JP3200095B2 - The hydrophilic heat film and manufacturing method thereof - Google Patents

The hydrophilic heat film and manufacturing method thereof

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JP3200095B2
JP3200095B2 JP18421491A JP18421491A JP3200095B2 JP 3200095 B2 JP3200095 B2 JP 3200095B2 JP 18421491 A JP18421491 A JP 18421491A JP 18421491 A JP18421491 A JP 18421491A JP 3200095 B2 JP3200095 B2 JP 3200095B2
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film
saponification
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hydrophilic
polyvinyl acetate
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博義 大屋
幸平 渡辺
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旭化成株式会社
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【発明の詳細な説明】 DETAILED DESCRIPTION OF THE INVENTION

【0001】 [0001]

【産業上の利用分野】本発明はポリフッ化ビニリデン系ポリマーとポリビニルアルコール系ポリマーのブレンドポリマーからなる高度に親水化された親水性耐熱膜、及びその製造方法に関する。 The present invention relates to a highly hydrophilic hydrophilic heat film made of a blend polymer of polyvinylidene fluoride polymer and a polyvinyl alcohol polymer, and a method of manufacturing the same.

【0002】 [0002]

【従来の技術】従来、人工膜の素材としては、セルロースアセテート等のセルロース誘導体、ポリアクリロニトリル、ポリスルホン、ポリメタクリル酸メチル、ポリアミド等、多くの高分子化合物が用いられてきた。 Conventionally, as a material of the artificial membrane, cellulose derivatives such as cellulose acetate, polyacrylonitrile, polysulfone, polymethyl methacrylate, polyamide, etc., many polymer compounds have been used. 一方、 on the other hand,
ポリフッ化ビニリデン樹脂は、機械的に強固で、熱安定性がよく耐熱性に優れており135℃で大部分の薬品に侵されない、また耐放射線性、耐侯性に優れており、更に耐薬品性に極めて優れており、ハロゲン化合物、炭化水素、アルコール、有機酸、塩素系溶剤、酸、 Polyvinylidene fluoride resins, mechanically robust thermal stability in well-135 ° C. excellent heat resistance not attacked for most chemicals, also radiation resistance, has excellent weather resistance, further chemical resistance It is very excellent, halogen compounds, hydrocarbons, alcohols, organic acids, chlorinated solvents, acids,
アルカリ、大部分の強酸化剤、還元剤、塩類に全くおかされず耐薬品性ではポリスルホン、ポリエーテルスルホンより優れた素材である。 Alkali, most of the strong oxidizing agent, a reducing agent, at all affected without chemical resistance salt which is a material excellent polysulfone, than polyethersulfone.

【0003】しかしながらポリフッ化ビニリデン樹脂膜は臨界表面張力が25.0dyne/cmと小さく、ポリフッ化ビニリデン樹脂膜はセルロース等の親水性樹脂膜と比較して、さらにはポリスルホン、ポリエーテルスルホン等の疎水性樹脂膜と比較しても極めて疎水性が強く、「一度乾燥すると濡れにくい」、「透水性能が低い」、「膜面が疎水性相互作用により汚染されやすい」 However polyvinylidene fluoride resin film the critical surface tension as small as 25.0dyne / cm, polyvinylidene fluoride resin film is compared to the hydrophilic resin film such as cellulose, more polysulfone, hydrophobic polyether sulfone rESIN film extremely hydrophobic is strong even in comparison, "once the hard wet dry", "water permeability is low", "membrane surface is likely to be contaminated by a hydrophobic interaction"
など数多くの欠点があった。 There has been a number of disadvantages, such as. 特に医薬品製造工程においてタンパク質等の生理活性物質の分離・精製等に使用される場合、膜面への吸着・変性は回収率の低下を招くと同時に、膜孔の閉塞によるろ過速度の急激な低下を引き起こすため、深刻な問題となっていた。 Especially when used in separation and purification of physiologically active substances such as proteins in the pharmaceutical manufacturing process, and at the same time the adsorption and denaturation of the membrane surface leads to a decrease of recovery rate, a sharp drop in filtration rate due to clogging of the membrane pores to cause, it had become a serious problem.

【0004】疎水性樹脂膜を親水化する方法として例えば、特開昭53−13679号公報、特開昭59−19 [0004] For example as a method for hydrophilizing a hydrophobic resin film, JP 53-13679, JP-Sho 59-19
6322号公報などはスルホン酸基を、特開昭57−1 Publication such as a sulfonic acid group No. 6322, JP-A-57-1
74104号公報は主鎖にポリエチレンイミンポリマー類を、それぞれ導入もしくはグラフトして親水化している。 74104 Patent Publication No. polyethyleneimine polymers in the main chain, and hydrophilic respectively introduced or grafted. また特開昭62−125802号公報は親水性ポリマーであるビニル系重合体のポリビニルピロリドンを疎水性樹脂膜にブレンドしている。 The JP 62-125802 discloses is a blend of polyvinylpyrrolidone of the vinyl polymer is a hydrophilic polymer to a hydrophobic resin layer. しかし、いずれの親水基、親水性ポリマーも極性が強く、荷電を有する溶質、 However, any hydrophilic group, the hydrophilic polymer also strongly polar solutes have charged,
特に両性電解質であるタンパク質などを含む溶液に対してはむしろ逆効果であった。 It was counterproductive rather to a solution, particularly including proteins, an amphoteric electrolyte.

【0005】極性が水分子と同程度である親水性に優れたポリマーとしてポリビニルアルコール系ポリマーがあるが、ポリビニルアルコール系ポリマーは親水性が強過ぎるため、ポリフッ化ビニリデン樹脂のような分子凝集力が大きいポリマーとの均一なブレンド体を得ることは困難であった。 [0005] polarity is polyvinyl alcohol polymer as an excellent polymer hydrophilic is comparable with water molecules, but because the polyvinyl alcohol-based polymer is hydrophilic is too strong, the molecular cohesive force, such as polyvinylidene fluoride resin to obtain a homogeneous blend with the big polymer has been difficult.

【0006】 [0006]

【発明が解決しようとする課題】これまでに提案されたポリフッ化ビニリデン樹脂膜を親水化する方法はいずれも親水化が意味のある程度に達成されていないか、もしくは親水化が達成されても極性が強すぎるため、タンパク質等の荷電を有する溶質を含む溶液に対しては効果がない方法ばかりである。 THE INVENTION Problems to be Solved] It Any method for hydrophilizing the proposed polyvinylidene fluoride resin film before or not to some extent achieved hydrophilizing meaning, or even hydrophilization is achieved polarity because too strong, it is only ineffective way to a solution containing a solute having a charge such as proteins. 従って、本発明が解決しようとする課題は極性が水分子と同程度である高度に親水化された親水性耐熱膜及びその製造方法を提供することである。 Accordingly, an object of the present invention is to provide is that polarity is to provide a highly hydrophilic hydrophilic heat film and its manufacturing method of the same order as water molecules.

【0007】 [0007]

【課題を解決するための手段】上記課題を解決するため鋭意検討した結果本発明に至った。 Means for Solving the Problems] accomplished the present invention result of intensive studies for solving the above problems. 即ち、本発明の第1 That is, the first invention
は、ポリフッ化ビニリデン系ポリマーとポリビニルアルコール系ポリマーのブレンドポリマーからなることを特徴とする親水性耐熱膜、である。 A hydrophilic heat film, which consists of a polyvinylidene fluoride polymer and blend polymer of polyvinyl alcohol-based polymer, a. この親水性耐熱膜において、ポリビニルアルコール系ポリマーのポリマー全体量に対する割合が1〜60%であることが好ましい。 In this hydrophilic heat film, it is preferable ratio polymer total amount of the polyvinyl alcohol-based polymer is 1 to 60%.

【0008】また、本発明の親水性耐熱膜において、ポリビニルアルコール系ポリマーがポリビニルアルコールであるか、又はけん化度10モル%以上100%未満に部分けん化されたポリ酢酸ビニルであることが好ましい。 Further, in the hydrophilic heat film of the present invention, the polyvinyl alcohol-based polymer or a polyvinyl alcohol, or preferably a partially hydrolyzed polyvinyl acetate saponification degree less than 10 mol% to 100%. 本発明の第2は、ポリフッ化ビニリデン系ポリマーとポリ酢酸ビニルを混和溶解した溶液により製膜し、その後ポリ酢酸ビニルをけん化度10モル%以上100% The second of the present invention, a polyvinylidene fluoride polymer and polyvinyl acetate to form a film by solution mixing dissolved, after which the polyvinyl acetate saponification degree of 10 mol% to 100%
未満に部分けん化されたポリ酢酸ビニル、あるいはけん化度100%のポリビニルアルコールにけん化することを特徴とする親水性耐熱膜の製造方法、である。 Is a manufacturing method, a hydrophilic heat film, characterized in that the saponified partially saponified polyvinyl acetate or saponification of 100% polyvinyl alcohol, below.

【0009】以下本発明を詳細に記述する。 [0009] describing the invention in detail below. 本発明で用いるポリフッ化ビニリデン樹脂膜は通常、 ( CF 2 −CH 2 )r (rは正の整数) の化学構造を持ち、一分子中の平均フッ素含有量が50 Polyvinylidene fluoride resin film used in the present invention typically has a chemical structure has an average fluorine content in one molecule of (CF 2 -CH 2) r ( r is a positive integer) 50
%〜60%のフッ素化合物であり、好ましくはメチレン基とフッ化メチレン基が交互に安定した形で結合した結晶化度の高く、また平均分子量が5×10 3以上と高いものである。 % It is 60% of the fluorine compound is preferably higher and higher of bound crystallinity in the form of methylene and methylene fluoride group is stable alternately, the average molecular weight of at least 5 × 10 3 ones. このようなポリフッ化ビニリデン樹脂は溶媒中で長期にわたり安定であり製膜しやすい。 Such polyvinylidene fluoride resin tends to a stable film for a long time in a solvent. また本発明に用いるポリ酢酸ビニルは平均重合度100〜500 The polyvinyl acetate used in the present invention has an average polymerization degree of from 100 to 500
0であるが、製膜の容易さから平均重合度500〜15 It is zero, the average polymerization degree of the ease of film 500-15
00が特に望ましい。 00 is particularly desirable. 本発明の親水性耐熱膜はポリフッ化ビニリデン系ポリマーとポリ酢酸ビニルをある混合比に溶解した溶液を用いて、公知技術により中空状もしくは平膜状に製膜した後、ポリ酢酸ビニルをけん化度10 The hydrophilic heat film of the present invention using a solution obtained by dissolving the mixture ratio with a polyvinylidene fluoride-based polymer and polyvinyl acetate, hollow or after film formation to flat film, a polyvinyl acetate saponification degree by known techniques 10
%以上100%未満に部分けん化されたポリ酢酸ビニル、あるいはけん化度100%のポリビニルアルコールにけん化処理することを特徴とする。 Partially saponified polyvinyl acetate less than 100% or more%, or wherein the saponification treatment to the degree of saponification of 100% polyvinyl alcohol.

【0010】製膜原液に使用する有機溶剤はポリフッ化ビニリデン樹脂及びポリ酢酸ビニルを溶解するものであればいずれも用い得るが、特に好ましくは100℃以下の温度範囲でこれらのポリマーを30%重量以上の濃度に溶解し得る能力を持つもので、そのような溶剤として例えばN−メチル−2−ピロリドン、ジメチルホルムアミド、ジメチルアセトアミド等があげられる。 [0010] Film organic solvent used in the dope may use any as long as it dissolves the polyvinylidene fluoride resin and polyvinyl acetate, but particularly preferably 30% by weight of these polymers in a temperature range of 100 ° C. or less those having the ability to be dissolved in a concentration of above, such solvents as for example N- methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide and the like.

【0011】該製膜原液におけるポリフッ化ビニリデン樹脂の濃度組成は製膜可能でかつ膜としての性能を有する範囲であればよく、10〜50重量%である。 [0011] Concentration Composition of polyvinylidene fluoride resin in the formulation the spinning solution may be in the range having the properties as film-forming possible and film, from 10 to 50 wt%. また高い透水性、大きな分画分子量を得るためにはポリマー濃度は下げるべきで、この場合望ましくは10〜25重量%である。 The high water permeability, large in order to obtain a fractional molecular weight polymer concentration should decrease, this case is preferably 10 to 25 wt%. ポリ酢酸ビニルの濃度組成はけん化処理後に十分な親水性が得られる範囲であればよく、またけん化度を調整することにより親水性を自由に調整できるが、 Concentration composition of polyvinyl acetate may be in the range sufficient hydrophilicity is obtained after saponification treatment, also it can be freely adjusted hydrophilic by adjusting the degree of saponification,
望ましくは1〜15重量%がよい。 Preferably it is 1-15 wt%. また、原液の溶解性、粘度を制御する目的で無機塩、界面活性剤、グリコール類等の第4成分、第5成分を添加することも可能であり、それは求める透水性や分画分子量により随意行えばよい。 Further, the solubility of the stock solution, inorganic salts for the purpose of controlling the viscosity, surface active agents, fourth component such as glycols, it is also possible to add a fifth component, it optionally by water permeability and fractional molecular weight of obtaining it may be performed.

【0012】以上の条件により調整した製膜原液を用いて公知技術により製膜を行う。 Performing film by a known technique using a film-forming solution was adjusted by [0012] or more. 平膜の場合、該製膜原液を平坦な基盤上に流展しその後凝固浴中に浸漬する。 For flat membrane is immersed in angel then coagulating bath flow the formulation film stock on a flat foundation. また中空糸状膜については、中空形態を保つため注入液を用いる。 With respect to the hollow fiber membranes, using infusion to keep the hollow form. 注入液は求める透水性、分画分子量により適宜最良組成を決めればよいし、また気体を注入させることも可能である。 Injectate permeable to seek, may be determined as appropriate best composition by fractional molecular weight, it is also possible to inject the gas. 同様に凝固浴中の凝固剤も平膜、中空糸膜いずれの場合でも求める膜性能により適宜最良組成を決めればよく特に限定されるものではない。 But the invention is particularly well be determined as appropriate best composition defined by similarly coagulation bath of coagulant also flat membrane, membrane performance to determine any case the hollow fiber membranes. 中空糸膜の場合、紡口から凝固浴までの距離は0cm以上150c For hollow fiber membranes, the distance from the spinneret to the coagulation bath 0cm more 150c
m以下であり、特に0cm以上30cm以下が紡糸安定性から望ましい。 m or less, particularly 0cm than 30cm or less is desirable from the spinning stability.

【0013】上記のようにしてつくられた平膜あるいは中空糸膜はこのままでは親水性の効力はほとんどなく、 [0013] a flat membrane or a hollow fiber membrane made as described above is almost no effect of the hydrophilic remains this,
以下に記述する方法によりポリ酢酸ビニルをけん化度1 Saponification degree 1 polyvinylacetate by the method described below
0%以上にけん化処理することによりはじめて意味のある親水化が達成される。 First meaningful hydrophilization is achieved by saponification to 0% or more. 平膜あるいは中空糸膜を水洗処理により十分に溶剤を除去した後、けん化処理液に浸漬する。 After sufficiently removing the solvent by water washing the planar membrane or hollow fiber membrane is immersed in saponification treatment solution. けん化処理液はポリ酢酸ビニルのエーテル結合部分を加水分解によって水酸基に置換するするものであればいずれでもよく、一般にアルカリ性溶液である。 Saponified solution may be any as long as it replaces the ether linkage portion of the polyvinyl acetate to hydroxyl by hydrolysis, generally an alkaline solution. またその濃度、処理時間、処理温度によりけん化度を自由に調整できることはいうまでもない。 The concentration, treatment time, can of course be freely adjusted saponification degree by the processing temperature.

【0014】以下に本発明の実施例を示すが、本発明はこれらに限定されるものではない。 [0014] Examples of the present invention below, the present invention is not limited thereto.

【0015】 [0015]

【実施例1】ジメチルアセトアミド(以下DMACと略記)65.0g、分散溶媒としてジオキサン5.0g、 EXAMPLE 1 dimethylacetamide (hereinafter DMAC abbreviated) 65.0 g, dioxane 5.0g as a dispersion solvent,
界面活性剤としてポリオキシエチレンソルビタンモノオレート(花王アトラス社製、商品名Tween80)5 Surfactants as polyoxyethylene sorbitan monooleate (manufactured by Kao Atlas Co., Ltd., trade name Tween 80) 5
gの混合溶媒にポリ酢酸ビニル(平均重合度1500、 g mixed solvent of the polyvinyl acetate (average degree of polymerization 1500,
和光純薬社製)5gを室温で溶解後、ポリフッ化ビニリデン樹脂(三菱油化社、商品名Kynar)15gを加えさらに60℃で9時間溶解し真空脱胞後製膜原液とした。 After dissolving manufactured by Wako Pure Chemical Industries, Ltd.) 5 g at room temperature, polyvinylidene fluoride resin (Mitsubishi Petrochemical Co., was tradename Kynar) 15 g 9 hours dissolved in the added further 60 ° C. vacuum de 胞後 casting dope. 通常の方法によりベーカー式アプリケーターを用い40℃保温でガラス板上に流展後、60℃の水浴中で凝固させた後水洗により十分に溶剤を除去し平膜を得た。 After leveling the usual manner on a glass plate at 40 ° C. incubated using a baker type applicator gave flat membrane sufficiently removing the solvent by washing with water was allowed to coagulate in a water bath at 60 ° C..
この平膜 100gを50℃、1N NaOH 50 The flat membrane 100g 50 ℃, 1N NaOH 50
%エタノール水溶液 1000mlに3時間浸漬しけん化処理を行った。 3 hours immersion Watashiken treatment was performed% aqueous ethanol 1000 ml. 表1に処理時間、けん化度、透水性能及び各種タンパク質の吸着量を示した。 Processing time Table 1, saponification degree, showed an adsorption amount of water permeability and various proteins. けん化度は加水分解物の定量により求めた。 Degree of saponification was determined by quantification of hydrolyzate. なおタンパク質吸着量は以下の方法で測定した。 Note protein adsorption was measured by the following method.

【0016】放射性同位元素でラベルされたタンパク質を0.01mg/mlになるようにリン酸緩衝液(pH [0016] Radioactive isotopes phosphate buffer to the labeled protein to 0.01 mg / ml in (pH
=7.0、イオン強度0.15)に溶解し試験液とした。 = 7.0, was dissolved in ionic strength 0.15) test liquid. 膜面積 1×10 -32の被試験膜を容量 100 Capacity under test film membrane area 1 × 10 -3 m 2 100
mlの試験液に38℃で1時間浸漬した後、水中で15 After soaking for 1 hour at 38 ° C. in ml of the test solution, 15 in water
時間被試験膜を洗浄し十分に非吸着タンパク質を洗い落とした。 Time was washed under test film was washed off sufficiently non-adsorbed proteins. その後ガイガーカウンターで吸着タンパク質量を直接定量した。 It was quantified adsorbed protein mass directly in the subsequent Geiger counter. なお平膜の膜面積は表及び裏の表面積の和とした。 Note membrane area of ​​the flat film was the sum of the surface area of ​​the front and back.

【0017】 [0017]

【実施例2】実施例1と同様な方法により平膜を得た。 EXAMPLE 2 to obtain a flat film by a method similar to the first embodiment.
この平膜 100gを50℃、1NNaOH 50% The flat membrane 100g 50 ℃, 1NNaOH 50%
エタノール溶液 1000mlに20時間浸漬しけん化処理を行った。 It was 20 hours immersion Watashiken treatment in an ethanol solution 1000 ml. 表1に処理時間、けん化度、透水性能及び各種タンパク質の吸着量を示した。 Processing time Table 1, saponification degree, showed an adsorption amount of water permeability and various proteins. けん化度、タンパク質吸着量は実施例1と同様の方法で測定した。 Degree of saponification, protein adsorption was measured in the same manner as in Example 1.

【0018】 [0018]

【比較例1】実施例1と同様な方法で平膜を得た。 [Comparative Example 1] was obtained flat film in the same manner as in Example 1. 但しけん化処理は行わなかった。 However saponification process was not carried out. 表1にけん化度、透水性能、分画分子量及び各種タンパク質の吸着量を示した。 Degree of saponification Table 1 shows water permeability, the adsorption amount of a fractional molecular weight and various proteins.
けん化度、タンパク質吸着量は実施例1と同様の方法で測定した。 Degree of saponification, protein adsorption was measured in the same manner as in Example 1.

【0019】 [0019]

【比較例2】実施例1と同様な方法により平膜を得た。 [Comparative Example 2] was obtained flat film in the same manner as described in Example 1.
この平膜 100gを50℃、1NNaOH 50% The flat membrane 100g 50 ℃, 1NNaOH 50%
エタノール溶液 1000mlに1時間浸漬しけん化処理を行った。 It was carried out for 1 hour immersion Watashiken treatment in an ethanol solution 1000 ml. 表1に処理時間、けん化度、透水性能及び各種タンパク質の吸着量を示した。 Processing time Table 1, saponification degree, showed an adsorption amount of water permeability and various proteins. けん化度、タンパク質吸着量は実施例1と同様の方法で測定した。 Degree of saponification, protein adsorption was measured in the same manner as in Example 1.

【0020】 [0020]

【実施例3】実施例1と同等の製膜原液を注入液にDM EXAMPLE 3 DM The film-forming solution equivalent to Example 1 infusion
AC/水=1/1を用いて、内径0.64mm、外径1.04mmの環状オリフィスからなる紡口より吐出させ、紡口から30cm下方に設置した60℃の水浴中を通過させ、通常の方法で水洗後カセに巻き取り中空糸膜を得た。 With AC / water = 1/1, an inner diameter of 0.64 mm, was discharged from the spinneret comprising a circular orifice with an outer diameter of 1.04 mm, and passed through a 60 ° C. water bath which was placed 30cm downward from the spinneret, usually to obtain a winding hollow fiber membrane after washing with water hank in ways. この中空糸膜 100gを50℃、1N Na The hollow fiber membrane 100g 50 ℃, 1N Na
OH 50%エタノール水溶液 1000mlに5時間浸漬しけん化処理を行った。 The 5 hour immersion Watashiken treatment was performed OH 50% aqueous ethanol 1000 ml. 表2に処理時間、けん化度、透水性能及び各種タンパク質の吸着量を示した。 Processing time Table 2, degree of saponification, showed an adsorption amount of water permeability and various proteins. けん化度、タンパク質吸着量は実施例1と同様の方法で測定した。 Degree of saponification, protein adsorption was measured in the same manner as in Example 1. なお中空糸膜の膜面積は外表面、内表面の膜面積の和とした。 Note membrane area of ​​the hollow fiber membranes was the sum of the membrane area of ​​the outer surface, the inner surface.

【0021】 [0021]

【実施例4】実施例3と同様な方法により中空糸膜を得た。 To obtain a hollow fiber membrane by Example 4 the same manner as in Example 3. この中空糸膜 100gを50℃、1N NaO The hollow fiber membrane 100g 50 ℃, 1N NaO
H 50%エタノール溶液 1000mlに15時間浸漬しけん化処理を行った。 15 hour immersion Watashiken treatment was carried out H 50% ethanol solution 1000 ml. 表2に処理時間、けん化度、透水性能及び各種タンパク質の吸着量を示した。 Processing time Table 2, degree of saponification, showed an adsorption amount of water permeability and various proteins. けん化度、タンパク質吸着量は実施例1と同様の方法で測定した。 Degree of saponification, protein adsorption was measured in the same manner as in Example 1.

【0022】 [0022]

【比較例3】実施例3と同様な方法により中空糸膜を得た。 To obtain a hollow fiber membrane by [Comparative Example 3] the same manner as in Example 3. 但しけん化処理は行わなかった。 However saponification process was not carried out. 表2に処理時間、 Processing time in Table 2,
けん化度、透水性能及び各種タンパク質の吸着量を示した。 Degree of saponification, showed an adsorption amount of water permeability and various proteins. けん化度、タンパク質吸着量は実施例1と同様の方法で測定した。 Degree of saponification, protein adsorption was measured in the same manner as in Example 1.

【0023】 [0023]

【比較例4】実施例3と同様な方法により中空糸膜を得た。 To obtain a hollow fiber membrane by [Comparative Example 4] the same manner as in Example 3. この中空糸膜 100gを50℃、1N NaO The hollow fiber membrane 100g 50 ℃, 1N NaO
H 50%エタノール 1000mlに1時間浸漬しけん化処理を行った。 1 hour immersion Watashiken treatment was carried out H 50% ethanol 1000 ml. 表2に処理時間、けん化度、透水性能及び各種タンパク質の吸着量を示した。 Processing time Table 2, degree of saponification, showed an adsorption amount of water permeability and various proteins. けん化度、タンパク質吸着量は実施例1と同様の方法で測定した。 Degree of saponification, protein adsorption was measured in the same manner as in Example 1.

【0024】 [0024]

【表1】 [Table 1]

【0025】 [0025]

【表2】 [Table 2]

【0026】 [0026]

【発明の効果】本発明のポリフッ化ビニリデン系ポリマーとポリビニルアルコール系ポリマーのブレンドポリマーからなる親水性耐熱膜は、ポリビニルアルコール系ポリマーの優れた親水性、ポリフッ化ビニリデン樹脂の優れた耐熱性、耐薬品性を合わせ持つ全く新規な人工膜であり、医薬品製造、食品製造など一般工業分野のみならず、濾過型人工腎臓をはじめとする医療分野などにおいて使用するに十分な性能を持つものである。 Hydrophilic resistant film made of a polyvinylidene fluoride polymer and blend polymer of poly vinyl alcohol polymer of the present invention exhibits excellent hydrophilic polyvinyl alcohol-based polymers, excellent heat resistance of the polyvinylidene fluoride resin, resistant is quite novel artificial membrane having both chemical resistance, pharmaceutical production, food not general industrial areas only and manufacturing, and has a sufficient performance to be used in medical fields including filtration type artificial kidney.

Claims (2)

    (57)【特許請求の範囲】 (57) [the claims]
  1. 【請求項1】 ポリフッ化ビニリデン系ポリマーとポリ酢酸ビニルを混和溶解した溶液から製膜され、その後ポリ酢酸ビニルが、けん化度100モル%のポリビニルアルコールにけん化されたことを特徴とする親水性耐熱膜。 1. A formed as a film of polyvinylidene fluoride-based polymer and polyvinyl acetate from a solution was mixed dissolved, then polyvinyl acetate, a hydrophilic heat, characterized in that it is saponified to a degree of saponification of 100 mol% of polyvinyl alcohol film.
  2. 【請求項2】 ポリフッ化ビニリデン系ポリマーとポリ酢酸ビニルを混和溶解した溶液により製膜し、その後ポリ酢酸ビニルをけん化度10モル%以上100 モル %未満に部分けん化されたポリ酢酸ビニル、あるいはけん化度100% モルのポリビニルアルコールにけん化することを特徴とする親水性耐熱膜の製造方法。 Wherein the polyvinylidene fluoride-based polymer and polyvinyl acetate to form a film by solution mixing dissolved, then polyvinyl acetate partially saponified polyvinyl acetate to a degree of saponification of less than 10 mol% to 100 mol%, or saponification method for producing a hydrophilic heat film, characterized in that the saponified degree 100% mole of polyvinyl alcohol.
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