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公开(公告)号：US20080078718A1
公开(公告)日：2008-04-03
申请号：US11630896
申请日：2005-06-27
申请人： Yasuhiro Tada , Shingo Taniguchi , Masayuki Hino , Takeo Takahashi , Kenichi Suzuki , Toshiya Mizuno
发明人： Yasuhiro Tada , Shingo Taniguchi , Masayuki Hino , Takeo Takahashi , Kenichi Suzuki , Toshiya Mizuno
CPC分类号： B01D71/34 , B01D67/0027 , B01D67/003 , B01D69/02 , B01D69/08 , B01D71/38 , B01D2323/20 , B01D2325/24 , B01D2325/30
摘要： A porous membrane for water treatment of the present invention is made of a resin composition containing 100 parts by weight of a polyvinylidene fluoride based resin, and 5 to 13 parts by weight of a polyvinyl alcohol based polymer having a degree of saponification of 10 to 80 mol %. The porous membrane has a permeation wetting tension of 38 to 72 mN/m, and a tensile strength of 7 to 20 MPa, and thus is characterized by having the excellent mechanical strength and wettability. This is a porous membrane for water treatment essentially containing the polyvinylidene fluoride based resin, which allows water treatment to be highly efficiently performed on raw water (river water, industrial waste water, and the like), in particular. The porous membrane is manufactured, firstly, by melt-extruding a mixture composition containing a polyvinylidene fluoride based resin, a polyvinyl alcohol based polymer, a plasticizer, and a solvent, and then by extracting the plasticizer and the solvent from the substance thus extruded.
摘要翻译： 本发明的水处理用多孔膜由含有100重量份聚偏二氟乙烯类树脂的树脂组合物和5〜13重量份皂化度为10〜80的聚乙烯醇系聚合物 mol％。 多孔膜的渗透润湿张力为38〜72mN / m，拉伸强度为7〜20MPa，其特征在于具有优异的机械强度和润湿性。 这是一种基本上含有聚偏二氟乙烯类树脂的水处理用多孔膜，特别是能够对原水（河水，工业废水等）高效地进行水处理。 首先，通过熔融挤出含有聚偏二氟乙烯系树脂，聚乙烯醇类聚合物，增塑剂和溶剂的混合物组合物，然后从由此挤出的物质中提取增塑剂和溶剂来制造多孔膜。
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2.发明授权公开(公告)号：US07780014B2
公开(公告)日：2010-08-24
申请号：US11578425
申请日：2005-04-07
申请人： Yasuhiro Tada , Takeo Takahashi , Masayuki Hino , Shingo Taniguchi , Kenichi Suzuki , Toshiya Mizuno
发明人： Yasuhiro Tada , Takeo Takahashi , Masayuki Hino , Shingo Taniguchi , Kenichi Suzuki , Toshiya Mizuno
CPC分类号： B01D71/34 , B01D67/0011 , B01D67/0018 , B01D67/0027 , B01D67/003 , B01D67/0088 , B01D69/02 , B01D69/08 , B01D2323/20 , B01D2323/48 , B01D2325/24 , B01D2325/32 , B01D2325/34 , D01D5/24 , D01F6/12
摘要： A composition is formed by blending a vinylidene fluoride resin having a relatively high molecular weight and an improved crystallinity represented by a difference Tm2−Tc of at most 32° C. between an inherent melting point Tm2 and a crystallization temperature Tc of the resin with a plasticizer and a good solvent for vinylidene fluoride resin, and the composition is melt-extruded into a hollow fiber-form. The hollow fiber-form extrudate is then cooled to be solidified from an outside thereof by introduction into cooling medium and subjected to extraction of the plasticizer and stretching, thereby forming a hollow fiber porous membrane of vinylidene fluoride resin characterized by co-presence of crystal oriented portion and crystal non-oriented portion recognizable by X-ray diffraction method. The resultant hollow fiber porous membrane of vinylidene fluoride resin has micro-pores of appropriate size and distribution, is excellent in mechanical strength represented by tensile strength and elongation at break and is useful as a water microfiltration membrane.
摘要翻译： 通过将具有相对较高分子量和改善的结晶度的偏二氟乙烯树脂与具有至少32℃的差Tm2-Tc表示的固有熔点Tm2和树脂的结晶温度Tc混合形成组合物， 增塑剂和偏氟乙烯树脂的良溶剂，并将组合物熔融挤出成中空纤维形式。 然后将中空纤维状挤出物从外部冷却，通过引入冷却介质中进行固化，并进行增塑剂的提取和拉伸，形成偏氟乙烯树脂的中空纤维多孔膜，其特征在于，以晶体取向共存 部分和晶体非取向部分可通过X射线衍射法识别。 得到的偏氟乙烯树脂中空纤维多孔膜具有适当尺寸和分布的微孔，机械强度优异，以拉伸强度和断裂伸长率为代表，可用作水微滤膜。
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3.发明授权公开(公告)号：US07455772B2
公开(公告)日：2008-11-25
申请号：US11629350
申请日：2005-06-08
申请人： Yasuhiro Tada , Takeo Takahashi , Masayuki Hino , Shingo Taniguchi , Kenichi Suzuki , Toshiya Mizuno
发明人： Yasuhiro Tada , Takeo Takahashi , Masayuki Hino , Shingo Taniguchi , Kenichi Suzuki , Toshiya Mizuno
CPC分类号： B01D69/08 , B01D67/0011 , B01D67/0018 , B01D67/0027 , B01D67/003 , B01D69/02 , B01D71/34 , B01D2323/20 , B01D2325/24 , B01D2325/30 , B01D2325/32 , B01D2325/34 , Y10T428/249978
摘要： A vinylidene fluoride resin having a weight-average molecular weight as relatively high as 300,000 or higher is mixed with a plasticizer and good solvent for the vinylidene fluoride resin to obtain a composition. A molten extrudate of the composition in a hollow-fiber membrane state is contacted, on its outer side, with a cooling liquid inert to the vinylidene fluoride resin to thereby cool the extrudate. During the solidification, the vinylidene fluoride resin is moderately and mildly crystallized. Thus, a hollow-fiber porous vinylidene fluoride resin membrane is produced which has a high crystallinity represented by an enthalpy of crystal melting 58 J/g or higher. The hollow-fiber porous membrane obtained is excellent in mechanical strength represented by tensile strength and elongation at break and in chemical resistance. It is effectively used as a water microfiltration membrane.
摘要翻译： 将重均分子量相对高达30万以上的偏氟乙烯树脂与偏二氟乙烯树脂的增塑剂和良溶剂混合，得到组合物。 中空纤维膜状态的组合物的熔融挤出物在其外侧与对偏二氟乙烯树脂惰性的冷却液体接触，从而冷却挤出物。 在固化期间，偏二氟乙烯树脂中等温和地结晶。 因此，制造出具有高结晶度的中空纤维多孔偏氟乙烯树脂膜，其结晶度为58J / g以上。 获得的中空纤维多孔膜由拉伸强度和断裂伸长率和耐化学性表现的机械强度优异。 它被有效地用作水微滤膜。
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4.发明申请Vinylidene Fluoride Resin Hollow Filament Porous Membrane, Water Filtration Method Using the Same, and Process for Producing Said Vinylidene Fluoride Resin Hollow Filament Porous Membrane 审中-公开亚乙烯基氟化物树脂空心丝多孔膜，使用其的水过滤方法以及用于生产所述偏氟乙烯树脂中空丝多孔膜的方法公开(公告)号：US20090206035A1
公开(公告)日：2009-08-20
申请号：US11884371
申请日：2006-02-09
申请人： Takeo Takahashi , Yasuhiro Tada , Kenichi Suzuki , Masayuki Hino , Shingo Taniguchi , Toshiya Mizuno
发明人： Takeo Takahashi , Yasuhiro Tada , Kenichi Suzuki , Masayuki Hino , Shingo Taniguchi , Toshiya Mizuno
CPC分类号： B01D69/02 , B01D67/0018 , B01D69/08 , B01D71/34 , B01D2323/20 , B01D2325/022 , B01D2325/24
摘要： A hollow-fiber porous membrane, comprising a hollow fiber-form porous membrane in a network texture of vinylidene fluoride resin showing a pore size distribution in a direction of its membrane thickness including an outer surface-average pore size P1 as measured by a scanning electron microscope and a membrane layer-average pore size P2 as measured by half-dry method giving a ratio P1/P2 of at least 2.5. The hollow-fiber porous membrane is excellent in long-term water filtration performance including efficiency of regeneration by air scrubbing. The hollow-fiber porous membrane is produced through a process, wherein a mixture of vinylidene fluoride resin, a plasticizer and a good solvent for vinylidene fluoride resin, is melt-extruded in a hollow-fiber film and cooled and formed into a solidified film within a cooling medium containing at least a certain proportion of a good solvent for vinylidene fluoride resin.
摘要翻译： 一种中空纤维多孔膜，其包含在偏二氟乙烯树脂的网状结构中的中空纤维状多孔膜，其表现出通过扫描电子测量的包括外表面平均孔径P1的膜厚度方向上的孔径分布 显微镜和通过半干法测量的膜层平均孔径P2，其比值P1 / P2至少为2.5。 中空纤维多孔膜的长期水过滤性能优异，包括通过空气洗涤再生的效率。 中空纤维多孔膜通过以下方法制造，其中偏二氟乙烯树脂，增塑剂和偏二氟乙烯树脂的良溶剂的混合物在中空纤维膜中熔融挤出并冷却并形成固化膜 含有至少一定比例的偏二氟乙烯树脂的良溶剂的冷却介质。
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5.发明申请公开(公告)号：US20070241050A1
公开(公告)日：2007-10-18
申请号：US11578425
申请日：2005-04-07
申请人： Yasuhiro Tada , Takeo Takahashi , Masayuki Hino , Shingo Taniguchi , Kenichi Suzuki , Toshiya Mizuno
发明人： Yasuhiro Tada , Takeo Takahashi , Masayuki Hino , Shingo Taniguchi , Kenichi Suzuki , Toshiya Mizuno
CPC分类号： B01D71/34 , B01D67/0011 , B01D67/0018 , B01D67/0027 , B01D67/003 , B01D67/0088 , B01D69/02 , B01D69/08 , B01D2323/20 , B01D2323/48 , B01D2325/24 , B01D2325/32 , B01D2325/34 , D01D5/24 , D01F6/12
摘要： A composition is formed by blending a vinylidene fluoride resin having a relatively high molecular weight and an improved crystallinity represented by a difference Tm2−Tc of at most 32° C. between an inherent melting point Tm2 and a crystallization temperature Tc of the resin with a plasticizer and a good solvent for vinylidene fluoride resin, and the composition is melt-extruded into a hollow fiber-form. The hollow fiber-form extrudate is then cooled to be solidified from an outside thereof by introduction into cooling medium and subjected to extraction of the plasticizer and stretching, thereby forming a hollow fiber porous membrane of vinylidene fluoride resin characterized by co-presence of crystal oriented portion and crystal non-oriented portion recognizable by X-ray diffraction method. The resultant hollow fiber porous membrane of vinylidene fluoride resin has micro-pores of appropriate size and distribution, is excellent in mechanical strength represented by tensile strength and elongation at break and is useful as a water microfiltration membrane.
摘要翻译： 通过将具有相对较高分子量和改进的结晶度的偏二氟乙烯树脂混合在一起，通过将不同Tm 2 -Tc表示为至多32℃的固有熔点Tm 2和树脂的结晶温度Tc之间的混合物形成组合物 用增塑剂和偏氟乙烯树脂的良溶剂，将组合物熔融挤出成中空纤维形式。 然后将中空纤维状挤出物从外部冷却，通过引入冷却介质中进行固化，并进行增塑剂的提取和拉伸，形成偏氟乙烯树脂的中空纤维多孔膜，其特征在于，以晶体取向共存 部分和晶体非取向部分可通过X射线衍射法识别。 得到的偏氟乙烯树脂中空纤维多孔膜具有适当尺寸和分布的微孔，机械强度优异，以拉伸强度和断裂伸长率为代表，可用作水微滤膜。
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6.发明申请Holow-Fiber Porous Water Filtration Membrane of Vinyldene Fluoride Resin and Process for Producing the Same 有权乙烯基氟树脂的水性纤维多孔水过滤膜及其制备方法公开(公告)号：US20070215540A1
公开(公告)日：2007-09-20
申请号：US11629350
申请日：2005-06-08
申请人： Yasuhiro Tada , Takeo Takahashi , Masayuki Hino , Shingo Taniguchi , Kenichi Suzuki , Toshiya Mizuno
发明人： Yasuhiro Tada , Takeo Takahashi , Masayuki Hino , Shingo Taniguchi , Kenichi Suzuki , Toshiya Mizuno
CPC分类号： B01D69/08 , B01D67/0011 , B01D67/0018 , B01D67/0027 , B01D67/003 , B01D69/02 , B01D71/34 , B01D2323/20 , B01D2325/24 , B01D2325/30 , B01D2325/32 , B01D2325/34 , Y10T428/249978
摘要： A hollow fiber-form porous membrane of vinylidene fluoride resin having a high crystallinity as represented by a crystal melting enthalpy of at least 58 J/g is produced by forming a composition of a vinylidene fluoride resin having a relatively high weight-average molecular weight of at least 3×105 blended with a plasticizer and a good solvent for vinylidene fluoride resin, melt-extruding the composition into a hollow fiber-form film, and solidifying the film by cooling it from an outside thereof by contact with a cooling liquid inert to vinylidene fluoride resin while crystallizing the vinylidene fluoride resin at an appropriately moderate speed. The resultant hollow fiber-form porous membrane is excellent in mechanical strength represented by tensile strength and elongation at break, and also excellent in chemical resistance, thus being effectively used as a water micro-filtration membrane.
摘要翻译： 通过形成具有至少58J / g的结晶熔融焓所表示的具有高结晶度的偏氟乙烯树脂的中空纤维状多孔膜通过形成具有相对高的重均分子量的偏二氟乙烯树脂 与增塑剂和用于偏二氟乙烯树脂的良溶剂共混至少3×10 5，将组合物熔融挤出成中空纤维形式的膜，并通过接触从其外部冷却来固化该膜 与偏二氟乙烯树脂呈惰性的冷却液体，同时以适度适度的速度使偏氟乙烯树脂结晶。 得到的中空纤维状多孔质膜以拉伸强度和断裂伸长率为代表的机械强度优异，耐化学性优异，因此有效地用作水微滤膜。
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7.发明申请Vinylidene Fluoride Resin Hollow Fiber Porous Membrane and Method for Production Thereof 审中-公开亚乙烯基氟树脂中空纤维多孔膜及其生产方法公开(公告)号：US20090261034A1
公开(公告)日：2009-10-22
申请号：US11991955
申请日：2006-09-12
CPC分类号： B01D71/34 , B01D63/024 , B01D67/0027 , B01D67/0086 , B01D69/02 , B01D69/08 , B01D69/087 , B01D2313/24 , B01D2323/12 , B01D2323/20 , C02F1/444 , D01D5/247 , D01F6/12
摘要： A hollow-fiber porous membrane comprising a hollow-fiber form of vinylidene fluoride resin and satisfying the following properties (A) and (B), is provided as a hollow-fiber porous membrane of vinylidene fluoride resin having an average pore size and a further uniform pore size distribution (A) and a large water permeation rate regardless of good efficiency of blocking minute particles (bacteria) (B), as represented by: (A) a ratio Pmax (1 m)/Pm of at most 4.0 between a maximum pore size Pmax (1 m) measured at a test length of 1 m according to the bubble point method and an average pore size Pm of 0.05-0.20 μm measured according to the half dry method; and (B) a ratio F (L=200 mm, v=70%)/PM2 of at least 3000 (m/day·μm2), wherein the ratio F (L=200 mm, v=70%)/Pm2 denotes a ratio between F (L=200 mm, v=70%) which is a value normalized to a porosity v=70% of a water permeation rate F (100 kPa, L=200 mm) measured at a test length L=200 mm under the conditions of a pressure difference of 100 kPa and a water temperature of 25° C. and a square Pm2 of an average pore size Pm. The hollow-fiber porous membrane is produced by a process, comprising: subjecting a stretched hollow-fiber porous membrane of vinylidene fluoride resin to at least two stages of relaxation treatment in a non-wetting environment.
摘要翻译： 提供一种中空纤维多孔膜，其包含中空纤维形式的偏氟乙烯树脂，并满足以下性质（A）和（B））作为平均孔径和另外的平均孔径的偏氟乙烯树脂的中空纤维多孔膜 均匀的孔径分布（A）和大的水渗透速率，而不管堵塞微小颗粒（细菌）（B）的良好效率，如下所示：（A）比值Pmax（1m）/ Pm在 根据泡点法测试的测试长度为1μm的最大孔径Pmax（1μm）和根据半干法测量的平均孔径Pm为0.05-0.20μm; 和（B）比例F（L = 200mm，v = 70％）/ PM2为至少3000（m / day.mum2），其中比率F（L = 200mm，v = 70％）/ Pm2表示 F（L = 200mm，v = 70％）之间的比率，其是在试验长度L = 200时测量的孔隙率v = 70％的渗透速率F（100kPa，L = 200mm）的归一化值 压力差为100kPa，水温为25℃的条件下为平均孔径Pm的平方Pm2。 中空纤维多孔膜通过以下方法制造，该方法包括：使偏氟乙烯树脂的拉伸中空纤维多孔膜在非润湿环境中进行至少两个阶段的松弛处理。
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公开(公告)号：US20080156722A1
公开(公告)日：2008-07-03
申请号：US12007788
申请日：2008-01-15
申请人： Kenichi Suzuki , Yasuhiro Tada , Takeo Takahashi , Masayuki Hino , Kosuke Abe , Toshiya Mizuno
发明人： Kenichi Suzuki , Yasuhiro Tada , Takeo Takahashi , Masayuki Hino , Kosuke Abe , Toshiya Mizuno
CPC分类号： B01D71/34 , B01D67/0011 , B01D67/0018 , B01D67/0027 , B01D67/003 , B01D69/02 , B01D69/08 , B01D2323/12 , B01D2323/20 , B01D2325/02 , D01D5/24 , D01F6/12
摘要： A hollow-fiber porous membrane comprising a hollow fiber-form porous membrane of vinylidene fluoride resin and having an average pore size Pm of 0.05-0.20 μm, a maximum pore size Pmax giving a ratio Pmax/Pm of at most 2.0 between the maximum pore size Pmax and the average pore size Pm and a standard deviation of pore size distribution of at most 0.20 μm based on a pore size distribution according to the half dry/bubble point method (ASTM•F316 and ASTM•E1294) is provided, as a hollow-fiber porous membrane of vinylidene fluoride resin having minute pores with a size (average pore diameter) and a further uniform pore size distribution suitable for water (filtration) treatment. The hollow-fiber porous membrane is produced through a process of producing a hollow-fiber porous membrane by melt-extruding a mixture of a vinylidene fluoride resin, a plasticizer and a good solvent for vinylidene fluoride resin into a hollow fiber-form, followed by cooling and extraction of the plasticizer, wherein the proportion of the good solvent in the total amount of the plasticizer and the good solvent contained in the mixture is increased to 20-35 wt. %.
摘要翻译： 一种中空纤维多孔膜，其包含偏氟乙烯树脂的中空纤维状多孔膜，平均孔径Pm为0.05〜0.20μm，最大孔径Pmax的最大孔径Pmax / Pm为2.0以下， 提供基于根据半干/泡点法（ASTMF316和ASTM.E1294）的孔径分布，孔径分布的平均孔径Pm和孔径分布的至多0.20μm的标准偏差，作为 具有尺寸（平均孔径）的微孔和适于水（过滤）处理的更均匀的孔径分布的偏氟乙烯树脂的中空纤维多孔膜。 中空纤维多孔膜通过将偏氟乙烯树脂，增塑剂和偏氟乙烯树脂的良溶剂的混合物熔融挤出成中空纤维状而制造中空纤维多孔膜的方法制造，然后通过 冷却和提取增塑剂，其中良溶剂在增塑剂和混合物中所含的良溶剂总量中的比例增加到20-35wt。 ％。
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9.发明授权Resin compositions, monofilaments, process for producing the same and fishing lines 失效树脂组合物，单丝，其制造方法和钓鱼线公开(公告)号：US07582353B2
公开(公告)日：2009-09-01
申请号：US11341329
申请日：2006-01-26
申请人： Satoshi Hashimoto , Shingo Taniguchi , Yasuhiro Tada , Masayuki Hino , Masaru Satou , Takeo Takahashi
发明人： Satoshi Hashimoto , Shingo Taniguchi , Yasuhiro Tada , Masayuki Hino , Masaru Satou , Takeo Takahashi
CPC分类号： D01F6/32 , A01K91/00 , Y10T428/2913 , Y10T428/2929 , Y10T428/2931 , Y10T428/2933 , Y10T428/2967
摘要： Monofilaments comprising resin compositions which contain 1% by mass or more of a comonomer component (for example, hexafluoropropylene), have an intrinsic viscosity of 1.3 dl/g or more and a melting point of 165° C. or higher and contain a PVDF-based resin. Owing to the above composition and physical properties, the crystallinity and elastic modulus of the PVDF-based resin are altered. As a result, an appropriate flexibility can be imparted to the monofilaments while preventing deterioration in the mechanical properties.
摘要翻译： 含有1质量％以上的共聚单体成分（例如六氟丙烯）的树脂组合物的单丝的特性粘度为1.3dl / g以上，熔点为165℃以上，含有PVDF- 基树脂。 由于上述组成和物理性质，改变了PVDF基树脂的结晶度和弹性模量。 结果，可以在防止机械性能劣化的同时赋予单丝适当的柔性。
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10.发明授权Vinylidene fluoride based resin porous hollow yarn and method for production thereof 有权偏二氟乙烯系树脂多孔中空丝及其制造方法公开(公告)号：US07569145B2
公开(公告)日：2009-08-04
申请号：US10574111
申请日：2004-09-24
申请人： Yasuhiro Tada , Takeo Takahashi , Masayuki Hino , Toshiya Mizuno , Kosuke Abe
发明人： Yasuhiro Tada , Takeo Takahashi , Masayuki Hino , Toshiya Mizuno , Kosuke Abe
CPC分类号： B01D67/002 , B01D67/0027 , B01D67/003 , B01D67/0088 , B01D69/02 , B01D69/08 , B01D71/34 , B01D2323/20 , B01D2325/12 , B01D2325/20 , D01F6/12
摘要： There is provided a porous hollow fiber of vinylidene fluoride resin which has a water permeation rate that is large per fiber and little dependent on the length, has a large treatment capacity per volume of a filtering module, and is therefore suitable as a microfilter element. That is, a porous hollow fiber, comprising a vinylidene fluoride resin having a weight-average molecular weight of at least 3×105, having a water permeation rate F (m3/m2·day) measured at a pressure difference of 100 kPa and at a water temperature of 25° C. in a range of test length L=0.2-0.8 (m) and expressed in a linear relationship with the test length L of: F=C·L+F0 (formula 1) and satisfying requirements (a)-(d) shown below: (a) a average slope C (/day) of: −20≦C≦0, (b) an intercept (basic permeability) F0 (m3/m2·day) of: F0≧30, (c) a relation between F0 (m3/m2·day) and an average pore diameter P (μm) according to half-dry method of F0/P≧300, and (d) an outer diameter of at most 3 mm.
摘要翻译： 提供了一种偏氟乙烯树脂的多孔中空纤维，其具有每纤维的水渗透速率大，并且几乎不依赖于长度，每个体积的过滤组件具有大的处理能力，因此适合作为微过滤器元件。 也就是说，一种多孔中空纤维，其包含重均分子量为至少3×10 5的偏二氟乙烯树脂，其具有在100千帕的压力差下测得的水渗透速率F（m3 / m2.day） 在测试长度L = 0.2-0.8（m）的范围内，温度为25℃，并且与试验长度L呈线性关系：F = C.L + F0（式1）并满足要求（a） （d）如下所示：（a）平均斜率C（/天）：-20 <= C <= 0，（b）截距（基本渗透率）F0（m3 / m2.day）：F0> = 30，（c）根据F0 / P> = 300的半干法，F0（m3 / m2.day）与平均孔径P（母）之间的关系，（d）最大外径 3毫米。
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