41/46—Heating or cooling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/08—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of polarising materials
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- Physics & Mathematics (AREA)
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- Manufacturing & Machinery (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polarising Elements (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
本發明為一種PVA薄膜,在相對於薄膜面,利用由垂直的方向朝薄膜之寬度方向傾斜的方向之入射光,測定該PVA薄膜之各面的折射率A及B時(但是,A≧B),A為1.524以上1.530以下;及一種PVA薄膜之製造方法,其係使用具備旋轉軸相互平行的乾燥輥與熱處理輥之製膜裝置,在第1乾燥輥上,將包含PVA的製膜原液吐出為膜狀並進行部分乾燥後,以第2乾燥輥以後的乾燥輥進一步進行乾燥,之後,以多個熱處理輥進行熱處理而製造PVA薄膜,在此,使該熱處理輥中的位於最下游側的熱處理輥(Y)之圓周速度(SY)相對於位於最上游側之熱處理輥(X)的圓周速度(SX)的比(SY/SX)成為0.993以上0.997以下。 The present invention is a PVA film. When the incident light in a direction inclined from the vertical direction to the width direction of the film with respect to the film surface is used, the refractive indexes A and B of each surface of the PVA film are measured (however, A ≧ B ), A is 1.524 or more and 1.530 or less; and a method for manufacturing a PVA film, which uses a film forming apparatus having a drying roll and a heat treatment roll in which rotation axes are parallel to each other. On the first drying roll, a film forming stock solution containing PVA is used. After being discharged into a film shape and being partially dried, it is further dried with a drying roller after the second drying roller, and then heat-treated with a plurality of heat-treatment rollers to produce a PVA film. Here, the heat-treatment roller is positioned at the most downstream side. the heat roller (Y) of the circumferential velocity (S Y) with respect to the heat roller located most upstream side (X) of the circumferential velocity (S X) ratio (S Y / S X) becomes 0.993 or less than 0.997.
Description
本發明係關於一種拉伸伸度高且延伸性優異的聚乙烯醇薄膜。 The present invention relates to a polyvinyl alcohol film having high tensile elongation and excellent extensibility.
聚乙烯醇薄膜(以下有時將「聚乙烯醇」簡稱為「PVA」),其力學物性、透明性、氧阻隔性、耐油性等優異,以往係使用於纖維包裝材料、農業用薄膜(蔬菜保溫用、蔬菜生長用等之薄膜)、氣體阻隔材、過濾器、偏光薄膜製造用的原料薄膜等之用途。 Polyvinyl alcohol film (hereinafter sometimes referred to as "polyvinyl alcohol" is simply referred to as "PVA"). It has excellent mechanical properties, transparency, oxygen barrier properties, and oil resistance. It has been used in fiber packaging materials and agricultural films (vegetables) in the past. Films for thermal insulation, vegetable growth, etc.), gas barriers, filters, raw film for polarizing film manufacturing, etc.
將偏光薄膜之面內均勻性作為目的,已知有各別將PVA薄膜的雙方及厚度方向中心部之折射率作為特定者的方法(參照專利文獻1及2)。 For the purpose of in-plane uniformity of a polarizing film, a method has been known in which the refractive index of both the PVA film and the central portion in the thickness direction are individually specified (see Patent Documents 1 and 2).
[專利文獻1]日本特開2006-219638號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2006-219638
[專利文獻2]日本特開2006-305923號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2006-305923
然,偏光薄膜,一般為了將PVA薄膜高度地 延伸製造,而有解決延伸PVA薄膜之際的斷裂問題之課題。然而,根據記載於專利文獻1或2的方法,無法充分提升延伸性。因此,本發明的目的在於提供一種延伸性優異的PVA薄膜及使用其之偏光薄膜等之光學薄膜。 Of course, polarizing films are generally used to Stretch manufacturing has the problem of solving the problem of fracture when stretching PVA films. However, according to the method described in Patent Documents 1 or 2, the extensibility cannot be sufficiently improved. Therefore, an object of the present invention is to provide a PVA film having excellent stretchability, and an optical film using a polarizing film or the like.
本案發明人為了達成上述目的而重複仔細探討的結果發現:PVA薄膜之表面的特定方向之折射率與PVA薄膜之延伸性具有密切的關係。又,發現該折射率為特定的PVA薄膜,利用將製膜時之熱處理輥的圓周速度作為特定者,可順暢地連續製造。本案發明人基於該等之知識進一步重複探討而完成本發明。 In order to achieve the above-mentioned object, the inventors of the present invention repeatedly and carefully studied and found that the specific refractive index of the surface of the PVA film is closely related to the elongation of the PVA film. In addition, it was found that this PVA thin film having a specific refractive index can be smoothly and continuously produced by using the peripheral speed of the heat treatment roller during film formation as the specific one. Based on such knowledge, the inventor of the present case further repeated the discussion to complete the present invention.
亦即,本發明與下述相關: That is, the present invention is related to the following:
[1]一種PVA薄膜,在相對於PVA薄膜之薄膜面,利用由垂直的方向朝薄膜之寬度方向傾斜的方向之入射光,測定該PVA薄膜之各面的折射率,於將一面之折射率當作為A,將另一面之折射率當作為B時(其中,A≧B),A為1.524以上1.530以下。 [1] A PVA film, in which the refractive index of each side of the PVA film is measured using incident light in a direction inclined from the vertical direction toward the width direction of the film with respect to the film surface of the PVA film, When A is taken as the refractive index of the other surface as B (where A ≧ B), A is 1.524 or more and 1.530 or less.
[2]如上述[1]之PVA薄膜,其中A為1.526以上1.530以下。 [2] The PVA film according to the above [1], wherein A is 1.526 or more and 1.530 or less.
[3]如上述[1]或[2]之PVA薄膜,其中A+B為3.050以上3.060以下。 [3] The PVA film according to the above [1] or [2], wherein A + B is 3.050 or more and 3.060 or less.
[4]一種PVA薄膜之製造方法,其係使用具備旋轉軸相互平行的乾燥輥與熱處理輥之製膜裝置,在該乾燥輥中之位於最上游側的第1乾燥輥上,將包含PVA的製膜原液吐出為膜狀並進行部分乾燥後,接著,以第2乾燥輥以 後的乾燥輥進一步進行乾燥,之後,以多個熱處理輥進行熱處理而製造PVA薄膜,在此,使該熱處理輥中的位於最下游側的熱處理輥(Y)之圓周速度(SY)相對於位於最上游側之熱處理輥(X)的圓周速度(SX)的比(SY/SX)成為0.993以上0.997以下。 [4] A method for manufacturing a PVA film, which uses a film forming apparatus having a drying roll and a heat treatment roll in which rotation axes are parallel to each other. A first drying roll on the most upstream side of the drying rolls will include a PVA-containing film. After the film-forming stock solution is discharged into a film shape and partially dried, it is further dried with a drying roller after the second drying roller, and then heat-treated with a plurality of heat-treatment rollers to produce a PVA film. heat treatment roll (Y) of the downstream side of the most peripheral speed (S Y) with respect to the circumferential velocity (S X) located in the heat treatment roll most upstream side of the (X) of the ratio (S Y / S X) becomes 0.993 or more 0.997 the following.
[5]如上述[4]之製造方法,其係使第2乾燥輥的圓周速度(S2)相對於第1乾燥輥的圓周速度(S1)之比(S2/S1)成為1.000以上1.040以下。 [5] The manufacturing method according to the above [4], wherein the ratio (S 2 / S 1 ) of the peripheral speed (S2) of the second drying roller to the peripheral speed (S 1 ) of the first drying roller is 1.000 or more Below 1.040.
[6]如上述[4]或[5]之製造方法,其係使最終乾燥輥之表面溫度小於60℃。 [6] The manufacturing method according to the above [4] or [5], wherein the surface temperature of the final drying roller is less than 60 ° C.
[7]一種光學薄膜,其係由如上述[1]至[3]中任一項之PVA薄膜製造。 [7] An optical film manufactured from the PVA film according to any one of [1] to [3] above.
[8]如上述[7]之光學薄膜,其係為偏光薄膜。 [8] The optical film according to the above [7], which is a polarizing film.
[9]一種光學薄膜之製造方法,其係具有使用如上述[1]至[3]中任一項之PVA薄膜進行單軸延伸的步驟。 [9] A method for producing an optical film, which comprises the step of uniaxially stretching using the PVA film according to any one of the above [1] to [3].
[10]如上述[9]之製造方法,其係為偏光薄膜之製造方法。 [10] The manufacturing method as described in [9] above, which is a manufacturing method of a polarizing film.
本發明的PVA薄膜,其拉伸伸度高且延伸性優異。因此,只要將本發明的PVA薄膜使用於原料薄膜上,則可以良好的生產性製造光學性能優異的偏光薄膜等之光學薄膜。又,根據本發明的PVA薄膜之製造方法,可順暢地連續製造上述PVA薄膜。 The PVA film of the present invention has high stretch elongation and excellent extensibility. Therefore, as long as the PVA film of the present invention is used for a raw material film, an optical film such as a polarizing film having excellent optical properties can be manufactured with good productivity. Moreover, according to the manufacturing method of the PVA film of this invention, the said PVA film can be manufactured continuously smoothly.
以下,對於本發明具體地說明。 Hereinafter, the present invention will be specifically described.
〔PVA薄膜〕 〔PVA film〕
本發明的PVA薄膜,在相對於其薄膜面,利用由垂直的方向朝薄膜之寬度方向傾斜的方向之入射光,測定該PVA薄膜之各面的折射率,於將一面之折射率當作為A,將另一面之折射率當作為B時(其中,A≧B),A為1.524以上1.530以下。 In the PVA film of the present invention, the refractive index of each side of the PVA film is measured using incident light in a direction inclined from the vertical direction to the width direction of the film with respect to the film surface, and the refractive index of one side is taken as A When the refractive index of the other surface is taken as B (where A ≧ B), A is 1.524 or more and 1.530 or less.
A小於1.524時,有皺摺容易產生於PVA薄膜的問題。又,A超過1.530時,有延伸性下降的問題。本發明並沒有特別限定,但作為A對延伸性造成影響的理由,被認為如下述。亦即,PVA薄膜之延伸性,相較於PVA薄膜之厚度方向中心部的折射率,表面的折射率之關聯性較高,而且相較於相對於PVA薄膜之薄膜面,利用由垂直的方向朝薄膜之流動方向(MD)傾斜的方向之入射光測定的折射率,相對於薄膜面,利用由垂直的方向朝薄膜之寬度方向(TD)傾斜的方向之入射光測定的折射率之關聯性較高,PVA薄膜之斷裂成為破壞薄膜之表面部的起點而產生,然後該影響係因為折射率高的面更大所致。 When A is less than 1.524, there is a problem that wrinkles are easily generated in the PVA film. In addition, when A exceeds 1.530, there is a problem that the extensibility decreases. The present invention is not particularly limited, but the reason why A affects extensibility is considered as follows. That is, the extensibility of the PVA film is higher than the refractive index of the central portion of the PVA film in the thickness direction, and the correlation of the refractive index of the surface is higher, and compared with the film surface of the PVA film, the vertical direction is used. Relativity of refractive index measured with incident light inclined in the direction of flow (MD) of the film with respect to the film surface using incident light inclined in the direction perpendicular to the film's width direction (TD) The higher the breakage of the PVA film is, the more the starting point of the surface portion of the film is destroyed. Then, the effect is caused by the larger refractive index surface.
從如上述的觀點,A超過1.524較佳,1.526以上更佳,超過1.526特佳,1.527以上進一步更佳,超過1.527最佳,而且,小於1.530較佳,1.529以下更佳。 From the viewpoints described above, A is preferably more than 1.524, more preferably 1.526 or more, particularly preferably more than 1.526, more preferably 1.527 or more, most preferably more than 1.527, and more preferably less than 1.530, and more preferably 1.529 or less.
再者,A及B,可使用稜鏡偶合裝置,基於波 長532nm之雷射光而以測定值形式求出。在此,相對於PVA薄膜之薄膜面,利用由垂直的方向朝薄膜之寬度方向傾斜的方向之入射光,係為使該入射光相對於薄膜面投影於垂直方向之際,其方向成為與PVA薄膜之寬度方向(TD)平行(與PVA薄膜之長度方向(MD)垂直)的方向之入射光,可藉由上述稜鏡偶合裝置之稜鏡得到。A及B,具體而言,在實施例中可利用後述的方法測定。 Furthermore, A and B can use a 稜鏡 coupling device, based on the wave Laser light having a length of 532 nm was obtained as a measured value. Here, with respect to the film surface of the PVA film, the incident light in a direction inclined from the vertical direction to the width direction of the film is used so that when the incident light is projected in a vertical direction with respect to the film surface, the direction is the same as that of the PVA. The incident light in a direction in which the width direction (TD) of the film is parallel (perpendicular to the length direction (MD) of the PVA film) can be obtained by using the above-mentioned 稜鏡 coupling device. A and B are specifically measured by the method mentioned later in an Example.
本發明的PVA薄膜中,A+B為3.050以上較佳,3.055以上更佳,3.057以上特佳,又,3.060以下較佳,3.059以下更佳,3.058以下特佳。根據A+B為上述下限以上,可更有效地抑制PVA薄膜的皺摺之產生。另一方面,根據A+B為上述上限以下,可進一步提升延伸性。 In the PVA film of the present invention, A + B is preferably 3.050 or more, more preferably 3.055 or more, particularly preferably 3.057 or more, and preferably 3.060 or less, more preferably 3.059 or less, and particularly preferably 3.058 or less. When A + B is at least the above lower limit, the occurrence of wrinkles in the PVA film can be more effectively suppressed. On the other hand, if A + B is equal to or less than the above upper limit, the extensibility can be further improved.
作為形成本發明的PVA薄膜之PVA,例如,可舉出將聚合乙烯酯得到之聚乙烯酯皂化而得到的PVA、在PVA之主鏈使共聚單體接枝共聚合的改性PVA、藉由將使乙烯酯與共聚單體共聚合的改性聚乙烯酯皂化而製造的改性PVA、將未改性PVA或改性PVA之羥基的一部分以甲醛、丁醛、苯甲醛等之醛類予以交聯之所謂的聚乙烯縮醛等。 Examples of the PVA forming the PVA film of the present invention include PVA obtained by saponifying a polyvinyl ester obtained by polymerizing vinyl esters, modified PVA graft-copolymerized with a comonomer in the main chain of PVA, and Modified PVA manufactured by saponifying a modified polyvinyl ester copolymerized with a vinyl ester and a comonomer, and unmodified PVA or a part of the hydroxyl groups of the modified PVA are provided with aldehydes such as formaldehyde, butyraldehyde, benzaldehyde, and the like. Cross-linked so-called polyvinyl acetals and the like.
形成本發明的PVA薄膜之PVA為改性PVA時,PVA之改性量為15莫耳%以下較佳,5莫耳%以下更佳。 When the PVA forming the PVA film of the present invention is a modified PVA, the modified amount of PVA is preferably 15 mol% or less, and more preferably 5 mol% or less.
作為在PVA之製造時所使用的前述乙烯酯,例如,可舉出甲酸乙烯酯、乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、三甲基乙酸乙烯酯、新癸酸乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯、苯甲酸乙烯酯等。該等之乙 烯酯,可單獨使用1種、或組合2種以上而使用。該等之乙烯酯之中,從生產性之觀點,乙酸乙烯酯較佳。 Examples of the vinyl ester used in the production of PVA include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, trimethyl vinyl acetate, vinyl neodecanoate, and laurel. Acid vinyl ester, vinyl stearate, vinyl benzoate and the like. The other The ene ester can be used singly or in combination of two or more kinds. Among these vinyl esters, vinyl acetate is preferred from the viewpoint of productivity.
又,作為前述的共聚單體,例如,可舉出乙烯、丙烯、1-丁烯、異丁烯等之碳數2~30的烯烴類(α-烯烴等);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、丙烯酸十八酯等之丙烯酸酯類(例如,丙烯酸之碳數1~18的烷酯);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、甲基丙烯酸十八酯等之甲基丙烯酸酯類(例如,甲基丙烯酸之碳數1~18的烷酯);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、丙烯醯胺丙基二甲胺或其鹽、N-羥甲基丙烯醯胺或其衍生物等之丙烯醯胺衍生物;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胺或其鹽、N-羥甲基甲基丙烯醯胺或其衍生物等之甲基丙烯醯胺衍生物;N-乙烯甲醯胺、N-乙烯乙醯胺、N-乙烯吡咯啶酮等之N-乙烯醯胺類;甲基乙烯醚、乙基乙烯醚、正丙基乙烯醚、異丙基乙烯醚、正丁基乙烯醚、異丁基乙烯醚、第三丁基乙烯醚、十二基乙烯醚、硬脂基乙烯醚等之乙烯醚類;丙烯腈、甲基丙烯腈等之 腈類;氯乙烯、偏二氯乙烯、氟乙烯、偏二氟乙烯等之鹵化乙烯類;乙酸烯丙酯、烯丙氯等之烯丙化合物;馬來酸、衣康酸等之不飽和二羧酸、其鹽或其酯等之衍生物;乙烯三甲氧矽烷等之乙烯矽基化合物;乙酸異丙烯酯;不飽和磺酸或其衍生物等。該等之中,尤以α-烯烴較佳,特別是乙烯較佳。 Examples of the comonomer include olefins (α-olefins, etc.) having 2 to 30 carbon atoms, such as ethylene, propylene, 1-butene, and isobutylene; acrylic acid or a salt thereof; methyl acrylate, Acrylic acid such as ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, third butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, stearyl acrylate, etc. Esters (for example, alkyl esters of 1 to 18 carbon atoms of acrylic acid); methacrylic acid or its salts; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, Methacrylic acid such as n-butyl methacrylate, isobutyl methacrylate, third butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, stearyl methacrylate, etc. Esters (for example, alkyl esters of methacrylic acid having 1 to 18 carbons); acrylamide; N-methacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, Diacetone acrylamide, acrylamide propanesulfonic acid or its salt, acrylamide propyldimethylamine or its salt, N-hydroxymethyl Acrylamide derivatives of methacrylamide or derivatives thereof; methacrylamide; N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamine propanesulfonic acid Or a salt thereof, methacrylamide propyl dimethylamine or a salt thereof, a methacrylamide derivative such as N-methylolmethacrylamide or a derivative thereof; N-vinylmethaneamine, N -N-vinylamines such as ethylene acetamide, N-vinyl pyrrolidone; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isopropyl Vinyl ethers such as butyl vinyl ether, tertiary butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether, etc .; acrylonitrile, methacrylonitrile, etc. Nitriles; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride; allyl compounds such as allyl acetate, allyl chloride; unsaturated dicarboxylic acids such as maleic acid and itaconic acid Derivatives of carboxylic acids, their salts or their esters; vinyl silyl compounds such as ethylene trimethoxysilane; isopropenyl acetate; unsaturated sulfonic acids or their derivatives, etc. Of these, α-olefins are particularly preferred, and ethylene is particularly preferred.
從得到之偏光薄膜的偏光性能及耐久性等之觀點,形成本發明的PVA薄膜之PVA的平均聚合度為1500以上較佳,1700以上更佳,2000以上特佳。另一方面,從均質的PVA薄膜之製造的容易性、延伸性等之觀點,PVA的平均聚合度之上限為8000以下較佳,特別是6000以下較佳。 From the viewpoint of the polarization performance and durability of the obtained polarizing film, the average degree of polymerization of the PVA forming the PVA film of the present invention is preferably 1500 or more, more preferably 1700 or more, and particularly preferably 2000 or more. On the other hand, the upper limit of the average degree of polymerization of the PVA is preferably 8,000 or less, and particularly preferably 6000 or less, from the viewpoints of ease of production and extensibility of a homogeneous PVA film.
在此,本說明書的PVA之「平均聚合度」係指依據JIS K6726-1994測定的平均聚合度,可自將PVA再皂化,於精製後,在30℃之水中測定的極限黏度而求出。 Here, the "average degree of polymerization" of PVA in the present specification refers to the average degree of polymerization measured in accordance with JIS K6726-1994, which can be determined from the limiting viscosity measured after re-saponification of PVA in 30 ° C water.
從使用得到的PVA薄膜製造之偏光薄膜的耐水性之觀點,上述PVA的皂化度為98.0莫耳%以上較佳,98.5莫耳%以上更佳,99.0莫耳%以上特佳。皂化度小於98.0莫耳%時,有得到的偏光薄膜之耐水性變差的傾向。再者,本說明書的PVA之皂化度係指PVA具有之相對於利用皂化變換為乙烯醇單元而得到之結構單元(典型而言為乙烯酯單元)與乙烯醇單元之合計莫耳數,該乙烯醇單元之莫耳數所佔的比例(莫耳%)。皂化度,可依據JIS K6726-1994之記載進行測定。 From the viewpoint of the water resistance of the polarizing film produced using the obtained PVA film, the saponification degree of the PVA is preferably 98.0 mol% or more, more preferably 98.5 mol% or more, and particularly preferably 99.0 mol% or more. When the degree of saponification is less than 98.0 mol%, the water resistance of the obtained polarizing film tends to deteriorate. In addition, the degree of saponification of PVA in this specification refers to the total number of moles of structural units (typically vinyl ester units) and vinyl alcohol units that PVA has relative to vinyl alcohol units obtained by saponification conversion. The proportion of moles of alcohol units (mole%). The degree of saponification can be measured in accordance with JIS K6726-1994.
本發明的PVA薄膜包含可塑劑較佳。藉由包 含可塑劑,可進一步提升延伸性。可塑劑,只要在用以製膜PVA薄膜的製膜原液之製備時摻合即可,如前述進行的話,可促進PVA對液體媒體之溶解或熔融,而且提升薄膜製造時之步驟通過性。 The PVA film of the present invention preferably contains a plasticizer. By package Contains plasticizer to further improve elongation. The plasticizer may be blended during the preparation of the film forming stock solution used to form the PVA film. As described above, it can promote the dissolution or melting of PVA to the liquid medium, and improve the passability of the steps in film production.
作為可塑劑,宜使用多元醇。作為該多元醇,例如,可舉出乙二醇、丙三醇、二丙三醇、丙二醇、二乙二醇、三乙二醇、四乙二醇、三羥甲基丙烷等。可塑劑,可單獨使用1種、或合併使用2種以上。該等之中,從延伸性之提升效果佳的觀點,丙三醇較佳。 As the plasticizer, a polyhydric alcohol is preferably used. Examples of the polyhydric alcohol include ethylene glycol, glycerol, diglycerol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and trimethylolpropane. The plasticizer may be used alone or in combination of two or more. Among these, glycerin is preferred from the standpoint of good elongation improvement effect.
可塑劑之含量,相對於PVA 100質量份而為0質量份以上30質量份以下較佳,3質量份以上25質量份以下更佳,5質量份以上20質量份以下特佳。根據可塑劑之含量為上述上限以下,可提升得到的PVA薄膜之處理性。 The content of the plasticizer is preferably 0 to 30 parts by mass relative to 100 parts by mass of PVA, more preferably 3 to 25 parts by mass, and even more preferably 5 to 20 parts by mass. When the content of the plasticizer is below the above upper limit, the rationality of the obtained PVA film can be improved.
本發明的PVA薄膜包含界面活性劑較佳。藉由包含界面活性劑,可提升PVA薄膜之處理性。界面活性劑,只要在用以製膜PVA薄膜的製膜原液之製備時摻合即可,如前述進行的話,可提升自製造PVA薄膜之際的乾燥輥之剝離性。 The PVA film of the present invention preferably contains a surfactant. By including a surfactant, the rationality of the PVA film can be improved. The surfactant may be blended during the preparation of the film-forming dope used to form the PVA film. As described above, the peelability of the drying roller during the production of the PVA film can be improved.
界面活性劑之種類沒有特別限制,宜使用陰離子系界面活性劑或非離子系界面活性劑等。 The type of the surfactant is not particularly limited, and an anionic surfactant or a nonionic surfactant is preferably used.
作為陰離子性界面活性劑,例如,可舉出月桂酸鉀等之羧酸型、硫酸辛酯等之硫酸酯型、苯磺酸十二酯等之磺酸型等。 Examples of the anionic surfactant include a carboxylic acid type such as potassium laurate, a sulfate type such as octyl sulfate, and a sulfonic acid type such as dodecylbenzenesulfonate.
又,作為非離子性界面活性劑,例如,可舉出聚氧乙烯油醚等之烷醚型、聚氧乙烯辛基苯醚等之烷基苯醚 型、聚氧乙烯月桂酸酯等之烷酯型、聚氧乙烯月桂基胺醚等之烷胺型、聚氧乙烯月桂酸醯胺等之烷基醯胺型、聚氧乙烯聚氧丙烯醚等之聚丙二醇醚型、月桂酸二乙醇醯胺、油酸二乙醇醯胺等之烷醇醯胺型、聚氧烷烯丙基苯醚等之烯丙基苯醚型等。界面活性劑可單獨使用1種,亦可合併使用2種以上。 Examples of the nonionic surfactant include alkyl ether types such as polyoxyethylene oleyl ether, and alkylphenyl ethers such as polyoxyethylene octylphenyl ether. Type, alkyl ester type such as polyoxyethylene laurate, alkylamine type such as polyoxyethylene lauryl ether, alkylamine type such as polyoxyethylene laurate, polyoxyethylene polyoxypropylene ether, etc. Polypropylene glycol ether type, alkanolamine type such as diethanolammonium laurate, diethanolamide oleate, and allylphenyl ether type such as polyoxyalkylallyl phenyl ether. The surfactant may be used singly or in combination of two or more kinds.
界面活性劑的含量,相對於PVA 100質量份而為0.01質量份以上1質量份以下較佳,0.02質量份以上0.5質量份以下更佳,0.05質量份以上0.3質量份以下特佳。根據界面活性劑之含量為上述下限以上,可提升製膜性或剝離性。另一方面,根據界面活性劑之含量為上述上限以下,可提升得到的PVA薄膜之處理性。 The content of the surfactant is preferably 0.01 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of PVA, more preferably 0.02 parts by mass or more and 0.5 parts by mass or less, and particularly preferably 0.05 parts by mass or more and 0.3 parts by mass or less. When the content of the surfactant is greater than or equal to the above-mentioned lower limit, film-forming properties or peeling properties can be improved. On the other hand, according to the content of the surfactant being below the above upper limit, the rationality of the obtained PVA film can be improved.
本發明的PVA薄膜,可包含上述PVA、可塑劑及界面活性劑以外之其他的成分,例如,安定化劑(抗氧化劑、紫外線吸收劑、熱安定劑等)、相溶化劑、抗結塊劑、阻燃劑、抗靜電劑、滑劑、分散劑、流動化劑、抗菌劑等。該等之其他的成分,可單獨使用1種,亦可合併使用2種以上。 The PVA film of the present invention may contain components other than the above-mentioned PVA, plasticizer, and surfactant, such as stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), compatibilizers, and anticaking agents. , Flame retardant, antistatic agent, slip agent, dispersant, fluidizer, antibacterial agent, etc. These other components may be used alone or in combination of two or more.
PVA薄膜的厚度沒有特別限制,例如,可定為100μm以下,甚至80μm以下。又,該厚度,可定為10μm以上,甚至20μm以上,亦可為超過50μm的厚度。 The thickness of the PVA film is not particularly limited, and may be set to 100 μm or less, or even 80 μm or less, for example. The thickness may be set to be 10 μm or more, or even 20 μm or more, and may be more than 50 μm.
PVA薄膜之寬度沒有特別限制,但因為近年來液晶電視或監視器發展大畫面化,所以為了可有效地用於該等,寬度為2m以上較佳,3m以上更佳,4m以上特佳。又,在工業上製造偏光薄膜時,薄膜之寬度變得過 廣的話,均勻的單軸延伸變困難,因此PVA薄膜之寬度為8m以下較佳。 The width of the PVA film is not particularly limited, but in recent years, as LCD televisions or monitors have developed large screens, in order to be effectively used in these, a width of 2 m or more is preferred, 3 m or more is preferred, and 4 m or more is particularly preferred. When industrially manufacturing a polarizing film, the width of the film becomes excessive. If it is wide, uniform uniaxial extension becomes difficult, so the width of the PVA film is preferably 8 m or less.
PVA薄膜之形狀沒有特別限制,但從可連續製造更均勻的PVA薄膜,同時在使用其而製造偏光薄膜的情況等中也可連續使用之觀點,長條形的薄膜較佳。長條形的薄膜之長度(流動方向之長度)沒有特別限制,可因應用途等而適當設定,例如,可定為5m以上20,000m以下之範圍內。 The shape of the PVA film is not particularly limited, but from the viewpoint that a more uniform PVA film can be continuously produced, and a polarizing film can also be continuously used, the long film is preferred. The length (length in the direction of flow) of the elongated film is not particularly limited and can be appropriately set depending on the application and the like. For example, it can be set to a range of 5 m to 20,000 m.
本發明的PVA薄膜,其質量膨潤度為150%以上250%以下較佳,160%以上240%以下更佳,170%以上230%以下特佳。根據質量膨潤度為上述下限以上,可進一步提升延伸性。另一方面,根據質量膨潤度為上述上限以下,可提升延伸時之步驟通過性,而且,可提升得到的偏光薄膜之耐久性。 The PVA film of the present invention preferably has a mass swelling degree of 150% to 250%, more preferably 160% to 240%, and particularly preferably 170% to 230%. According to the mass swelling degree, the extensibility can be further improved by being above the lower limit. On the other hand, according to the mass swelling degree being equal to or lower than the above-mentioned upper limit, it is possible to improve the passability of the step at the time of stretching, and also to improve the durability of the obtained polarizing film.
再者,本說明書所謂之質量膨潤度,意指將在30℃的蒸餾水中浸漬PVA薄膜30分鐘之際的質量,除以將前述浸漬後之PVA薄膜在105℃乾燥16小時後的質量而得到的數值之百分率。PVA薄膜之膨潤度,可藉由增強熱處理之條件而使其下降。 The term “mass swelling degree” as used in this specification refers to the mass obtained by immersing a PVA film in distilled water at 30 ° C. for 30 minutes, divided by the mass obtained by drying the PVA film after the impregnation at 105 ° C. for 16 hours. The percentage of the value. The swelling degree of PVA film can be reduced by enhancing the conditions of heat treatment.
〔PVA薄膜之製造方法〕 [Manufacturing method of PVA film]
用以製造本發明的PVA薄膜之方法沒有特別限制,但根據以下之本發明的製造方法,可順暢地連續製造上述本發明的PVA薄膜而較佳。 The method for manufacturing the PVA film of the present invention is not particularly limited, but according to the following manufacturing method of the present invention, it is preferable that the PVA film of the present invention described above can be smoothly and continuously manufactured.
亦即,用以製造PVA薄膜之本發明的方法為一種製造方法,使用具備旋轉軸相互平行的乾燥輥(由最 上游側朝向下游側,依序稱為第1乾燥輥、第2乾燥輥···)與熱處理輥之製膜裝置,在該乾燥輥中之位於最上游側的第1乾燥輥上,將包含PVA的製膜原液吐出為膜狀並進行部分乾燥後,接著,以第2乾燥輥以後的乾燥輥進一步進行乾燥,之後,以多個熱處理輥進行熱處理而製造PVA薄膜,在此,使該熱處理輥中的位於最下游側的熱處理輥(Y)之圓周速度(SY)相對於位於最上游側之熱處理輥(X)的圓周速度(SX)的比(SY/SX)成為0.993以上0.997以下。 That is, the method of the present invention for manufacturing a PVA film is a manufacturing method using drying rollers having rotation axes parallel to each other (from the most upstream side to the downstream side, and are sequentially referred to as a first drying roller and a second drying roller. ··) Film forming device with heat treatment roller, on the first drying roller on the most upstream side among the drying rollers, the film-forming dope containing PVA is discharged into a film shape and partially dried, and then the second The drying rollers subsequent to the drying roller are further dried, and thereafter, a plurality of heat treatment rollers are subjected to heat treatment to produce a PVA film. Here, the peripheral speed (S Y ) of the heat treatment roller (Y) located on the most downstream side among the heat treatment rollers is made. The ratio (S Y / S X ) to the peripheral speed (S X ) of the heat treatment roll (X) located on the most upstream side is 0.993 or more and 0.997 or less.
用以製造PVA薄膜之本發明的方法中,使用具備旋轉軸相互平行的乾燥輥與熱處理輥之製膜裝置,在該乾燥輥中之位於最上游側的第1乾燥輥上,將包含PVA的製膜原液吐出為膜狀並進行部分乾燥後,接著,以第2乾燥輥以後的乾燥輥進一步進行乾燥,之後,以多個熱處理輥進行熱處理而製造PVA薄膜。該製膜裝置中,乾燥輥之數目為4個以上較佳,5個以上更佳,6~30個特佳。 In the method of the present invention for producing a PVA film, a film forming apparatus including a drying roll and a heat treatment roll having rotation axes parallel to each other is used. On the first drying roll on the most upstream side of the drying roll, a PVA-containing After the film-forming stock solution is discharged into a film shape and partially dried, it is further dried with a drying roller subsequent to the second drying roller, and then heat-treated with a plurality of heat-treatment rollers to produce a PVA film. In the film forming device, the number of the drying rollers is preferably 4 or more, more preferably 5 or more, and particularly preferably 6 to 30.
乾燥輥及/或熱處理輥,例如,由鎳、鉻、銅、鐵、不銹鋼等之金屬形成較佳,特別是輥的表面,由不容易腐蝕,而且具有鏡面光澤的金屬材料形成更佳。又,為了提高乾燥輥及/或熱處理輥之耐久性,將電鍍單層或組合2層以上鎳層、鉻層、鎳/鉻合金層等之輥當作為乾燥輥及/或熱處理輥而使用較佳。 The drying roll and / or the heat-treating roll, for example, are preferably formed of a metal such as nickel, chromium, copper, iron, stainless steel, etc. In particular, the surface of the roll is more preferably formed of a metal material that is not easily corroded and has a mirror gloss. In addition, in order to improve the durability of the drying roller and / or the heat-treating roller, a single-layer or a combination of two or more nickel, chromium, and nickel / chromium alloy layers are used as the drying roller and / or the heat-treating roller. good.
上述的製膜裝置,除了乾燥輥及熱處理輥以外,視需要亦可進一步具有熱風爐式之熱風乾燥裝置、 熱風爐式之熱處理裝置、調濕裝置等。 In addition to the drying roll and the heat-treating roll, the above-mentioned film forming device may further include a hot-air furnace type hot-air drying device, Hot air furnace type heat treatment device, humidity control device, etc.
關於將由第1乾燥輥到達最終乾燥輥之過程的薄膜乾燥之際的加熱方向,從可更均勻地乾燥薄膜之觀點,在薄膜之任意的部分中,使與第1乾燥輥接觸的膜面(以下有時稱為「第1乾燥輥接觸面」)、及沒有與第1乾燥輥接觸的膜面(以下有時稱為「第1乾燥輥非接觸面」)與由第1乾燥輥至最終乾燥輥為止的各乾燥輥交互地相對向而進行乾燥較佳。 Regarding the heating direction when the film is dried from the first drying roller to the final drying roller, from the viewpoint that the film can be dried more uniformly, the film surface in contact with the first drying roller in any part of the film ( Hereinafter, it is sometimes referred to as "the first drying roller contact surface"), and the film surface that is not in contact with the first drying roller (hereinafter sometimes referred to as the "first drying roller non-contact surface") and the first drying roller to the final It is preferable that the drying rollers up to the drying rollers alternately face each other and dry.
在製膜裝置的第1乾燥輥上將包含PVA的製膜原液吐出為膜狀時,例如,使用T型縫模、料斗板、I-模、唇嘴塗布機模等之已知的膜狀吐出裝置(膜狀流延裝置),將包含PVA的製膜原液在第1乾燥輥上吐出(流延)為膜狀即可。 When the film-forming stock solution containing PVA is discharged into a film form on the first drying roll of a film forming apparatus, for example, a known film form such as a T-slot die, a hopper plate, an I-die, and a lip nozzle applicator is used. The discharge device (film-like casting device) may discharge (cast) the film-forming stock solution containing PVA into a film shape on a first drying roll.
作為包含PVA的製膜原液,可藉由將PVA與液體媒體混合而作成為溶液、將包含液體媒體等之PVA丸粒熔融而作成為熔融液等而製備。PVA對液體媒體之溶解、或包含液體媒體等之PVA丸粒的熔融,可使用攪拌式混合裝置、熔融擠製機等進行。作為此時使用的液體媒體,例如,可舉出水、二甲亞碸、二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯啶酮、乙二胺、二乙三胺等,該等之液體媒體,可單獨使用1種,或者亦可合併使用2種以上。該等之中,宜使用水、二甲亞碸、或兩者之混合物,且尤能適用水。 The film-forming dope containing PVA can be prepared by mixing PVA with a liquid medium as a solution, and melting PVA pellets containing a liquid medium or the like into a molten liquid. The dissolution of PVA into a liquid medium or the melting of PVA pellets including a liquid medium can be performed using a stirring type mixing device, a melt extruder, or the like. Examples of the liquid medium used at this time include water, dimethylformamide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylenediamine, and diethylenetriamine. These liquid media can be used alone or in combination of two or more. Among these, water, dimethylarsin, or a mixture of the two is preferably used, and water is particularly applicable.
製膜原液中,視所需在PVA薄膜之說明中如上述之以上述量摻合可塑劑、界面活性劑、其他的成分 等之1種或2種以上較佳。 In the film-forming dope, if necessary, in the description of the PVA film, the plasticizer, the surfactant, and other components are blended in the above-mentioned amounts as described above. One or more of them are preferable.
使用於PVA薄膜之製造的製膜原液之揮發分率為50質量%以上90質量%以下較佳,60質量%以上75質量%以下更佳。根據製膜原液之揮發分率為上述下限以上,可將製膜原液之黏度維持為低,且過濾或脫泡變容易,製膜本身也變容易。另一方面,根據製膜原液之揮發分率為上述上限以下,可防止製膜原液之黏度變得過低,且提升得到的PVA薄膜之厚度均勻性。 The volatile content of the film-forming dope used in the production of a PVA film is preferably 50% by mass to 90% by mass, and more preferably 60% by mass to 75% by mass. According to the volatile content of the film-forming dope, the viscosity of the film-forming dope can be kept low, and filtration or defoaming becomes easier, and the film-making itself becomes easier. On the other hand, according to the volatile content of the film-forming solution, the viscosity of the film-forming solution can be prevented from becoming too low, and the thickness uniformity of the obtained PVA film can be improved.
第1乾燥輥之表面溫度沒有特別限制,但從薄膜之乾燥的均勻性、生產性等之觀點,80℃以上99℃以下較佳,85℃以上99℃以下更佳,90℃以上98℃以下特佳。根據第1乾燥輥之表面溫度為99℃以下,可更有效地防止製膜原液在第1乾燥輥上發泡。另一方面,根據第1乾燥輥之表面溫度為80℃以上,可提升自第1乾燥輥之剝離性。 The surface temperature of the first drying roller is not particularly limited, but from the viewpoint of uniformity and productivity of the drying of the film, 80 ° C to 99 ° C is preferred, 85 ° C to 99 ° C is more preferred, and 90 ° C to 98 ° C is preferred. Extraordinary. Since the surface temperature of the first drying roller is 99 ° C. or lower, it is possible to more effectively prevent the film-forming dope from foaming on the first drying roller. On the other hand, when the surface temperature of the first drying roll is 80 ° C. or higher, the peelability from the first drying roll can be improved.
在吐出為膜狀之製膜原液的第1乾燥輥上之乾燥,可僅進行來自第1乾燥輥之加熱,但從乾燥之均勻性、或乾燥速度等之觀點,亦與採用第1乾燥輥加熱的同時,一起針對第1乾燥輥非接觸面噴吹熱風,自薄膜之兩面賦予熱而進行乾燥較佳。 The drying on the first drying roller that discharges the film-forming film-forming solution can be performed by heating only from the first drying roller. However, from the viewpoint of uniformity of drying and drying speed, it is also the same as using the first drying roller. While heating, it is preferable to blow hot air against the non-contact surface of the first drying roll together, and apply heat from both sides of the film to dry.
在位於第1乾燥輥上的薄膜之第1乾燥輥非接觸面噴吹熱風時,從進一步提升得到的PVA薄膜之延伸性的觀點,相對於第1乾燥輥非接觸面之全部區域噴吹風速1~10m/秒之熱風較佳,噴吹風速2~8m/秒之熱風更佳,噴吹風速3~8m/秒之熱風特佳。在第1乾燥輥非接觸面噴 吹的熱風之風速過小時,在第1乾燥輥上之乾燥時產生水蒸氣等之凝結,且其水滴滴落於薄膜,最終得到的PVA薄膜有容易產生缺陷的可能。另一方面,在第1乾燥輥非接觸面噴吹的熱風之風速過大時,在最後得到的PVA薄膜產生厚度不均,且伴隨前述變得容易產生染色不均之產生等之問題。 When the hot air is sprayed on the non-contact surface of the first drying roller of the film on the first drying roller, from the viewpoint of further improving the stretchability of the PVA film obtained, the blowing speed is relative to the entire area of the non-contact surface of the first drying roller. Hot air with a speed of 1 ~ 10m / s is better, hot air with a speed of 2 ~ 8m / s is better, and hot air with a speed of 3 ~ 8m / s is particularly good. Spray on the non-contact surface of the first drying roller When the wind speed of the hot wind is too small, condensation of water vapor and the like occurs during drying on the first drying roller, and water droplets drip on the film, and the resulting PVA film may be prone to defects. On the other hand, when the wind speed of the hot air sprayed from the non-contact surface of the first drying roll is too large, the thickness of the PVA film finally obtained is uneven, and the problems of uneven dyeing and the like are likely to occur with the foregoing.
從乾燥效率、乾燥的均勻性等之觀點,在薄膜之第1乾燥輥非接觸面噴吹的熱風之溫度為50℃以上99℃以下較佳,70℃以上98℃以下更佳,80℃以上95℃以下特佳。又,在薄膜之第1乾燥輥非接觸面噴吹的熱風之露點溫度為10℃以上15℃以下較佳。 From the viewpoints of drying efficiency and drying uniformity, the temperature of the hot air sprayed on the non-contact surface of the first drying roll of the film is preferably 50 ° C or higher and 99 ° C or lower, more preferably 70 ° C or higher and 98 ° C or lower, and 80 ° C or higher. Particularly preferred below 95 ° C. The dew point temperature of the hot air sprayed on the non-contact surface of the first drying roll of the film is preferably 10 ° C or higher and 15 ° C or lower.
用以在薄膜之第1乾燥輥非接觸面噴吹熱風的方式並沒有特別限制,可採用任何可將風速或溫度均勻的熱風噴吹於薄膜的第1乾燥輥非接觸面,較佳為在其整體均勻地噴吹的方式,其中,宜採用噴嘴方式、整流板方式或組合該等之方式等。對於薄膜的第1乾燥輥非接觸面之熱風的噴吹方向,可為與第1乾燥輥非接觸面相對向的方向,亦可為幾乎沿著薄膜的第1乾燥輥非接觸面之圓周形狀的方向(幾乎沿著第1乾燥輥的輥表面之圓周的方向),或者也可為前述以外的方向。 The method for blowing hot air on the non-contact surface of the first drying roller of the film is not particularly limited, and any hot air with uniform wind speed or temperature can be sprayed on the non-contact surface of the first drying roller of the film, preferably on the non-contact surface of the first drying roller of the film. As a method of uniformly blowing the whole, a nozzle method, a rectifying plate method, or a combination of these methods is preferable. The blowing direction of the hot air on the non-contact surface of the first drying roller of the film may be a direction opposite to the non-contact surface of the first drying roller, or may be a circumferential shape almost along the non-contact surface of the first drying roller of the film. The direction (a direction almost along the circumference of the roll surface of the first drying roll) or a direction other than the above may be used.
又,在第1乾燥輥上的薄膜之乾燥時,根據乾燥將自薄膜產生的揮發分與噴吹後的熱風予以排氣較佳。排氣的方法並沒有特別限制,但採用不會在薄膜的第1乾燥輥非接觸面產生噴吹的熱風之風速不均以及溫度不均的排氣方法較佳。 When drying the film on the first drying roller, it is preferable to exhaust the volatiles generated from the film and the hot air after blowing according to the drying. The method of exhausting is not particularly limited, but it is preferable to adopt an exhaust method that does not cause uneven wind speed and uneven temperature of the hot air that is not blown on the non-contact surface of the first drying roll of the film.
從乾燥之均勻性、乾燥速度及PVA薄膜的生產性等之觀點,第1乾燥輥的圓周速度(S1)為5m/分以上50m/分以下較佳,10m/分以上45m/分以下更佳,15m/分以上40m/分以下特佳。第1乾燥輥的圓周速度(S1)為上述下限以上時,可使折射率的數值下降。另一方面,第1乾燥輥的圓周速度(S1)為上述上限以下時,可提升得到的PVA薄膜之厚度的均勻性。 From the viewpoints of uniformity of drying, drying speed, and productivity of the PVA film, the peripheral speed (S 1 ) of the first drying roller is preferably 5 m / min or more and 50 m / min or less, and more preferably 10 m / min or more and 45 m / min or less. Good, 15m / min or more and 40m / min or less are particularly good. When the peripheral speed (S 1 ) of the first drying roller is equal to or more than the above lower limit, the value of the refractive index can be reduced. On the other hand, when the peripheral speed (S 1 ) of the first drying roller is equal to or lower than the above-mentioned upper limit, the thickness uniformity of the obtained PVA film can be improved.
在第1乾燥輥上吐出為膜狀之製膜原液,在第1乾燥輥上進行乾燥,在薄膜之揮發分率(自第1乾燥輥之剝離時的薄膜之揮發分率),較佳成為17質量%以上30質量%以下,更佳成為17質量%以上29質量%以下,特佳成為18質量%以上28質量%以下時,可自第1乾燥輥剝離。 The film-forming dope is discharged on the first drying roll, and dried on the first drying roll. The volatile content of the film (the volatile content of the film when peeled from the first drying roll) is preferably When it is 17% by mass or more and 30% by mass or less, more preferably 17% by mass or more and 29% by mass or less, and particularly preferably 18% by mass or more and 28% by mass or less, it can be peeled off from the first drying roll.
將在第1乾燥輥上乾燥直到較佳為揮發分率17質量%以上30質量%以下的薄膜自第1乾燥輥剝離,接著,使薄膜之第1乾燥輥非接觸面與第2乾燥輥相對向,以第2乾燥輥將薄膜乾燥較佳。 The film is dried on the first drying roller until the film having a volatile content of preferably 17% by mass or more and 30% by mass or less is peeled from the first drying roller, and then the non-contact surface of the first drying roller of the film is opposed to the second drying roller. It is preferred to dry the film with a second drying roller.
第2乾燥輥的圓周速度(S2)相對於第1乾燥輥的圓周速度(S1)之比(S2/S1)為1.000以上1.040以下較佳。根據比(S2/S1)在上述範圍內,可更順暢地製造本發明的PVA薄膜。再者,比(S2/S1)過低時,自第1乾燥輥之薄膜的剝離位置變不均勻,且有寬度方向之雙折射率不均變大的傾向。從如上述的觀點,比(SY/SX)為1.020以上較佳,1.030以上更佳,又,1.038以下較佳。 The ratio (S 2 / S 1 ) of the peripheral speed (S 2 ) of the second drying roller to the peripheral speed (S 1 ) of the first drying roller is preferably 1.000 or more and 1.040 or less. When the ratio (S 2 / S 1 ) is within the above range, the PVA film of the present invention can be produced more smoothly. When the ratio (S 2 / S 1 ) is too low, the peeling position of the film from the first drying roll becomes uneven, and the birefringence unevenness in the width direction tends to become large. From the viewpoint described above, the ratio (S Y / S X ) is preferably 1.020 or more, more preferably 1.030 or more, and still more preferably 1.038 or less.
將以第2乾燥輥乾燥的PVA薄膜,自第2乾燥輥剝離,因應設置於製膜裝置之乾燥輥的數目等,藉由 第3乾燥輥、第4乾燥輥、第5乾燥輥、···等之多個乾燥輥依序乾燥即可。 The PVA film dried by the second drying roller is peeled from the second drying roller, and the number of the drying rollers installed in the film forming apparatus is controlled by A plurality of drying rollers such as a third drying roller, a fourth drying roller, a fifth drying roller, ..., etc. may be sequentially dried.
由第2乾燥輥至最終乾燥輥為止之各乾燥輥的表面溫度為40℃以上較佳,45℃以上更佳,50℃以上特佳,又,小於100℃較佳,98℃以下更佳,96℃以下特佳,亦可小於90℃。 The surface temperature of each drying roller from the second drying roller to the final drying roller is preferably 40 ° C or higher, more preferably 45 ° C or higher, particularly preferably 50 ° C or higher, and preferably less than 100 ° C, and more preferably 98 ° C or lower, It is particularly preferred below 96 ° C, and can also be lower than 90 ° C.
又,從可更順暢地製造本發明的PVA薄膜,而且更有效地防止皺摺之產生等之觀點,最終乾燥輥(位於熱處理輥正前方的乾燥輥)之表面溫度小於60℃較佳,小於57℃更佳。 In addition, from the viewpoint that the PVA film of the present invention can be manufactured more smoothly and the occurrence of wrinkles is more effectively prevented, the surface temperature of the final drying roll (drying roll located directly in front of the heat treatment roll) is preferably less than 60 ° C, and less than 57 ° C is better.
相對於如上述進行經由以乾燥輥之乾燥的薄膜,利用多個熱處理輥實施熱處理。在此,用以製造PVA薄膜之本發明的方法中,使上述多個熱處理輥中的位於最下游側的熱處理輥(Y)之圓周速度(SY)相對於位於最上游側之熱處理輥(X)的圓周速度(SX)的比(SY/SX)成為0.993以上0.997以下。比(SY/SX)超出上述範圍時,變得難以得到本發明的PVA薄膜。從如上述之觀點,比(SY/SX)為0.994以上較佳,0.995以上更佳,又,0.996以下較佳。 The heat treatment is performed using a plurality of heat treatment rollers with respect to the film dried by the drying roller as described above. Here, in the method of the present invention for producing a PVA film, the peripheral speed (S Y ) of the heat-treatment roll (Y) located on the most downstream side among the plurality of heat-treatment rolls described above is made relative to the heat-treatment roll (located on the most upstream side) ( X) The peripheral velocity (S X ) ratio (S Y / S X ) is 0.993 or more and 0.997 or less. When the ratio (S Y / S X ) exceeds the above range, it becomes difficult to obtain the PVA film of the present invention. From the viewpoint described above, the ratio (S Y / S X ) is preferably 0.994 or more, more preferably 0.995 or more, and still more preferably 0.996 or less.
熱處理輥之表面溫度為100℃以上較佳,又,140℃以下較佳,130℃以下更佳,120℃以下特佳。再者,在用以製造PVA薄膜之本發明的方法中,只要將表面溫度為100℃以上的輥當作為熱處理輥,並將表面溫度小於100℃的輥當作為乾燥輥即可。 The surface temperature of the heat-treating roller is preferably 100 ° C or higher, more preferably 140 ° C or lower, more preferably 130 ° C or lower, and particularly preferably 120 ° C or lower. Furthermore, in the method of the present invention for producing a PVA film, a roll having a surface temperature of 100 ° C or higher may be regarded as a heat treatment roll, and a roll having a surface temperature of less than 100 ° C may be regarded as a drying roll.
在用以製造PVA薄膜之本發明的方法中,熱處理輥,可僅存在熱處理輥(X)及熱處理輥(Y)之兩個, 亦可進一步存在其以外的熱處理輥於該等之熱處理輥間,何者均可。 In the method of the present invention for manufacturing a PVA film, the heat treatment roll may include only two heat treatment rolls (X) and heat treatment rolls (Y). There may be other heat treatment rolls among these heat treatment rolls, and any of them may be used.
利用熱處理輥實施熱處理之際的熱處理時間沒有特別限制,但從更有效率地製造本發明的PVA薄膜之觀點,3秒以上較佳,4秒以上更佳,5秒以上特佳,又,120秒以下較佳,90秒以下更佳,60秒以下特佳。 The heat treatment time when heat treatment is performed by a heat treatment roller is not particularly limited, but from the viewpoint of more efficiently manufacturing the PVA film of the present invention, 3 seconds or more is preferable, 4 seconds or more is preferable, 5 seconds or more is particularly preferable, and 120 It is preferably less than 90 seconds, more preferably less than 90 seconds, and particularly preferably less than 60 seconds.
如上述進行而實施熱處理的薄膜,視需要可進一步藉由進行調濕處理、薄膜兩端部(耳部)之切割等,並以最後既定的長度捲取為捲筒狀而得到本發明的PVA薄膜。 The film subjected to the heat treatment as described above may be further subjected to humidity control treatment, cutting at both ends (ear portions) of the film, etc., and wound into a roll shape with a final predetermined length to obtain the PVA of the present invention. film.
藉由上述一連串的處理而最終得到之PVA薄膜的揮發分率在1質量%以上5質量%以下的範圍較佳,在2質量%以上4質量%以下之範圍更佳。 The PVA film finally obtained through the above-mentioned series of treatments preferably has a volatile content ranging from 1% by mass to 5% by mass, and more preferably from 2% by mass to 4% by mass.
〔PVA薄膜之用途〕 〔Application of PVA film〕
本發明的PVA薄膜之用途沒有特別限制,但從本發明的PVA薄膜,其拉伸伸度高且延伸性優異之觀點,當作為偏光薄膜或相位差薄膜等之光學薄膜製造用的原料薄膜來使用較佳。如前述的光學薄膜,例如,可藉由使用本發明的PVA薄膜,實施單軸延伸等之處理而製造。 The application of the PVA film of the present invention is not particularly limited, but from the viewpoint that the PVA film of the present invention has high tensile elongation and excellent extensibility, it is used as a raw material film for producing optical films such as polarizing films and retardation films. Use better. The optical film as described above can be produced, for example, by using the PVA film of the present invention and performing a treatment such as uniaxial stretching.
將本發明的PVA薄膜當作原料薄膜使用而製造偏光薄膜之際的方法沒有特別限制,亦可採用來自以往的任一者之方法。作為如前述的方法,例如,可舉出對於PVA薄膜實施染色及單軸延伸、或對於含有染料的PVA薄膜實施單軸延伸的方法。作為用以製造偏光薄膜之更具體的方法,可舉出對於本發明的PVA薄膜,實施 膨潤、染色、單軸延伸、及視需要進一步實施固定處理、乾燥等之方法。該情況中,膨潤、染色、單軸延伸、固定處理等之各處理的順序沒有特別限制,而可同時進行1個或2個以上的處理,例如,可在單軸延伸之前進行染色,亦可與單軸延伸同時進行染色,也可在單軸延伸之後進行染色。再者,也可將各處理之1個或2個以上進行2次或其以上。 The method for producing a polarizing film by using the PVA film of the present invention as a raw material film is not particularly limited, and any method from the past may be used. Examples of the method described above include a method of dyeing and uniaxially stretching a PVA film, or a method of uniaxially stretching a PVA film containing a dye. As a more specific method for producing a polarizing film, the PVA film of the present invention can be implemented by Methods such as swelling, dyeing, uniaxial stretching, and further carrying out fixing treatment and drying if necessary. In this case, the order of the respective processes such as swelling, dyeing, uniaxial stretching, and fixed processing is not particularly limited, and one or two or more processes may be performed simultaneously. For example, dyeing may be performed before uniaxial stretching, or Dyeing is performed at the same time as uniaxial extension, or dyeing can be performed after uniaxial extension. Furthermore, one or two or more of the processes may be performed twice or more.
膨潤,可藉由將PVA薄膜浸漬於水而進行。作為浸漬於水之際的水之溫度為20℃以上40℃以下的範圍內較佳,22℃以上38℃以下的範圍內更佳,25℃以上35℃以下的範圍內特佳。又,作為浸漬於水的時間,例如,0.1分鐘以上5分鐘以下的範圍內較佳,0.5分鐘以上3分鐘以下的範圍內更佳。再者,浸漬於水之際的水沒有限定於純水,可為溶解有各種成分的水溶液,亦可為水與水性媒體之混合物。 Swelling can be performed by immersing a PVA film in water. The temperature of water when immersed in water is preferably in a range of 20 ° C to 40 ° C, more preferably in a range of 22 ° C to 38 ° C, and particularly preferably in a range of 25 ° C to 35 ° C. The time for immersion in water is, for example, preferably within a range of 0.1 minutes to 5 minutes, and more preferably within a range of 0.5 minutes to 3 minutes. The water to be immersed in water is not limited to pure water, and may be an aqueous solution in which various components are dissolved, or a mixture of water and an aqueous medium.
作為使用於染色的染料,可使用碘系色素或二色性有機染料(例如,DirectBlack 17、19、154;DirectBrown 44、106、195、210、223;DirectRed 2、23、28、31、37、39、79、81、240、242、247;DirectBlue 1、15、22、78、90、98、151、168、202、236、249、270;DirectViolet 9、12、51、98;DirectGreen 1、85;DirectYellow 8、12、44、86、87;DirectOrange 26、39、106、107等之二色性染料)等。該等之染料,可單獨使用1種或組合2種以上而使用。染色,通常可藉由將PVA薄膜浸漬於含有上述染料的溶液(染色浴)中而進行,但 其處理條件或處理方法並沒有特別限制。 As the dye used for dyeing, an iodine-based dye or a dichroic organic dye (for example, DirectBlack 17, 19, 154; DirectBrown 44, 106, 195, 210, 223; DirectRed 2, 23, 28, 31, 37, 39, 79, 81, 240, 242, 247; DirectBlue 1, 15, 22, 78, 90, 98, 151, 168, 202, 236, 249, 270; DirectViolet 9, 12, 51, 98; DirectGreen 1, 85 ; DirectYellow 8, 12, 44, 86, 87; DirectOrange 26, 39, 106, 107 and other dichroic dyes); These dyes can be used alone or in combination of two or more. Dyeing can usually be performed by immersing a PVA film in a solution (dyeing bath) containing the above dye, but The processing conditions or methods are not particularly limited.
使用碘系色素作為染料時,一般將含有碘及碘化鉀的溶液用於染色浴。該情況中,染色浴之碘的濃度為0.01質量%以上0.5質量%以下的範圍內較佳,碘化鉀的濃度為0.01質量%以上10質量%以下的範圍內較佳。又,使用二色性有機染料作為染料時,染色浴之二色性有機染料的濃度為0.1質量%以上5質量%以下的範圍內較佳。染色浴的溫度為20℃以上50℃以下,特別是定為25℃以上40℃以下較佳。 When an iodine-based dye is used as a dye, a solution containing iodine and potassium iodide is generally used in a dyeing bath. In this case, the concentration of iodine in the dyeing bath is preferably in a range of 0.01% by mass to 0.5% by mass, and the concentration of potassium iodide is preferably in a range of 0.01% by mass to 10% by mass. When a dichroic organic dye is used as the dye, the concentration of the dichroic organic dye in the dyeing bath is preferably within a range of 0.1% by mass to 5% by mass. The temperature of the dyeing bath is preferably 20 ° C or higher and 50 ° C or lower, particularly preferably 25 ° C or higher and 40 ° C or lower.
單軸延伸,可以任何濕式延伸法或乾熱延伸法進行。濕式延伸法的情況中,亦可在包含硼酸的水溶液中進行,也可在上述染色浴中或後述之固定處理浴中進行。又,乾式延伸法的情況中,可使用吸水後之PVA薄膜在空氣中進行。該等之中,濕式延伸法較佳,在包含硼酸的水溶液中單軸延伸更佳。硼酸水溶液之硼酸的濃度為0.5質量%以上6.0質量%以下之範圍內較佳,該濃度為1.0質量%以上5.0質量%以下之範圍內更佳,1.5質量%以上4.0質量%以下之範圍內特佳。又,硼酸水溶液可含有碘化鉀,其濃度為0.01質量%以上10質量%以下之範圍內較佳。單軸延伸,在PVA薄膜之流動方向進行較佳。 Uniaxial stretching can be performed by any wet stretching method or dry heat stretching method. In the case of the wet elongation method, it may be performed in an aqueous solution containing boric acid, or it may be performed in the above-mentioned dyeing bath or a fixed treatment bath described later. In the case of the dry stretching method, it can be performed in the air using a water-absorbent PVA film. Among these, the wet stretching method is preferable, and uniaxial stretching is more preferable in an aqueous solution containing boric acid. The concentration of boric acid in the aqueous boric acid solution is preferably within a range of 0.5% by mass to 6.0% by mass, and more preferably within a range of 1.0% by mass to 5.0% by mass, and within a range of 1.5% by mass to 4.0% by mass. good. The boric acid aqueous solution may contain potassium iodide, and its concentration is preferably within a range of 0.01% by mass to 10% by mass. Uniaxial stretching is better in the flow direction of PVA film.
單軸延伸之延伸溫度沒有特別限定,但濕式延伸法的情況中,30℃以上90℃以下之範圍內較佳,40℃以上70℃以下之範圍內更佳,45℃以上65℃以下之範圍內特佳,乾熱延伸法的情況中,50℃以上180℃以下之範圍內較佳。 The stretching temperature for uniaxial stretching is not particularly limited, but in the case of the wet stretching method, it is preferably in the range of 30 ° C to 90 ° C, more preferably in the range of 40 ° C to 70 ° C, and in the range of 45 ° C to 65 ° C. The range is particularly preferable. In the case of the dry heat stretching method, a range of 50 ° C to 180 ° C is preferred.
單軸延伸之延伸倍率(以多段進行單軸延伸時為合計的延伸倍率),從偏光性能之觀點,盡可能延伸直到薄膜即將斷裂之前較佳,具體而言,4倍以上較佳,5倍以上更佳,5.5倍以上特佳。延伸倍率之上限,只要薄膜不會斷裂,則沒有特別限制,為了進行均勻的延伸,8倍以下較佳。 For uniaxial stretching, the stretching ratio (total stretching ratio when uniaxial stretching is performed in multiple stages) is better from the viewpoint of polarizing performance until the film is about to break. Specifically, 4 times or more is better, 5 times is better. Above is better, 5.5 times is especially good. The upper limit of the stretching ratio is not particularly limited as long as the film does not break, and it is preferably 8 times or less for uniform stretching.
延伸後的薄膜(偏光薄膜)之厚度為5μm以上35μm以下,特別是20μm以上30μm以下較佳。 The thickness of the stretched film (polarizing film) is 5 μm or more and 35 μm or less, particularly preferably 20 μm or more and 30 μm or less.
在偏光薄膜之製造時,為了強固染料對於單軸延伸過之薄膜的吸附,大多會進行固定處理。固定處理,一般係廣泛採用在添加硼酸及/或硼化合物的固定處理浴中浸漬薄膜的方法。此時,視需要亦可在固定處理浴中添加碘化合物。 In the manufacture of polarizing films, in order to strengthen the adsorption of dyes on films stretched uniaxially, most of them are fixed. The fixing treatment is generally a method in which a thin film is immersed in a fixing treatment bath in which boric acid and / or a boron compound is added. In this case, if necessary, an iodine compound may be added to the fixed treatment bath.
接著,將已進行單軸延伸、或單軸延伸與固定處理的薄膜進行乾燥較佳。乾燥的溫度為30℃以上150℃以下,特別是50℃以上140℃以下較佳。乾燥的溫度過低時,得到的偏光薄膜之尺寸安定性變得容易下降,另一方面,過高時,變得容易產生伴隨染料的分解等之偏光性能的下降。 Next, it is preferable to dry the film that has been subjected to uniaxial stretching, or uniaxial stretching and fixing. The drying temperature is preferably from 30 ° C to 150 ° C, particularly preferably from 50 ° C to 140 ° C. When the drying temperature is too low, the dimensional stability of the obtained polarizing film tends to decrease. On the other hand, when the drying temperature is too high, it is easy to cause degradation in polarizing performance due to decomposition of the dye and the like.
可在如前述進行而得到的偏光薄膜之雙面或單面,貼合光學上為透明且具有機械強度的保護薄膜而作為偏光板。作為該情況中的保護薄膜,係使用三乙酸纖維素(TAC)薄膜、環烯烴聚合物(COP)薄膜、乙酸/丁酸纖維素(CAB)薄膜、丙烯酸系薄膜、聚酯系薄膜、聚丙烯系薄膜、降烯系樹脂薄膜等。又,作為用以貼合保護 薄膜的接著劑,一般使用PVA系接著劑、丙烯酸酯系接著劑、胺基甲酸酯系接著劑等,其中尤宜使用PVA系接著劑。 A protective film that is optically transparent and has mechanical strength can be bonded on both sides or single sides of the polarizing film obtained as described above to serve as a polarizing plate. As the protective film in this case, cellulose triacetate (TAC) film, cyclic olefin polymer (COP) film, acetate / cellulose butyrate (CAB) film, acrylic film, polyester film, polypropylene are used. Thin film, drop Ethylene resin film and the like. Moreover, as an adhesive agent for bonding a protective film, a PVA-type adhesive agent, an acrylate-type adhesive agent, a urethane-type adhesive agent, etc. are used normally, Especially among these, a PVA-type adhesive agent is used suitably.
如前述進行而得到的偏光板,被覆丙烯酸系等之黏著劑後,可貼合於玻璃基板,並作為液晶顯示器裝置之零件使用。在將偏光板貼合於玻璃基板之際,亦可同時貼合相位差薄膜、視角提升薄膜、亮度提升薄膜等。 The polarizing plate obtained as described above can be adhered to a glass substrate after being coated with an acrylic adhesive or the like, and used as a part of a liquid crystal display device. When a polarizing plate is bonded to a glass substrate, a retardation film, a viewing angle enhancement film, a brightness enhancement film, and the like can also be bonded at the same time.
以下,利用實施例進一步詳細地說明本發明,但本發明並沒有限定於該等之實施例。再者,以下係表示在以下的實施例及比較例中所採用的PVA薄膜的表面之流動方向的折射率之測定方法及PVA薄膜的拉伸伸度之測定方法。 Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. In addition, the following shows the measuring method of the refractive index in the flow direction of the surface of the PVA film used in the following Examples and Comparative Examples, and the measuring method of the tensile elongation of the PVA film.
[PVA薄膜之折射率] [Refractive index of PVA film]
將以下的實施例或比較例所得到之PVA薄膜,在23℃、50%RH之環境下進行調濕7天,之後,在相同環境下使用Metricon公司製稜鏡偶合裝置(Model 2010/M),將波長532nm之雷射光藉由該稜鏡偶合裝置之稜鏡,作為對於PVA薄膜之薄膜面,由垂直的方向朝薄膜之寬度方向傾斜的方向之光,將其作為入射光,在該PVA薄膜之一面上,自該反射光得到該面之折射率(基於該表面的折射率)。對於PVA薄膜之其他面也同樣進行,得到折射率。關於所得到的2個折射率之數值,以滿足A≧B的關係的方式,各別設為A及B。 The PVA films obtained in the following examples or comparative examples were humidity-conditioned for 7 days in an environment of 23 ° C and 50% RH, and thereafter, a tritium coupling device (Model 2010 / M) manufactured by Metricon was used in the same environment. The laser light with a wavelength of 532 nm is used by the 稜鏡 coupling device as the light for the film surface of the PVA film, which is inclined from the vertical direction to the width direction of the film, and is used as the incident light in the PVA film. The refractive index (based on the refractive index of the surface) of the surface of the thin film is obtained from the reflected light. The other surfaces of the PVA film were also processed in the same manner to obtain a refractive index. The two numerical values of the obtained refractive indices are set to A and B, respectively, so as to satisfy the relationship of A ≧ B.
[PVA薄膜之拉伸伸度] [Stretch of PVA film]
將以下的實施例或比較例所得到之PVA薄膜,在20℃、65%RH之環境下保管24小時並進行調濕處理,之後,在相同環境下使用島津製作所公司製自動繪圖儀進行拉伸試驗。再者,PVA薄膜樣本之寬度定為15mm,夾具間距離定為30mm,拉伸速度定為500mm/分,拉伸方向定為PVA薄膜之流動方向。在該拉伸試驗中,將PVA薄膜斷裂時之夾具間距離除以原本的夾具間距離(30mm),作為拉伸伸度(%),並以測定10次的平均值進行評價。 The PVA films obtained in the following examples or comparative examples were stored in an environment of 20 ° C. and 65% RH for 24 hours and subjected to a humidity-conditioning treatment, and then stretched in the same environment using an automatic plotter manufactured by Shimadzu Corporation. test. Furthermore, the width of the PVA film sample is set to 15 mm, the distance between the clamps is set to 30 mm, the stretching speed is set to 500 mm / min, and the stretching direction is set to the flow direction of the PVA film. In this tensile test, the inter-clamp distance when the PVA film was broken was divided by the original inter-clamp distance (30 mm) as the tensile elongation (%), and the average value was measured 10 times and evaluated.
[實施例1] [Example 1]
自T型模將包含藉由皂化聚乙酸乙烯酯之單獨聚合物得到的PVA(皂化度99.9莫耳%、聚合度2400)100質量份、丙三醇12質量份、月桂酸二乙醇醯胺0.1質量份以及水之揮發分率66質量%的製膜原液,在第1乾燥輥(表面溫度90℃、圓周速度(S1)13.5m/分)上吐出為膜狀,並於第1乾燥輥上,一邊對第1乾燥輥非接觸面之整體以5m/秒的風速噴吹90℃的熱風,一邊進行部分乾燥。 100 parts by mass of PVA (degree of saponification 99.9 mol%, degree of polymerization 2400) obtained from a separate polymer of saponified polyvinyl acetate from a T-die, 12 parts by mass of glycerol, and diethanolamine laurate 0.1 The film-forming stock solution with a mass part and a volatile content of 66% by mass of water is discharged into a film form on a first drying roll (surface temperature of 90 ° C. and a peripheral speed (S 1 ) of 13.5 m / min), and is discharged on the first drying roll. On the other hand, the entire non-contact surface of the first drying roll was partially dried while blowing hot air at 90 ° C at a wind speed of 5 m / sec.
接著,自第1乾燥輥剝離,使第1乾燥輥非接觸面與第2乾燥輥相對向而進一步進行乾燥。此時,第2乾燥輥的圓周速度(S2)相對於第1乾燥輥的圓周速度(S1)之比(S2/S1)為1.035。接著,使薄膜之正面及背面與各乾燥輥交互地相對向而以第3乾燥輥以後的乾燥輥進一步進行乾燥。再者,由第2乾燥輥至位於最終乾燥輥正前方的乾燥輥為止之乾燥輥的表面溫度為約85℃,最終乾燥輥的表面溫度為55℃。 Then, it peeled from the 1st drying roll, and made the non-contact surface of a 1st drying roll oppose a 2nd drying roll, and further dried. At this time, the ratio (S 2 / S 1 ) of the peripheral speed (S 2 ) of the second drying roller to the peripheral speed (S 1 ) of the first drying roller was 1.035. Next, the front and back surfaces of the film are alternately opposed to each of the drying rollers, and further dried by the drying rollers subsequent to the third drying roller. The surface temperature of the drying roller from the second drying roller to the drying roller located immediately in front of the final drying roller was about 85 ° C, and the surface temperature of the final drying roller was 55 ° C.
之後,以表面溫度104℃的熱處理輥(X)與連接於其之表面溫度109℃的熱處理輥(Y)進行熱處理後,進行捲取,得到長條形的PVA薄膜(厚度60μm、寬度3m)。在此,熱處理輥(Y)的圓周速度(SY)相對於熱處理輥(X)的圓周速度(SX)之比(SY/SX)為0.995。 Then, the heat treatment roll (X) with a surface temperature of 104 ° C and the heat treatment roll (Y) connected to the surface temperature of 109 ° C were heat-treated, and then rolled up to obtain a long PVA film (thickness: 60 μm, width: 3 m). . Here, the heat treatment roll (Y) of the circumferential velocity (S Y) with respect to the heat roll (X), the circumferential velocity (S X) ratio (S Y / S X) is 0.995.
對於得到的PVA薄膜之薄膜面,利用由垂直的方向朝薄膜之寬度方向傾斜的方向之入射光所測定的上述折射率,在一面為1.529,在另一面為1.529(A=B=1.529、A+B=3.058)。又,測定得到的PVA薄膜之拉伸伸度時為438%。 As for the film surface of the obtained PVA film, the above-mentioned refractive index measured by incident light from a direction inclined perpendicular to the film width direction was 1.529 on one side and 1.529 on the other side (A = B = 1.529, A + B = 3.058). The tensile elongation of the obtained PVA film was 438%.
[實施例2] [Example 2]
自T型模將包含藉由皂化聚乙酸乙烯酯之單獨聚合物得到的PVA(皂化度99.9莫耳%、聚合度2400)100質量份、丙三醇12質量份、月桂酸二乙醇醯胺0.1質量份以及水之揮發分率66質量%的製膜原液,在第1乾燥輥(表面溫度90℃、圓周速度(S1)13.5m/分)上吐出為膜狀,並於第1乾燥輥上,一邊對第1乾燥輥非接觸面之整體以5m/秒的風速噴吹90℃的熱風,一邊進行部分乾燥。 100 parts by mass of PVA (degree of saponification 99.9 mol%, degree of polymerization 2400) obtained from a separate polymer of saponified polyvinyl acetate from a T-die, 12 parts by mass of glycerol, and diethanolamine laurate 0.1 The film-forming stock solution with a mass part and a volatile content of 66% by mass of water is discharged into a film form on a first drying roll (surface temperature of 90 ° C. and a peripheral speed (S 1 ) of 13.5 m / min), and is discharged on the first drying roll. On the other hand, the entire non-contact surface of the first drying roll was partially dried while blowing hot air at 90 ° C at a wind speed of 5 m / sec.
接著,自第1乾燥輥剝離,使第1乾燥輥非接觸面與第2乾燥輥相對向而進一步進行乾燥。此時,第2乾燥輥的圓周速度(S2)相對於第1乾燥輥的圓周速度(S1)之比(S2/S1)為1.035。接著,使薄膜之正面及背面與各乾燥輥交互地相對向而以第3乾燥輥以後的乾燥輥進一步進行乾燥。再者,由第2乾燥輥至位於最終乾燥輥正前方的乾燥輥為止之乾燥輥的表面溫度為約85℃,最終乾燥輥的 表面溫度為50℃。 Then, it peeled from the 1st drying roll, and made the non-contact surface of a 1st drying roll oppose a 2nd drying roll, and further dried. At this time, the ratio (S 2 / S 1 ) of the peripheral speed (S 2 ) of the second drying roller to the peripheral speed (S 1 ) of the first drying roller was 1.035. Next, the front and back surfaces of the film are alternately opposed to each of the drying rollers, and further dried by the drying rollers subsequent to the third drying roller. The surface temperature of the drying roller from the second drying roller to the drying roller located immediately in front of the final drying roller was about 85 ° C, and the surface temperature of the final drying roller was 50 ° C.
之後,以表面溫度101℃的熱處理輥(X)與連接於其之表面溫度107℃的熱處理輥(Y)進行熱處理後,進行捲取,得到長條形的PVA薄膜(厚度60μm、寬度3m)。在此,熱處理輥(Y)的圓周速度(SY)相對於熱處理輥(X)的圓周速度(SX)之比(SY/SX)為0.995。 Then, the heat treatment roll (X) with a surface temperature of 101 ° C. and the heat treatment roll (Y) connected to the surface temperature of 107 ° C. were heat-treated, and then rolled up to obtain a long PVA film (thickness: 60 μm, width: 3 m). . Here, the heat treatment roll (Y) of the circumferential velocity (S Y) with respect to the heat roll (X), the circumferential velocity (S X) ratio (S Y / S X) is 0.995.
對於得到的PVA薄膜之薄膜面,利用由垂直的方向朝薄膜之寬度方向傾斜的方向之入射光所測定的上述折射率,在一面為1.530,在另一面為1.528(A=1.530、B=1.528、A+B=3.058)。又,測定得到的PVA薄膜之拉伸伸度時,為437%。 For the film surface of the obtained PVA film, the above-mentioned refractive index measured by incident light from a direction inclined perpendicular to the width direction of the film was 1.530 on one side and 1.528 on the other side (A = 1.530, B = 1.528). , A + B = 3.058). The tensile elongation of the obtained PVA film was 437%.
[實施例3] [Example 3]
自T型模將包含藉由皂化聚乙酸乙烯酯之單獨聚合物得到的PVA(皂化度99.9莫耳%、聚合度2400)100質量份、丙三醇12質量份、月桂酸二乙醇醯胺0.1質量份以及水之揮發分率66質量%的製膜原液,在第1乾燥輥(表面溫度90℃、圓周速度(S1)13.5m/分)上吐出為膜狀,並於第1乾燥輥上,一邊對第1乾燥輥非接觸面之整體以5m/秒的風速噴吹90℃的熱風,一邊進行部分乾燥。 100 parts by mass of PVA (degree of saponification 99.9 mol%, degree of polymerization 2400) obtained from a separate polymer of saponified polyvinyl acetate from a T-die, 12 parts by mass of glycerol, and diethanolamine laurate 0.1 The film-forming stock solution with a mass part and a volatile content of 66% by mass of water is discharged into a film form on a first drying roll (surface temperature of 90 ° C. and a peripheral speed (S 1 ) of 13.5 m / min), and is discharged on the first drying roll. On the other hand, the entire non-contact surface of the first drying roll was partially dried while blowing hot air at 90 ° C at a wind speed of 5 m / sec.
接著,自第1乾燥輥剝離,使第1乾燥輥非接觸面與第2乾燥輥相對向而進一步進行乾燥。此時,第2乾燥輥的圓周速度(S2)相對於第1乾燥輥的圓周速度(S1)之比(S2/S1)為1.035。接著,使薄膜之正面及背面與各乾燥輥交互地相對向而以第3乾燥輥以後的乾燥輥進一步進行乾燥。再者,由第2乾燥輥至位於最終乾燥輥正前方的乾 燥輥為止之乾燥輥的表面溫度為約85℃,最終乾燥輥的表面溫度為50℃。 Then, it peeled from the 1st drying roll, and made the non-contact surface of a 1st drying roll oppose a 2nd drying roll, and further dried. At this time, the ratio (S 2 / S 1 ) of the peripheral speed (S 2 ) of the second drying roller to the peripheral speed (S 1 ) of the first drying roller was 1.035. Next, the front and back surfaces of the film are alternately opposed to each of the drying rollers, and further dried by the drying rollers subsequent to the third drying roller. The surface temperature of the drying roller from the second drying roller to the drying roller located immediately in front of the final drying roller was about 85 ° C, and the surface temperature of the final drying roller was 50 ° C.
之後,以表面溫度104℃的熱處理輥(X)與連接於其之表面溫度109℃的熱處理輥(Y)進行熱處理後,進行捲取,得到長條形的PVA薄膜(厚度60μm、寬度3m)。在此,熱處理輥(Y)的圓周速度(SY)相對於熱處理輥(X)的圓周速度(SX)之比(SY/SX)為0.997。 Then, the heat treatment roll (X) with a surface temperature of 104 ° C and the heat treatment roll (Y) connected to the surface temperature of 109 ° C were heat-treated, and then rolled up to obtain a long PVA film (thickness: 60 μm, width: 3 m). . Here, the heat treatment roll (Y) of the circumferential velocity (S Y) with respect to the heat roll (X), the circumferential velocity (S X) ratio (S Y / S X) was 0.997.
對於得到的PVA薄膜之薄膜面,利用由垂直的方向朝薄膜之寬度方向傾斜的方向之入射光所測定的上述折射率,在一面為1.530,在另一面為1.529(A=1.530、B=1.529、A+B=3.059)。又,測定得到的PVA薄膜之拉伸伸度時,為435%。 As for the film surface of the obtained PVA film, the above-mentioned refractive index measured by incident light from a direction inclined perpendicular to the width direction of the film was 1.530 on one side and 1.529 on the other side (A = 1.530, B = 1.529). , A + B = 3.059). When the tensile elongation of the obtained PVA film was measured, it was 435%.
[比較例1] [Comparative Example 1]
自T型模將包含藉由皂化聚乙酸乙烯酯之單獨聚合物得到的PVA(皂化度99.9莫耳%、聚合度2400)100質量份、丙三醇12質量份、月桂酸二乙醇醯胺0.1質量份以及水之揮發分率66質量%的製膜原液,在第1乾燥輥(表面溫度90℃、圓周速度(S1)13m/分)上吐出為膜狀,並於第1乾燥輥上,一邊對第1乾燥輥非接觸面之整體以5m/秒的風速噴吹90℃的熱風,一邊進行部分乾燥。 100 parts by mass of PVA (degree of saponification 99.9 mol%, degree of polymerization 2400) obtained from a separate polymer of saponified polyvinyl acetate from a T-die, 12 parts by mass of glycerol, and diethanolamine laurate 0.1 The film-forming stock solution with a mass part and a volatile content of 66% by mass of water is discharged into a film form on a first drying roll (surface temperature of 90 ° C., peripheral speed (S 1 ) 13 m / min), and is placed on the first drying roll. Partial drying was performed while blowing hot air at 90 ° C. at a wind speed of 5 m / sec on the entire non-contact surface of the first drying roll.
接著,自第1乾燥輥剝離,使第1乾燥輥非接觸面與第2乾燥輥相對向而進一步進行乾燥。此時,第2乾燥輥的圓周速度(S2)相對於第1乾燥輥的圓周速度(S1)之比(S2/S1)為1.050。接著,使薄膜之正面及背面與各乾燥輥交互地相對向而以第3乾燥輥以後的乾燥輥進一步進行 乾燥。再者,由第2乾燥輥至位於最終乾燥輥正前方的乾燥輥為止之乾燥輥的表面溫度為約85℃,最終乾燥輥的表面溫度為60℃。 Then, it peeled from the 1st drying roll, and made the non-contact surface of a 1st drying roll oppose a 2nd drying roll, and further dried. At this time, the ratio (S 2 / S 1 ) of the peripheral speed (S 2 ) of the second drying roller to the peripheral speed (S 1 ) of the first drying roller was 1.050. Next, the front and back surfaces of the film are alternately opposed to each of the drying rollers, and further dried by the drying rollers subsequent to the third drying roller. The surface temperature of the drying roller from the second drying roller to the drying roller located immediately in front of the final drying roller was about 85 ° C, and the surface temperature of the final drying roller was 60 ° C.
之後,以表面溫度102℃的熱處理輥(X)與連接於其之表面溫度107℃的熱處理輥(Y)進行熱處理後,進行捲取,得到長條形的PVA薄膜(厚度60μm、寬度3m)。在此,熱處理輥(Y)的圓周速度(SY)相對於熱處理輥(X)的圓周速度(SX)之比(SY/SX)為1.000。 Thereafter, the heat treatment roll (X) with a surface temperature of 102 ° C. and the heat treatment roll (Y) connected to the surface temperature of 107 ° C. were heat-treated, and then rolled up to obtain a long PVA film (thickness 60 μm, width 3 m). . Here, the heat treatment roll (Y) of the circumferential velocity (S Y) with respect to the heat roll (X), the circumferential velocity (S X) ratio (S Y / S X) is 1.000.
對於得到的PVA薄膜之薄膜面,利用由垂直的方向朝薄膜之寬度方向傾斜的方向之入射光所測定的上述折射率,在一面為1.531,在另一面為1.530(A=1.531、B=1.530、A+B=3.061)。又,測定得到的PVA薄膜之拉伸伸度時,為415%。 For the film surface of the obtained PVA film, the above-mentioned refractive index measured by incident light from a direction inclined perpendicular to the film width direction was 1.531 on one side and 1.530 on the other side (A = 1.531, B = 1.530 , A + B = 3.061). When the tensile elongation of the obtained PVA film was measured, it was 415%.
[比較例2] [Comparative Example 2]
自T型模將包含藉由皂化聚乙酸乙烯酯之單獨聚合物得到的PVA(皂化度99.9莫耳%、聚合度2400)100質量份、丙三醇12質量份、月桂酸二乙醇醯胺0.1質量份以及水之揮發分率66質量%的製膜原液,在第1乾燥輥(表面溫度90℃、圓周速度(S1)15.5m/分)上吐出為膜狀,並於第1乾燥輥上,一邊對第1乾燥輥非接觸面之整體以5m/秒的風速噴吹90℃的熱風,一邊進行部分乾燥。 100 parts by mass of PVA (degree of saponification 99.9 mol%, degree of polymerization 2400) obtained from a separate polymer of saponified polyvinyl acetate from a T-die, 12 parts by mass of glycerol, and diethanolamine laurate 0.1 The film-forming stock solution with a mass part and a volatile content of 66% by mass of water is discharged into a film form on a first drying roll (surface temperature 90 ° C., peripheral speed (S 1 ) 15.5 m / min), and the first drying roll On the other hand, the entire non-contact surface of the first drying roll was partially dried while blowing hot air at 90 ° C at a wind speed of 5 m / sec.
接著,自第1乾燥輥剝離,使第1乾燥輥非接觸面與第2乾燥輥相對向而進一步進行乾燥。此時,第2乾燥輥的圓周速度(S2)相對於第1乾燥輥的圓周速度(S1)之比(S2/S1)為1.050。接著,使薄膜之正面及背面與各乾燥輥 交互地相對向而以第3乾燥輥以後的乾燥輥進一步進行乾燥。再者,由第2乾燥輥至位於最終乾燥輥正前方的乾燥輥為止之乾燥輥的表面溫度為約85℃,最終乾燥輥的表面溫度為72℃。 Then, it peeled from the 1st drying roll, and made the non-contact surface of a 1st drying roll oppose a 2nd drying roll, and further dried. At this time, the ratio (S 2 / S 1 ) of the peripheral speed (S 2 ) of the second drying roller to the peripheral speed (S 1 ) of the first drying roller was 1.050. Next, the front and back surfaces of the film are alternately opposed to each of the drying rollers, and further dried by the drying rollers subsequent to the third drying roller. The surface temperature of the drying roller from the second drying roller to the drying roller located immediately in front of the final drying roller was about 85 ° C, and the surface temperature of the final drying roller was 72 ° C.
之後,以表面溫度108℃的熱處理輥(X)與連接於其之表面溫度114℃的熱處理輥(Y)進行熱處理後,進行捲取,得到長條形的PVA薄膜(厚度60μm、寬度3m)。在此,熱處理輥(Y)的圓周速度(SY)相對於熱處理輥(X)的圓周速度(SX)之比(SY/SX)為0.998。 Thereafter, the heat treatment roll (X) with a surface temperature of 108 ° C. and the heat treatment roll (Y) connected to the surface temperature of 114 ° C. were heat-treated, and then rolled up to obtain a long PVA film (thickness 60 μm, width 3 m). . Here, the heat treatment roll (Y) of the circumferential velocity (S Y) with respect to the heat roll (X), the circumferential velocity (S X) ratio (S Y / S X) of 0.998.
對於得到的PVA薄膜之薄膜面,利用由垂直的方向朝薄膜之寬度方向傾斜的方向之入射光所測定的上述折射率,在一面為1.531,在另一面為1.529(A=1.531、B=1.529、A+B=3.060)。又,測定得到的PVA薄膜之拉伸伸度時,為431%。 With respect to the film surface of the obtained PVA film, the above-mentioned refractive index measured by incident light in a direction oblique to the width direction of the film was 1.531 on one side and 1.529 on the other side (A = 1.531, B = 1.529 , A + B = 3.060). The tensile elongation of the obtained PVA film was 431%.
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