JP5147679B2 - Oil / water separation filter - Google Patents
Oil / water separation filter Download PDFInfo
- Publication number
- JP5147679B2 JP5147679B2 JP2008333425A JP2008333425A JP5147679B2 JP 5147679 B2 JP5147679 B2 JP 5147679B2 JP 2008333425 A JP2008333425 A JP 2008333425A JP 2008333425 A JP2008333425 A JP 2008333425A JP 5147679 B2 JP5147679 B2 JP 5147679B2
- Authority
- JP
- Japan
- Prior art keywords
- inorganic fine
- fine particles
- oil
- substrate
- water separation
- 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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- 238000000926 separation method Methods 0.000 title claims description 59
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- 239000000178 monomer Substances 0.000 claims description 70
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 61
- 229910000077 silane Inorganic materials 0.000 claims description 61
- 239000000758 substrate Substances 0.000 claims description 60
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- 238000000034 method Methods 0.000 claims description 17
- 230000018044 dehydration Effects 0.000 claims description 15
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- 239000000126 substance Substances 0.000 claims description 15
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- 238000010526 radical polymerization reaction Methods 0.000 claims description 5
- 239000003921 oil Substances 0.000 description 58
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- 239000011347 resin Substances 0.000 description 19
- 239000002245 particle Substances 0.000 description 13
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- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Filtering Materials (AREA)
Description
本発明は、油中の水と油を分離するためのフィルターに用いるのに好適な油水分離用フィルター部材に関する。 The present invention relates to an oil / water separation filter member suitable for use in a filter for separating water in oil from oil.
石油ファンヒーターやガソリンや軽油などを使用する内燃機関は、使用する油に水滴が存在すると、該水滴が配管内壁や噴射ノズルの先端に付着して、配管内壁の腐食の発生や噴射ノズル先端の目詰まりの原因になったり、或いは、燃焼効率の低下や出力低下などの問題を引き起こすことが知られている。 In internal combustion engines that use oil fan heaters, gasoline, light oil, etc., if water drops are present in the oil used, the water drops adhere to the inner wall of the pipe and the tip of the injection nozzle, causing corrosion of the inner wall of the pipe and the tip of the injection nozzle. It is known to cause clogging or to cause problems such as reduction in combustion efficiency and output.
これまで、油中の水と油を分離する方法としては、親水性且つ非親油性高分子からなる多孔質膜を燃料タンクの底に設置する方法（特許文献１）、親水化処理した極細繊維からなるシートを充填したフィルターを利用する方法（特許文献２）、微細孔を有する疎水性多孔質膜をフィルターに用いる方法（特許文献３）、撥水性樹脂繊維と無機繊維とを含有する織布をフィルターに用いる方法（特許文献４）などが提案されている。
しかしながら、特許文献１に開示されている親水性高分子を燃料タンクの底に設置する方法では、油水分離膜材が機能するには油水分離膜に十分な水分が常に含まれることが必要であり、比較的含水率が低い燃料に使用する場合には、油水分離膜が乾燥しないように注意を払う必要がある。また、特許文献２では、親水化処理した極細繊維を束ねたフィルターを使用することからフィルターの細孔径が細く、そのため、分離した水滴を粗大化することが困難であり、比重差で分離する油水分離システムには適応できない。さらに、特許文献３では、０．０３μｍ〜５μｍの細孔を有した疎水性多孔質膜を使用するため、油に浮遊している微細な塵などが細孔を閉塞し、時間の経過と共に圧力損失が高くなる問題がある。また、特許文献４では、撥水性樹脂繊維と無機繊維とからなる織布をフィルターとして用いることから、撥水性樹脂繊維と無機繊維の構成比率によっては、含水率が変動したときに分離が不十分になるなどの問題があった。 However, in the method of installing the hydrophilic polymer disclosed in Patent Document 1 at the bottom of the fuel tank, it is necessary for the oil / water separation membrane to always contain sufficient moisture in order for the oil / water separation membrane material to function. When using it for a fuel having a relatively low water content, it is necessary to pay attention so that the oil-water separation membrane does not dry. Moreover, in patent document 2, since the pore diameter of a filter is thin because the filter which bundled the ultrafine fiber which carried out the hydrophilization treatment is used, it is difficult to coarsen the isolate | separated water droplet, The oil water isolate | separated by specific gravity difference Not applicable to separation systems. Furthermore, in Patent Document 3, since a hydrophobic porous membrane having pores of 0.03 μm to 5 μm is used, fine dust or the like floating in the oil blocks the pores, and the pressure increases with time. There is a problem of high loss. Moreover, in patent document 4, since the woven fabric which consists of a water-repellent resin fiber and an inorganic fiber is used as a filter, depending on the composition ratio of a water-repellent resin fiber and an inorganic fiber, isolation | separation is insufficient when a moisture content changes There were problems such as becoming.
そこで本発明は、上記課題を解決するために、従来よりも多様な使用環境に適応可能である油水分離用フィルター部材を提供するものである。 Therefore, in order to solve the above-described problems, the present invention provides an oil-water separation filter member that can be adapted to various usage environments as compared with the conventional art.
すなわち、第１の発明は、基体と、親水性を有する第１の無機微粒子と、前記第１の無機微粒子を基体上に保持するための、シランモノマーが表面に化学結合した第２の無機微粒子の群とを備え、前記第２の無機微粒子の群は、前記第２の無機微粒子同士が表面の前記シランモノマー間の化学結合を介して結合し、且つ、前記第２の無機微粒子の群が前記シランモノマーと基体との化学結合によって基体と結合することにより、前記第１の無機微粒子を保持するためのスペースを形成していることを特徴とする油水分離用フィルター部材である。 That is, the first invention is the second inorganic fine particles in which the silane monomer is chemically bonded to the surface for holding the substrate, the first inorganic fine particles having hydrophilicity, and the first inorganic fine particles on the substrate. A group of the second inorganic fine particles, the second inorganic fine particles are bonded to each other through a chemical bond between the silane monomers on the surface, and the second inorganic fine particles are The oil-water separation filter member is characterized in that a space for holding the first inorganic fine particles is formed by being bonded to the substrate by a chemical bond between the silane monomer and the substrate.
また、第２の発明は、親水性を有する第１の無機微粒子および不飽和結合部または反応性官能基を有するシランモノマーが表面に化学結合した第２の無機微粒子の群が分散されたスラリーを基体に塗布し、前記第２の無機微粒子同士を表面の前記シランモノマー間の化学結合により結合させるとともに、前記シランモノマーの不飽和結合部または反応性官能基と基体表面との化学結合により、前記第２の無機微粒子の群を基体と結合させて前記第１の無機微粒子を保持するためのスペースを形成し、前記第１の無機微粒子を当該スペースにて保持することを特徴とする油水分離用フィルター部材である。 The second invention is a slurry in which a group of second inorganic fine particles in which a first inorganic fine particle having hydrophilicity and a silane monomer having an unsaturated bond portion or a reactive functional group are chemically bonded to the surface are dispersed. It is applied to a substrate, and the second inorganic fine particles are bonded to each other by a chemical bond between the silane monomers on the surface, and the chemical bond between the unsaturated bond portion or reactive functional group of the silane monomer and the substrate surface, Separating a group of second inorganic fine particles with a substrate to form a space for holding the first inorganic fine particles, and holding the first inorganic fine particles in the space It is a filter member.
さらに、第１または第２の発明において、前記シランモノマーと無機微粒子間の化学結合が脱水縮合による共有結合であり、前記シランモノマー間の化学結合がラジカル重合による共有結合であり、かつ前記シランモノマーと前記基体との化学結合がグラフト重合による共有結合であることを特徴とする油水分離フィルター部材である。 Furthermore, in the first or second invention, the chemical bond between the silane monomer and the inorganic fine particles is a covalent bond by dehydration condensation, the chemical bond between the silane monomers is a covalent bond by radical polymerization, and the silane monomer The oil-water separation filter member is characterized in that the chemical bond between the substrate and the substrate is a covalent bond by graft polymerization.
第４の発明は、上記第１から第３のいずれかの発明において、前記第１の無機微粒子は、モノマー、オリゴマー、またはそれらの混合物であるバインダー成分を介して前記第２の無機微粒子と結合していることを特徴とする油水分離用フィルター部材である。 According to a fourth invention, in any one of the first to third inventions, the first inorganic fine particles are bonded to the second inorganic fine particles through a binder component that is a monomer, an oligomer, or a mixture thereof. This is a filter member for oil / water separation.
第５の発明は、上記第１から第４の発明のいずれか１つにおいて、基体が繊維構造体であることを特徴とする油水分離用フィルター部材である。 A fifth invention is the filter member for oil / water separation according to any one of the first to fourth inventions, wherein the substrate is a fiber structure.
本発明によれば、基体に結合した第２の無機微粒子の群により形成されたスペースにおいて親水性を有する第１の無機微粒子が基体上に強固に保持されるため、剥がれなどを抑制することができる。つまり、第１の無機微粒子の水に対する濡れ性が良好に維持され、油に含まれる水滴は親水性の高い無機微粒子膜の表面に付着して拡散することから、効率良く油から水滴を分離することが可能となり、フィルターの孔径を用途から想定される孔径よりも極端に小さくすることも要しない、自由な設計の油水分離フィルター部材が提供できる。 According to the present invention, since the first inorganic fine particles having hydrophilicity are firmly held on the substrate in the space formed by the group of second inorganic fine particles bonded to the substrate, it is possible to suppress peeling and the like. it can. That is, the wettability of the first inorganic fine particles to water is well maintained, and the water droplets contained in the oil adhere to the surface of the highly hydrophilic inorganic fine particle film and diffuse, thereby efficiently separating the water droplets from the oil. Therefore, it is possible to provide an oil-water separation filter member having a free design that does not require the pore diameter of the filter to be extremely smaller than the pore diameter assumed from the application.
また、第２の無機微粒子の群をその表面のシランモノマーを介して基体上に固定したことにより、本実施形態の油水分離用フィルター部材は当該フィルター部材の表面に微細な細孔を有しているので、この細孔に含浸した水分は安定にフィルター部材表面に留まり、長期間親水性が維持できる。よって、従来よりも多様な使用環境に適応可能な油水分離フィルター部材を提供することができる。 In addition, by fixing the group of second inorganic fine particles on the substrate via the silane monomer on the surface, the oil / water separation filter member of this embodiment has fine pores on the surface of the filter member. Therefore, the water impregnated in the pores stays stably on the surface of the filter member and can maintain hydrophilicity for a long time. Therefore, it is possible to provide an oil / water separation filter member that can be adapted to various usage environments as compared with the conventional case.
図１は、本発明の実施形態の油水分離用フィルター部材１００の断面の一部を模式的に表した図である。本実施形態の油水分離用フィルター部材１００は、油中の水分と油を分離するための油水分離用フィルター部材であって、通液性を有する基体１上に親水性を有する無機微粒子２−ｂ（本発明の第１の無機微粒子に相当）が、無機微粒子２−ａ（本発明の第２の無機微粒子に相当）の群１０により、基体１上に保持される構成である。 FIG. 1 is a diagram schematically showing a part of a cross section of an oil / water separation filter member 100 according to an embodiment of the present invention. The oil / water separation filter member 100 of the present embodiment is an oil / water separation filter member for separating water and oil in oil, and has hydrophilic fine particles 2-b on the substrate 1 having liquid permeability. The structure (corresponding to the first inorganic fine particles of the present invention) is held on the substrate 1 by the group 10 of inorganic fine particles 2-a (corresponding to the second inorganic fine particles of the present invention).
なお、図１では本発明の実施形態を判りやすく模式的に示すため、無機微粒子２−ａ、２−ｂは異なる無機化合物であって、それぞれ１種類の無機化合物である場合を表したが、これに限定されない。すなわち、無機微粒子２−ａと２−ｂは同種の無機微粒子でもよいし、それぞれが２種類以上の無機微粒子からなるようにしてもよい。 In addition, in order to show the embodiment of the present invention schematically in an easy-to-understand manner in FIG. 1, the inorganic fine particles 2-a and 2-b are different inorganic compounds, and each represents a case of one kind of inorganic compound. It is not limited to this. That is, the inorganic fine particles 2-a and 2-b may be the same kind of inorganic fine particles, or each may be composed of two or more kinds of inorganic fine particles.
以下、本実施形態の油水分離用フィルター部材１００の構成について、詳細に説明する。本実施形態の油水分離用フィルター部材１００に用いられる基体１としては、シランモノマー３による共有結合５が可能なものであれば良い。このような基体１としては、少なくとも基体１表面が、例えば、各種樹脂や、合成繊維や、綿、麻、絹等の天然繊維や、天然繊維から得られた和紙などにより構成されたものが挙げられる。 Hereinafter, the configuration of the oil / water separation filter member 100 of the present embodiment will be described in detail. The substrate 1 used in the oil / water separation filter member 100 of the present embodiment may be any substrate that can form the covalent bond 5 by the silane monomer 3. Examples of such a substrate 1 include those in which at least the surface of the substrate 1 is composed of various resins, synthetic fibers, natural fibers such as cotton, hemp, and silk, Japanese paper obtained from natural fibers, and the like. It is done.
基体１の表面ないし全体を構成する樹脂としては、石油や灯油或いは軽油などの油で膨潤や溶解しない材料であれば良く、合成樹脂や天然樹脂が用いられる。その一例としては、ポリエチレン樹脂、ポリプロピレン樹脂、ポリ塩化ビニリデン樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリエチレンテレフタレート樹脂、ポリスルホン樹脂、ポリフッ化ビニリデン樹脂、ＰＴＦＥなどの熱可塑性樹脂、ポリ乳酸樹脂、ポリヒドロキシブチレート樹脂、ポリカプロラクト樹脂、ポリブチレンサクシネート樹脂、ポリブチレンアジペートテレフタレート樹脂、ポリブチレンサクシネートテレフタレート樹脂、フェノール樹脂、ユリア樹脂、メラミン樹脂、不飽和ポリエステル樹脂、ジアリルフタレート樹脂、エポキシ樹脂、エポキシアクリレート樹脂、ケイ素樹脂、アクリルウレタン樹脂、ウレタン樹脂などの熱硬化性樹脂などが挙げられる。 The resin constituting the surface or the whole of the substrate 1 may be any material that does not swell or dissolve with oil such as petroleum, kerosene, or light oil, and synthetic resin or natural resin is used. Examples include polyethylene resin, polypropylene resin, polyvinylidene chloride resin, polyamide resin, polyimide resin, polyethylene terephthalate resin, polysulfone resin, polyvinylidene fluoride resin, PTFE and other thermoplastic resins, polylactic acid resin, polyhydroxybutyrate resin , Polycaprolacto resin, polybutylene succinate resin, polybutylene adipate terephthalate resin, polybutylene succinate terephthalate resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, epoxy acrylate resin, Examples thereof include thermosetting resins such as silicon resins, acrylic urethane resins, and urethane resins.
また、本実施形態では、基体１の形態は通液性を有する限り特に限定されず、使用目的や処理対象となる油の種類などに応じて変更可能であるが、例えば樹脂からなる繊維状材料から構成される織物・編物・不織布などを含む繊維構造体とすることができる。さらに、種々の形状及びサイズ等についても、使用目的に合ったものとすることができる。なお、本明細書において、基体上とは、基体１が不織布状の場合は不織布を形成する糸の表面を意味する。 Further, in the present embodiment, the form of the substrate 1 is not particularly limited as long as it has liquid permeability, and can be changed according to the purpose of use or the type of oil to be treated. For example, a fibrous material made of resin It can be set as the fiber structure containing the woven fabric, the knitted fabric, the nonwoven fabric, etc. comprised from these. Furthermore, various shapes and sizes can be adapted to the intended use. In addition, in this specification, when the base | substrate 1 is a nonwoven fabric form, on the base | substrate means the surface of the thread | yarn which forms a nonwoven fabric.
本実施形態の油水分離用フィルター部材１００に係る基体１上には、無機微粒子２−ａの群１０が固定されている。無機微粒子２−ａは、表面に脱水縮合反応による共有結合７によりシランモノマー３が結合しており、また、無機微粒子２−ａ同士は、表面のシランモノマー３間で形成されたラジカル重合による共有結合６（以下、単に共有結合６と称す）により、結合している。さらに、無機微粒子２−ａの群１０は、シランモノマー３と基体１との間に形成される共有結合５（後述するグラフト重合による共有結合）により、基体１に結合している。そして、無機微粒子２−ａ同士の結合、および無機微粒子２−ａの群１０と基体１との結合により、基体１上には、無機微粒子２−ｂを保持するためのスペース８が形成される。 A group 10 of inorganic fine particles 2-a is fixed on the substrate 1 according to the filter member 100 for oil / water separation of the present embodiment. The inorganic fine particles 2-a have the silane monomer 3 bonded to the surface by a covalent bond 7 by a dehydration condensation reaction, and the inorganic fine particles 2-a are shared by radical polymerization formed between the silane monomers 3 on the surface. The bonds are connected by a bond 6 (hereinafter simply referred to as a covalent bond 6). Further, the group 10 of inorganic fine particles 2-a is bonded to the substrate 1 by a covalent bond 5 (covalent bond by graft polymerization described later) formed between the silane monomer 3 and the substrate 1. A space 8 for holding the inorganic fine particles 2-b is formed on the substrate 1 by the bonding between the inorganic fine particles 2-a and the bonding between the group 10 of inorganic fine particles 2-a and the substrate 1. .
ここで、シランモノマー３が不飽和結合部や反応性官能基を無機微粒子２−ａの外側に向けて配向して結合する理由について詳述する。これは、シランモノマー３の片末端であるシラノール基が親水性であるため、同じく親水性である無機微粒子２−ａの表面に引きつけられやすく、一方、逆末端の不飽和結合部や反応性官能基は疎水性であるため、無機微粒子２−ａの表面から離れようとするからである。このため、シランモノマー３のシラノール基は、無機微粒子２−ａの表面に脱水縮合反応により共有結合７し、シランモノマー３は不飽和結合部を外側に向けて配向しやすい。したがって、多くのシランモノマー３については、不飽和結合部を外側に向けて無機微粒子２−ａと共有結合７している。 Here, the reason why the silane monomer 3 aligns and bonds the unsaturated bond portion and the reactive functional group toward the outside of the inorganic fine particle 2-a will be described in detail. This is because the silanol group at one end of the silane monomer 3 is hydrophilic, so that it is easily attracted to the surface of the inorganic fine particle 2-a, which is also hydrophilic, while the unsaturated bond portion or reactive functional group at the reverse end. This is because the group is hydrophobic and tends to be separated from the surface of the inorganic fine particle 2-a. For this reason, the silanol group of the silane monomer 3 is covalently bonded 7 to the surface of the inorganic fine particle 2-a by a dehydration condensation reaction, and the silane monomer 3 is easily oriented with the unsaturated bond portion facing outward. Therefore, many silane monomers 3 are covalently bonded 7 to the inorganic fine particles 2-a with the unsaturated bond portion facing outward.
すなわち、本実施形態の油水分離用フィルター１００は、不飽和結合部又は反応性官能基を有する反応性に優れたシランモノマー３を用いることで、シランモノマー３が有するシラノール基の共有結合６により基体１上の複数の無機微粒子２−ａ同士を結合するとともに、基体１と対向する無機微粒子２−ａ表面のシランモノマー３との間で共有結合５を形成することで、無機微粒子２−ａの群１０を基体１上に固定している。そして、無機微粒子２−ａ同士の結合および無機微粒子２−ａの群１０と基体１との結合により形成されたスペース８に無機微粒子２−ｂを保持している。当該スペース７は外部と連通しており、無機微粒子２−ｂは、その親水性が維持された状態で基体１上に保持されている。すなわち本発明の１つの態様において、無機微粒子２−ｂは、親水性が維持された状態で、基体１上において少なくとも無機微粒子２−ａおよび当該無機微粒子２−ａに結合したシランモノマー３によって囲まれている。 That is, the oil / water separation filter 100 according to the present embodiment uses the silane monomer 3 having an unsaturated bond portion or a reactive functional group and having excellent reactivity, whereby the substrate is formed by the covalent bond 6 of the silanol group of the silane monomer 3. 1, the inorganic fine particles 2-a on the surface of the inorganic fine particles 2-a are bonded to each other, and a covalent bond 5 is formed between the inorganic fine particles 2-a facing the substrate 1 and the silane monomer 3 on the surface. The group 10 is fixed on the substrate 1. The inorganic fine particles 2-b are held in the space 8 formed by the bonding between the inorganic fine particles 2-a and the bonding between the group 10 of inorganic fine particles 2-a and the substrate 1. The space 7 communicates with the outside, and the inorganic fine particles 2-b are held on the substrate 1 while maintaining the hydrophilicity. That is, in one embodiment of the present invention, the inorganic fine particles 2-b are surrounded by at least the inorganic fine particles 2-a and the silane monomer 3 bonded to the inorganic fine particles 2-a on the substrate 1 while maintaining hydrophilicity. It is.
無機微粒子２−ａに脱水縮合により共有結合７するシランモノマー３が有する不飽和結合部としては、ビニル基、エポキシ基、スチリル基、メタクリロ基、アクリロキシ基、イソシアネート基などが挙げられる。 Examples of the unsaturated bond portion of the silane monomer 3 that covalently bonds 7 to the inorganic fine particles 2-a by dehydration condensation include a vinyl group, an epoxy group, a styryl group, a methacrylo group, an acryloxy group, and an isocyanate group.
本実施形態の油水分離用フィルター部材１００で用いられるシランモノマー３の一例としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリアセトキシシラン、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシラン、Ｎ−（ビニルベンジル）−２−アミノエチル−３−アミノプロピルトリメトキシシランの塩酸塩、２−（３、４エポキシシクロヘキシル）エチルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−グリシドキシプロピルトリエトキシシラン、ｐ−スチリルトリメトキシシラン、３−メタクリロキシプロピルメチルジメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−メタクリロキシプロピルメチルジエトキシシラン、３−メタクリロキシプロピルトリエトキシシラン、３−アクリロキシプロピルトリメトキシシラン、３−イソシアネートプロピルトリエトキシシランなどが挙げられる。 Examples of the silane monomer 3 used in the oil / water separation filter member 100 of the present embodiment include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ. -Aminopropyltrimethoxysilane, hydrochloride of N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-me Examples include tacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.
本実施形態の油水分離用フィルター部材１００に係る無機微粒子２−ａ、および無機微粒子２−ｂとしては、非金属酸化物、金属酸化物、金属複合酸化物などの親水性を示すものが好適に用いられる。無機微粒子２の結晶性は、非晶性あるいは結晶性のどちらでも良い。非金属酸化物としては、酸化珪素が挙げられる。また、金属酸化物としては、酸化マグネシウム、酸化バリウム、過酸化バリウム、ギブサイト、ベーマイト、ダイスポア、γ、δ、θなどの結晶性を有する酸化アルミニウム、酸化スズ、酸化チタン、酸化亜鉛、過酸化チタン、酸化ジルコニウム、酸化鉄、水酸化鉄、酸化タングステン、酸化ビスマス、酸化インジウムなどが挙げられる。また、金属複合酸化物としては、高シリカゼオライト、ソーダライト、モルデナイト、アナルサイト、エリナイトなどのゼオライト類、ハイドロキシアパタイトなどのアパタイト類、酸化チタンバリウム、酸化コバルトアルミニウム、酸化ジルコニウム鉛、酸化ニオブ鉛、ＴｉＯ2−ＷＯ3、ＡｌＯ３−ＳｉＯ２、ＷＯ３−ＺｒＯ２、ＷＯ３−ＳｎＯ２などが挙げられる。これらの無機微粒子は単体で用いても２種以上混合して用いても良い。 As the inorganic fine particles 2-a and the inorganic fine particles 2-b according to the oil-water separation filter member 100 of the present embodiment, those showing hydrophilicity such as non-metal oxides, metal oxides, and metal composite oxides are suitable. Used. The crystallinity of the inorganic fine particles 2 may be either amorphous or crystalline. Examples of the non-metal oxide include silicon oxide. Examples of the metal oxide include magnesium oxide, barium oxide, barium peroxide, gibbsite, boehmite, die pore, γ, δ, θ and other crystalline aluminum oxide, tin oxide, titanium oxide, zinc oxide, titanium peroxide. , Zirconium oxide, iron oxide, iron hydroxide, tungsten oxide, bismuth oxide, indium oxide and the like. Also, as the metal composite oxide, zeolites such as high silica zeolite, sodalite, mordenite, analsite, and elite, apatites such as hydroxyapatite, titanium barium oxide, cobalt aluminum oxide, lead zirconium oxide, lead niobium oxide, Examples thereof include TiO 2 —WO 3 , AlO 3 —SiO 2 , WO 3 —ZrO 2 , and WO 3 —SnO 2 . These inorganic fine particles may be used alone or in combination of two or more.
本実施形態において、含有される無機微粒子２（２−ａ、２−ｂ）の粒子径としては、平均の粒子径が５００ｎｍ以下とすることが好ましい。５００ｎｍより大きい場合では、基体１に対する無機微粒子２の密着性が低下して５００ｎｍ以下である場合よりも無機微粒子２が剥がれやすくなるため、メンテナンスの手間やコストが多くかかってしまう。また、その使用環境や使用経時などにより、無機微粒子２の剥離が発生する場合があることから、無機微粒子２同士の密着強度を考慮すると、無機微粒子２の平均粒子径は１０ｎｍから３００ｎｍ以下であることが特に好ましい。 In the present embodiment, the average particle size is preferably 500 nm or less as the particle size of the inorganic fine particles 2 (2-a, 2-b) to be contained. When the thickness is larger than 500 nm, the adhesion of the inorganic fine particles 2 to the substrate 1 is lowered, and the inorganic fine particles 2 are more easily peeled off than when the thickness is 500 nm or less. Moreover, since the peeling of the inorganic fine particles 2 may occur depending on the usage environment or usage time, the average particle diameter of the inorganic fine particles 2 is 10 nm to 300 nm or less in consideration of the adhesion strength between the inorganic fine particles 2. It is particularly preferred.
さらに、本実施形態の油水分離用フィルター部材においては、無機微粒子２−ｂは、モノマー、オリゴマー、またはこれらの混合物からなるバインダー成分４を介して無機微粒子２−ａに結合するようにしてもよい。言い換えれば、本実施形態の油水分離用フィルター部材は、無機微粒子２−ｂの親水性が維持された状態（無機微粒子２−ｂの表面のうち少なくとも一部が外部に露出された状態）で当該無機微粒子２−ｂと無機微粒子２−ａを結合する、モノマー、オリゴマー、またはこれらの混合物からなるバインダー成分４を備えるようにしてもよい。これにより、石油や灯油或いは軽油などによる無機微粒子２−ｂの基体１上からの脱落を防止できるため、親水性の低下を抑制することができる。なお、図１に示すように、バインダー成分４は、無機微粒子２−ａと無機微粒子２−ｂとを結合させるだけでなく、無機微粒子２−ｂと基体１とを結合したり、無機微粒子２−ａ同士、および無機微粒子２−ｂ同士を結合するようにしてもよい。また、無機微粒子２−ａの表面に、バインダー成分４によって無機微粒子２−ｂを固定するような構成とすることもできる。さらに、本実施形態では、以下に例を示したバインダー成分４について、脱水縮合反応による共有結合を形成して無機微粒子２−ａ、２−ｂ、および基体１に結合しているがこれに限定されるものではなく、他の態様によって結合または吸着するようにしてもよい。 Furthermore, in the oil / water separation filter member of the present embodiment, the inorganic fine particles 2-b may be bonded to the inorganic fine particles 2-a via the binder component 4 made of a monomer, an oligomer, or a mixture thereof. . In other words, the oil / water separation filter member of the present embodiment is in a state where the hydrophilicity of the inorganic fine particles 2-b is maintained (at least a part of the surface of the inorganic fine particles 2-b is exposed to the outside). You may make it provide the binder component 4 which consists of a monomer, an oligomer, or a mixture which couple | bonds the inorganic fine particle 2-b and the inorganic fine particle 2-a. Accordingly, it is possible to prevent the inorganic fine particles 2-b from dropping off from the base 1 due to petroleum, kerosene, light oil, or the like, and thus it is possible to suppress a decrease in hydrophilicity. As shown in FIG. 1, the binder component 4 not only binds the inorganic fine particles 2-a and the inorganic fine particles 2-b but also bonds the inorganic fine particles 2-b and the substrate 1 or the inorganic fine particles 2. You may make it couple | bond -a and inorganic fine particles 2-b. Moreover, it can also be set as the structure which fixes inorganic fine particle 2-b by the binder component 4 on the surface of inorganic fine particle 2-a. Furthermore, in the present embodiment, the binder component 4 shown as an example below is bonded to the inorganic fine particles 2-a and 2-b and the substrate 1 by forming a covalent bond by a dehydration condensation reaction. However, it may be bound or adsorbed by other modes.
モノマー及びオリゴマーとしては不飽和結合部を有する単官能、２官能、多官能のビニル系モノマー、例えば、アクリル酸、メチルエチルメタクリレート、エチルアクリレート、ｎ−ブチルアクリレート、２−ヒドロキシエチルアクリレート、メチルメタクリレート、２−ヒドロキシエチルアクリレート、アクリルアミド、メタクリルアミド、アクリロニトリル、酢酸ビニル、スチレン、イタコン酸、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレートなどが用いられる。 Monofunctional, bifunctional and polyfunctional vinyl monomers having unsaturated bonds as monomers and oligomers such as acrylic acid, methyl ethyl methacrylate, ethyl acrylate, n-butyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, acrylamide, methacrylamide, acrylonitrile, vinyl acetate, styrene, itaconic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate and the like are used.
また、バインダー成分４として、不飽和結合を有するシランモノマーである、例えば、ビニルトリメトキシシランや、ビニルトリエトキシシランや、ビニルトリアセトキシシランや、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシランなどが用いられる。 The binder component 4 is a silane monomer having an unsaturated bond, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, or N-β- (N-vinylbenzylaminoethyl)-. γ-aminopropyltrimethoxysilane or the like is used.
さらに、バインダー成分４としては、Ｓｉ（ＯＲ1）4（式中、Ｒ１は炭素数１〜４のアルキル基を示す）で示されるアルコキシラン化合物、例えば、テトラメトキシシランや、テトラエトキシシランなどや、Ｒ2nＳｉ（ＯＲ3）4n（式中、Ｒ2は炭素数１〜６の炭化水素基、Ｒ3は炭素数１〜４のアルキル基、ｎは１〜３の整数を示す）で示されるアルコキシシラン化合物、例えば、メチルトリメトキシシランや、メチルトリエトキシシランや、ジメチルジエトキシシランや、フェニルトリエトキシシランや、ヘキサメチルジシラザンや、ヘキシルトリメトキシシランなどが用いられるようにしてもよい。当該アルコキシシランを結合させることにより、無機微粒子２−ｂがより強く保持されるようになるほか、油水分離用フィルター部材の親水性もより高くなる。 Furthermore, as the binder component 4, an alkoxylane compound represented by Si (OR 1 ) 4 (wherein R 1 represents an alkyl group having 1 to 4 carbon atoms), for example, tetramethoxysilane, tetraethoxysilane, etc. , R 2n Si (OR 3 ) 4n (wherein R 2 is a hydrocarbon group having 1 to 6 carbon atoms, R 3 is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 3). Alkoxysilane compounds such as methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, hexyltrimethoxysilane, etc. may be used. . By bonding the alkoxysilane, the inorganic fine particles 2-b are more strongly retained, and the hydrophilicity of the oil / water separation filter member is also increased.
バインダー成分４の量は、バインダーとしての機能を発揮し、且つ無機微粒子２−ｂの親水性が維持される範囲で適宜設定することができるが、例えばシランモノマー３が結合した無機微粒子２−ａおよび無機微粒子２−ｂの合計１００質量％に対して、０．１質量％以上の含有量となるように、バインダー成分４を添加すればよい。バインダー成分４を有することにより、無機微粒子２の石油や灯油或いは軽油に対する耐久性、および本実施形態の油水分離用フィルター部材１００の親水性の低下をさらに抑制することができる。 The amount of the binder component 4 can be set as appropriate as long as it functions as a binder and the hydrophilicity of the inorganic fine particles 2-b is maintained. For example, the inorganic fine particles 2-a to which the silane monomer 3 is bonded. The binder component 4 may be added so that the content is 0.1% by mass or more with respect to 100% by mass in total of the inorganic fine particles 2-b. By having the binder component 4, it is possible to further suppress the durability of the inorganic fine particles 2 against petroleum, kerosene, or light oil, and the decrease in the hydrophilicity of the oil / water separation filter member 100 of the present embodiment.
また、バインダー成分４だけではなく、さらに何らかの性能を付与するための機能性材料も用いる事ができる。例えば、後述する製造工程において、親水性のモノマーやオリゴマーを添加すると、さらに親水性能を向上させることが可能となるし、撥水性のモノマーやオリゴマーを添加すると、親水性能と撥水性能を併せ持つため、含水率の変動があるような油水の分離に、より柔軟に対応できる油水分離用フィルター部材１００を提供できる。また、バインダー成分４や他の機能性材料は１種類だけでなく、複数種類用いることも可能であり、それぞれの添加濃度については使用環境にあわせて適宜選択できる。これら機能性材料の結合または吸着方法も特に限定されず、油水分離用フィルター部材１００の使用目的等に応じて適宜変更可能である。 Further, not only the binder component 4 but also a functional material for imparting some performance can be used. For example, when a hydrophilic monomer or oligomer is added in the manufacturing process described later, it is possible to further improve the hydrophilic performance, and when a water repellent monomer or oligomer is added, it has both hydrophilic performance and water repellency performance. The oil / water separation filter member 100 can be provided more flexibly to the separation of the oil / water such that the water content varies. Moreover, the binder component 4 and other functional materials can be used not only in one type but also in a plurality of types, and the respective addition concentrations can be appropriately selected according to the use environment. The method for bonding or adsorbing these functional materials is not particularly limited, and can be appropriately changed according to the purpose of use of the filter member 100 for oil / water separation.
次に、本実施形態の油水分離用フィルター部材１００の製造方法について説明する。まず、無機微粒子２、具体的にはシランモノマー３が脱水縮合により共有結合７して当該シランモノマー３により被覆された無機微粒子２−ａ、および親水性を有する無機微粒子２−ｂをメタノールやエタノール、ＭＥＫ，アセトン、キシレン、トルエンなどの分散媒に混合し、分散させる。ここで、分散を促進させる為に、必要に応じて界面活性剤や、塩酸、硫酸などの鉱酸や、酢酸、クエン酸などのカルボン酸などを加えるようにしてもよい。続いて、ビーズミルやボールミル、サンドミル、ロールミル、振動ミル、ホモジナイザーなどの装置を用いて無機微粒子２を分散媒中で解砕・分散させ、無機微粒子２を含むスラリーを作製する。 Next, the manufacturing method of the filter member 100 for oil-water separation of this embodiment is demonstrated. First, the inorganic fine particles 2, specifically, the inorganic fine particles 2-a that are covalently bonded 7 by dehydration condensation with the silane monomer 3 and coated with the silane monomer 3, and the inorganic fine particles 2-b having hydrophilicity are mixed with methanol or ethanol. , Mixed with a dispersion medium such as MEK, acetone, xylene, toluene, and dispersed. Here, in order to promote the dispersion, a surfactant, a mineral acid such as hydrochloric acid or sulfuric acid, a carboxylic acid such as acetic acid or citric acid, or the like may be added as necessary. Subsequently, the inorganic fine particles 2 are pulverized and dispersed in a dispersion medium using an apparatus such as a bead mill, a ball mill, a sand mill, a roll mill, a vibration mill, or a homogenizer to produce a slurry containing the inorganic fine particles 2.
なお、無機微粒子２−ａと不飽和結合部または反応性官能基を有するシランモノマー３との共有結合７は通常の方法により形成させることができ、例えば、分散液に、シランモノマー３を加え、その後、還流下で加熱させながら、無機微粒子２−ａの表面にシランモノマー３を脱水縮合反応により共有結合７させてシランモノマー３からなる薄膜を形成する方法や、粉砕により微粒子化して得られた分散液にシランモノマー３を加えた後、或いは、シランモノマー３を加えて粉砕により微粒子化した後、固液分離して１００℃から１８０℃で加熱してシランモノマー３を無機微粒子２−ａの表面に脱水縮合反応により共有結合７させ、次いで、粉砕・解砕して再分散する方法が挙げられる。 In addition, the covalent bond 7 between the inorganic fine particles 2-a and the silane monomer 3 having an unsaturated bond portion or a reactive functional group can be formed by an ordinary method. For example, the silane monomer 3 is added to the dispersion, Thereafter, while heating under reflux, the surface of the inorganic fine particles 2-a was obtained by covalently bonding the silane monomer 3 by a dehydration condensation reaction 7 to form a thin film composed of the silane monomer 3, or by pulverization to obtain fine particles. After adding the silane monomer 3 to the dispersion, or adding the silane monomer 3 to make fine particles by pulverization, solid-liquid separation and heating at 100 ° C. to 180 ° C. make the silane monomer 3 of the inorganic fine particles 2-a Examples include a method in which the surface is covalently bonded 7 by a dehydration condensation reaction and then pulverized and pulverized and redispersed.
ここで、還流下、または、粉砕により微粒子化して得られた分散液にシランモノマー３を加えた後、或いは、シランモノマー３を加えて粉砕により微粒子化した後、固液分離して１００℃から１８０℃で加熱してシランモノマー３を無機微粒子２−ａの表面に脱水縮合反応による共有結合７させる場合、シランモノマー３の量は、無機微粒子２−ａの平均粒子径にもよるが、無機微粒子２−ａの質量に対して０．０１％質量から４０．０質量％であれば無機微粒子２−ａ同士、および無機微粒子２−ａの群１０と基体１との結合強度は実用上問題ない。また、結合に預からない余剰のシランカップリングモノマー３があっても良い。 Here, after adding the silane monomer 3 to the dispersion liquid obtained by refluxing or pulverizing, or by adding the silane monomer 3 and pulverizing to fine particles, solid-liquid separation is performed from 100 ° C. When the silane monomer 3 is heated to 180 ° C. and covalently bonded 7 to the surface of the inorganic fine particle 2-a by dehydration condensation reaction, the amount of the silane monomer 3 depends on the average particle diameter of the inorganic fine particle 2-a, but is inorganic. If the amount of the fine particles 2-a is 0.01% to 40.0% by weight, the bonding strength between the inorganic fine particles 2-a and between the inorganic fine particles 2-a 10 and the substrate 1 is a practical problem. Absent. There may also be an excess of silane coupling monomer 3 that is not deposited.
続いて、以上のようにして得られた無機微粒子２が分散したスラリーに、必要に応じてバインダー成分４を添加し充分に混合した後、当該スラリーを固定する基体１の表面に塗布する。具体的な無機微粒子２が分散したスラリーの塗布方法としては、一般に行われているスピンコート法、ディップコート法、スプレーコート法、キャストコート法、バーコート法、マイクログラビアコート法、グラビアコート法を用いればよく、目的に合った塗布ができれば特に限定されない。 Subsequently, the binder component 4 is added to the slurry in which the inorganic fine particles 2 obtained as described above are dispersed, if necessary, and mixed sufficiently, and then applied to the surface of the substrate 1 on which the slurry is fixed. Specific examples of the application method of the slurry in which the inorganic fine particles 2 are dispersed include a spin coating method, a dip coating method, a spray coating method, a cast coating method, a bar coating method, a micro gravure coating method, and a gravure coating method. It may be used, and is not particularly limited as long as it can be applied according to the purpose.
次に、必要に応じて、加熱乾燥などで分散媒を除去した後、基体１と、無機微粒子２と、バインダー成分４とを化学結合する。具体的には、無機微粒子２−ａの表面のシランモノマー３間で共有結合６を形成させることにより無機微粒子２−ａ同士を結合させるとともに、結合した無機微粒子２−ａの群１０を、シランモノマー３と基材１表面との間の共有結合５を形成させることにより、基体１上に固定させる。このとき、無機微粒子２−ｂは、無機微粒子２−a同士の間や無機微粒子２−aと基体１との間に形成されたスペース８に嵌ることにより、当該スペース８において保持される。また、併せて、バインダー成分４を無機微粒子２−ａおよび無機微粒子２−ｂに結合させることにより、無機微粒子２−ａと無機微粒子２−ｂとを結合させる。本実施形態においては、基体１とシランモノマー３とを共有結合５させる方法として、グラフト重合による結合方法を用いるのが好ましい。 Next, if necessary, after removing the dispersion medium by heat drying or the like, the substrate 1, the inorganic fine particles 2, and the binder component 4 are chemically bonded. Specifically, the inorganic fine particles 2-a are bonded to each other by forming a covalent bond 6 between the silane monomers 3 on the surface of the inorganic fine particles 2-a. It is fixed on the substrate 1 by forming a covalent bond 5 between the monomer 3 and the surface of the substrate 1. At this time, the inorganic fine particles 2-b are held in the space 8 by fitting into the spaces 8 formed between the inorganic fine particles 2-a or between the inorganic fine particles 2-a and the substrate 1. In addition, by binding the binder component 4 to the inorganic fine particles 2-a and the inorganic fine particles 2-b, the inorganic fine particles 2-a and the inorganic fine particles 2-b are bonded. In this embodiment, it is preferable to use a bonding method by graft polymerization as a method for covalently bonding the substrate 1 and the silane monomer 3.
本実施形態の油水分離用フィルター部材１００におけるグラフト重合としては、例えばパーオキサイド触媒を用いるグラフト重合、熱や光エネルギーを用いるグラフト重合、放射線によるグラフト重合（放射線グラフト重合）などが挙げられ、形状や形態に応じて適宜選択して用いられる。なお、パーオキサイド触媒による処理、熱や光エネルギーによる処理、および放射線による処理によって、無機微粒子２−ａ表面のシランモノマー間のラジカル重合による共有結合６、およびバインダー成分４と無機微粒子２−ａおよび２−ｂとの脱水縮合反応により共有結合が形成されたことによる無機微粒子２−ａおよび２−ｂの結合についても、併せて形成させることができる。 Examples of the graft polymerization in the oil / water separation filter member 100 of the present embodiment include graft polymerization using a peroxide catalyst, graft polymerization using heat and light energy, and graft polymerization by radiation (radiation graft polymerization). It is appropriately selected and used depending on the form. In addition, by the process by a peroxide catalyst, the process by a heat | fever or light energy, and the process by radiation, the covalent bond 6 by radical polymerization between the silane monomers on the surface of the inorganic fine particles 2-a, and the binder component 4 and the inorganic fine particles 2-a and A bond between inorganic fine particles 2-a and 2-b resulting from the formation of a covalent bond by a dehydration condensation reaction with 2-b can also be formed together.
ここで、シランモノマー３のグラフト重合を効率良く、かつ、均一に行わせるために、予め、基体１の表面を、コロナ放電処理やプラズマ放電処理や、火炎処理や、クロム酸や過塩素酸などの酸化性酸水溶液や水酸化ナトリウムなどを含むアルカリ性水溶液による化学的な処理などの親水化処理をしてもよい。 Here, in order to perform the graft polymerization of the silane monomer 3 efficiently and uniformly, the surface of the substrate 1 is previously subjected to corona discharge treatment, plasma discharge treatment, flame treatment, chromic acid, perchloric acid, etc. Hydrophilic treatment such as chemical treatment with an alkaline aqueous solution containing an oxidizing acid aqueous solution or sodium hydroxide may be performed.
以上、本実施形態の油水分離用フィルター部材１００によれば、基体１に結合した無機微粒子２−ａの群１０により形成されたスペース８において親水性を有する無機微粒子２−ｂが保持される。このため、無機微粒子２−ｂは強固に基体１上で保持されるので、剥がれなどを抑制することができる。また、無機微粒子２−ｂが無機微粒子２−ａの群１０によって形成されたスペース８で基体１上に保持されることにより、無機微粒子２−ｂは水に対する良好な濡れ性を有している。したがって、油に含まれる水滴は親水性の高い無機微粒子２−ｂの表面に付着して拡散するため、効率良く油から水滴を分離することが可能となり、フィルターの孔径を用途から想定される孔径よりも極端に小さくすることも要しない、自由な設計の油水分離フィルター部材が提供できる。また、従来よりも油水分離作用の維持（メンテナンス）についても、孔径を極端に小さくした場合と比較して目詰まり等が抑制されてより長期間の使用が可能となるため、容易となる。 As described above, according to the oil / water separation filter member 100 of the present embodiment, the inorganic fine particles 2-b having hydrophilicity are held in the space 8 formed by the group 10 of the inorganic fine particles 2-a bonded to the substrate 1. For this reason, since the inorganic fine particles 2-b are firmly held on the substrate 1, peeling or the like can be suppressed. Further, the inorganic fine particles 2-b are held on the base 1 in the space 8 formed by the group 10 of the inorganic fine particles 2-a, so that the inorganic fine particles 2-b have good wettability with respect to water. . Therefore, since the water droplets contained in the oil adhere to the surface of the highly hydrophilic inorganic fine particles 2-b and diffuse, it is possible to efficiently separate the water droplets from the oil, and the pore size of the filter is assumed from the application. It is possible to provide an oil / water separation filter member having a free design that does not need to be extremely small. Also, the maintenance (maintenance) of the oil / water separation effect is easier than in the prior art because clogging and the like are suppressed compared to the case where the pore diameter is extremely small, and the use can be performed for a longer period of time.
また、基体１上にシランモノマーが脱水縮合により共有結合７した無機微粒子２−ａの群１０を固定したことにより、本実施形態の油水分離用フィルター部材１００は、その表面に微細な細孔が形成されている。この細孔に含浸した水分は安定に油水分離用部材の表面に留まる。よって、無機繊維を用いてフィルターを構成した場合よりも長期間親水性が維持できるため、従来よりも多様な使用環境（例えば、含水率や使用されるフィルター部材が実装される構造体の形式などが異なる場合）に適応可能である。 Further, by fixing the group 10 of inorganic fine particles 2-a in which the silane monomer is covalently bonded 7 by dehydration condensation on the substrate 1, the oil-water separation filter member 100 of this embodiment has fine pores on the surface thereof. Is formed. The water impregnated in the pores remains stably on the surface of the oil / water separating member. Therefore, since hydrophilicity can be maintained for a longer period than when a filter is configured using inorganic fibers, the environment is more diverse than before (for example, the moisture content and the type of structure on which the filter member to be used is mounted) Can be applied to different cases.
さらに、本実施形態に係る基体１上に固定された無機微粒子２は、無機微粒子２−ｂと、不飽和結合部や反応性官能基を有するシランモノマー３が脱水縮合反応により表面に共有結合７（図中の黒丸で示した部分）した無機微粒子２−ａとから構成されているため、これらの無機微粒子２の混合比率を変えることで、必要とする濡れ性が容易に得られることから、目的に合わせた自由なフィルターの構造設計が可能となる。 Further, the inorganic fine particles 2 fixed on the substrate 1 according to the present embodiment have the inorganic fine particles 2-b and the silane monomer 3 having an unsaturated bond portion or a reactive functional group covalently bonded to the surface 7 by a dehydration condensation reaction. Since it is composed of inorganic fine particles 2-a (parts indicated by black circles in the figure), the required wettability can be easily obtained by changing the mixing ratio of these inorganic fine particles 2. It is possible to design the filter structure freely according to the purpose.
次に、実施例を挙げて本発明をより具体的に説明する。ただし、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。 Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples.
＜油水分離用フィルター部材の作製＞
実施例１：
無機微粒子としてγ―アルミナ（大明化学工業株式会社製、ＴＭ−３００）、および不飽和結合を有するシランモノマーであるメタクリロキシプロピルトリメトキシシラン（信越化学工業株式会社製、ＫＢＭ−５０３）を通常の方法により脱水縮合させ表面に共有結合させた酸化ジルコニウム粒子（日本電工株式会社製、ＰＣＳ、）をメタノールにプレ分散後、ビーズミルにて平均粒子径が３７ｎｍとなるように解砕・分散し、それぞれの粒子が分散したスラリーを得た。γ―アルミナの充填量は固形分に対して（１）３０質量％、（２）５０質量％、（３）７０質量％とした。次に固形分が５質量％になるようにメタノールを加えて調整した。なお、ここでいう平均粒子径とは、体積平均粒子径のことをいう。
<Production of filter member for oil / water separation>
Example 1:
As inorganic fine particles, γ-alumina (manufactured by Daimei Chemical Co., Ltd., TM-300) and methacryloxypropyltrimethoxysilane (KBS-503, manufactured by Shin-Etsu Chemical Co., Ltd.) which is a silane monomer having an unsaturated bond are usually used. Zirconium oxide particles dehydrated and condensed by the method and covalently bonded to the surface (Nippon Denko Co., Ltd., PCS) were pre-dispersed in methanol, and then crushed and dispersed with a bead mill so that the average particle size was 37 nm. A slurry in which the particles were dispersed was obtained. The filling amount of γ-alumina was (1) 30% by mass, (2) 50% by mass, and (3) 70% by mass with respect to the solid content. Next, it adjusted by adding methanol so that solid content might be 5 mass%. In addition, the average particle diameter here means a volume average particle diameter.
また、メッシュ数８０のナイロン製メッシュ（ＮＢＣ株式会社製、ＮＢ０６８０）の表面をコロナ処理により親水化処理した後、固形分を５質量％に調整したスラリーにナイロンメッシュを浸漬し、余剰分のスラリーを除去した後、１００℃、５分間乾燥した。その後、２００ｋＶの加速電圧で電子線を５Ｍｒａｄ照射し、油水分離用フィルター部材を得た。 Further, the surface of a nylon mesh having a mesh number of 80 (NB0680, manufactured by NBC Co., Ltd.) was hydrophilized by corona treatment, and then the nylon mesh was immersed in a slurry whose solid content was adjusted to 5% by mass to obtain a surplus slurry. Then, the film was dried at 100 ° C. for 5 minutes. Then, the electron beam was irradiated 5Mrad with the acceleration voltage of 200 kV, and the filter member for oil-water separation was obtained.
実施例２：
γ―アルミナ、およびメタクリロキシプロピルトリメトキシシランを酸化ジルコニウム粒子の固形分に対し、５．０質量％になるように脱水縮合により表面に結合させた酸化ジルコニウム粒子が分散されており、γ―アルミナが７０質量％である実施例１で用いたスラリーに、オルガノシラン（信越化学工業株式会社製、ＫＭＢ−０４）を、メタクリロキシプロピルトリメトキシシランが結合した酸化ジルコニウム粒子とγ―アルミナ粒子の固形分に対して４．０質量％になるように加えて分散した。その後、メタノールにて固形分を５．０質量％に調整した以外は実施例１と同一の条件でナイロンメッシュからなる油水分離用フィルター部材を得た。
Example 2:
Zirconium oxide particles in which γ-alumina and methacryloxypropyltrimethoxysilane are bonded to the surface by dehydration condensation so as to be 5.0% by mass with respect to the solid content of the zirconium oxide particles are dispersed. Is a solid of zirconium oxide particles and γ-alumina particles in which organosilane (manufactured by Shin-Etsu Chemical Co., Ltd., KMB-04) is bonded to methacryloxypropyltrimethoxysilane is added to the slurry used in Example 1 in which is 70% by mass. It was added and dispersed so as to be 4.0% by mass with respect to the minute. Then, the filter member for oil-water separation which consists of nylon meshes was obtained on the same conditions as Example 1 except having adjusted solid content to 5.0 mass% with methanol.
実施例３：
実施例２で用いたナイロン製メッシュの代わりに、ナイロン製不織布（旭化成繊維株式会社製、１０２０）を用い、実施例２で用いたスラリーに不織布を浸漬してスラリーを塗布した以外は、実施例２と同様の条件で油水分離用フィルター部材を得た。
Example 3:
A nylon nonwoven fabric (manufactured by Asahi Kasei Fibers Co., Ltd., 1020) was used instead of the nylon mesh used in Example 2, and the slurry was applied by immersing the nonwoven fabric in the slurry used in Example 2. A filter member for oil / water separation was obtained under the same conditions as in No. 2.
比較例１：
実施例１で用いたナイロン製メッシュを実施例と同一の条件でコロナ処理し、油水分離用フィルター部材として用いた。
Comparative Example 1:
The nylon mesh used in Example 1 was corona treated under the same conditions as in Example 1 and used as a filter member for oil / water separation.
比較例２：
実施例２で用いたナイロン製不織布を実施例と同一の条件でコロナ処理し、油水分離用フィルター部材として用いた。
Comparative Example 2:
The nylon nonwoven fabric used in Example 2 was corona treated under the same conditions as in Example, and used as a filter member for oil / water separation.
（親水性の評価）
親水性の評価は、メッシュや不織布では正確な親水性が評価できない為、５０μｍの厚さのナイロンフィルム（東レ株式会社製、レイファン８０００）を用いて実施した。実施例１および実施例２、３の場合では、作成時に用いたスラリーをナイロンフィルム表面にバーコーターで塗布し、１００℃、５分間乾燥後、２００ｋＶの加速電圧で電子線を５Ｍｒａｄ照射し親水性の評価に用いた。また、比較例１および２の場合では、ナイロンフィルムに比較例１と同様の条件でコロナ処理を実施し親水性の評価に用いた。親水性は協和界面科学株式会社製固液界面解析装置ＤｒｏｐＭａｓｔｅｒ３００を用いて、それぞれのナイロンフィルム表面に蒸留水を１．０μＬ滴下し、形成した水滴の接触角を測定することで評価した。
(Evaluation of hydrophilicity)
The hydrophilicity was evaluated using a nylon film (Reyfan 8000 manufactured by Toray Industries, Inc.) having a thickness of 50 μm because accurate hydrophilicity cannot be evaluated with a mesh or nonwoven fabric. In the case of Example 1 and Examples 2 and 3, the slurry used at the time of preparation was applied to the nylon film surface with a bar coater, dried at 100 ° C. for 5 minutes, and then irradiated with 5 Mrad of an electron beam at an acceleration voltage of 200 kV for hydrophilicity. Used for evaluation. In the case of Comparative Examples 1 and 2, the nylon film was subjected to corona treatment under the same conditions as in Comparative Example 1 and used for hydrophilicity evaluation. Hydrophilicity was evaluated by dropping 1.0 μL of distilled water onto the surface of each nylon film using a solid-liquid interface analyzer DropMaster 300 manufactured by Kyowa Interface Science Co., Ltd., and measuring the contact angle of the formed water droplets.
（油水分離性の評価）
イオン交換水に直接染料（日本化薬株式会社製、Ｓｕｐｒａ Ｂｒｏｗｎ ＧＬ １２５）を加えて褐色に着色した。次に、当該着色したイオン交換水を灯油に３質量％となるように加え、ホモジナイザーで３分間分散し、水を懸濁させた灯油を調製した。実施例１〜３の油水分離用フィルター部材および比較例１、２をそれぞれ２．７ｍｍの厚さに重ね、ガラス製の焼結フィルター上に設置し、その上にガラス製ファンネルを固定した。固定したファンネルに水を懸濁させた灯油を注ぎ、減圧下で２００ｍＬ／分の流量で吸引し、ろ過後の染色した水の分離性を目視にて観察し評価した。これらの得られた結果を表１に示す。
(Evaluation of oil / water separation)
A dye (Supra Brown GL 125, manufactured by Nippon Kayaku Co., Ltd.) was directly added to ion-exchanged water to give a brown color. Next, the colored ion-exchanged water was added to kerosene so as to be 3% by mass, and dispersed with a homogenizer for 3 minutes to prepare kerosene in which water was suspended. The oil / water separation filter members of Examples 1 to 3 and Comparative Examples 1 and 2 were each stacked to a thickness of 2.7 mm, placed on a sintered glass filter, and a glass funnel was fixed thereon. Kerosene, in which water was suspended, was poured into a fixed funnel and suctioned at a flow rate of 200 mL / min under reduced pressure, and the separability of the dyed water after filtration was visually observed and evaluated. The obtained results are shown in Table 1.
上記結果より、無機微粒子とシランモノマーで被覆した無機微粒子とを分散したスラリーで処理したナイロンフィルム、言い換えれば、シランモノマーが結合した無機微粒子の群を基体上に固定することにより形成されたスペースに親水性を有する無機微粒子を保持させた実施例１〜３に関連するナイロンフィルムの親水性は、処理しない比較例１および２に関連するナイロンメッシュと比較して著しく優れていることが確認できた。当該結果から、基体１をナイロン製メッシュ、またはナイロン製不織布とした実施例１〜３についても、通水性について、同様の差があるものと考えられる。また、灯油に分散した水は実施例１〜３の油水分離用フィルター部材では完全に分離できたのに対し、比較例１のナイロン製メッシュ、および比較例２のナイロン製不織布では油水分離ができなかった。さらにバインダー成分としてアルコキシシランを加えた実施例２および３では親水性がさらに高まり、実施例１と同様に灯油と水を分離できることも示された。以上のとおり、本発明の油水分離用フィルター部材は、油水分離に優れた有用な油水分離用フィルター部材であることが確認できた。 From the above results, a nylon film treated with a slurry in which inorganic fine particles and inorganic fine particles coated with a silane monomer are dispersed, in other words, a space formed by fixing a group of inorganic fine particles bonded with silane monomers on a substrate. It was confirmed that the hydrophilicity of the nylon film related to Examples 1 to 3 in which inorganic fine particles having hydrophilicity were retained was remarkably superior to the nylon mesh related to Comparative Examples 1 and 2 that were not treated. . From these results, it is considered that Examples 1 to 3 in which the substrate 1 is made of nylon mesh or nylon nonwoven fabric have the same difference in water permeability. In addition, the water dispersed in kerosene could be completely separated by the oil / water separation filter members of Examples 1 to 3, whereas the nylon mesh of Comparative Example 1 and the nylon nonwoven fabric of Comparative Example 2 were capable of oil / water separation. There wasn't. Further, in Examples 2 and 3 in which alkoxysilane was added as a binder component, the hydrophilicity further increased, and it was shown that kerosene and water can be separated in the same manner as in Example 1. As described above, it was confirmed that the oil / water separation filter member of the present invention was a useful oil / water separation filter member excellent in oil / water separation.
１： 基体
２ａ： 無機微粒子（第２の無機微粒子）
２ｂ： 無機微粒子（第１の無機微粒子）
３： シランモノマー
４： バインダー成分
５： グラフト重合による共有結合
６： ラジカル重合による共有結合
７： シランモノマーと無機微粒子２ａとの脱水縮合反応による共有結合
８： 空間部（スペース）
１０： 無機微粒子２ａの群
１００： 油水分離用フィルター
1: Substrate 2a: Inorganic fine particles (second inorganic fine particles)
2b: Inorganic fine particles (first inorganic fine particles)
3: Silane monomer 4: Binder component 5: Covalent bond by graft polymerization 6: Covalent bond by radical polymerization 7: Covalent bond by dehydration condensation reaction between silane monomer and inorganic fine particle 2a 8: Space part (space)
10: Group of inorganic fine particles 2a 100: Oil-water separation filter
Claims (5)
親水性を有する第１の無機微粒子と、
前記第１の無機微粒子を基体上に保持するための、化学結合により表面にシランモノマーが結合した第２の無機微粒子の群とを備え、
前記第２の無機微粒子の群は、前記第２の無機微粒子同士が表面の前記シランモノマー間の化学結合を介して結合し、且つ、前記第２の無機微粒子の群が前記シランモノマーとの化学結合によって基体と結合することにより、前記第１の無機微粒子を保持するためのスペースを形成していることを特徴とする油水分離用フィルター部材。 A substrate;
First inorganic fine particles having hydrophilicity;
A group of second inorganic fine particles in which a silane monomer is bonded to the surface by a chemical bond for holding the first inorganic fine particles on a substrate;
The group of the second inorganic fine particles is such that the second inorganic fine particles are bonded to each other through a chemical bond between the silane monomers on the surface, and the second group of inorganic fine particles is a chemistry with the silane monomer. A filter member for oil / water separation, wherein a space for holding the first inorganic fine particles is formed by bonding to a substrate by bonding.
前記第２の無機微粒子同士を表面の前記シランモノマー間の化学結合により結合させるとともに、前記シランモノマーの不飽和結合部または反応性官能基と基体表面との化学結合により、前記第２の無機微粒子の群を基体と結合させて前記第１の無機微粒子を保持するためのスペースを形成し、前記第１の無機微粒子を当該スペースにて保持することを特徴とする油水分離用フィルター部材。 A slurry in which a group of second inorganic fine particles in which a first inorganic fine particle having hydrophilicity and a silane monomer having an unsaturated bond portion or a reactive functional group are chemically bonded to the surface is dispersed is applied to a substrate,
The second inorganic fine particles are bonded to each other by a chemical bond between the silane monomers on the surface, and the second inorganic fine particles are formed by a chemical bond between the unsaturated bond portion or the reactive functional group of the silane monomer and the substrate surface. A filter member for oil / water separation, wherein a group for holding the first inorganic fine particles is formed by bonding the group of the above to a substrate, and the first inorganic fine particles are held in the space.
前記シランモノマー間の化学結合がラジカル重合による共有結合であり、かつ、
前記シランモノマーと前記基体との化学結合がグラフト重合による共有結合であることを特徴とする請求項１または２に記載の油水分離用フィルター部材。 The chemical bond between the silane monomer and the inorganic fine particles is a covalent bond by dehydration condensation,
The chemical bond between the silane monomers is a covalent bond by radical polymerization, and
The oil-water separation filter member according to claim 1 or 2, wherein the chemical bond between the silane monomer and the substrate is a covalent bond by graft polymerization.
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