JPH0326097B2 - - Google Patents
Info
- Publication number
- JPH0326097B2 JPH0326097B2 JP58211470A JP21147083A JPH0326097B2 JP H0326097 B2 JPH0326097 B2 JP H0326097B2 JP 58211470 A JP58211470 A JP 58211470A JP 21147083 A JP21147083 A JP 21147083A JP H0326097 B2 JPH0326097 B2 JP H0326097B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- support
- membrane
- porous
- deposited
- 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.)
- Expired
Links
- 239000012528 membrane Substances 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 17
- 239000002131 composite material Substances 0.000 claims description 10
- 238000007733 ion plating Methods 0.000 claims description 10
- 239000010409 thin film Substances 0.000 claims description 8
- 239000002861 polymer material Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 229920002492 poly(sulfone) Polymers 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 229920006370 Kynar Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Description
【発明の詳細な説明】
本発明は、複合半透膜に関する。更に詳しく
は、多孔質高分子支持体上に高分子薄膜を設けて
なる複合半透膜に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composite semipermeable membrane. More specifically, the present invention relates to a composite semipermeable membrane comprising a thin polymer film provided on a porous polymer support.
従来、逆浸透膜などとして有効に使用されてい
る複合半透膜は、大きく分けて以下の３つのタイ
プに類別される。 Conventionally, composite semipermeable membranes that have been effectively used as reverse osmosis membranes and the like can be broadly classified into the following three types.
(1) 重合体コーテイング型
これは最も基本的なものであり、代表的なも
のとしてUOP社の複合膜などがある。(1) Polymer coating type This is the most basic type, and a representative example is UOP's composite membrane.
(2) 重合体コーテイング架橋型
NS−100膜といわれ、界面重合により複合膜
を形成させたもので、その代表例としては
UOP社のPA−100、PA−300、更にMSI社の
MSI100などが挙げられる。具体的には、上記
PA−300では、エピアミン−イソフタロイルク
ロリド橋かけ膜が形成されている。(2) It is called a polymer coating cross-linked NS-100 membrane, and a composite membrane is formed by interfacial polymerization.A typical example is
UOP's PA-100, PA-300, and MSI's
Examples include MSI100. Specifically, the above
In PA-300, an epiamine-isophthaloyl chloride cross-linked film is formed.
(3) 重合性単量体架橋型
NS−200膜と呼ばれているものが、代表的な
ものである。(3) A typical example is a polymerizable monomer crosslinked membrane called NS-200 membrane.
これらの中、重合体コーテイング架橋型および
重合性単量体架橋型のものは、架橋反応を行わせ
るのに多くの熱エネルギーを必要とし、従つて省
エネルギーという点からみて問題がある。また、
架橋反応時の熱処理条件、コーテイングされる重
合体の濃度あるいは重合性単量体溶液の濃度など
が膜性能に影響を及ぼすので、その管理が大変で
ある。 Among these, the polymer coating crosslinking type and the polymerizable monomer crosslinking type require a large amount of thermal energy to carry out the crosslinking reaction, and are therefore problematic from the point of view of energy saving. Also,
The heat treatment conditions during the crosslinking reaction, the concentration of the polymer to be coated, the concentration of the polymerizable monomer solution, etc. affect membrane performance and are difficult to manage.
従つて、これらの問題点を有する架橋型のもの
よりは重合体コーテイング型の方が製造面からみ
ると望ましいが、反面重合体コーテイング型のも
のはそれの製法上活性層となる高分子薄膜層の厚
さが厚くなり、従つて透水率があまり良くないと
いう難点がみられる。また、高分子薄膜層自体不
均一になり易く、ピンホールなどの膜欠陥を生ず
る危険性がかなり存在する。 Therefore, the polymer coating type is more desirable from a manufacturing standpoint than the crosslinked type, which has these problems, but on the other hand, the polymer coating type requires a thin polymer film layer that becomes the active layer due to its manufacturing method. The problem is that the thickness of the water becomes thick, and therefore the water permeability is not very good. Furthermore, the polymer thin film layer itself tends to be non-uniform, and there is a considerable risk of film defects such as pinholes occurring.
本発明者らは、活性層たる高分子薄膜層を薄く
かつ均一に形成させ、それによつて透水率が良好
でかつ膜欠陥のないものを得る目的で種々検討の
結果、イオンプレーテイングによつて高分子薄膜
を形成させるときわめて有効であることを見出し
た。 The inventors of the present invention have conducted various studies with the aim of forming a thin and uniform polymer thin film layer, which is an active layer, and thereby having good water permeability and no membrane defects. We have found that forming a thin polymer film is extremely effective.
従つて、本発明は複合半透膜に係り、この複合
半透膜は、多孔質高分子支持体上に支持体を形成
する高分子物質と同種または異種の高分子薄膜を
イオンプレーテイングにより蒸着させてなる。 Therefore, the present invention relates to a composite semipermeable membrane, which comprises a porous polymeric support, and a thin polymeric film of the same type or different type as the polymeric substance forming the support, deposited by ion plating. I'll let you.
多孔質高分子支持体としては、ポリスルホン、
ポリフツ化ビニリデン、芳香族ポリアミド、ポリ
プロピレン、ポリアクリロニトリル、ポリビニル
アルコールなどの高分子物質を、乾湿式法、溶融
法などにより多孔質化した膜状体が用いられる。
具体的には、例えば乾湿式法の場合には、所望濃
度の高分子物質溶液をスペーサーを用いてガラス
板上に一定の厚みにキヤステイングし、それを乾
燥させた後、ガラス板と共に水などの凝固浴中に
浸漬させることによりそれをゲル化させ、膜表面
に約20〜30〓程度の孔を形成させた膜状物を得る
方法によつて、多孔質高分子支持体が製造され
る。 Porous polymer supports include polysulfone,
A membrane-like body made of a polymeric material such as polyvinylidene fluoride, aromatic polyamide, polypropylene, polyacrylonitrile, polyvinyl alcohol, etc., made porous by a dry-wet method, a melting method, or the like is used.
Specifically, for example, in the case of the wet-dry method, a solution of a polymeric substance with a desired concentration is casted onto a glass plate to a certain thickness using a spacer, and after drying, water etc. are casted along with the glass plate. A porous polymer support is produced by a method of gelling it by immersing it in a coagulation bath to obtain a membrane-like material with approximately 20 to 30 pores formed on the membrane surface. .
これらの支持体上に蒸着される高分子物質は、
支持体を形成する高分子物質と同種または異種の
ものであり、例えばポリフツ化ビニリデン、ポリ
テトラフルオロエチレンなどのフツ素系樹脂が好
んで用いられる。これらの蒸着高分子物質は、イ
オンプレーテイング、好ましくは高周波法イオン
プレーテイングにより、蒸気として蒸発した後途
中でイオン化され、多孔質高分子支持体に向けて
加速されるので、大きな蒸着強度で（セロフアン
テープ剥離試験で剥離せず）支持体上に蒸着され
る。勿論、このような蒸着は、一般の真空蒸着で
も可能であるが、蒸着膜を強度や均一性などの点
からはイオンプレーテイングがはるかにすぐれて
おり、従つてピンホールなどの膜欠陥が殆んど考
えられない高分子薄膜層を支持体上に形成させる
ことができる。 The polymeric substances deposited on these supports are
The polymer material may be the same or different from the polymer material forming the support, and fluororesins such as polyvinylidene fluoride and polytetrafluoroethylene are preferably used. These vapor-deposited polymeric substances are vaporized as a vapor by ion plating, preferably radio-frequency ion plating, and then ionized midway through the process and accelerated toward the porous polymer support, resulting in a high vapor deposition intensity ( Deposited onto the support (without peeling in cellophane tape peel test). Of course, this kind of vapor deposition can be done by general vacuum vapor deposition, but ion plating is far superior in terms of strength and uniformity of the vapor-deposited film, and therefore almost eliminates film defects such as pinholes. Most inconceivable polymeric thin film layers can be formed on the support.
このような高分子物質の蒸着薄膜を形成させる
イオンプレーテイングは、例えば図示された態様
に従つて行なうことができる。即ち、イオンプレ
ーテイング装置としては、日本真空(株)製EBV−
6DHが用いられ、その基板ホルダー１に多孔質
高分子支持体を貼着し、蒸発源として無酸素銅ル
ツボ２中にフツ素系樹脂を収容した後、装置内の
圧力を10-5〜10-6Torrのオーダーに減圧し、ガ
ス入口３からアルゴンなどの不活性ガスを
10-4Torrのオーダー迄導入する。その後、可変
直流電源４を用いて200Vの電圧を印加し、次に
高周波電源５およびマツチングボツクス６によ
り、高周波コイル７に13.56MHzの高周波を20W
の有効電力でかける。約３分後、更にフイラメン
ト８に直流電源（EG−20M）９より、10ｍＡの
電流で5KVの電圧を約５分間かけて、イオンプ
レーテイングを行なう。 Ion plating to form such a vapor-deposited thin film of a polymeric substance can be performed, for example, according to the illustrated embodiment. That is, as an ion plating device, EBV- manufactured by Nippon Vacuum Co., Ltd.
6DH is used, and after pasting a porous polymer support on the substrate holder 1 and placing a fluorine-based resin in an oxygen-free copper crucible 2 as an evaporation source, the pressure inside the device is reduced to 10 -5 to 10 Reduce the pressure to the order of -6 Torr and supply inert gas such as argon from gas inlet 3.
Introduced up to the order of 10 -4 Torr. After that, a voltage of 200V is applied using the variable DC power supply 4, and then a high frequency of 13.56MHz is applied to the high frequency coil 7 for 20W using the high frequency power supply 5 and the matching box 6.
Multiply by the effective power of . After about 3 minutes, ion plating is performed by applying a voltage of 5 KV at a current of 10 mA to the filament 8 from a DC power supply (EG-20M) 9 for about 5 minutes.
このようにして、多孔質高分子支持体上に厚さ
約0.2〜0.3μｍ程度の高分子薄膜を蒸着させた複
合半透膜は、活性層の厚さが薄いので透水率およ
び性能の安定性の点での著しい改善が達成されて
おり、従つて逆浸透膜その他の膜用途に有効に使
用することができる。 In this way, a composite semipermeable membrane in which a thin polymer film with a thickness of about 0.2 to 0.3 μm is deposited on a porous polymer support has a thin active layer, so it has stable water permeability and performance. Significant improvements have been achieved in this respect, and therefore they can be effectively used in reverse osmosis membranes and other membrane applications.
次に、実施例について本発明を説明する。 Next, the present invention will be explained with reference to examples.
実施例 １
ポリスルホン（日産化学製品Ｐ−1700）を15重
量％含有するジメチルホルムアミド溶液を、スペ
ーサー厚0.2mmでガラス板上にキヤストし、水を
凝固剤とする乾湿式法により、厚さ0.12mmの多孔
質高分子支持体を製造した。Example 1 A dimethylformamide solution containing 15% by weight of polysulfone (Nissan Chemical Products P-1700) was cast onto a glass plate with a spacer thickness of 0.2 mm, and a thickness of 0.12 mm was cast by a wet-dry method using water as a coagulant. A porous polymeric support was produced.
この多孔質ポリスルホン支持体を用い、図示さ
れた態様に従つてイオンプレーテイングが行われ
た。蒸着される高分子物質としてはポリフツ化ビ
ニリデン（ベンウオリト社製品カイナー4600）が
用いられ、不活性ガスとしてはアルゴンが７×
10-4Torrの圧力になる迄導入された。 Ion plating was performed using this porous polysulfone support according to the illustrated embodiment. Polyvinylidene fluoride (Kynar 4600, manufactured by Benwolito) was used as the polymer material to be vapor-deposited, and argon was used as the inert gas at 7×
It was introduced to a pressure of 10 -4 Torr.
このようにして多孔質ポリスルホン支持体上に
ポリフツ化ビニリデンの薄膜（厚さ0.3μｍ）を蒸
着させた複合半透膜は、これに2500ppmの塩化ナ
トリウム水溶液を操作圧50Kg／cm3で透過させたと
ころ、透水率については0.10cm3／cm2・hr・Kg／cm2
の値が、また排除率については92.1％の値がそれ
ぞれ得られた。 A composite semipermeable membrane in which a thin film (thickness: 0.3 μm) of polyvinylidene fluoride was deposited on a porous polysulfone support was fabricated through which a 2500 ppm aqueous sodium chloride solution was permeated at an operating pressure of 50 Kg/cm 3 . However, the water permeability is 0.10cm 3 /cm 2・hr・Kg/cm 2
and the exclusion rate was 92.1%.
実施例 ２
実施例１において、ポリフツ化ビニリデン（ベ
ントウオルト社製カイナー4600）20重量％および
ボピエチレングリコール（関東化学製品PEG
＃6000）２重量％をそれぞれ含有するジメチルホ
ルムアミド溶液から乾湿式法により製造された多
孔質ポリフツ化ビニリデン支持体（厚さ0.10mm）
が用いられた。Example 2 In Example 1, 20 wt.
#6000) Porous polyvinylidene fluoride supports (thickness 0.10 mm) produced by wet-dry method from dimethylformamide solutions containing 2% by weight, respectively.
was used.
実施例１と同様にして測定された透水率は0.08
cm2／cm3・hr・Kg／cm2であり、また排除率は85.8％
であつた。 The water permeability measured in the same manner as in Example 1 was 0.08.
cm 2 /cm 3・hr・Kg/cm 2 , and the rejection rate is 85.8%
It was hot.
図面は、本発明に用いられるイオンプレーテイ
ング装置の概略図である。
（符号の説明）、１……基板ホルダー、２……
ルツボ、３……不活性ガス入口、４……可変直流
電源、５……高周波電源、６……マツチングボツ
クス、７……高周波コイル、８……フイラメン
ト、９……直流電源。
The drawing is a schematic diagram of an ion plating apparatus used in the present invention. (Explanation of symbols), 1...Substrate holder, 2...
Crucible, 3... Inert gas inlet, 4... Variable DC power supply, 5... High frequency power supply, 6... Matching box, 7... High frequency coil, 8... Filament, 9... DC power supply.
Claims (1)
高分子物質と同種または異種の高分子薄膜をイオ
ンプレーテイングにより蒸着させてなる複合半透
膜。 ２ 高分子薄膜としてフツ素系樹脂薄膜を蒸着さ
せた特許請求の範囲第１項記載の複合半透膜。[Scope of Claims] 1. A composite semipermeable membrane formed by depositing on a porous polymer support a polymer thin film of the same type or different type as the polymer material forming the support by ion plating. 2. The composite semipermeable membrane according to claim 1, in which a fluororesin thin film is deposited as the polymer thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58211470A JPS60102903A (en) | 1983-11-10 | 1983-11-10 | Composite semipermeable membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58211470A JPS60102903A (en) | 1983-11-10 | 1983-11-10 | Composite semipermeable membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60102903A JPS60102903A (en) | 1985-06-07 |
| JPH0326097B2 true JPH0326097B2 (en) | 1991-04-09 |
Family
ID=16606470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58211470A Granted JPS60102903A (en) | 1983-11-10 | 1983-11-10 | Composite semipermeable membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60102903A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0574957B1 (en) * | 1989-04-14 | 2002-01-02 | Membrane Products Kiryat Weizmann Ltd. | Acrylonitrile- and polyvinylidene fluoride-derived membranes |
-
1983
- 1983-11-10 JP JP58211470A patent/JPS60102903A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60102903A (en) | 1985-06-07 |
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