JP6226535B2 - Anionic polyketone porous membrane - Google Patents
Anionic polyketone porous membrane Download PDFInfo
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- JP6226535B2 JP6226535B2 JP2013047322A JP2013047322A JP6226535B2 JP 6226535 B2 JP6226535 B2 JP 6226535B2 JP 2013047322 A JP2013047322 A JP 2013047322A JP 2013047322 A JP2013047322 A JP 2013047322A JP 6226535 B2 JP6226535 B2 JP 6226535B2
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- Prior art keywords
- polyketone
- porous membrane
- polyketone porous
- particle size
- minutes
- Prior art date
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Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
本発明は、アニオン性ポリケトン多孔膜及びその用途に関する。さらに詳しくは、本発明は、該アニオン性ポリケトン多孔膜を含む粒子分画性、ゲル吸着性、及びイオン吸着性に優れた液体ろ過フィルターに関する。 The present invention relates to an anionic polyketone porous membrane and use thereof. More specifically, the present invention relates to a liquid filtration filter excellent in particle fractionation, gel adsorption, and ion adsorption including the anionic polyketone porous membrane.
近年、半導体・電子部品製造、バイオ医薬品分野、ケミカル分野、食品工業分野の製造プロセスにおいて、微粒子、ゲル、ウイルス等の不純物を効率的に除去することができる濾材が求められている。濾過対象物のサイズよりも小さい孔径の濾材を使用すれば、上記不純物はある程度までは除去可能である。しかしながら、一般に孔径が小さくなる程、濾過における圧力損失が大きくなり、透過流速が減少してしまう。そこで、極めて小さい不純物を十分に濾過でき、なおかつ圧力損失が少ない濾材が求められている。 In recent years, filter media capable of efficiently removing impurities such as fine particles, gels and viruses have been demanded in manufacturing processes in semiconductor / electronic component manufacturing, biopharmaceutical field, chemical field and food industry field. If a filter medium having a pore size smaller than the size of the object to be filtered is used, the impurities can be removed to some extent. However, in general, the smaller the pore size, the greater the pressure loss in filtration and the lower the permeate flow rate. Therefore, there is a demand for a filter medium that can sufficiently filter very small impurities and has little pressure loss.
近年、例えば積層セラミックコンデンサーの分野などでは、高容量化や小型化が進み、積層の厚みの低減化が求められ、原料粒子の小孔径化技術が求められている。粗大粒子が存在すると短絡の要因となるため、これらを確実に除去する粒子分画用フィルターが必要になっている。また、原料粒子のスラリーは極めて粘度が高いため、濾過抵抗が低く、詰まり難いフィルター性能が要求されている。現在使用されている分画フィルター用濾材としてはポリプロピレン不織布等が挙げられるが、濾過精度が低く、また、濾過抵抗が高いという問題がある。 In recent years, for example, in the field of multilayer ceramic capacitors and the like, higher capacity and smaller size have progressed, and a reduction in the thickness of the multilayer has been demanded, and a technology for reducing the pore size of raw material particles has been demanded. The presence of coarse particles causes a short circuit, and thus a particle fraction filter that reliably removes these particles is required. Further, since the slurry of raw material particles has a very high viscosity, filter performance is required that has a low filtration resistance and is difficult to clog. As a filter material for a fraction filter currently used, polypropylene nonwoven fabric and the like can be mentioned. However, there are problems that filtration accuracy is low and filtration resistance is high.
また、一部のフィルターでは、処理気液が有機溶媒である場合、腐食性を有する場合があり、また、高温環境下で使用される場合もある。このような場合、フィルターには耐薬品性、化学安定性、耐熱性が要求される場合が多い。現在、微小な不純物等の除去が可能で、かつ耐薬品性を持つ濾材として、ポリエチレン多孔膜またはポリテトラフルオロエチレン多孔膜が用いられている。しかしながら、ポリエチレン多孔膜は耐熱性が低いという問題がある。また、ポリテトラフルオロエチレン多孔膜は非常に高価であり、１０ｎｍ程度の微小な不純物を除去できる孔径を持った濾材を作りにくいという問題がある。更に、上記濾材は共に疎水性であり、水系の処理液を濾過する場合には、濾材に予め親水化処理を施しておくか、濾材を使用前にアルコール浸漬してから使用しなければならないという問題がある。 Further, in some filters, when the treatment gas / liquid is an organic solvent, the filter may be corrosive and may be used in a high temperature environment. In such cases, the filter is often required to have chemical resistance, chemical stability, and heat resistance. Currently, a polyethylene porous membrane or a polytetrafluoroethylene porous membrane is used as a filter medium that can remove minute impurities and has chemical resistance. However, the polyethylene porous membrane has a problem of low heat resistance. Further, the polytetrafluoroethylene porous membrane is very expensive, and there is a problem that it is difficult to make a filter medium having a pore diameter capable of removing minute impurities of about 10 nm. Furthermore, both of the above filter media are hydrophobic, and when filtering an aqueous treatment liquid, the filter media must be subjected to hydrophilic treatment in advance, or the filter media must be used after being immersed in alcohol before use. There's a problem.
ところで、パラジウム又はニッケルを触媒として一酸化炭素とオレフィンとを重合させることにより得られる、一酸化炭素とオレフィンとが完全交互共重合した脂肪族ポリケトン（以下、ポリケトンともいう。）が知られている。ポリケトンは、その高い結晶性により、繊維又はフィルムとしたときに、高力学物性、高融点、耐有機溶媒性、耐薬品性等の特性を有する。特に、オレフィンがエチレンの場合、該ポリケトンの融点は２４０℃以上となる。このようなポリケトンは、例えばポリエチレンと比較して耐熱性に優れる。従って、ポリケトンを加工して多孔膜とすることで得られるポリケトン多孔膜も、耐熱性と耐薬品性とを持つ。更に、ポリケトンは水及び各種有機溶媒との親和性があること、また、原料の一酸化炭素及びエチレンは比較的安価であり、ポリケトンのポリマー価格が安くなる可能性があることから、孔径の小さいポリケトン多孔膜は濾材として産業上の活用が期待できる。 By the way, an aliphatic polyketone (hereinafter also referred to as a polyketone) obtained by polymerizing carbon monoxide and an olefin using palladium or nickel as a catalyst and in which carbon monoxide and an olefin are completely alternately copolymerized is known. . Due to its high crystallinity, polyketone has properties such as high mechanical properties, high melting point, organic solvent resistance, and chemical resistance when it is made into a fiber or film. In particular, when the olefin is ethylene, the melting point of the polyketone is 240 ° C. or higher. Such a polyketone is excellent in heat resistance as compared with, for example, polyethylene. Therefore, the polyketone porous film obtained by processing polyketone to form a porous film also has heat resistance and chemical resistance. In addition, since the polyketone has an affinity with water and various organic solvents, and since carbon monoxide and ethylene as raw materials are relatively inexpensive, the polymer price of the polyketone may be reduced, so the pore size is small. Polyketone porous membranes are expected to be industrially utilized as filter media.
ポリケトン多孔膜が濾材として有用であることは、例えば、以下の特許文献１及び特許文献２に記載されている。しかしながら、特許文献１及び特許文献２に開示されたポリケトン多孔膜は、孔径より大きなサイズの粒子の除去は可能であるものの、濾過抵抗が大きく、交換頻度も高く、濾過寿命が不十分であるという問題を有しており、また、小さなゲル状異物に対しては、濾過精度が不十分であった。 The fact that the polyketone porous membrane is useful as a filter medium is described in, for example, Patent Document 1 and Patent Document 2 below. However, although the polyketone porous membrane disclosed in Patent Document 1 and Patent Document 2 can remove particles having a size larger than the pore diameter, it has high filtration resistance, high replacement frequency, and insufficient filtration life. There is a problem, and the filtration accuracy was insufficient for small gel-like foreign matters.
一方、特許文献１及び特許文献２に開示されたポリケトン多孔膜を粒子分画フィルターに用いた場合は、分画性能についてはある程度目的を達成することが可能であるものの、吸着による収率低下や濾過寿命が短くなるという問題があった。 On the other hand, when the polyketone porous membrane disclosed in Patent Document 1 and Patent Document 2 is used for a particle fraction filter, the objective of the fractionation performance can be achieved to some extent, There was a problem that the filtration life was shortened.
本発明が解決しようとする課題は、耐熱性、耐薬品性を有し、アニオン性粒子の高精度の分画が可能であり、かつ、寿命が長い濾過用フィルターとして、並びに、カチオン性粒子、ゲル、及びカチオンの除去が可能な濾過用フィルターとして有用なアニオン性ポリケトン多孔膜を提供することである。 Problems to be solved by the present invention include heat resistance, chemical resistance, high-accuracy fractionation of anionic particles, and a long-life filter for filtration, as well as cationic particles, An object is to provide an anionic polyketone porous membrane useful as a filter for filtration capable of removing gels and cations.
本発明者らは、上記課題を解決すべく鋭意研究し実験を重ねた結果、負のゼータ電位を有するポリケトン多孔膜が上記課題を解決することを見出し、本発明を完成するに至ったものである。
すなわち本発明は、以下の［１］〜［７］に記載する通りのものである。
As a result of intensive studies and experiments to solve the above problems, the present inventors have found that a polyketone porous film having a negative zeta potential can solve the above problems, and have completed the present invention. is there.
That is, the present invention is as described in [1] to [ 7 ] below.
［１］下記化学式（１）：
［２］前記ポリケトン多孔膜が平膜状又は中空糸状である、前記［１］に記載のポリケトン多孔膜。
［３］前記［１］又は［２］に記載のポリケトン多孔膜を含む濾過用フィルター。
［４］粒子分画用の、前記［３］に記載の濾過用フィルター。
［５］イオン吸着用の、前記［３］に記載の濾過用フィルター。
［６］粒子又はゲル吸着除去用の、前記［３］に記載の濾過用フィルター。
［７］半導体・電子部品、及びバイオ医薬品製造用の、前記［３］〜［６］のいずれかに記載の濾過用フィルター。
[1] The following chemical formula (1):
[2] The polyketone porous membrane according to [1], wherein the polyketone porous membrane has a flat membrane shape or a hollow fiber shape .
[3] A filter for filtration comprising the polyketone porous membrane according to [1] or [2].
[4] The filter for filtration according to [3], for particle fractionation.
[5] The filtration filter according to [3], for ion adsorption.
[6] The filter for filtration according to [3], for removing particles or gel by adsorption.
[7] The filter for filtration according to any one of [ 3 ] to [6], which is used for manufacturing semiconductor / electronic parts and biopharmaceuticals.
本発明のポリケトン多孔膜をアニオン性粒子のスラリーの分画用フィルターとして用いた場合、負のゼータ電位を有するためアニオン性粒子の吸着を抑制することが可能で、目詰まりが極めて少なく、長時間その性能が維持されるため、フィルター交換の頻度を少なくすることが可能となる。また、目的の微粒子の収率も向上し、コストダウンにも貢献することが可能である。また、カチオン性の微粒子に対しては、吸着力に優れ、多孔膜の孔径よりも小さなカチオン性粒子を除去することが可能となり、目詰まりが極めて少なく、長時間その性能が維持されるため、フィルター交換の頻度を少なくすることが可能となる。 When the polyketone porous membrane of the present invention is used as a filter for fractionating slurry of anionic particles, it has a negative zeta potential, so that adsorption of anionic particles can be suppressed, clogging is extremely small, and it takes a long time. Since the performance is maintained, the frequency of filter replacement can be reduced. In addition, the yield of the target fine particles can be improved, which can contribute to cost reduction. In addition, for cationic fine particles, it is excellent in adsorption power, it becomes possible to remove cationic particles smaller than the pore size of the porous membrane, clogging is very little, and its performance is maintained for a long time, It becomes possible to reduce the frequency of filter replacement.
以下、本発明を詳細に説明する。
本発明の一態様は、一酸化炭素とエチレン性不飽和化合物が交互に共重合した下記化学式（１）：
One embodiment of the present invention is the following chemical formula (1) in which carbon monoxide and an ethylenically unsaturated compound are alternately copolymerized:
ポリケトン多孔膜中のポリケトンの含有率は、ポリケトンが本来持つ耐熱性及び耐薬品性を反映させるという観点から、多いほど好ましい。別の材料と複合化されない平膜状である場合、ポリケトン多孔膜中のポリケトン含有率は、７０〜１００質量％が好ましく、８０〜１００質量％がより好ましく、９０〜１００質量％が更に好ましい。また、不織布等が複合化されているポリケトン多孔複合膜では、ポリケトンが持つ耐熱性及び耐薬品性と、不織布等が持つ力学特性を両立させるという観点から、ポリケトン多孔複合膜中のポリケトン含有率は、１０〜７０質量％が好ましく、１０〜６０質量％がより好ましく、１０〜５０質量％が更に好ましい。ポリケトン多孔膜中のポリケトンには、０〜３０質量％の割合で他の繰り返し単位があってもよい。ポリケトン多孔膜中のポリケトンの含有率は、該多孔膜を構成する成分のうちポリケトンのみを溶解する溶媒によってポリケトンを溶解除去する方法、又は、ポリケトン以外を溶解する溶媒によってポリケトン以外を溶解除去する方法によって確認される。 The content of the polyketone in the polyketone porous film is preferably as large as possible from the viewpoint of reflecting the heat resistance and chemical resistance inherent in the polyketone. In the case of a flat film that is not combined with another material, the polyketone content in the polyketone porous film is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass. In addition, in the polyketone porous composite film in which a nonwoven fabric or the like is combined, the polyketone content in the polyketone porous composite film is from the viewpoint of achieving both the heat resistance and chemical resistance of the polyketone and the mechanical properties of the nonwoven fabric and the like. 10-70 mass% is preferable, 10-60 mass% is more preferable, 10-50 mass% is still more preferable. The polyketone in the polyketone porous film may have other repeating units at a ratio of 0 to 30% by mass. The polyketone content in the polyketone porous membrane is determined by a method of dissolving and removing the polyketone with a solvent that dissolves only the polyketone among the components constituting the porous membrane, or a method of dissolving and removing other than the polyketone with a solvent that dissolves other than the polyketone Confirmed by.
本発明のポリケトン多孔膜は、空隙率５〜９０％を有する。空隙率は、下記数式：
空隙率（％）＝（１−Ｇ／ρ／Ｖ）×１００
｛式中、Ｇはポリケトン多孔膜の質量（ｇ）であり、ρはポリケトン多孔膜を構成する全ての樹脂の質量平均密度（ｇ／ｃｍ3）であり、そしてＶはポリケトン多孔膜の体積（ｃｍ3）である。｝により算出される。上記数式において、質量平均密度ρは、ポリケトン多孔膜が、ポリケトンとは密度の異なる樹脂と、ポリケトン樹脂との複合化によって構成される場合、各々の樹脂の密度にその構成質量比率を乗じた値の和である。例えば、ρA及びρBの密度をそれぞれ持つ繊維がＧA及びＧBの質量比率で構成された不織布に、密度ρpのポリケトンがＧpの質量比率で複合されているときには、質量平均密度は、下記数式：
質量平均密度＝（ρA・ＧA＋ρB・ＧB＋ρp・Ｇp）／（ＧA＋ＧB＋Ｇp）
で表される。空隙率が５％より低いポリケトン多孔膜は、例えば、濾材として用いられる場合、透過流束が小さい、粒子捕集効率が悪い、閉塞までの時間が短い等の不具合を生じる。したがって、本発明のポリケトン多孔膜の空隙率としては３０〜９０％がより好ましく、４０〜９０％が更に好ましく、５０〜９０％が最も好ましい。
The polyketone porous membrane of the present invention has a porosity of 5 to 90%. The porosity is the following formula:
Porosity (%) = (1−G / ρ / V) × 100
{Wherein G is the mass (g) of the polyketone porous membrane, ρ is the mass average density (g / cm 3 ) of all resins constituting the polyketone porous membrane, and V is the volume of the polyketone porous membrane ( cm 3 ). }. In the above formula, the mass average density ρ is a value obtained by multiplying the density of each resin by its constituent mass ratio when the polyketone porous film is composed of a resin having a density different from that of the polyketone and a polyketone resin. Is the sum of For example, when a polyketone having a density ρp is combined with a mass ratio of Gp on a non-woven fabric in which fibers having a density of ρA and ρB are configured by a mass ratio of GA and GB, the mass average density is expressed by the following formula:
Mass average density = (ρA · GA + ρB · GB + ρp · Gp) / (GA + GB + Gp)
It is represented by For example, when the polyketone porous membrane having a porosity of less than 5% is used as a filter medium, problems such as a small permeation flux, poor particle collection efficiency, and a short time until clogging occur. Therefore, the porosity of the polyketone porous membrane of the present invention is more preferably 30 to 90%, still more preferably 40 to 90%, and most preferably 50 to 90%.
ポリケトン多孔膜は、平均貫通孔径１０〜５００００ｎｍを有する。平均貫通孔径は、ハーフドライ法（ＡＳＴＭ Ｅ１２９４−８９に準拠）により測定される値である。平均貫通孔径が１０ｎｍより小さいポリケトン多孔膜が例えば濾材として用いられた場合、平均貫通孔径が小さすぎるために圧力損失の著しい増大又は透過流束の著しい減少が起こる。一方、平均貫通孔径が５００００ｎｍより大きいポリケトン多孔膜が例えば濾過用フィルターとして用いられた場合、平均貫通孔径が大きすぎて除去可能な粒子が限られてしまう。ポリケトン多孔膜の平均貫通孔径は、２０〜４００００ｎｍがより好ましく、３０〜３００００ｎｍが更に好ましく、５０〜２００００ｎｍが特に好ましい。 The polyketone porous membrane has an average through-hole diameter of 10 to 50000 nm. The average through-hole diameter is a value measured by a half dry method (based on ASTM E1294-89). When a polyketone porous membrane having an average through-hole diameter of less than 10 nm is used, for example, as a filter medium, the average through-hole diameter is too small, resulting in a significant increase in pressure loss or a significant decrease in permeation flux. On the other hand, when a polyketone porous membrane having an average through-hole diameter larger than 50000 nm is used as a filter for filtration, for example, the average through-hole diameter is too large and the particles that can be removed are limited. The average through-hole diameter of the polyketone porous membrane is more preferably 20 to 40000 nm, still more preferably 30 to 30000 nm, and particularly preferably 50 to 20000 nm.
本発明のポリケトン多孔膜は、ゼータ電位−８０ｍＶ〜−１０ｍＶを有する。ゼータ電位が−１０ｍＶより高いポリケトン多孔膜では、分画フィルターにおいてアニオン性の微粒子の吸着を抑制する十分な効果が得られず、吸着によるロスにより得られる粒子の収率が減るという問題が生じる。また、カチオン性微粒子や陽イオンに対する吸着力が弱く、十分な除去性能を発揮できない。一方、ゼータ電位が−８０ｍＶより低い、ポリケトン膜の強度低下が起こり使用できない、また、目詰まりが起こり、流量圧損が大きくなるなどの問題が生じる場合がある。ポリケトン多孔膜のゼータ電位は−８０ｍＶ〜−１０ｍＶが好ましく、−６０ｍＶ〜−１０ｍＶが更に好ましい。 The polyketone porous membrane of the present invention has a zeta potential of −80 mV to −10 mV. In a polyketone porous membrane having a zeta potential higher than −10 mV, a sufficient effect of suppressing adsorption of anionic fine particles cannot be obtained in the fractionation filter, resulting in a problem that the yield of particles obtained due to loss due to adsorption decreases. Further, the adsorptive power to cationic fine particles and cations is weak, and sufficient removal performance cannot be exhibited. On the other hand, there are cases where the zeta potential is lower than −80 mV, the strength of the polyketone film is lowered and cannot be used, and clogging occurs and flow pressure loss increases. The zeta potential of the polyketone porous membrane is preferably -80 mV to -10 mV, more preferably -60 mV to -10 mV.
ポリケトン多孔膜の形状は特に限定されないが、例えば、平膜状であり、あるいは長手方向に貫通した１つ以上の空隙を有する中空糸膜である。ポリケトン多孔膜の形状は目的・用途に応じて使い分けることができる。また、本発明のポリケトン多孔膜は、ポリケトンと少なくとも１つの不織布とが複合化されたものであることができる。 The shape of the polyketone porous membrane is not particularly limited. For example, it is a flat membrane or a hollow fiber membrane having one or more voids penetrating in the longitudinal direction. The shape of the polyketone porous membrane can be properly used according to the purpose and application. In addition, the polyketone porous membrane of the present invention can be a composite of polyketone and at least one nonwoven fabric.
本発明のポリケトン多孔膜は、無機フィラー、光安定剤、酸化防止剤、帯電防止剤、親水性高分子、タンパク吸着性物質等の、機能性物質を含んでもよい。具体的には、ポリケトン多孔膜は、機械的強度、耐衝撃性、及び耐熱性を上げるために、無機フィラーとしてガラス繊維、カーボン繊維等の無機繊維、又はカーボンナノチューブ等を含んでもよい。また、ポリケトン多孔膜は、光及び酸化に対する安定性を向上させるために、光安定剤として紫外線吸収剤、ヒンダードアミン系光安定剤等を含んでもよく、酸化防止剤としてフェノール系、リン系、又は硫黄系の酸化防止剤等を含んでもよい。更に、ポリケトン多孔膜は、帯電防止剤として各種界面活性剤等を含んでもよい。 The polyketone porous film of the present invention may contain a functional substance such as an inorganic filler, a light stabilizer, an antioxidant, an antistatic agent, a hydrophilic polymer, and a protein adsorbing substance. Specifically, the polyketone porous film may contain glass fibers, inorganic fibers such as carbon fibers, or carbon nanotubes as inorganic fillers in order to increase mechanical strength, impact resistance, and heat resistance. In addition, the polyketone porous film may contain an ultraviolet absorber, a hindered amine light stabilizer, etc. as a light stabilizer in order to improve stability against light and oxidation, and a phenol, phosphorus, or sulfur as an antioxidant. A system antioxidant or the like may also be included. Further, the polyketone porous film may contain various surfactants as an antistatic agent.
本発明のポリケトン多孔膜は、ポリケトン多孔膜に負のゼータ電位を付与するという観点から、スルホン酸基、スルホン酸エステル基、カルボン酸基、カルボン酸エステル基、リン酸基、リン酸エステル基、水酸基からなる群から選ばれる一つ以上の官能基を有する。
官能基を有する形態の例としては、化学結合や物理的に結合した状態が挙げられる。化学結合としては、共有結合のようなものであってもよい。共有結合としては、Ｃ−Ｃ結合、Ｃ＝Ｎ結合、ピロール環を介する結合などが挙げられる。化学結合する物質としては、ポリマーであってもよいし、分子量の小さいモノマーのようなものであってもよい。一方、物理的に結合した状態としては、水素結合、ファンデルワールス力、静電引力、疎水相互作用のような分子間力によって化学結合を介さずに結合した吸着や付着の様な状態が挙げられる。物理的に結合した状態としては、ポリマーが付着された状態などが挙げられる。ポリマーの分子量が１０００以上である場合、物理的な結合力が強く水溶液中でも安定したゼータ電位を発現する。負のゼータ電位を付与するためのポリマーとしては、ポリスチレンスルホン酸、ポリスチレンスルホン酸ナトリウム、ポリビニルスルホン酸、ポリビニルスルホン酸ナトリウム、ポリ（メタ）アクリル酸、ポリ（メタ）アクリル酸ナトリウム、アニオン性ポリアクリルアミド、ポリ（２−アクリルアミド−２−メチル基プロパンスルホン酸）、ポリ（２−アクリルアミド−２−メチル基プロパンスルホン酸ナトリウム）、カルボキシメチルセルロース、アニオン化ポリビニルアルコール、ポリビニルホスホン酸が挙げられる。また、上記ポリマーあるいはポリマーの酸塩は、他のポリマーとの共重合体であってもよい。十分なゼータ電位を有するという点で、上記ポリマーあるいはポリマーの酸塩の割合は、５〜１００重量％、好ましくは３０〜１００重量％、より好ましくは５０〜１００重量％である。
From the viewpoint of imparting a negative zeta potential to the polyketone porous membrane, the polyketone porous membrane of the present invention has a sulfonic acid group, a sulfonic acid ester group, a carboxylic acid group, a carboxylic acid ester group, a phosphoric acid group, a phosphoric acid ester group, It has one or more functional groups selected from the group consisting of hydroxyl groups.
Examples of the form having a functional group include a chemical bond and a physically bonded state. The chemical bond may be a covalent bond. Examples of the covalent bond include a C—C bond, a C═N bond, and a bond via a pyrrole ring. The substance to be chemically bonded may be a polymer or a monomer having a small molecular weight. On the other hand, the physically bonded state includes an adsorbed or adhered state that is bonded without intermediary force such as hydrogen bond, van der Waals force, electrostatic attraction, and hydrophobic interaction. It is done. Examples of the physically bonded state include a state where a polymer is attached. When the molecular weight of the polymer is 1000 or more, the physical binding force is strong and a stable zeta potential is expressed even in an aqueous solution. Polymers for imparting a negative zeta potential include polystyrene sulfonic acid, sodium polystyrene sulfonate, polyvinyl sulfonic acid, sodium polyvinyl sulfonate, poly (meth) acrylic acid, poly (meth) acrylic acid sodium, anionic polyacrylamide , Poly (2-acrylamido-2-methyl group propanesulfonic acid), poly (2-acrylamido-2-methyl group propanesulfonic acid sodium), carboxymethylcellulose, anionized polyvinyl alcohol and polyvinylphosphonic acid. The polymer or the acid salt of the polymer may be a copolymer with another polymer. In terms of having a sufficient zeta potential, the proportion of the polymer or the acid salt of the polymer is 5 to 100% by weight, preferably 30 to 100% by weight, more preferably 50 to 100% by weight.
また、ポリケトン多孔膜に負のゼータ電位を付与するという観点から、ポリケトンは、下記化学式（２）〜（５）：
スルホン酸基としては、−Ｒ１−ＳＯ３Ｈ（Ｒ１は炭素数１〜２０の直鎖状又は分岐状のアルキレン鎖である。）、−Ｒ２−Ｃ６Ｈ４−ＳＯ３Ｈ（Ｒ２は炭素数１〜２０の直鎖状又は分岐状のアルキレン鎖である。）などが挙げられる。また、上記スルホン酸基は、ナトリウムイオン、カリウムイオン、リチウムイオンなどの１価の金属イオンとの塩であってもよい。スルホン酸エステル基としては、−Ｒ１−ＳＯ３Ｒ３（Ｒ１とＲ３は炭素数１〜２０の直鎖状又は分岐状のアルキレン鎖である。）、−Ｒ２−Ｃ６Ｈ４−ＳＯ３Ｒ３（Ｒ２とＲ３は炭素数１〜２０の直鎖状又は分岐状のアルキレン鎖である。）等が挙げられる。カルボン酸基としては、−Ｒ１−ＣＯ２Ｈ（Ｒ１は炭素数１〜２０の直鎖状又は分岐状のアルキレン鎖である。）、−Ｒ２−Ｃ６Ｈ（５−ｎ）−ｎＣＯ２Ｈ（ｎは１〜５の整数であり、Ｒ２は炭素数１〜２０の直鎖状又は分岐状のアルキレン鎖である。）等が挙げられる。また、上記カルボン酸基は、ナトリウムイオン、カリウムイオン、リチウムイオンなどの１価の金属イオンとの塩であってもよい。カルボン酸エステル基としては、−Ｒ１−ＣＯ２Ｒ３（Ｒ１とＲ３は炭素数１〜２０の直鎖状又は分岐状のアルキレン鎖である。）、−Ｒ２−Ｃ６Ｈ（５−ｎ）−ｎＣＯ２Ｒ３（ｎは１〜５の整数であり、Ｒ２とＲ３は炭素数１〜２０の直鎖状又は分岐状のアルキレン鎖である。）等が挙げられる。
リン酸基としては、−Ｒ１−ＯＰＯ（ＯＨ）２（Ｒ１は炭素数１〜２０の直鎖状又は分岐状のアルキレン鎖である。）などが挙げられる。また、上記リン酸基は、ナトリウムイオン、カリウムイオン、リチウムイオンなどの１価の金属イオンやカルシウムイオンやマグネシウムイオンとの塩であってもよい。リン酸エステル基としては−Ｒ１−ＯＰＯ（ＯＨ）（ＯＲ２）（Ｒ１とＲ２は炭素数１〜２０の直鎖状又は分岐鎖状のアルキレン鎖である。）あるいは−Ｒ１−ＯＰＯ（ＯＲ２）（ＯＲ３）（Ｒ１、Ｒ２及びＲ３は炭素数１〜２０の直鎖状または分岐鎖状のアルキレン鎖である。）が挙げられる。そして水酸基としては、−ＣｎＨ２ｎ−ｍ（ＯＨ）ｍ＋１（ｍとｎは１〜２０の整数）あるいは−Ｒ１−Ｃ６Ｈ５−ｎ（ＯＨ）ｎ（Ｒ１は炭素数１〜２０のアルキレン鎖であり、そしてｎは１〜５の整数である。）が挙げられる。
The sulfonic acid group, -R1-SO 3 H, (is R1 is a linear or branched alkylene chain having 1 to 20 carbon atoms.) - R2-C 6 H 4 -SO 3 H (R2 carbon A linear or branched alkylene chain of 1 to 20). The sulfonic acid group may be a salt with a monovalent metal ion such as sodium ion, potassium ion or lithium ion. The sulfonic acid ester group, -R1-SO 3 R3, ( R1 and R3 is a straight or branched alkylene chain having 1 to 20 carbon atoms.) - R2-C 6 H 4 -SO 3 R3 ( R2 and R3 are linear or branched alkylene chains having 1 to 20 carbon atoms.) And the like. The carboxylic acid group, -R1-CO 2 H, ( R1 is a linear or branched alkylene chain having 1 to 20 carbon atoms.) - R2-C 6 H (5-n) -nCO 2 H (N is an integer of 1 to 5, and R2 is a linear or branched alkylene chain having 1 to 20 carbon atoms). The carboxylic acid group may be a salt with a monovalent metal ion such as sodium ion, potassium ion or lithium ion. The carboxylic acid ester group, -R1-CO 2 R3, (the R1 and R3 is a linear or branched alkylene chain having 1 to 20 carbon atoms.) - R2-C 6 H (5-n) - nCO 2 R3 (n is an integer of 1 to 5, and R2 and R3 are linear or branched alkylene chains having 1 to 20 carbon atoms).
Examples of the phosphoric acid group include -R 1 -OPO (OH) 2 (R1 is a linear or branched alkylene chain having 1 to 20 carbon atoms). The phosphate group may be a salt with a monovalent metal ion such as sodium ion, potassium ion or lithium ion, calcium ion or magnesium ion. -R1-OPO (OH) (OR2) (R1 and R2 are linear or branched alkylene chains having 1 to 20 carbon atoms) or -R1-OPO (OR2) ( OR3) (R1, R2 and R3 are linear or branched alkylene chains having 1 to 20 carbon atoms). And include hydroxyl, -C n H 2n-m ( OH) m + 1 (m and n are an integer of 1 to 20) or -R1-C 6 H 5-n (OH) n (R1 is C20 An alkylene chain, and n is an integer of 1 to 5.).
本発明の一態様に係るポリケトン多孔膜の陽イオン交換容量は、０．０１〜１０ミリ当量／ｇであることが好ましい。陽イオン交換容量は、該膜を一定量の水酸化ナトリウムで処理し、消費された水酸化ナトリウム量を塩酸で中和滴定した場合、下記の方法により求められる。
５重量％塩酸２００ｍｌをビーカー（ビーカーＡとする）に入れ、ポリケトン多孔膜を３０分間浸漬した後、取り出す。取り出したポリケトン多孔膜を更に１５分間水洗した後、別のビーカー（ビーカーＢとする）に入れる。これに、濃度Ｘモル／ｌの水酸化ナトリウム水溶液をＹｍｌ入れて、上記のポリケトン膜３０分間浸漬した後、ポリケトン多孔膜を取り出す。取り出したポリケトン多孔膜は５０ｍｌの水で洗浄し、洗浄液をビーカーＢ内の液に加える。これを、濃度１モル／ｌの塩酸で滴定し、下記数式にて容量を算出する。
陽イオン交換容量（ミリ当量／ｇ）＝［Ｘ（モル／ｌ） × Ｙ（ｍｌ） − １（モル／ｌ）× 滴定に要した塩酸量（ｍｌ）］／サンプル重量（ｇ）
The cation exchange capacity of the polyketone porous membrane according to one embodiment of the present invention is preferably 0.01 to 10 meq / g. The cation exchange capacity is determined by the following method when the membrane is treated with a certain amount of sodium hydroxide and the amount of sodium hydroxide consumed is neutralized with hydrochloric acid.
200 ml of 5 wt% hydrochloric acid is put into a beaker (beaker A), the polyketone porous membrane is immersed for 30 minutes, and then taken out. The removed polyketone porous membrane is further washed with water for 15 minutes, and then placed in another beaker (beaker B). Into this, Yml of a sodium hydroxide aqueous solution having a concentration of X mol / l is put, and after the polyketone film is immersed for 30 minutes, the polyketone porous film is taken out. The removed polyketone porous membrane is washed with 50 ml of water, and the washing solution is added to the solution in the beaker B. This is titrated with hydrochloric acid having a concentration of 1 mol / l, and the volume is calculated by the following mathematical formula.
Cation exchange capacity (milli equivalent / g) = [X (mol / l) × Y (ml) −1 (mol / l) × amount of hydrochloric acid required for titration (ml)] / sample weight (g)
陽イオン交換容量が０．０１ミリ当量／ｇより小さいポリケトン多孔膜は、安定して−１０ｍＶより低いゼータ電位が得られない場合があり、分画用フィルター濾材に用いた場合では、安定してアニオン性粒子吸着を防ぐ効果が得られず、粒子の収率が低い、昇圧が早くフィルター寿命が短いなどの不具合を生じる場合がある。また、微粒子吸着やイオン吸着用フィルター濾材に用いた場合では、カチオン性粒子や陽イオンに対する吸着力が弱く、十分な除去性能を発揮できない場合がある。一方、容量が１０ミリ当量／ｇより大きい場合は、ゼータ電位の値がばらつき、性能が安定したフィルターを作ることが出来ない。安定したゼータ電位が得られるという点で、上記容量は、０．０１〜５ミリ当量／ｇであることがより好ましく、０．０１〜２ミリ当量／ｇであることが更に好ましい。 A polyketone porous membrane having a cation exchange capacity of less than 0.01 meq / g may not be able to stably obtain a zeta potential lower than −10 mV, and when used as a filter material for fractionation, The effect of preventing adsorption of anionic particles may not be obtained, and problems such as low particle yield, fast pressurization, and short filter life may occur. In addition, when used as a filter medium for fine particle adsorption or ion adsorption, the adsorptive power to cationic particles or cations is weak, and sufficient removal performance may not be exhibited. On the other hand, when the capacity is larger than 10 meq / g, the value of the zeta potential varies and a filter with stable performance cannot be produced. In terms of obtaining a stable zeta potential, the capacity is more preferably 0.01 to 5 meq / g, and still more preferably 0.01 to 2 meq / g.
以下、本発明のポリケトン多孔膜の製造方法の一例について説明する。
ポリケトンの重合方法としては、特に制限はないが、例えば、オートクレーブ等の反応容器の溶媒中で、エチレンと一酸化炭素を反応させる。溶媒としては、水、メタノール、エタノール、プロパノール、ブタノール、ヘキサフルオロイソプロパノールが挙げられ、これらの混合溶媒として使用してもよい。より好ましい溶媒としては、重合活性等のコストの観点から、溶媒は、水、メタノールである。ポリケトンの原料としては、一酸化炭素とエチレンが主体となるが、ポリケトンの加工性を考慮して、エチレン以外のプロペン、ヘキセン、シクロヘキセン、スチレン等のエチレン性不飽和化合物を混合させる場合がある。
Hereinafter, an example of the manufacturing method of the polyketone porous membrane of this invention is demonstrated.
The polyketone polymerization method is not particularly limited, but, for example, ethylene and carbon monoxide are reacted in a solvent in a reaction vessel such as an autoclave. Examples of the solvent include water, methanol, ethanol, propanol, butanol, and hexafluoroisopropanol, and may be used as a mixed solvent thereof. As a more preferable solvent, from the viewpoint of costs such as polymerization activity, the solvent is water or methanol. The raw materials for polyketone are mainly carbon monoxide and ethylene, but in consideration of the processability of polyketone, ethylenically unsaturated compounds such as propene, hexene, cyclohexene and styrene other than ethylene may be mixed.
ポリケトンの重合は、溶媒に溶解した有機金属錯体触媒の存在下で進行する。なお、有機金属錯体触媒とは、周期律表の（ａ）第１０族遷移金属化合物、（ｂ）第１５族の原子を有する配位子からなるものである。更に、かかる（ａ）第１０族又は（ｂ）第１５族の原子を有する配位子に、第３成分として（ｃ）酸を加えてもよい。（ａ）成分中の第１０族遷移金属化合物の例としては、ニッケル又はパラジウムの錯体、カルボン酸塩、リン酸塩、カルバミン酸塩、スルホン酸塩を挙げることができ、その具体例としては、酢酸ニッケル、ニッケルアセチルアセトネート、酢酸パラジウム、トリフルオロ酢酸パラジウム、パラジウムアセチルアセトネート、塩化パラジウム等を挙げることができる。（ｂ）成分の第１５族の原子を有する配位子の例としては、１，３−ビス（ジフェニルホスフィノ）プロパン、１，３−ビス｛ジ（２−メトキシフェニル）ホスフィノ｝プロパン等のリン二座配位子を挙げることができる。（ｃ）酸の例としては、トリフルオロ酢酸、メタンスルホン酸、ｐ−トルエンスルホン酸のｐＫａが４以下の有機酸の陰イオンを挙げることができる。 Polymerization of polyketone proceeds in the presence of an organometallic complex catalyst dissolved in a solvent. The organometallic complex catalyst is composed of (a) a Group 10 transition metal compound of the periodic table and (b) a ligand having a Group 15 atom. Further, an acid (c) may be added as a third component to the ligand having an atom of (a) Group 10 or (b) Group 15. Examples of Group 10 transition metal compounds in component (a) include nickel or palladium complexes, carboxylates, phosphates, carbamates, and sulfonates. Specific examples thereof include: Examples thereof include nickel acetate, nickel acetylacetonate, palladium acetate, palladium trifluoroacetate, palladium acetylacetonate, and palladium chloride. Examples of ligands having a Group 15 atom of component (b) include 1,3-bis (diphenylphosphino) propane, 1,3-bis {di (2-methoxyphenyl) phosphino} propane, and the like. Mention may be made of phosphorus bidentate ligands. (C) As an example of an acid, the anion of organic acid whose pKa of trifluoroacetic acid, methanesulfonic acid, and p-toluenesulfonic acid is 4 or less can be mentioned.
有機金属錯体触媒として用いる遷移金属化合物（ａ）の使用量は、他の重合条件によってその好適な値が異なるため、一概にその範囲を定めることはできないが、好ましくは、反応帯域の容量１リットル当り０．１〜１０００マイクロモルである。反応帯域の容量とは、反応器中の液相容量をいう。配位子（ｂ）の使用量も制限されるものではないが、遷移金属化合物１モル当たり０．８〜３モルである。酸（ｃ）の使用量は、パラジウム化合物１モル当たり、０．１〜１００モルである。 The amount of the transition metal compound (a) used as the organometallic complex catalyst varies depending on other polymerization conditions, and therefore the range cannot generally be determined. However, the reaction zone volume is preferably 1 liter. 0.1 to 1000 micromoles per unit. The capacity of the reaction zone refers to the liquid phase capacity in the reactor. Although the usage-amount of a ligand (b) is not restrict | limited, It is 0.8-3 mol per mol of transition metal compounds. The usage-amount of an acid (c) is 0.1-100 mol per mol of palladium compounds.
有機金属錯体触媒は、遷移金属化合物（ａ）、配位子（ｂ）、及び好ましくは酸（ｃ）を混合することによって生成する。有機金属錯体触媒の使用法についての制限はないが、各成分の混合物からなる有機金属錯体触媒を予め調製してから反応容器内に添加することが好ましい。有機金属錯体触媒を調製する場合には、先ず、遷移金属化合物（ａ）及び配位子（ｂ）を混合し、次いで、酸（ｃ）を混合することが好ましい。触媒組成物の調製に用いる溶媒は、アルコール、アセトン、及びメチルエチルケトンから選ばれる有機溶媒が好ましい。また、上記（ａ）、（ｂ）、及び（ｃ）３成分からなる触媒に、重合活性を維持する効果が高いという観点から、ベンゾキノン、ナフトキノンの酸化剤を添加することが好ましい。これらキノン類の添加量は、遷移金属化合物１モル当たり１０〜２００モルである。キノン類の添加は、触媒組成物に添加してから反応容器に添加する方法、重合溶媒に添加する方法のいずれであってもよく、必要に応じて、反応中に反応容器内に連続的に添加してもよい。 The organometallic complex catalyst is produced by mixing the transition metal compound (a), the ligand (b), and preferably the acid (c). Although there is no restriction | limiting about the usage method of an organometallic complex catalyst, It is preferable to prepare the organometallic complex catalyst which consists of a mixture of each component previously, and to add in reaction container. When preparing an organometallic complex catalyst, it is preferable to first mix the transition metal compound (a) and the ligand (b), and then mix the acid (c). The solvent used for preparing the catalyst composition is preferably an organic solvent selected from alcohol, acetone, and methyl ethyl ketone. Moreover, it is preferable to add the oxidizing agent of a benzoquinone and a naphthoquinone to the catalyst which consists of said (a), (b) and (c) three components from a viewpoint that the effect which maintains a polymerization activity is high. The addition amount of these quinones is 10-200 mol per 1 mol of transition metal compounds. The addition of quinones may be either a method of adding to the catalyst composition and then adding to the reaction vessel, or a method of adding to the polymerization solvent, and if necessary, continuously into the reaction vessel during the reaction. It may be added.
重合温度は７０〜１５０℃、重合圧力は１〜５０ＭＰａであることが好ましく、重合時間は１〜１０時間である。重合が完了したポリケトンは懸濁液の状態で反応容器内から抜き出される。反応容器から抜き出された懸濁液は必要に応じてフラッシュタンクを通過させて、懸濁液内に残留する未反応の一酸化炭素およびエチレンを除去する。次いで、ポリケトン懸濁液を、重合溶媒に用いた溶媒と同一種類の溶媒を用いて洗浄しながら、遠心脱水機等の公知の遠心分級器によりポリケトン粉体と液体成分とを分離する。その後、加熱気体を吹き付ける方法、ポリケトン粉体を攪拌しながら加熱気体を通す方法等、公知の装置、方法を用いポリケトン粉体に残存する液体成分を乾燥、除去し、ポリケトンを単離する。 The polymerization temperature is preferably 70 to 150 ° C., the polymerization pressure is preferably 1 to 50 MPa, and the polymerization time is 1 to 10 hours. The polyketone that has been polymerized is withdrawn from the reaction vessel in the form of a suspension. The suspension extracted from the reaction vessel is passed through a flash tank as necessary to remove unreacted carbon monoxide and ethylene remaining in the suspension. Next, the polyketone suspension and the liquid component are separated by a known centrifugal classifier such as a centrifugal dehydrator while washing the polyketone suspension using the same type of solvent as the polymerization solvent. Thereafter, the liquid component remaining in the polyketone powder is dried and removed using a known apparatus and method such as a method of blowing heated gas, a method of passing the heated gas while stirring the polyketone powder, and the polyketone is isolated.
以上のようにして得られたポリケトンをレゾルシン水溶液に溶解する。レゾルシン水溶液の濃度は６０〜７２ｗｔ％の範囲である。また、ポリマー濃度は５〜３０ｗｔ％の範囲である。レゾルシン水溶液の濃度とポリマー濃度との組合せにより、ポリケトン多孔質膜の孔径がコントロール可能であり、所望の孔径により適宜決められる。ポリケトンの極限粘度に特に制限は無いが、溶解性や多孔質膜への成形しやすさの観点から、０．５〜５ｄｌ／ｇである。 The polyketone obtained as described above is dissolved in a resorcin solution. The concentration of the resorcinol aqueous solution is in the range of 60 to 72 wt%. The polymer concentration is in the range of 5-30 wt%. The pore diameter of the polyketone porous membrane can be controlled by the combination of the concentration of the resorcin solution and the polymer concentration, and can be appropriately determined depending on the desired pore diameter. Although there is no restriction | limiting in particular in the intrinsic viscosity of a polyketone, it is 0.5-5 dl / g from a viewpoint of solubility or the ease of shaping | molding to a porous membrane.
以上のようにレゾルシン水溶液にポリケトンを溶解したドープを凝固剤で凝固させることで、平膜状又は中空糸状のポリケトン多孔質膜を作成する。平膜形状であれば、Ｔダイ等のフィルムダイからドープを吐出して凝固浴中で凝固させる方法や、基材にダイコーター、ロールコーター、バーコーター等の装置を用いてドープを塗工した後に凝固浴中で凝固させる方法等、従来公知のものがそのまま適用できる。中空糸形状であれば、二重管オリフィスやＣ型オリフィスなどを用いて、外側の輪状オリフィスからはドープを、また、内側の円状オリフィスからは凝固剤を吐出しながら凝固浴中で凝固させる方法等、従来公知のものがそのまま適応できる。 As described above, a dope obtained by dissolving a polyketone in an aqueous resorcinol solution is solidified with a coagulant, thereby creating a flat or hollow fiber polyketone porous membrane. If it is a flat film shape, the dope is applied using a method such as discharging a dope from a film die such as a T die and solidifying it in a coagulation bath, or using a device such as a die coater, roll coater or bar coater. Conventionally known methods such as a method of coagulating in a coagulation bath later can be applied as they are. If it is a hollow fiber shape, it is solidified in a coagulation bath using a double-tube orifice or C-type orifice while discharging dope from the outer ring-shaped orifice and coagulant from the inner circular orifice. Conventionally known methods such as methods can be applied as they are.
凝固剤は、メタノール、エタノール、及びプロパノールから選択される水溶液であり、その濃度は３５〜７０ｗｔ％である。このようにして得られた凝固膜を、必要に応じて凝固剤や水等でさらに洗浄した後、７０〜１００℃の温水中に１〜３０分間浸漬する。
上述の温水処理後のポリケトン多孔質膜を、必要に応じて、メタノール、エタノール、及びプロパノールから選択される溶媒に浸漬して、多孔質膜に含まれる水を溶媒と置換する。その後、加熱ロールに接触させる方法、熱風を吹きかける方法、電熱ヒーターで非接触加熱して乾燥する方法等、又はこれらを組み合わせた方法等、公知の乾燥方法で乾燥する。加熱ロールに接触させる方法が最も効率が良いため好適に選ばれる。乾燥温度は、６０〜２００℃の範囲で、乾燥させる液体の種類により適宜選ばれる。本発明のポリケトン多孔膜の乾燥では、乾燥時に収縮や延伸による面方向への変形が少ない方法であることが重要である。許容される面方向への変形倍率は０．９〜１．１の範囲である。
The coagulant is an aqueous solution selected from methanol, ethanol, and propanol, and its concentration is 35 to 70 wt%. The coagulated film thus obtained is further washed with a coagulant, water or the like as required, and then immersed in warm water at 70 to 100 ° C. for 1 to 30 minutes.
The polyketone porous membrane after the above-mentioned hot water treatment is immersed in a solvent selected from methanol, ethanol, and propanol as necessary to replace the water contained in the porous membrane with the solvent. Then, it dries with a well-known drying method, such as the method of making it contact with a heating roll, the method of spraying a hot air, the method of drying by non-contact heating with an electric heater, or the method of combining these. The method of contacting the heating roll is preferably selected because it is the most efficient. The drying temperature is appropriately selected depending on the type of liquid to be dried in the range of 60 to 200 ° C. In the drying of the polyketone porous membrane of the present invention, it is important that the method is less susceptible to deformation in the surface direction due to shrinkage or stretching during drying. The allowable deformation ratio in the plane direction is in the range of 0.9 to 1.1.
乾燥後に、膜構造を安定化するために８０〜２００℃の範囲で熱処理を行う場合がある。熱処理を行うことで、ポリケトン多孔質膜を５０〜１５０℃での加温状態で使用する場合や、水等の表面張力の高い溶媒を含浸させた後に再び乾燥させた場合に、膜構造の変形を抑制することが可能となる。その際にも、収縮や延伸による面方向への変形倍率が少ない方法が重要であり、許容される面方向への変形倍率は０．９〜１．１の範囲である。 After drying, heat treatment may be performed in the range of 80 to 200 ° C. in order to stabilize the film structure. Deformation of the membrane structure when the polyketone porous membrane is used in a heated state at 50 to 150 ° C. by heat treatment or when it is impregnated with a solvent having a high surface tension such as water and then dried again. Can be suppressed. Also in this case, a method having a small deformation ratio in the plane direction due to shrinkage or stretching is important, and the allowable deformation ratio in the plane direction is in the range of 0.9 to 1.1.
官能基を含ませる方法については特に制限はないが、化学反応による方法、物理反応による方法、コーティングによる方法、さらにこれらを組み合わせた方法などが挙げられる。化学反応による方法は、パール・クノール反応などが挙げられる。また、物理反応による方法はプラズマ処理やコロナ処理などが挙げられる。コーティングによる方法はポリマーを含む水溶液などに含浸させる方法が挙げられる。その他の方法としては電子線グラフト反応などが挙げられる。 There are no particular restrictions on the method of incorporating the functional group, but examples thereof include a chemical reaction method, a physical reaction method, a coating method, and a combination of these. Examples of the chemical reaction method include the Pearl-Kunol reaction. Examples of the physical reaction method include plasma treatment and corona treatment. Examples of the coating method include a method of impregnating an aqueous solution containing a polymer. Other methods include electron beam graft reaction.
ポリケトン多孔膜に負のゼータ電位を付与するという観点で、ポリケトン多孔膜に負のゼータ電位を有するポリマーなどを付着又はコーティングさせてもよい。付着又はコーティングさせる方法としては、水や有機溶剤などにポリマーを溶解させた溶液にポリケトンを含浸させた後、取り出して乾燥させる方法などが挙げられる。乾燥の前後に加熱処理や水洗などを行ってもよい。負のゼータ電位を有するポリマーとしては、ポリスチレンスルホン酸、ポリスチレンスルホン酸ナトリウム、ポリビニルスルホン酸、ポリビニルスルホン酸ナトリウム、ポリ（メタ）アクリル酸、ポリ（メタ）アクリル酸ナトリウム、アニオン性ポリアクリルアミド、ポリ（２−アクリルアミド−２−メチル基プロパンスルホン酸）、ポリ（２−アクリルアミド−２−メチル基プロパンスルホン酸ナトリウム）、カルボキシメチルセルロース、アニオン化ポリビニルアルコール、ポリビニルホスホン酸等が挙げられる。また、上記ポリマーあるいはポリマーの酸塩は、他のポリマーとの共重合体であってもよい。十分なゼータ電位を有するという点で、上記ポリマーあるいはポリマーの酸塩の割合は、５〜１００重量％、好ましくは３０〜１００重量％、より好ましくは５０〜１００重量％である。 From the viewpoint of imparting a negative zeta potential to the polyketone porous membrane, a polymer having a negative zeta potential may be attached or coated on the polyketone porous membrane. Examples of the method of attaching or coating include a method of impregnating a polyketone with a solution in which a polymer is dissolved in water or an organic solvent, and then taking out and drying. Heat treatment or washing with water may be performed before and after drying. Polymers having a negative zeta potential include polystyrene sulfonic acid, sodium polystyrene sulfonate, polyvinyl sulfonic acid, sodium polyvinyl sulfonate, poly (meth) acrylic acid, poly (meth) acrylic acid sodium, anionic polyacrylamide, poly ( 2-acrylamido-2-methyl group propanesulfonic acid), poly (2-acrylamido-2-methyl group propanesulfonic acid sodium), carboxymethylcellulose, anionized polyvinyl alcohol, polyvinylphosphonic acid and the like. The polymer or the acid salt of the polymer may be a copolymer with another polymer. In terms of having a sufficient zeta potential, the proportion of the polymer or the acid salt of the polymer is 5 to 100% by weight, preferably 30 to 100% by weight, more preferably 50 to 100% by weight.
ポリケトン多孔膜に負のゼータ電位を付与するという観点で、ポリケトン多孔膜を構成するポリケトンの少なくとも１つの水素原子を他の基に置換する場合、置換方法としては、例えば電子線、γ線、プラズマ等の照射によってポリケトンにラジカルを発生させた後、望みの機能を発現する官能基を有する反応性モノマーを付加させる方法が挙げられる。反応性モノマーの例としては、スルホン酸基、スルホン酸エステル基、カルボン酸基、カルボン酸エステル基、リン酸基、リン酸エステル基、水酸基を含むアクリル酸、メタクリル酸、ビニルスルホン酸の誘導体等が挙げられる。より具体的な例としては、アクリル酸、メタクリル酸、ビニルスルホン酸、スチレンスルホン酸、及びそれらのナトリウム塩、2-アクリルアミド-2-メチルプロパンスルホン酸、2-メタクリルアミド-2-メチルプロパンスルホン酸、2-アクリルアミド-2-メチルプロパンカルボン酸、2-メタクリルアミド-2-メチルプロパンカルボン酸などが挙げられる。上記の置換処理は、ポリケトンを多孔膜に成型する前に行ってもよいし、多孔膜に成型した後に行ってもよいが、成型性の観点から、多孔膜に成型した後に行う方が好ましい。 In the case of substituting at least one hydrogen atom of the polyketone constituting the polyketone porous membrane with another group from the viewpoint of imparting a negative zeta potential to the polyketone porous membrane, examples of the substitution method include electron beam, γ-ray, plasma For example, a radical may be generated in the polyketone by irradiation, and then a reactive monomer having a functional group that exhibits a desired function may be added. Examples of reactive monomers include sulfonic acid groups, sulfonic acid ester groups, carboxylic acid groups, carboxylic acid ester groups, phosphoric acid groups, phosphoric acid ester groups, acrylic acid, methacrylic acid, vinyl sulfonic acid derivatives containing hydroxyl groups, etc. Is mentioned. More specific examples include acrylic acid, methacrylic acid, vinyl sulfonic acid, styrene sulfonic acid, and sodium salts thereof, 2-acrylamido-2-methylpropane sulfonic acid, 2-methacrylamide-2-methylpropane sulfonic acid 2-acrylamido-2-methylpropanecarboxylic acid, 2-methacrylamide-2-methylpropanecarboxylic acid, and the like. The substitution treatment may be performed before the polyketone is molded into the porous film or may be performed after the polyketone is molded into the porous film, but is preferably performed after the polyketone is molded into the porous film from the viewpoint of moldability.
また、下記化学式（２）：
以下、実施例によって本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
実施例及び比較例における各測定値の測定方法は以下の通りであった。
１．ポリケトンの極限粘度［η］
以下の定義式に基づいて極限粘度を求めた。
The measuring method of each measured value in an Example and a comparative example was as follows.
1. Intrinsic viscosity of polyketone [η]
The intrinsic viscosity was determined based on the following definition formula.
２．平均孔径（ｎｍ）
ＰＭＩ社のパームポロメーター（型式：ＣＦＰ−１２００ＡＥＸ）を用い、浸液にＰＭＩ社製のガルウィック（表面張力＝１５．６ｄｙｎｅｓ／ｃｍ）を用い、ＡＳＴＭ Ｅ１２９４−８９に準拠し、ハーフドライ法により測定した。
2. Average pore diameter (nm)
Using a PMI palm porometer (model: CFP-1200AEX), PMI Gullwick (surface tension = 15.6 dynes / cm) as the immersion liquid, according to ASTM E1294-89, and by the half-dry method It was measured.
３．膜厚（μｍ）
ダイヤルゲージ（尾崎製作所：ＰＥＡＣＯＣＫ Ｎｏ．２５）にて、ポリケトン多孔膜の膜厚を、格子状に５ｍｍ間隔で９箇所（３点×３点）選んだ測定点にて測定し、数平均値として得られる平均厚みＬp（μｍ）を膜厚とした。
3. Film thickness (μm)
Using a dial gauge (Ozaki Seisakusho: PEACOCK No. 25), measure the thickness of the polyketone porous film at 9 measurement points (3 points x 3 points) at 5 mm intervals in a lattice shape, and use it as the number average value. The average thickness Lp (μm) obtained was taken as the film thickness.
４．空隙率（ε）（％）
空隙率（ε）は、下記の数式（２）：
ε＝１−Ｇ／ρ／（ｔ・Ａ） （２）
｛式中、Ｇは、ポリケトン膜の重量（ｇ）であり、ρは、ポリケトン多孔膜を構成する高分子の密度（ｇ／ｃｍ３）であり、ｔは、ポリケトン多孔膜の平均厚み（ｃｍ）であり、そしてＡは、ポリケトン多孔膜の面積（ｃｍ２）である。｝により求めた。
4). Porosity (ε) (%)
The porosity (ε) is expressed by the following formula (2):
ε = 1−G / ρ / (t · A) (2)
{In the formula, G is the weight (g) of the polyketone membrane, ρ is the density (g / cm 3 ) of the polymer constituting the polyketone porous membrane, and t is the average thickness (cm ) And A is the area (cm 2 ) of the polyketone porous membrane. }.
５．透気抵抗度（ｓｅｃ／１００ｍｌ）
ＪＩＳ Ｐ８１１７（ガーレー法）に準拠して、透気抵抗度を測定した。
5. Air permeability resistance (sec / 100ml)
The air resistance was measured according to JIS P8117 (Gurley method).
６．引張強度（ＭＰａ）、伸度、及び強度低下率（％）
横型引張強度試験機（熊谷理機工業製）を用い、１５ｍｍ幅の短冊状に切り出したサンプルについて、チャック間距離：８０ｍｍ、伸長速度：８０ｍ／ｍｉｎの条件で５点の破断強度を測定し、その数平均を引張強度（ＭＰａ）とした。
また、下記式により、破断時の伸度を算出した。
伸度（％）＝［破断時のチャック間距離（ｍｍ）−８０（ｍｍ）］／８０（ｍｍ） × １００
また、下記式により、強度低下率を算出した。
強度低下率（％）＝（ポリケトン多孔膜の強度−元のポリケトン多孔膜の強度）／元のポリケトン多孔膜の強度 ｘ １００
6). Tensile strength (MPa), elongation, and strength reduction rate (%)
Using a horizontal tensile strength tester (manufactured by Kumagai Riki Kogyo Co., Ltd.), about a sample cut into a strip shape having a width of 15 mm, the breaking strength at 5 points was measured under the conditions of a distance between chucks: 80 mm and an elongation rate: 80 m / min. The number average was taken as the tensile strength (MPa).
Further, the elongation at break was calculated by the following formula.
Elongation (%) = [Distance between chucks at break (mm) −80 (mm)] / 80 (mm) × 100
Further, the strength reduction rate was calculated by the following formula.
Strength reduction rate (%) = (strength of polyketone porous membrane−strength of original polyketone porous membrane) / strength of original polyketone porous membrane × 100
７．単位厚み当たりの圧力損失（ｋＰａ／μｍ）
ポリケトン多孔平膜を円形に打ち抜き、ステンレス製ホルダ（アドバンテック製、有効濾過面積３．５ｃｍ2）に平膜を固定し、１．４ｍＬ／ｍｉｎ／ｃｍ2で２５℃の蒸留水を２４０分間濾過して１０分後及び２４０分後の圧力損失を測定し、厚み（μｍ）で割って、単位厚み当たりの圧力損失（ｋＰａ／μｍ）を算出した。
7). Pressure loss per unit thickness (kPa / μm)
The polyketone porous flat membrane is punched into a circle, fixed to a stainless steel holder (manufactured by Advantech, effective filtration area 3.5 cm 2 ), and distilled water at 25 ° C. is filtered for 240 minutes at 1.4 mL / min / cm 2. The pressure loss after 10 minutes and 240 minutes was measured and divided by the thickness (μm) to calculate the pressure loss per unit thickness (kPa / μm).
８．粒子透過率（％）
平膜状のポリケトン多孔膜を濾材として、粒子濃度２．０ｐｐｍのアニオン基でコーティングされたポリスチレンラテックスの水分散液を、差圧１００ｋＰａ、有効濾過面積３．５ｃｍ2で５分間全量濾過した。濾液の粒子濃度Ｃ（ｐｐｍ）を測定し、下記式より粒子透過率（％）を算出した。
粒子透過率（％）＝Ｃ／２×１００
尚、濾液のポリスチレン粒子の濃度Ｃ（ｐｐｍ）濃度は、紫外可視分光光度計（日本分光：Ｖ−６５０）を用い、濃度既知のポリスチレンラテックス水分散液から検量線を作成して測定した。
8). Particle transmittance (%)
Using a flat polyketone porous membrane as a filter medium, an aqueous dispersion of polystyrene latex coated with anion groups having a particle concentration of 2.0 ppm was filtered for 5 minutes at a differential pressure of 100 kPa and an effective filtration area of 3.5 cm 2 . The particle concentration C (ppm) of the filtrate was measured, and the particle transmittance (%) was calculated from the following formula.
Particle transmittance (%) = C / 2 × 100
In addition, the density | concentration C (ppm) density | concentration of the polystyrene particle of a filtrate produced the analytical curve from the polystyrene latex aqueous dispersion liquid of a density | concentration using the ultraviolet visible spectrophotometer (JASCO Corporation: V-650), and measured it.
９．ゼータ電位（ｍＶ）
ポリケトン膜のゼータ電位は、ゼータ電位測定システムＥＬＳ−Ｚ（大塚電子株式会社製）を用いて、電気泳動光散乱法により測定した。平板試料用セルユニット（大塚電子株式会社製）のセル上面にポリケトン膜を取り付け、モニター粒子（大塚電子製）を分散させたｐＨ＝６〜７の１０ｍＭ塩化ナトリウム水溶液でセルを満たし、モニター粒子の電気泳動を行い、セル上下面間の７点においてモニター粒子の電気移動度を測定した。得られた電気移動度のデータを森・岡本の式およびSmoluchowskiの式で解析することにより、ポリケトン膜のゼータ電位を算出した。
9. Zeta potential (mV)
The zeta potential of the polyketone film was measured by an electrophoretic light scattering method using a zeta potential measurement system ELS-Z (manufactured by Otsuka Electronics Co., Ltd.). A polyketone film was attached to the upper surface of a cell unit for flat plate cell (Otsuka Electronics Co., Ltd.), and the cells were filled with 10 mM sodium chloride aqueous solution with pH = 6 to 7 in which monitor particles (Otsuka Electronics) were dispersed. Electrophoresis was performed, and the electric mobility of the monitor particles was measured at 7 points between the upper and lower surfaces of the cell. The zeta potential of the polyketone film was calculated by analyzing the obtained electrical mobility data using the Mori-Okamoto equation and the Smoluchowski equation.
１０．陽イオン交換容量測定
５重量％塩酸２００ｍｌをビーカー（ビーカーＡとする）に入れ、ポリケトン多孔膜を３０分間浸漬した後、取り出した。取り出したポリケトン多孔膜を更に１５分間水洗した後、別のビーカー（ビーカーＢとする）に入れた。これに、濃度Ｘモル／ｌの水酸化ナトリウム水溶液をＹｍｌ入れて、上記のポリケトン膜３０分間浸漬した後、ポリケトン多孔膜を取り出した。取り出したポリケトン多孔膜は５０ｍｌの水で洗浄し、ビーカーＢ内の液に加えた。これを、濃度１モル／ｌの塩酸で滴定し、下記数式にて容量を算出した。
陽イオン交換容量（ミリ当量／ｇ）＝［Ｘ（モル／ｌ） × Ｙ（ｍｌ） − １（モル／ｌ）× 滴定に要した塩酸量（ｍｌ）］／サンプル重量（ｇ）
10. Cation exchange capacity measurement 200 ml of 5% by weight hydrochloric acid was placed in a beaker (beaker A), the polyketone porous membrane was immersed for 30 minutes, and then taken out. The removed polyketone porous membrane was further washed with water for 15 minutes, and then placed in another beaker (beaker B). Into this, Yml of a sodium hydroxide aqueous solution having a concentration of X mol / l was put, and the polyketone membrane was immersed for 30 minutes, and then the polyketone porous membrane was taken out. The removed polyketone porous membrane was washed with 50 ml of water and added to the liquid in the beaker B. This was titrated with hydrochloric acid having a concentration of 1 mol / l, and the volume was calculated by the following formula.
Cation exchange capacity (milli equivalent / g) = [X (mol / l) × Y (ml) −1 (mol / l) × amount of hydrochloric acid required for titration (ml)] / sample weight (g)
［実施例１］
エチレンと一酸化炭素が完全交互共重合した極限粘度３．４ｄｌ／ｇのポリケトンを、ポリマー濃度１２ｗｔ％で６１ｗｔ％レゾルシン水溶液に添加し、８０℃で２時間攪拌したところ、ポリケトンは溶解して均一透明なドープが得られた。
得られたドープをアプリケータでガラス板に塗布した。これを５０ｗｔ％のメタノール水溶液中に１０分間浸漬して凝固させた後、水で洗浄し、さらに８０℃の温水中に３０分間浸漬した。これを２−プロパノールで溶媒置換した後、枠固定して８０℃で乾燥を行った。
このポリケトン膜を、酢酸１重量％を含む１重量％アミノメタンスルホン酸水溶液に８０℃で３０分間浸漬させた。次いで、ポリケトン多孔膜を取り出して水、メタノール、アセトンの順で良く洗浄した後６０℃で乾燥して、スルホン酸基含有ポリケトン多孔膜を作製した。
このようにして得られたポリケトン多孔膜の平均孔径は５０ｎｍであり、厚みは１０５μｍ、空隙率は７８％、透気抵抗度は４５秒／１００ｍｌ、引張強度は３．６ＭＰａ、伸度は１８．０％であった。また、陽イオン交換容量は０．０１ミリ当量／ｇ、ゼータ電位は−１０ｍＶであった。圧力損失は、１０分後で２２．５ｋＰａ／μｍ、２４０分後では２２．５ｋＰａ／μｍであった。アニオン性ポリスチレンラテックスの粒子透過率は９０％（粒子径：５０ｎｍ）、０％（粒子径：１００ｎｍ）、０％（粒子径：２００ｎｍ）、０％（粒子径：３００ｎｍ）、０％（粒子径：４００ｎｍ）、０％（粒子径：５００ｎｍ）、０％（粒子径：６００ｎｍ）であった。圧力損失が小さく、５０ｎｍと１００ｎｍの粒子を篩い分けることが可能で、優れた分画性能を持っていた。
[Example 1]
When a polyketone having an intrinsic viscosity of 3.4 dl / g in which ethylene and carbon monoxide are completely alternately copolymerized is added to a 61 wt% resorcin solution at a polymer concentration of 12 wt% and stirred at 80 ° C. for 2 hours, the polyketone dissolves and becomes homogeneous. A transparent dope was obtained.
The obtained dope was applied to a glass plate with an applicator. This was immersed in a 50 wt% aqueous methanol solution for 10 minutes to solidify, washed with water, and further immersed in warm water at 80 ° C. for 30 minutes. This was subjected to solvent substitution with 2-propanol, fixed in a frame, and dried at 80 ° C.
This polyketone membrane was immersed in a 1% by weight aminomethanesulfonic acid aqueous solution containing 1% by weight of acetic acid at 80 ° C. for 30 minutes. Subsequently, the polyketone porous membrane was taken out, washed well in order of water, methanol, and acetone, and then dried at 60 ° C. to prepare a sulfonic acid group-containing polyketone porous membrane.
The polyketone porous membrane thus obtained has an average pore diameter of 50 nm, a thickness of 105 μm, a porosity of 78%, a gas permeability resistance of 45 seconds / 100 ml, a tensile strength of 3.6 MPa, and an elongation of 18. 0%. The cation exchange capacity was 0.01 meq / g and the zeta potential was −10 mV. The pressure loss was 22.5 kPa / μm after 10 minutes and 22.5 kPa / μm after 240 minutes. The particle transmittance of the anionic polystyrene latex is 90% (particle size: 50 nm), 0% (particle size: 100 nm), 0% (particle size: 200 nm), 0% (particle size: 300 nm), 0% (particle size) : 400 nm), 0% (particle diameter: 500 nm), and 0% (particle diameter: 600 nm). The pressure loss was small, particles of 50 nm and 100 nm could be screened, and the fractionation performance was excellent.
［実施例２］
エチレンと一酸化炭素が完全交互共重合した極限粘度３．４ｄｌ／ｇのポリケトンを、ポリマー濃度１０．７ｗｔ％で６３ｗｔ％レゾルシン水溶液に添加し、８０℃で２時間攪拌したところ、ポリケトンは溶解して均一透明なドープが得られた。
得られたドープをアプリケータでガラス板に塗布した。これを５０ｗｔ％のメタノール水溶液中に１０分間浸漬して凝固させた後、水で洗浄し、さらに８０℃の温水中に３０分間浸漬した。これを２−プロパノールで溶媒置換した後、枠固定して８０℃で乾燥を行った。
このポリケトン膜を、実施例１と同様に、酢酸１重量％を含む１重量％アミノメタンスルホン酸水溶液に８０℃で３０分間浸漬させた。次いで、ポリケトン多孔膜を取り出して水、メタノール、アセトンの順で良く洗浄した後６０℃で乾燥して、スルホン酸基含有ポリケトン多孔膜を作製した。
このようにして得られたポリケトン多孔膜の平均孔径は９８ｎｍであり、厚みは１０１μｍ、空隙率は８０％、透気抵抗度は４０秒／１００ｍｌ、引張強度は３．６ＭＰａ、伸度は１８．２％であった。また、陽イオン交換容量は０．０１ミリ当量／ｇ、ゼータ電位は−１０ｍＶであった。圧力損失は、１０分後で２０．５ｋＰａ／μｍ、２４０分後では２０．５ｋＰａ／μｍであった。アニオン性ポリスチレンラテックスの粒子透過率は１００％（粒子径：５０ｎｍ）、９２％（粒子径：１００ｎｍ）、０％（粒子径：２００ｎｍ）、０％（粒子径：３００ｎｍ）、０％（粒子径：４００ｎｍ）、０％（粒子径：５００ｎｍ）、０％（粒子径：６００ｎｍ）であった。圧力損失が小さく、１００ｎｍと２００ｎｍの粒子を篩い分けることが可能で、優れた分画性能を持っていた。
[Example 2]
When a polyketone having an intrinsic viscosity of 3.4 dl / g in which ethylene and carbon monoxide are completely alternately copolymerized is added to a 63 wt% resorcin solution at a polymer concentration of 10.7 wt% and stirred at 80 ° C for 2 hours, the polyketone dissolves. And a uniform transparent dope was obtained.
The obtained dope was applied to a glass plate with an applicator. This was immersed in a 50 wt% aqueous methanol solution for 10 minutes to solidify, washed with water, and further immersed in warm water at 80 ° C. for 30 minutes. This was subjected to solvent substitution with 2-propanol, fixed in a frame, and dried at 80 ° C.
In the same manner as in Example 1, this polyketone membrane was immersed in a 1% by weight aminomethanesulfonic acid aqueous solution containing 1% by weight acetic acid at 80 ° C. for 30 minutes. Subsequently, the polyketone porous membrane was taken out, washed well in order of water, methanol, and acetone, and then dried at 60 ° C. to prepare a sulfonic acid group-containing polyketone porous membrane.
The polyketone porous membrane thus obtained has an average pore diameter of 98 nm, a thickness of 101 μm, a porosity of 80%, a gas permeability resistance of 40 seconds / 100 ml, a tensile strength of 3.6 MPa, and an elongation of 18. 2%. The cation exchange capacity was 0.01 meq / g and the zeta potential was −10 mV. The pressure loss was 20.5 kPa / μm after 10 minutes and 20.5 kPa / μm after 240 minutes. The particle transmittance of the anionic polystyrene latex is 100% (particle size: 50 nm), 92% (particle size: 100 nm), 0% (particle size: 200 nm), 0% (particle size: 300 nm), 0% (particle size) : 400 nm), 0% (particle diameter: 500 nm), and 0% (particle diameter: 600 nm). The pressure loss was small, particles of 100 nm and 200 nm could be screened, and the fractionation performance was excellent.
［実施例３］
エチレンと一酸化炭素が完全交互共重合した極限粘度３．４ｄｌ／ｇのポリケトンを、ポリマー濃度１０．７ｗｔ％で６５ｗｔ％レゾルシン水溶液に添加し、８０℃で２時間攪拌したところ、ポリケトンは溶解して均一透明なドープが得られた。
得られたドープをアプリケータでガラス板に塗布した。これを５０ｗｔ％のメタノール水溶液中に１０分間浸漬して凝固させた後、水で洗浄し、さらに８０℃の温水中に３０分間浸漬した。これを２−プロパノールで溶媒置換した後、枠固定して８０℃で乾燥を行った。
このポリケトン膜を、実施例１と同様に、酢酸１重量％を含む１重量％アミノメタンスルホン酸水溶液に８０℃で３０分間浸漬させた。次いで、ポリケトン多孔膜を取り出して水、メタノール、アセトンの順で良く洗浄した後６０℃で乾燥して、スルホン酸基含有ポリケトン多孔膜を作製した。
このようにして得られたポリケトン多孔膜の平均孔径は２０２ｎｍであり、厚みは９７μｍ、空隙率は８１％、透気抵抗度は２８秒／１００ｍｌ、引張強度は３．６ＭＰａ、伸度は１８．１％であった。また、陽イオン交換容量は０．０１ミリ当量／ｇ、ゼータ電位は−１０ｍＶであった。圧力損失は、１０分後で１８．６ｋＰａ／μｍ、２４０分後では１８．４ｋＰａ／μｍであった。アニオン性ポリスチレンラテックスの粒子透過率は１００％（粒子径：５０ｎｍ）、１００％（粒子径：１００ｎｍ）、９１％（粒子径：２００ｎｍ）、０％（粒子径：３００ｎｍ）、０％（粒子径：４００ｎｍ）、０％（粒子径：５００ｎｍ）、０％（粒子径：６００ｎｍ）であった。圧力損失が小さく、２００ｎｍと３００ｎｍの粒子を篩い分けることが可能で、優れた分画性能を持っていた。
[Example 3]
When a polyketone having an intrinsic viscosity of 3.4 dl / g in which ethylene and carbon monoxide are completely alternately copolymerized is added to a 65 wt% resorcin solution at a polymer concentration of 10.7 wt% and stirred at 80 ° C. for 2 hours, the polyketone dissolves. And a uniform transparent dope was obtained.
The obtained dope was applied to a glass plate with an applicator. This was immersed in a 50 wt% aqueous methanol solution for 10 minutes to solidify, washed with water, and further immersed in warm water at 80 ° C. for 30 minutes. This was subjected to solvent substitution with 2-propanol, fixed in a frame, and dried at 80 ° C.
In the same manner as in Example 1, this polyketone membrane was immersed in a 1% by weight aminomethanesulfonic acid aqueous solution containing 1% by weight acetic acid at 80 ° C. for 30 minutes. Subsequently, the polyketone porous membrane was taken out, washed well in order of water, methanol, and acetone, and then dried at 60 ° C. to prepare a sulfonic acid group-containing polyketone porous membrane.
The polyketone porous membrane thus obtained has an average pore diameter of 202 nm, a thickness of 97 μm, a porosity of 81%, a gas permeability resistance of 28 seconds / 100 ml, a tensile strength of 3.6 MPa, and an elongation of 18. 1%. The cation exchange capacity was 0.01 meq / g and the zeta potential was −10 mV. The pressure loss was 18.6 kPa / μm after 10 minutes and 18.4 kPa / μm after 240 minutes. The particle transmittance of the anionic polystyrene latex is 100% (particle size: 50 nm), 100% (particle size: 100 nm), 91% (particle size: 200 nm), 0% (particle size: 300 nm), 0% (particle size) : 400 nm), 0% (particle diameter: 500 nm), and 0% (particle diameter: 600 nm). The pressure loss was small, particles of 200 nm and 300 nm could be sieved, and the fractionation performance was excellent.
［実施例４］
エチレンと一酸化炭素が完全交互共重合した極限粘度３．４ｄｌ／ｇのポリケトンを、ポリマー濃度１０．７ｗｔ％で６８ｗｔ％レゾルシン水溶液に添加し、８０℃で２時間攪拌したところ、ポリケトンは溶解して均一透明なドープが得られた。
得られたドープをアプリケータでガラス板に塗布した。これを５０ｗｔ％のメタノール水溶液中に１０分間浸漬して凝固させた後、水で洗浄し、さらに８０℃の温水中に３０分間浸漬した。これを２−プロパノールで溶媒置換した後、枠固定して８０℃で乾燥を行った。
このポリケトン膜を、実施例１と同様に、酢酸１重量％を含む１重量％アミノメタンスルホン酸水溶液に８０℃で３０分間浸漬させた。次いで、ポリケトン多孔膜を取り出して水、メタノール、アセトンの順で良く洗浄した後６０℃で乾燥して、スルホン酸基含有ポリケトン多孔膜を作製した。
このようにして得られたポリケトン多孔膜の平均孔径は４９７ｎｍであり、厚みは１１０μｍ、空隙率は８２％、透気抵抗度は１０秒／１００ｍｌ、引張強度は３．５ＭＰａ、伸度は１８．０％であった。また、陽イオン交換容量は０．０１ミリ当量／ｇ、ゼータ電位は−１０ｍＶであった。圧力損失は、１０分後で１５．５ｋＰａ／μｍ、２４０分後では１５．４ｋＰａ／μｍであった。アニオン性ポリスチレンラテックスの粒子透過率は１００％（粒子径：５０ｎｍ）、１００％（粒子径：１００ｎｍ）、１００％（粒子径：２００ｎｍ）、１００％（粒子径：３００ｎｍ）、１００％（粒子径：４００ｎｍ）、９２％（粒子径：５００ｎｍ）、０％（粒子径：６００ｎｍ）であった。圧力損失が小さく、５００ｎｍと６００ｎｍの粒子を篩い分けることが可能で、優れた分画性能を持っていた。
[Example 4]
When a polyketone having an intrinsic viscosity of 3.4 dl / g in which ethylene and carbon monoxide are completely alternately copolymerized is added to a 68 wt% resorcin solution at a polymer concentration of 10.7 wt% and stirred at 80 ° C. for 2 hours, the polyketone dissolves. And a uniform transparent dope was obtained.
The obtained dope was applied to a glass plate with an applicator. This was immersed in a 50 wt% aqueous methanol solution for 10 minutes to solidify, washed with water, and further immersed in warm water at 80 ° C. for 30 minutes. This was subjected to solvent substitution with 2-propanol, fixed in a frame, and dried at 80 ° C.
In the same manner as in Example 1, this polyketone membrane was immersed in a 1% by weight aminomethanesulfonic acid aqueous solution containing 1% by weight acetic acid at 80 ° C. for 30 minutes. Subsequently, the polyketone porous membrane was taken out, washed well in order of water, methanol, and acetone, and then dried at 60 ° C. to prepare a sulfonic acid group-containing polyketone porous membrane.
The thus obtained polyketone porous membrane has an average pore diameter of 497 nm, a thickness of 110 μm, a porosity of 82%, an air resistance of 10 seconds / 100 ml, a tensile strength of 3.5 MPa, and an elongation of 18. 0%. The cation exchange capacity was 0.01 meq / g and the zeta potential was −10 mV. The pressure loss was 15.5 kPa / μm after 10 minutes and 15.4 kPa / μm after 240 minutes. The particle transmittance of the anionic polystyrene latex is 100% (particle size: 50 nm), 100% (particle size: 100 nm), 100% (particle size: 200 nm), 100% (particle size: 300 nm), 100% (particle size) : 400 nm), 92% (particle diameter: 500 nm), and 0% (particle diameter: 600 nm). The pressure loss was small, particles of 500 nm and 600 nm could be sieved, and the fractionation performance was excellent.
［実施例５］
３重量％アミノメタンスルホン酸を用いた以外は、実施例２と同じ条件でスルホン酸基含有ポリケトン多孔膜を作製した。
このようにして得られたポリケトン多孔膜の平均孔径は９９ｎｍであり、厚みは１０３μｍ、空隙率は８５％、透気抵抗度は４０秒／１００ｍｌ、引張強度は３．８ＭＰａ、伸度は１８．４％であった。また、陽イオン交換容量は０．０２ミリ当量／ｇ、ゼータ電位は−１５ｍＶであった。圧力損失は、１０分後で２０．１ｋＰａ／μｍ、２４０分後では２０．２ｋＰａ／μｍであった。アニオン性ポリスチレンラテックスの粒子透過率は１００％（粒子径：５０ｎｍ）、９１％（粒子径：１００ｎｍ）、０％（粒子径：２００ｎｍ）、０％（粒子径：３００ｎｍ）、０％（粒子径：４００ｎｍ）、０％（粒子径：５００ｎｍ）、０％（粒子径：６００ｎｍ）であった。圧力損失が小さく、１００ｎｍと２００ｎｍの粒子を篩い分けることが可能で、優れた分画性能を持っていた。
[Example 5]
A sulfonic acid group-containing polyketone porous membrane was prepared under the same conditions as in Example 2 except that 3 wt% aminomethanesulfonic acid was used.
The thus obtained polyketone porous membrane has an average pore size of 99 nm, a thickness of 103 μm, a porosity of 85%, a gas permeability resistance of 40 seconds / 100 ml, a tensile strength of 3.8 MPa, and an elongation of 18. 4%. The cation exchange capacity was 0.02 meq / g and the zeta potential was −15 mV. The pressure loss was 20.1 kPa / μm after 10 minutes and 20.2 kPa / μm after 240 minutes. The particle transmittance of the anionic polystyrene latex is 100% (particle size: 50 nm), 91% (particle size: 100 nm), 0% (particle size: 200 nm), 0% (particle size: 300 nm), 0% (particle size) : 400 nm), 0% (particle diameter: 500 nm), and 0% (particle diameter: 600 nm). The pressure loss was small, particles of 100 nm and 200 nm could be screened, and the fractionation performance was excellent.
［実施例６］
１０重量％アミノメタンスルホン酸を用いた以外は、実施例２と同じ条件でスルホン酸基含有ポリケトン多孔膜を作製した。
このようにして得られたポリケトン多孔膜の平均孔径は１０２ｎｍであり、厚みは９９μｍ、空隙率は８０％、透気抵抗度は４０秒／１００ｍｌ、引張強度は３．７ＭＰａ、伸度は１７．３％であった。また、陽イオン交換容量は０．２１ミリ当量／ｇ、ゼータ電位は−２３ｍＶであった。圧力損失は、１０分後で２０．５ｋＰａ／μｍ、２４０分後では２０．８ｋＰａ／μｍであった。アニオン性ポリスチレンラテックスの粒子透過率は１００％（粒子径：５０ｎｍ）、９４％（粒子径：１００ｎｍ）、０％（粒子径：２００ｎｍ）、０％（粒子径：３００ｎｍ）、０％（粒子径：４００ｎｍ）、０％（粒子径：５００ｎｍ）、０％（粒子径：６００ｎｍ）であった。圧力損失が小さく、１００ｎｍと２００ｎｍの粒子を篩い分けることが可能で、優れた分画性能を持っていた。
[Example 6]
A sulfonic acid group-containing polyketone porous membrane was prepared under the same conditions as in Example 2 except that 10 wt% aminomethanesulfonic acid was used.
The polyketone porous membrane thus obtained has an average pore size of 102 nm, a thickness of 99 μm, a porosity of 80%, a gas permeability resistance of 40 seconds / 100 ml, a tensile strength of 3.7 MPa, and an elongation of 17. 3%. The cation exchange capacity was 0.21 meq / g, and the zeta potential was −23 mV. The pressure loss was 20.5 kPa / μm after 10 minutes and 20.8 kPa / μm after 240 minutes. The particle transmittance of the anionic polystyrene latex is 100% (particle size: 50 nm), 94% (particle size: 100 nm), 0% (particle size: 200 nm), 0% (particle size: 300 nm), 0% (particle size) : 400 nm), 0% (particle diameter: 500 nm), and 0% (particle diameter: 600 nm). The pressure loss was small, particles of 100 nm and 200 nm could be screened, and the fractionation performance was excellent.
［実施例７］
１０重量％アミノメタンスルホン酸を用いて、８０℃、２時間で処理を行った以外は、実施例２と同じ条件でスルホン酸基含有ポリケトン多孔膜を作製した。
このようにして得られたポリケトン多孔膜の平均孔径は１０１ｎｍであり、厚みは１００μｍ、空隙率は８０％、透気抵抗度は４０秒／１００ｍｌ、引張強度は３．６ＭＰａ、伸度は１７．６％であった。また、陽イオン交換容量は１．２０ミリ当量／ｇ、ゼータ電位は−３０ｍＶであった。圧力損失は、１０分後で２０．４ｋＰａ／μｍ、２４０分後では２０．４ｋＰａ／μｍであった。アニオン性ポリスチレンラテックスの粒子透過率は１００％（粒子径：５０ｎｍ）、９２％（粒子径：１００ｎｍ）、０％（粒子径：２００ｎｍ）、０％（粒子径：３００ｎｍ）、０％（粒子径：４００ｎｍ）、０％（粒子径：５００ｎｍ）、０％（粒子径：６００ｎｍ）であった。圧力損失が小さく、１００ｎｍと２００ｎｍの粒子を篩い分けることが可能で、優れた分画性能を持っていた。
[Example 7]
A sulfonic acid group-containing polyketone porous membrane was produced under the same conditions as in Example 2 except that the treatment was performed at 80 ° C. for 2 hours using 10 wt% aminomethanesulfonic acid.
The polyketone porous membrane thus obtained has an average pore diameter of 101 nm, a thickness of 100 μm, a porosity of 80%, a gas permeability resistance of 40 seconds / 100 ml, a tensile strength of 3.6 MPa, and an elongation of 17. It was 6%. The cation exchange capacity was 1.20 meq / g, and the zeta potential was −30 mV. The pressure loss was 20.4 kPa / μm after 10 minutes and 20.4 kPa / μm after 240 minutes. The particle transmittance of the anionic polystyrene latex is 100% (particle size: 50 nm), 92% (particle size: 100 nm), 0% (particle size: 200 nm), 0% (particle size: 300 nm), 0% (particle size) : 400 nm), 0% (particle diameter: 500 nm), and 0% (particle diameter: 600 nm). The pressure loss was small, particles of 100 nm and 200 nm could be screened, and the fractionation performance was excellent.
［実施例８］
酢酸１％を含む１０重量％アミノメタンスルホン酸のジメチルホルムアミド溶液を用いた以外は、実施例２と同じ条件でポリケトン多孔膜を作製した。
このようにして得られたポリケトン多孔膜の平均孔径は１００ｎｍであり、厚みは１０２μｍ、空隙率は８０％、透気抵抗度は４０秒／１００ｍｌ、引張強度は３．４ＭＰａ、伸度は１６．７％であった。また、陽イオン交換容量は２．３２ミリ当量／ｇ、ゼータ電位は−５５ｍＶであった。圧力損失は、１０分後で２０．０ｋＰａ／μｍ、２４０分後では１９．０ｋＰａ／μｍであった。アニオン性ポリスチレンラテックスの粒子透過率は１００％（粒子径：５０ｎｍ）、９７％（粒子径：１００ｎｍ）、０％（粒子径：２００ｎｍ）、０％（粒子径：３００ｎｍ）、０％（粒子径：４００ｎｍ）、０％（粒子径：５００ｎｍ）、０％（粒子径：６００ｎｍ）であった。圧力損失が小さく、１００ｎｍと２００ｎｍの粒子を篩い分けることが可能で、優れた分画性能を持っていた。
[Example 8]
A polyketone porous membrane was prepared under the same conditions as in Example 2 except that a dimethylformamide solution of 10% by weight aminomethanesulfonic acid containing 1% acetic acid was used.
The average pore diameter of the polyketone porous membrane thus obtained is 100 nm, the thickness is 102 μm, the porosity is 80%, the air resistance is 40 seconds / 100 ml, the tensile strength is 3.4 MPa, and the elongation is 16. 7%. The cation exchange capacity was 2.32 meq / g, and the zeta potential was -55 mV. The pressure loss was 20.0 kPa / μm after 10 minutes and 19.0 kPa / μm after 240 minutes. The particle transmittance of the anionic polystyrene latex is 100% (particle size: 50 nm), 97% (particle size: 100 nm), 0% (particle size: 200 nm), 0% (particle size: 300 nm), 0% (particle size) : 400 nm), 0% (particle diameter: 500 nm), and 0% (particle diameter: 600 nm). The pressure loss was small, particles of 100 nm and 200 nm could be screened, and the fractionation performance was excellent.
［実施例９］
１２０℃の１０重量％アミノメタンスルホン酸／酢酸懸濁液に３０分間浸漬させた以外は、実施例２と同じ条件でポリケトン多孔膜を作製した。
このようにして得られたポリケトン多孔膜の平均孔径は９８ｎｍであり、厚みは９８μｍ、空隙率は８０％、透気抵抗度は４０秒／１００ｍｌ、引張強度は３．２ＭＰａ、伸度は５．２％であった。また、陽イオン交換容量は６．７１ミリ当量／ｇ、ゼータ電位は−６７ｍＶであった。圧力損失は、１０分後で２０．６ｋＰａ／μｍ、２４０分後では１８．０ｋＰａ／μｍであった。アニオン性ポリスチレンラテックスの粒子透過率は１００％（粒子径：５０ｎｍ）、１００％（粒子径：１００ｎｍ）、０％（粒子径：２００ｎｍ）、０％（粒子径：３００ｎｍ）、０％（粒子径：４００ｎｍ）、０％（粒子径：５００ｎｍ）、０％（粒子径：６００ｎｍ）であった。圧力損失が小さく、１００ｎｍと２００ｎｍの粒子を篩い分けることが可能で、優れた分画性能を持っていた。
[Example 9]
A polyketone porous membrane was produced under the same conditions as in Example 2 except that the suspension was immersed in a 10 wt% aminomethanesulfonic acid / acetic acid suspension at 120 ° C. for 30 minutes.
The thus obtained polyketone porous membrane has an average pore diameter of 98 nm, a thickness of 98 μm, a porosity of 80%, a gas permeability resistance of 40 seconds / 100 ml, a tensile strength of 3.2 MPa, and an elongation of 5. 2%. The cation exchange capacity was 6.71 meq / g, and the zeta potential was -67 mV. The pressure loss was 20.6 kPa / μm after 10 minutes and 18.0 kPa / μm after 240 minutes. The particle transmittance of the anionic polystyrene latex is 100% (particle size: 50 nm), 100% (particle size: 100 nm), 0% (particle size: 200 nm), 0% (particle size: 300 nm), 0% (particle size) : 400 nm), 0% (particle diameter: 500 nm), and 0% (particle diameter: 600 nm). The pressure loss was small, particles of 100 nm and 200 nm could be screened, and the fractionation performance was excellent.
［実施例１０］
アミノエタンスルホン酸を用いた以外は、実施例５と同じ条件でスルホン酸基含有ポリケトン多孔膜を作製した。
このようにして得られたポリケトン多孔膜の平均孔径は１０１ｎｍであり、厚みは１００μｍ、空隙率は８０％、透気抵抗度は４０秒／１００ｍｌ、引張強度は３．８ＭＰａ、伸度は１７．３％であった。また、陽イオン交換容量は０．０２ミリ当量／ｇ、ゼータ電位は−１０ｍＶであった。圧力損失は、１０分後で１９．９ｋＰａ／μｍ、２４０分後では２０．０ｋＰａ／μｍであった。アニオン性ポリスチレンラテックスの粒子透過率は１００％（粒子径：５０ｎｍ）、９３％（粒子径：１００ｎｍ）、０％（粒子径：２００ｎｍ）、０％（粒子径：３００ｎｍ）、０％（粒子径：４００ｎｍ）、０％（粒子径：５００ｎｍ）、０％（粒子径：６００ｎｍ）であった。圧力損失が小さく、１００ｎｍと２００ｎｍの粒子を篩い分けることが可能で、優れた分画性能を持っていた。
[Example 10]
A sulfonic acid group-containing polyketone porous membrane was produced under the same conditions as in Example 5 except that aminoethanesulfonic acid was used.
The polyketone porous membrane thus obtained has an average pore diameter of 101 nm, a thickness of 100 μm, a porosity of 80%, a gas permeability resistance of 40 seconds / 100 ml, a tensile strength of 3.8 MPa, and an elongation of 17. 3%. The cation exchange capacity was 0.02 meq / g, and the zeta potential was −10 mV. The pressure loss was 19.9 kPa / μm after 10 minutes and 20.0 kPa / μm after 240 minutes. The particle transmittance of the anionic polystyrene latex is 100% (particle size: 50 nm), 93% (particle size: 100 nm), 0% (particle size: 200 nm), 0% (particle size: 300 nm), 0% (particle size) : 400 nm), 0% (particle diameter: 500 nm), and 0% (particle diameter: 600 nm). The pressure loss was small, particles of 100 nm and 200 nm could be screened, and the fractionation performance was excellent.
［実施例１１］
アミノメタンカルボン酸を用いた以外は、実施例５と同じ条件でスルホン酸基含有ポリケトン多孔膜を作製した。
このようにして得られたポリケトン多孔膜の平均孔径は１００ｎｍであり、厚みは９７μｍ、空隙率は８２％、透気抵抗度は３８秒／１００ｍｌ、引張強度は３．８ＭＰａ、伸度は１７．４％であった。また、陽イオン交換容量は０．０２ミリ当量／ｇ、ゼータ電位は−１４ｍＶであった。圧力損失は、１０分後で２０．１ｋＰａ／μｍ、２４０分後では１９．９Ｐａ／μｍであった。アニオン性ポリスチレンラテックスの粒子透過率は１００％（粒子径：５０ｎｍ）、８９％（粒子径：１００ｎｍ）、０％（粒子径：２００ｎｍ）、０％（粒子径：３００ｎｍ）、０％（粒子径：４００ｎｍ）、０％（粒子径：５００ｎｍ）、０％（粒子径：６００ｎｍ）であった。圧力損失が小さく、１００ｎｍと２００ｎｍの粒子を篩い分けることが可能で、優れた分画性能を持っていた。
[Example 11]
A sulfonic acid group-containing polyketone porous membrane was produced under the same conditions as in Example 5 except that aminomethanecarboxylic acid was used.
The polyketone porous membrane thus obtained has an average pore diameter of 100 nm, a thickness of 97 μm, a porosity of 82%, a gas permeability resistance of 38 seconds / 100 ml, a tensile strength of 3.8 MPa, and an elongation of 17. 4%. The cation exchange capacity was 0.02 meq / g, and the zeta potential was -14 mV. The pressure loss was 20.1 kPa / μm after 10 minutes and 19.9 Pa / μm after 240 minutes. The particle transmittance of the anionic polystyrene latex is 100% (particle size: 50 nm), 89% (particle size: 100 nm), 0% (particle size: 200 nm), 0% (particle size: 300 nm), 0% (particle size) : 400 nm), 0% (particle diameter: 500 nm), and 0% (particle diameter: 600 nm). The pressure loss was small, particles of 100 nm and 200 nm could be screened, and the fractionation performance was excellent.
［実施例１２］
２−アミノ−１、３−プロパンジオールを用いた以外は、実施例５と同じ条件でスルホン酸基含有ポリケトン多孔膜を作製した。
このようにして得られたポリケトン多孔膜の平均孔径は１０３ｎｍであり、厚みは９８μｍ、空隙率は８１％、透気抵抗度は４１秒／１００ｍｌ、引張強度は３．８ＭＰａ、伸度は１８．２％であった。また、陽イオン交換容量は０．０４ミリ当量／ｇ、ゼータ電位は−１３ｍＶであった。圧力損失は、１０分後で２０．１ｋＰａ／μｍ、２４０分後では２０．１Ｐａ／μｍであった。アニオン性ポリスチレンラテックスの粒子透過率は１００％（粒子径：５０ｎｍ）、９２％（粒子径：１００ｎｍ）、０％（粒子径：２００ｎｍ）、０％（粒子径：３００ｎｍ）、０％（粒子径：４００ｎｍ）、０％（粒子径：５００ｎｍ）、０％（粒子径：６００ｎｍ）であった。圧力損失が小さく、１００ｎｍと２００ｎｍの粒子を篩い分けることが可能で、優れた分画性能を持っていた。
[Example 12]
A sulfonic acid group-containing polyketone porous membrane was produced under the same conditions as in Example 5 except that 2-amino-1,3-propanediol was used.
The average pore diameter of the polyketone porous membrane thus obtained is 103 nm, the thickness is 98 μm, the porosity is 81%, the air resistance is 41 seconds / 100 ml, the tensile strength is 3.8 MPa, and the elongation is 18. 2%. The cation exchange capacity was 0.04 meq / g, and the zeta potential was −13 mV. The pressure loss was 20.1 kPa / μm after 10 minutes and 20.1 Pa / μm after 240 minutes. The particle transmittance of the anionic polystyrene latex is 100% (particle size: 50 nm), 92% (particle size: 100 nm), 0% (particle size: 200 nm), 0% (particle size: 300 nm), 0% (particle size) : 400 nm), 0% (particle diameter: 500 nm), and 0% (particle diameter: 600 nm). The pressure loss was small, particles of 100 nm and 200 nm could be screened, and the fractionation performance was excellent.
［実施例１３］
エチレンと一酸化炭素が完全交互共重合した極限粘度３．４ｄｌ／ｇのポリケトンを、ポリマー濃度１０．７ｗｔ％で６３ｗｔ％レゾルシン水溶液に添加し、８０℃で２時間攪拌したところ、ポリケトンは溶解して均一透明なドープが得られた。
得られたドープをアプリケータでガラス板に塗布した。これを５０ｗｔ％のメタノール水溶液中に１０分間浸漬して凝固させた後、水で洗浄し、さらに８０℃の温水中に３０分間浸漬した。これを２−プロパノールで溶媒置換した後、枠固定して８０℃で乾燥を行った。このポリケトン多孔膜をドライアイスで冷やしながら２００ｋＧｙの電子線を数秒間照射して、ラジカル化ポリケトン多孔膜を作製した。窒素バブリングによって溶存酸素を除去した１重量％２−メタクリルアミド−２−メチルプロパンスルホン酸水溶液に、上記ラジカル化ポリケトン多孔膜を窒素雰囲気下、４０℃で１時間浸漬させた。次いで、水、メタノール、アセトンの順でよく洗浄した後６０℃で乾燥して、スルホン酸基含有ポリケトン多孔膜を得た。
このようにして得られたポリケトン多孔膜の平均孔径は９８ｎｍであり、厚みは９８μｍ、空隙率は８２％、透気抵抗度は４０秒／１００ｍｌ、引張強度は３．９ＭＰａ、伸度は２０．７％であった。また、陽イオン交換容量は０．０６ミリ当量／ｇ、ゼータ電位は−２０ｍＶであった。圧力損失は、１０分後で２０．０ｋＰａ／μｍ、２４０分後では２０．０Ｐａ／μｍであった。アニオン性ポリスチレンラテックスの粒子透過率は１００％（粒子径：５０ｎｍ）、９０％（粒子径：１００ｎｍ）、０％（粒子径：２００ｎｍ）、０％（粒子径：３００ｎｍ）、０％（粒子径：４００ｎｍ）、０％（粒子径：５００ｎｍ）、０％（粒子径：６００ｎｍ）であった。圧力損失が小さく、１００ｎｍと２００ｎｍの粒子を篩い分けることが可能で、優れた分画性能を持っていた。
[Example 13]
When a polyketone having an intrinsic viscosity of 3.4 dl / g in which ethylene and carbon monoxide are completely alternately copolymerized is added to a 63 wt% resorcin solution at a polymer concentration of 10.7 wt% and stirred at 80 ° C for 2 hours, the polyketone dissolves. And a uniform transparent dope was obtained.
The obtained dope was applied to a glass plate with an applicator. This was immersed in a 50 wt% aqueous methanol solution for 10 minutes to solidify, washed with water, and further immersed in warm water at 80 ° C. for 30 minutes. This was subjected to solvent substitution with 2-propanol, fixed in a frame, and dried at 80 ° C. While this polyketone porous membrane was cooled with dry ice, an electron beam of 200 kGy was irradiated for several seconds to produce a radicalized polyketone porous membrane. The radicalized polyketone porous membrane was immersed in a 1 wt% 2-methacrylamide-2-methylpropanesulfonic acid aqueous solution from which dissolved oxygen was removed by nitrogen bubbling at 40 ° C. for 1 hour in a nitrogen atmosphere. Subsequently, after washing | cleaning in order of water, methanol, and acetone well, it dried at 60 degreeC and obtained the sulfonic acid group containing polyketone porous membrane.
The thus obtained polyketone porous membrane has an average pore diameter of 98 nm, a thickness of 98 μm, a porosity of 82%, an air resistance of 40 seconds / 100 ml, a tensile strength of 3.9 MPa, and an elongation of 20. 7%. The cation exchange capacity was 0.06 meq / g and the zeta potential was −20 mV. The pressure loss was 20.0 kPa / μm after 10 minutes and 20.0 Pa / μm after 240 minutes. The particle transmittance of the anionic polystyrene latex is 100% (particle size: 50 nm), 90% (particle size: 100 nm), 0% (particle size: 200 nm), 0% (particle size: 300 nm), 0% (particle size) : 400 nm), 0% (particle diameter: 500 nm), and 0% (particle diameter: 600 nm). The pressure loss was small, particles of 100 nm and 200 nm could be screened, and the fractionation performance was excellent.
［実施例１４］
浸漬時間を３時間にした以外は、実施例１３と同じ条件でスルホン酸基含有ポリケトン多孔膜を作製した。
このようにして得られたポリケトン多孔膜の平均孔径は９７ｎｍであり、厚みは１０７μｍ、空隙率は８１％、透気抵抗度は４２秒／１００ｍｌ、引張強度は３．９ＭＰａ、伸度は２０．２％であった。また、陽イオン交換容量は０．６３ミリ当量／ｇ、ゼータ電位は−２５ｍＶであった。圧力損失は、１０分後で２０．５ｋＰａ／μｍ、２４０分後では２０．８Ｐａ／μｍであった。アニオン性ポリスチレンラテックスの粒子透過率は１００％（粒子径：５０ｎｍ）、９４％（粒子径：１００ｎｍ）、０％（粒子径：２００ｎｍ）、０％（粒子径：３００ｎｍ）、０％（粒子径：４００ｎｍ）、０％（粒子径：５００ｎｍ）、０％（粒子径：６００ｎｍ）であった。圧力損失が小さく、１００ｎｍと２００ｎｍの粒子を篩い分けることが可能で、優れた分画性能を持っていた。
[Example 14]
A sulfonic acid group-containing polyketone porous membrane was produced under the same conditions as in Example 13 except that the immersion time was 3 hours.
The polyketone porous membrane thus obtained has an average pore diameter of 97 nm, a thickness of 107 μm, a porosity of 81%, a gas permeability resistance of 42 seconds / 100 ml, a tensile strength of 3.9 MPa, and an elongation of 20. 2%. The cation exchange capacity was 0.63 meq / g and the zeta potential was −25 mV. The pressure loss was 20.5 kPa / μm after 10 minutes and 20.8 Pa / μm after 240 minutes. The particle transmittance of the anionic polystyrene latex is 100% (particle size: 50 nm), 94% (particle size: 100 nm), 0% (particle size: 200 nm), 0% (particle size: 300 nm), 0% (particle size) : 400 nm), 0% (particle diameter: 500 nm), and 0% (particle diameter: 600 nm). The pressure loss was small, particles of 100 nm and 200 nm could be screened, and the fractionation performance was excellent.
［実施例１５］
５重量％２−メタクリルアミド−２−メチルプロパンスルホン酸水溶液を用いて、６０℃で３時間浸漬させた以外は、実施例１３と同じ条件でスルホン酸基含有ポリケトン多孔膜を作製した。
このようにして得られたポリケトン多孔膜の平均孔径は９７ｎｍであり、厚みは１０６μｍ、空隙率は８０％、透気抵抗度は４５秒／１００ｍｌ、引張強度は３．９ＭＰａ、伸度は２０．１％であった。また、陽イオン交換容量は１．１２ミリ当量／ｇ、ゼータ電位は−３５ｍＶであった。圧力損失は、１０分後で２１．０ｋＰａ／μｍ、２４０分後では２２．５ｋＰａ／μｍであった。アニオン性ポリスチレンラテックスの粒子透過率は１００％（粒子径：５０ｎｍ）、８９％（粒子径：１００ｎｍ）、０％（粒子径：２００ｎｍ）、０％（粒子径：３００ｎｍ）、０％（粒子径：４００ｎｍ）、０％（粒子径：５００ｎｍ）、０％（粒子径：６００ｎｍ）であった。圧力損失が小さく、１００ｎｍと２００ｎｍの粒子を篩い分けることが可能で、優れた分画性能を持っていた。
[Example 15]
A sulfonic acid group-containing polyketone porous membrane was prepared under the same conditions as in Example 13 except that it was immersed in a 5 wt% 2-methacrylamide-2-methylpropanesulfonic acid aqueous solution at 60 ° C. for 3 hours.
The polyketone porous membrane thus obtained has an average pore diameter of 97 nm, a thickness of 106 μm, a porosity of 80%, a gas permeability resistance of 45 seconds / 100 ml, a tensile strength of 3.9 MPa, and an elongation of 20. 1%. The cation exchange capacity was 1.12 meq / g and the zeta potential was -35 mV. The pressure loss was 21.0 kPa / μm after 10 minutes and 22.5 kPa / μm after 240 minutes. The particle transmittance of the anionic polystyrene latex is 100% (particle size: 50 nm), 89% (particle size: 100 nm), 0% (particle size: 200 nm), 0% (particle size: 300 nm), 0% (particle size) : 400 nm), 0% (particle diameter: 500 nm), and 0% (particle diameter: 600 nm). The pressure loss was small, particles of 100 nm and 200 nm could be screened, and the fractionation performance was excellent.
［実施例１６］
実施例２と同じ条件で作製したポリケトンドープをアプリケータを用いて、平均繊維径１６μｍのポリエチレンテレフタレート繊維からなる、目付１４．７ｇ／ｍ２の不織布の片面に塗布した。このポリケトンドープ／不織布複合体を、実施例２と同じ条件で凝固、洗浄、および乾燥して、ポリエステル不織布複合ポリケトン多孔膜を得た。このポリケトン多孔膜の全質量に対するポリケトン質量割合は２０質量％であった。
この複合膜を実施例６と同条件で処理して、スルホン酸基を有するポリエステル不織布複合ポリケトン多孔膜を得た。
このようにして得られたポリケトン多孔膜の平均孔径は９９ｎｍであり、厚みは２０５μｍ、空隙率は７５％、透気抵抗度は４３秒／１００ｍｌ、引張強度は２５．１ＭＰａ、伸度は１８．９％であった。また、陽イオン交換容量は０．２３ミリ当量／ｇ、ゼータ電位は−１６ｍＶであった。圧力損失は、１０分後で２１．１ｋＰａ／μｍ、２４０分後では２０．９Ｐａ／μｍであった。アニオン性ポリスチレンラテックスの粒子透過率は１００％（粒子径：５０ｎｍ）、８８％（粒子径：１００ｎｍ）、０％（粒子径：２００ｎｍ）、０％（粒子径：３００ｎｍ）、０％（粒子径：４００ｎｍ）、０％（粒子径：５００ｎｍ）、０％（粒子径：６００ｎｍ）であった。圧力損失が小さく、１００ｎｍと２００ｎｍの粒子を篩い分けることが可能で、優れた分画性能を持っていた。
[Example 16]
The polyketone dope produced on the same conditions as Example 2 was apply | coated to the single side | surface of the nonwoven fabric of 14.7 g / m < 2 > of fabric weight which consists of a polyethylene terephthalate fiber with an average fiber diameter of 16 micrometers using the applicator. This polyketone dope / nonwoven fabric composite was coagulated, washed and dried under the same conditions as in Example 2 to obtain a polyester nonwoven fabric composite polyketone porous membrane. The polyketone mass ratio with respect to the total mass of the polyketone porous membrane was 20 mass%.
This composite membrane was treated under the same conditions as in Example 6 to obtain a polyester nonwoven fabric composite polyketone porous membrane having sulfonic acid groups.
The polyketone porous membrane thus obtained has an average pore size of 99 nm, a thickness of 205 μm, a porosity of 75%, a gas permeability resistance of 43 seconds / 100 ml, a tensile strength of 25.1 MPa, and an elongation of 18. It was 9%. The cation exchange capacity was 0.23 meq / g, and the zeta potential was −16 mV. The pressure loss was 21.1 kPa / μm after 10 minutes and 20.9 Pa / μm after 240 minutes. The particle transmittance of the anionic polystyrene latex is 100% (particle size: 50 nm), 88% (particle size: 100 nm), 0% (particle size: 200 nm), 0% (particle size: 300 nm), 0% (particle size) : 400 nm), 0% (particle diameter: 500 nm), and 0% (particle diameter: 600 nm). The pressure loss was small, particles of 100 nm and 200 nm could be screened, and the fractionation performance was excellent.
［実施例１７］
エチレンと一酸化炭素が完全交互共重合した極限粘度３．４ｄｌ／ｇのポリケトンを、ポリマー濃度１０．７ｗｔ％で６３ｗｔ％レゾルシン水溶液に添加し、８０℃で２時間攪拌したところ、ポリケトンは溶解して均一透明なドープが得られた。
得られたドープをアプリケータでガラス板に塗布した。これを５０ｗｔ％のメタノール水溶液中に１０分間浸漬して凝固させた後、水で洗浄し、さらに８０℃の温水中に３０分間浸漬した。これを２−プロパノールで溶媒置換した後、枠固定して８０℃で乾燥を行った。
このポリケトン多孔膜を、０．１重量％ポリスチレンスルホン酸（ポリスチレンの分子量：１００万）水溶液に１０分間浸漬させた後、取り出して、１００℃で２分間加熱した。これを１５分間流水で洗浄した後、１００℃で乾燥させた。
このようにして得られたポリケトン多孔膜の平均孔径は９８ｎｍであり、厚みは１０２μｍ、空隙率は８０％、透気抵抗度は４２秒／１００ｍｌ、引張強度は４．１ＭＰａ、伸度は１９．３％であった。また、陽イオン交換容量は０．３０ミリ当量／ｇ、ゼータ電位は−２４ｍＶであった。圧力損失は、１０分後で２０．１ｋＰａ／μｍ、２４０分後では２０．１ｋＰａ／μｍであった。アニオン性ポリスチレンラテックスの粒子透過率は１００％（粒子径：５０ｎｍ）、８８％（粒子径：１００ｎｍ）、０％（粒子径：２００ｎｍ）、０％（粒子径：３００ｎｍ）、０％（粒子径：４００ｎｍ）、０％（粒子径：５００ｎｍ）、０％（粒子径：６００ｎｍ）であった。圧力損失が小さく、１００ｎｍと２００ｎｍの粒子を篩い分けることが可能で、優れた分画性能を持っていた。
[Example 17]
When a polyketone having an intrinsic viscosity of 3.4 dl / g in which ethylene and carbon monoxide are completely alternately copolymerized is added to a 63 wt% resorcin solution at a polymer concentration of 10.7 wt% and stirred at 80 ° C for 2 hours, the polyketone dissolves. And a uniform transparent dope was obtained.
The obtained dope was applied to a glass plate with an applicator. This was immersed in a 50 wt% aqueous methanol solution for 10 minutes to solidify, washed with water, and further immersed in warm water at 80 ° C. for 30 minutes. This was subjected to solvent substitution with 2-propanol, fixed in a frame, and dried at 80 ° C.
This polyketone porous membrane was immersed in a 0.1 wt% polystyrene sulfonic acid (polystyrene molecular weight: 1,000,000) aqueous solution for 10 minutes, then taken out and heated at 100 ° C. for 2 minutes. This was washed with running water for 15 minutes and then dried at 100 ° C.
The polyketone porous membrane thus obtained has an average pore diameter of 98 nm, a thickness of 102 μm, a porosity of 80%, a gas permeability resistance of 42 seconds / 100 ml, a tensile strength of 4.1 MPa, and an elongation of 19. 3%. The cation exchange capacity was 0.30 meq / g and the zeta potential was −24 mV. The pressure loss was 20.1 kPa / μm after 10 minutes and 20.1 kPa / μm after 240 minutes. The particle transmittance of the anionic polystyrene latex is 100% (particle size: 50 nm), 88% (particle size: 100 nm), 0% (particle size: 200 nm), 0% (particle size: 300 nm), 0% (particle size) : 400 nm), 0% (particle diameter: 500 nm), and 0% (particle diameter: 600 nm). The pressure loss was small, particles of 100 nm and 200 nm could be screened, and the fractionation performance was excellent.
［比較例１］（実施例２と同じ：反応させていないだけ）
エチレンと一酸化炭素が完全交互共重合した極限粘度３．４ｄｌ／ｇのポリケトンを、ポリマー濃度１０．７ｗｔ％で６３ｗｔ％レゾルシン水溶液に添加し、８０℃で２時間攪拌したところ、ポリケトンは溶解して均一透明なドープが得られた。
得られたドープをアプリケータでガラス板に塗布した。これを５０ｗｔ％のメタノール水溶液中に１０分間浸漬して凝固させた後、水で洗浄し、さらに８０℃の温水中に３０分間浸漬した。これを２−プロパノールで溶媒置換した後、枠固定して８０℃で乾燥を行った。
このようにして得られたポリケトン多孔膜の平均孔径は１００ｎｍであり、厚みは１００μｍ、空隙率は８０％、透気抵抗度は３８秒／１００ｍｌ、引張強度は３．６ＭＰａ、伸度は１８．８％であった。また、陽イオン交換容量は０．００ミリ当量／ｇ、ゼータ電位は−５ｍＶであった。圧力損失は、１０分後で１９．９ｋＰａ／μｍ、２４０分後では２０．１ｋＰａ／μｍであった。アニオン性ポリスチレンラテックスの粒子透過率は５０％（粒子径：５０ｎｍ）、２１％（粒子径：１００ｎｍ）、０％（粒子径：２００ｎｍ）、０％（粒子径：３００ｎｍ）、０％（粒子径：４００ｎｍ）、０％（粒子径：５００ｎｍ）、０％（粒子径：６００ｎｍ）であった。孔径より小さな粒子に対しても吸着が起こり、収率が低下し、分画精度も悪かった。
[Comparative Example 1] (Same as in Example 2: not reacted)
When a polyketone having an intrinsic viscosity of 3.4 dl / g in which ethylene and carbon monoxide are completely alternately copolymerized is added to a 63 wt% resorcin solution at a polymer concentration of 10.7 wt% and stirred at 80 ° C for 2 hours, the polyketone dissolves. And a uniform transparent dope was obtained.
The obtained dope was applied to a glass plate with an applicator. This was immersed in a 50 wt% aqueous methanol solution for 10 minutes to solidify, washed with water, and further immersed in warm water at 80 ° C. for 30 minutes. This was subjected to solvent substitution with 2-propanol, fixed in a frame, and dried at 80 ° C.
The thus obtained polyketone porous membrane has an average pore diameter of 100 nm, a thickness of 100 μm, a porosity of 80%, a gas permeability resistance of 38 seconds / 100 ml, a tensile strength of 3.6 MPa, and an elongation of 18. It was 8%. The cation exchange capacity was 0.00 meq / g and the zeta potential was −5 mV. The pressure loss was 19.9 kPa / μm after 10 minutes and 20.1 kPa / μm after 240 minutes. The particle transmittance of the anionic polystyrene latex is 50% (particle size: 50 nm), 21% (particle size: 100 nm), 0% (particle size: 200 nm), 0% (particle size: 300 nm), 0% (particle size) : 400 nm), 0% (particle diameter: 500 nm), and 0% (particle diameter: 600 nm). Adsorption also occurred on particles smaller than the pore size, yield decreased, and fractionation accuracy was poor.
［比較例２］
浸漬時間を５分にした以外は、実施例２と同じ条件でスルホン酸基含有ポリケトン多孔膜を作製した。
このようにして得られたポリケトン多孔膜の平均孔径は１０２ｎｍであり、厚みは９８μｍ、空隙率は８０％、透気抵抗度は３９秒／１００ｍｌ、引張強度は３．６ＭＰａ、伸度は１８．２％であった。また、陽イオン交換容量は０．００５ミリ当量／ｇ、ゼータ電位は−６ｍＶであった。圧力損失は、１０分後で２０．０ｋＰａ／μｍ、２４０分後では２０．１ｋＰａ／μｍであった。アニオン性ポリスチレンラテックスの粒子透過率は７０％（粒子径：５０ｎｍ）、４５％（粒子径：１００ｎｍ）、０％（粒子径：２００ｎｍ）、０％（粒子径：３００ｎｍ）、０％（粒子径：４００ｎｍ）、０％（粒子径：５００ｎｍ）、０％（粒子径：６００ｎｍ）であった。孔径より小さな粒子に対しても吸着が起こり、収率が低下し、分画精度も悪かった。
[Comparative Example 2]
A sulfonic acid group-containing polyketone porous membrane was produced under the same conditions as in Example 2 except that the immersion time was 5 minutes.
The average pore diameter of the polyketone porous membrane thus obtained was 102 nm, the thickness was 98 μm, the porosity was 80%, the air permeability resistance was 39 seconds / 100 ml, the tensile strength was 3.6 MPa, and the elongation was 18. 2%. The cation exchange capacity was 0.005 meq / g, and the zeta potential was −6 mV. The pressure loss was 20.0 kPa / μm after 10 minutes and 20.1 kPa / μm after 240 minutes. The particle transmittance of the anionic polystyrene latex is 70% (particle size: 50 nm), 45% (particle size: 100 nm), 0% (particle size: 200 nm), 0% (particle size: 300 nm), 0% (particle size) : 400 nm), 0% (particle diameter: 500 nm), and 0% (particle diameter: 600 nm). Adsorption also occurred on particles smaller than the pore size, yield decreased, and fractionation accuracy was poor.
［比較例３］
浸漬時間を１２０分にした以外は、実施例９と同じ条件でポリケトン多孔膜を作製した。
このようにして得られたポリケトン多孔膜の平均孔径は１０２ｎｍであり、厚みは１０２μｍ、空隙率は８０％、透気抵抗度は４０秒／１００ｍｌ、引張強度は２．９ＭＰａ、伸度は３．１％であった。また、陽イオン交換容量は１０．８ミリ当量／ｇ、ゼータ電位は−８３ｍＶであった。圧力損失及びアニオン性ポリスチレンラテックスの粒子捕捉率は、測定中に破膜が生じたため、評価不可能であった。
[Comparative Example 3]
A polyketone porous membrane was produced under the same conditions as in Example 9 except that the immersion time was 120 minutes.
The average pore diameter of the polyketone porous membrane thus obtained was 102 nm, the thickness was 102 μm, the porosity was 80%, the air permeability resistance was 40 seconds / 100 ml, the tensile strength was 2.9 MPa, and the elongation was 3. 1%. The cation exchange capacity was 10.8 meq / g and the zeta potential was -83 mV. The pressure loss and the particle capture rate of the anionic polystyrene latex could not be evaluated because a film breakage occurred during the measurement.
［比較例４］
１０重量％Ｎ，Ｎ−ジメチルアミノ−１，３−プロパンジアミンを用いた以外は、実施例２と同じ条件でスルホン酸基含有ポリケトン多孔膜を作製した。
このようにして得られたポリケトン多孔膜の平均孔径は９８ｎｍであり、厚みは１０２μｍ、空隙率は８０％、透気抵抗度は４０秒／１００ｍｌ、引張強度は３．６ＭＰａ、伸度は１７．３％であった。また、陽イオン交換容量は０．００ミリ当量／ｇ、ゼータ電位＋１５ｍＶであった。圧力損失は、１０分後で２０．１ｋＰａ／μｍ、２４０分後では２０．１ｋＰａ／μｍであった。アニオン性ポリスチレンラテックスの粒子透過率は０％（粒子径：５０ｎｍ）、０％（粒子径：１００ｎｍ）、０％（粒子径：２００ｎｍ）、０％（粒子径：３００ｎｍ）、０％（粒子径：４００ｎｍ）、０％（粒子径：５００ｎｍ）、０％（粒子径：６００ｎｍ）であった。孔径より小さな粒子を完全に吸着してしまい、全く分画できなかった。
[Comparative Example 4]
A sulfonic acid group-containing polyketone porous membrane was produced under the same conditions as in Example 2 except that 10 wt% N, N-dimethylamino-1,3-propanediamine was used.
The thus obtained polyketone porous membrane has an average pore diameter of 98 nm, a thickness of 102 μm, a porosity of 80%, a gas permeability resistance of 40 seconds / 100 ml, a tensile strength of 3.6 MPa, and an elongation of 17. 3%. The cation exchange capacity was 0.00 meq / g, zeta potential +15 mV. The pressure loss was 20.1 kPa / μm after 10 minutes and 20.1 kPa / μm after 240 minutes. The particle transmittance of the anionic polystyrene latex is 0% (particle size: 50 nm), 0% (particle size: 100 nm), 0% (particle size: 200 nm), 0% (particle size: 300 nm), 0% (particle size) : 400 nm), 0% (particle diameter: 500 nm), and 0% (particle diameter: 600 nm). Particles smaller than the pore size were completely adsorbed and could not be fractionated at all.
本発明のポリケトン多孔膜は、ポリケトン由来の高い耐熱性と耐薬品性を有し、かつ、負のゼータ電位を有するために、アニオン性の粒子に対して優れたファウリング効果を発揮し、高精度の分画が可能なフィルター濾材として有用である。また、カチオン性微粒子やゲル及びカチオンに対して優れた吸着性能をもつため、吸着用のフィルター濾材としても有用である。該フィルター濾材は、高粘度スラリー分画用、水処理用、メンブレンバイオリアクタ用、工業用液体濾過用、脱気用、気体除塵用、ケミカルフィルター用、及び医療用のろ過フィルターとして好適に利用可能である。 Since the polyketone porous membrane of the present invention has high heat resistance and chemical resistance derived from polyketone and has a negative zeta potential, it exhibits an excellent fouling effect on anionic particles, It is useful as a filter medium capable of accurate fractionation. Furthermore, since having excellent adsorption performance for the cationic fine particles or gel and cations are also useful as a filter medium for adsorption. The filter media can be suitably used as high-viscosity slurry fractionation, water treatment, membrane bioreactor, industrial liquid filtration, degassing, gas dust removal, chemical filter, and medical filtration filters. It is.
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