WO2009104366A1 - 強酸ポリマーシート製造用フィルム - Google Patents
強酸ポリマーシート製造用フィルム Download PDFInfo
- Publication number
- WO2009104366A1 WO2009104366A1 PCT/JP2009/000503 JP2009000503W WO2009104366A1 WO 2009104366 A1 WO2009104366 A1 WO 2009104366A1 JP 2009000503 W JP2009000503 W JP 2009000503W WO 2009104366 A1 WO2009104366 A1 WO 2009104366A1
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- WIPO (PCT)
- Prior art keywords
- film
- layer
- release layer
- strong acid
- polyethylene naphthalate
- Prior art date
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/1062—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the physical properties of the porous support, e.g. its porosity or thickness
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
Definitions
- the present invention relates to a polyethylene naphthalate film suitably used for production of a polymer electrolyte membrane used for a fuel cell or the like.
- Electrolyte membranes made of this polymer electrolyte especially electrode membranes in which platinum catalyst-carrying carbon and the like are dispersed in the electrolyte, are formed in a paste-like or ink-like form with a solvent in the formation. It is often formed by casting on a material film.
- a release film used here for example, as described in Patent Document 1, (1) a polyester film coated with silicone, (2) a stretched polypropylene film, (3) a fluororesin film, (4 ) Polyester film laminated with fluororesin is known, but silicone used as a release agent has a risk of contamination, and fluororesin is generally expensive. Regardless of whether it is laminated to a material or coated on another substrate, the release film as a consumable material has cost limitations, and is not suitable for reducing the cost of electrolyte membranes to be advanced in the future. Polyolefins such as polypropylene or polymers having long-chain alkyl side chains are inexpensive and have a certain releasability, but they are not necessarily releasable. Use is limited.
- Patent Document 2 a film in which a polyethylene terephthalate film having excellent heat resistance is used as a base material and a release layer made of polyolefin is provided has been proposed (Patent Document 2).
- the release layer becomes a molten state, so that a channel is temporarily formed and the strong acid electrolyte polymer directly contacts the base polyethylene terephthalate film.
- the possibility increases and the polyethylene terephthalate film is attacked, which may lead to defects.
- the present invention has been made in view of the above circumstances, and its solution is a mold release suitable for cast molding of a sheet-like polymer structure such as an electrolyte membrane, which simultaneously satisfies non-contamination, low cost, and excellent heat resistance. To provide a film.
- the first gist of the present invention is a polyethylene naphthalate film having a release layer containing a copolymerized polyolefin, and the thickness of the release layer converted from the maximum wavelength of the reflectance of the release layer surface. It exists in the film for strong acid polymer sheet manufacture characterized by being 75-150 nm.
- the second gist of the present invention is that a layer of polyethylene terephthalate (A layer) and a layer (B layer) of polyethylene naphthalate as a main component are laminated on layer B of a laminated polyester film.
- the film of the present invention is suitable for cast molding of a sheet-like polymer structure such as an electrolyte membrane made of a polymer electrolyte, and is excellent in non-contaminating property, and at the same time satisfies low cost and excellent heat resistance.
- the film for manufacturing a strong acid polymer sheet can be provided, and its industrial value is high.
- polyethylene naphthalate refers to a polyester in which 2,6-naphthalenedicarboxylic acid and ethylene glycol are condensed. If it is 10 mol% or less, components other than 2,6-naphthalenedicarboxylic acid and ethylene glycol are present. It may be copolymerized. Further, other polyesters, polymers, and auxiliaries may be mixed as long as the characteristics are not impaired.
- polyethylene terephthalate refers to a polyester obtained by condensing terephthalic acid and ethylene glycol, and if it is 10 mol% or less, components other than terephthalic acid and ethylene glycol may be copolymerized. Further, other polyesters, polymers, and auxiliaries may be mixed as long as the characteristics are not impaired.
- the coating liquid is used to form a release layer by coating on a base film as described later.
- the copolymerized polyolefin is preferably a copolymerized polyethylene.
- Polyolefins generally have a low melting point, but are inferior in heat resistance, but are excellent in acid resistance, and also have releasability from strong acid polymers, and are therefore suitable as a material constituting the carrier surface of a strong acid polymer sheet production film.
- a polyolefin layer on a heat resistant substrate. is there.
- the polyolefin coating liquid from the viewpoint of not deteriorating the cleanness of the strong acid polymer sheet to be formed, it is desirable not to include a component that can be an impurity as much as possible, and it is preferable to apply the solution rather than a dispersion liquid that requires a surfactant or the like. .
- examples of the component copolymerized with polyethylene include ⁇ -olefins, particularly propylene, n-butene, n-pentene, n-hexene and the like. From the viewpoint of ensuring a certain level of solubility, it is recommended that the molar ratio of the copolymerization component be 10 mol% or more.
- toluene, xylene and the like having high affinity for polyethylene are suitable.
- various organic solvents such as alcohols, ketones and alkanes may be mixed in a small amount.
- the present invention relates to a polyethylene naphthalate film having a release layer containing a copolymerized polyolefin, and the release layer thickness converted from the maximum wavelength of the reflectance of the release layer surface is 75 to 150 nm.
- the present invention relates to a film for producing a strong acid polymer sheet.
- polyethylene naphthalate Compared to polyethylene terephthalate and polybutylene terephthalate, polyethylene naphthalate is resistant to attack by strong acid polymer even when it comes into contact with heat, and has excellent heat resistance. It is suitable as.
- Conventional methods such as a bar coating method, a gravure coating method, and a reverse roll coating method can be used as a coating method of the coating liquid when forming the release layer.
- the thickness of the release layer converted from the maximum wavelength of the release surface reflectance is 75 to 150 nm. If the release layer thickness is less than 75 nm, even if polyethylene naphthalate having relatively excellent acid resistance, the acid-protective effect by the release layer is insufficient, and the base material may be affected by the strong acid polymer. When the release layer thickness exceeds 150 nm, the peeling force from the strong acid polymer becomes too heavy.
- the upper limit guide for the release layer thickness is 150 nm.
- the release layer of the present invention may be cross-linked in order to improve heat resistance.
- a crosslinking method a small amount of a functional group-containing polyolefin that is compatible with the copolymer polyethylene constituting the release layer is blended, and a functional group is introduced into the main chain of the copolymer polyethylene constituting the release layer. And a method of cross-linking this.
- the method of introducing a hydroxyl group into the copolymer polyethylene main chain and crosslinking it with a polyfunctional isocyanate can provide not only crosslinking between polyolefins but also crosslinking with a hydroxyl group terminal of a base polyethylene naphthalate, and a release layer. It is particularly recommended because of its improved adhesion to the substrate and the ability to alleviate substrate erosion by strong acid polymers.
- the present invention relates to a mold release containing a copolymerized polyolefin on the B layer of a laminated polyester film comprising a layer mainly composed of polyethylene terephthalate (A layer) and a layer mainly composed of polyethylene naphthalate (B layer).
- a layer having a thickness of 0.5 to 2.5 ⁇ m, and a release layer thickness converted from the maximum wavelength of the reflectance of the release layer surface is 75 to 150 nm.
- the present invention relates to a laminated film for producing a strong acid polymer sheet.
- a laminated polyester film including a layer mainly composed of polyethylene terephthalate and a surface layer mainly composed of polyethylene naphthalate is used as a base material.
- the surface on which the release layer is provided must be a layer mainly composed of polyethylene naphthalate, but the surface on the opposite side is not necessarily a surface layer mainly composed of polyethylene naphthalate.
- the surface on which the release layer is provided is mainly composed of polyethylene naphthalate, which has a relatively high resistance, because strong acid polymers may come into contact through channels that are accidentally formed in the release layer when heated at high temperatures. Must consist of layers.
- Polyethylene naphthalate film may be applied as a base material only from the viewpoint of resistance to strong acid polymer, but polyethylene naphthalate is several times more expensive than polyethylene terephthalate.
- polyethylene terephthalate film manufacturing equipment it is necessary to cope with the equipment in terms of high-temperature stretching. Therefore, it is not necessarily optimal in terms of cost to apply to a carrier sheet, which is a standard use form.
- the base material is a laminated polyester film in which a polyethylene terephthalate layer is provided with a polyethylene naphthalate surface layer, as a whole, which can be produced in accordance with a polyethylene terephthalate film and also has resistance to a strong acid polymer.
- the stretching process is performed under a temperature condition that is not necessarily optimum for any of the materials.
- the base film of the present invention generally conforms to polyethylene terephthalate, and it is desirable that the stretching conditions also conform to that of polyethylene terephthalate.
- the polyethylene naphthalate surface layer is cooled below the glass transition temperature. Since it becomes extending
- the thickness of the polyethylene naphthalate surface layer must be 0.5 ⁇ m or more. Even if the thickness of the polyethylene naphthalate surface layer is 2.5 ⁇ m or less, if the ratio of the polyethylene naphthalate surface layer in the total thickness is too high, uniform stretching becomes difficult.
- the polyethylene naphthalate surface layer is 5% of the total thickness. The following is desirable.
- the release layer can be formed in the same manner as in the case of the release layer in the invention according to the second aspect.
- parts means “parts by weight” as a solid content.
- the evaluation method used in the present invention is as follows.
- a release film and a strong acid polymer film are cut into a width of 50 mm according to the size of the adhesive tape. Then, at a peeling speed of 300 mm / min, No. 31B is peeled 180 °. The value obtained by dividing the average peel load measured at that time by the width of 50 mm was taken as the peel force.
- Release layer thickness A black vinyl tape (No. 21; manufactured by Nitto Denko) is attached to the opposite side of the measurement surface, and a spectrophotometer (UV-3100PC; manufactured by Shimadzu Corporation) is used to measure 5 of the measurement surface in the wavelength range of 200 to 2000 nm. Measure reflectivity. A value obtained by dividing the peak wavelength of the maximum peak on the longest wavelength side among the maximum peaks of reflectance by 3.0 was defined as the release layer thickness. In this conversion, the refractive index of the copolymer polyethylene constituting the release layer is assumed to be 1.5.
- copolymerized polyethylene coating solution coating solution A
- a mixture of 2-hydroxyethyl methacrylate and peroxide (trade name Perhexa 25; manufactured by Nippon Shokubai Co., Ltd.) (weight ratio 19: 1) was added to ethylene / propylene rubber (trade name EP02P; manufactured by JSR) at 200 ° C. Kneaded to prepare a modified copolymer polyethylene grafted with 1% by weight of 2-hydroxyethyl methacrylate.
- This modified copolymer polyethylene was mixed with toluene and stirred for 5 hours under reflux to obtain a solution having a polyolefin concentration of 3% by weight.
- a polyfunctional isocyanate (MYTEC NY718A; manufactured by Mitsubishi Chemical) was added to the solution so as to be 2.9% by weight based on the copolymerized polyethylene to obtain coating solution A.
- coating solution B 99 parts of ethylene / propylene rubber (trade name EP02P; manufactured by JSR) and 1 part of polyolefin polyol (trade name Polytail H; manufactured by Mitsubishi Chemical) are mixed with toluene and stirred at reflux for 5 hours to obtain a solution having a polyolefin concentration of 3% by weight. It was.
- a coating solution B was prepared by adding 1% by weight with respect to the polyolefin solid content.
- the polyethylene naphthalate obtained by the above preparation method is melted at 300 ° C. with a twin screw extruder, extruded into a sheet form from a T-die onto a cast drum, and rapidly cooled by an electrostatic application cooling method to be an amorphous sheet.
- This amorphous sheet was subjected to a longitudinal stretching of 130 ° C. by 4.2 times, followed by a transverse stretching of 135 ° C. by a factor of 4.4, and finally heat setting at 220 ° C.
- a phthalate film was obtained.
- Example 1A The coating solution A diluted with toluene at 40 ° C. to a polyolefin concentration of 0.75% by weight was applied on a polyethylene naphthalate film using a Mayer bar # 4, and then heat-treated at 150 ° C. for 5 seconds. It was kept at 23 ° C. for 48 hours to obtain a release film.
- Example 2A A coating solution A diluted with toluene at 40 ° C. to a polyolefin concentration of 1.6% by weight was applied on a polyethylene naphthalate film using a Mayer bar # 6, followed by heat treatment at 150 ° C. for 5 seconds. It was kept at 23 ° C. for 48 hours to obtain a release film.
- Example 3A A release film was obtained in the same manner as in Example 2A except that the coating liquid A was changed to the coating liquid B.
- Comparative Example 1A A coating solution A diluted with toluene at 40 ° C. to a polyolefin concentration of 0.5% by weight was applied on a polyethylene naphthalate film using a Mayer bar # 3, and then heat-treated at 150 ° C. for 5 seconds. It was kept at 23 ° C. for 48 hours to obtain a release film.
- Comparative Example 2A The coating solution A was applied on a polyethylene naphthalate film using a Mayer bar # 7, then heat-treated at 150 ° C. for 5 seconds, and kept at 23 ° C. for 48 hours to obtain a release film.
- Comparative Example 3A A release film was obtained in the same manner as in Example 2A, except that the base film was changed from a polyethylene naphthalate film to a polyethylene terephthalate film (trade name Diafoil T100-50S; manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.).
- Polyester film A except that it is not a three-layer structure of polyethylene naphthalate surface layer / polyethylene terephthalate layer / polyethylene naphthalate surface layer, but a two-layer structure of polyethylene naphthalate surface layer / polyethylene terephthalate layer (the discharge ratio is 1/19) Similarly, a polyester film B having a thickness of 50 ⁇ m was obtained.
- polyester film C having a thickness was obtained in the same manner as the polyester film A, except that the discharge amount ratio of polyethylene naphthalate surface layer / polyethylene terephthalate layer / polyethylene naphthalate surface layer was set to 1/198/1.
- Preparation of base polyester film D A polyester film was obtained in the same manner as the polyester film A except that the discharge amount of the polyethylene naphthalate surface layer / polyethylene terephthalate layer / polyethylene naphthalate surface layer was changed to 5/40/5. Whitening occurred and could not be applied as a substrate film.
- Example 1B The coating solution A was diluted with toluene at 40 ° C. to a polyolefin concentration of 0.75% by weight on the polyester film A using the Mayer bar # 4, and then heat-treated at 150 ° C. for 5 seconds. The laminated film was obtained by maintaining at a temperature of 48 ° C. for 48 hours.
- Example 2B The coating solution A was diluted with toluene at 40 ° C. to a polyolefin concentration of 1.6% by weight. The coating solution was applied onto the polyester film A using the Mayer bar # 6, and then heat-treated at 150 ° C. for 5 seconds. The laminated film was obtained by maintaining at a temperature of 48 ° C. for 48 hours.
- Example 3B A laminated film was obtained in the same manner as in Example 2B except that the coating liquid A was changed to the coating liquid B.
- Example 4B A laminated film was obtained in the same manner as in Example 1B except that the polyester film B was used instead of the polyester film A.
- Comparative Example 1B The coating solution A was diluted with toluene at 40 ° C. to give a polyolefin concentration of 0.5% by weight on the polyester film A using the Mayer bar # 3, and then heat-treated at 150 ° C. for 5 seconds. The laminated film was obtained by maintaining at a temperature of 48 ° C. for 48 hours.
- Comparative Example 2B The coating liquid A was applied on the polyester film A using the Mayer bar # 7, and then heat-treated at 150 ° C. for 5 seconds and kept at 23 ° C. for 48 hours to obtain a laminated film.
- Comparative Example 3B A laminated film was obtained in the same manner as in Example 1B except that the polyester film C was used instead of the polyester film A.
- Comparative Example 4B A film was obtained in the same manner as in Example 2B except that a polyethylene terephthalate film (trade name Diafoil T100-50S; manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) was used instead of the polyester film A.
- a polyethylene terephthalate film (trade name Diafoil T100-50S; manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) was used instead of the polyester film A.
- the film of the present invention can be suitably used, for example, for the production of polymer electrolyte membranes used for fuel cells and the like.
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Abstract
Description
本発明でいうポリエチレンナフタレートとは、2,6-ナフタレンジカルボン酸とエチレングリコールとが縮合されたポリエステルをいい、10モル%以下であれば2,6-ナフタレンジカルボン酸、エチレングリコール以外の成分が共重合されていてもよい。また、特性を損ねない範囲で他のポリエステル、ポリマー、助剤類が混合されていてもよい。
本発明でいうポリエチレンテレフタレートとは、テレフタル酸とエチレングリコールとが縮合されたポリエステルをいい、10モル%以下あればテレフタル酸、エチレングリコール以外の成分が共重合されていてもよい。また、特性を損ねない範囲で他のポリエステル、ポリマー、助剤類が混合されていてもよい。
上記の塗布液は、後述するように基材フィルムに塗布して離型層を形成するために使用される。共重合ポリオレフィンは好ましくは共重合ポリエチレンである。
この発明は、共重合ポリオレフィンを含有する離型層を有するポリエチレンナフタレートフィルムであり、当該離型層表面の反射率の極大波長から換算される離型層の厚みが75~150nmであることを特徴とする強酸ポリマーシート製造用フィルムに関する。
この発明は、ポリエチレンテレフタレートを主成分とする層(A層)とポリエチレンナフタレートを主成分とする層(B層)とを含む積層ポリエステルフィルムのB層上に、共重合ポリオレフィンを含有する離型層を有するフィルムであり、B層の厚みが0.5~2.5μmであり、離型層表面の反射率の極大波長から換算される離型層厚みが75~150nmであることを特徴とする強酸ポリマーシート製造用積層フィルムに関する。
デュポン社製強酸ポリマーの分散溶液ナフィオン(登録商標)分散溶液DE2021を試料離型面に2ml滴下し、ベーカー式アプリケータにて厚み10milのウェットシートを形成する。これを直ちに雰囲気温度160℃の熱風炉にて10分間乾燥し、試料離型面上に膜を形成する。引き続き、膜の背面に厚み25μmの粘着テープNo.31B(日東電工製)を貼り合わせ、剥離速度30m/分にて、膜ごと試料離型面よりNo.31Bを180°剥離する。膜を剥離した後の離型面を共焦点型レーザー顕微鏡にて観察し、深さが0.5μm以上の移行跡(窪み)の有無を確認する。移行跡が皆無であるもの強酸ポリマー耐性良好とする。
デュポン社製強酸ポリマーの分散溶液ナフィオン(登録商標)分散溶液DE2021を試料離型面に2ml滴下し、ベーカー式アプリケータにて厚み10milのウェットシートを形成する。これを直ちに雰囲気温度160℃の熱風炉にて10分間乾燥し、試料離型面上に膜を形成する。引き続き、膜の背面に幅50mmの粘着テープNo.31B(日東電工製)を貼り合わせたのち、粘着テープサイズに合わせて離型フィルムおよび強酸ポリマー膜を50mm幅に切り出す。そして、剥離速度300mm/分にて、膜ごと試料離型面よりNo.31Bを180°剥離する。その際に計測される平均剥離荷重を幅50mmで除した値を剥離力とした。
測定面の反対面に黒いビニールテープ(No.21;日東電工製)を貼り合わせ、分光光度計(UV-3100PC;島津製作所製)を用いて、200~2000nmの波長域における測定面の5 絶対反射率を測定する。反射率の極大ピークのうち最も長波長側にある極大ピークのピーク波長を3.0で除した値を離型層厚みとした。なお、本換算では離型層を構成する共重合ポリエチレンの屈折率を1.5と仮定する。
メタクリル酸-2-ヒドロキシエチルとパーオキサイド(商品名パーヘキサ25;日本触媒製)とを混合したもの(重量比19:1)をエチレン・プロピレンゴム(商品名EP02P;JSR製)に加え200℃で混練し、メタクリル酸-2-ヒドロキシエチルが1重量%グラフトされた変性共重合ポリエチレンを調製する。この変性共重合ポリエチレンをトルエンと混合し、5時間還流攪拌してポリオレフィン濃度3重量%の溶液を得た。塗布直前にこの溶解液に多官能イソシアネート(マイテックNY718A;三菱化学製)を共重合ポリエチレンに対して2.9重量%となるよう添加して塗布液Aとした。
エチレン・プロピレンゴム(商品名EP02P;JSR製)99部とポリオレフィンポリオール(商品名ポリテールH;三菱化学製)1部とをトルエンに混合し5時間還流攪拌してポリオレフィン濃度3重量%の溶液を得た。塗布直前にこの溶解液に多官能イソシアネート(商品名マイテックNY718A;三菱化学製)とトリエチルジアミン(商品名1,4-ジアザビシクロ[2.2.2]オクタン;和光純薬工業製)とをそれぞれポリオレフィン固形分に対して1重量%となるように添加して塗布液Bとした。
ジメチル-2,6-ナフタレート100部、エチレングリコール60部および酢酸マグネシウム0.08部を反応器にとり、エステル交換反応を行った。次に無定形シリカを0.15部添加し、さらにエチルアシッドホスフェートを0.04部、三酸化アンチモンを0.04部加えた後、常法に従って重合を行い、固有粘度0.55dl/gのポリエチレンナフタレートを得た。次いで固相重合を行い、固有粘度を0.60dl/gまで高めた。
前記の調製法で得られたポリエチレンナフタレートを二軸押出機にて300℃で溶融し、Tダイよりシート状にキャストドラム上へ押し出し、静電印加冷却法で急冷することで非晶質シートを得た。この非晶質シートを、130℃4.2倍の縦延伸を施し、続いて135℃4.4倍の横延伸を施し、最後に220℃で熱固定を施して、厚さ50μmのポリエチレンナフタレートフィルムを得た。
塗布液Aを40℃のトルエンで希釈してポリオレフィン濃度0.75重量%とした塗布液をメイヤーバー#4を用いてポリエチレンナフタレートフィルム上に塗布した後、150℃で5秒間熱処理を行い、23℃で48時間保持して離型フィルムを得た。
塗布液Aを40℃のトルエンで希釈してポリオレフィン濃度1.6重量%とした塗布液をメイヤーバー#6を用いてポリエチレンナフタレートフィルム上に塗布した後、150℃で5秒間熱処理を行い、23℃で48時間保持して離型フィルムを得た。
塗布液Aを塗布液Bとしたほかは実施例2Aと同様にして離型フィルムを得た。
塗布液Aを40℃のトルエンで希釈してポリオレフィン濃度0.5重量%とした塗布液をメイヤーバー#3を用いてポリエチレンナフタレートフィルム上に塗布した後、150℃で5秒間熱処理を行い、23℃で48時間保持して離型フィルムを得た。
塗布液Aをメイヤーバー#7を用いてポリエチレンナフタレートフィルム上に塗布した後、150℃で5秒間熱処理を行い、23℃48時間保持して離型フィルムを得た。
基材フィルムをポリエチレンナフタレートフィルムからポリエチレンテレフタレートフィルム(商品名ダイアホイルT100-50S;三菱化学ポリエステルフィルム社製)に代えた他は実施例2Aと同様にして離型フィルムを得た。
ポリエチレンナフタレートとポリエチレンテレフタレートをそれぞれ別の二軸押出機で300℃に溶融した後、ポリエチレンナフタレートが両表層、ポリエチレンテレフタレートが中間層を構成するようにTダイ内で合流させた。表層/中間層/表層の吐出量はそれぞれ1/98/1となるようにギアポンプで制御した。この積層融液をTダイよりキャストドラム上へシート状に押し出し、静電印加冷却法で急冷することで、非晶質シートを得た。この非晶質シートを、100℃3.6倍の縦延伸を施し、続いて110℃4.0倍の横延伸を施し、最後に220℃で熱固定を施して、厚さ50μmのポリエステルフィルムAを得た。
ポリエチレンナフタレート表層/ポリエチレンテレフタレート層/ポリエチレンナフタレート表層の三層構成ではなく、ポリエチレンナフタレート表層/ポリエチレンテレフタレート層(ただし吐出量比は1/19)の二層構成としたほかはポリエステルフィルムAと同様にして厚さ50μmのポリエステルフィルムBを得た。
ポリエチレンナフタレート表層/ポリエチレンテレフタレート層/ポリエチレンナフタレート表層の吐出量比を1/198/1としたほかはポリエステルフィルムAと同様にして厚さポリエステルフィルムCを得た。
ポリエチレンナフタレート表層/ポリエチレンテレフタレート層/ポリエチレンナフタレート表層の吐出量を5/40/5としたほかはポリエステルフィルムAと同様にしてポリエステルフィルムを得ようとしたが、ポリエチレンナフタレート表層に不均一な白化を生じ、基材フィルムとして適用することができなかった。
塗布液Aを40℃のトルエンで希釈してポリオレフィン濃度0.75重量%とした塗布液をメイヤーバー#4を用いてポリエステルフィルムA上に塗布した後、150℃で5秒間熱処理を行い、23℃で48時間保持して積層フィルムを得た。
塗布液Aを40℃のトルエンで希釈してポリオレフィン濃度1.6重量%とした塗布液をメイヤーバー#6を用いてポリエステルフィルムA上に塗布した後、150℃で5秒間熱処理を行い、23℃で48時間保持して積層フィルムを得た。
塗布液Aを塗布液Bとしたほかは実施例2Bと同様にして積層フィルムを得た。
基材フィルムをポリエステルフィルムAに代えてポリエステルフィルムBとしたほかは実施例1Bと同様にして積層フィルムを得た。
塗布液Aを40℃のトルエンで希釈してポリオレフィン濃度0.5重量%とした塗布液をメイヤーバー#3を用いてポリエステルフィルムA上に塗布した後、150℃で5秒間熱処理を行い、23℃で48時間保持して積層フィルムを得た。
塗布液Aをメイヤーバー#7を用いてポリエステルフィルムA上に塗布した後、150℃で5秒間熱処理を行い、23℃48時間保持して積層フィルムを得た。
基材フィルムをポリエステルフィルムAに代えてポリエステルフィルムCを使用したほかは実施例1Bと同様にして積層フィルムを得た。
基材フィルムをポリエステルフィルムAに代えてポリエチレンテレフタレートフィルム(商品名ダイアホイルT100-50S;三菱化学ポリエステルフィルム社製)を使用したほかは実施例2Bと同様にしてフィルムを得た。
Claims (2)
- 共重合ポリオレフィンを含有する離型層を有するポリエチレンナフタレートフィルムであり、当該離型層表面の反射率の極大波長から換算される離型層の厚みが75~150nmであることを特徴とする強酸ポリマーシート製造用フィルム。
- ポリエチレンテレフタレートを主成分とする層(A層)とポリエチレンナフタレートを主成分とする層(B層)とを含む積層ポリエステルフィルムのB層上に、共重合ポリオレフィンを含有する離型層を有するフィルムであり、B層の厚みが0.5~2.5μmであり、離型層表面の反射率の極大波長から換算される離型層厚みが75~150nmであることを特徴とする強酸ポリマーシート製造用積層フィルム。
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US12/918,397 US20110027579A1 (en) | 2008-02-21 | 2009-02-09 | Film for production of strong acid polymer sheets |
CN2009801057216A CN101945761B (zh) | 2008-02-21 | 2009-02-09 | 强酸聚合物片制造用膜 |
EP09712377.2A EP2246187B1 (en) | 2008-02-21 | 2009-02-09 | Film for production of strong acid polymer sheet |
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JP2008040602A JP2009196221A (ja) | 2008-02-21 | 2008-02-21 | 強酸ポリマーシート製造用フィルム |
JP2008-040606 | 2008-02-21 | ||
JP2008040606A JP5270927B2 (ja) | 2008-02-21 | 2008-02-21 | 強酸ポリマーシート製造用積層フィルム |
JP2008-040602 | 2008-02-21 |
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US (1) | US20110027579A1 (ja) |
EP (1) | EP2246187B1 (ja) |
KR (1) | KR20100117606A (ja) |
CN (1) | CN101945761B (ja) |
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US20190081341A1 (en) * | 2016-03-11 | 2019-03-14 | W.L. Gore & Associates, Inc. | Reflective laminates |
KR20210084363A (ko) | 2021-06-04 | 2021-07-07 | 김수환 | 해상에 설치되는 담수를 이용한 연료생산장치 |
KR20210105852A (ko) | 2021-06-04 | 2021-08-27 | 김수환 | 해수를 이용한 에너지 생산용 해상터미널 |
KR20210105853A (ko) | 2021-06-04 | 2021-08-27 | 김수환 | 벙커링선박에서 공급받는 담수를 이용한 에너지 생산용 해상터미널 |
KR20210105854A (ko) | 2021-06-04 | 2021-08-27 | 김수환 | 벙커링선박으로 공급하는 에너지 생산용 해상터미널 |
KR20210084362A (ko) | 2021-06-04 | 2021-07-07 | 김수환 | 해상에 설치되는 담수를 이용한 연료생산장치 |
KR20210084366A (ko) | 2021-06-04 | 2021-07-07 | 김수환 | 벙커링 선박 |
KR20210105851A (ko) | 2021-06-04 | 2021-08-27 | 김수환 | 에너지 생산용 해상터미널 |
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2009
- 2009-02-09 WO PCT/JP2009/000503 patent/WO2009104366A1/ja active Application Filing
- 2009-02-09 CN CN2009801057216A patent/CN101945761B/zh active Active
- 2009-02-09 EP EP09712377.2A patent/EP2246187B1/en active Active
- 2009-02-09 KR KR1020107018176A patent/KR20100117606A/ko not_active Application Discontinuation
- 2009-02-09 US US12/918,397 patent/US20110027579A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
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EP2246187A4 (en) | 2012-12-19 |
CN101945761A (zh) | 2011-01-12 |
CN101945761B (zh) | 2013-07-24 |
US20110027579A1 (en) | 2011-02-03 |
KR20100117606A (ko) | 2010-11-03 |
EP2246187B1 (en) | 2014-04-09 |
EP2246187A1 (en) | 2010-11-03 |
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