JP5182793B2 - Cartridge filter for liquid filtration - Google Patents
Cartridge filter for liquid filtration Download PDFInfo
- Publication number
- JP5182793B2 JP5182793B2 JP2007266125A JP2007266125A JP5182793B2 JP 5182793 B2 JP5182793 B2 JP 5182793B2 JP 2007266125 A JP2007266125 A JP 2007266125A JP 2007266125 A JP2007266125 A JP 2007266125A JP 5182793 B2 JP5182793 B2 JP 5182793B2
- Authority
- JP
- Japan
- Prior art keywords
- nonwoven fabric
- graft
- group
- fiber
- polymerized
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000001914 filtration Methods 0.000 title claims description 67
- 239000007788 liquid Substances 0.000 title claims description 37
- 239000004745 nonwoven fabric Substances 0.000 claims description 171
- 239000000835 fiber Substances 0.000 claims description 92
- 238000010559 graft polymerization reaction Methods 0.000 claims description 42
- 239000011148 porous material Substances 0.000 claims description 28
- 238000005342 ion exchange Methods 0.000 claims description 27
- 239000004744 fabric Substances 0.000 claims description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 20
- 125000000524 functional group Chemical group 0.000 claims description 18
- 239000004750 melt-blown nonwoven Substances 0.000 claims description 14
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical group OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 13
- 239000004952 Polyamide Substances 0.000 claims description 12
- 229920002647 polyamide Polymers 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 229920000098 polyolefin Polymers 0.000 claims description 7
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- 238000007731 hot pressing Methods 0.000 claims description 6
- 239000002657 fibrous material Substances 0.000 claims description 4
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 3
- 238000000034 method Methods 0.000 description 34
- 239000010419 fine particle Substances 0.000 description 31
- 239000000178 monomer Substances 0.000 description 26
- -1 polytetrafluoroethylene Polymers 0.000 description 26
- 239000000758 substrate Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000004743 Polypropylene Substances 0.000 description 16
- 229920001155 polypropylene Polymers 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 14
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 13
- 229920001903 high density polyethylene Polymers 0.000 description 13
- 239000004700 high-density polyethylene Substances 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000013522 chelant Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
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- 230000005855 radiation Effects 0.000 description 7
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- 239000004094 surface-active agent Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 235000011089 carbon dioxide Nutrition 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
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- 239000012528 membrane Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
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- 239000011347 resin Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229920001213 Polysorbate 20 Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005349 anion exchange Methods 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
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- 238000011161 development Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 3
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
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- 239000004711 α-olefin Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- 229920003188 Nylon 3 Polymers 0.000 description 2
- 229920001007 Nylon 4 Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
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- 239000011230 binding agent Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
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- 238000010894 electron beam technology Methods 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
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- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- GWCJNVUIVCCXER-UHFFFAOYSA-N 2-(1-phenylprop-2-enoxymethyl)oxirane Chemical compound C=1C=CC=CC=1C(C=C)OCC1CO1 GWCJNVUIVCCXER-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
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- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
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- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 1
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- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Description
本発明は、液体濾過用カートリッジフィルタに関し、さらに詳しくは、イオン除去と微粒子除去の能力を兼ね備えた液体濾過用カートリッジフィルタに関する。 The present invention relates to a cartridge filter for liquid filtration, and more particularly to a cartridge filter for liquid filtration having both ion removal and particulate removal capabilities.
従来、工業用途に使用する液中に含まれる微量金属陽イオン、或いは塩素などの陰イオンの除去には、ビーズ状のイオン交換樹脂やキレート樹脂をカラムに充填し、通液中に金属や各種イオン類を吸着する方法が採られている。このような場合、吸着は樹脂表面から内部への拡散によるため、通液速度はビーズ間の対流・接触時間と被吸着イオンの樹脂内拡散速度に依存する。
このため、通液速度を増加させるには、専ら、樹脂のカラムへの充填量を増大させることになるが、装置上の制約が大きく、処理能力の向上に限界があった。
また、液中に含まれる微粒子を効率よく除去する機能も有しない。例えば、半導体製造工程で用いられる洗浄用純水には、各種の遊離金属イオンの他に、装置部材として用いられているポリテトラフルオロエチレンなどから発生するポリマー微粒子、配管や継ぎ手などから発生する金属微粒子、金属イオンのコロイド状凝集物が含まれるが、ビーズ状充填物では十分に除去する濾過機能を有しない。
Conventionally, in order to remove trace metal cations or anions such as chlorine contained in liquids used for industrial applications, a column is filled with a bead-shaped ion exchange resin or a chelate resin, and metals and various kinds are passed through the liquid flow. A method of adsorbing ions is employed. In such a case, since adsorption is due to diffusion from the resin surface to the inside, the liquid passing speed depends on the convection / contact time between the beads and the diffusion speed of the adsorbed ions in the resin.
For this reason, in order to increase the liquid flow rate, the amount of resin packed into the column is exclusively increased. However, restrictions on the apparatus are large, and there is a limit to improvement of the processing capacity.
Further, it does not have a function of efficiently removing fine particles contained in the liquid. For example, in cleaning pure water used in semiconductor manufacturing processes, in addition to various free metal ions, polymer fine particles generated from polytetrafluoroethylene used as a device member, metal generated from pipes and joints, etc. Fine particles and colloidal aggregates of metal ions are included, but bead-like packings do not have a filtration function to remove them sufficiently.
また、微粒子の高度濾過素材として、微多孔質の膜や中空糸膜が使用されているが、金属イオンの除去機能がないため、これまでにイオン交換基またはキレート基を導入する試みもなされている。しかしながら、これらの素材の膜厚が小さいため、膜内流路の空隙が小さいので、高容量のグラフト重合による官能基の付加には量的限界がある。
従って、イオン交換容量が小さいため、わずかな通液処理量で金属イオンの除去能力を失う。また、膜自体がグラフト重合にともなう素材劣化により、カートリッジの加工において、クラックが生成するなどの問題を生じている。
In addition, microporous membranes and hollow fiber membranes are used as high-filtration materials for fine particles. However, since there is no metal ion removal function, attempts have been made to introduce ion exchange groups or chelate groups. Yes. However, since the film thickness of these materials is small, the gap in the in-membrane flow path is small, so there is a quantitative limit in adding functional groups by high-capacity graft polymerization.
Accordingly, since the ion exchange capacity is small, the ability to remove metal ions is lost with a small amount of liquid passing through. Further, due to the deterioration of the material of the film itself due to graft polymerization, problems such as generation of cracks have occurred in the processing of the cartridge.
このような状況において、近年、不織布基材をグラフト重合し、フィルタ濾材として用いることが提案されている（例えば、特許文献１〜３参照。）。また、これらのフィルタ基材を用いたカートリッジフィルタも、提案されている。
不織布をフィルタ基材とする利点は、イオン交換樹脂に比べて単位重量あたりの表面積が大きく、通液処理速度の増加が可能になることや、膜に比べて、グラフト重合が容易で高グラフト量を得ることができることにある。また、適度の粒子捕捉能力も、持ち合わせている。
そこで、グラフト重合した不織布をカートリッジフィルタに加工する例や、膜と組み合わせた例が提案されている（例えば、特許文献４〜６参照。）。
Under such circumstances, in recent years, it has been proposed to graft polymerize a nonwoven fabric substrate and use it as a filter medium (see, for example, Patent Documents 1 to 3). Cartridge filters using these filter base materials have also been proposed.
The advantages of using a non-woven fabric as a filter substrate are that the surface area per unit weight is larger than that of an ion exchange resin, the liquid passing rate can be increased, and the graft polymerization is easier and the amount of grafting is higher than that of a membrane. Is that you can get It also has a moderate particle trapping capability.
Then, the example which processed the graft-polymerized nonwoven fabric into a cartridge filter, and the example combined with the film | membrane are proposed (for example, refer patent documents 4-6).
しかしながら、上記提案された例では、実用上、以下に述べる課題や問題点があると
指摘されている。
すなわち、同一の不織布基材において、イオン交換基／キレート基の付加量と微粒子捕捉能力が同時に制御できない。言い換えると、微粒子の濾過精度を高めようとすれば、繊維径を小さく、かつ繊維密度を高くする必要があるが、その反面、グラフト重合においてモノマーの不織布内部への浸透性が低下し、グラフト反応が不均一になり、品質の安定しないことや、モノマーが繊維上にグラフトすることによって、ポリマーに生長し、繊維間を塞ぐか、または押し拡げ、フィルタとしてのポアサイズがグラフト重合によって変化するために、微粒子除去の精度が保障されない。
However, it has been pointed out that the proposed example has the following problems and problems in practice.
That is, in the same nonwoven fabric substrate, the amount of ion exchange groups / chelate groups added and the ability to capture fine particles cannot be controlled simultaneously. In other words, in order to increase the filtration accuracy of the fine particles, it is necessary to reduce the fiber diameter and the fiber density. On the other hand, in the graft polymerization, the permeability of the monomer into the nonwoven fabric decreases, and the graft reaction Due to non-uniformity, unstable quality, and monomer grafting onto the fiber, which grows into a polymer, plugs or spreads between the fibers, and the pore size as a filter changes due to graft polymerization Therefore, the accuracy of particle removal is not guaranteed.
一般に、グラフト重合法によって、イオン交換基・キレート基の容量を高めるためには、不織布基材の目付け重量または厚みを一定とした場合、繊維径を小さくすれば、繊維本数が増え、従って、全繊維表面積の増加につながり、グラフト効率を高めることに寄与する。
しかしながら、繊維径を過小にすると、前記グラフト重合処理における放射線照射に伴う高分子の崩壊劣化の影響を受けて、著しい強度低下を来たすため、繊維径については、適当な範囲を選択する必要がある。
さらには、グラフト重合において、繊維上のグラフトモノマーの成長には、不織布内空間に、ある程度の空隙が必要である。即ち、グラフト重合に適する不織布基材としては、単位重量あたりの不織布においては、繊維の充填密度（＝繊維充填率）または繊維間の空隙度（＝空隙率）の両者が適切にバランスしていることが高いグラフト率を付与させるために必要である。ここで繊維充填率は下式で表現される。また、空隙率は、繊維充填率と以下の関係がある。
繊維充填率（％）＝［目付け重量（ｇ／ｍ２）／厚み（ｍｍ）／有機繊維材料の比重／１０００］×１００
空隙率（％）＝１００−繊維充填率
In general, in order to increase the capacity of ion exchange groups and chelate groups by the graft polymerization method, if the basis weight or thickness of the nonwoven fabric substrate is constant, the number of fibers increases if the fiber diameter is reduced, and therefore the total number of fibers increases. This leads to an increase in the fiber surface area and contributes to an increase in graft efficiency.
However, if the fiber diameter is made too small, the strength of the polymer is significantly deteriorated due to the degradation of the polymer due to the radiation irradiation in the graft polymerization process, so it is necessary to select an appropriate range for the fiber diameter. .
Furthermore, in graft polymerization, a certain amount of voids are required in the interior space of the nonwoven fabric in order to grow the graft monomer on the fiber. That is, as a nonwoven fabric substrate suitable for graft polymerization, in the nonwoven fabric per unit weight, both the fiber packing density (= fiber filling rate) or the void degree between fibers (= porosity) are appropriately balanced. Is necessary to provide a high grafting ratio. Here, the fiber filling rate is expressed by the following equation. Further, the porosity has the following relationship with the fiber filling rate.
Fiber filling rate (%) = [weight per unit area (g / m 2 ) / thickness (mm) / specific gravity of organic fiber material / 1000] × 100
Porosity (%) = 100−Fiber filling rate
また、イオン交換濾材としての観点からは、不織布の厚みが重要である。これは、液体の不織布内の通過流路長に関連し、充填率または空隙率とともに、濾過液体との接触度に関連する。これらの要素を適正に選択することが、イオン捕捉の際の通液速度向上に不可欠である。
以上のことから、当該用途におけるグラフト用不織布基材としては、基材の繊維径、繊維充填率または空隙率、および厚みが適切な範囲に選択されることが求められている。
From the above, as the nonwoven fabric base material for grafting in the application, it is required that the fiber diameter, fiber filling rate or porosity, and thickness of the base material are selected within an appropriate range.
本発明の目的は、上記従来技術の問題点に鑑み、濾過性能とイオン交換能を高いレベルでバランスさせた、イオン除去と微粒子除去の能力を兼ね備えた液体濾過用カートリッジフィルタを提供することにある。 An object of the present invention is to provide a cartridge filter for liquid filtration that has both ion removal and fine particle removal capabilities, which balances filtration performance and ion exchange performance at a high level in view of the above-described problems of the prior art. .
本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、官能基付与グラフト重合不織布と非グラフト重合不織布との種々の組み合わせを検討し、特に、イオン交換基を導入したグラフト重合不織布を複数種用い、また、非グラフト重合不織布においても、単層単種のみならず、平均繊維径（以下単に「繊維径」と言う）、平均孔径の異なるもの数種を熱プレス加工により、積層一体化し、さらにこれをグラフト不織布と組み合わせて濾材として、プリーツ形状またはロール巻き形状のカートリッジフィルタを試作すると、イオン除去と微粒子除去の能力を高度に兼ね備えた液体濾過用カートリッジフィルタを提供できることを見出し、これらの知見に基づき、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have studied various combinations of functionalized graft-polymerized nonwoven fabrics and non-grafted polymerized nonwoven fabrics, and in particular, graft-polymerized nonwoven fabrics introduced with ion-exchange groups. In non-grafted non-woven fabrics, not only single layers but also several types with different average fiber diameters (hereinafter simply referred to as “fiber diameters”) and average pore diameters are laminated by hot pressing. It is found that by combining this with a grafted nonwoven fabric as a filter medium and making a prototype pleated or roll-shaped cartridge filter, it is possible to provide a cartridge filter for liquid filtration that has a high degree of ion removal and fine particle removal capability. Based on these findings, the present invention has been completed.
すなわち、本発明の第１の発明によれば、複数の不織布を積層一体化して、プリーツ状またはロール状に巻き回してなるカートリッジフィルタであって、該複数の不織布の少なくとも一種は、グラフト重合によりイオン交換基を有するグラフト重合不織布であり、該グラフト重合不織布は、イオン交換基がスルホン酸基、リン酸基、カルボン酸基、アミノ基、グルカミン酸基、又はイミノジ酢酸基から選択される少なくとも一種の官能基であり、かつグラフト重合される不織布原反は、ポリアミド、ポリオレフィン又はポリビニルアルコールを繊維原料とし、（ｉ）繊維径が５〜３０μｍ、（ｉｉ）平均孔径が３２〜６０μｍ、（ｉｉｉ）目付け重量が１０〜１００ｇ／ｍ ２ 、（ｉｖ）繊維充填率が５〜３０％、及び（ｖ）厚みが０．１〜１．０ｍｍであり、他の一種は、該グラフト重合不織布より繊維径及び平均孔径が小さい非グラフト重合不織布であり、該非グラフト重合不織布は、ポリオレフィン又はポリアミドを繊維原料としたメルトブロー法不織布であって、（ｉ）繊維径が０．２〜５μｍ、（ｉｉ）平均孔径が６．０〜２０μｍ、（ｉｉｉ）目付け重量が２〜６０ｇ／ｍ ２ 、（ｉｖ）繊維充填率が１０〜４０％、及び（ｖ）厚みが０．０２〜０．６ｍｍである、繊維径勾配型の複数濾材からなることを特徴とする液体濾過用カートリッジフィルタが提供される。 That is, according to the first invention of the present invention, there is provided a cartridge filter in which a plurality of nonwoven fabrics are laminated and integrated and wound in a pleated shape or a roll shape, and at least one of the plurality of nonwoven fabrics is obtained by graft polymerization. A graft-polymerized nonwoven fabric having an ion-exchange group, wherein the graft-polymerized nonwoven fabric has at least one ion-exchange group selected from a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, an amino group, a glucamic acid group, or an iminodiacetic acid group The nonwoven fabric raw material which is a functional group of the above and is graft-polymerized is made of polyamide, polyolefin or polyvinyl alcohol as a fiber raw material, and (i) fiber diameter is 5 to 30 μm, (ii) average pore diameter is 32 to 60 μm, (iii) basis weight weight 10~100g / m 2, (iv) the fiber packing ratio is 5-30%, and (v) thickness 0.1 Is 0 mm, the other one is Ri fiber diameter and the average pore diameter is smaller ungrafted polymerized nonwoven der than the graft polymerization nonwoven, non-graft polymerization nonwoven, a polyolefin or a polyamide and a melt blown nonwoven fabric with fiber material, (I) the fiber diameter is 0.2-5 μm, (ii) the average pore diameter is 6.0-20 μm, (iii) the basis weight is 2-60 g / m 2 , (iv) the fiber filling ratio is 10-40%, and (v) thick Ru 0.02~0.6mm der, liquid filtration cartridge filter characterized by comprising a plurality filter media fibers size gradient type is provided.
本発明の第２の発明によれば、第１の発明において、前記非グラフト重合不織布は、熱プレス加工により圧密一体化されて、厚みが当初の厚みに対して４０〜７０％であることを特徴とする液体濾過用カートリッジフィルタが提供される。 According to a second invention of the present invention, in the first invention, the non-grafted non-woven fabric is consolidated and consolidated by hot pressing, and the thickness is 40 to 70% of the initial thickness. A cartridge filter for liquid filtration is provided.
本発明の液体濾過用カートリッジフィルタは、高効率のイオン捕捉に適したグラフト重合不織布と、微粒子捕捉効率の高い非グラフト重合不織布とを複合化することによって、濾過性能とイオン交換能を高いレベルでバランスさせているので、イオン除去と微粒子除去の能力を高度に兼ね備え、信頼性が高いという効果を奏する。また、非グラフト重合不織布のみを熱カレンダー加工などにより圧密化し、これをグラフト重合不織布と複合することにより、濾過精度を一段と向上させることができる。さらに、一つのカートリッジフィルタにおいて、種類の異なるイオン類や金属の捕捉、例えば、陽イオンと陰イオン、又は陽イオンと特定の重金属イオン等、様々な微粒子を同時に捕捉することができ、液体濾過装置全体を小型化することができる。 The cartridge filter for liquid filtration of the present invention has a high level of filtration performance and ion exchange capacity by combining a graft-polymerized nonwoven fabric suitable for high-efficiency ion trapping and a non-graft-polymerized nonwoven fabric with high particulate trapping efficiency. Since the balance is achieved, the ability of ion removal and fine particle removal is highly combined, and the reliability is high. Moreover, only the non-graft polymerized non-woven fabric is consolidated by thermal calendering or the like and combined with the graft polymerized non-woven fabric, the filtration accuracy can be further improved. Furthermore, in one cartridge filter, various types of fine particles such as cations of different types and metals, for example, cations and anions, or cations and specific heavy metal ions can be captured at the same time. The whole can be reduced in size.
本発明の液体濾過用カートリッジフィルタは、異なる機能を有する複数の不織布を積層一体化して、プリーツ状またはロール状に巻き回してなるカートリッジフィルタであって、該不織布の少なくとも一種は、グラフト重合によりイオン交換基を有するグラフト重合不織布であり、他の一種は、該グラフト重合不織布より繊維径及び平均孔径が小さい非グラフト重合不織布であり、繊維径勾配型の複数濾材からなることを特徴とするものである。
以下、本発明の液体濾過用カートリッジフィルタについて、項目毎に詳細に説明する。
The cartridge filter for liquid filtration of the present invention is a cartridge filter formed by laminating and integrating a plurality of nonwoven fabrics having different functions and winding them into a pleat shape or a roll shape, and at least one of the nonwoven fabrics is ionized by graft polymerization. A graft-polymerized non-woven fabric having an exchange group, and the other kind is a non-graft-polymerized non-woven fabric having a smaller fiber diameter and average pore diameter than the graft-polymerized non-woven fabric, and is characterized by comprising a plurality of fiber diameter gradient type filter media. is there.
Hereinafter, the cartridge filter for liquid filtration of the present invention will be described in detail for each item.
１．グラフト重合不織布
本発明の液体濾過用カートリッジフィルタに用いられるグラフト重合不織布は、不織布基材（原反）に、グラフト重合法により、イオン交換基及び／又はキレート基を導入したものである。グラフト重合法としては、放射線グラフト重合法を好適に用いることができる。
放射線グラフト重合法とは、有機高分子基材に放射線を照射してラジカルを生成させ、それにグラフトモノマーを反応させることによって、所望のグラフト重合体側鎖を基材の高分子主鎖上に導入することのできる方法であり、グラフト鎖の数や長さを自由にコントロールすることができ、また、各種形状の既存の高分子材料に重合体側鎖を導入することができるので、本発明の目的のために用いるのに最適である。放射線グラフト重合法を用いた場合には、イオン交換基及び／又はキレート基は、これらの基を有する重合体側鎖の形態で高分子基材に導入される。
1. Graft Polymerized Nonwoven Fabric The graft polymerized nonwoven fabric used in the cartridge filter for liquid filtration of the present invention is obtained by introducing an ion exchange group and / or a chelate group into a nonwoven fabric substrate (raw fabric) by a graft polymerization method. As the graft polymerization method, a radiation graft polymerization method can be suitably used.
Radiation graft polymerization is a method in which a radical is generated by irradiating an organic polymer substrate with radiation, and a graft monomer is reacted therewith to introduce a desired graft polymer side chain onto the polymer main chain of the substrate. The number and length of graft chains can be freely controlled, and polymer side chains can be introduced into existing polymer materials of various shapes. Ideal for use. When the radiation graft polymerization method is used, ion exchange groups and / or chelate groups are introduced into the polymer substrate in the form of polymer side chains having these groups.
上記グラフト重合法としては、具体的には、例えば、液相グラフト重合法が挙げられ、不織布を、γ線や電子線などの放射線照射によって活性化した後、水、界面活性剤および反応性モノマーを含むエマルジョンに浸漬して、前記の不織布基材にグラフト重合を完了させ、次に、前記基材に形成されたグラフト鎖に、スルホン酸基、アミノ基、グルカミン酸基やイミノ二酢酸基（イミノジ酢酸基）などの機能性官能基、すなわちイオン交換基及び／又はキレート基を導入することが望ましい。本発明においては、特に液相グラフト重合法に限定されず、モノマーの蒸気に基材を接触させて重合を行う気相グラフト重合法、基材をモノマー溶液に浸漬した後、モノマー溶液から取り出して気相中で反応を行わせる含浸気相グラフト重合法なども、用いることができる。
尚、本明細書中における「エマルジョン」とは、一般に、水に対して不溶性である反応性モノマー液の小滴が水溶媒中に分散した系をいう。反応性モノマー液の小滴の大きさに限定はなく、数ｎｍ〜数十ｎｍ程度のマイクロエマルジョンや１ｎｍ程度のナノエマルジョンも含むものとする。したがって、水に対して不溶性である反応性モノマー液と水溶媒が存在する限り、界面活性剤の添加により、水／油間の界面張力を低下させて、見かけ上一様に混ざり合った状態の系も含むものとする。
Specific examples of the graft polymerization method include a liquid phase graft polymerization method. After the nonwoven fabric is activated by irradiation with radiation such as γ rays and electron beams, water, a surfactant and a reactive monomer are used. In the non-woven fabric substrate, the graft polymerization is completed, and then the sulfonate group, amino group, glucamic acid group and iminodiacetic acid group ( It is desirable to introduce a functional functional group such as an iminodiacetic acid group), that is, an ion exchange group and / or a chelate group. In the present invention, the method is not particularly limited to the liquid phase graft polymerization method. The gas phase graft polymerization method in which the substrate is brought into contact with the vapor of the monomer to perform polymerization, the substrate is immersed in the monomer solution, and then taken out from the monomer solution. An impregnation gas phase graft polymerization method in which the reaction is performed in a gas phase can also be used.
In the present specification, “emulsion” generally refers to a system in which droplets of a reactive monomer liquid that is insoluble in water are dispersed in an aqueous solvent. The size of the droplets of the reactive monomer liquid is not limited, and includes a microemulsion of about several nm to several tens of nm and a nanoemulsion of about 1 nm. Therefore, as long as there is a reactive monomer solution and an aqueous solvent that are insoluble in water, the addition of a surfactant reduces the interfacial tension between water / oil and makes it appear to be uniformly mixed. The system is also included.
また、グラフト重合される不織布原反は、ポリアミド、ポリオレフィン又はポリビニルアルコール（ＰＶＡ）を繊維原料とし、（ｉ）繊維径が５〜３０μｍ、（ｉｉ）平均孔径が２０〜６０μｍ、（ｉｉｉ）目付け重量が１０〜１００ｇ／ｍ２、（ｉｖ）繊維充填率が５〜３０％、（ｖ）厚みが０．１〜１．０ｍｍであることが望ましい。
本発明では、高効率のイオン捕捉のために、イオン交換・キレート容量には、グラフト官能基の絶対量が必要であり、繊維数の絶対量としての目付け重量、繊維表面積比例要素としての繊維径、通液のパスの長さとしての厚みが重要である。目付け重量と厚みについては、プリーツ加工とカートリッジ加工性、一定寸法の容器への収納性から、上記範囲が好適である。
また、不織布は、グラフト重合性を考慮すると、ノーバインダで繊維が固定されていることが重要であり、さらに、繊維配列がランダムで均質性の高い不織布が好ましい。
そのような不織布を得る製法としては、繊維径が凡そ２０〜３０μｍの短繊維を用いたカード法乾式不織布、湿式（抄紙）法不織布、繊維径が凡そ５〜２０μｍの連続繊維からなるメルトブロー法不織布、スパンボンド法不織布などが挙げられる。
Moreover, the nonwoven fabric raw material which is graft-polymerized uses polyamide, polyolefin or polyvinyl alcohol (PVA) as a fiber raw material, and (i) fiber diameter is 5 to 30 μm, (ii) average pore diameter is 20 to 60 μm, (iii) weight per unit weight Is preferably 10 to 100 g / m 2 , (iv) a fiber filling ratio of 5 to 30%, and (v) a thickness of 0.1 to 1.0 mm.
In the present invention, in order to capture ions with high efficiency, the ion exchange / chelate capacity requires an absolute amount of the graft functional group, the basis weight as the absolute amount of the number of fibers, and the fiber diameter as the fiber surface area proportional element. The thickness as the length of the liquid passing path is important. About the fabric weight and thickness, the said range is suitable from a pleating process, cartridge processability, and the accommodation property in the container of a fixed dimension.
Further, considering the graft polymerizability of the nonwoven fabric, it is important that the fibers are fixed with a no binder, and a nonwoven fabric having a random fiber arrangement and high homogeneity is preferable.
As a production method for obtaining such a nonwoven fabric, a card method dry nonwoven fabric using a short fiber having a fiber diameter of approximately 20 to 30 μm, a wet (papermaking) nonwoven fabric, and a melt blown nonwoven fabric comprising continuous fibers having a fiber diameter of approximately 5 to 20 μm. And a spunbond nonwoven fabric.
グラフト重合用不織布基材としては、ポリプロピレン、ポリアミド、高密度ポリエチレンまたはポリビニルアルコール（ＰＶＡ）が挙げられる。
その理由としては、これらの素材が液体濾過の使用下において、化学・物理的安定性であるのみならず、前記の好ましい不織布の製法に容易に適用される。例えば、ポリプロピレン、高密度ポリエチレン、ポリアミドについては、メルトブロー法またはスパンボンド法不織布製法が適用される。また、高密度ポリエチレン、ポリプロピレン、ＰＶＡは、短繊維ステープルとして市販されているものを、乾式または湿式不織布製法にて、容易に不織布化できる。
Examples of the nonwoven fabric substrate for graft polymerization include polypropylene, polyamide, high density polyethylene, and polyvinyl alcohol (PVA).
The reason for this is that these materials are not only chemically and physically stable under the use of liquid filtration, but are also easily applied to the preferred method for producing nonwoven fabrics. For example, for polypropylene, high-density polyethylene, and polyamide, a melt-blowing method or a spunbond nonwoven fabric manufacturing method is applied. Further, high-density polyethylene, polypropylene, and PVA can be easily made into a non-woven fabric by a dry or wet non-woven fabric manufacturing method from commercially available short fiber staples.
ポリアミド（ＰＡ）としては、特に限定されなく、ナイロンの一般名をもつ、酸アミド（−ＣＯＮＨ−）を繰り返し単位に持つ合成高分子であり、例えば、ポリアミド３（ナイロン３）、ポリアミド４（ナイロン４）、ポリアミド６（ナイロン６）、ポリアミド６−６（ナイロン６−６）、ポリアミド１２（ナイロン１２）などが挙げられる。 Polyamide (PA) is not particularly limited, and is a synthetic polymer having a general name of nylon, acid amide (-CONH-) as a repeating unit. For example, polyamide 3 (nylon 3), polyamide 4 (nylon) 4), polyamide 6 (nylon 6), polyamide 6-6 (nylon 6-6), polyamide 12 (nylon 12) and the like.
また、ポリオレフィンとしては、プロピレン、エチレン、ブテン−１、ヘキセン−１、オクテン−１、４−メチルペンテン−１などのα―オレフィンの単独重合体、あるいはこれらα−オレフィンの２種類以上のランダムあるいはブロック共重合体が挙げられる。中でもポリプロピレン（ＰＰ）としては、ポリプロピレン単独重合体、又はエチレン・プロピレン系共重合体などであり、そのエチレン含量については特に特定されないが、メタロセン触媒により製造されたものは、放射線の損傷による物性低下が少なく好ましい。
また、ポリエチレン（ＰＥ）としては、特に限定されなく、高密度ポリエチレン、中密度ポリエチレン、低密度ポリエチレン、エチレン−酢酸ビニル共重合体等のいずれでもよい。
As the polyolefin, homopolymers of α-olefins such as propylene, ethylene, butene-1, hexene-1, octene-1, 4-methylpentene-1, or two or more kinds of these α-olefins are random or A block copolymer is mentioned. Among them, polypropylene (PP) is a polypropylene homopolymer or an ethylene / propylene copolymer, and its ethylene content is not particularly specified, but those produced with a metallocene catalyst are deteriorated in physical properties due to radiation damage. Is preferable.
Moreover, it does not specifically limit as polyethylene (PE), Any, such as a high density polyethylene, a medium density polyethylene, a low density polyethylene, an ethylene-vinyl acetate copolymer, may be sufficient.
さらに、ポリビニルアルコール（ＰＶＡ）は、その基本骨格と分子構造、形態、各種変性により、水溶性または親水性の程度を変えることができることが知られるが、本発明では、水溶性のポリビニルアルコール（ＰＶＡ）繊維は用いない。
本発明に用いられるポリビニルアルコール（ＰＶＡ）は、ビニルエステル系重合体のビニルエステル単位をけん化することにより得られる。
ビニルエステル単位を形成するためのビニル化合物単量体としては、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、バレリン酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、安息香酸ビニル、ピバリン酸ビニル、バーサティック酸ビニル等が挙げられる。
また、ポリビニルアルコール（ＰＶＡ）は、ホモポリマーであっても共重合単位を導入した変成ＰＶＡであってもよい。共重合単量体の種類としては、例えば、エチレン、プロピレン、１−ブテン、イソブテン、１−ヘキセン等のα−オレフィン類、アクリル酸およびその塩、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−プロピル、アクリル酸ｉ−プロピル等のアクリル酸エステル類、メチルビニルエーテル、エチルビニルエーテル、ｎ−プロピルビニルエーテル、ｉ−プロピルビニルエーテル、ｎ−ブチルビニルエーテル等のビニルエーテル類などが挙げられる。これらの単量体の含有量は、共重合ＰＶＡを構成する全単位のモル数を１００％とした場合の通常その２０モル％以下である。また、共重合されていることのメリットを発揮するためには、０．０１モル％以上が上記共重合単位であることが好ましい。なお、低融点の共重合タイプのＰＶＡはＰＶＡ繊維と混合して湿式または乾式不織布におけるバインダー繊維としても利用できる。
Furthermore, it is known that polyvinyl alcohol (PVA) can change the degree of water-solubility or hydrophilicity by its basic skeleton, molecular structure, form, and various modifications, but in the present invention, water-soluble polyvinyl alcohol (PVA) ) No fiber is used.
The polyvinyl alcohol (PVA) used in the present invention is obtained by saponifying the vinyl ester unit of the vinyl ester polymer.
As vinyl compound monomers for forming vinyl ester units, vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, Examples thereof include vinyl versatate.
The polyvinyl alcohol (PVA) may be a homopolymer or a modified PVA having a copolymer unit introduced therein. Examples of the comonomer include α-olefins such as ethylene, propylene, 1-butene, isobutene, and 1-hexene, acrylic acid and salts thereof, methyl acrylate, ethyl acrylate, and acrylic acid n- Examples thereof include acrylic acid esters such as propyl and i-propyl acrylate, and vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether and n-butyl vinyl ether. The content of these monomers is usually 20 mol% or less when the number of moles of all units constituting the copolymerized PVA is 100%. Moreover, in order to exhibit the merit of being copolymerized, it is preferable that 0.01 mol% or more is the said copolymerization unit. The low melting point copolymer type PVA can be mixed with PVA fibers and used as binder fibers in wet or dry nonwoven fabrics.
また、不織布原反（不織布基材）にグラフト重合させる反応性モノマ−としては、ビニル基を有するモノマーが挙げられ、特に限定はなく、例えば、アクリロニトリル（ＣＨ２＝ＣＨＣＮ）、アクロレイン、グリシジルメタクリレート（ＧＭＡ）、クロロメチルスチレン、ビニルベンジルグリシジルエーテルなどが挙げられる。
また、反応性モノマーにおけるビニル基を有するモノマーとして、リン酸基を有するビニルモノマーも挙げられ、例えば、モノ（２−メタクリロイルオキシエチル）アシッドホスフェート：ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）２ＯＰＯ（ＯＨ）２、ジ（２−メタクリロイルオキシエチル）アシッドホスフェート：［ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）２Ｏ］２ＰＯ（ＯＨ）、モノ（２−アクリロイルオキシエチル）アシッドホスフェート：ＣＨ２＝ＣＨＣＯＯ（ＣＨ２）２ＯＰＯ（ＯＨ）２、ジ（２−アクリロイルオキシエチル）アシッドホスフェート：［ＣＨ２＝ＣＨＣＯＯ（ＣＨ２）２Ｏ］２ＰＯ（ＯＨ）、又はこれらの混合モノマーなどである。
The reactive monomer to be graft-polymerized on the nonwoven fabric (nonwoven fabric substrate) includes a monomer having a vinyl group, and is not particularly limited. For example, acrylonitrile (CH 2 = CHCN), acrolein, glycidyl methacrylate ( GMA), chloromethyl styrene, vinyl benzyl glycidyl ether and the like.
Examples of the monomer having a vinyl group in the reactive monomer also include a vinyl monomer having a phosphate group. For example, mono (2-methacryloyloxyethyl) acid phosphate: CH 2 = C (CH 3 ) COO (CH 2 ) 2 OPO (OH) 2 , di (2-methacryloyloxyethyl) acid phosphate: [CH 2 ═C (CH 3 ) COO (CH 2 ) 2 O] 2 PO (OH), mono (2-acryloyloxyethyl) acid phosphate: CH 2 = CHCOO (CH 2 ) 2 OPO (OH) 2, di (2-acryloyloxyethyl) acid phosphate: [CH 2 = CHCOO (CH 2) 2 O] 2 PO (OH), or a mixture thereof Monomers and the like.
このビニル基を有するモノマー、例えば、ＧＭＡを基材にグラフトし、次に、このグラフト側鎖にイオン交換機能のある官能基を導入し、例えば、亜硫酸ナトリウムなどのスルホン化剤を反応させてスルホン化し、カチオン交換基に転化させたり、ジエタノールアミンなどを用いてアミノ化し、アニオン交換基を導入したりすることができる。また、イミノジ酢酸などのキレート化剤を作用させてイミノジ酢酸基（イミノ二酢酸基、ＩＤＡ基：−Ｎ（ＣＨ２ＣＯＯＨ）２）をグラフト鎖に導入し、鉛など重金属の吸着機能を付与することができる。 A monomer having a vinyl group, such as GMA, is grafted onto a substrate, and then a functional group having an ion exchange function is introduced into the graft side chain, and a sulfonating agent such as sodium sulfite is reacted to react with the sulfone. And can be converted into a cation exchange group or aminated with diethanolamine or the like to introduce an anion exchange group. In addition, an iminodiacetic acid group (iminodiacetic acid group, IDA group: —N (CH 2 COOH) 2 ) is introduced into the graft chain by allowing a chelating agent such as iminodiacetic acid to act, thereby providing an adsorption function for heavy metals such as lead. be able to.
グラフト重合用の反応性モノマーをエマルジョン化する界面活性剤としては、陰イオン系、陽イオン系、両性イオン系、非イオン系界面活性剤のいずれも、使用することができる。また、これらの数種を併用してもよい。
具体的には、陰イオン系界面活性剤としては、特に限定はないが、アルキルベンゼン系、アルコール系、オレフィン系、リン酸系、アミド系の界面活性剤などであり、例えば、ドデシル硫酸ナトリウムが挙げられる。
また、陽イオン系界面活性剤は、特に限定はないが、オクタデシルアミン酢酸塩、トリメチルアンモニウムクロライドが挙げられる。非イオン系界面活性剤は、特に限定はないが、エトキシル化脂肪アルコール、脂肪酸エステルなどであり、例えば、Ｔｗｅｅｎ ８０が挙げられる。両性イオン系界面活性剤は、特に限定はないが、例えば、アンヒトール（商標）（花王株式会社）が挙げられる。
As the surfactant for emulsifying the reactive monomer for graft polymerization, any of anionic, cationic, zwitterionic and nonionic surfactants can be used. Moreover, you may use these several types together.
Specifically, the anionic surfactant is not particularly limited, and examples thereof include alkylbenzene-based, alcohol-based, olefin-based, phosphoric acid-based, and amide-based surfactants. Examples thereof include sodium dodecyl sulfate. It is done.
Further, the cationic surfactant is not particularly limited, and examples thereof include octadecylamine acetate and trimethylammonium chloride. The nonionic surfactant is not particularly limited, and examples thereof include ethoxylated fatty alcohol and fatty acid ester, and examples thereof include Tween 80. The zwitterionic surfactant is not particularly limited, and examples thereof include Amphital (trademark) (Kao Corporation).
使用する界面活性剤の濃度は、特に限定はなく、反応性モノマーの種類、濃度に依存して、適宜決定することができる。界面活性剤の濃度は、溶媒の全重量を基準として、０．１〜１０％が好ましい。 The concentration of the surfactant to be used is not particularly limited and can be appropriately determined depending on the type and concentration of the reactive monomer. The concentration of the surfactant is preferably 0.1 to 10% based on the total weight of the solvent.
界面活性剤を使用することにより、水に対して不溶性の反応性モノマーの分散を促進することができる。エマルジョンの外観は、分散相の液滴の大きさに依存して種々変化するが、一般的には、乳濁状態であり、マイクロエマルジョンからナノエマルジョンへと液滴の大きさが小さくなるにつれ、透明を呈するようになる。 By using the surfactant, it is possible to promote the dispersion of the reactive monomer insoluble in water. The appearance of the emulsion varies depending on the size of the droplets in the dispersed phase, but is generally in an emulsion state, and as the droplet size decreases from microemulsion to nanoemulsion, It becomes transparent.
エマルジョン化のための水は、特に限定はないが、イオン交換水、純水、超純水が使われる。溶媒として有機溶媒ではなく、水を使用することにより、廃液処理および作業環境の問題を排除することができ、環境保護面に資することとなる。 The water for emulsification is not particularly limited, but ion exchange water, pure water, and ultrapure water are used. By using water instead of an organic solvent as a solvent, problems of waste liquid treatment and working environment can be eliminated, which contributes to environmental protection.
ここで、上述のエマルジョン化モノマーのグラフト重合条件については、モノマーの反応性にもよるが、１０℃〜６０℃、好ましくは２０℃〜６０℃である。反応時間は、１分〜２時間、好ましくは５分〜６０分の範囲であり、エマルジョン中のモノマー濃度は、１％〜３０％、好ましくは２％〜２０％のなかで、適宜選択される。 Here, the graft polymerization conditions of the above-mentioned emulsifying monomer are 10 ° C. to 60 ° C., preferably 20 ° C. to 60 ° C., although depending on the reactivity of the monomer. The reaction time is in the range of 1 minute to 2 hours, preferably 5 minutes to 60 minutes, and the monomer concentration in the emulsion is appropriately selected from 1% to 30%, preferably 2% to 20%. .
また、前記イオン交換基としては、強酸性カチオン交換基としてのスルホン酸基、弱酸性カチオン交換基としてのリン酸基やカルボン酸（又はカルボキシル）基、アニオン交換基としてのアミノ基、キレート基としてのグルカミン酸基、又はキレート基としてのイミノジ酢酸基（イミノ二酢酸基）から選択される少なくとも一種の官能基が挙げられる。 As the ion exchange group, a sulfonic acid group as a strongly acidic cation exchange group, a phosphate group or carboxylic acid (or carboxyl) group as a weak acid cation exchange group, an amino group as an anion exchange group, and a chelate group And at least one functional group selected from an iminodiacetic acid group (iminodiacetic acid group) as a chelating group.
上記スルホン基又はスルホン酸基は、半導体、液晶の製造工程で使用される超純水に含まれるナトリウム、マグネシウム、ニッケル、亜鉛などの陽イオンを捕捉するために、導入される。また、リン酸基やカルボン酸基は、各種金属イオン、スカンジウムなどの貴金属を捕捉するために、導入される。さらに、アミノ基は、工業用純水に含まれる塩素などの陰イオンの除去、グルカミン酸基は、排水中に含まれるホウ素、砒素などの陰イオンの除去に導入される。また、イミノジ酢酸基は、水道水に含まれる鉄、銅、マンガン除去や、工業排水中に含まれるカドミニウム、鉛などの重金属の除去に導入される。
イオン交換基及びキレート基としては、上記以外に、所望する機能、例えば重金属（鉛、カドミニウム、砒素など）の吸着機能により、４級アンモニウム基などの強塩基性アニオン交換基、アミドキシム基、エチレンジアミン三酢酸基、イミノジエタノール基などが挙げられる。
The sulfone group or sulfonic acid group is introduced in order to capture cations such as sodium, magnesium, nickel and zinc contained in ultrapure water used in the production process of semiconductors and liquid crystals. Moreover, a phosphoric acid group and a carboxylic acid group are introduced in order to capture noble metals such as various metal ions and scandium. Furthermore, amino groups are introduced to remove anions such as chlorine contained in industrial pure water, and glucamic acid groups are introduced to remove anions such as boron and arsenic contained in waste water. The iminodiacetic acid group is introduced for removing iron, copper, and manganese contained in tap water and removing heavy metals such as cadmium and lead contained in industrial wastewater.
In addition to the above, the ion exchange group and chelate group include a strongly basic anion exchange group such as a quaternary ammonium group, an amidoxime group, an ethylenediamine group depending on a desired function, for example, an adsorption function of heavy metals (lead, cadmium, arsenic, etc.). Examples include acetic acid groups and iminodiethanol groups.
本発明では、カートリッジ化の際に複層化できるという利点を活かし、グラフト重合不織布として、２種以上の異なる官能基付与のグラフト重合不織布を複数組み込むことができる。例えば、工業的に利用価値が高い組み合わせとして、（ｉ）スルホン基付与不織布とアミノ基付与不織布の組み合わせ、（ｉｉ）スルホン基付与の不織布とグルカミン酸基付与の不織布基材の組み合わせ、（ｉｉｉ）スルホン基付与の不織布基材とキレート基（イミノジ酢酸基）付与の不織布基材の組み合わせ、などが挙げられる。 In the present invention, taking advantage of the fact that it can be multi-layered when making a cartridge, a plurality of graft-polymerized nonwoven fabrics with two or more different functional groups can be incorporated as graft-polymerized nonwoven fabrics. For example, as a combination having industrially high utility value, (i) a combination of a sulfone group-added non-woven fabric and an amino group-added non-woven fabric, (ii) a combination of a sulfone group-added non-woven fabric and a non-woven fabric substrate having a glucamic acid group added, (iii) Examples include a combination of a nonwoven fabric substrate provided with a sulfone group and a nonwoven fabric substrate provided with a chelate group (iminodiacetic acid group).
２．非グラフト重合不織布
本発明の液体濾過用カートリッジフィルタに用いられる非グラフト重合不織布は、上記のグラフト重合不織布と組み合わせるものであり、グラフト重合不織布より、繊維径及び平均孔径が小さいものである。
この非グラフト重合不織布基材は、グラフト重合処理をしないため、専ら微粒子の除去に特化した不織布構成をとることができ、ポリオレフィン又はポリアミドを繊維原料としたメルトブロー法不織布であって、（ｉ）繊維径が０．２〜５μｍ、（ｉｉ）平均孔径が０．２〜２０μｍ、（ｉｉｉ）目付け重量が２〜６０ｇ／ｍ２、（ｉｖ）繊維充填率が１０〜４０％、及び（ｖ）厚みが０．０２〜０．６ｍｍであることが望ましい。
尚、上記厚みは、不織布原反及び後述の熱プレスして調整した加工不織布の厚みを含む範囲である。
2. Non-graft polymerized nonwoven fabric The non-graft polymerized nonwoven fabric used in the cartridge filter for liquid filtration of the present invention is combined with the above graft polymerized nonwoven fabric, and has a smaller fiber diameter and average pore diameter than the graft polymerized nonwoven fabric.
This non-grafted non-woven fabric substrate is a melt-blown non-woven fabric made of polyolefin or polyamide as a fiber raw material, because it does not undergo graft polymerization treatment, and can be used exclusively for removing fine particles, and (i) Fiber diameter is 0.2-5 μm, (ii) average pore diameter is 0.2-20 μm, (iii) basis weight is 2-60 g / m 2 , (iv) fiber filling is 10-40%, and (v) It is desirable that the thickness is 0.02 to 0.6 mm.
In addition, the said thickness is a range including the thickness of the nonwoven fabric raw fabric and the processed nonwoven fabric adjusted by the hot press mentioned later.
また、非グラフト重合不織布は、液体濾過の性能（微粒子除去機能）に寄与するものであるから、非グラフト重合不織布の繊維構造をグラフト重合不織布より密にし、上記の範囲が好ましい。
特に濾過精度は、繊維径と平均孔径が小なるほど向上するので、そのような性状を付与できる不織布としては、極細連続繊維からなるメルトブロー法不織布が好ましい。その素材には、ポリエチレン、ポリアミド、ポリプロピレン、ポリブチレンテレフタレートなどが挙げられる。その中では、ポリマー本来の紡出性が高く、細繊維が得やすいというほか、熱カレンダ処理も容易に可能であるという観点から、ポリプロピレンが微粒子除去用の不織布濾材として、好適である。
非グラフト重合不織布は、メルトブロー不織布製造工程において、繊維径、目付け重量、厚み、充填率、通気度、ポアサイズ（孔径）などの諸性状が定められ、管理された原反として供給される。それによって、様々なレベルの微粒子濾過精度が付与される。
Further, since the non-grafted non-woven fabric contributes to the performance of liquid filtration (fine particle removing function), the fiber structure of the non-grafted non-woven fabric is made denser than the graft-polymerized non-woven fabric, and the above range is preferable.
In particular, the filtration accuracy improves as the fiber diameter and the average pore diameter become smaller. Therefore, as the nonwoven fabric capable of imparting such properties, a melt blown nonwoven fabric made of ultrafine continuous fibers is preferable. Examples of the material include polyethylene, polyamide, polypropylene, and polybutylene terephthalate. Among them, polypropylene is suitable as a non-woven filter medium for removing fine particles from the viewpoint of high spinnability inherent in the polymer, easy to obtain fine fibers, and easy heat calendering.
In the melt blown nonwoven fabric manufacturing process, the non-grafted nonwoven fabric has various properties such as fiber diameter, weight per unit area, thickness, filling rate, air permeability, pore size (pore diameter), and is supplied as a controlled raw material. Thereby, various levels of particulate filtration accuracy are imparted.
また、本発明における非グラフト重合不織布については、以下の用例を包含するものである。
（ｉ）原反単層をそのまま使用する。
（ｉｉ）複数の原反を重ね合わせて使用する。
（ｉｉｉ）上記単数または複数の原反を熱プレス加工により圧密・一体化して使用する。
これらの方法によって、微粒子濾過の精度を用途目的に応じて調節できることも、本発明の特徴である。特に、熱プレス加工による厚み調整により、繊維間の空隙率を減少させ、その結果、平均孔径を更に小さくして、濾過精度を向上させることができる。
なお、熱プレス加工の場合には、原反の厚みは、当初の厚みに対して、４０〜７０％の厚みになることが好ましい。圧縮が当初の厚みの４０％以下に圧縮されると、不織布がフィルム化するため、過度の濾過通液抵抗を招き、一方、７０％以上に厚みが保持されると期待するプレス効果が得にくい。
さらに、本発明では、繊維径、平均孔径などが異なる複数の非グラフト不織布を各種揃え、積層して、繊維径、孔径の勾配をもつ積層濾材を構成することができる。これは、いわゆるデプス型（深層型）濾材に分類され、微粒子の濾過精度ととともに捕捉容量（＝濾材寿命）をバランスよく向上させることができる。
また、非グラフト重合不織布の繊維径及び平均孔径を、グラフト重合不織布のそれよりも小さくすることによって、濾過原液に含まれる微粒子がグラフト重合不織布に付与されたイオン交換基と接触することを予防し、イオン交換能を健全に保ち、寿命を保持するための保護層の役目を担うこともできる。
Moreover, the following examples are included about the non-graft polymerization nonwoven fabric in this invention.
(I) The raw fabric monolayer is used as it is.
(Ii) A plurality of original fabrics are overlapped and used.
(Iii) One or a plurality of original fabrics are used by being consolidated and integrated by hot pressing.
It is also a feature of the present invention that the accuracy of particulate filtration can be adjusted according to the purpose of use by these methods. In particular, by adjusting the thickness by hot pressing, the porosity between the fibers can be reduced, and as a result, the average pore diameter can be further reduced and the filtration accuracy can be improved.
In the case of hot pressing, the thickness of the original fabric is preferably 40 to 70% of the original thickness. When the compression is compressed to 40% or less of the original thickness, the nonwoven fabric forms a film, which causes excessive filtration resistance, and on the other hand, it is difficult to obtain the press effect expected to maintain the thickness to 70% or more. .
Furthermore, in the present invention, a plurality of non-grafted nonwoven fabrics having different fiber diameters, average pore diameters, and the like can be prepared and laminated in various ways to constitute a laminated filter medium having a fiber diameter and pore diameter gradient. This is classified into a so-called depth type (deep layer) filter medium, and it is possible to improve the trapping capacity (= filter medium life) in a well-balanced manner together with the filtration accuracy of fine particles.
In addition, by making the fiber diameter and average pore diameter of the non-grafted polymer nonwoven fabric smaller than that of the graft polymerized nonwoven fabric, it is possible to prevent the fine particles contained in the filtration stock solution from coming into contact with the ion exchange groups attached to the graft polymerized nonwoven fabric. It can also serve as a protective layer for keeping the ion exchange capacity healthy and maintaining the lifetime.
３．液体濾過用カートリッジフィルタ
本発明の液体濾過用カートリッジフィルタは、上記異種・複数の不織布の濾材をロール上に巻き回す加工（ワインドタイプ）またはプリーツ加工（プリーツタイプ）して、ハウジングに収納するカートリッジフィルタである。また、円盤上に打ち抜き、カラム内に積層することにも、応用することができる。
前記したように、本発明では、カートリッジフィルタにおける濾材が、単層単独ではなく、異なる性状・性能をもった異種素材の不織布よりなる複層品、すなわち、グラフト重合によってイオン交換基及び／又はキレート基を有する不織布と、繊維径、平均孔径の異なる非グラフト重合不織布との組み合わせである。このような構成により、高度の化学吸着性と微粒子濾過寿命・精度を両立させた精密液体濾過用カートリッジフィルタとすることができる。例えば、同一のカートリッジフィルタを用いて、半導体製造プロセスなどで使用される洗浄用水やフォトレジストなどの薬液から、微粒子のみならず遊離の金属イオン、更にはコロイド微粒子の除去をも可能となる。
3. Cartridge Filter for Liquid Filtration The cartridge filter for liquid filtration of the present invention is a cartridge filter that is wound (wind type) or pleated (pleat type) on the roll of the above-mentioned different / non-woven fabric filter media and accommodated in a housing. It is. It can also be applied to punching on a disk and stacking in a column.
As described above, in the present invention, the filter medium in the cartridge filter is not a single layer alone, but a multilayer product composed of different types of nonwoven fabrics having different properties and performances, that is, ion exchange groups and / or chelates by graft polymerization. This is a combination of a nonwoven fabric having a group and a non-grafted polymerized nonwoven fabric having different fiber diameters and average pore diameters. With such a configuration, it is possible to provide a cartridge filter for precision liquid filtration that achieves both high chemical adsorption and fine particle filtration life and accuracy. For example, by using the same cartridge filter, not only fine particles but also free metal ions and further colloidal fine particles can be removed from chemicals such as cleaning water and photoresist used in a semiconductor manufacturing process.
４．用途
本発明の液体濾過用カートリッジフィルタは、例えば、半導体素子製造プロセスの薬液供給ラインにおいて、薬液タンクを循環する経路の途中に設置することなどにより、従来の濾過工程に何ら変更を加える必要がなく、半導体製造プロセスなどで現在使用されている実装置への適用が非常に容易である。
また、本発明の液体濾過用カートリッジフィルタは、半導体デバイスや液晶を製造する工程で必要な洗浄水における金属イオンなどの陽イオンや塩素などの陰イオンの除去、医薬用および医薬器具洗浄に必要な水からの不純物の除去、或いは、精製水の製造や食品分野における原料水からの塩類除去や有害な有機物、金属の除去など精密液体濾過に関する分野、家庭用飲料水の精製などに適用される。また、工業排水における有価金属の回収、または有害金属の除去に関する分野に使用されるフィルタ分野にも、適用される。
中でも、超ＬＳＩ製造プロセスにおけるシリコンウエハの洗浄水は、ＬＳＩ集積度が年々増加するに伴い最も不純物の少ない水が要求されるため、この分野に好適に用いられる。
4). Applications The cartridge filter for liquid filtration of the present invention does not require any changes to the conventional filtration process, for example, by installing it in the middle of the path for circulating the chemical tank in the chemical supply line of the semiconductor element manufacturing process. It is very easy to apply to actual devices currently used in semiconductor manufacturing processes.
Further, the cartridge filter for liquid filtration of the present invention is necessary for removing cations such as metal ions and anions such as chlorine in the washing water necessary in the process of manufacturing semiconductor devices and liquid crystals, and for washing pharmaceuticals and medical instruments. It is applied to the field of precision liquid filtration, such as the removal of impurities from water, the production of purified water, the removal of salts from raw water in the food field, the removal of harmful organic substances and metals, and the purification of domestic drinking water. Moreover, it is applied also to the filter field | area used in the field | area regarding collection | recovery of valuable metals in industrial wastewater, or removal of a toxic metal.
Above all, the cleaning water for silicon wafers in the VLSI manufacturing process is preferably used in this field because water with the least amount of impurities is required as the degree of LSI integration increases year by year.
以下に本発明を実施例で具体的に説明するが、本発明は、これらの実施例のみに限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to only these examples.
実施例で評価した物性の測定方法の概要を以下に示す。
（１）不織布の（平均）繊維径：
対象の不織布基材を電子線走査型顕微鏡にて観察し、その拡大写真上の繊維の径を、ランダムに１０本以上計測し、その算術平均より求める。その際の適用倍率は、その基布の繊維径にもよるが、１，０００〜５，０００倍より、適宜選定する。
（２）不織布の厚み：
厚み測定器（（株）ミツトヨ製、商品名ＡＢＳＯＬＵＴＥ ＩＤ−Ｃ１０１２Ｃ）を用いて、２．９４ｃＮ／ｃｍ２荷重で５箇所測定し、その平均値を求めた。
（３）不織布の目付け重量：
試料長さ方向より、１００×１００ｍｍの試験片を採取し、水分平衡状態の重さを測定し、１ｍ２当たりに換算して求めた。
（４）不織布の平均孔径：
バブルポイント法（ＡＳＴＭ Ｆ３１６−８６、ＪＩＳ Ｋ３８３２）に基づき、ＰＭＩ社製自動細孔径分布測定器によって測定した。
（５）不織布の繊維充填率：
次の数式から算出した。
繊維充填率（％）＝［目付け重量（ｇ／ｍ２）／厚み（ｍｍ）／有機繊維材料の比重／１０００］×１００
The outline of the method for measuring physical properties evaluated in Examples is shown below.
(1) (Average) fiber diameter of nonwoven fabric:
The target nonwoven fabric substrate is observed with an electron beam scanning microscope, and the diameter of the fibers on the enlarged photograph is randomly measured and 10 or more are obtained from the arithmetic average. The application magnification at that time is appropriately selected from 1,000 to 5,000 times depending on the fiber diameter of the base fabric.
(2) Thickness of the nonwoven fabric:
Using a thickness measuring instrument (trade name ABSOLUTE ID-C1012C, manufactured by Mitutoyo Corporation), five points were measured with a 2.94 cN / cm 2 load, and the average value was obtained.
(3) Weight of nonwoven fabric:
From the sample length direction, a test piece of 100 × 100 mm was collected, and the weight in a water equilibrium state was measured and calculated per 1 m 2 .
(4) Average pore diameter of nonwoven fabric:
Based on the bubble point method (ASTM F316-86, JIS K3832), it measured with the automatic pore diameter distribution measuring device by PMI.
(5) Fiber filling rate of nonwoven fabric:
It was calculated from the following formula.
Fiber filling rate (%) = [weight per unit area (g / m 2 ) / thickness (mm) / specific gravity of organic fiber material / 1000] × 100
（６）不織布のグラフト率：
グラフト前後の不織布重量より、下式に基づき算出した。
グラフト率（％）＝１００×（Ｂ―Ａ）／Ａ
（式中、Ａはグラフト前の不織布基材重量、Ｂはグラフト後の不織布基材重量を表す。）
（７）不織布の官能基密度：
以下の式にて算出される。
官能基密度（ｍ−ｍｏｌ／ｇ）＝導入された官能基のモル数［ｍ−ｍｏｌ］／機能性不織布の重量［ｇ］
ここで機能性不織布とは、官能基導入後の不織布をいう。
（８）粒子濾過率：
グラフト／非グラフト重合不織布を重ね併せて円盤状に切り抜いて測定濾材とし、吸引フラスコとフィルターホルダーに固定し、平均１μｍ径の標準微粒子を懸濁させた水の濾過を行い、この濾過液を微粒子カウンター（パーティクルカウンター）にて計測し、濾過前後の微粒子数を測定し、粒子濾過率を算出した。
(6) Graft ratio of nonwoven fabric:
Based on the weight of the nonwoven fabric before and after grafting, calculation was performed based on the following formula.
Graft ratio (%) = 100 × (BA) / A
(In the formula, A represents the nonwoven fabric substrate weight before grafting, and B represents the nonwoven fabric substrate weight after grafting.)
(7) Functional group density of nonwoven fabric:
It is calculated by the following formula.
Functional group density (m-mol / g) = number of moles of introduced functional group [m-mol] / weight of functional nonwoven fabric [g]
Here, the functional non-woven fabric refers to a non-woven fabric after introduction of a functional group.
(8) Particle filtration rate:
Graft / non-grafted non-woven fabrics are overlapped and cut into a disk shape to make a measurement filter medium, fixed to a suction flask and filter holder, filtered with water in which standard fine particles with an average diameter of 1 μm are suspended, and the filtrate is finely divided. The particle filtration rate was calculated by measuring with a counter (particle counter), measuring the number of fine particles before and after filtration.
［実施例１］
繊維径が９．６μｍの高密度ポリエチレン（ＨＤＰＥ）原料のメルトブロー法不織布（目付け重量８０ｇ／ｍ２）を用い、窒素雰囲気下で、ドライアイスで冷却しつつ、２０ｋＧｙのガンマ線（コバルト６０）を照射した。
次に、照射後のメルトブロー不織布を、Ｔｗｅｅｎ２０（関東化学株式会社）０．５％を含む水溶液にグリシジルメタクリレート（ＧＭＡ）５％を加えて調整したエマルジョン溶液に、大気下にて浸漬し、４０℃に保持しながらグラフト重合を行い、ＧＭＡグラフト率が１５０％のグラフト重合不織布を得た。
このＧＭＡグラフト重合不織布を、１０％亜硫酸ナトリウム水溶液で８０℃、４時間浸漬処理し、基材の単位重量（ｇ）当たりの官能基密度２．６５ｍ−ｍｏｌ／ｇのスルホン酸基を導入したグラフト重合不織布を得た。
[Example 1]
Using a melt blown nonwoven fabric (weight per unit weight of 80 g / m 2 ) made of high-density polyethylene (HDPE) with a fiber diameter of 9.6 μm, irradiated with 20 kGy of gamma rays (cobalt 60) while being cooled with dry ice in a nitrogen atmosphere did.
Next, the melt-blown nonwoven fabric after irradiation was immersed in an emulsion solution prepared by adding 5% glycidyl methacrylate (GMA) to an aqueous solution containing 0.5% Tween 20 (Kanto Chemical Co., Ltd.) at 40 ° C. Graft polymerization was carried out while maintaining the same, and a graft-polymerized nonwoven fabric having a GMA graft ratio of 150% was obtained.
This GMA graft-polymerized non-woven fabric was immersed in a 10% aqueous sodium sulfite solution at 80 ° C. for 4 hours, and grafted with a sulfonic acid group having a functional group density of 2.65 m-mol / g per unit weight (g) of the substrate. A polymerized nonwoven fabric was obtained.
一方、繊維径０．６μｍのメルトブロー法ポリプロピレン（ＰＰ）不織布原反（目付け重量１５ｇ／ｍ２）１枚を用い、上記のグラフト重合不織布と積層し、円盤状に切り抜いて測定濾材とした。この試料に対して平均１μｍ径の標準微粒子を懸濁させた水の濾過を行い、濾過液を微粒子カウンター（パーティクルカウンター）にて計測し、濾過前後の微粒子数を測定した結果、８０％の粒子濾過率を得た。 On the other hand, one melt blown polypropylene (PP) non-woven fabric (fiber weight: 15 g / m 2 ) having a fiber diameter of 0.6 μm was laminated with the above graft-polymerized non-woven fabric and cut into a disk shape to obtain a measurement filter medium. The sample was filtered with water in which standard fine particles with an average diameter of 1 μm were suspended, the filtrate was measured with a fine particle counter (particle counter), and the number of fine particles before and after filtration was measured. A filtration rate was obtained.
上記濾材を幅２５ｃｍに裁断し、高密度ポリエチレン製コアの周囲を取り巻くように設置し、山高さ１２ｍｍ、山数８０にプリーツ加工し、継ぎ目を超音波加工にてつなぎ、端面を、エンドキャップを用いて、熱板加工にてシールし、内径７６ｍｍの円筒形カートリッジ容器に収納した（以下の実施例において共通操作）。
この時の濾材の展開面積は、０．５ｍ２であった。また、上記コア材に、非グラフト重合不織布及びグラフト重合不織布を交互に継ぎ巻きにしたロールフィルタを、カートリッジ容器に収納した。この時の総巻長さは、１．８ｍであり、本実施例１では、グラフト重合不織布を１．２ｍ，非グラフト重合不織布を０．６ｍの長さに配分した。このロールフィルタの場合も幅２５ｃｍとしてので、その展開面積は、０．３ｍ２に設定された。
このようにして製作したカートリッジフィルタの性能を表１に示す。
なお、カートリッジフィルタの１本当たりの官能基量（ｍ−ｍｏｌ／フィルタ）は、上述に示すプリーツ又はロール加工による展開面積と、基材の官能基密度（ｍ−ｍｏｌ／ｇ）を基材の目付け重量（ｇ／ｍ２）当たりに換算した値（ｍ−ｍｏｌ／ｍ２）との積によって求めた。（尚、表１などでは、Ｔｏｔａｌ ｍ−ｍｏｌ／プリーツ又はロールなどと表記した。）
The filter medium is cut to a width of 25 cm, installed so as to surround the periphery of the high-density polyethylene core, pleated to a height of 12 mm and with a number of peaks of 80, the seams are joined by ultrasonic processing, and the end face is attached to the end cap. It was sealed by hot plate processing and stored in a cylindrical cartridge container having an inner diameter of 76 mm (common operation in the following examples).
The development area of the filter medium at this time was 0.5 m 2 . Further, a roll filter in which a non-graft polymerized nonwoven fabric and a graft polymerized nonwoven fabric were alternately joined to the core material was housed in a cartridge container. The total winding length at this time was 1.8 m. In Example 1, the graft-polymerized nonwoven fabric was distributed to a length of 1.2 m, and the non-grafted polymerized nonwoven fabric was distributed to a length of 0.6 m. In the case of this roll filter, the width is set to 25 cm, so that the development area is set to 0.3 m 2 .
The performance of the cartridge filter thus manufactured is shown in Table 1.
In addition, the amount of functional groups per cartridge filter (m-mol / filter) is determined based on the development area by pleating or roll processing described above and the functional group density (m-mol / g) of the substrate. It calculated | required by the product with the value (m-mol / m < 2 >) converted per basis weight (g / m < 2 >). (In Table 1, etc., it is expressed as Total m-mol / pleat or roll)
［実施例２（参考例）］
平均繊維径１８μｍの高密度ポリエチレン原料の短繊維を、カード法サーマルボンド不織布化し、窒素雰囲気下でドライアイス冷却しつつ、１００ｋＧｙのガンマ線（コバルト６０）を照射した。
グラフト重合処理は、実施例１と同様に行った結果、ＧＭＡのグラフト率１６０％のグラフト重合不織布を得た。
これを実施例１と同様の方法で、スルホン化し、基材の単位重量当たりの官能基密度２．７１ｍ−ｍｏｌ／ｇを導入したグラフト重合不織布を得た。
[Example 2 (reference example) ]
Short fibers of a high-density polyethylene material having an average fiber diameter of 18 μm were made into a card method thermal bond nonwoven fabric and irradiated with 100 kGy of gamma rays (cobalt 60) while being cooled with dry ice in a nitrogen atmosphere.
The graft polymerization treatment was carried out in the same manner as in Example 1. As a result, a graft polymer nonwoven fabric having a GMA graft ratio of 160% was obtained.
This was sulfonated in the same manner as in Example 1 to obtain a graft-polymerized nonwoven fabric introduced with a functional group density of 2.71 m-mol / g per unit weight of the substrate.
一方、非グラフト基材として、平均繊維径０．６μｍのメルトブロー法ポリプロピレン不織布原反（目付け重量１５ｇ／ｍ２）１枚を用い、グラフト重合不織布と積層し、円盤状に切り抜いて吸引フラスコとフィルターホルダに固定し、これを測定濾材として、１μｍ径の標準微粒子を懸濁させた水の濾過を行い、濾過液をパーティクルカウンターにて計測し、濾過前後の微粒子数を測定した結果、７２％の粒子濾過率を得た。
また、この不織布積層品を、実施例１に示す要領にて、プリーツ及びロール巻き加工してカートリッジフィルタを製作した。その性能を表１に示す。
On the other hand, as a non-graft base material, a melt blown polypropylene nonwoven fabric having an average fiber diameter of 0.6 μm (weight per unit weight 15 g / m 2 ) is used, laminated with a graft-polymerized nonwoven fabric, cut out into a disk shape, and a suction flask and filter The sample was fixed to a holder, and this was used as a measurement filter medium. Water was suspended in 1 μm diameter standard fine particles, the filtrate was measured with a particle counter, and the number of fine particles before and after filtration was measured. As a result, 72% Particle filtration rate was obtained.
In addition, this nonwoven fabric laminate product was pleated and rolled in the manner shown in Example 1 to produce a cartridge filter. The performance is shown in Table 1.
［実施例３（参考例）］
平均繊維径が６．３μｍの高密度ポリエチレン原料のメルトブロー法不織布（目付け重量４９ｇ／ｍ２）を用い、窒素雰囲気下、ドライアイスで冷却しつつ、２０ｋＧｙのガンマ線（コバルト６０）を照射した。
次に、照射後のメルトブロー不織布を、Ｔｗｅｅｎ２０（関東化学株式会社）０．５％を含む水溶液にグリシジルメタクリレート（ＧＭＡ）５％を加えて調整したエマルジョン溶液に、大気下にて浸漬し、４０℃に保持しながらグラフトを行い、ＧＭＡグラフト率が１８０％のグラフト重合不織布を得た。
得られたＧＭＡグラフト重合不織布用い、アミノ化処理を行った。即ち、トリメチルアミン塩酸塩の１０％水溶液を調整し、この水溶液に１ＮのＮａＯＨを投入してＰＨ９．４とした後、上記ＧＭＡ不織布を投入し６０℃、１時間処理し、イオン交換容量２．８１ｍｅｑ／ｇのトリメチルアミン基付与型メルトブロー不織布、すなわち、アミノ基を導入したグラフト重合不織布を得た。
[Example 3 (reference example) ]
A melt blown non-woven fabric (weighing weight 49 g / m 2 ) of a high-density polyethylene material having an average fiber diameter of 6.3 μm was used and irradiated with 20 kGy gamma rays (cobalt 60) while being cooled with dry ice in a nitrogen atmosphere.
Next, the melt-blown nonwoven fabric after irradiation was immersed in an emulsion solution prepared by adding 5% glycidyl methacrylate (GMA) to an aqueous solution containing 0.5% Tween 20 (Kanto Chemical Co., Ltd.) at 40 ° C. Grafting was carried out while holding, and a graft-polymerized nonwoven fabric having a GMA graft ratio of 180% was obtained.
Amination treatment was performed using the obtained GMA graft-polymerized nonwoven fabric. That is, a 10% aqueous solution of trimethylamine hydrochloride was prepared, and 1N NaOH was added to this aqueous solution to make pH 9.4. Then, the above-mentioned GMA nonwoven fabric was added, treated at 60 ° C. for 1 hour, and an ion exchange capacity of 2.81 meq. / G trimethylamine group-added meltblown nonwoven fabric, that is, a graft-polymerized nonwoven fabric having an amino group introduced therein.
一方、非グラフト基材として、平均繊維径４．３μｍのメルトブロー法ポリプロピレン不織布原反（目付け重量３０ｇ／ｍ２）１枚を、上記グラフト重合不織布と積層し、測定濾材とした。
上記濾材を、円盤状に切り抜いて吸引フラスコとフィルターホルダに固定し、１μｍ径の標準微粒子を懸濁させた水の濾過を行い、濾過液をパーティクルカウンターにて計測し、濾過前後の微粒子数を測定した結果、６１％の粒子濾過率を得た。この濾材を用いて、実施例１に示す要領にて製作したカートリッジフィルタの性能を表１に示す。
On the other hand, as a non-graft base material, one melt blown polypropylene nonwoven fabric (weight per unit area: 30 g / m 2 ) having an average fiber diameter of 4.3 μm was laminated with the graft polymerized nonwoven fabric to obtain a measurement filter medium.
The filter medium is cut out in a disk shape and fixed to a suction flask and a filter holder, filtered with water in which standard fine particles with a diameter of 1 μm are suspended, the filtrate is measured with a particle counter, and the number of fine particles before and after filtration is determined. As a result of the measurement, a particle filtration rate of 61% was obtained. Table 1 shows the performance of the cartridge filter manufactured by the procedure shown in Example 1 using this filter medium.
［実施例４］
実施例１と実施例３により得られた２種のイオン交換性不織布と、一方、非グラフト重合不織布として、実施例１で用いたメルトブロー法ポリプロピレン不織布原反（目付重量１５ｇ／ｍ２、繊維径０．６μｍ）を積層して濾材とし、実施例１と同様の濾過試験を行った結果、８５％の濾過率を得た。
これらの濾材を用いて、実施例１に示す要領にて製作したカートリッジフィルタの性能を表１に示す。
[Example 4]
The two types of ion-exchangeable nonwoven fabrics obtained in Example 1 and Example 3, and the melt blown polypropylene nonwoven fabric used in Example 1 (weight per unit area 15 g / m 2 , fiber diameter) 0.6 μm) was used as a filter medium, and the same filtration test as in Example 1 was performed. As a result, a filtration rate of 85% was obtained.
Table 1 shows the performance of the cartridge filter manufactured by using these filter media according to the procedure shown in Example 1.
［実施例５（参考例）］
平均繊維径が５μｍのメルトブロー法ポリアミド６（ＰＡ６）不織布に、窒素雰囲気下、ドライアイスで冷却しつつ、２０ｋＧｙのガンマ線（コバルト６０）を照射した。
次に、実施例１と同様の方法にてＧＭＡをグラフトし、１８３％のグラフト率を得た。
この不織布をイミノジ酢酸ナトリウム８．５％水溶液に浸漬し、８０℃、２０時間処理を行い、基材の単位重量当たりの官能基密度２．５５ｍ−ｍｏｌ／ｇのイミノジ酢酸基付与型機能性不織布を得た。
[Example 5 (reference example) ]
A melt blown polyamide 6 (PA6) nonwoven fabric having an average fiber diameter of 5 μm was irradiated with 20 kGy of gamma rays (cobalt 60) while being cooled with dry ice in a nitrogen atmosphere.
Next, GMA was grafted in the same manner as in Example 1 to obtain a graft ratio of 183%.
This non-woven fabric is immersed in an 8.5% aqueous solution of sodium iminodiacetate, treated at 80 ° C. for 20 hours, and an iminodiacetate group-added functional non-woven fabric having a functional group density of 2.55 m-mol / g per unit weight of the substrate. Got.
一方、非グラフト重合不織布として、平均繊維径０．６μｍのメルトブロー法ポリプロピレン不織布原反（目付け重量１５ｇ／ｍ２）１枚を用い、上記グラフト重合不織布と積層し、測定濾材とした。
上記濾材を、実施例１と同様の濾過試験を行った結果、８１％の濾過率を得た。
この濾材を用いて、実施例１に示す要領にて製作したカートリッジフィルタの性能を表２に示す。
On the other hand, as a non-grafted non-woven fabric, one melt blown polypropylene non-woven fabric having an average fiber diameter of 0.6 μm (weighing weight 15 g / m 2 ) was laminated with the above graft-polymerized non-woven fabric to obtain a measurement filter medium.
The filter medium was subjected to the same filtration test as in Example 1. As a result, an filtration rate of 81% was obtained.
Table 2 shows the performance of a cartridge filter manufactured by the procedure shown in Example 1 using this filter medium.
［実施例６］
平均繊維径２０μｍのＰＶＡ短繊維を使用し、湿式法にて目付け重量６０ｇ／ｍ２に調製された不織布を、窒素雰囲気下、ドライアイスで冷却しつつ、３０ｋＧｙのガンマ線（コバルト６０）を照射した。
次に、照射後のメルトブロー不織布を、Ｔｗｅｅｎ２０（関東化学株式会社）０．５％を含む水溶液にグリシジルメタクリレート（ＧＭＡ）５％を加えて調整したエマルジョン溶液に、大気下にて浸漬し、４０℃に保持しながらグラフトを行い、ＧＭＡグラフト率が１１５％のグラフト重合不織布を得た。
このグラフト重合不織布を１０％亜硫酸ナトリウム水溶液で８０℃、４時間処理し、基材の単位重量当たりの官能基密度２．５９ｍ−ｍｏｌ／ｇのスルホン酸基を導入したグラフト重合不織布を得た。
[Example 6]
A non-woven fabric prepared using a PVA short fiber having an average fiber diameter of 20 μm and a basis weight of 60 g / m 2 by a wet method was irradiated with 30 kGy gamma rays (cobalt 60) while being cooled with dry ice in a nitrogen atmosphere. .
Next, the melt-blown nonwoven fabric after irradiation was immersed in an emulsion solution prepared by adding 5% glycidyl methacrylate (GMA) to an aqueous solution containing 0.5% Tween 20 (Kanto Chemical Co., Ltd.) at 40 ° C. Grafting was carried out while maintaining the temperature, and a graft-polymerized nonwoven fabric having a GMA graft ratio of 115% was obtained.
This graft-polymerized nonwoven fabric was treated with a 10% aqueous sodium sulfite solution at 80 ° C. for 4 hours to obtain a graft-polymerized nonwoven fabric into which a sulfonic acid group having a functional group density of 2.59 m-mol / g per unit weight of the substrate was introduced.
一方、非グラフト重合不織布として、平均繊維径０．６μｍのメルトブロー法ポリプロピレン不織布原反（目付け重量１５ｇ／ｍ２）１枚を用い、上記グラフト重合不織布と積層し、濾材とした。
上記濾材を、これまでと同様の濾過試験を行った結果、７５％の濾過率を得た。
この濾材を用いて、実施例１に示す要領にて製作したカートリッジフィルタの性能を表２に示す。
On the other hand, as a non-graft polymerized nonwoven fabric, one melt blown polypropylene nonwoven fabric having a mean fiber diameter of 0.6 μm (weight per unit area: 15 g / m 2 ) was used and laminated with the graft polymerized nonwoven fabric to obtain a filter medium.
The filter medium was subjected to the same filtration test as before, and a filtration rate of 75% was obtained.
Table 2 shows the performance of a cartridge filter manufactured by the procedure shown in Example 1 using this filter medium.
［実施例７（参考例）］
グラフト重合不織布として、実施例２で得られた、スルホン酸基を導入したカード法サーマルボンド法高密度ポリエチレン不織布を用いた。
一方、非グラフト重合不織布として、平均繊維径０．６μｍのメルトブロー法ポリプロピレン不織布原反（目付け重量１５ｇ／ｍ２、厚み０．１２ｍｍ）を熱カレンダロールでプレス加工（加工温度１３０℃）を施し、厚みを０．０５ｍｍまでに圧密した。その結果、平均孔径が６μｍから３．５μｍに減少した。
上記グラフト重合不織布に、この非グラフト重合不織布を積層し、濾材にして、実施例１と同様の方法にて、濾過率を測定したところ、８８％であった。この濾材を用いて、実施例１に示す要領にて製作したカートリッジフィルタの性能を表２に示す。
[Example 7 (reference example) ]
The card polymerization thermal bond method high density polyethylene nonwoven fabric which introduce | transduced the sulfonic acid group obtained in Example 2 was used as the graft polymerization nonwoven fabric.
On the other hand, as a non-graft polymerized non-woven fabric, a melt blown polypropylene non-woven fabric with an average fiber diameter of 0.6 μm (weight per unit weight 15 g / m 2 , thickness 0.12 mm) is subjected to press processing (processing temperature 130 ° C.) with a heat calender roll, The thickness was consolidated to 0.05 mm. As a result, the average pore diameter decreased from 6 μm to 3.5 μm.
When this non-grafted non-woven fabric was laminated on the above graft-polymerized non-woven fabric and used as a filter medium, the filtration rate was measured by the same method as in Example 1. As a result, it was 88%. Table 2 shows the performance of a cartridge filter manufactured by the procedure shown in Example 1 using this filter medium.
［実施例８（参考例）］
グラフト重合不織布として、実施例３で得られたアミノ基導入のメルトブロー法高密度ポリエチレン不織布（目付重量４９ｇ／ｍ２）を用いた。
一方、非グラフト重合不織布として、繊維径５．６μｍのメルトブロー法高密度ポリエチレン不織布原反（目付け重量８１ｇ／ｍ２、厚み０．５３ｍｍ、平均孔径１６μｍ）を、熱ロールでプレス加工（加工温度１３０℃）を施し、厚みを０．３２ｍｍまでに圧密した。その結果、平均孔径が９μｍに減少した。
上記グラフト重合不織布に、この非グラフト重合不織布を積層して、濾材にして、実施例１と同様の方法にて、濾過率を測定したところ、６６％であった。
この濾材を用いて、実施例１に示す要領にて製作したカートリッジフィルタの性能を表２に示す。
[Example 8 (reference example) ]
As the graft polymerization nonwoven fabric, the amino group-introduced melt-blowing high-density polyethylene nonwoven fabric (weight per unit area 49 g / m 2 ) obtained in Example 3 was used.
On the other hand, as a non-graft polymerized nonwoven fabric, a melt blown high-density polyethylene nonwoven fabric having a fiber diameter of 5.6 μm (weight per unit area 81 g / m 2 , thickness 0.53 mm, average pore diameter 16 μm) is pressed with a hot roll (processing temperature 130). C.) and the thickness was consolidated to 0.32 mm. As a result, the average pore diameter was reduced to 9 μm.
When this non-grafted non-woven fabric was laminated on the above graft-polymerized non-woven fabric to obtain a filter medium, the filtration rate was measured by the same method as in Example 1. As a result, it was 66%.
Table 2 shows the performance of a cartridge filter manufactured by the procedure shown in Example 1 using this filter medium.
［実施例９（参考例）］
グラフト重合不織布として、実施例３で得られたアミノ基導入のメルトブロー法高密度ポリエチレン不織布（目付重量４９ｇ／ｍ２）を用いた。
一方、非グラフト重合不織布として、平均繊維径０．６μｍのメルトブロー法ポリプロピレン不織布原反（目付け重量１５ｇ／ｍ２、厚み０．１２ｍｍ）を２枚重ねて、熱ロールでプレス加工（加工温度）を施し、全厚みを０．１０ｍｍまでに、圧密した。その結果、平均孔径が１．６μｍとなった。
上記グラフト重合不織布に、この非グラフト重合不織布を積層し、濾材にして、濾過率を測定したところ、９５％であった。
この濾材を用いて、実施例１に示す要領にて製作したカートリッジフィルタの性能を表３に示す。
[Example 9 (Reference example) ]
As the graft polymerization nonwoven fabric, the amino group-introduced melt-blowing high-density polyethylene nonwoven fabric (weight per unit area 49 g / m 2 ) obtained in Example 3 was used.
On the other hand, as a non-grafted non-woven fabric, two sheets of melt blown polypropylene non-woven fabric (weight per unit weight 15 g / m 2 , thickness 0.12 mm) with an average fiber diameter of 0.6 μm are stacked and pressed with a hot roll (processing temperature). And then consolidated to a total thickness of 0.10 mm. As a result, the average pore diameter was 1.6 μm.
When this non-grafted non-woven fabric was laminated on the above graft-polymerized non-woven fabric to make a filter medium and the filtration rate was measured, it was 95%.
Table 3 shows the performance of a cartridge filter manufactured using the filter medium in the manner shown in Example 1.
［比較例１］
非グラフト重合不織布を用いずに、実施例１のグラフト重合不織布であるスルホン化メルトブロー不織布単層の濾過率を、前記実施例１と同様の方法にて測定した。その濾過率は、１０％であった。評価結果を表３に示す。
[Comparative Example 1]
The filtration rate of the sulfonated meltblown nonwoven single layer which is the graft polymerization nonwoven fabric of Example 1 was measured by the same method as in Example 1 without using the non-graft polymerization nonwoven fabric. The filtration rate was 10%. The evaluation results are shown in Table 3.
［比較例２］
非グラフト重合不織布を用いずに、実施例２のグラフト重合不織布であるスルホン化短繊維不織布単層の濾過効率を、前記実施例１と同様の方法にて測定した。その濾過効率は、０％であった。評価結果を表３に示す。
[Comparative Example 2]
The filtration efficiency of the sulfonated short fiber nonwoven fabric single layer, which is the graft polymerized nonwoven fabric of Example 2, was measured by the same method as in Example 1 without using the non-grafted nonwoven fabric. The filtration efficiency was 0%. The evaluation results are shown in Table 3.
［比較例３］
非グラフト重合不織布を用いずに、実施例３のグラフト重合不織布であるアミノ化メルトブロー不織布の濾過効率を測定したところ、その濾過効率は２３％であった。評価結果を表３に示す。
[Comparative Example 3]
When the filtration efficiency of the aminated melt blown nonwoven fabric which is the graft polymerized nonwoven fabric of Example 3 was measured without using the non-grafted polymer nonwoven fabric, the filtration efficiency was 23%. The evaluation results are shown in Table 3.
表１〜３や、実施例と比較例の対比から明らかなように、非グラフト重合不織布では、原反そのものの繊維径、平均孔径をグラフト重合不織布のそれよりも小さく設定でき、また、熱ロールで、単独または複数重ねて、圧密することによって、さらに平均孔径を小さくすることができるので、微粒子の濾過に好適であって、この非グラフト重合不織布とイオン交換基を付与したグラフト重合不織布とを複合することによって、イオン交換能と高精度の微粒子濾過機能を具備したカートリッジフィルタを実現することができる。
一方、比較例１〜３で示すように、グラフト重合不織布のみでは、１μｍ径の微粒子の除去は、殆ど不可能であることがわかる。
As is clear from Tables 1 to 3 and the comparison between Examples and Comparative Examples, in the non-graft polymerized nonwoven fabric, the fiber diameter and average pore diameter of the raw fabric itself can be set smaller than that of the graft polymerized nonwoven fabric, and the heat roll The average pore diameter can be further reduced by single or multiple overlapping and consolidation, so that it is suitable for filtration of fine particles, and this non-graft polymerized nonwoven fabric and a graft polymerized nonwoven fabric provided with an ion exchange group are used. By combining them, it is possible to realize a cartridge filter having an ion exchange capacity and a highly accurate fine particle filtering function.
On the other hand, as shown in Comparative Examples 1 to 3, it is found that removal of fine particles having a diameter of 1 μm is almost impossible with only the graft-polymerized nonwoven fabric.
本発明の液体濾過用カートリッジフィルタは、高効率のイオン捕捉に適したグラフト重合不織布と、微粒子捕捉効率の高い非グラフト重合不織布とを複合することによって、濾過性能とイオン交換能を高いレベルでバランスさせた、イオン除去と微粒子除去の能力を高度に兼ね備え、信頼性が高いという効果を奏し、精密液体濾過用として、好適に用いられる。特に、半導体産業において使用される純水、薬液或いは溶剤などの精製に特に好ましく利用することのでき、超ＬＳＩ製造プロセスにおけるシリコンウエハの洗浄水向け濾過の分野などで有用であり、産業上また安全上において寄与することが大である。 The cartridge filter for liquid filtration of the present invention balances filtration performance and ion exchange capacity at a high level by combining a graft-polymerized nonwoven fabric suitable for high-efficiency ion trapping and a non-graft-polymerized nonwoven fabric with high particulate trapping efficiency. It has the ability to remove ions and fine particles, and has the effect of high reliability, and is suitably used for precision liquid filtration. In particular, it can be used particularly preferably for the purification of pure water, chemicals or solvents used in the semiconductor industry, and is useful in the field of filtration for cleaning water for silicon wafers in the VLSI manufacturing process. It is important to contribute to the above.
Claims (2)
該複数の不織布の少なくとも一種は、グラフト重合によりイオン交換基を有するグラフト重合不織布であり、該グラフト重合不織布は、イオン交換基がスルホン酸基、リン酸基、カルボン酸基、アミノ基、グルカミン酸基、又はイミノジ酢酸基から選択される少なくとも一種の官能基であり、かつグラフト重合される不織布原反は、ポリアミド、ポリオレフィン又はポリビニルアルコールを繊維原料とし、（ｉ）繊維径が５〜３０μｍ、（ｉｉ）平均孔径が３２〜６０μｍ、（ｉｉｉ）目付け重量が１０〜１００ｇ／ｍ ２ 、（ｉｖ）繊維充填率が５〜３０％、及び（ｖ）厚みが０．１〜１．０ｍｍであり、
他の一種は、該グラフト重合不織布より繊維径及び平均孔径が小さい非グラフト重合不織布であり、該非グラフト重合不織布は、ポリオレフィン又はポリアミドを繊維原料としたメルトブロー法不織布であって、（ｉ）繊維径が０．２〜５μｍ、（ｉｉ）平均孔径が６．０〜２０μｍ、（ｉｉｉ）目付け重量が２〜６０ｇ／ｍ ２ 、（ｉｖ）繊維充填率が１０〜４０％、及び（ｖ）厚みが０．０２〜０．６ｍｍである、
繊維径勾配型の複数濾材からなることを特徴とする液体濾過用カートリッジフィルタ。 A cartridge filter in which a plurality of non-woven fabrics are laminated and integrated, and wound into a pleated shape or a roll shape,
At least one of the plurality of nonwoven fabrics is a graft polymerization nonwoven fabric having an ion exchange group by graft polymerization, and the graft polymerization nonwoven fabric has an ion exchange group of a sulfonic acid group, a phosphate group, a carboxylic acid group, an amino group, and a glucamic acid. The nonwoven fabric raw material which is at least one functional group selected from a group or iminodiacetic acid group and is graft-polymerized is made of polyamide, polyolefin or polyvinyl alcohol as a fiber raw material, and (i) a fiber diameter of 5 to 30 μm, ( ii) an average pore diameter of 32 to 60 μm, (iii) a weight per unit area of 10 to 100 g / m 2 , (iv) a fiber filling ratio of 5 to 30%, and (v) a thickness of 0.1 to 1.0 mm,
Other kind is Ri fiber diameter and the average pore diameter is smaller ungrafted polymerized nonwoven der than the graft polymerization nonwoven, non-graft polymerization nonwoven, a polyolefin or a polyamide and a melt blown nonwoven fabric and fiber material, (i) Fibers The diameter is 0.2 to 5 μm, (ii) the average pore diameter is 6.0 to 20 μm, (iii) the basis weight is 2 to 60 g / m 2 , (iv) the fiber filling ratio is 10 to 40%, and (v) the thickness. There Ru 0.02~0.6mm der,
A cartridge filter for liquid filtration, comprising a plurality of filter media of a fiber diameter gradient type.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011104568A (en) * | 2009-11-20 | 2011-06-02 | Asahi Kasei Fibers Corp | High discreteness liquid filter |
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| US10722848B2 (en) * | 2015-10-23 | 2020-07-28 | 3M Innovative Properties Company | Filtration medium sequence for biomaterial purification |
| JP2018040772A (en) * | 2016-09-09 | 2018-03-15 | 旭化成メディカル株式会社 | Ion exchange chromatography carrier |
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| US20220096978A1 (en) * | 2019-03-11 | 2022-03-31 | Nissan Chemical Corporation | Method for producing an organic solvent |
| US20220193586A1 (en) * | 2019-03-28 | 2022-06-23 | Jnc Corporation | Depth filter |
| US20240123435A1 (en) * | 2021-02-19 | 2024-04-18 | Toyo Roshi Kaisha, Ltd. | Metal Removal Filtering Material and Cartridge Filter |
| JP7259919B1 (en) * | 2021-12-01 | 2023-04-18 | 栗田工業株式会社 | Method for removing impurities from organic solvent |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000218113A (en) * | 1999-01-29 | 2000-08-08 | Toyobo Co Ltd | Laminated nonwoven fabric for filter and filtration method using the same |
| JP2000254456A (en) * | 1999-03-11 | 2000-09-19 | Fuji Photo Film Co Ltd | Micro filter formed from fiber sheet laminate |
| JP2001149720A (en) * | 1999-11-29 | 2001-06-05 | Chisso Corp | Filter |
| JP2001321620A (en) * | 2000-05-17 | 2001-11-20 | Japan Vilene Co Ltd | Cylindrical filter |
| JP2003251118A (en) * | 2002-02-27 | 2003-09-09 | Ebara Corp | Filter cartridge having high performance metal capturing capacity |
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