JP2012040526A - Filter for liquid filtration, and liquid filtration method - Google Patents
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- Filtering Materials (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Filtration Of Liquid (AREA)
- Artificial Filaments (AREA)
- Woven Fabrics (AREA)
Abstract
Description
本発明は、液体濾過用のフィルタと、このフィルタを用いた液体濾過方法に関するものであり、さらに詳しくは、半導体製造工程における薬品の高純度化や超純水中の不純物除去に好適に用いられる液体濾過用フィルタ及び液体濾過方法に関する。 The present invention relates to a filter for liquid filtration and a liquid filtration method using the filter. More specifically, the present invention is suitably used for improving the purity of chemicals in semiconductor manufacturing processes and removing impurities in ultrapure water. The present invention relates to a filter for liquid filtration and a liquid filtration method.
Ｉ． 水や薬液などの液体の濾過に用いられるフィルタとして、筒状の有孔芯材の外周に不織布を巻回したものが広く用いられている（例えば下記特許文献１，２）。
I. As a filter used for filtration of liquids such as water and chemicals, those obtained by winding a nonwoven fabric around the outer periphery of a cylindrical perforated core material are widely used (for example,
また、濾過面積を大きくすると共に、濾過層の厚みを大きくしたものとして、プリーツ型フィルタが知られている（例えば特許文献２）。しかしながら、このプリーツ型フィルタは、プリーツの折り込み部分に流れが偏り易く、十分な除去率が得られないことがある。即ち、このプリーツの折り込み部分では、水などの被処理流体は不織布の厚み方向に透過することになり、吸着層が薄い。また、この折り込み部分に流れが集中することにより、この折り込み部分では早期に破過してしまう。 In addition, a pleated filter is known as an example in which the filtration area is increased and the thickness of the filtration layer is increased (eg, Patent Document 2). However, in this pleated filter, the flow tends to be biased at the fold-in portion of the pleat, and a sufficient removal rate may not be obtained. That is, in the folded portion of the pleat, the fluid to be treated such as water is transmitted in the thickness direction of the nonwoven fabric, and the adsorption layer is thin. Further, when the flow concentrates on the folded portion, the folded portion breaks out early.
II． 一般に、繊維によって形成されたフィルタは、使用する繊維の太さにより、孔径及び単位体積当たりの表面積が決定する。細い繊維を使用すると、フィルタの孔径は小さくなり、液体を透過させたり、接触させる際の除粒子、除濁、除コロイド性能が高くなる。また、単位体積当たりの表面積（比表面積）も大きくなるため、イオン交換基といった官能基を付与する際の付与可能な量を多くすることができ、液体中の不純物濃度が低濃度であっても接触効率が高いため、濾過性能が高くなる。そこで、フィルタ用の繊維として、相当直径がナノオーダー（１〜１０００ｎｍ）である繊維（ナノファイバー）が用いられるようになってきた。しかしながら、ナノファイバー製のフィルタは、透過抵抗や拡散抵抗が大きい。 II. In general, in a filter formed of fibers, the pore diameter and the surface area per unit volume are determined by the thickness of the fibers used. When fine fibers are used, the pore size of the filter is reduced, and the performance of removing particles, removing turbidity, and removing colloids when a liquid is allowed to permeate or contact is increased. In addition, since the surface area per unit volume (specific surface area) also increases, the amount that can be imparted when functional groups such as ion exchange groups are imparted can be increased, and even if the impurity concentration in the liquid is low Since the contact efficiency is high, the filtration performance is high. Accordingly, fibers (nanofibers) having an equivalent diameter in the order of nanometers (1 to 1000 nm) have been used as filter fibers. However, a nanofiber filter has high transmission resistance and diffusion resistance.
なお、ナノファイバーの製造方法として電界紡糸法（静電紡糸法）が公知である（下記特許文献３，４等）。この電界紡糸法では、ノズルとターゲットとの間に電界を形成しておき、該ノズルから液状原料を細繊維状に吐出させて紡糸が行われる。細繊維は、ターゲット上に集積されて繊維体となる。 An electrospinning method (electrostatic spinning method) is known as a method for producing nanofibers (Patent Documents 3 and 4 below). In this electrospinning method, an electric field is formed between a nozzle and a target, and spinning is performed by discharging a liquid raw material from the nozzle in the form of fine fibers. The fine fibers are accumulated on the target to form a fibrous body.
また、ナノファイバーの他の製造方法としては海島溶融紡糸法が公知である（特開２００４−１６９２６１）。海島溶融紡糸法とは、海成分内部に、海成分とは化学構造を異にするポリマー又は無機物質で島成分としての多角形断面繊維を複数形成して紡糸した後、あるいは無撚糸、撚糸、合糸、編織布、不織布、植毛品、起毛品等の繊維製品を製造した後、最終的に海成分のみを溶剤処理、アルカリ処理、高温処理、熱水処理や高圧流体処理、ブラシング、擦過等、島成分は耐性を有する化学的、物理的処理により除去することによって、多角形断面繊維を露出させるものである。 As another method for producing nanofibers, the sea-island melt spinning method is known (Japanese Patent Laid-Open No. 2004-169261). The sea-island melt spinning method is a method in which a plurality of polygonal cross-section fibers as island components are formed and spun in a sea component, a polymer or an inorganic substance having a chemical structure different from that of the sea component, or untwisted yarn, twisted yarn, After manufacturing fiber products such as synthetic yarn, knitted fabric, non-woven fabric, flocked product, raised product, etc., finally only sea components are treated with solvents, alkali treatment, high temperature treatment, hot water treatment, high pressure fluid treatment, brushing, rubbing, etc. The island component is removed by a chemical or physical treatment having resistance, thereby exposing the polygonal cross-section fiber.
III． また、一般に、フィルタの吸着層が薄いと、吸着平衡の関係から破過寿命（除去しきれずにリークを始めるまでの時間）が短くなる。そこで吸着層を厚くするために、上述のようにプリーツ型フィルタが用いられてきたが、プリーツの折り込み部分に流れが偏り易く、十分な破過寿命が得られないという問題があった。即ち、ひだの伸びる方向（吸着層が厚い）に濾過せず、不織布面に直角な方向（吸着層が薄い）方向に濾過してしまう。 III. In general, if the adsorption layer of the filter is thin, the breakthrough life (time until leakage starts without being completely removed) is shortened due to adsorption equilibrium. Therefore, in order to increase the thickness of the adsorption layer, a pleated filter has been used as described above. However, there is a problem in that the flow tends to be biased in the folded portion of the pleat and a sufficient breakthrough life cannot be obtained. That is, it does not filter in the direction in which the folds extend (the adsorption layer is thick), but filters in the direction perpendicular to the nonwoven fabric surface (the adsorption layer is thin).
IV． 以上のことを踏まえ、高い濾過性能を達成するためにナノファイバーを用い、また長い破過寿命を達成するためにプリーツ型に替えてロール型を用いて構造上の問題を解消すると共に濾過層を厚くすることが考えられる。 IV. Based on the above, nanofiber is used to achieve high filtration performance, and roll type is used instead of pleat type to achieve a long breakthrough life and the structural problem is solved. It is possible to increase the thickness.
しかし、ロール型ではフィルタのショートパスは発生しないものの、圧力損失が大きくなってしまい、特にナノファイバーを用いる場合は圧力損失が過大となり実用的ではない。 However, in the roll type, although a short path of the filter does not occur, the pressure loss becomes large. In particular, when nanofibers are used, the pressure loss becomes excessive and is not practical.
ロール型を使用するためにフィルタ前段にブースターポンプを設置して加圧することが考えられるが、ブースターポンプから排出される不純物がフィルタの負荷となってしまうという新たな問題が生じるため好ましくない。 In order to use a roll type, it is conceivable to install a booster pump in front of the filter and pressurize it, but this is not preferable because impurities discharged from the booster pump become a load on the filter.
また、圧力損失を下げるべくフィルタ内のナノファイバーの繊維密度を下げることが考えられるが、繊維密度を下げると機械的強度が保てないため、製造困難となり、実用的ではない。 Further, it is conceivable to reduce the fiber density of the nanofibers in the filter in order to reduce the pressure loss. However, if the fiber density is lowered, the mechanical strength cannot be maintained, which makes it difficult to manufacture and is not practical.
このように従来技術では、高い濾過性能と長い破過寿命と低い濾過抵抗を有した高性能の液体濾過用フィルタは存在しなかった。 Thus, in the prior art, there has been no high-performance liquid filtration filter having high filtration performance, long breakthrough life, and low filtration resistance.
本発明は、高い濾過性能と長い破過寿命と低い圧力損失とを併せ持つ液体濾過用フィルタと、このフィルタを用いた液体濾過方法とを提供することを目的とする。 An object of the present invention is to provide a filter for liquid filtration having both high filtration performance, a long breakthrough life, and low pressure loss, and a liquid filtration method using the filter.
請求項１の液体濾過用フィルタは、筒状の有孔芯材の外周に織編物を巻回した液体濾過用フィルタであって、該織編物は、相当直径１〜１０００ｎｍの複数本の単繊維を集束した繊維束を織編成したものであり、該単繊維にアニオン交換基、カチオン交換基、及びキレート基からなる群から選ばれる少なくとも１種の官能基が付与されていることを特徴とするものである。 The filter for liquid filtration according to claim 1 is a filter for liquid filtration in which a woven or knitted fabric is wound around an outer periphery of a cylindrical perforated core material, and the woven or knitted fabric focuses a plurality of single fibers having an equivalent diameter of 1 to 1000 nm. The fiber bundle is woven and knitted, and the single fiber is provided with at least one functional group selected from the group consisting of an anion exchange group, a cation exchange group, and a chelate group. is there.
請求項２の液体濾過用フィルタは、請求項１において、前記織編物が織物であることを特徴とするものである。 According to a second aspect of the present invention, the liquid filtration filter according to the first aspect is characterized in that the woven or knitted fabric is a woven fabric.
請求項３の液体濾過用フィルタは、請求項１又は２において、前記織編物は、少なくとも１種の異なる官能基が付与されている２種以上の単繊維を集束した繊維束を織編成したものであることを特徴とするものである。 A filter for liquid filtration according to a third aspect is the filter according to the first or second aspect, wherein the woven or knitted fabric is a woven / knitted fiber bundle in which two or more types of single fibers to which at least one different functional group is added are bundled. It is characterized by being.
請求項４の液体濾過用フィルタは、請求項１ないし３のいずれか１項において、単繊維は、官能基を有するモノマーを共重合させたポリマーよりなることを特徴とするものである。 A filter for liquid filtration according to a fourth aspect is characterized in that, in any one of the first to third aspects, the single fiber is made of a polymer obtained by copolymerizing a monomer having a functional group.
請求項５の液体濾過用フィルタは、請求項１ないし４のいずれか１項において、織編物の官能基容量が０．１〜３ｍｍｏｌ／ｇである。 The filter for liquid filtration according to claim 5 is the filter according to any one of claims 1 to 4, wherein the functional group capacity of the woven or knitted fabric is 0.1 to 3 mmol / g.
請求項６の液体濾過用フィルタは、請求項１ないし５のいずれか１項において、織編物の示差走査熱量の溶融ピーク温度が１７０〜２５０℃であることを特徴とするものである。 The filter for liquid filtration according to a sixth aspect is characterized in that, in any one of the first to fifth aspects, the melting peak temperature of the differential scanning calorific value of the woven or knitted fabric is 170 to 250 ° C.
請求項７の液体濾過用フィルタは、請求項１ないし６のいずれか１項に記載の液体濾過用フィルタによって液体を濾過することを特徴とするものである。 A liquid filtration filter according to a seventh aspect is characterized in that the liquid is filtered by the liquid filtration filter according to any one of the first to sixth aspects.
請求項８の液体濾過用フィルタは、請求項７において、液体は金属イオン濃度：０．５〜５ｎｇ／Ｌ、ＴＯＣ：５ｐｐｂ以上〜５０ｐｐｂ未満、微粒子数：０．１μｍ以上の微粒子が５個／ｍＬ以下の水質の純水であることを特徴とするものである。 The filter for liquid filtration according to claim 8 is the filter for liquid filtration according to claim 7, wherein the liquid has a metal ion concentration: 0.5 to 5 ng / L, TOC: 5 ppb to less than 50 ppb, and number of fine particles: 5 fine particles of 0.1 μm or more / It is characterized by being pure water having a water quality of not more than mL.
本発明の液体濾過用フィルタは、相当直径１〜１０００ｎｍの極細の単繊維を集束して繊維束とし、これを織編成した織編物を有孔芯材に巻回したものであり、この単繊維にアニオン交換基、カチオン交換基又はキレート基を付与したものである。この液体濾過用フィルタは、極細の繊維を用いており、０．１μｍ程度、すなわち１００ｎｍ程度の微粒子を繊維間に捕捉でき、濾過性能に優れる。また、この繊維束を不織布状でなく織編物状に形成しこれをプリーツ型ではなくロール型フィルタとしているので、高い濾過性能と長い破過寿命を維持しつつ空隙率を高くして圧力損失を下げることができ、透過抵抗や拡散抵抗の増加を抑えることができる。 The filter for liquid filtration of the present invention is obtained by concentrating ultrafine single fibers having an equivalent diameter of 1 to 1000 nm into a fiber bundle, and winding a woven or knitted fabric obtained by weaving this on a perforated core material. An exchange group, a cation exchange group or a chelate group is added. This filter for liquid filtration uses ultrafine fibers, can capture fine particles of about 0.1 μm, that is, about 100 nm between the fibers, and is excellent in filtration performance. In addition, this fiber bundle is formed in a woven or knitted shape instead of a non-woven shape, and this is not a pleat type but a roll type filter, so that the pressure loss is increased by increasing the porosity while maintaining high filtration performance and a long breakthrough life. The increase in transmission resistance and diffusion resistance can be suppressed.
単繊維に、アニオン交換基、カチオン交換基又はキレート基を付与することにより、イオン交換作用又はイオン捕捉作用が奏され、透過水のイオン濃度を低下させることができ、純水や超純水の製造に用いるのに好適なものとなる。本発明のフィルタは、特に半導体製造工程における薬品の高純度化や超純水中の不純物除去に用いるのに好適である。 By adding an anion exchange group, a cation exchange group or a chelate group to a single fiber, an ion exchange action or an ion trapping action can be achieved, and the ion concentration of permeated water can be lowered. It is suitable for use in manufacturing. The filter of the present invention is particularly suitable for use in increasing the purity of chemicals in semiconductor manufacturing processes and removing impurities in ultrapure water.
溶融紡糸法では、高熱によりポリマーを溶解し、紡糸、冷却を行うため、繊維の結晶性が高くなる傾向がある。特に、海島溶融紡糸法では、海成分内部に、海成分とは化学構造を異にするポリマーで島成分としての多角形断面繊維を複数形成して紡糸した後、海成分を除去するため、島成分は海成分を除去する工程に対して耐性を有する。即ち、結晶性が高く、物理的、化学的強度が高い織編物が得られる傾向がある。 In the melt spinning method, the polymer is melted by high heat, and spinning and cooling are performed, so that the fiber crystallinity tends to be high. In particular, in the sea-island melt spinning method, a plurality of polygonal cross-section fibers as island components are formed and spun inside a sea component with a polymer having a chemical structure different from that of the sea component. The component is resistant to the process of removing sea components. That is, a woven or knitted fabric having high crystallinity and high physical and chemical strength tends to be obtained.
発明者らが鋭意検討した結果、織編物の結晶性が高すぎると繊維の内部に水が浸透し難くなり、繊維が有する官能基が有効に活用されないという課題があることが分かった。そして繊維が有する官能基を有効に活用するためには、示差走査熱量（ＤＳＣ）の溶融ピーク温度（融点）が２５０℃以下、さらには、２２０℃以下であることが好ましいことを見出した。 As a result of intensive studies by the inventors, it has been found that if the crystallinity of the woven or knitted fabric is too high, it is difficult for water to penetrate into the inside of the fiber and the functional group of the fiber is not effectively utilized. And in order to utilize the functional group which a fiber has effectively, it discovered that the melting peak temperature (melting | fusing point) of differential scanning calorie | heat amount (DSC) was 250 degrees C or less, Furthermore, it is preferable that it is 220 degrees C or less.
その一方で、示差走査熱量（ＤＳＣ）の溶融ピーク温度（融点）が低すぎると、ポリエステルの融点の関係で繊維の強度が低くなり、素材の耐久性が低くなる懸念がある。さらにＴＯＣの溶出量が若干増加するのでその点でも問題がある。そのため示差走査熱量の溶融ピーク温度には好ましい下限値が存在し、１７０℃以上であることが好ましい。 On the other hand, if the melting peak temperature (melting point) of the differential scanning calorific value (DSC) is too low, there is a concern that the strength of the fiber is lowered due to the melting point of the polyester and the durability of the material is lowered. Furthermore, since the TOC elution amount slightly increases, there is a problem in that respect. Therefore, a preferable lower limit exists in the melting peak temperature of the differential scanning calorific value, and it is preferably 170 ° C. or higher.
以下、図面を参照して実施の形態について説明する。 Hereinafter, embodiments will be described with reference to the drawings.
第１図は実施の形態に係る液体濾過用フィルタ１の概略的な内部透視斜視図である。 FIG. 1 is a schematic internal perspective view of a filter 1 for liquid filtration according to an embodiment.
第１図の通り、この液体濾過用フィルタ１は、筒状有孔芯材２の外周囲に織布３を巻回したものである。この織布３は、相当直径１〜１０００ｎｍの複数本の単繊維を集束した繊維束を紡織したものである。
As shown in FIG. 1, the filter 1 for liquid filtration is obtained by winding a woven fabric 3 around the outer periphery of a cylindrical
以下、まず、この織布３を構成する単繊維及び繊維束について詳細に説明する。 Hereinafter, first, the single fiber and the fiber bundle constituting the woven fabric 3 will be described in detail.
本発明で用いる単繊維は、相当直径が１〜１０００ｎｍ好ましくは５０〜８００ｎｍの範囲内にある繊維である。「相当直径」とは、１本の繊維（ファイバ）の断面積と断面の外周長さとから、（相当直径）＝４×（断面積）／（断面の外周長さ）によって算出される値である。 The single fiber used in the present invention is a fiber having an equivalent diameter in the range of 1 to 1000 nm, preferably 50 to 800 nm. The “equivalent diameter” is a value calculated from (the equivalent diameter) = 4 × (cross-sectional area) / (the outer peripheral length of the cross section) from the cross-sectional area of one fiber (fiber) and the outer peripheral length of the cross-section. is there.
この単繊維は、形態的には、いわゆる繊維状の形態であればよく、単繊維がバラバラに分散したもの、単繊維が部分的に結合しているもの、複数の単繊維が凝集した集合体などのいずれの形態のものであってもよい。 This single fiber may be in the form of a so-called fibrous form. The single fiber is dispersed in pieces, the single fibers are partially bonded, or an aggregate in which a plurality of single fibers are aggregated. Or any other form.
単繊維の長さには特に制限はないが、繊維束を形成するためには、長さは１０ｍｍ以上特に１００ｍｍ以上であることが好ましい。この単繊維は、溶融紡糸や電界紡糸によって製造することができる。なお、溶融紡糸で作製した場合、連続的に紡糸することもできるため、１０００ｍｍ以上に長くすることができる。 Although there is no restriction | limiting in particular in the length of a single fiber, In order to form a fiber bundle, it is preferable that length is 10 mm or more, especially 100 mm or more. This single fiber can be produced by melt spinning or electrospinning. In addition, since it can also spin continuously when producing by melt spinning, it can be lengthened to 1000 mm or more.
単繊維の断面形状は、円形、角形、スター形などのいずれであってもよい。 The cross-sectional shape of the single fiber may be any of a circular shape, a square shape, a star shape, and the like.
単繊維の材料としては、ポリエチレン、ポリプロピレン等のポリオレフィン、ポリエチレンテレフタレート、ポリカーボネート等のポリエステル、ポリアミド、芳香族ポリアミド、アクリル、ポリアクリロニトリル、ポリ塩化ビニル、ＰＴＦＥ、ポリフッ化ビニリデン等のハロゲン化ポリオレフィンなどを用いることができるが、特にポリアクリルニトリル、ポリエステルが好ましい。ポリエステルとしては、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレンナフタレート（ＰＥＮ）、その誘導体などが挙げられる。なお、繊維は無機繊維であってもよい。 Single fiber materials include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polycarbonate, polyamides, aromatic polyamides, halogenated polyolefins such as acrylic, polyacrylonitrile, polyvinyl chloride, PTFE, and polyvinylidene fluoride. However, polyacrylonitrile and polyester are particularly preferable. Examples of the polyester include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and derivatives thereof. The fiber may be an inorganic fiber.
単繊維には、アニオン交換基、カチオン交換基及びキレート基の少なくとも１種の官能基を付与する。このような官能基を付与することにより、フィルタの金属不純物捕捉（吸着）能を向上させることができる。 A single fiber is provided with at least one functional group of an anion exchange group, a cation exchange group and a chelate group. By adding such a functional group, the metal impurity capturing (adsorption) ability of the filter can be improved.
カチオン交換基としては、スルホン酸基などの強酸性カチオン交換基、リン酸基、カルボキシル基などの弱酸性カチオン交換基が挙げられる。アニオン交換基としては、４級アンモニウム基などの強塩基性アニオン交換基、１級、２級又は３級アミノ基などの弱塩基性アニオン交換基を挙げることができる。また、キレート基としては、イミノジ酢酸及びそのナトリウム塩から誘導される官能基、各種アミノ酸基、例えばグルタミン酸、アスパラギン酸、リジン及びプロリンなどから誘導される官能基、イミノジエタノールから誘導される官能基、ジチオカルバミン酸基、チオ尿素基などを挙げることができる。 Examples of the cation exchange group include strongly acidic cation exchange groups such as sulfonic acid groups, and weak acid cation exchange groups such as phosphate groups and carboxyl groups. Examples of the anion exchange group include strong basic anion exchange groups such as quaternary ammonium groups, and weak basic anion exchange groups such as primary, secondary, and tertiary amino groups. In addition, as the chelating group, a functional group derived from iminodiacetic acid and its sodium salt, various amino acid groups such as a functional group derived from glutamic acid, aspartic acid, lysine and proline, a functional group derived from iminodiethanol, Examples thereof include a dithiocarbamic acid group and a thiourea group.
単繊維にこのような官能基を付与するには、上記の単繊維材料を合成するためのモノマーと、上記官能基を有するモノマー（重合性単量体）とを共重合させるのが好ましいが、グラフト重合法たとえばプラズマグラフト重合法や放射線グラフト重合法を用いてもよい。 In order to impart such a functional group to a single fiber, it is preferable to copolymerize a monomer for synthesizing the single fiber material and a monomer having a functional group (polymerizable monomer), A graft polymerization method such as a plasma graft polymerization method or a radiation graft polymerization method may be used.
イオン交換基を有する重合性単量体としては、例えば、スルホン酸基を有する重合性単量体として、スチレンスルホン酸、ビニルスルホン酸及びこれらのナトリウム塩、アンモニウム塩等；カルボキシル基を有する重合性単量体として、アクリル酸、メタクリル酸等；アミン系イオン交換基を有する重合性単量体として、ビニルベンジルトリメチルアンモニウムクロライド（ＶＢＴＡＣ）、ジメチルアミノエチルメタクリレート（ＤＭＡＥＭＡ）、ジエチルアミノエチルメタクリレート（ＤＥＡＥＭＡ）、ジメチルアミノプロピルアクリルアミド（ＤＭＡＰＡＡ）等；を挙げることができる。また、それ自体はイオン交換基及び／又はキレート基を有していないが、イオン交換基及び／又はキレート基に変換可能な官能基を有する重合性単量体としては、メタクリル酸グリシジル、スチレン、アクリロニトリル、アクロレイン、クロロメチルスチレンなどを挙げることができる。 As the polymerizable monomer having an ion exchange group, for example, as a polymerizable monomer having a sulfonic acid group, styrene sulfonic acid, vinyl sulfonic acid and their sodium salts, ammonium salts, etc .; As monomers, acrylic acid, methacrylic acid, etc .; as polymerizable monomers having an amine ion exchange group, vinylbenzyltrimethylammonium chloride (VBTAC), dimethylaminoethyl methacrylate (DMAEMA), diethylaminoethyl methacrylate (DEAEMA), Dimethylaminopropylacrylamide (DMAPAA) and the like. Further, as a polymerizable monomer having a functional group that does not have an ion exchange group and / or a chelate group per se but can be converted into an ion exchange group and / or a chelate group, glycidyl methacrylate, styrene, Examples include acrylonitrile, acrolein, and chloromethylstyrene.
イオン交換基により付与される官能基容量は０．１ｍｍｏｌ／ｇ以上例えば０．１〜３ｍｍｏｌ／ｇが好ましく特に０．６ｍｍｏｌ／ｇ以上とりわけ０．６〜２ｍｍｏｌ／ｇが好ましい。官能基を有するモノマーの割合は１．０ｍｏｌ％以上が好ましく、特に４ｍｏｌ％以上１０ｍｏｌ％以下が好ましい。１０ｍｏｌ％を超える添加量になると、ポリマーの強度が極端に弱くなり繊維化が出来なくなるおそれがある。 The functional group capacity imparted by the ion exchange group is preferably 0.1 mmol / g or more, for example, 0.1 to 3 mmol / g, particularly preferably 0.6 mmol / g or more, particularly preferably 0.6 to 2 mmol / g. The proportion of the monomer having a functional group is preferably 1.0 mol% or more, particularly preferably 4 mol% or more and 10 mol% or less. If the added amount exceeds 10 mol%, the polymer strength becomes extremely weak and fiber formation may not be possible.
この単繊維を集束して強度１．０〜８．０ｃＮ／ｄｔｅｘ程度の繊維束とし、この繊維束を織編成して織編物とする。 The single fibers are converged to form a fiber bundle having a strength of about 1.0 to 8.0 cN / dtex, and the fiber bundle is knitted to form a woven or knitted fabric.
かかる織編物（布帛）は、前記官能基をもつポリエステルフィラメントと、必要に応じてその他の繊維を用いて織編物を織編成した後、必要に応じて、該布帛にアルカリ水溶液処理を施し、海島型複合繊維の海成分をアルカリ水溶液で溶解除去し海島型複合繊維フィラメント糸を単繊維径が１０〜１０００ｎｍの共重合ポリエステルマルチフィラメント糸とすることにより得られる。その際、前記官能基をもつポリエステルフィラメント糸の布帛の全重量に対する重量割合は２０重量％以上（より好ましくは５０重量％以上、特に好ましくは１００重量％）であることが好ましい。 Such a woven or knitted fabric (fabric) is obtained by knitting a woven or knitted fabric using the polyester filament having the functional group and, if necessary, other fibers, and then subjecting the fabric to an alkaline aqueous solution treatment as necessary. It is obtained by dissolving and removing the sea component of the type composite fiber with an alkaline aqueous solution and making the sea-island type composite fiber filament yarn into a copolyester multifilament yarn having a single fiber diameter of 10 to 1000 nm. At that time, the weight ratio of the polyester filament yarn having the functional group to the total weight of the fabric is preferably 20% by weight or more (more preferably 50% by weight or more, particularly preferably 100% by weight).
また、布帛の織編組織は特に限定されないが、布帛を上面又は下面から見て布帛上の単繊維の分布が均一であることが好ましい。織物の織組織は、平織、斜文織、朱子織等の三原組織、変化組織、変化斜文織等の変化組織、たて二重織、よこ二重織等の片二重組織、たてビロード、タオル、ベロア等のたてパイル織、別珍、よこビロード、ベルベット、コール天等のよこパイル織などが例示される。なお、これらの織組織を有する織物は、レピア織機やエアージェット織機など通常の織機を用いて通常の方法により製織することができる。層数も特に限定されず単層でもよいし２層以上の多層構造を有する織物でもよい。 Further, the woven or knitted structure of the fabric is not particularly limited, but it is preferable that the distribution of single fibers on the fabric is uniform when the fabric is viewed from the upper surface or the lower surface. The woven structure of the woven fabric is a three-fold structure such as plain weave, oblique weave, satin weave, etc. Examples include vertical pile weaves such as velvet, towels and velours, and weave pile weaves such as benjin, weft velvet, velvet, and call heaven. In addition, the textile fabric which has these woven structures can be woven by a normal method using normal looms, such as a rapier loom and an air jet loom. The number of layers is not particularly limited and may be a single layer or a woven fabric having a multilayer structure of two or more layers.
編物の種類は、よこ編物であってもよいしたて編物であってもよい。よこ編組織としては、平編、ゴム編、両面編、パール編、タック編、浮き編、片畔編、レース編、添え毛編等が好ましく例示され、たて編組織としては、シングルデンビー編、シングルアトラス編、ダブルコード編、ハーフトリコット編、裏毛編、ジャガード編等が好ましく例示される。なお、製編は、丸編機、横編機、トリコット編機、ラッシェル編機等通常の編機を用いて通常の方法により製編することができる。層数も特に限定されず単層でもよいし２層以上の多層構造を有する編物でもよい。 The type of knitted fabric may be a weft knitted fabric or a newly knitted fabric. Preferred examples of the weft knitting structure include flat knitting, rubber knitting, double-sided knitting, pearl knitting, tuck knitting, float knitting, one-sided knitting, lace knitting, bristle knitting, and the like. Preferred examples include single atlas knitting, double cord knitting, half tricot knitting, back hair knitting, jacquard knitting and the like. The knitting can be knitted by a normal method using a normal knitting machine such as a circular knitting machine, a flat knitting machine, a tricot knitting machine, and a Raschel knitting machine. The number of layers is not particularly limited and may be a single layer or a knitted fabric having a multilayer structure of two or more layers.
なお、異なる官能基が付与されている２種以上の単繊維を集束した繊維束を織編成してもよい。織編物の目付けは１０〜３００ｇ／ｍ２程度が好ましく、また濾過速度１００ｃｃ／ｃｍ２・ｓｅｃ時の差圧が０．５ｋＰａ以下、特に０．１ｋＰａ以下となる目開きを有することが好ましい。 In addition, you may knitted the fiber bundle which bundled 2 or more types of single fiber to which the different functional group was provided. The basis weight of the woven or knitted fabric is preferably about 10 to 300 g / m 2 , and preferably has a mesh opening at which the differential pressure at a filtration rate of 100 cc / cm 2 · sec is 0.5 kPa or less, particularly 0.1 kPa or less.
この織布３を筒状の有孔芯材２の外周に巻回することにより液体濾過用フィルタ１が構成される。有孔芯材としては、多孔質の合成樹脂製のものが好適であるが、緻密質の合成樹脂の筒体に穿孔したものであってもよい。合成樹脂としては、ポリエチレン、ポリプロピレンなどのポリオレフィンや、ＰＴＦＥ、ＰＦＡなどのフッ素樹脂が好適であるが、これに限定されない。
The filter 1 for liquid filtration is comprised by winding this woven fabric 3 around the outer periphery of the cylindrical
有孔芯材の直径（外径）は５〜５０ｍｍ特に２０〜４０ｍｍが好適である。有孔芯材の長さｂは特には限定されないが、通常は８０〜５００ｍｍ程度とされる。 The diameter (outer diameter) of the perforated core material is preferably 5 to 50 mm, particularly 20 to 40 mm. The length b of the perforated core material is not particularly limited, but is usually about 80 to 500 mm.
有孔芯材に巻き付けた織編物層の厚さａは、濾過性能を確保すると共に濾過圧損を抑制するために、５〜５０ｍｍ特に１０〜４０ｍｍ程度が好適である。巻き付けた織編物の末端を溶着、接着などにより、織編物巻回体の外周面に対して固定するのが好ましい。巻き付けた端面については円板形のプレートなどにより封じるのが好ましい。 The thickness a of the woven or knitted layer wound around the perforated core material is preferably about 5 to 50 mm, particularly about 10 to 40 mm in order to ensure filtration performance and suppress filtration pressure loss. It is preferable to fix the end of the wound woven or knitted fabric to the outer peripheral surface of the woven or knitted wound body by welding, adhesion or the like. The wound end face is preferably sealed with a disk-shaped plate or the like.
このように構成された液体濾過用フィルタ１に対しては、被処理液を織編物巻回体の外周面から透過させ、透過液を有孔芯材２内から取り出す。通常の場合、フィルタ１を円筒形のケーシング内に該ケーシングと同軸状に配置する。そして、フィルタ１の外周面から求心方向に被処理液を透過させ、透過液を、有孔芯材２を通して、該ケーシングの一端面側の取出口からケーシング外へ流出させる。なお、被処理液の導入口の位置は、特に限定されないが、該ケーシングの外周面又は該ケーシングの他端面に設けておくのが好ましい。
With respect to the liquid filtration filter 1 configured as described above, the liquid to be treated is permeated from the outer peripheral surface of the woven or knitted wound body, and the permeated liquid is taken out from the
この被処理液としては、水が好適である。特に、この液体濾過用フィルタは、超純水製造工程において純水の濾過に用いるのに好適である。純水の水質としては、金属イオン濃度：０．５〜５ｎｇ／Ｌ、ＴＯＣ：５ｐｐｂ以上〜５０ｐｐｂ未満、微粒子数：０．１μｍ以上の微粒子が５個／ｍＬ以下が好ましい。 As the liquid to be treated, water is suitable. In particular, this filter for liquid filtration is suitable for use in filtering pure water in the ultrapure water production process. The water quality of the pure water is preferably a metal ion concentration: 0.5 to 5 ng / L, TOC: 5 ppb to less than 50 ppb, and fine particle number: 0.1 μm or more, 5 particles / mL or less.
この液体濾過用フィルタ１において、吸着は平衡に従って導入口側から取出口側まで吸着カーブを形成する。この吸着カーブが時間に従って取出口側へ平行に移動して破過が起こるようにするためには、
(1) 吸着の効率を高めて吸着カーブをより取出口から遠い（導入口に近い）位置でカーブが終了するようにする、
(2) 巻き付け厚さａを厚くして吸着カーブが取出口に移動するまでの時間を長く取る、
といったことが有効である。
本発明では、比表面積が大きいので(1)の効果が得られる。また、織編物であり、圧力損失が小さいので、巻き付けの厚みａを厚くすることが出来、(2)の効果を得ることができる。
In this liquid filtration filter 1, the adsorption forms an adsorption curve from the inlet side to the outlet side according to the equilibrium. In order for this adsorption curve to move parallel to the outlet side according to time and breakthrough occurs,
(1) Increase the efficiency of adsorption so that the curve ends at a position farther from the outlet (closer to the inlet).
(2) Increase the winding thickness a and increase the time until the adsorption curve moves to the outlet.
Is effective.
In the present invention, since the specific surface area is large, the effect (1) can be obtained. Moreover, since it is a woven or knitted fabric and the pressure loss is small, the winding thickness a can be increased and the effect (2) can be obtained.
以下、実施例及び比較例について説明する。 Hereinafter, examples and comparative examples will be described.
［実施例１］
まず、次のように溶融紡糸法により織布を製造した。島成分に５−ナトリウムスルホイソフタル酸を共重合した変性ポリブチレンテレフタレート、海成分に島成分よりＮａＯＨ水溶液に対する溶解速度の速いポリマーを用い、海島型複合繊維紡糸口金を用いて紡糸し、得られた吐出糸をさらに延伸し、島成分の直径が１０００ｎｍ以下の複合繊維を得た。この延伸糸を経糸及び緯糸に、全量配し、通常の製織方法により平組織の織布を得た。そして、前記海島型複合延伸糸の海成分を除去するために、ＮａＯＨ水溶液で、アルカリ減量した。このとき示差走査熱量の溶融ピーク温度（融点）は２２０℃であった。
[Example 1]
First, a woven fabric was manufactured by the melt spinning method as follows. A modified polybutylene terephthalate copolymerized with 5-sodiumsulfoisophthalic acid was used for the island component, and a polymer having a faster dissolution rate in the NaOH aqueous solution than the island component was used for the sea component, and spinning was performed using a sea island type composite fiber spinneret. The discharged yarn was further stretched to obtain a composite fiber having an island component diameter of 1000 nm or less. The drawn yarn was all distributed over warps and wefts, and a plain woven fabric was obtained by a normal weaving method. Then, in order to remove the sea component of the sea-island type composite drawn yarn, the alkali was reduced with an aqueous NaOH solution. At this time, the melting peak temperature (melting point) of the differential scanning calorific value was 220 ° C.
得られた織物を走査型電子顕微鏡ＳＥＭで織布表面及び経糸及び緯糸断面を観察したところ、海成分は完全に溶解除去されており、織布の経糸及び緯糸全量が均一性に優れた超極細繊維により構成されていることが確認された。得られた織布において、経糸カバーファクターＣＦｐは１２８９、緯糸カバーファクターＣＦｆは７９１であった。 When the surface of the woven fabric and the cross section of the warp and the weft were observed with a scanning electron microscope SEM, the sea component was completely dissolved and removed, and the total amount of warp and weft of the woven fabric was excellent in uniformity. It was confirmed that it was composed of fibers. In the obtained woven fabric, the warp cover factor CFp was 1289, and the weft cover factor CFf was 791.
外周３６ｍｍ、長さ２２５ｍｍのポリプロピレン製の有孔芯材の外周にこの織布を厚み２０ｍｍになるように巻きつけて液体濾過用フィルタを製作した。このフィルタを１ｗｔ％塩酸でスルホ基を水素化処理し、超純水でリンスした。原子吸光用の標準液を用いて調製したＮａ濃度５ｎｇ／Ｌ、ＴＯＣ濃度０．５μｇ／Ｌ、粒子径０．１μｍ以上の微粒子濃度５個／ｍＬの水をこの液体濾過用フィルタに対し２０Ｌ／ｍｉｎで通水した。１０日間通水後の処理水をＩＣＰ−ＭＳを用いて分析したところ、Ｎａ濃度は０．５ｎｇ／Ｌであり、ＴＯＣは０．６μｇ／Ｌ、粒子径０．１μｍ以上の微粒子は２個／ｍＬ、圧力損失は０．０２ＭＰａであった。 A filter for liquid filtration was produced by winding this woven fabric to a thickness of 20 mm around the outer periphery of a polypropylene perforated core material having an outer periphery of 36 mm and a length of 225 mm. This filter was hydrotreated with 1 wt% hydrochloric acid for sulfo groups and rinsed with ultrapure water. Water having a Na concentration of 5 ng / L, a TOC concentration of 0.5 μg / L, and a fine particle concentration of 5 particles / mL with a particle diameter of 0.1 μm or more, prepared using a standard solution for atomic absorption, was added to the liquid filtration filter at 20 L / L. Water was passed in min. When the treated water after passing for 10 days was analyzed using ICP-MS, the Na concentration was 0.5 ng / L, the TOC was 0.6 μg / L, and the number of fine particles having a particle diameter of 0.1 μm or more was 2 / mL, pressure loss was 0.02 MPa.
［実施例２］
島成分に５−ナトリウムスルホイソフタル酸を共重合した変性ポリエチレンテレフタレートを使用したこと以外は実施例１と同様の条件で織布を製造した。このとき示差走査熱量の溶融ピーク温度（融点）は２４０℃であった。
[Example 2]
A woven fabric was produced under the same conditions as in Example 1 except that a modified polyethylene terephthalate copolymerized with 5-sodium sulfoisophthalic acid was used as the island component. At this time, the melting peak temperature (melting point) of the differential scanning calorific value was 240 ° C.
このようにして得られた布帛を用いたこと以外は実施例１と同様の方法で液体濾過用フィルタを製作し、水素化処理した後、超純水でリンスした。このフィルタを用いたこと以外は実施例１と同様に通水実験を行った。 A liquid filtration filter was produced in the same manner as in Example 1 except that the fabric thus obtained was used, and after hydrogenation treatment, rinsed with ultrapure water. A water flow experiment was conducted in the same manner as in Example 1 except that this filter was used.
［実施例３］
島成分に５−ナトリウムスルホイソフタル酸を共重合した変性ポリエチレンナフタレートを使用したこと以外は、実施例１と同様の条件で織布を製造した。このとき示差走査熱量の溶融ピーク温度（融点）は、２５０℃であった。
[Example 3]
A woven fabric was produced under the same conditions as in Example 1, except that modified polyethylene naphthalate copolymerized with 5-sodium sulfoisophthalic acid was used as the island component. At this time, the melting peak temperature (melting point) of the differential scanning calorific value was 250 ° C.
このようにして得られた布帛を用いたこと以外は実施例１と同様の方法で液体濾過用フィルタを製作し、水素化処理した後、超純水でリンスした。このフィルタを用いたこと以外は実施例１と同様に通水実験を行った。 A liquid filtration filter was produced in the same manner as in Example 1 except that the fabric thus obtained was used, and after hydrogenation treatment, rinsed with ultrapure water. A water flow experiment was conducted in the same manner as in Example 1 except that this filter was used.
［比較例１］
島成分にポリエチレンナフタレートを使用したこと以外は実施例１と同様にして織布を製造した。得られた布帛を用いて、実施例１と同様の方法で液体濾過用フィルタを製作し、実施例１と同様に、水素化処理して超純水でリンスした。実施例１と同様に、原子吸光用の標準液を用いて調製したＮａ濃度１０ｎｇ／Ｌの水をこの液体濾過用フィルタに対し２０Ｌ／ｍｉｎで通水した。１０日間通水後の処理水をＩＣＰ−ＭＳを用いて分析したところ、Ｎａ濃度は５ｎｇ／Ｌ、ＴＯＣ濃度は０．５μｇ／Ｌ、粒子径０．１μｍ以上の微粒子の濃度は２個／ｍＬ、圧力損失は０．０２ＭＰａであり、圧力損失は低いが濾過性能は不十分であった。
[Comparative Example 1]
A woven fabric was produced in the same manner as in Example 1 except that polyethylene naphthalate was used as the island component. Using the obtained fabric, a filter for liquid filtration was produced in the same manner as in Example 1, and was hydrogenated and rinsed with ultrapure water in the same manner as in Example 1. In the same manner as in Example 1, water having an Na concentration of 10 ng / L prepared using a standard solution for atomic absorption was passed through this liquid filtration filter at 20 L / min. The treated water after passing for 10 days was analyzed using ICP-MS. As a result, the Na concentration was 5 ng / L, the TOC concentration was 0.5 μg / L, and the concentration of fine particles having a particle diameter of 0.1 μm or more was 2 / mL. The pressure loss was 0.02 MPa, and the pressure loss was low, but the filtration performance was insufficient.
［比較例２］
ポリエチレンフィルムからなる直径７０ｍｍ、長さ２２５ｍｍの、プリーツ型の市販イオン交換フィルタ（日本ポール（株）製イオンクリーン）に上記と同様のＮａ濃度５ｎｇ／Ｌの水を２０Ｌ／ｍｉｎで通水した。１０日間通水後の処理水をＩＣＰ−ＭＳを用いて分析した。
[Comparative Example 2]
Water having a Na concentration of 5 ng / L was passed through the pleated commercial ion exchange filter (Nippon Pole Co., Ltd., Ion Clean) made of a polyethylene film at a diameter of 70 mm and a length of 225 mm at a rate of 20 L / min. The treated water after passing for 10 days was analyzed using ICP-MS.
その結果、Ｎａ濃度は２ｎｇ／Ｌ、ＴＯＣ濃度は０．５μｇ／Ｌ、粒子径０．１μｍ以上の微粒子は４個／ｍＬ、圧力損失は０．０２ＭＰａであり、圧力損失は低いものの濾過性能は不十分であった。 As a result, the Na concentration was 2 ng / L, the TOC concentration was 0.5 μg / L, the fine particles having a particle diameter of 0.1 μm or more were 4 particles / mL, the pressure loss was 0.02 MPa, and the filtration performance was low although the pressure loss was low. It was insufficient.
実施例１〜３、及び比較例１，２の結果を表に示す。 The results of Examples 1 to 3 and Comparative Examples 1 and 2 are shown in the table.
［考察］
実施例１〜３の液体濾過用フィルタはいずれも比較例１，２と比較して高い濾過性能と低い圧力損失であった。
なお、実施例１〜３の中では、示差走査熱量の溶融ピーク温度が高いものほど、イオン交換能が若干低い（ただし、その反面わずかながらＴＯＣ溶出が抑制されている。）。これは、高い溶融ピーク温度での溶融により高分子の結晶性が高くなっており、高分子内のイオン拡散が起こりづらくなっているためであると推定される。これにより、高いイオン交換能を得るためには、示差走査熱量の溶融ピーク温度が比較的低い溶融条件にすることが好ましいことが認められた。
[Discussion]
The liquid filtration filters of Examples 1 to 3 all had higher filtration performance and lower pressure loss than Comparative Examples 1 and 2.
In Examples 1 to 3, the higher the melting peak temperature of the differential scanning calorific value, the slightly lower the ion exchange capacity (however, the TOC elution is suppressed slightly). This is presumably because the crystallinity of the polymer is increased by melting at a high melting peak temperature, and ion diffusion in the polymer is difficult to occur. Thereby, in order to obtain a high ion exchange capacity, it was recognized that it is preferable to set the melting conditions so that the melting peak temperature of the differential scanning calorific value is relatively low.
１ 液体濾過用フィルタ
２ 有孔芯材
３ 織布
1 Filter for
Claims (8)
該織編物は、相当直径１〜１０００ｎｍの複数本の単繊維を集束した繊維束を織編成したものであり、該単繊維にアニオン交換基、カチオン交換基、及びキレート基からなる群から選ばれる少なくとも１種の官能基が付与されていることを特徴とする液体濾過用フィルタ。 A filter for liquid filtration in which a woven or knitted fabric is wound around the outer periphery of a cylindrical perforated core material,
The woven or knitted fabric is a woven knitted fiber bundle obtained by bundling a plurality of single fibers having an equivalent diameter of 1 to 1000 nm, and the single fibers are selected from the group consisting of anion exchange groups, cation exchange groups, and chelate groups. At least 1 sort (s) of functional group is provided, The filter for liquid filtration characterized by the above-mentioned.
金属イオン濃度：０．５〜５ｎｇ／Ｌ
ＴＯＣ：５ｐｐｂ以上〜５０ｐｐｂ未満
微粒子数：０．１μｍ以上の微粒子が５個／ｍＬ以下
の水質の純水であることを特徴とする液体濾過方法。 8. The liquid according to claim 7, wherein the liquid has a metal ion concentration of 0.5 to 5 ng / L.
TOC: 5 ppb or more and less than 50 ppb Number of fine particles: A liquid filtration method characterized in that the number of fine particles of 0.1 μm or more is 5 / mL or less pure water.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018159723A1 (en) | 2017-02-28 | 2018-09-07 | 東レ株式会社 | Filter |
| JP2019531180A (en) * | 2016-08-05 | 2019-10-31 | スリーエム イノベイティブ プロパティズ カンパニー | Reservoir filter for handheld spray gun |
| WO2021085601A1 (en) * | 2019-10-31 | 2021-05-06 | 東レ株式会社 | Filter for liquid filtration |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04284853A (en) * | 1991-03-13 | 1992-10-09 | Japan Atom Energy Res Inst | Ion exchange filtering method and apparatus therefor |
| JP2009219952A (en) * | 2008-03-13 | 2009-10-01 | Kurita Water Ind Ltd | Fiber for filter, bobbin type filter, and water treatment method |
| JP2010158606A (en) * | 2009-01-06 | 2010-07-22 | Kurita Water Ind Ltd | Filter, method of manufacturing the same, and method of treating fluid |
-
2010
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04284853A (en) * | 1991-03-13 | 1992-10-09 | Japan Atom Energy Res Inst | Ion exchange filtering method and apparatus therefor |
| JP2009219952A (en) * | 2008-03-13 | 2009-10-01 | Kurita Water Ind Ltd | Fiber for filter, bobbin type filter, and water treatment method |
| JP2010158606A (en) * | 2009-01-06 | 2010-07-22 | Kurita Water Ind Ltd | Filter, method of manufacturing the same, and method of treating fluid |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019531180A (en) * | 2016-08-05 | 2019-10-31 | スリーエム イノベイティブ プロパティズ カンパニー | Reservoir filter for handheld spray gun |
| JP7018930B2 (en) | 2016-08-05 | 2022-02-14 | スリーエム イノベイティブ プロパティズ カンパニー | Reservoir filter for handheld spray gun |
| WO2018159723A1 (en) | 2017-02-28 | 2018-09-07 | 東レ株式会社 | Filter |
| US10662083B2 (en) | 2017-02-28 | 2020-05-26 | Toray Industries | Filter |
| WO2021085601A1 (en) * | 2019-10-31 | 2021-05-06 | 東レ株式会社 | Filter for liquid filtration |
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