JPS63100906A - Manufacture of semipermeable composite membrane - Google Patents
Manufacture of semipermeable composite membraneInfo
- Publication number
- JPS63100906A JPS63100906A JP61245929A JP24592986A JPS63100906A JP S63100906 A JPS63100906 A JP S63100906A JP 61245929 A JP61245929 A JP 61245929A JP 24592986 A JP24592986 A JP 24592986A JP S63100906 A JPS63100906 A JP S63100906A
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- composite membrane
- producing
- semipermeable
- water
- 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.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 102
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000004760 aramid Substances 0.000 claims abstract description 13
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 13
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 10
- 239000010409 thin film Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims description 11
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000012696 Interfacial polycondensation Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 abstract description 16
- 230000035699 permeability Effects 0.000 abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 3
- 238000006482 condensation reaction Methods 0.000 abstract 1
- 235000002639 sodium chloride Nutrition 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 238000000926 separation method Methods 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- 229920002301 cellulose acetate Polymers 0.000 description 6
- 238000010612 desalination reaction Methods 0.000 description 6
- 238000001223 reverse osmosis Methods 0.000 description 6
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 6
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- 150000001263 acyl chlorides Chemical group 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- -1 polybenzimidacylon Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920005575 poly(amic acid) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- ZFRBZRZEKIOGQI-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound C1=CC(O)=C2C(N)=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=C1 ZFRBZRZEKIOGQI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- 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
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野〕
本発明は、液状混合物の成分を選択透過分離するための
半透膜に関するものであり、特に海水およびカン水を脱
塩して淡水化することができ、また染色廃水や、電着塗
料廃水等の公害発生原因である汚水等から、その中に含
まれる汚染あるいは有効物質を選択的に除去又は回収し
、ひいては、廃水のクローズド化に寄与することができ
る半透性複合膜に関する。[Detailed Description of the Invention] (Industrial Application Field) The present invention relates to a semipermeable membrane for selectively permeating and separating components of a liquid mixture, and particularly for desalinating and desalinating seawater and can water. It also selectively removes or recovers pollutants or effective substances contained in wastewater that causes pollution, such as dyeing wastewater and electrocoating paint wastewater, thereby contributing to the closure of wastewater. The present invention relates to a semipermeable composite membrane capable of
〔従来の技術〕
従来、工業的に利用されている半透膜には、酢酸セルロ
ーズから作った非対称膜として、例えば米国特許用３．
１３３．１３２号明細書及び同第３．１３３．１３７号
明細書に記載されたロブ型の膜がある。しかし、この膜
は、耐加水分解性、耐微生物性、耐薬品性などに問題が
あり、特に透過性を向上しにうとすると耐圧性、耐久性
を兼ねＩＭえた膜が製造できず、一部使用されているが
広範囲の用途に実用化されるに至っていない。これらの
酢酸セルローズ非対称膜の欠点をなくした新しい素材に
対する研究は、米国、日本を中心に盛んに行なわれてい
るが、芳香族ポリアミド、ポリアミドヒドラジド（米国
特許用３．５６７、６３２号明細Ｂ）、ポリアミド酸（
特公昭５５−３．７２８２号公報）、架橋ポリアミド酸
（特公昭５６−３７６９号公報）、ポリイミダゾピロロ
ン、ポリスルホンアミド、ポリベンズイミダゾール、ポ
リベンズイミダシロン、ポリアリーレンオキシドなど、
その一部の欠点を改良する素材は得られているものの、
選択分離性あるいは透過性等の面では酢酸セルローズ膜
より劣っている。[Prior Art] Conventionally, semipermeable membranes that have been used industrially include asymmetric membranes made from cellulose acetate, such as those described in US Patent No. 3.
There are lob-type membranes described in 133.132 and 3.133.137. However, this membrane has problems with hydrolysis resistance, microbial resistance, chemical resistance, etc. Especially when trying to improve permeability, it is not possible to manufacture a membrane that has both pressure resistance and durability, and some Although it is used, it has not yet been put to practical use in a wide range of applications. Research into new materials that eliminate these drawbacks of cellulose acetate asymmetric membranes is being actively conducted mainly in the United States and Japan, but aromatic polyamides and polyamide hydrazides (U.S. Patent No. 3.567, 632 Specification B) , polyamic acid (
(Japanese Patent Publication No. 55-3.7282), crosslinked polyamic acid (Japanese Patent Publication No. 56-3769), polyimidazopyrrolone, polysulfonamide, polybenzimidazole, polybenzimidacylon, polyarylene oxide, etc.
Although materials have been obtained to improve some of the drawbacks,
It is inferior to cellulose acetate membranes in terms of selective separation or permeability.
一方、ロブ型とは型を異にする半透膜として多孔性支持
体（支持膜）上に実質的に膜性能を司どる活性層（超薄
膜）を被フした複合膜が開発されている。複合膜におい
ては、活性層と多孔性支持体を各々の用途に最適な素材
を選ぶことが可能となり、製膜技術の自由度が増す。ま
た常時湿潤状態で保存しなければならないロブ型膜とは
異なり乾燥状態での保存が可能であるなどの利点がある
。On the other hand, a composite membrane has been developed that is a semipermeable membrane of a different type from the lobe type, in which a porous support (support membrane) is covered with an active layer (ultra-thin membrane) that essentially controls membrane performance. . In composite membranes, it becomes possible to select the optimal materials for the active layer and porous support for each application, increasing the degree of freedom in membrane manufacturing technology. It also has the advantage of being able to be stored in a dry state, unlike a lobe-type membrane that must be stored in a constantly wet state.
これらの複合膜には多孔性支持体上に直接活性層を被覆
した型のものと、多孔性支持体上にゲル化層を介して活
性層を被覆した型のものとの２種類がある。前者の具体
例は米国特許用３．７４４．６４２号明細書、同第３．
９２６．７９８号明細書、特開昭５５−１４７１０６号
公報、米国特許用 ４，５５７，９４９ ＠明細書、同
第４．３６６、０６２号明細書、特開昭５８−２４３０
３号公報などがおり、後者の具体例としては、特開昭４
９−１３３２８２号公報、特公昭５５−４９５２４号公
報、特公昭５５−３８１６４号公報、ＰＢレポート８０
−１８２０９０＠、米国特許用４．３８７．０２４号明
細書、同第４．５５９．１３９号明細書などが知られて
いる。There are two types of these composite membranes: one in which the active layer is directly coated on a porous support, and one in which the active layer is coated on the porous support through a gelling layer. Specific examples of the former are given in U.S. Pat.
Specification No. 926.798, JP 55-147106, U.S. Patent No. 4,557,949 @ Specification, JP 4.366,062, JP 58-2430
3, etc., and a specific example of the latter is JP-A No. 4
9-133282, Japanese Patent Publication No. 55-49524, Japanese Patent Publication No. 55-38164, PB Report 80
-182090@, US Pat. No. 4.387.024, US Pat. No. 4.559.139, etc. are known.
これらの複合膜は、従来、膜に対する要求特性すなわち
、水中に溶解している無機および有機物に対する排除率
、高造水吊、塩濃度依存性、耐熱性、耐薬品性、耐圧性
、耐久性、耐塩素性および耐過酸化水素性といった特性
を全て満足するものは得られていない。Conventionally, these composite membranes have the characteristics required for membranes, such as rejection rate for inorganic and organic substances dissolved in water, high water production capacity, salt concentration dependence, heat resistance, chemical resistance, pressure resistance, durability, No material has been obtained that satisfies all properties such as chlorine resistance and hydrogen peroxide resistance.
［本発明が解決しようとする問題点コ
逆浸透法は、その応用分野も海水淡水化、カン水淡水化
、超純水製造、有価物の濃縮に至るまで非常に広範囲に
わたっている。[Problems to be Solved by the Present Invention] Reverse osmosis has a wide range of applications, including seawater desalination, plain water desalination, ultrapure water production, and concentration of valuable substances.
しかし、これらの広範囲な用途の中で、塩濃度依存性が
少なく、高い塩排除率と透水性を兼ねそなえた理想的な
膜はまだ出現していない。例えば、比較的塩濃度の低い
カン水淡水化では高い塩排除率と透水性を示す膜も、塩
濃度の高いカン水淡水化では塩排除率が低下する結果と
なってしまう。However, among these wide-ranging applications, an ideal membrane with low salt concentration dependence, high salt rejection rate, and water permeability has not yet appeared. For example, a membrane that exhibits a high salt rejection rate and water permeability in desalination of plain water with a relatively low salt concentration will result in a decreased salt rejection rate in desalination of plain water with a high salt concentration.
このような塩濃度依存性のある膜は、膜の荷電量の影響
を受けていると考えられる。現在開発されている膜は透
水性を上げるため、荷電基を導入することが用いられ、
中性膜と称される酢酸セルロース膜も僅かながら荷電を
有していると言われている。しかし酢酸セルロース膜程
度の荷電量では塩濃度依存性はあまりみられないが、相
対的に透水性は少ない。It is thought that such a salt concentration-dependent film is affected by the amount of charge on the film. The currently developed membranes use charged groups to be introduced to increase water permeability.
Cellulose acetate membranes, which are called neutral membranes, are also said to have a slight charge. However, with a charge level comparable to that of a cellulose acetate membrane, there is little dependence on salt concentration, but the water permeability is relatively low.
本発明は、高い透水性を維持しつつ、荷電最を減少し、
塩′ａ度依存性の少ない膜を得ることを目的とする。The present invention reduces electrical charge while maintaining high water permeability,
The purpose is to obtain a membrane with less dependence on salt content.
［問題点を解決するための手段］
上記目的を達成するために、本発明は下記の溝成を有す
る。[Means for Solving the Problems] In order to achieve the above object, the present invention has the following features.
すなわち、本発明は、
「 微多孔性支持膜と該支持膜を被覆する超薄膜からな
る複合半透膜において、前記微多孔性複合膜を熱水処理
し、かつ、下記のイ、口の界面重縮合反応によって得ら
れる架橋芳香族ポリアミドからなる、前記超薄膜を被覆
することを特徴とする半透性複合膜の製造方法。That is, the present invention provides a composite semipermeable membrane consisting of a microporous support membrane and an ultra-thin membrane covering the support membrane, in which the microporous composite membrane is treated with hot water, and A method for producing a semipermeable composite membrane, comprising coating the ultra-thin membrane made of a crosslinked aromatic polyamide obtained by a polycondensation reaction.
イ、２つのアミノ基を有する芳香族アミンを含有する水
溶液。B. An aqueous solution containing an aromatic amine having two amino groups.
口、平均官能度２．２５〜２．７５の芳香族酸塩化物を
含有する水と非混和性の有機溶媒溶液。」
に関する。A water-immiscible organic solvent solution containing an aromatic acid chloride with an average functionality of 2.25 to 2.75. ” regarding.
本発明において使用する芳香族アミンとは、下式［Ｉ］
または［■］で示されるもので、下式［Ｉ］のＲ１−Ｒ
６、または下式［ｎ］のＲ１〜ＲＩＯのうち２つは、反
応性アミノ基である。The aromatic amine used in the present invention has the following formula [I]
or [■], R1-R of the following formula [I]
6 or two of R1 to RIO in the following formula [n] are reactive amino groups.
式［Ｉ］ 式［■コ
上記式［１］、ｔ’；；よび［ＩＩｌのＲ１−Ｒ６、ま
たは、Ｒ１〜ＲＩＯのうちアミノ基以外の置換基として
は、−Ｈ，−０ＣＨ３、−ＣＨ３、−ｃ２ｈ５、−Ｃ３
Ｈ了 、−８Ｏ３Ｈｌ−Ｎｌ−１０Ｈ３、−ＯＨ。Formula [I] Formula [■Co Formula [1], t'; , -c2h5, -C3
H, -8O3Hl-Nl-10H3, -OH.
−ＣＣＨ３、−Ｆ、−ＣＤ、、−Ｂｒ、−Ｉなど架橋ポ
リアミドの形成を阻害しないものでおればいずれであっ
てもよく、好ましくは、−Ｈ，−ＱＣ）−１３、−ＯＨ
など水の透過性を増すために親水性を有する＠換基が用
いられる。-CCH3, -F, -CD, -Br, -I, etc., may be used as long as they do not inhibit the formation of crosslinked polyamide, preferably -H, -QC)-13, -OH
Hydrophilic @ substituents are used to increase water permeability.
また、式［ｎ］において×は単結合、
−ＮＨＣＯ−１−ＳＯ２−１−Ｓ−１−Ｃ−Ｏ−１Ｈ３
−Ｃ−１−〇−など、２つの芳香環を結合させう゛醒ゴ
るものであればいずれであってもよく、好ましくは、
０
−ＮＨＣＯ−１−ｓｏ２−１−ｃ−ｏ−１−〇−など酸
素を有する結合が水との相互作用の点で好ましく、更に
好ましくは、−〇−１ＮＨＣＯ−が水との親和性の点に
おいて好ましい。置換基の位置については特に限定され
ないが、分離性能を考慮すると立体障害の少ない位置が
好ましい。これらの芳香族アミンにおいて分離特性、耐
久性などを考慮すると、本発明における芳香族アミンは
、から選ばれる少なくとも１種の芳香族アミンが好まし
い。In the formula [n], x is a single bond, -NHCO-1-SO2-1-S-1-C-O-1H3 -C-1-〇-, etc. Any type of material may be used as long as it is, and preferably,
Bonds with oxygen such as 0 -NHCO-1-so2-1-c-o-1-〇- are preferable from the viewpoint of interaction with water, and more preferably -〇-1NHCO- has a high affinity with water. This is preferable in this respect. The position of the substituent is not particularly limited, but in consideration of separation performance, a position with little steric hindrance is preferred. Considering the separation characteristics, durability, etc. of these aromatic amines, the aromatic amine in the present invention is preferably at least one aromatic amine selected from the following.
本発明において醸塩化物とは、前記式［Ｉ］または［Ｉ
Ｉｌで示されるもので、式［Ｉ］においてＲ１−Ｒ６の
うち２つ以上は、反応性アシルクロライド基でおるが、
その数は２〜６が好ましく、化合物の取り扱い易さから
、更に好ましくは２〜３である。In the present invention, the chloride refers to the above formula [I] or [I
In the formula [I], two or more of R1 to R6 are reactive acyl chloride groups,
The number is preferably 2 to 6, and more preferably 2 to 3 from the viewpoint of ease of handling the compound.
上記式［Ｉ］のＲ１−Ｒ６のうちアシルクロライド基以
外の置換基としては、−日、−ＱＣ）（３、−ＣＨｌ、
−Ｃ２Ｈｓ 、−Ｃ３Ｈ？、一〇 〇 Ｈｌ、−Ｆ、−
ｃＤ、、−Ｂｒ、−Ｉなど架橋ポリアミドの形成を阻害
しないものであればいずれであってもよく、好ましくは
−Ｈ，ＯＣＨ３、など水の透過性を増すために親水性を
有する置換基が用いられる。Among R1 to R6 of the above formula [I], substituents other than the acyl chloride group include -day, -QC)(3, -CHl,
-C2Hs, -C3H? , 10 0 Hl, -F, -
Any substituent that does not inhibit the formation of the crosslinked polyamide, such as cD, -Br, -I, etc. may be used, and preferably -H, OCH3, or other substituents having hydrophilic properties are used to increase water permeability. used.
前記式［■］において、Ｒ１〜Ｒ１ｏのうち２つ以上は
アシルクロライド基であるが、この数は塩濃度依存性を
有する膜を得るということで好ましくは、２〜７であり
、原料の入手し易さ、取り扱い易ざからして更に好まし
くは、２〜４である。In the above formula [■], two or more of R1 to R1o are acyl chloride groups, but this number is preferably 2 to 7 in order to obtain a membrane with salt concentration dependence. The number is more preferably 2 to 4 in terms of ease of preparation and handling.
上記式［ＩＩｌにおいて、Ｒ１〜ＲＩＯのうち、上記以
外の置換基としては、−日、−００Ｈｌ、−〇Ｈ３、−
０２トＩｓ 、 −Ｃ３Ｈ７、−ＣＯＣＨ３、−Ｆ、
−０４、−Ｂｒ、−Ｉなど架橋ポリアミドの形成を阻害
しないものでおればいずれであってもよい。In the above formula [IIl, among R1 to RIO, substituents other than the above include -day, -00Hl, -〇H3, -
02ToIs, -C3H7, -COCH3, -F,
Any material may be used as long as it does not inhibit the formation of crosslinked polyamide, such as -04, -Br, and -I.
水の透過性を考えると好ましくは、−Ｈｌ−〇ＣＨ３、
など親水性を有する置換基が用いられる。Considering water permeability, -Hl-〇CH3,
Substituents having hydrophilic properties are used.
マタ、ｘは単結合、−ＮＨＣＯ−１−３Ｏ２−１ＣＨゴ
の芳香環を結合させうるちのであればいずれであっても
よく、好ましくは、−ＮＨＣＯ−１一３Ｏ２−１−Ｃ−
Ｏ−１−〇−など酸素を有する結合が水との相互作用の
点で好ましく、更に好ましくは、−０−１−ＮＨＣＯ−
が水との親和性の点において好ましい。置換基の位置に
ついては特に限定されるものでないが、分離性能を考慮
すると立体障害の少ない位置が好ましい。, x may be a single bond, -NHCO-1-3O2-1CH, and may be any bond as long as it can bond the aromatic ring, preferably -NHCO-1-3O2-1-C-
Bonds containing oxygen such as O-1-〇- are preferred from the viewpoint of interaction with water, and more preferably -0-1-NHCO-
is preferable in terms of affinity with water. The position of the substituent is not particularly limited, but in consideration of separation performance, a position with little steric hindrance is preferred.
従って、本発明における芳香族酸塩化物は、本発明にお
いて、芳香族酸塩化物の平均官能度とは、１種以上の２
官能以上の芳香族酸塩化物からなる芳香族酸塩化物にお
いて、アシルクロライド基の総和を分子数で割ることに
より得られる値に等しい。酸塩化物の平均官能度は、塩
濃度依存性の点から２．２５〜２．７５でおり、好まし
くは２．２５〜２．５０の範囲でおる。Therefore, in the present invention, the average functionality of the aromatic acid chloride refers to one or more types of aromatic acid chlorides.
In an aromatic acid chloride consisting of aromatic acid chlorides having a functional or higher functional level, it is equal to the value obtained by dividing the sum of acyl chloride groups by the number of molecules. The average functionality of the acid chloride is in the range of 2.25 to 2.75, preferably in the range of 2.25 to 2.50, from the viewpoint of salt concentration dependence.
本発明において、好ましい微多孔性支持膜としてはポリ
エステルまたは芳香族ポリアミドから選ばれる少なくと
も一種を主成分とする布帛により強化されたポリスルホ
ン支持膜を例示することができる。In the present invention, a preferred example of a microporous support membrane is a polysulfone support membrane reinforced with a fabric whose main component is at least one selected from polyester and aromatic polyamide.
多孔性支持体は、実質的には分離性能を有さない層で、
実質的に分離性能を有する薄膜に強度を与えるために用
いられるものであり、均一な微細な孔あるいは片面から
もう一方の面まで徐々に大きな微細な孔をもっていて、
その微細孔の大きさはその片面の表面が１０００Å以下
であるような構造の支持体が好ましい。上記の多孔性支
持体は、通常は、“オフィス・オブ・セイリーン・ウォ
ーター・リサーチ・アンド・ディベロップメント・プロ
グレス・レポート”Ｎ、３５９ （１９６８）に記載さ
れた方法に従って、製造できる。その素材にはポリスル
ホンや酢酸セルロース、硝酸セルロースやポリ塩化ビニ
ル等のホモポリマあるいはブレンドしたものが通常使用
され、例えば、ポリスルホンのジメチルホルムアミド（
ＤＭＦ）溶液を密に織ったポリエステル布あるいは不織
布の上に一定の厚さに注型し、それをドデシル硫酸ソー
ダ０．５重量％及びＤＭＦ２重量％含む水溶液中で湿式
凝固させることによって、表面の大部分が直径数１０止
以下の微細な孔を有した多孔性支持体が得られる。The porous support is a layer that does not substantially have separation performance,
It is used to give strength to a thin film that has substantial separation performance, and has uniform fine pores or gradually larger fine pores from one side to the other.
The support preferably has a structure in which the size of the micropores on one surface is 1000 Å or less. The above-mentioned porous support can generally be manufactured according to the method described in "Office of Saline Water Research and Development Progress Report" N, 359 (1968). Homopolymers or blends of polysulfone, cellulose acetate, cellulose nitrate, and polyvinyl chloride are usually used as materials. For example, polysulfone dimethylformamide (
DMF) solution is cast to a certain thickness onto a tightly woven polyester cloth or non-woven fabric, and the surface is wet-coagulated in an aqueous solution containing 0.5% by weight of sodium dodecyl sulfate and 2% by weight of DMF. A porous support having fine pores, most of which have a diameter of several tens of microns or less, is obtained.
このようにして、得られた支持体は、ざらに高造水性と
するために、５０℃から１００’Ｃの温度範囲の水中に
浸漬する。The support thus obtained is immersed in water at a temperature in the range of 50° C. to 100° C. in order to make it highly water-forming.
上記の如く熱水処理することにより、従来の造水量に比
べて２０〜３０％以上向上することができる。By performing the hot water treatment as described above, the amount of water produced can be increased by 20 to 30% or more compared to conventional water production.
本発明において、超薄膜層は通常界面重縮合反応により
形成された架橋芳香、族ポリアミドであり、その厚さは
１００人〜１０，０００人の間からその目的に応じて任
意に選ぶことができる。In the present invention, the ultra-thin film layer is usually a crosslinked aromatic polyamide formed by interfacial polycondensation reaction, and its thickness can be arbitrarily selected from between 100 and 10,000 depending on the purpose. .
本発明において有機溶媒とは、水と非混和性でありかつ
酸塩化物を溶解し微多孔性支持膜を破壊しないことが必
要であり、界面重縮合により架橋芳香族ポリアミドを形
成しうるちのであればいずれであっても良い。In the present invention, the organic solvent must be immiscible with water, dissolve acid chlorides, and not destroy the microporous support membrane, and must be capable of forming a crosslinked aromatic polyamide through interfacial polycondensation. Either one is fine if there is one.
好ましい例としては炭化水素化合物、シクロヘキサン、
トリフロロトリクロロエタンなどが挙げられるが、反応
速度、溶媒の揮発性からは好ましくはｎ−ヘキサン、ト
リフロロトリクロロエタンから選ばれる少なくとも１種
であり、引火性という安全上の問題を考慮すると更に好
ましくはトリフロロトリクロロエタンでおる。Preferred examples include hydrocarbon compounds, cyclohexane,
Examples include trifluorotrichloroethane, but in terms of reaction rate and volatility of the solvent, at least one selected from n-hexane and trifluorotrichloroethane is preferred, and in view of the safety issue of flammability, trifluorotrichloroethane is more preferred. Cover with fluorotrichloroethane.
［実施例］
以下に、アミン成分としてｍ−フエニレンジアミンを用
い、薗クロライド成分としてトリメシン酸クロライド、
テレフタル酸クロライドを用いることにより、製膜され
た逆浸透膜の膜性能を示す。[Example] Below, m-phenylenediamine was used as the amine component, and trimesic acid chloride and trimesic acid chloride were used as the chloride component.
The membrane performance of a reverse osmosis membrane formed using terephthalic acid chloride is shown.
選択分離性能として、食塩の排除率は、電気伝導度の測
定による通常の手段により決定し、透過性能として水速
過速度は単位面積、単位時間当りの水通過量で決定した
。As selective separation performance, the rejection rate of common salt was determined by the usual method of measuring electrical conductivity, and as permeation performance, water overrate was determined as the amount of water passing per unit area and unit time.
参考例１
本発明において使用した繊維補強ポリスルホン支持体は
、以下の手法により製造した。Reference Example 1 The fiber-reinforced polysulfone support used in the present invention was manufactured by the following method.
タテ３Ｑｃｍヨコ２０ｃｍの大きさのポリエステル繊維
からなるタフタ（タテ糸、ヨコ糸とも１５０デニールの
マルチフィラメント糸、織密度タテ９０本／インチ、ヨ
コ６７本／インチ、厚さ１６０μ）をガラス板上に固定
し、その上にポリスルホン（ユニオン・カーバイト社製
の１Ｊｄｅｌ−Ｐ３５００ ）の１５重口％ジメチルホ
ルムアミド（ＤＭＦ）溶液を２００μの厚みで室温（２
０″Ｃ）でキャストし、ただちに純水中に浸漬して５分
間放置することによって繊維補強ポリスルホン支持体（
以下ＦＲ−ＰＳ支持体と略す）を作製する。Taffeta made of polyester fibers with a length of 3Q cm and a width of 20 cm (both warp and weft are 150 denier multifilament yarns, weaving density of 90 pieces/inch vertically and 67 pieces/inch horizontally, thickness 160μ) is placed on a glass plate. A 15% dimethylformamide (DMF) solution of polysulfone (1Jdel-P3500, manufactured by Union Carbide) was placed on top of it at room temperature (200μ thick).
A fiber-reinforced polysulfone support (
A FR-PS support (hereinafter abbreviated as FR-PS support) is produced.
実施例１
参考例１により得られたＦＲ−ＰＳ支持体を９０°Ｃの
水中に２分間浸漬して熱水処理した（多、室温の水中に
入れ冷却した。Example 1 The FR-PS support obtained in Reference Example 1 was immersed in water at 90° C. for 2 minutes for hot water treatment (after cooling in water at room temperature).
次にこのＦＲ−ＰＳ支持体をｍ−フェニレンジアミン２
．０重量％を含有する水溶液中に２分間浸漬した。ＦＲ
−ＰＳ支持体の表面から余分な該水溶液を取り除いた後
、１〜リメシン酸クロライド０．３重量％、テレフタル
酸クロライド０．７重量％を含有する１、１．２−トリ
クロロ−１，２゜２−トリフロロエタン溶液を表面が完
全に濡れるようにコーティングして１分間静置した。膜
を垂直にして余分な該溶液を液切りして除去した後、０
．２重量％の炭酸ナトリウムを含む水溶液に５分間浸漬
してから水洗を行なった。得られた複合 。Next, this FR-PS support was coated with m-phenylenediamine 2
．． It was immersed in an aqueous solution containing 0% by weight for 2 minutes. F.R.
- After removing the excess aqueous solution from the surface of the PS support, 1,1,2-trichloro-1,2° containing 0.3% by weight of 1-rimesic acid chloride and 0.7% by weight of terephthalic acid chloride The 2-trifluoroethane solution was coated so that the surface was completely wetted and allowed to stand for 1 minute. After removing the excess solution by holding the membrane vertically,
．． After being immersed in an aqueous solution containing 2% by weight of sodium carbonate for 5 minutes, it was washed with water. The resulting composite.
半透膜を濃度１５００〜２００００ｐｐｍの食塩を使用
して、圧力３０に！ｌ］／ｃＪ、２５℃の条件下で逆浸
透性能を評価した結果第１表に示す結果が得られた。Use a semipermeable membrane with salt at a concentration of 1,500 to 20,000 ppm to create a pressure of 30! As a result of evaluating the reverse osmosis performance under the conditions of 1]/cJ and 25°C, the results shown in Table 1 were obtained.
実施例２
実施例１において酸クロライド成分、トリメシン酸クロ
ライド０．８０ｆｆｌｆｆ１％、テレフタル酸クロライ
ド０．２０重ω％である伯は全く同条件で製膜し、逆浸
透性能を測定した結果を第２表に示す。Example 2 In Example 1, the acid chloride components, trimesic acid chloride 0.80 fflff1%, and terephthalic acid chloride 0.20 wt %, were formed under exactly the same conditions, and the results of measuring the reverse osmosis performance were evaluated in the second example. Shown in the table.
比較例１
実施例１において支持体に熱水処理を施さないＦＲ−Ｐ
Ｓ、ｉ１ｍクロライド成分、トリメシン酸クロライド０
．９ｍｍ％、テレフタル酸クロライド０．１重四％であ
る他は全く同条件で製膜し、逆浸透性能を測定した結果
を第３表に示す。Comparative Example 1 FR-P in which the support was not subjected to hot water treatment in Example 1
S, i1m chloride component, trimesic acid chloride 0
．． Table 3 shows the results of measuring the reverse osmosis performance by forming a membrane under the same conditions except that the concentration of terephthalic acid chloride was 9 mm% and 0.1% by weight of terephthalic acid chloride.
比較例２
実施例１において支持体に熱水処理を施さないＦＲ−Ｐ
ＳＳ酸クロライド成分、トリメシン酸クロライド０．９
５重量％、テレフタル酸クロライド０．０５重量％であ
る他は全く同条件で製膜し、逆浸透性能を測定した結果
を第４表に示す。Comparative Example 2 FR-P in which the support was not subjected to hot water treatment in Example 1
SS acid chloride component, trimesic acid chloride 0.9
Table 4 shows the results of measuring the reverse osmosis performance by forming a membrane under the same conditions except that the amount of terephthalic acid chloride was 5% by weight and 0.05% by weight.
第１表
第２表
第３表
第４表
［発明の効果］
以上の実施例で示したように、本発明により高い脱塩率
、高い透水性を有し、かつ無機塩の濃度によらない性能
を維持できる複合半透膜を製造できることがわかった。Table 1 Table 2 Table 3 Table 4 [Effects of the invention] As shown in the above examples, the present invention has a high desalination rate and high water permeability, and is independent of the concentration of inorganic salts. It was found that it is possible to produce a composite semipermeable membrane that maintains its performance.
特に広範囲なカン水淡水化に適した膜を製造することが
できる。In particular, a membrane suitable for a wide range of water desalination can be manufactured.
特許出願人 東 し 株 式 会 社１、事件の表示
昭和６負年特許願第２４５９２９号
２、発明の名称
半透性複合膜の製造方法
事件との関係 特許出願人
住所 東京都中央区日本橋室町２丁目２番１号５、補正
により増加する発明の数 なし６、補正の対象
明細書の「特許請求の範囲」
および「発明の詳細な説明」の欄
（１）明細書 第１頁
［特許請求の範囲］を別紙のとおり補正します。Patent applicant Higashi Shi Co., Ltd. 1, Display of the case 1937 Patent Application No. 245929 2, Name of the invention Method for manufacturing semipermeable composite membranes Relationship to the case Patent applicant address Nihonbashi Muromachi, Chuo-ku, Tokyo 2-2-1 No. 5, Number of inventions increased by amendment None 6, "Claims" and "Detailed Description of the Invention" columns of the specification subject to amendment (1) Specification Page 1 [Patent Scope of Claims] will be amended as shown in the attached sheet.
（２）同 第７頁８行目〜１８行目
「微多孔性支持膜と該支持膜を被覆する超薄膜からなる
複合半透膜において、前記微多孔性複合膜を熱水処理し
、かつ、下記のイ、口の界面重縮合反応によって得られ
る架橋芳香族ポリアミドからなる、前記超薄膜を被覆す
ることを特徴とする半透性複合膜の製造方法。(2) Page 7, lines 8 to 18, “In a composite semipermeable membrane consisting of a microporous support membrane and an ultra-thin membrane covering the support membrane, the microporous composite membrane is treated with hot water, and A method for producing a semipermeable composite membrane, which comprises coating the ultra-thin membrane made of a crosslinked aromatic polyamide obtained by the interfacial polycondensation reaction described below.
イ、２つのアミノ基を有する芳香族アミンを含有する水
溶液。B. An aqueous solution containing an aromatic amine having two amino groups.
口、平均官能度２．２５〜２．７５の芳香族さ酸塩化物
を含有する水と非混和性の有機溶媒溶液。A water-immiscible organic solvent solution containing an aromatic acid chloride having an average functionality of 2.25 to 2.75.
」を「 微多孔性支持膜と該支持膜を被覆する超薄膜か
らなる複合膜の製造方法において、微多孔性支持膜を熱
水処理し、次いで該微多孔性支持膜上に、下記のイ、口
からなる反応原料を界面重縮合反応させることにより得
られる架橋芳香族ポリアミドを主成分としてなる超薄膜
を被覆することを特徴とする半透性複合膜の製造方法。"In a method for producing a composite membrane consisting of a microporous support membrane and an ultra-thin film covering the support membrane, the microporous support membrane is treated with hot water, and then the following items are applied on the microporous support membrane. A method for producing a semipermeable composite membrane, which comprises coating a semipermeable composite membrane with an ultra-thin film mainly composed of a cross-linked aromatic polyamide obtained by subjecting a reaction raw material consisting of .
イ、２つのアミン基を有する芳香族アミンを含有する水
溶液。B. An aqueous solution containing an aromatic amine having two amine groups.
口、平均官能度２．２５〜２．７５の芳香族酸塩化物を
含有する水と非混和性の有機溶媒溶液。」と補正します
。A water-immiscible organic solvent solution containing an aromatic acid chloride with an average functionality of 2.25 to 2.75. ” and correct it.
特許請求の範囲
「微多孔性支持膜と該支持膜を被覆する超薄膜からなる
複合半透膜の製造方法において、微多孔性支持膜を熱水
処理し、次いで該微多孔性支持膜の上に、下記のイ、口
からなる反応原料を界面重縮合反応させることにより待
丘れｌ架橋芳香族ポリアミド血土戊光之用てｌ１超薄膜
を被覆することを特徴とする半透性複合膜の製造方法。Claims: ``A method for producing a composite semipermeable membrane comprising a microporous support membrane and an ultra-thin membrane covering the support membrane, in which the microporous support membrane is treated with hot water, and then the microporous support membrane is treated with hot water; A semi-permeable composite membrane characterized in that an ultra-thin film is coated with a cross-linked aromatic polyamide by interfacial polycondensation reaction of the following reaction raw materials: manufacturing method.
イ、２つのアミノ基を有する芳香族アミンを含有する水
溶液。B. An aqueous solution containing an aromatic amine having two amino groups.
口、平均官能度２．２５〜２．７５の芳香族酸塩化物を
含有する水と非混和性の有機溶媒溶液。A water-immiscible organic solvent solution containing an aromatic acid chloride with an average functionality of 2.25 to 2.75.
（２）芳香族アミンが下記式で示される化合物を少なく
とも一種含むことを特徴とする特許請求の範囲第（１）
項記載の半透性複合膜の製造方法。(2) Claim (1) characterized in that the aromatic amine contains at least one compound represented by the following formula:
A method for producing a semipermeable composite membrane as described in Section 1.
（３） 芳香族酸塩化物が、下記式で示される化合物
を少なくとも一種含むことを特徴とする特許請求の範囲
第（１）項記載の半透性複合膜の製造方法。(3) The method for producing a semipermeable composite membrane according to claim (1), wherein the aromatic acid chloride contains at least one compound represented by the following formula.
（４）熱７ 理が ５０°ｃｐ上１００℃以下の水洗ｍ
ことを特徴とする特許請求の範囲第（１）項記載の半透
性複合膜の製造方法。(4) Heat 7 Washing with water at a temperature of 50°C to 100°C
A method for producing a semipermeable composite membrane according to claim (1).
（５）微多孔性支持膜がポリスルホンからなることを特
徴とする特許請求の範囲第（１）項記載の半透性複合膜
の製造方法。(5) The method for producing a semipermeable composite membrane according to claim (1), wherein the microporous support membrane is made of polysulfone.
（６）超薄膜の膜厚が、１０ｎｍ〜１１０００ｎの範囲
であることを特徴とする特許請求の範囲第（１）項記載
の半透性複合膜の製造方法。(6) The method for producing a semipermeable composite membrane according to claim (1), wherein the thickness of the ultra-thin film is in the range of 10 nm to 11,000 nm.
（７）有機溶媒が、ｎ−ヘキサン、トリクロロトリフロ
ロエタンから選ばれる少なくとも一種であることを特徴
とする特許請求の範囲第（１）項記載の半透性複合膜の
製造方法。(7) The method for producing a semipermeable composite membrane according to claim (1), wherein the organic solvent is at least one selected from n-hexane and trichlorotrifluoroethane.
（８）微多孔性支持膜が、ポリエステルまたは芳香族ポ
リアミドから運ばれる少なくとも一種を主成分とする布
帛によって強化されてなることを特徴とする特許請求の
範囲第（１）項記載の半透性複合膜の製造方法。(8) The semipermeability according to claim (1), characterized in that the microporous support membrane is reinforced with a fabric whose main component is at least one type of polyester or aromatic polyamide. Method of manufacturing composite membrane.
手続補正書 凍Procedural amendment Frozen
Claims (8)
なる複合半透膜の製造方法において、微多孔性複合膜を
熱水処理し、次いで前記微多孔性複合膜の上に、下記の
イ、ロからなる反応原料を界面重縮合反応させることに
より架橋芳香族ポリアミドからなる超薄膜を被覆するこ
とを特徴とする半透性複合膜の製造方法。 イ、２つのアミノ基を有する芳香族アミンを含有する水
溶液。 ロ、平均官能度２．２５〜２．７５の芳香族酸塩化物を
含有する水と非混和性の有機溶媒 溶液。(1) In a method for producing a composite semipermeable membrane consisting of a microporous support membrane and an ultra-thin membrane covering the support membrane, the microporous composite membrane is treated with hot water, and then on the microporous composite membrane, A method for producing a semipermeable composite membrane, which comprises coating an ultra-thin film made of a crosslinked aromatic polyamide by subjecting reaction materials consisting of the following (a) and (b) to an interfacial polycondensation reaction. B. An aqueous solution containing an aromatic amine having two amino groups. B. A water-immiscible organic solvent solution containing an aromatic acid chloride having an average functionality of 2.25 to 2.75.
とも一種含むことを特徴とする特許請求の範囲第（１）
項記載の半透性複合膜の製造方法▲数式、化学式、表等
があります▼、▲数式、化学式、表等があります▼、▲
数式、化学式、表等があります▼(2) Claim (1) characterized in that the aromatic amine contains at least one compound represented by the following formula:
Manufacturing method of semipermeable composite membrane described in section ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲
Contains mathematical formulas, chemical formulas, tables, etc.▼
なくとも一種含むことを特徴とする特許請求の範囲第（
１）項記載の半透性複合膜の製造方法。 ▲数式、化学式、表等があります▼▲数式、化学式、表
等があります▼▲数式、化学式、表等があります▼(3) The aromatic acid chloride contains at least one compound represented by the following formula (
1) A method for producing a semipermeable composite membrane as described in section 1). ▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼
度範囲の水中に浸漬された後、熱水処理されることを特
徴とする特許請求の範囲第（１）項記載の半透性複合膜
の製造方法。(4) The semi-permeable support membrane according to claim (1), wherein the microporous support membrane is pre-immersed in water at a temperature range of 50°C to 100°C and then subjected to hot water treatment. Method for producing a composite membrane.
徴とする特許請求の範囲第（１）項記載の半透性複合膜
の製造方法。(5) The method for producing a semipermeable composite membrane according to claim (1), wherein the microporous support membrane is made of polysulfone.
であることを特徴とする特許請求の範囲第（１）項記載
の半透性複合膜の製造方法。(6) The method for producing a semipermeable composite membrane according to claim (1), wherein the ultra-thin film has a thickness in the range of 10 nm to 1000 nm.
ロエタンから選ばれる少なくとも一種であることを特徴
とする特許請求の範囲第（１）項記載の半透性複合膜の
製造方法。(7) The method for producing a semipermeable composite membrane according to claim (1), wherein the organic solvent is at least one selected from n-hexane and trichlorotrifluoroethane.
リアミドから選ばれる少なくとも一種を主成分とする布
帛によつて強化されてなることを特徴とする特許請求の
範囲第（１）項記載の半透性複合膜の製造方法。(8) The semi-porous support membrane according to claim (1), wherein the microporous support membrane is reinforced with a fabric whose main component is at least one selected from polyester or aromatic polyamide. Method for producing a permeable composite membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61245929A JPS63100906A (en) | 1986-10-16 | 1986-10-16 | Manufacture of semipermeable composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61245929A JPS63100906A (en) | 1986-10-16 | 1986-10-16 | Manufacture of semipermeable composite membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63100906A true JPS63100906A (en) | 1988-05-06 |
Family
ID=17140951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61245929A Pending JPS63100906A (en) | 1986-10-16 | 1986-10-16 | Manufacture of semipermeable composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63100906A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0350279A2 (en) * | 1988-07-05 | 1990-01-10 | Texaco Development Corporation | Treatment of water by nanofiltration |
| JP2014500144A (en) * | 2011-05-20 | 2014-01-09 | エルジー・ケム・リミテッド | Method for producing reverse osmosis separation membrane and reverse osmosis separation membrane produced thereby |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62171713A (en) * | 1986-01-23 | 1987-07-28 | Toray Ind Inc | Production of semipermeable composite membrane |
-
1986
- 1986-10-16 JP JP61245929A patent/JPS63100906A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62171713A (en) * | 1986-01-23 | 1987-07-28 | Toray Ind Inc | Production of semipermeable composite membrane |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0350279A2 (en) * | 1988-07-05 | 1990-01-10 | Texaco Development Corporation | Treatment of water by nanofiltration |
| JP2014500144A (en) * | 2011-05-20 | 2014-01-09 | エルジー・ケム・リミテッド | Method for producing reverse osmosis separation membrane and reverse osmosis separation membrane produced thereby |
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