JPS6240041B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel permselective membrane, and more particularly to a high performance, particularly permselective membrane with excellent water permeability and flexibility, based on an amino-modified epoxy polymer, and a method for producing the same. A selectively permeable membrane is a membrane that has the ability to selectively permeate only certain molecules, and is used to separate and remove minute amounts of molecules dissolved or diffused in a liquid or gas from the liquid or gas. It is often used in In recent years, reverse osmosis has attracted great interest in its usefulness in fields such as liquid purification. This is particularly important in the purification of water, for example seawater and brine. It is also useful for removing impurities from water, treating blood in the field of dialysis, etc. The efficiency of this reverse osmosis method largely depends on the properties of the permselective membrane used, and therefore great efforts have been made to develop such membranes with high performance, and several proposals have been made. For example, US Patent No.
3133132 and 3133137 disclose lobe-shaped membranes obtained from so-called cellulose acetate. These membranes are characterized by a very thin, dense surface coating and a thicker support layer that provides overall support. This known cellulose acetate-based membrane has poor compaction, low resistance to chemical and biological degradation, and thus a short service life, as well as poor water permeability and salt rejection capabilities. There are some drawbacks such as not being enough. To overcome these drawbacks of such lobe-type membranes, a few membranes based on synthetic polymers have only recently been proposed. For example, U.S. Pat. No. 3,951,815 discloses a microporous material crosslinked with a di- or tri-functional compound (e.g., isophthalic acid chloride) disposed on one surface of the microporous material.
A composite permselective membrane has been described consisting of an ultrathin membrane of polyethyleneimine grafted with a grafting agent (e.g. acrylonitrile or epichlorohydrin), and U.S. Pat. A composite permselective membrane is disclosed that consists of an ultrathin membrane formed on a microporous material by treatment with a functional agent. Furthermore, U.S. Pat. No. 4,039,440 discloses that by first forming a layer of polyethyleneimine on a porous support and then interfacially reacting it with a polyfunctional agent to form a thin surface layer with salt scavenging ability. The resulting reverse osmosis membrane has been proposed. However, the membrane based on crosslinked polyethyleneimine described in the above-mentioned U.S. Pat. It has the disadvantage of low resistance to deterioration due to the presence of As one way to improve this poor oxidation resistance, the above-mentioned U.S. patent
No. 3,951,815 proposes grafting polyethyleneimine with acrylonitrile. However, although membranes based on polyethyleneimine grafted and crosslinked with acrylonitrile have improved oxidation resistance to some extent, they have the serious drawback of significantly reduced water permeation. On the other hand, the membrane based on amine-modified polyepihalohydrin disclosed in the above-mentioned US Pat. It is requested. The desired properties for a permselective membrane are that it must have high selectivity and water permeability as its basic performance, as well as high consolidation resistance.
In addition to being highly resistant to chemical and biological degradation, the permselective membrane is actually tubular;
Since it is used after being molded into modules in the form of spirals, hollow fibers, etc., it must have enough flexibility to withstand being molded into modules of these shapes. As mentioned above, the membranes proposed so far lack any of the above-mentioned characteristics and are not practically satisfactory as desirable permselective membranes. Therefore, there is a strong desire in this technical field for a membrane having the above-mentioned combination of desirable properties. An object of the present invention is to provide a permselective membrane that does not have the drawbacks of the conventional reverse osmosis membranes mentioned above. Another object of the present invention is to provide a permselective membrane having high selectivity and water permeability, excellent flexibility, and high resistance to compaction and chemical and biological degradation. That's true. Yet another object of the present invention is to provide a composite permselective material with high selectivity and water permeability, in particular very high water permeability, excellent flexibility, and high resistance to compaction, chemical and biological degradation. It is to provide a sexual membrane. Still another object of the present invention is to provide a method for producing a composite permselective membrane having high selectivity and water permeability, excellent flexibility, and high resistance to compaction, chemical and biological degradation. It is to provide. By utilizing the above-described permselective membrane of the present invention for reverse osmosis desalination of seawater or brine, pure water can be efficiently produced. Other objects and advantages of the invention will become apparent from the detailed description below. According to the present invention, an addition polymerization product of a polyepoxy compound and a polyamino compound containing at least two amino groups capable of reacting with an epoxy group can be added to an acid halide group, a sulfonyl halide group, an isocyanate group, and an acid anhydride group. A thin film having permselectivity, formed by crosslinking with a polyfunctional compound selected from the group consisting of aromatic, aliphatic and heterocyclic groups having at least two functional groups selected from the group consisting of: A permselective membrane is provided. A feature of the present invention is the use of a specific polymer derived from a polyepoxy compound, which has not been previously used in the field of permselective membranes, as a constituent material of the membrane. According to the present invention, the permselective thin film constituting the membrane specifies the addition polymerization product of a polyepoxy compound and a polyamine compound containing at least two amino groups capable of reacting with epoxy groups. It is formed by crosslinking with a polyfunctional compound. The polyepoxy compound used for producing the addition polymerization product has at least two epoxy groups in one molecule.

[However, R ₈ represents an alkyl group having 1 to 3 carbon atoms. ]

[2,2-(4,4'-diglycidyloxy)-dicyclohexylpropane] 1,2-di(5,6-epoxy-perhydroisoindole-1,3-dione-2-yl)ethane (dicyclopentadiene dioxide) (C) Aromatic polyepoxy compound (Resorcin diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol diglycidyl ether) (2-glycidyl phenyl glycidyl ether) (2,6-diglycidyl phenyl glycidyl ether) (Divinylbenzene dioxide) 2,2(4,4'-diglycidyloxy)diphenylpropane) (4,4'-diglycidyloxy)diphenylmethane (4,4'-diglycidyloxy)diphenyl ether (4,4'-diglycidyloxy)diphenyl sulfone (Phenol novolac epoxy resin) (D) Heterocyclic polyepoxy compound (triglycidyl isocyanurate) (N,N'-diglycidylhydantoin) (N,N'-diglycidyl-5,5-dimethylhydantoin) (Diglycidyl isocyanurate) N,N',N''-tri(glycidyloxybenzyl)melamine The polyepoxy compounds described above can be used alone or in combination of two or more.The polyepoxy compounds that can be preferably used in the present invention are at least two glycidyl groups

Something with [formula], specifically a general formula [In the formula, (i) A is (a+
b) represents a valent organic residue, a and b are each an integer from 0 to 6 and a+b is from 2 to 6; or A represents a direct bond and a and b are each 1; ] A polyglycidyl compound represented by the formula [In the formula, Q represents an oxygen atom or a direct bond; (a) When Q is an oxygen atom, R ₁ is an m-valent group which may contain a substituted or unsubstituted ether bond having up to 30 carbon atoms; represents a hydrocarbon group, and m is an integer from 2 to 4; (b) when Q is a direct bond, R ₁ is of the formula

is a group of [Formula] and m is 2 or 3, or
R ₁ is the formula [However, R ₉ is H or CH ₈ ] and m is 2. ] Polyepoxy compounds represented by these are particularly suitable. In the above formula (v), the organic residue represented by the symbol A may have a chain structure, a chain structure, or a combination of the two, and may have any structure such as a chain structure, a chain structure, or a combination of both. The structure may contain heteroatoms such as carbon atoms, halogen atoms, nitrogen atoms, and sulfur atoms, but generally the number of carbon atoms is 30 or less, preferably 20 or less, and more preferably 15 to 2. Anything within this range is suitable. Specific examples of such organic groups include (a+b)-valent aliphatic groups, alicyclic groups, aromatic groups, heterocyclic groups,
Examples include aromatic aliphatic groups, heterocyclic aliphatic groups, etc. These groups include, for example, hydroxyl groups, halogen atoms,
It can contain one or more substituents such as a halomethyl group, and can also contain an ether bond. Furthermore, in the above formula (), the hydrocarbon group which may contain an ether bond and is represented by the symbol R ₁ may also have any structure, such as a chain structure, a cyclic structure, or a combination of the two, The number of carbon atoms is preferably 30 or less, preferably 20 or less, particularly 15 to 2 carbon atoms.
Thus, specific examples of such hydrocarbon groups include divalent to hexavalent saturated aliphatic hydrocarbon groups having 10 to 2 carbon atoms, especially 6 to 2 carbon atoms, such as (-CH ₂ )- ₂ , (-CH ₂ ) _-3 ,

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula], etc.; Divalent to trivalent aromatic group having 6 to 10 carbon atoms, e.g.

【formula】 【formula】

[Formula] etc; and divalent bisphenol derivative residues, e.g.

【formula】

【formula】

【formula】

[Formula] [Z:

[Formula] -O -, -CH ₂ -], hydrogenated bisphenol derivative residues, etc. are included. Such a hydrocarbon group may have a substituent, and typical examples of the substituent that may be present include a halogen atom, a halomethyl group, a lower alkoxy group, a hydroxyl group, etc. When present, such a substituent is 6 or less, especially 1~
It is desirable that the number is four. Specific examples of hydrocarbon groups that may contain an ether bond represented by the symbol R ₁ in the above formula () having such a substituent include, for example:

【formula】

【formula】

Examples include [Formula]. A polyepoxy compound having such a substituent group is obtained, for example, by a condensation reaction between a polyhydroxy compound and an epihalohydrin as shown in the following formula. Therefore, common commercially available polyepoxy compounds that are manufactured using the above-mentioned manufacturing method include:
Halomethyl groups are often included, and their content can be determined by determining the halogen atom (often chlorine) content and epoxy equivalent. In this specification and claims, the term "lower" means that the group to which this term is attached has 4 carbon atoms.
, preferably 2 or less. Thus, representative examples of one group of polyepoxy compounds that can be used particularly advantageously in the present invention include ethylene glycol, propylene glycol, glycerin, trimethylolpropane, sorbitol, pentaerythritol, diglycerin, neopentyl glycol, resorcinol. , hydroquinone, pyrogallol, phloroglucinol, 2,2-(4,4'-dihydroxy)diphenylpropane (bisphenol A), 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylmethane. Examples include polyepoxy compounds represented by the above formula () obtained by a condensation reaction between a polyhydroxy compound selected from the above and epihalohydrin, or a mixture of two or more thereof, and these include a substituent such as a hydroxyl group or a halomethyl group. may also be included in the molecule. Representative compounds include glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol diglycidyl ether, sorbitol triglycidyl ether, sorbitol tetraglycidyl ether, Glycidyl ethers such as range glycidyl ether, benzenetriyl triglycidyl ether, bisphenol A diglycidyl ether, or
Some or most of the hydrogen atoms of the glycidyl group and/or hydroxyl group are β-halomethyl-β
-glycidyloxyethyl group (e.g.

[Formula]) and the like can be used either alone or as a mixture of two or more. In addition, representative examples of other groups include diglycidyl isocyanurate, triglycidyl isocyanurate,
Examples include diglycidylhydantoin or a mixture of two or more of these. When using a mixture of two or more of the polyepoxy compounds described above, the mixing ratio thereof is not particularly limited, and is selected so that the total epoxy equivalent of the mixed epoxy compound falls within the above range. Surprisingly, triglycidyl isocyanurate shown by the following formula () and the following formula [In the formula, R ₂ is substituted or unsubstituted carbon atom number 15
represents an n-valent hydrocarbon group which may contain up to 3 ether bonds, and n is an integer of 2 to 4. ] It has been found that by using a mixture with a polyglycidyl ether compound shown in the following, it is possible to provide a membrane with even further improved characteristics of salt rejection rate and/or water permeability. Here, the symbol R ₂ in the above formula () can be made synonymous with the hydrocarbon group which may include an ether bond as described for the symbol R ₁ in the above formula (). In this case, the mixing ratio of triglycidyl isocyanurate and the polyglycidyl ether compound of formula () is not critical and can be varied widely depending on the desired properties of the final membrane, but in general , the weight ratio of triglycidyl isocyanurate to the polyglycidyl ether compound of formula () is in the range of 10:1 to 1:5, preferably 7:1 to 1:2, especially 5:1 to 1:1. It's advantageous. Examples of the polyepoxy compound of the formula () include ethylene glycol, propylene glycol, glycerin, trimethylolpropane, sorbitol, pentaerythritol, diglycerin, neopentyl glycol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, 2,2
- A polyhydroxy compound selected from (4,4'-dihydroxy)diphenylpropane (bisphenol A), 4,4'-dihydroxydiphenyl ether, and 4,4'-dihydroxydiphenylmethane, and epihalohydrin. Examples include polyepoxy compounds represented by the above formula () obtained by a condensation reaction, and these may have a substituent such as a hydroxyl group or a halomethyl group in the molecule.
Typical examples of such polyepoxy compounds include glycerin diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol diglycidyl ether, sorbitol triglycidyl ether, and sorbitol tetraglycidyl ether. , phenylene diglycidyl ether, benzenetriyl triglycidyl ether, bisphenol A diglycidyl ether, etc., or a part or most of the hydrogen atoms of the glycidyl group and/or hydroxyl group thereof are β-halomethyl-β-glycidyl ether Roxyethyl group (e.g.

[Formula]) and the like can be used alone or as a mixture of two or more kinds. On the other hand, the polyamino compound to be polyadded with the polyepoxy compound as described above is an organic compound containing at least two amino groups capable of reacting with an epoxy group. means an amino group having one or two active hydrogen atoms bonded to a nitrogen atom, i.e., a primary amino group (-NH ₂ ) or a secondary amino group (

[Formula] This group is also referred to as an imino group), and hereinafter may be referred to as a reactive amino group. The polyamino compound used in the present invention is
The type is not particularly limited as long as it contains two or more primary amino groups, secondary amino groups, or both in one molecule; It can be used in a variety of forms, from solid to polymeric, and may be linear or branched, and may further contain an aromatic nucleus, a heterocyclic ring, or an alicyclic ring. In addition, in addition to carbon atoms and hydrogen atoms, the remaining structural parts of the polyamino compound except for the primary amino group and the secondary amino group include carbon atoms and hydrogen atoms.
Furthermore, different atoms such as oxygen atoms and sulfur atoms may be present. Further, the reactive amino group may be present at the end of the molecular chain or as a side chain, or in the case of a secondary amino group, it may be incorporated into the molecular chain. The first polyamino compound that may be present in the polyamino compound that can be used
The total number of primary amino groups and secondary amino groups is 2.
Although there is no strict restriction as long as it is more than 10
~40 milliequivalents (per 1g of polyamino compound) (hereinafter abbreviated as "meq"), preferably 15~
35 meq, particularly preferably in the range of 20 to 30 meq are suitable. In this specification and claims, the term "amino group equivalent" refers to the sum of primary and secondary amino groups contained per gram of the polyamino compound used in the present invention, and The sum of the equivalent numbers of primary and secondary amino groups is generally determined using a known quantitative method (eg, overbasic acid-glacial acetic acid method, azomethine quantitative method, etc.). In addition, it is desirable that the two or more reactive amino groups present in the polyamino compound are not too far apart from each other, so that one reactive amino group in the same molecule and the next reactive The number of constituent atoms of the chain connecting the amino group is generally 15 or less, preferably 10 or less, and more preferably 2 to 10 atoms.
Advantageously, the range is 5. Furthermore, the molecular weight of the polyamino compound is not critical and can be selected from a wide range from low molecular weight to high molecular weight, but from the viewpoint of the properties of the resulting membrane, especially oxidation resistance, it is generally
Below, preferably 60 to 500, particularly preferably 100 to
Anything in the 300 range is suitable. Therefore, as the polyamino compound that can be used in the present invention, any known polyamino compound can be selected as long as it has the above-mentioned characteristics, and representative examples thereof are as follows. ,
We do not intend to limit the scope of the invention by the following examples. (1) Aliphatic amines

【formula】

[Formula] H ₂ N−CH ₂ −CH ₂ −NH ₂ , H ₂ N(−CH ₂ −CH ₂ −NH)− _n3 H, H ₂ N(−
CH ₂ ) − _n4 NH ₂ ,

【formula】

R′ ₁₁ −NH(−CH ₂ )− _n5 NH ₂ , NC−CH ₂ −CH ₂ −NH
(−CH ₂ −CH ₂ −NH)− _n3 H, NC−CH ₂ −CH ₂ −NH
(−CH ₂ −CH ₂ −NH)− _n3 CH ₂ −CH ₂ −CN, H ₂ N−
CH ₂ −CH ₂ −O−CH ₂ −CH ₂ −NH ₂ , H ₂ N−CH ₂ −
_CH2 - _CH2 -O- _CH2 - _CH2 - _CH2 - _NH2 ,

[Formula] Cl−CH ₂ − CH ₂ −NH(−CH ₂ −CH ₂ −NH)− _n4 H, [However, m ₃ : 1-20, m ₄ : 1-10, m ₅ : 2-
10, R′ ₁₀ , R′ ₁₁ each represents lower alkyl. ] (2) Alicyclic polyamine

【formula】

[Formula] (R' ₁₂ : H, CH ₃ , C ₂ H ₅ , m ₆ : 1-8)

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】 (3) Aromatic polyamine

【formula】

【formula】

【formula】

[Formula] The polyamino compounds described above may be used alone or in combination of two or more. The polyamino compounds used advantageously in the present invention belong to the following groups: (i) Aliphatic polyamino compound represented by the following formula (), () or () R ₁₀ -HN-R ₆ -NH-R ₁₁ () R ₁₀ −HN−R ₁₃ (−R ₁₂ −O)− _e R ₁₄ −NH−R ₁₁
() [In each of the above formulas, R ₆ , R ₇ , R ₈ , R ₉ , R ₁₂ ,
R ₁₃ and R ₁₄ each independently represent a lower alkylene group, particularly an ethylene group, and R ₁₀ and R ₁₁ each independently represent a hydrogen atom or 1 to 2 selected from a cyano group, a hydroxyl group, a carboxyl group, and a sulfonic acid group. represents a lower alkyl group, particularly an ethyl group or a propyl group, which may have one or more substituents, c is an integer from 1 to 20, and d is an integer from 0 to 20.
is an integer of 5, and e is an integer of 1 to 3. However, c repeating units (-NH
−R ₇ −) and d repeating units

[Formula] can be arranged in any order. ] (ii) having 5 to 15 carbon atoms and 2 primary amino groups;
-4 alicyclic polyamino compounds, especially 1,4-diaminocyclohexane. (iii) Heterocyclic polyamino compounds represented by the following formulas () and () [In the above formulas, R ₁₅ and R ₁₆ each independently represent an alkylene group having 4 to 12 carbon atoms which may contain an ether bond, and R ₁₇ and R ₁₈ each independently represent a hydrogen atom or a group R ₁₀ −NH−R ₁₃ −
, where R ₁₀ and R ₁₃ are as defined above, R ₁₉ represents a trivalent saturated lower aliphatic hydrocarbon group, and R ₂₀ represents a lower alkylene group. ] Particularly preferred among the above polyamino compounds are those having the formula [In the formula, R ₃ is a hydrogen atom or a group -CH ₂ - CH ₂ -
represents NH ₂ , R ₄ and R ₅ each independently represent a hydrogen atom or a lower alkyl group optionally substituted with a cyano group or a hydroxyl group, p is a number from 2 to 10, provided that R ₅ is cyanoethyl When p is a group, R ₃ is a hydrogen atom, and when p is a number of 1 or more, one or more R ₃ may be the same or different. ]. Specific examples of polyamino compounds that can be particularly advantageously used in the present invention include the following. H ₂ N(−CH ₂ −CH ₂ −NH)− _n7 H, NC−CH ² −
CH ₂ −NH(−CH ₂ −CH ₂ −NH)− _n7 H, NC−CH ₂ −
CH ₂ −NH(−CH ₂ −CH ₂ −NH)− _n7 CH ₂ −CH ₂ −
CN, These polyamino compounds can be used alone or in combination of two or more. The polyaddition reaction between the polyepoxy compound and the polyamino compound described above can be carried out by a method known per se, for example, in a suitable inert medium such as water; lower alcohols such as methanol, ethanol, and propanol; diethyl ether; The polyepoxy compound can be reacted with the polyamino compound in an ether such as , tetrahydrofuran, dioxane, etc. at a temperature of about 50°C or less, preferably -30 to 30°C. The amount of the polyamino compound to be used in the polyepoxy compound can vary widely depending on the epoxy equivalent and amino group equivalent of the raw material polyepoxy compound and polyamino compound, but Expressed as an equivalent ratio to the reactive amino group in the compound, it is generally advantageous to range from 1/20 to 2/1, preferably from 1/10 to 1/1, particularly from 1/6 to 1/1. This polyaddition reaction proceeds almost quantitatively, and an addition polymerization product in which the polyepoxy compound and the polyamino compound are added in approximately the above equivalent ratio is obtained. In obtaining the addition polymerization product, a halohydrin compound, which is a precursor of the polyepoxy compound of the present invention, is used as a starting material and is reacted with the polyamine compound to simultaneously form an epoxy ring as shown in the following formula. It is also possible to obtain such addition polymerization products with polyamines. [However, X is a halogen atom. ] Therefore, the addition polymerization product obtained by the reaction of the halohydrin and the polyamine compound is also naturally included in the addition polymerization product of the present invention. Such a halohydrin compound can be easily obtained by ring-opening the epoxy group contained in the above-mentioned polyepoxy compound of the present invention with hydrogen halide. The raw materials and the polyaddition reaction conditions should be selected so that substantially no unreacted epoxy groups should remain in the addition polymerization product thus obtained, and a highly networked structure would not be formed. Furthermore, when carrying out the addition reaction between the polyepoxy compound and the polyamine, it is possible not only to mix both raw materials simultaneously, but also to adopt a so-called stepwise reaction in which one raw material is gradually added to the other raw material. It is possible. The addition polymerization product thus obtained is at least
It preferably has a water solubility (25°C) of 0.5g/100g water, and more preferably at least
It is advantageous to have a water solubility (at 25° C.) of 1.0 g/100 g water, especially 1.5 to 3.0 g/100 g water. Addition polymerization products are produced by an addition reaction involving ring-opening of the epoxy groups between the epoxy groups of a polyepoxy compound and the reactive amino groups of a polyamino compound.

The product formed as a result of the formula: The degree of polyaddition can therefore be determined by the number of equivalents of hydroxyl groups produced by ring opening of the epoxy group. Thus, the addition polymerization product that can be advantageously used in the present invention can contain hydroxyl groups resulting from ring opening of epoxy groups in a hydroxyl equivalent weight of at least 0.5 (meq)/(1 g of addition polymerization product). , preferably 1.0 to 40, particularly 3.0 to 15 (meq)/(1 g of addition polymerization product) hydroxyl group equivalent. Throughout this specification and claims, the "hydroxyl group" equivalent is a value determined by the following formula (), in which E ₁ , E ₂ , and E ₃ are determined using known hydroxyl group determination methods (for example, acid-catalyzed acetyl Law, BF ₃ −
Fisher method, etc.), epoxy equivalent determination method, and amino group determination method. E=E ₃ −E ₁ W ₁ +E ₂ W ₂ /W ₁ +W ₂ () [However, in the formula, E=the number of hydroxyl group equivalents E ₃ produced by ring opening of the epoxy group contained in 1 g of the addition polymerization product. = Total number of hydroxyl group equivalents contained in 1 g of the addition polymerization product E ₁ = Number of hydroxyl group equivalents contained in 1 g of the polyepoxy compound E ² = Number of hydroxyl group equivalents contained in 1 g of the polyamine W ₁ = Number of grams of the polyepoxy compound charged W ₂ = Number of grams of the polyamine charged] In addition, the amino group introduced into the addition polymerization product by the polytransfer-addition reaction provides a crosslinking point in the crosslinking reaction described below, and at the same time, It plays an important role in improving the water permeability of the final membrane, and the number (amount) of amino groups in the addition polymerization product, that is, the amino group equivalent, is an important factor that determines the properties of the final membrane. This is one of the factors. Therefore, the addition polymerization products according to the invention generally have a molecular weight of 1.0 to 40,
Preferably 2.0 to 30, more preferably 3.0 to
It is preferred to have an amino group equivalent weight of 20 meq. Particularly suitable addition polymerization products in the present invention are:
It is derived from a combination of the above-mentioned suitable polyepoxy compound and the above-mentioned suitable polyamino compound, and therefore has the following formula: [In the formula, Y is -O- or

Represents [formula]. ] It has two or more structural moieties shown in the following in its molecule. In the above formula (), the remaining two bonds of the leftmost nitrogen atom are bonded to the residues of the aforementioned polyamino compound, while the remaining bonds of the rightmost group Y are bonded to the residues of the polyepoxy compound. is combined with The addition polymerization product having the structural moiety of the formula () more preferably has at least the structural moiety represented by the formula () in terms of the number of equivalents of hydroxyl groups present in the structural moiety. 0.5, preferably 1.0 to 40, especially 3.0 to 15 milliequivalents/hydroxyl equivalent of 1 g of addition polymerization product, and the number of amino equivalents is 1.0 to 40, preferably 2.0 to 30, especially 3.0.
~20 meq/g of addition polymerization product. Such addition polymerization products can be formed into films before crosslinking. Formation of the membrane can be carried out in much the same manner as conventional methods such as those disclosed in the above-mentioned US patents, for example, thin membranes can be simultaneously formed on microporous substrates or by flotation deposition techniques. It can also be formed separately. The substrate can be anything commonly used in reverse osmosis processes. Examples of such substrates include porous glass materials, sintered metals, ceramics, and organic polymers such as cellulose esters, polystyrene, vinyl butyral, polysulfone, and vinyl chloride. Polysulfone membranes have particularly excellent performance as substrates in the present invention, and polyvinyl chloride is also effective. The manufacturing method for polysulfone porous substrates is described in the U.S. Salt Water Service Report (OSW Re-
port) No.359. Such substrates generally have a surface pore size of about 100
The surface pore size is preferably between ~1000 angstroms, but is not limited to this, depending on the final membrane application etc.
It can vary between 5000 Å. These substrates can be used in either symmetrical or asymmetrical structures, but asymmetrical structures are preferable. However, when the membrane constant of these base materials is less than 10 ^-4 g/cm ² sec atm, the water permeability becomes too low ^;
If it is higher than sec/atm, the desalination rate tends to be extremely low, which is not preferable. Therefore, a preferable support membrane constant is in the range of 1 to 10 ^-4 g/cm ² sec atm, particularly preferably in the range of 10 ^-1 to ^{10 -3} g/cm ² sec atm, which gives the most favorable results. . The membrane constant here is a value representing the amount of pure water permeated under a pressure of 2 Kg/cm ² , and the unit is g/cm ² ·sec·atm. It is preferable to use such a base material in a form in which the back side is reinforced with a woven fabric or non-woven fabric. Suitable examples of such woven or nonwoven fabrics include those made of polyethylene terephthalate, polystyrene, polypropylene, nylon, or vinyl chloride. For simultaneous formation of thin films, the microporous substrate is treated with a solution of the addition polymerization product to form a thin film of the addition polymerization product on the microporous substrate. The treatment includes applying a solution of the addition polymerization product to at least one surface of the substrate by, for example, a solution casting method, a brush coating method, a spray method, a wing coating method, a roll coating method, or the like; This can be achieved by immersing the substrate in a solution of the addition polymerization product. Examples of solvents used in preparing the solution of the addition polymerization product used in this treatment include water, methanol, ethanol, isopropyl alcohol,
Examples include tetrahydrofuran, dioxane, etc.
The concentration of the addition polymerization product in the solution is not critical and can vary widely depending on the type of product used and the properties required of the final membrane, but is generally at least 0.5% by weight. , preferably 1.0~
Advantageously it is 5.0% by weight, especially 1.5-3.0% by weight. The base material thus coated or immersed is then subjected to a drain treatment. This draining process can generally be carried out at room temperature for 1 to 30 minutes, preferably 5 to 20 minutes, and results in a total thickness of about 500 to about 10,000 Angstroms, preferably about
A pseudothin film of addition polymerization product having a thickness of 1000 to about 4000 Angstroms is formed. Next, the base material on which the thin film is formed is an aromatic, heterocyclic, or alicyclic group containing at least two functional groups selected from acid halide groups, sulfonyl halide groups, isocyanate groups, and acid anhydride groups. A thin pseudo-film of the addition polymerization product is crosslinked on the substrate by crosslinking using a polyfunctional compound selected from the group consisting of compounds. This crosslinking reaction is usually carried out by an interfacial reaction between the surface of the pseudo-membrane of the addition polymerization product and the polyfunctional compound, and as a result, a thin membrane having selective permselectivity is formed on the surface of the substrate. Since the main purpose of the polyfunctional compound is to perform an interfacial reaction substantially on the surface of the membrane of the addition polymerization product, the polyfunctional compound is preferably selected according to the principle of interfacial reaction. For example, if the addition polymerization product film is applied from an aqueous solution, the polyfunctional compound and its solution should be substantially water-insoluble. Together with these reasons, it is soluble in nonpolar solvents such as hydrocarbons,
Various polyfunctional compounds that are substantially insoluble in water are preferably used. The selection of polyfunctional compounds can also be
It is also influenced by the properties of the final membrane, such as salt rejection capacity, water permeability and compaction resistance. Such selections will be easily accomplished by one skilled in the art through small-scale experimentation. The functional groups possessed by the polyfunctional compound that can be used in the present invention include acid halide groups (-COX), sulfonyl halide groups (-SO ₂ X), and isocyanate groups (-NCO).
and acid anhydride group

[Formula], and one molecule can contain at least two, preferably two or three, of these functional groups. Particularly preferred functional groups are acid halide groups and sulfonyl halide groups. X here is a halogen atom, in particular a chlorine or bromine atom. The plurality of functional groups present in one molecule may be of the same type or may be different from each other. Additionally, polyfunctional compounds generally have a cyclic structure, i.e. they can be of either aromatic, heterocyclic or alicyclic structure, and for the purposes of the present invention, aromatic compounds are particularly preferred. It has been found that polyfunctional compounds having . Therefore, aromatic polyfunctional compounds that can be advantageously used in the present invention have at least 2, preferably 2 to 3 functional groups bonded to an aromatic nucleus,
As long as it contains 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, either mononuclear or polynuclear, especially dinuclear, can be suitably used. Further, it is preferable that no substituents exist on the aromatic nucleus other than the above-mentioned functional groups, but for example, one or two groups such as lower alkyl groups, lower alkoxy groups, halogen atoms, etc. that do not substantially affect the crosslinking reaction are present on the aromatic nucleus. There is no problem even if you have one. A particularly desirable group of such aromatic polyfunctional compounds includes the following formula: [Wherein, Ar is a benzene ring, a naphthalene ring, or a

The ring of [formula] [wherein Y is -CH ₂ -,

[Formula] -O-, -SO ₂ -or-CR-], and Z ₁ , Z _{2 and} Z ₃ each independently represent an acid halide group, a sulfonyl halide group, or an isocyanate group, or Together, Z ₂ represents an acid anhydride group. In particular, Z ₁ , Z ₂ and Z ₃ are preferably selected from acid halide groups or sulfonyl halide groups. ] Those shown are included. Representative examples of aromatic polyfunctional compounds include the following.

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】 (However, R:

Particularly preferred aromatic polyfunctional compounds are isophthalic acid chloride, terephthalic acid chloride, trimesic acid chloride and _{3 -} chlorosulfonylisophthalic acid chloride. In addition, the heterocyclic polyfunctional compound that can be used in the present invention includes 2 or 3 bonded to a heterocycle.
A 5- to 6-membered heteroaromatic or heteroalicyclic compound having 1 or 2 functional groups and containing 1 or 2 nitrogen, oxygen, or sulfur atoms as a heteroatom is preferable,
For example, the following can be exemplified.

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] [However, X=O, S] Further usable alicyclic polyfunctional compounds include those having 2 or 3 functional groups bonded to an aliphatic ring and having 5 to 20 carbon atoms, preferably 6 ~15 are suitable, for example, the following are exemplified.

【formula】

【formula】

[Formula] [However, R: -CH ₂ -

[Formula]-O-]

【formula】

[Formula] [However, R: -CH ₂ -,

[Formula] -O-] The above-mentioned aromatic, heterocyclic or alicyclic polyfunctional compounds can be used alone or in combination of two or more. According to the invention, the polyfunctional compound is trifunctional rather than difunctional when used alone, and even more advantageously when two or more are used in combination. It has been found that by using a combination of difunctional and trifunctional materials, the salt rejection rate and/or water permeability of the final membrane can be further improved. Thus, particularly suitable polyfunctional compounds in the present invention are trifunctional aromatic compounds or mixtures of difunctional and trifunctional aromatic compounds. When using a mixture of a bifunctional compound and a trifunctional compound, the mixing ratio of the two is not critical, but
It is generally advantageous to mix the 2/3-functional compounds in a weight ratio of 10:1 to 1:3, preferably 5:1 to 1:1. Crosslinking of the pseudo-membrane of the addition polymerization product can usually be carried out by bringing the membrane into contact with a solution of the above-mentioned polyfunctional compound. The solvent used to dissolve the polyfunctional compound is one that does not substantially dissolve the addition polymerization product and the base material, for example, n-
Examples include hydrocarbon solvents such as hexane, n-heptane, n-octane, cyclohexane, n-nonane, and n-decane. Although the suitable concentration of the polyfunctional compound in the solvent may vary depending on the type of the compound, the solvent, the substrate, and other conditions, the optimal value can be determined by experiment. However, generally about 0.5 to 5.0% by weight, preferably 1.0 to 3.0% by weight can exhibit sufficient effects. Crosslinking of the addition polymerization product membrane with the polyfunctional compound is preferably accomplished at the membrane-solution interface by immersing the membrane in a solution of the polyfunctional compound. At this time, it is also possible to previously include a crosslinking accelerator in the above-mentioned polyadduct film or in the above-mentioned crosslinking agent solution in order to promote this crosslinking reaction. As such a promoter, caustic alkali, sodium phosphate, pyridine, surfactant, sodium acetate, etc. are suitably used. Such an interfacial crosslinking reaction between the membrane surface and the polyfunctional compound can be carried out at a temperature of room temperature to about 100°C, preferably 20 to 50°C, for 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes. This interfacial reaction can be carried out so that it is mainly concentrated on the surface of the membrane, and there is no need to reduce the anti-water activity inside the membrane. Next, the membrane supported on the substrate is heated at a temperature of usually 70 to 150°C, preferably 90 to 130°C, for about 1 to 2 minutes after draining excess polyfunctional compound solution for 10 seconds to 2 minutes, if necessary. 30 minutes, preferably about 5-20
Heat treat for minutes. Thereby, the crosslinking reaction can be completed and the addition polymerization product film can be rendered water-insoluble. A composite membrane is thus obtained having a thin membrane of crosslinked addition polymerization product having permselectivity on the surface of the microporous substrate. The membrane thus obtained can be used as it is for the purposes described below, but may be subjected to the following post-treatment process if necessary. For example, by treating the membrane with a solution of a compound containing a metal atom that has the ability to chelate a primary amino group, a secondary amino group, a hydroxyl group, a carboxyl group, and/or a sulfonic acid group, Primary amino groups, secondary amino groups, hydroxyl groups, carboxyl groups, and/or sulfonic acid groups that may exist in the crosslinked thin film are chelated with metal atoms that have chelate-forming ability for these groups. It is possible to obtain a film that is Thereby, it is also possible to obtain a membrane with particularly improved water permeability compared to an untreated membrane. Metal compounds that can be used for such treatment include:
For example, BaCl ₂ , MgCl ₂ , HgCl ₂ , CuCl ₂ , HgCl ₂ ,
Examples include CaCl ₂ , FeCl ₃ , AlCl ₃ , CoCl ₃ and the like, and among them, FeCl ₃ , BaCl ₂ , CaCl ₂ and MgCl ₂ are preferred. This treatment can be easily accomplished by immersing the membrane in an aqueous solution (concentration of about 1 to 30% by weight) of such a metal compound at room temperature for about 10 to 60 minutes. In addition, the membrane thus obtained is a liquid polyepoxy compound represented by the above formula ();
By treating with acrylonitrile; lactones such as γ-butyrolactone, β-lactone; or propane salt, a membrane with improved oxidation resistance and salt exclusion property can be obtained. This treatment can also be carried out by immersing the membrane in a solution of the above-mentioned treatment agent (concentration approximately 0.5 to 3% by weight) at room temperature for 1 to 10 minutes. Thus, according to the present invention, a composite permselective membrane consisting of a microporous substrate and the permselective membrane formed on its surface can be obtained. The thickness of the permselective membrane in the membrane is not strictly defined, but can have a total thickness of at least 110 angstroms, and typically from 1000 to 4000 angstroms. It is also within the scope of the present invention to provide a protective film on the surface of the composite membrane of the present invention thus obtained. Water-soluble polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyacrylic acid, polyvinyl methyl ether, polyvinylethyl ether, methylcellulose, ethylcellulose, and polyethylene glycol are used as the protective coating applied to the surface of the composite membrane.
Among these, preferred are polyvinyl alcohol and polyvinylpyrrolidone. These polymers are present in an amount of 1-15 wt%, preferably 3-10 wt%
Used as an aqueous solution. As a method for forming the above-mentioned protective film, a method of immersing the dried composite film in the above-mentioned aqueous solution of the polymer for a protective film, and a known coating method such as a spray coating method, a brush coating method, a roller coating method, etc. can be adopted. Subsequently, a protective film made of the above polymer is formed on the composite film by heat treatment at 90 to 100° C. for 5 to 10 minutes to dry the surface of the film. In particular, the membrane of the present invention can be used under pressure using a reverse osmosis membrane.
It can be particularly advantageously used as a reverse osmosis membrane to remove salt from seawater or brine. Such methods are known per se, such as those used in industrial engineering chemistry fundamentals.
3206 (1964) and the like can be used. Next, the present invention will be explained in more detail with reference to Examples. Method for manufacturing a non-woven reinforced polysulfone porous membrane A densely woven Dacron non-woven fabric (basis weight 180 g/m ² ) was fixed on a glass plate. Next, a solution containing 12.5 wt% polysulfone, 12.5 wt% methylcellosolve, and the balance dimethylformamide was cast on the nonwoven fabric in a layer having a thickness of about 0.2 μm, and the polysulfone layer was immediately gelled in an aqueous solution at room temperature. , a nonwoven reinforced porous polysulfone membrane was obtained. Electron micrographs show that the porous polysulfone layer obtained in this way has a thickness of about 40 to 70μ, has an asymmetric structure, and has many micropores of about 50 to 600Å on the surface. observed. In addition, these porous substrates have a pure water permeation rate (membrane constant) of approximately 3.0 to 7.0×10 ^-2 g/cm ² at 2 kg/cm ² G.
It was sec/atm. Reverse osmosis test method: Using a regular continuous pump type reverse osmosis device, PH
7.0, 5000ppm NaCl aqueous solution or
A 10,000 ppm NaCl aqueous solution was used as the stock solution, and the operating pressures were 42.5 Kg/cm ² G and 40 Kg/cm ² G, respectively. Note that the salt rejection rate in the examples is a value determined by the following formula. Salt rejection rate (%) = (1-NaCl concentration in permeated water/NaC in stock solution
l concentration) x 100 Measuring method for each equivalent (1) Epoxy equivalent Hydrochloric acid-dioxane titration method (2) Amine equivalent Perchloric acid-acetic acid titration method Azomethyl titration method (3) Hydroxy equivalent BF ₃ -Fitscher method Acetic anhydride method (4) ) Amine equivalent in addition polymerization product Total amine determination: Perchloric acid-glacial acetic acid method Tertiary amine determination: Acetylation-perchloric acid method (Primary amine + secondary amine) equivalent = Total amine equivalent - Tertiary amine equivalent (5) -OH equivalent in addition polymerization product BF ₃ - Fischer method example 1 In a three-necked flask equipped with a stirrer, thermometer and dropping funnel, 80 g of distilled water and triethylenetetramine (Tokyo Manufactured by Kasei Kogyo Co., Ltd., amino equivalent weight 27.2 (meq/
g)) 21.9g (0.15mol), mixed and dissolved, then triglycidyl isocyanurate (manufactured by Nagase Sangyo Co., Ltd., "ARALDITE" TGIC epoxy equivalent)
105 (g/eq)) 7.4 g (0.025 mol) and the system was filled with N ₂
After the substitution, the temperature was raised to 50℃, and the system was stirred for about 3 hours until it became a homogeneous solution.
Co., Ltd., "DENACOL" EX-611, epoxy equivalent
170, chlorine content 14.0 wt%) was added from the dropping funnel over 30 minutes. After stirring continuously at the same temperature for 3 hours, it was allowed to cool to room temperature, and about
It was left for 20 hours. The hydroxy equivalent of the obtained addition polymerization product was 2.8 milliequivalent, and the amino group equivalent was
It was 18.6 milliequivalent. The reaction mixture thus obtained was filtered through a microfilter, and the resulting solution was diluted with distilled water so that the addition polymerization product was 2.5 wt%. Nonwoven fabric reinforced polysulfone porous membrane obtained by the above method (polysulfone membrane thickness approximately 60μ, membrane constant 5.2
×10 ^-2 g/cm ² ·sec · atm) was immersed in the diluted solution for 2 minutes at room temperature, the membrane was taken out, stood vertically, and drained for 10 minutes. The thus drained membrane was treated with isophthaloyl chloride and trimesoyl chloride as cross-linking agents.
After immersing it in a 1.5% n-hexane solution (isophthalic acid chloride: trimesic acid chloride = 5:1 (weight basis)) at room temperature for 2 minutes, the membrane was taken out and left in the air for 1 minute to allow it to adhere to the membrane surface. n-
The hexane was stripped off. The thus dried membrane was dried at 115-120℃ in a hot air dryer.
Heat treated for 10 minutes. When the thus obtained composite membrane was subjected to a reverse osmosis test (0.5% NaCl aqueous solution, 42.5 Kg/cm ² G) using the method described above, water permeability was 151.9/m ² hr. (91.1 GFD).
) and showed an initial performance of 98.2% salt rejection. When this product was operated continuously for 100 hours, it exhibited water permeability of 142/m ² hr. (85.2GFD), salt rejection rate of 98.5%, and excellent consolidation resistance. Examples 2-3 Triethylenetetramine used in Example 1,
Exactly the same experiment as in Example 1 was carried out by changing the amount of triglycidyl isocyanurate used as shown in Table 1 below and using glycerin polyglycidyl ether ("DENACOL" EX-314) instead of sorbitol polyglycidyl ether. A composite membrane having initial performance as shown in Table 1 below was obtained.

[Table] Examples 4 to 6 Diethylenetriamine (manufactured by Tokyo Kasei Kogyo Co., Ltd., amino group equivalent) instead of triethylenetetramine
29.1 meq/g) and the amounts used are as shown in Table 2 below, in the same manner as in Example 1.
A composite membrane was obtained which exhibited an initial performance similar to No. 2.

[Table] Examples 7 to 18 1,1,1-trimethylolpropane polyglycidyl ether (manufactured by Nagase Sangyo Co., Ltd., "DENACOL") instead of sorbitol polyglycidyl ether
EX321 epoxy equivalent 130, Cl content 1.0wt%) or
Glycerin polyglycidyl ether (Nagase Sangyo Co., Ltd.)
"DENACOL" EX314 (epoxy equivalent: 145, Cl content: 12.5 wt%) was used to prepare the above-mentioned triglycidyl isocyanurate (hereinafter abbreviated as TGIC) and diethylenetriamine (hereinafter abbreviated as DETA) or triethylenetetramine (hereinafter abbreviated as TETA). A composite membrane was prepared in exactly the same manner as in Example 1, except that the combinations of amounts used were as shown in Table 3 below. The initial performance of the membrane obtained by a similar reverse osmosis test was as shown in Table 3 below.

[Table] Examples 19 to 37 Isophthalic acid chloride (hereinafter referred to as
A composite membrane was prepared in the same manner as in Example 1, using either IPC (abbreviated as IPC) or trimesic acid chloride (hereinafter abbreviated as TMC) alone, and using the crosslinking agent and other components in the amounts shown in Table 4 below. . The initial performance of the membrane obtained by the same reverse osmosis test as in Example 1 was as shown in Table 4 below.

【table】

[Table] Examples 38-39 Instead of sorbitol polyglycidyl ether, bisphenol A-diglycidyl ether (“Epicote” 828 manufactured by Siel Corporation, epoxy equivalent 184-194)
The amounts of each component used are shown in the table below for each case of IPC alone, TMC alone, and a mixture thereof (IPC/TMC = 5/1 (weight basis)) as a crosslinking agent.
A composite membrane was prepared in the same manner as in Example 1. Reverse osmosis test (0.5% NaCl, 42.5Kg/cm ²
As a result of G), initial performance as shown in Table 5 below was obtained.

[Table] Examples 40 to 41 Bisphenol A-diglycidyl ether was used instead of triglycidyl isocyanurate, and glycerin polyglycidyl ether (manufactured by Nagase Sangyo Co., Ltd.) was used instead of sorbitol polyglycidyl ether.
“DENACOL” 314) was used as the crosslinking agent, IPC alone, TMC alone, and a mixture thereof (IPC/
For each case (TMC=5/1 (weight basis)), membrane formation and reverse osmosis tests were conducted in the same manner as in Example 1, using the amounts of each component as shown in Table 6 below.
The results are also shown in Table 6.

[Table] Examples 42-43 Phloroglucinol triglycidyl ether *2 instead of sorbitol polyglycidyl ether
(epoxy equivalent: 107) or hydroquinone diglycidyl ether *3 (epoxy equivalent: 121),
In addition, as a crosslinking agent, IPC alone and IPC/TMC mixture (IPC/TMC = 5/1 (weight basis)) were used in the same manner as in Example 1, with the amounts of each component used as shown in Table 7 below. A composite membrane was created and a reverse osmosis test was conducted. Table 7 shows the initial performance of the obtained membrane. *2 Phloroglucinol triglycidyl ether *3 Hydroquinone diglycidyl ether

[Table] Examples 44 to 45 Phloroglucinol triglycidyl ether or hydroquinone diglycidyl ether was used instead of triglycidyl isocyanurate, and trimethylolpropane polyglycidyl ether (“DENACOL” 321) was used instead of sorbitol polyglycidyl ether. , also as a crosslinking agent
IPC alone and IPC/TMC mixture (IPC/TMC=5/
1 (weight basis)) In each case, a composite membrane was prepared in the same manner as in Example 1 using the amounts of each component as shown in Table 8 below, and a reverse osmosis test was conducted. The initial performance of the obtained membrane is also shown in Table 8.

[Table] Examples 46-52 Triethylenetetramine (TETA), pentaethylenehexamine (PEHA), triglycidyl isocyanurate (TGIC), glycerin polyglycidyl ether (“DENACOL” 314) and 1,
1,1-Trimethylolpropane polyglycidyl ether (“DENACOL” 321) was used in the combinations shown in Table 9 below and reacted under the same conditions as in Example 1, and the solution obtained in the same manner was diluted with distilled water. It was diluted to the concentration listed in the table (concentration A column). The diluted solution was applied to a polysulfone porous membrane having a membrane thickness of about 60 μm obtained by the above method and a membrane constant shown in the same table by the dipping method or single-sided coating method as described below. (i) Immersion method: The polysulfone porous membrane is immersed in the diluted solution for a predetermined time (described in the "Immersion B" column) at room temperature, and drained according to the method of Example 1. (ii) Single-sided coating method: After coating the diluted solution on the polysulfone membrane surface of the polysulfone porous membrane,
Scrape off the coating solution with a glass rod and drain for about 1 minute. The thus drained membrane was mixed with the crosslinking agent, the same concentration, and the mixing ratio (weight ratio) listed in the "Crosslinking agent" column of the same table.
A composite membrane was prepared according to the method of Example 1 after being immersed in a crosslinking agent solution under the conditions at room temperature for the time indicated in the "Immersion C" column of the same table. The obtained membrane was subjected to a reverse osmosis test (1% NaCl aqueous solution, 40 Kg/cm ² G), and the obtained initial performance is also shown in Table 9 below.

[Table] Examples 53 to 55 130 g of distilled water and the polyamine components shown in Table 10 below were charged into a three-necked flask equipped with a stirrer, thermometer, and dropping funnel. After mixing and dissolving at room temperature, the system was heated with N After ₂ substitutions, the polyepoxy components shown in the same table were added from the dropping funnel over 30 minutes. Stirring was continued for 3 hours at the same temperature and left for about 20 hours. Using the reaction solution thus obtained, a membrane was formed in the same manner as in Example 1 except for using the following crosslinking agent, and a reverse osmosis test (NaCl 1% aqueous solution, 40Kg/cm ²
G) I did. The obtained initial performance is shown in the same table.

[Table] Examples 56 to 65 Film forming and reverse osmosis tests were conducted according to the method of Example 1 using each component shown in Table 11 below. however,
When triglycidyl isocyanurate was not used as the polyepoxy component, the method of Example 53 was followed.

【table】

[Table] Examples 66 to 73 Film forming and reverse osmosis tests were conducted according to the method of Example 1 using each component shown in Table 12 below. The results are shown in the same table.

【table】

[Table] Example 75 and Comparative Examples 1 and 2 The chlorine resistance of the composite membrane obtained in the same manner as in Example 1 was examined. Chlorine resistance was measured using a continuous reverse immersion test at 70 kg/cm ² G using a 3.5% NaCl aqueous solution adjusted to PH = 5.0 to 6.0 and chlorine concentration = 3 ppm using a sodium hypochlorite aqueous solution and a buffer solution as the stock solution. This was judged based on the deterioration of the membrane performance.
Table 13 below shows the results along with the results for other membranes.

[Table] Example 76 The composite membrane obtained in Example 74 was examined for chlorine resistance in the same manner as in Example 75. However, the test was carried out under reverse osmosis conditions of 42.5 Kg/cm ² G using a 0.5% NaCl aqueous solution adjusted to PH = 5 and chlorine concentration = 4 ppm. The results are shown in Table 14 below.

[Table] Example 77 A composite membrane obtained in the same manner as in Example 1 was immersed in a 1 wt% ethanol solution of sorbitol polyglycidyl ether (“DENACOL” EX-611) used in Example 1 for 10 minutes, and then reversely immersed. A penetration test showed a water permeability of 74.5/m ² hr and a salt removal rate of 99.5%. (Reverse osmosis test conditions are from Example 1.
Examples 78 to 81 A composite membrane obtained in the same manner as in Example 1 was chelated with an aqueous metal salt solution as shown in Table 15 below. The results are shown in Table-15.

[Table] Values measured at °C.
Example 82 In Example 1, instead of triglycidyl isocyanurate, its precursor N, N', N''-
Tri(-2-hydroxy-3-chloropropyl)isocyanurate An addition polymerization product was obtained in the same manner using 10.2 g. When this material was similarly composited, water permeability was 173.4/
A composite membrane was obtained with an initial performance of m ² ·hr and a salt removal rate of 93.2%.

Claims (1)

[Claims] 1. An addition polymerization product of a polyepoxy compound and a polyamino compound containing at least two amino groups capable of reacting with an epoxy group, an acid halide group,
Crosslinked with a polyfunctional compound selected from the group consisting of aromatic, alicyclic, and heterocyclic compounds having at least two functional groups selected from sulfonyl halide groups, isocyanate groups, and acid anhydride groups. A permselective membrane consisting of a thin film having selective permselectivity, which is formed by 2 The addition polymerization product has a hydroxyl group generated by ring opening of an epoxy group, and 1 g of the addition polymerization product
A permselective membrane according to claim 1, containing at least 0.5 meq of hydroxyl groups per membrane. 3. The permselective membrane according to any one of claims 1 to 2, wherein the addition polymerization product has at least 1.0 to 40 milliequivalents of amino groups per gram of addition polymerization product. 4 The addition polymerization product has hydroxyl groups generated by epoxy ring opening per 1 g of the addition polymerization product.
Contains hydroxyl group equivalents of 1.0 to 15.0 milliequivalents, and amino group equivalents per gram of addition polymerization product.
The permselective membrane according to claim 1, which has a weight of 3.0 to 20.0 milliequivalents. 5. The permselective membrane according to claim 1, wherein the polyepoxy compound is a compound having at least two glycidyl groups. 6 The following formula () in which the addition polymerization product is formed by an addition reaction between the epoxy group of the epoxy compound and the amino group of the polyamino compound [However, in the formula, Y represents -O- or [Formula]. ] is contained in an amount of at least 0.5 milliequivalent hydroxyl group per 1 g of addition polymerization product in terms of the number of equivalents of hydroxyl groups present in the structural portion, and the number of amino group equivalents is The permselective membrane according to any one of claims 1 to 5, wherein the amount is 1.0 to 40 milliequivalents per gram of polymerization product. 7 The following formula () in which the addition polymerization product is formed by an addition reaction between the epoxy group of the polyepoxy compound and the amino group of the polyamino compound [However, in the formula, Y represents -O- or [Formula]. ] is contained in a hydroxyl group equivalent of 1.0 to 15.0 milliequivalents per 1 g of the addition polymerization product in terms of the number of equivalents of hydroxyl groups present in the structural portion, and an amino group is contained in the addition polymerization product. The permselective membrane according to any one of claims 1 to 5, containing 3.0 to 20.0 milliequivalents per gram of polymerization product. 8 The addition polymerization product is at least 0.5g/100g
The permselective membrane according to claim 1, which has a water solubility of _H2O . 9 The addition polymerization product is at least 1.0g/100g
The permselective membrane according to claim 1, which has a water solubility of _H2O . 10. The permselective membrane according to claim 1, wherein the addition polymerization product is substantially free of unreacted epoxy groups. 11 The epoxy equivalent of the polyepoxy compound is
500 or less, the permselective membrane according to claim 1. 12 The epoxy equivalent of the polyepoxy compound is 40
200. The permselective membrane according to claim 1, wherein the permselective membrane has a molecular weight of 200. 13 The polyepoxy compound has the following formula () [However, in the formula, Q represents an oxygen atom or a direct bond; (a) When Q is an oxygen atom, R ₁ may contain an ether bond having up to 15 substituted or unsubstituted carbon atoms; represents an m-valent hydrocarbon group,
and m is a number from 2 to 4; (b) If Q is a direct bond, R ₁ is the formula and m is 2 or 3, or
R ₁ is the formula (wherein R ₂ is a hydrogen atom or a methyl group), and m is 2. ] The permselective membrane according to claim 1, which is a polyepoxy compound represented by: 14 R ₁ is an m-valent hydrocarbon group having 15 or less carbon atoms and optionally containing an ether bond and having a hydroxyl group and/or a halomethyl group as a substituent, m is an integer of 2 to 4, Q 14. The permselective membrane according to claim 13, wherein is an oxygen atom. 15 The polyepoxy compound is glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol diglycidyl ether, sorbitol triglycidyl ether, sorbitol tetraglycidyl ether, phenylene diglycidyl ether , benzenetriyl triglycidyl ether, bisphenol A diglycidyl ether, and one or more compounds selected from the group consisting of halogenated alkyl and/or halohydroxyalkyl group-substituted products having 1 to 5 carbon atoms. 14. A permselective membrane according to claim 13, consisting essentially of: 16 The polyepoxy compound is diglycidyl isocyanurate, triglycidyl isocyanurate, N,N-diglycidylhydantoin, N,N
14. The permselective membrane according to claim 13, which is selected from the group consisting of -diglycidyl-5,5-dimethylhydantoin and mixtures of two or more thereof. 17 The polyepoxy compound has triglycidyl isocyanurate and the following formula () [However, in the formula, R ₂ represents a substituted or unsubstituted n-valent hydrocarbon group having up to 15 carbon atoms and which may contain an ether bond, and n is an integer of 2 to 4. ] The permselective membrane according to claim 1, which is a mixture with a polyepoxy compound represented by: 18 The polyepoxy compound of the formula () is glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol diglycidyl ether, sorbitol triglycidyl ether,
The permselective membrane according to claim 17, which is selected from the group consisting of sorbitol tetraglycidyl ether, phenylene diglycidyl ether, benzenetriyl triglycidyl ether, bisphenol A diglycidyl ether, and mixtures of two or more thereof. . 19 The polyepoxy compound of the formula () is the following group [] Group []: ethylene glycol, propylene glycol, glycerin, trimethylolpropane, sorbitol, pentaerythritol, diglycerin, neopentyl glycol, resorcinol, hydroquinone, pyrogallol, phlorog Rucinol, 2,2(-4,4'-dihydroxy)diphenylpropane, 4,4'-
dihydroxydiphenyl ether,
A patent claim that is a polyepoxy compound selected from the group consisting of a polyepoxy compound obtained by a condensation reaction of a polyhydroxy compound selected from 4,4'-dihydroxydiphenylmethane and epihalohydrin, or a mixture of two or more thereof. 14. The permselective membrane according to item 13. 20. The permselective membrane according to claim 1, wherein the polyamino compound has a molecular weight of 1000 or less. 21. The permselective membrane according to claim 1, wherein the polyamino compound has a molecular weight of 60 to 500. 22 The polyamino compound is polyamino compound 1
The permselective membrane according to claim 1, having an amino group equivalent of 10 to 35 milliequivalents per gram. 23 The polyamino compound has the following formula () [However, in the formula, R ₃ is a hydrogen atom or a group -CH ₂ -CH _2
-NH2 , _R4 and _R5 each independently represent a hydrogen atom or a lower alkyl group optionally substituted with a cyano group or a hydroxyl group, and p is an integer of 2 to 10. However, when R ₅ is a cyanoethyl group, R ₃ is a hydrogen atom, and when p is an integer of 2 or more, p R ₃ 's may be the same or different. ] The permselective membrane according to claim 1, which is a compound represented by: 24. Claim 1, wherein the addition polymerization product is an addition polymerization product of the polyepoxy compound and the polyamino compound in an epoxy group/amino group equivalent ratio of 1/1 to 1/6. selectively permeable membrane. 25. The permselective membrane according to claim 1, wherein the polyfunctional compound is a bifunctional or trifunctional aromatic compound having two or three functional groups selected from acid halide groups and sulfonyl halide groups. 26. The permselective membrane according to claim 1, wherein the polyfunctional compound is a trifunctional aromatic compound or a mixture of a bifunctional aromatic compound and a trifunctional aromatic compound. 27. The permselective membrane according to claim 25, wherein the di- or trifunctional aromatic compound is isophthaloyl chloride, terephthaloyl chloride, trimesoyl chloride, or 3-chlorosulfonyl isophthaloyl chloride. 28. The permselective membrane according to claim 1, which is in the form of a composite membrane comprising a microporous substrate and a permselective membrane formed thereon. 29. The permselective membrane according to claim 1, which has a thickness of at least 100 Å. 30. The permselective membrane according to claim 28, wherein the microporous substrate is made of polysulfone. 31 (a) treating a microporous substrate with a solution of an addition polymerization product of a polyepoxy compound and a polyamino compound containing at least two amino groups capable of reacting with epoxy groups; The microporous substrate is made of aromatic, alicyclic and heterocyclic groups containing at least two functional groups selected from the group consisting of acid halide groups, sulfonyl halide groups, isocyanate groups and acid anhydride groups. (c) heating to form a thin film of a crosslinked addition polymerization product having permselectivity on one side of the microporous substrate; A method for producing a composite permselective membrane.