JP6535164B2 - Separation membrane - Google Patents

Description

  The present invention relates to separation membranes.

  Problems such as marine pollution due to oil spills into rivers and oceans, environmental pollution due to treated water from oil resources at mining sites and waste oil discharged from factories, and pollution from edible oils discharged from kitchens in daily life It has become.

  Conventionally, as a method of treating water contaminated with oil, for example, Patent Document 1 discloses a method of installing a porous membrane made of hydrophilic and non-lipophilic polymer at the bottom of a fuel tank, Patent Document 2 discloses a method of using a filter filled with a sheet made of hydrophilized ultrafine fibers, and Patent Document 3 discloses a method of using a hydrophobic porous membrane having fine pores for the filter. Furthermore, Patent Document 4 discloses a method of using a woven fabric containing water-repellent resin fibers and inorganic fibers as a filter, and Patent Document 5 further discloses a technique of using two types of inorganic particles in combination. It is disclosed.

Japanese Patent Application Laid-Open No. 61-216701 Japanese Patent Application Laid-Open No. 04-313312 Unexamined-Japanese-Patent No. 2000-312802 JP 2007-181819 A Japanese Patent Application Laid-Open No. 2010-155177

  However, the porous membranes and filters described in Patent Documents 1 to 5 require a baking treatment at a high temperature or a treatment with ultraviolet light, so that the applicable substrates are limited, and the separation performance is insufficient. There is a problem in at least one point of using the fluorine component which is restricted as and resources.

  Then, an object of the present invention is to obtain a separation membrane which exhibits hydrophilicity and is excellent in durability without treatment with high temperature and ultraviolet light and without using a fluorine-based material.

  As a result of intensive studies to solve the problems of the prior art described above, the present inventors have a substrate and a film located on the surface of the substrate, and the opening diameter of the substrate is within a specific range. It has been found that a separation membrane containing a specific material exhibits hydrophilicity and is excellent in durability, and the present invention has been completed.

That is, the present invention is as follows.
[1] It has a substrate and a coating located on the surface of the substrate,
The opening diameter of the substrate is 0.1 μm or more and 200 μm or less,
The film is a separation membrane comprising a non-fluorinated hydrophilic material.
[2] The separation membrane according to [1], wherein the opening diameter of the separation membrane is 20 μm or more and 120 μm or less.
[3] The non-fluorinated hydrophilic material is at least one non-fluorine selected from the group consisting of acrylic emulsion particles, styrene emulsion particles, acrylic styrene emulsion particles, acrylic silicone emulsion particles, silicone emulsion particles, and urethane resin emulsion particles. The separation membrane according to [1] or [2], which is a hydrophilic system material.
[4] The separation membrane according to any one of [1] to [3], wherein the film further comprises a condensate of a hydrolyzable silicon compound.
[5] The separation membrane according to any one of [1] to [4], wherein the weight average molecular weight of the condensate of the hydrolyzable silicon compound is 8,000 or more and less than 500,000.
[6] The separation membrane according to any one of [1] to [5], wherein the film further includes metal oxide fine particles.
[7] The separation membrane according to any one of [1] to [6], which is used for oil-water separation.

  According to the separation membrane of the present invention, it is possible to exhibit hydrophilicity and obtain excellent durability without using a high temperature and ultraviolet light, without using a fluorine-based material.

  Hereinafter, modes for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail. The following present embodiment is an example for describing the present invention, and the present invention is not limited to the following embodiment. The present invention can be implemented with various modifications within the scope of the gist. In the present specification, “(meth) acryloyl group”, “(meth) acrylic” and “(meth) acrylate” mean both an acryloyl group and a corresponding methacryloyl group, acrylic and corresponding methacrylic By both is meant both acrylate and its corresponding methacrylate.

[Separation membrane]
The separation membrane of the present embodiment has a substrate and a film located on the surface of the substrate. Moreover, the opening diameter of the said base | substrate is 0.1 to 200 micrometer. Furthermore, the film contains a non-fluorinated hydrophilic material.

  The opening diameter of the separation membrane is preferably 20 μm or more and 120 μm or less, more preferably 40 μm or more and 110 μm or less, and still more preferably 60 μm or more and 110 μm or less. When the opening diameter is 20 μm or more, the reduction in the separation speed tends to be suppressed, and when the opening diameter is 120 μm or more, the reduction in the separation performance tends to be suppressed. Further, in order to obtain a separation membrane having an opening diameter in such a range, the coverage on the substrate surface may be controlled according to the opening diameter of the substrate. In addition, the opening diameter of the separation membrane is measured by the method described in the examples described later.

[Substrate (A)]
The separation membrane of the present embodiment has a substrate (A). The material of the substrate (A) is not particularly limited as long as it is a material which does not swell or dissolve in oil such as petroleum, kerosene, light oil etc. Specifically, glass, metal; polyester resin, polyolefin resin, acrylic resin, polyamide Thermoplastic resins such as resin, polyvinylidene chloride resin, ethylene-vinyl acetate resin, polyimide resin, polyethylene terephthalate resin, polysulfone resin, polyvinylidene fluoride resin, PTFE, etc .; polylactic acid resin, polyhydroxybutyrate resin, polycaprolactone resin, Polybutylene succinate resin, polybutylene adipate terephthalate resin, polybutylene succinate terephthalate resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, epoxy acrylate resin Silicon resins, acrylic urethane resins, and thermosetting resins such as urethane resin.

  The form of the substrate is not particularly limited because it can be appropriately changed according to the purpose of use and the type of oil to be treated, but specifically, it includes woven fabric, knitted fabric, non-woven fabric, etc. composed of fibrous material made of resin. A fiber structure is mentioned. Further, various shapes and sizes may be adapted to the purpose of use.

  The opening diameter of the substrate of the present embodiment is 0.1 μm to 200 μm from the viewpoint of the separation performance of oil and water, preferably 20 μm to 120 μm, more preferably 50 μm to 100 μm, and further 60 μm to 80 μm. preferable. When the opening diameter is 0.1 μm or more, the separation speed can be maintained high, and when the opening diameter is 200 μm or less, the separation performance of oil and water can be improved. In order to obtain a substrate having an opening diameter in such a range, fibers are bonded by a method of obtaining a fibrous substrate by plain weave or twill weave, thermal bonding, chemical bonding, needle punching, or water flow bonding. There is a method, a method of drilling a hole in a sheet and a method of drilling a hole. Further, the opening diameter of the substrate is measured by the method described in the examples described later.

[Coating]
The separation membrane of the present embodiment has a coating. The film is obtained by curing at a temperature of 20 ° C. or more and 200 ° C. or less after being formed on the substrate surface. 40 degreeC or more and 150 degrees C or less are preferable, and, as for the said temperature, 50 degreeC or more and 90 degrees C or less are more preferable. When the temperature is 200 ° C. or less, deterioration of the substrate (A) is suppressed, and energy loss tends to be small also in the production process. In addition, when the temperature is 20 ° C. or higher, the productivity for film formation is maintained, and variations in performance expression such as durability tend not to occur.

  The film produced by the method described above preferably has a water contact angle of 30 ° or less at 25 ° C., more preferably 20 ° or less, and still more preferably 10 ° or less. When the water contact angle of the surface at 25 ° C. is 30 degrees or less, the hydrophilicity of the coating film tends to be excellent. In order to obtain a coating having a surface water contact angle in such a range, the water content of the coating may be increased. Moreover, the water contact angle of the surface is measured by the method described in the examples described later.

  The film produced by the method described above preferably has a hexadecane contact angle of 25 degrees or more, more preferably 40 degrees or more, and still more preferably 50 degrees or more. When the hexadecane contact angle is 25 degrees or more, the oil repellency of the separation membrane tends to be excellent. In order to obtain a coating having a hexadecane contact angle in such a range, it is sufficient to increase the moisture content of the coating with a material insoluble in hexadecane. Moreover, the hexadecane contact angle is measured by the method as described in the Example mentioned later.

<Non-fluorinated hydrophilic material (B)>
The film of the present embodiment contains a non-fluorinated hydrophilic material. The non-fluorinated hydrophilic material (B) (hereinafter sometimes simply referred to as "component (B)") is an emulsion resin particle having a hydrophilic functional group which does not contain a fluorine atom. Specifically, (meth) acrylic emulsion resin particles obtained by polymerizing a compound having a (meth) acryloyl group having an unsaturated bond or a compound having a vinyl group through the presence of a radical, a cation, or an anion Examples thereof include vinyl emulsion resin particles, and urethane emulsion resin particles having a urethane bond in the molecule by a polyaddition reaction of an isocyanate group and a polyol. Among these, the non-fluorinated hydrophilic material (B) is at least one selected from the group consisting of acrylic emulsion particles, styrene emulsion particles, acrylic styrene emulsion particles, acrylic silicone emulsion particles, silicone emulsion particles, and urethane emulsion particles. Non-fluorinated hydrophilic materials are preferred. The non-fluorinated hydrophilic material (B) is a non-fluorinated hydrophilic material obtained by polymerizing at least one compound selected from the group consisting of a hydrolyzable silicon compound (b1) and a vinyl compound (b2) described later. Is also more preferable.

  Component (B) As component (B), other than the above-mentioned, as anionic type polyurethane particles, trade names "Superflex 126", "Superflex 130", "Superflex 150", "Superflex" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. 170 "," Superflex 210 "," Superflex 300 "," Superflex 420 "," Superflex 460 "," Superflex 470 "," Superflex 740 "," Superflex 800 "," Superflex 860 " DMS company trade name "NeoRez R-9660", "NeoRez R-972", "NeoRez R-9637", "NeoRez R-9679", "NeoRez R-989", "NeoRez R-2150", "N oRez R-966 "," NeoRez R-967 "," NeoRez R-9603 "," NeoRez R-940 "," NeoRez R-9403 ", trade name" U-Coat UX-485 "manufactured by Sanyo Chemical Industries, Ltd.," U-Coat UWS " -145 "," Permarine UA-368T "," Permarine UA-200 "," Euprene UXA 307 ", trade name" NeoRez R-600 "manufactured by DSM," NeoRez R-650 "," NeoRez R-9617 "," NeoRez R-9621 "," NeoRez R-9330 "as non-ionic polyurethane particles, trade name" Superflex 500M "," Superflex E 2000 "," Superflex E 4800 ", manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; cationic type Polyurethane particles Trade names “Superflex 620” and “Superflex 650” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

  The number average particle diameter of the component (B) is preferably 10 nm or more and 800 nm or less, more preferably 10 nm or more and 150 nm or less, and more preferably 10 nm or more and 100 nm in an aqueous dispersion state from the viewpoint of improving the durability of the separation membrane. It is more preferable that it is the following. In order to obtain the component (B) having a number average particle diameter in such a range, polymerization using seed particles having a uniform particle diameter or phase transition using a solvent which is insoluble in nonionic surfactant and water After removing the solvent, the solvent is removed to produce particles, or the number of revolutions and time of the high-pressure homogenizer are adjusted to produce particles forcibly. In addition, the number average particle diameter of a component (B) is measured by the method as described in the below-mentioned Example.

<Hydrolyzable silicon compound (b1)>
As a hydrolyzable silicon compound (b1) having hydrolyzability and containing a silicon atom, it is represented by a hydrolyzable silicon-containing compound (h1) represented by the following formula (1), and the following formula (2) Examples include at least one compound selected from the group consisting of a hydrolyzable silicon-containing compound (h2) and a hydrolyzable silicon-containing compound (h3) represented by the following formula (3).

R ¹ _n SiX _4-n (1)
(In formula (1), R ¹ is a hydrogen atom, a halogen group, a hydroxy group, a mercapto group, an amino group, a (meth) acryloyl group, or an alkyl group having 1 to 10 carbon atoms which may have an epoxy group And any one selected from an alkenyl group, an alkynyl group and an aryl group, X is a hydrolyzable group, and n is an integer of 0 to 3.)

X ₃ Si-R ² _n -SiX ₃ (2)
(In formula (2), X shows a hydrolysable group, R ² shows a C1-C6 alkylene group or a phenylene group. N is 0 or 1.)

  The hydrolyzable group in the above formula (1) and the above formula (2) is not particularly limited as long as it is a group that generates a hydroxyl group by hydrolysis, and specifically, a halogen atom, an alkoxy group, an acyloxy group, an amino group, A phenoxy group and an oxime group are mentioned.

R ^3- (O-Si (OR ³ ) ₂ ) _n -OR ³ (3)
(In formula (3), R ³ represents an alkyl group having 1 to 6 carbon atoms. N is an integer of 2 to 8)

  As hydrolyzable silicon-containing compounds (h1) and (h2), specifically, tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, tetra (i-propoxy) silane, tetra (n-butoxy) Silane, tetra (i-butoxy) silane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxy Silane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxysilane, diethoxysilane, methyl dimetho Sisilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (triphenoxysilyl) methane, bis (trimethoxysilyl) ethane, bis ( Triethoxysilyl) ethane, bis (triphenoxysilyl) ethane, 1,3-bis (trimethoxysilyl) propane, 1,3-bis (triethoxysilyl) propane, 1,3-bis (triphenoxysilyl) propane, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3- Hydroxypropyl Trieto Sisilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acrylic Roxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, tetraacetoxysilane, tetrakis (trichloroacetoxy) silane, tetrakis (trifluoroacetoxy) silane, triacetoxysilane, tris (trichloro) Acetoxy) silane, tris (trifluoroacetoxy) silane, methyltriacetoxysilane, methyltris (trichloroacetoxy) silane, tetrachlorosilane, tetrasilane Trabromosilane, tetrafluorosilane, trichlorosilane, tribromosilane, trifluorosilane, methyltrichlorosilane, methyltribromosilane, methyltrifluorosilane, tetrakis (methylethyl ketoxime) silane, tris (methylethyl ketoxime) silane, methyl tris (methyl ethyl keto) Xime) silane, phenyltris (methylethyl ketoxime) silane, bis (methylethyl ketoxime) silane, methyl bis (methylethyl ketoxime) silane, hexamethyldisilazane, hexamethylcyclotrisilazane, bis (dimethylamino) dimethylsilane, bis (diethylamino) dimethyl Examples include silane, bis (dimethylamino) methylsilane, and bis (diethylamino) methylsilane. These may be used alone or in combination of two or more.

  As the hydrolyzable silicon-containing compound (h3), specifically, a partial hydrolytic condensate of tetramethoxysilane (for example, trade name “M Silicate 51” manufactured by Tama Chemical Co., Ltd., trade name “MSI 51 manufactured by Corcoat Co., Ltd. “Mitsubishi Chemical Co., Ltd. trade name“ MS 51 ”,“ MS 56 ”), Partial hydrolysis condensate of tetraethoxysilane (eg, trade name“ Tamasu Chemical Industry Co., Ltd. ”trade name“ Silicate 35 ”,“ Silicate 45 ”, Colcoat Co., Ltd. Brand names "ESI 40" and "ESI 48"), co-partial hydrolytic condensate of tetramethoxysilane and tetraethoxysilane (trade name "FR-3" manufactured by Tama Chemical Co., Ltd., trade name "Colcoat" EMS i 48 "). These may be used singly or in combination of two or more.

<Vinyl compound (b2)>
The vinyl compound (b2) (hereinafter sometimes simply referred to as "component (b2)") is selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, an ether group, an amide group, an epoxy group, and a sulfonic acid group It is a vinyl compound having at least one functional group. Component (b2) tends to be able to further enhance the hydrophilicity of the separation membrane by having these functional groups.

  Specifically as a vinyl compound (b2) which has a hydroxyl group, hydroxyalkyl (meth) acrylates, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. Hydroxyl group-containing vinyl ethers such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether; hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether; polyether polyols such as polyethylene glycol; and (meth) acrylic acid Monoesters of polyoxyalkylene glycols obtained from unsaturated carboxylic acids; adducts of various hydroxyl group-containing compounds described above with lactones such as ε-caprolactone; Epoxides such as glycidyl (meth) acrylate An adduct of an unsaturated group-containing unsaturated monomer and an acid such as acetic acid; other than an unsaturated carboxylic acid such as (meth) acrylic acid and an epoxide of an α-olefin such as "CARDURA E" manufactured by Shell Corporation of the Netherlands And adducts thereof with monoepoxy compounds of

  Specific examples of the vinyl compound (b2) having a carboxyl group include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, crotonic acid, itaconic acid, unsaturated carboxylic acids such as maleic acid and fumaric acid; Monoesters of unsaturated dicarboxylic acids such as monomethyl acid, mono-n-butyl itaconate, monomethyl n-maleate, mono-n-butyl maleate, monomethyl fumarate, mono-n-butyl fumarate and saturated monohydric alcohols (Half esters); monovinyl esters of saturated dicarboxylic acids such as monovinyl adipate and monovinyl succinic acid; anhydrides of saturated polycarboxylic acids such as succinic anhydride, glutaric anhydride, phthalic anhydride and trimellitic anhydride Products of addition reaction of the above with vinyl compounds (b2) having a hydroxyl group as described above; Compounds obtained by addition reaction between these and lactones thereof.

  Specifically as the vinyl compound (b2) having an amino group, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-di-n-propylaminoethyl (meth) acrylate, 3 -(Meth) acrylic acid esters having a tertiary amino group such as -dimethylaminopropyl (meth) acrylate, 4-dimethylaminobutyl (meth) acrylate, N- [2- (meth) acryloyloxy] ethyl morpholine; vinyl pyridine Aromatic vinyl compounds having a tertiary amino group such as N-vinylcarbazole and N-vinylquinoline; N- (2-dimethylamino) ethyl (meth) acrylamide, N- (2-diethylamino) ethyl (meth) Acrylamide, N- (2-di-n-propylamino) ethyl (meth) ester ) Tertiary amino groups such as acrylamide, N- (3-dimethylamino) propyl (meth) acrylamide, N- (4-dimethylamino) butyl (meth) acrylamide, N- [2- (meth) acrylamide] ethyl morpholine, etc. N- (2-dimethylamino) ethyl crotonic acid amide, N- (2-diethylamino) ethyl crotonic acid amide, N- (2-di-n-propylamino) ethyl crotonic acid amide, N having (meth) acrylamides; Crotonic acid amides having a tertiary amino group such as-(3-dimethylamino) propyl crotonic acid amide and N- (4-dimethylamino) butyl crotonic acid amide; 2-dimethylaminoethyl vinyl ether, 2-diethyl amino ethyl vinyl ether, 3-Dimethylaminopropyl vinyl ether, 4-dime Vinyl ethers having a tertiary amino group, such as Le aminobutyl vinyl ether.

  Specifically as the vinyl compound (b2) having an ether group, polys such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene higher fatty acid ester, polyoxyethylene-polyoxypropylene block copolymer, etc. Vinyl ethers having an ether chain in the side chain, allyl ethers, and (meth) acrylic acid esters are included. Here, as for the polyoxyethylene chain which said compound has, 2 or more and 30 or less are preferable as a number of oxyethylene units. When the number of oxyethylene units is 2 or more, the flexibility of the separation membrane tends to be maintained, and when the number of oxyethylene units is 30 or less, the separation membrane is not too soft and blocking resistance Tend to be better.

  The vinyl compound (b2) having an ether group is a commercially available product manufactured by Nippon Oil and Fats Co., Ltd., trade name “Blenmer PE-90”, “PE-200”, “PE-350”, “PME-100”, “PME- 200 "," PME-400 "," AE-350 ", manufactured by Nippon Emulsifier, trade name" MA-30 "," MA-50 "," MA-100 "," MA-150 "," RA-1120 " “RA-2614”, “RMA-564”, “RMA-568”, “RMA-1114”, “MPG130-MA”.

  Specific examples of the vinyl compound (b2) having an amide group include N-alkyl (meth) acrylamide and N-alkylene substituted (meth) acrylamide. More specifically, N-methyl acrylamide, N-methyl methacrylamide, N-ethyl acrylamide, N, N-dimethyl acrylamide, N, N-dimethyl methacrylamide, N, N-diethyl acrylamide, N-ethyl methacrylamide, N-methyl-N-ethyl acrylamide, N-methyl-N-ethyl methacrylamide, N-isopropyl acrylamide, N-n-propyl acrylamide, N-isopropyl methacrylamide, N-n-propyl methacrylamide, N-methyl-N -N-propyl acrylamide, N-methyl-N-isopropyl acrylamide, N-acryloyl pyrrolidine, N-methacryloyl pyrrolidine, N-acryloyl piperidine, N-methacryloyl piperidine, N-acryloyl hexahydroarene Pin, N-acryloyl morpholine, N-methacryloyl morpholine, N-vinyl pyrrolidone, N-vinyl caprolactam, N, N'- methylene bis acrylamide, N, N'- methylene bis methacrylamide, N- vinyl acetamide, diacetone acrylamide, Diacetone methacrylamide, N-methylol acrylamide, N- methylol methacrylamide is mentioned.

  Specifically as a vinyl compound (b2) which has an epoxy group, the vinyl compound which has a glycidyl group is mentioned. Examples of the vinyl compound having a glycidyl group include glycidyl (meth) acrylate, allyl glycidyl ether and allyl dimethyl glycidyl ether.

  0.01 mass% or more and 50 mass% or less are preferable with respect to all vinyl compounds (b2) (100 mass%), and, as for the usage-amount of the vinyl compound which has an epoxy group, 0.05 mass% or more and 20 mass% or less More preferable.

  As a vinyl compound (b2) which has a sulfonic acid group, a vinyl sulfonic acid can be mentioned specifically ,.

  Component (b2) is preferably a primary amide group, a secondary amide group, a tertiary amide group, and a vinyl compound having two or more of these, from the viewpoint of further enhancing the hydrophilicity of the separation membrane. As the component (b2), one type may be used alone, or two or more types may be used in combination.

<Hydrolyzable silicon compound (C)>
The film of the present embodiment preferably further includes a condensate of a hydrolyzable silicon compound (C) (hereinafter sometimes simply referred to as “component (C)”). By including the condensate of the component (C), the hydrophilicity and the durability of the separation membrane tend to be improved. In addition, a condensation product means a thing which component (C) produced dehydration reaction under predetermined conditions, and was condensed.

  Component (C) is a hydrolyzable silicon-containing compound (c1) represented by the following formula (4), a hydrolyzable silicon-containing compound (c2) represented by the following formula (5), and the following formula (6) And at least one compound selected from the group consisting of hydrolyzable silicon-containing compounds (c3) represented by

R ¹ nSiX _4- n (4)
(In formula (4), R ¹ is a hydrogen atom, a halogen group, a hydroxy group, a mercapto group, an amino group, an (meth) acryloyl group or an epoxy group, an alkyl group having 1 to 10 carbon atoms, Represents an alkenyl group, an alkynyl group or an aryl group, X represents a hydrolyzable group, and n is an integer of 0 to 3.)

X ₃ Si-R ² _n -SiX ₃ (5)
(In formula (5), X shows a hydrolysable group, R ² shows a C1-C6 alkylene group or a phenylene group. N is 0 or 1.)

  The hydrolyzable group in the above formula (4) and the above formula (5) is not particularly limited as long as it is a group which generates a hydroxyl group by hydrolysis, and specifically, a halogen atom, an alkoxy group, an acyloxy group, an amino group, A phenoxy group and an oxime group are mentioned.

R ^3- (O-Si (OR ³ ) ₂ ) _n -OR ³ (6)
(In formula (6), R ³ represents an alkyl group having 1 to 6 carbon atoms. N is an integer of 2 to 8)

  Specific examples of hydrolyzable silicon-containing compounds (c1) and (c2) include tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, tetra (i-propoxy) silane, and tetra (n-butoxy). Silane, tetra (i-butoxy) silane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxy Silane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxysilane, diethoxysilane, methyl dimetho Sisilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (triphenoxysilyl) methane, bis (trimethoxysilyl) ethane, bis ( Triethoxysilyl) ethane, bis (triphenoxysilyl) ethane, 1,3-bis (trimethoxysilyl) propane, 1,3-bis (triethoxysilyl) propane, 1,3-bis (triphenoxysilyl) propane, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3- Hydroxypropyl Trieto Sisilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acrylic Roxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, tetraacetoxysilane, tetrakis (trichloroacetoxy) silane, tetrakis (trifluoroacetoxy) silane, triacetoxysilane, tris (trichloro) Acetoxy) silane, tris (trifluoroacetoxy) silane, methyltriacetoxysilane, methyltris (trichloroacetoxy) silane, tetrachlorosilane, tetrasilane Trabromosilane, tetrafluorosilane, trichlorosilane, tribromosilane, trifluorosilane, methyltrichlorosilane, methyltribromosilane, methyltrifluorosilane, tetrakis (methylethyl ketoxime) silane, tris (methylethyl ketoxime) silane, methyl tris (methyl ethyl keto) Xime) silane, phenyltris (methylethyl ketoxime) silane, bis (methylethyl ketoxime) silane, methyl bis (methylethyl ketoxime) silane, hexamethyldisilazane, hexamethylcyclotrisilazane, bis (dimethylamino) dimethylsilane, bis (diethylamino) dimethyl Examples include silane, bis (dimethylamino) methylsilane, and bis (diethylamino) methylsilane. These may be used alone or in combination of two or more.

  As the hydrolyzable silicon-containing compound (c3), specifically, a partial hydrolytic condensate of tetramethoxysilane (for example, trade name “M Silicate 51” manufactured by Tama Chemical Co., Ltd., trade name “MSI 51 manufactured by Corcoat Co., Ltd. , Mitsubishi Chemical's "MS 51", "MS 56"), Partial hydrolysis condensate of tetoethoxysilane (for example, trade name "Silicate 35", manufactured by Tama Chemical Industry Co., Ltd., "Silicate 45", manufactured by Corcoat Co., Ltd.) Trade names “ESI 40”, “ESI 48”), co-partial hydrolytic condensate of tetramethoxysilane and tetraethoxysilane (eg, trade name “FR-3” manufactured by Tama Chemical Co., Ltd., trade name “Colcoat”) EMS i 48 "). These may be used alone or in combination of two or more.

  In addition, as hydrolyzable silicon-containing compounds (c3), trade names “KBE-402”, “KBM-803”, “KBM-802”, “KBE-403”, “KBM-303” manufactured by Shin-Etsu Chemical Co., Ltd. “KBM-1403”, “KBM-9659”, “KBM-585”, “KBM-846”, “KBM-9007”, “KP-64”, “KP-851”, “KR-220L”, “KR-242A”, “KR-251”, “KC-89”, “KR-500”, “KR-400”, “KR-255”, “KR-271”, “KR-282”, “KR There may also be mentioned various silane coupling agents such as -300 "," KR-311 "," KR-212 "," KR-213 "and" KR-9218 ".

  The weight average molecular weight of the condensate of the hydrolyzable silicon-containing compound (C) is preferably 5,000 or more and less than 500000, more preferably 8,000 or more and 500000 or less, still more preferably 8,000 or more and 85,000 or less, and 8,000 or more and 80000 or less. It is further more preferable, and 10000 or more and 50000 or less is still more preferable. When the weight average molecular weight is 5,000 or more, the hydrophilicity of the film tends to be maintained, and when the weight average molecular weight is less than 500,000, the durability of the film is maintained, so peeling is caused. It tends to be difficult. As a measuring method of weight average molecular weight, Tosoh Corporation HLC-8220GPC (gel permeation chromatography) is used, the column is TSKgel superAWM-H, the eluent is DMF (LiBr 5 mmol / L, sample amount 50 μl (1 mg / ml) The detector is measured as polystyrene-equivalent molecular weight according to RI measurement conditions.

(Metal oxide particles (D))
The film of the present embodiment preferably further includes metal oxide particles (D) (hereinafter sometimes simply referred to as “component (D)”).

  The number average particle diameter of the component (D) (may be a mixture of primary particles and secondary particles, or may be only one of primary particles and secondary particles) is 1 nm or more and 400 nm or less. The thickness is preferably 1 nm or more and 100 nm or less, more preferably 3 nm or more and 80 nm or less, and still more preferably 5 nm or more and 50 nm or less. By setting the number average particle diameter of the component (D) in such a range, it tends to be able to contribute to both the hydrophilicity and oil repellency of the separation membrane.

  The metal oxide which is the material constituting the component (D) is not particularly limited, and known materials may be used, but from the viewpoint of interaction with the component (B) mentioned above, silicon dioxide, aluminum oxide, At least one metal oxide selected from the group consisting of antimony oxide, titanium oxide, silica-coated titanium oxide, indium oxide, tin oxide, zirconium oxide, lead oxide, iron oxide, calcium silicate, magnesium oxide, niobium oxide, and cerium oxide Are preferred. Among these metal oxides, silicon dioxide (silica), aluminum oxide (alumina, γ-alumina), zirconium oxide, antimony oxide, and complex oxides thereof from the viewpoint of having many surface hydroxyl groups and improvement in strength. And more preferably at least one metal oxide selected from the group consisting of

  As the component (D), one type may be used alone, or two or more types may be used in combination.

  Component (D) is preferably in the form of powder, dispersion, or sol. The “dispersion liquid” and “sol” as referred to herein are components (D) in a concentration of 0.01% by mass or more and 80% by mass or less, preferably 0, in water, a hydrophilic organic solvent, or a mixed solvent thereof. .1 state of being dispersed as at least one of primary particles or secondary particles at a concentration of 1% by mass or more and 50% by mass or less.

  Among the above components (D), acidic colloidal silica with water as a dispersion medium, basic colloidal silica with water as a dispersion medium, and colloidal silica with a water-soluble solvent as a dispersion medium are the components (B) and It is preferable from the viewpoint of formulation stability of

  Trade name "Snowtex (registered trademark) -O", "Snowtex-OS", "Snowtex-OL", "Lightstar" (trade name) manufactured by Nissan Chemical Industries, Ltd. as acidic colloidal silica using water as a dispersion medium "Trademark", trade name "ADELITE (registered trademark) AT-20Q" manufactured by ADEKA, trade name "Clevozole (registered trademark) 20H12" manufactured by Clariant Japan, "Clevozole 30 CAL 25", trade name "NALCO 1115" manufactured by Nalco "Is mentioned.

  Specific examples of basic colloidal silica using water as a dispersion medium include silica stabilized by the addition of an alkali metal ion, an ammonium ion or an amine. As a commercial item, brand names "Snowtex-20", "Snowtex-30", "Snowtex-C", "Snowtex-C30", "Snowtex-CM40", "Snowtex-CM40", manufactured by Nissan Chemical Industries, Ltd. Tex-N, Snowtex-N30, Snowtex-K, Snowtex-XL, Snowtex-YL, Snowtex-ZL, Snowtex PS-M, Snow Tex PS-L ", trade name" ADELITE AT-20 "," ADELITE AT-30 "," ADELITE AT-20N "," ADELITE AT-30N "," ADELITE AT-20A "," ADELITE AT "manufactured by ADEKA -30A "," Adelight AT-40 "," Adelight AT-50 ", trade name" Klebosor "manufactured by Clariant Japan Ltd. 30R9 ”,“ Clevozole 30R50 ”,“ Clevozole 50R50 ”, trade names“ RUDOX® HS-40 ”manufactured by DuPont,“ RUDOX HS-30 ”,“ RUDOX LS ”,“ RUDOX SM-30 ” Be

  Specifically, as colloidal silica using a water-soluble solvent as a dispersion medium, "MA-ST-M" (methanol dispersion type with a number average particle diameter of 20 nm to 25 nm) manufactured by Nissan Chemical Industries, Ltd., "IPA-ST" (Isopropyl alcohol dispersion type with a number average particle size of 10 nm to 15 nm), “EG-ST” (ethylene glycol dispersion type with a number average particle size of 10 nm to 15 nm), “EG-ST-ZL” (number average particle size with Examples include ethylene glycol dispersion types of 70 nm to 100 nm, and "NPC-ST" (ethylene glycol monopropyl ether tail dispersion types with a number average particle diameter of 10 nm to 15 nm).

  The various types of colloidal silica described above may be used alone or in combination of two or more.

  From the viewpoint of hydrophilicity and strength, the mass ratio ((D) / (B)) of the component (D) to the component (B) described above is preferably 50/100 or more and 10000/100 or less, and 110/100 or more and 1000 / 100 or less is more preferable, and 150/100 or more and 300/100 or less is more preferable. By setting the mass ratio in such a range, the hydrophilicity, oil repellency and strength of the obtained separation membrane tend to be improved.

  1/100 or more and 1000/100 or less are preferable, and, as for mass ratio ((C) / (D)) of the component (C) mentioned above with respect to a component (D) component, 10/100 or more and 200/100 or less are more preferable, and 40 / 100 or more and 120/100 or less are more preferable. When the mass ratio is 1/100 or more, the separation membrane obtained tends to improve the erosion resistance due to the fact that hydrophilic oil repellency can be maintained even in flowing water.

[Use]
The separation membrane of the present embodiment is preferably used for oil-water separation, and more preferably used for oil-water separation for industrial drainage, household drainage, drainage during resource digging, and the like. In addition, oil-water separation is separation of oil from water mixed with oil.

  Hereinafter, the present embodiment will be described in more detail with reference to specific examples and comparative examples, but the present embodiment is not limited at all by the following examples and comparative examples as long as the gist thereof is not exceeded. . Various physical properties and evaluations in synthesis examples, examples, and comparative examples described later were measured by the following methods. In the examples and comparative examples, "%" and "parts" are based on mass unless otherwise noted.

(Physical Properties 1) Number Average Particle Size in Water (nm)
A sample of polymer emulsion particles is diluted by adding purified water so that the solid content in the sample is 0.1% by mass or more and 20% by mass or less, and a wet particle size analyzer (manufactured by Nikkiso Co., Ltd., trade name) It measured using "micro track UPA-9230".

(Physical properties 2) Weight-average molecular weight A sample of a hydrolytic condensate of a hydrolyzable silicon compound is manufactured by Tosoh Corporation HLC-8220GPC (column: TSKgel superAWM-H, eluent: DMF (LiBr 5 mmol / L, sample amount 50 μl (1 mg) / ML), detector: RI, polystyrene equivalent molecular weight).

(Physical property 3) Water contact angle (degree)
The coating composition was applied on a 100 μm-thick PET film and dried at room temperature in an open air environment for 24 hours. After that, a drop of deionized water was placed on the coated surface and left at 23 ° C. for 10 seconds, and then measured using a contact angle measuring device (DM-501 contact angle meter manufactured by Kyowa Interface Science Co., Ltd.).

(Physical property 4) Hexadecane contact angle (degree)
The coating composition was applied on a 100 μm-thick PET film and dried at room temperature in an open air environment for 24 hours. After that, a drop of water is dropped on the coated surface, and a drop of hexadecane (reagent special grade manufactured by Wako Pure Chemical Industries, Ltd.) is placed thereon, and left at 23 ° C. for 10 seconds. Contact angle measuring device (DM manufactured by Kyowa Interface Science) It measured using -501 type contact angle meter).

(Physical Properties 5) Opening diameter Opening diameter of the substrate and the separation membrane is 10 samples randomly selected from the sample surface of the substrate or the separation membrane with a microscope (VHX-2000 manufactured by Keyence Corporation), The longest diameters of the openings were measured, respectively, and determined from their average value. Or you may measure and obtain | require by the bubble point method similarly to the above.

(Evaluation 1) Separation Performance Purified water was recovered from a mixture of hexadecane and purified water through a separation membrane, and the filtered state and separated state of the purified water were visually observed, and judged based on the following criteria.
:: no clogging of filtration, no separated component of hexadecane in the recovered purified water ○: slow in filtration but no separated component of hexadecane in the recovered purified water Δ: hexadecane phase in the recovered purified water Is separated ×: All pass through the separation membrane without separation.

(Test 1) Durability test A predetermined cycle (65 ° C., 50% RH, 60 w / m ² for 112 minutes, then water spray for 18 minutes) is repeated with Suga Test Instruments Co., Ltd. trade name “Xenon Weather Meter X 75”. A total of 1000 hours were tested.

Synthesis Example 1 Synthesis of Polymer Emulsion Particles (B-1) 1600 g of ion exchanged water and 4 g of dodecylbenzenesulfonic acid are introduced into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, and the mixture is then stirred. The temperature was warmed to 80 ° C. below. To this, a mixture of 185 g of dimethyldimethoxysilane and 117 g of phenyltrimethoxysilane is added dropwise over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C., after which the temperature in the reaction vessel is 80 ° C. The mixture was stirred for about 1 hour. Next, a mixture of 150 g of butyl acrylate, 30 g of tetraethoxysilane, 145 g of phenyltrimethoxysilane, and 1.3 g of 3-methacryloxypropyltrimethoxysilane, 165 g of diethyl acrylamide, 3 g of acrylic acid, a reactive emulsifier (manufactured by ADEKA Co., Ltd.) The temperature of the reaction vessel was kept at 80 ° C. with a mixed solution of 13 g of trade name “ADEKAREASOAP SR-1025”, solid content of 25 mass%, 40 g of 2 mass% aqueous solution of ammonium persulfate, and 1900 g of ion exchanged water. It dripped simultaneously over about 2 hours in the state. Furthermore, as heat curing, the temperature in the reaction vessel was changed to a state of 80 ° C. and stirring was performed for about 4 hours. Then, it cooled to room temperature and filtered with a 400 mesh wire mesh, and obtained a polymer emulsion particle (B-1) having a solid content of 14% by mass and a number average particle diameter of 131 nm.

Synthesis Example 2 Synthesis of Polymer Emulsion Particles (B-2) After charging 1600 g of ion exchanged water and 4 g of dodecylbenzenesulfonic acid into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, the mixture is stirred. The temperature was warmed to 80 ° C. below. To this, a mixture of 185 g of dimethyldimethoxysilane and 117 g of phenyltrimethoxysilane is added dropwise over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C., after which the temperature in the reaction vessel is 80 ° C. The mixture was stirred for about 1 hour. Next, a mixture of 150 g of butyl acrylate, 30 g of tetraethoxysilane, 145 g of phenyltrimethoxysilane, and 1.3 g of 3-methacryloxypropyltrimethoxysilane, 153 g of butyl acrylate, 15 g of acrylic acid, reactive emulsifier (manufactured by ADEKA Co., Ltd.) Keep the temperature in the reaction vessel at 80 ° C with a mixed solution of 13 g of a commercial product "ADEKAREASOAP SR-1025" (solid content of 25 mass% aqueous solution), 40 g of a 2 mass% aqueous solution of ammonium persulfate, and 1900 g of ion exchanged water. It dripped simultaneously over about 2 hours in the state. Furthermore, as heat curing, the temperature in the reaction vessel was changed to a state of 80 ° C. and stirring was performed for about 4 hours. Then, it cooled to room temperature and filtered with a 400 mesh wire mesh, and obtained a polymer emulsion particle (B-2) having a solid content of 14% by mass and a number average particle diameter of 100 nm.

Synthesis Example 3 Synthesis of Polymer Emulsion Particles (B-3) After charging 1600 g of ion exchanged water and 4 g of dodecylbenzenesulfonic acid into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, the mixture is stirred. The temperature was warmed to 80 ° C. below. To this, a mixture of 185 g of dimethyldimethoxysilane and 117 g of phenyltrimethoxysilane is added dropwise over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C., after which the temperature in the reaction vessel is 80 ° C. The mixture was stirred for about 1 hour. Next, a mixed solution of 150 g of butyl acrylate, 30 g of tetraethoxysilane, 145 g of phenyltrimethoxysilane, and 1.3 g of 3-methacryloxypropyltrimethoxysilane, 168 g of butyl acrylate, and a reactive emulsifier (trade name “ADEKA” About a mixture of 13 g of Adekaria Soap SR-1025, solid content 25% by weight aqueous solution, 40 g of a 2% by weight aqueous solution of ammonium persulfate, and 1900 g of ion-exchanged water while maintaining the temperature in the reaction vessel at 80 ° C. It dripped simultaneously over 2 hours. Furthermore, as heat curing, the temperature in the reaction vessel was changed to a state of 80 ° C. and stirring was performed for about 4 hours. Thereafter, it was cooled to room temperature and filtered through a 400 mesh wire mesh to obtain polymer emulsion particles (B-3) having a solid content of 14% by mass and a number average particle diameter of 180 nm.

Synthesis Example 4 Synthesis of Polymer Emulsion Particles (B-4) In a reaction container having a reflux condenser, a dropping tank, a thermometer and a stirrer, 212 parts of water and a product made by ADEKA, trade name "ADEKAREASOAP SE1025N" 1 part of a 25% aqueous solution was added, and the inside of the reaction vessel was adjusted to 80.degree. Next, 2 parts of acrylic acid, 2 parts of diacetone acrylamide, 51 parts of methyl methacrylate, 5 parts of butyl acrylate and 1 part of 2-hydroxy ethyl methacrylate are mixed, and the monomer mixture is manufactured by ADEKA, trade name A mixed solution of 10 parts of a 25% aqueous solution of "ADECARIATE SOAP SE1025N" and 10 parts of a 2% aqueous solution of ammonium persulfate was used as a pre-emulsifiable liquid by a homogenizer, and added to the reaction vessel from the dropping tank over 2 hours. The temperature in the reaction vessel was maintained at 80 ° C. during the addition and for an additional hour after the addition was completed. The number average particle size of the emulsion at this stage was 10 nm. Subsequently, a mixture of 10 parts of a 2% aqueous solution of ammonium persulfate, 105 parts of N-isopropylacrylamide, 35 parts of 2-hydroxyethyl methacrylate and 600 parts of water starts to be added to the reaction vessel from the dropping tank, for 2.5 hours The addition was terminated. The liquid temperature in the reaction vessel was maintained at 80 ° C. during the addition and for one hour after the addition, and then cooled to 50 ° C., and 780 parts of a 60% aqueous solution of ethanol was gradually added into the reaction vessel. After completion of the addition of the aqueous ethanol solution, the solution was cooled to room temperature to obtain polymer emulsion particles (B-4) having a solid content of 11.2% by mass and a number average particle diameter of 100 nm.

Synthesis Example 5 Synthesis of Polymer Emulsion Particles (B-5) In a reaction vessel having a reflux condenser, a dropping tank, a thermometer and a stirrer, 212 parts of water and a product made by ADEKA, trade name "ADEKAREASOAP SE1025N" 1 part of a 25% aqueous solution of the above was charged, and the inside of the reaction vessel was adjusted to Next, 2 parts of acrylic acid, 2 parts of diacetone acrylamide, 51 parts of methyl methacrylate, 5 parts of butyl acrylate and 1 part of 2-hydroxy ethyl methacrylate are mixed, and the monomer mixture is manufactured by ADEKA, trade name A mixed solution of 10 parts of a 25% aqueous solution of "ADECARIATE SOAP SE1025N" and 10 parts of a 2% aqueous solution of ammonium persulfate was used as a pre-emulsifiable liquid by a homogenizer, and added to the reaction vessel from the dropping tank over 2 hours. The temperature in the reaction vessel was maintained at 80 ° C. during the addition and for an additional hour after the addition was completed. The number average particle size of the emulsion at this stage was 10 nm. Subsequently, a mixed solution of 150 parts of butyl acrylate, 30 parts of tetraethoxysilane, 145 parts of phenyltrimethoxysilane, 1.3 parts of 3-methacryloxypropyltrimethoxysilane, 165 parts of diethylacrylamide, 3 parts of acrylic acid, reactive emulsifier A mixed solution of 13 parts of (ADEKA, trade name "ADEKAREASOAP SR-1025", solid content of 25% by mass aqueous solution, 40 parts of 2% by mass aqueous solution of ammonium persulfate, and 1900 parts of ion exchange water in a reaction vessel The mixture was simultaneously added dropwise over about 2 hours while maintaining the temperature of 80.degree. Furthermore, as heat curing, the temperature in the reaction vessel was changed to a state of 80 ° C. and stirring was performed for about 4 hours. Thereafter, it was cooled to room temperature, filtered through a 400 mesh wire mesh, and adjusted with ion exchange water to obtain polymer emulsion particles (B-5) having a solid content of 10% by mass and a number average particle diameter of 90 nm.

Example 1
The 1 mol / L nitric acid aqueous solution should be 20 times the molar amount of tetraethoxysilane so that the tetraethoxysilane (made by Shin-Etsu Chemical Co., Ltd.) as hydrolyzable silicon compound (C) is 16 mass% in terms of SiO ₂ concentration. To 2-propanol. This was reacted at 30 ° C. for 48 hours to obtain a condensate (C ′). Next, polymer emulsion particles (B-1) synthesized in Synthesis Example 1 and water-dispersed colloidal silica having an average particle diameter of 5 nm as a metal oxide (D) (manufactured by Nissan Chemical Industries, Ltd., trade name “Snowtex OXS ( In the table, “described as“ ST-OXS ”)”, solid content of 10% by mass) and condensation product (C ′) are mixed so as to achieve the solid content mass ratio described in Table 1, and the solid content is 6% The coating composition (1) was obtained after adjustment with 20% ethanol water to obtain The “D / B / C ′ ratio” in Table 1 refers to the mass of the metal oxide (D) as the composition ratio (similar to the mass ratio of each component calculated in terms of the solid content of the coating composition). The mass of the polymer emulsion particles (B-1) to (B-7) and the mass of the condensate (C ') of the hydrolyzable silicon compound are represented by a ratio. In addition, let (C ') be a hydrolysis-condensation product of a hydrolysable silicon compound (C). When the molecular weight of (C ') was measured, it was 39500 in weight average molecular weight.

The SUS mesh (# 200, opening diameter 100 μm, indicated as “SUS # 200” in the table) was washed with acetone and water, and then immersed in the coating composition (1) for 5 seconds. After withdrawal, it was dried at room temperature to obtain a separation membrane. The dry film weight of the coating composition (1) at that time was 1 g / m ² , and the opening diameter was 80 μm. The obtained separation membrane is set on a metal filter plate of a separation type filter device, and after slightly moistening the separation membrane with purified water, then 5 cc of hexadecane (special grade Wako Pure Chemical Industries reagent) is weighed. The solution was dropped onto the separation membrane (Method 1), and it was visually confirmed that hexadecane did not pass through the separation membrane for 1 minute. Next, 2 cc of purified water is weighed and dropped over the hexadecane phase. At that time, purified water could be recovered through the separation membrane, and no phase separation occurred in the recovered liquid. It was confirmed that hexadecane did not pass through the separation membrane, and the separation performance was evaluated. Furthermore, the durability test (Test 1) was performed on the separation membrane, and the separation performance of the obtained separation membrane was evaluated in the same manner as described above. The results are shown in Table 1.

Example 2
The SUS mesh (# 100, opening diameter 200 μm, indicated as “SUS # 100” in the table) was washed with acetone and water, and then immersed in the coating composition (1) for 5 seconds. After withdrawal, it was dried at room temperature to obtain a separation membrane. The dry film weight of the coating composition (1) at that time was 1 g / m ² , and the opening diameter was 180 μm. The obtained separation membrane is set on a metal filter plate of a separation type filter device, the separation membrane is slightly moistened with purified water, and then 5 cc of hexadecane (special grade Wako Pure Chemical Industries reagent) is weighed. It dripped on the separation membrane (method 1), and evaluated the separation performance. The results are shown in Table 1. Furthermore, the durability test (Test 1) was performed on the separation membrane, and the separation performance of the obtained separation membrane was evaluated in the same manner as described above. The results are shown in Table 1.

[Example 3]
The SUS mesh (# 400, opening diameter 50 μm, indicated as “SUS # 400” in the table) was washed with acetone and water, and then immersed in the coating composition (1) for 5 seconds. After withdrawal, it was dried at room temperature to obtain a separation membrane. The dry film weight of the coating composition (1) at that time was 1 g / m ² , and the opening diameter was 25 μm. The obtained separation membrane is set on a metal filter plate of a separation type filter device, the separation membrane is slightly moistened with purified water, and then 5 cc of hexadecane (special grade Wako Pure Chemical Industries reagent) is weighed. It dripped on the separation membrane (method 1), and evaluated the separation performance. The results are shown in Table 1. Furthermore, the durability test (Test 1) was performed on the separation membrane, and the separation performance of the obtained separation membrane was evaluated in the same manner as described above. The results are shown in Table 1.

Example 4
A non-woven fabric (polyester / nylon, basis weight 85 g / m ² , thickness 0.5 mm, maximum opening diameter 60 μm, indicated as “non-woven fabric 1” in the table) was immersed in the coating composition (1) for 5 seconds. After withdrawal, it was dried at room temperature to obtain a separation membrane. The dry film weight of the coating composition at that time was 1 g / m ² and the opening diameter was 50 μm. The obtained separation membrane is set on a metal filter plate of a separation type filter device, 5 cc of hexadecane (reagent grade, made by Wako Pure Chemical Industries, Ltd.) is weighed and dropped onto the separation membrane, and then 2 cc of purified water is weighed. And dropped from above the hexadecane phase (Method 2). At that time, purified water could be recovered through the separation membrane, and no phase separation occurred in the recovered liquid. It was confirmed that hexadecane did not pass through the separation membrane, and the separation performance was evaluated. Furthermore, the durability test (Test 1) was performed on the separation membrane, and the separation performance of the obtained separation membrane was evaluated in the same manner as described above. The results are shown in Table 1.

Comparative Example 1
A non-woven fabric (polyester / nylon, basis weight 85 g / m ² , thickness 0.5 mm, maximum opening diameter 60 μm) is set as a separation membrane on a metal filtration plate of a separate type filtration device, hexadecane (Wako Pure Chemical Industries, Ltd. Reagent special grade 5) was weighed and dropped onto the separation membrane, then 2 cc of purified water was weighed and dropped over the hexadecane phase (Method 2), but the purified water did not pass through the separation membrane And the separation performance was evaluated. The results are shown in Table 3.

[Example 5]
1 mol / L nitric acid aqueous solution was added to “tetramethoxysilane” so that the tetramethoxysilane oligomer (Mitsubishi Chemical Co., Ltd., trade name “MS56”) as hydrolyzable silicon compound (C) would be 16 mass% in terms of SiO ₂ concentration. It was added to 2-propanol so as to be 20 times the molar amount of the oligomer MS56 ". This was reacted at 30 ° C. for 48 hours to obtain a condensate (C ′). Next, polymer emulsion particles (B-6) (acrylic emulsion, solid content 32%, pH 8.0, acid value 39, glass transition temperature 74 ° C., minimum film forming temperature 10 ° C.) and condensate (C ′) Were mixed so as to obtain the solid content mass ratio described in Table 1, and adjusted with 20% ethanol water to obtain a solid content of 6% to obtain a coating composition (2). When the molecular weight of (C ′) was measured, the weight average molecular weight was 42,500.

The SUS mesh (# 200, opening diameter 100 μm) is washed with acetone and water, and then immersed in the coating composition (2) for 5 seconds. After withdrawal, it was dried at room temperature to obtain a separation membrane. The dry film weight of the coating composition (2) at that time was 1 g / m ² , and the opening diameter was 80 μm. Place the separation membrane on the metal filter plate of the separation type filter device. After the separation membrane was slightly moistened with purified water, then 5 cc of hexadecane (reagent special grade manufactured by Wako Pure Chemical Industries, Ltd.) was weighed and dropped onto the separation membrane (Method 1), and the separation performance was evaluated. The results are shown in Table 1. Furthermore, the durability test (Test 1) was performed on the separation membrane, and the separation performance of the obtained separation membrane was evaluated in the same manner as described above. The results are shown in Table 1.

[Example 6]
1 mol / L nitric acid aqueous solution with 20 times the molar amount of water of tetraethoxysilane so that tetraethoxysilane (made by Shin-Etsu Chemical Co., Ltd.) as hydrolyzable silicon compound (C) is 16 mass% in terms of SiO ₂ concentration The mixture was added to 2-propanol as follows. This was reacted at 60 ° C. for 96 hours to obtain a condensate (C ′). Polymer emulsion particles (B-1) synthesized in Synthesis Example 1 and water-dispersed colloidal silica having an average particle diameter of 5 nm as a metal oxide (D) (trade name “Snowtex OXS (in the table,“ ST-OXS ”) Described), Nissan Chemical Industries, Ltd. (solid content: 10% by mass) and condensation product (C ′) are mixed to achieve the solid content mass ratio described in Table 1, and the solid content is 6%. The mixture was adjusted with 20% ethanol water to obtain a coating composition (3). When the molecular weight of (C ′) was measured, the weight average molecular weight was 500,000.

The SUS mesh (# 200, opening diameter 100 μm) is washed with acetone and water, and then immersed in the coating composition (3) for 5 seconds. After withdrawal, it was dried at room temperature to obtain a separation membrane. The dry film weight of the coating composition (3) at that time was 1 g / m ² , and the opening diameter was 80 μm. The obtained separation membrane is set on a metal filter plate of a separation type filter device, and after slightly moistening the separation membrane with purified water, then 5 cc of hexadecane (special grade Wako Pure Chemical Industries reagent) is weighed. The solution was dropped onto the separation membrane (Method 1), and the separation performance was evaluated. The results are shown in Table 1. Furthermore, the durability test (Test 1) was performed on the separation membrane, and the separation performance of the obtained separation membrane was evaluated in the same manner as described above. The results are shown in Table 1.

[Example 7]
A 0.1 mol / L nitric acid aqueous solution is used in an amount of 4 times the molar amount of tetraethoxysilane so that the tetraethoxysilane (made by Shin-Etsu Chemical Co., Ltd.) as the hydrolyzable silicon compound (C) becomes 16 mass% in terms of SiO ₂ concentration. It was added to 2-propanol to be water. This was reacted at 25 ° C. for 24 hours to obtain a condensate (C ′). Polymer emulsion particles (B-1) synthesized in Synthesis Example 1 and water-dispersed colloidal silica having an average particle diameter of 5 nm as a metal oxide (D) (manufactured by Nissan Chemical Industries, Ltd., trade name “Snowtex OXS (in the table, Mix “ST-OXS”) ”, solid content of 10% by mass) and condensation product (C ′) so that the solid content mass ratio described in Table 1 will be 6% of solid content The mixture was adjusted with 80% ethanol water to obtain a coating composition (4). When the molecular weight of (C ′) was measured, the weight average molecular weight was 9900.

The SUS mesh (# 200, opening diameter 100 μm) was washed with acetone and water, and then immersed in the coating composition (4) for 5 seconds. After withdrawal, it was dried at room temperature to obtain a separation membrane. The dry film weight of the coating composition (4) at that time was 1 g / m ² , and the opening diameter was 80 μm. The obtained separation membrane is set on a metal filter plate of a separation type filter device, and after slightly moistening the separation membrane with purified water, then 5 cc of hexadecane (special grade Wako Pure Chemical Industries reagent) is weighed. The solution was dropped onto the separation membrane (Method 1), and the separation performance was evaluated. The results are shown in Table 1. Furthermore, the durability test (Test 1) was performed on the separation membrane, and the separation performance of the obtained separation membrane was evaluated in the same manner as described above. The results are shown in Table 1.

Example 8
The polymer emulsion particles (B-2) synthesized in Synthesis Example 2 were adjusted with 20% ethanol water to a solid content of 6% to obtain a coating composition (5).

The SUS mesh (# 200, opening diameter 100 μm) was washed with acetone and water, and then immersed in the coating composition (5) for 5 seconds. After withdrawal, it was dried at room temperature to obtain a separation membrane. The dry film weight of the coating composition (5) at that time was 1 g / m ² , and the opening diameter was 80 μm. The obtained separation membrane is set on a metal filter plate of a separation type filter device, and after slightly moistening the separation membrane with purified water, then 5 cc of hexadecane (special grade Wako Pure Chemical Industries reagent) is weighed. The solution was dropped onto the separation membrane (Method 1), and the separation performance was evaluated. The results are shown in Table 1. Furthermore, the durability test (Test 1) was performed on the separation membrane, and the separation performance of the obtained separation membrane was evaluated in the same manner as described above. The results are shown in Table 1.

[Examples 9 to 15]
A coating composition was prepared in the same manner as in Example 1 except that the type and composition ratio of the composition of the coating composition were set in Tables 1 and 2 (coating compositions (6) to (12)) The same evaluation as in Example 1 was made. The results are shown in Tables 1 and 2.

[Example 16]
Coating composition in the same manner as in Example 3 except that the non-woven fabric was changed (polyester / nylon, basis weight 100 g / m ² , thickness 0.4 mm, maximum opening diameter 50 μm, indicated as “non-woven fabric 2” in the table). An article was prepared (coating composition (13)) and evaluated as in Example 3. The results are shown in Table 2.

[Example 17]
Coating composition was changed in the same manner as in Example 3 except that the non-woven fabric was changed (made of polyester / nylon, basis weight 250 g / m 2, thickness 3.1 mm, maximum opening diameter 110 μm, shown as “non-woven fabric 3” in the table). It was prepared (coating composition (14)) and evaluated as in Example 3. The results are shown in Table 2.

[Example 18]
A 1 mol / L nitric acid aqueous solution is used as a tetramethoxysilane oligomer so that the tetramethoxysilane oligomer (Mitsubishi Chemical Co., Ltd., trade name “MS56”) as the hydrolyzable silicon compound (C) is 16 mass% in terms of SiO ₂ concentration. It was added to 2-propanol to be 20 times the molar amount of This was reacted at 30 ° C. for 48 hours to obtain a condensate (C ′). Next, the above-mentioned condensate (C ') is added to polymer emulsion particles (B-6) (solid content 32%, pH 8.0, acid value 39, glass transition temperature 74 ° C, minimum film forming temperature 10 ° C), A shell layer of (C ') was formed around (B-6). Subsequently, water-dispersed colloidal silica having an average particle diameter of 4 nm (manufactured by NalcoCompany, trade name "NALCO 1115", solid content 16.5 mass%) as a spherical metal oxide (D) and the solid content mass ratio described in Table 2 The resulting mixture was mixed and adjusted with 20% ethanol water so as to have a solid content of 6% to obtain a coating composition (15). When the molecular weight of (C ′) was measured, the weight average molecular weight was 42,500.

The SUS mesh (# 200, opening diameter 100 μm) was washed with acetone and water, and then immersed in the coating composition (15) for 5 seconds. After withdrawal, it was dried at room temperature to obtain a separation membrane. The dry film weight of the coating liquid at that time was 1 g / m ² and the opening diameter was 80 μm. The obtained separation membrane is set on a metal filter plate of a separation type filter device, and after slightly moistening the separation membrane with purified water, then 5 cc of hexadecane (special grade Wako Pure Chemical Industries reagent) is weighed. The solution was dropped onto the separation membrane (Method 1), and the separation performance was evaluated. The results are shown in Table 1. Furthermore, the durability test (Test 1) was performed on the separation membrane, and the separation performance of the obtained separation membrane was evaluated in the same manner as described above. The results are shown in Table 2.

[Example 19]
A 1 mol / L nitric acid aqueous solution was added to a tetramethoxysilane oligomer as the hydrolyzable silicon compound (C) so that the concentration in terms of SiO ₂ would be 16 mass% as tetramethoxysilane oligomer (Mitsubishi Chemical Co., Ltd., trade name "MS56"). It was added to 2-propanol so as to be 20 moles of This was reacted at 30 ° C. for 48 hours to obtain a condensate (C ′). Next, 20% ethanol water is added to polymer emulsion particles (B-7) (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name "Superflex 126") to adjust the solid content to 10%, and the above condensate (C ') Was added to form a shell layer of (C') around (B-7). Subsequently, water-dispersed colloidal silica having an average particle diameter of 4 nm (manufactured by NalcoCompany, trade name "NALCO 1115", solid content 16.5 mass%) as a spherical metal oxide (D) and the solid content mass ratio described in Table 2 The resulting mixture was mixed and adjusted with 20% ethanol water so as to have a solid content of 6% to obtain a coating composition (16). When the molecular weight of (C ′) was measured, the weight average molecular weight was 42,500.

The SUS mesh (# 200, opening diameter 100 μm) was washed with acetone and water, and then immersed in the coating composition (16) for 5 seconds. After withdrawal, it was dried at room temperature to obtain a separation membrane. The dry film weight of the coating composition (16) at that time was 1 g / m ² , and the opening diameter was 80 μm. The obtained separation membrane is set on a metal filter plate of a separation type filtration device, and after slightly moistening the separation membrane with purified water with purified water, next, 5 cc of hexadecane (special grade Wako Pure Chemical Industries reagent) It measured and dripped on the separation membrane (method 1), and evaluated the separation performance. The results are shown in Table 1. Furthermore, the durability test (Test 1) was performed on the separation membrane, and the separation performance of the obtained separation membrane was evaluated in the same manner as described above. The results are shown in Table 2.

Comparative Example 2
A non-woven fabric (polyester / nylon, basis weight 85 g / m ² , thickness 0.5 mm, maximum opening diameter 60 μm) cut into 10 cm × 10 cm is pre-saturated with nitrogen gas, 20 mass% acrylic acid, distilled water 76. The substrate was immersed in a solution consisting of 7% by mass, 0.2% by mass of benzophenone, 0.1% by mass of ferrous sulfate, and 3.0% by mass of a nonionic surfactant at room temperature for 10 minutes. After removing the excess solution from the non-woven fabric after immersion, ultraviolet light was applied for 5 minutes using a low pressure mercury lamp to obtain a grafted separation membrane. The obtained separation membrane is set on a metal filter plate of a separation type filter device, the separation membrane is slightly moistened with purified water, and then 5 cc of hexadecane (special grade Wako Pure Chemical Industries reagent) is weighed. It dripped on the separation membrane (method 1), and confirmed visually that hexadencan did not pass through the separation membrane for 1 minute. Next, 2 cc of purified water was weighed and dropped over the hexadecane phase. At that time, purified water could be recovered through the separation membrane, and no phase separation occurred in the recovered liquid. It was confirmed that hexadecane did not pass through the separation membrane, and the separation performance was evaluated. Furthermore, the durability test (Test 1) was performed on the separation membrane, and the separation performance of the obtained separation membrane was evaluated in the same manner as described above. The results are shown in Table 3.

Comparative Example 3
1 mol / L nitric acid aqueous solution with 20 times the molar amount of water of tetraethoxysilane so that tetraethoxysilane (made by Shin-Etsu Chemical Co., Ltd.) as hydrolyzable silicon compound (C) is 16 mass% in terms of SiO ₂ concentration The mixture was added to 2-propanol as follows. This was reacted at 30 ° C. for 48 hours to obtain a condensate (C ′). The solid content mass described in Table 3 is a silica-coated titanium oxide hydrosol having a number average particle diameter of 10 nm as a metal oxide (D) (manufactured by Ishihara Sangyo Co., Ltd., trade name "TSK-5", solid content 30%) The mixture was mixed to give a ratio, and adjusted with 20% ethanol water to obtain a solid content of 6%, to obtain a coating composition (18). The molecular weight of (C ′) was 39500 in weight average molecular weight.

Non-woven fabric (polyester / nylon, basis weight 85 g / m ² , thickness 0.5 mm, maximum opening diameter 60 μm) is immersed in the coating composition (18) for 5 seconds. After withdrawal, it was dried at room temperature to obtain a separation membrane. The dry film weight of the coating liquid at that time was 1 g / m ² and the opening diameter was 80 μm. Furthermore, UV light (manufactured by Funakoshi, trade name “UVL-56 Handheld UV Lamp”, power consumption: 6 w, ultraviolet output: 0.16 Amps, wavelength of ultraviolet light to be irradiated: 365 nm) is applied for 3 hours from a distance of 10 cm. Thus, a separation membrane which has been made hydrophilic is obtained. The obtained separation membrane is set on a metal filter plate of a separation type filter device, and after slightly moistening the separation membrane with purified water, then 5 cc of hexadecane (special grade Wako Pure Chemical Industries reagent) is weighed. The solution was dropped onto the separation membrane (Method 1), and it was visually confirmed that the hexadencan did not pass through the separation membrane for 1 minute. Next, 2 cc of purified water was weighed and dropped over the hexadecane phase. At that time, purified water could be recovered through the separation membrane, and no phase separation occurred in the recovered liquid. It was confirmed that hexadecane did not pass through the separation membrane, and the separation performance was evaluated. Furthermore, the durability test (Test 1) was performed on the separation membrane, and the separation performance of the obtained separation membrane was evaluated in the same manner as described above. The results are shown in Table 3.

Comparative Example 4
As metal oxide (D), γ-alumina (made by Daimei Chemical Industries, Ltd., trade name “TM-300”) and methacryloxypropyltrimethoxysilane (made by Shin-Etsu Chemical Co., Ltd., trade name “KBM-503”) A methanol dispersion of surface-modified zirconium oxide particles (Nippon Denko Co., Ltd., trade name "PCS") was prepared with an ultrasonic homogenizer. It is dispersed so as to have an average volume average particle diameter of 40 nm, and formulated so that the solid content ratio of γ-alumina to the total solid content is 70% by mass, and then tetraethoxy as a hydrolyzable silicon compound (C) The coating composition (19) was prepared by adding 3% by mass of silane (Shin-Etsu Chemical Co., Ltd.) to total solids and finally adding methanol so that the total solids became 5% by mass.

A non-woven fabric (polyester / nylon, basis weight 85 g / m ² , thickness 0.5 mm, maximum opening diameter 60 μm) was immersed in the coating composition (19) for 5 seconds. After withdrawal, it was dried at room temperature. The dry film weight of the coating composition (19) at that time was 1 g / m ² , and the opening diameter was 90 μm. Next, an electron beam was irradiated at 5 Mrad at an acceleration voltage of 200 kV to obtain a separation film. The obtained separation membrane is set on a metal filter plate of a separation type filter device, and after slightly moistening the separation membrane with purified water, then 5 cc of hexadecane (special grade Wako Pure Chemical Industries reagent) is weighed. The solution was dropped onto the separation membrane (Method 1), and it was visually confirmed that the hexadencan did not pass through the separation membrane for 1 minute. Next, 2 cc of purified water was weighed and dropped over the hexadecane phase. At that time, purified water could be recovered through the separation membrane, and no phase separation occurred in the recovered liquid. It was confirmed that hexadecane did not pass through the separation membrane, and the separation performance was evaluated. Furthermore, a durability test (Test 1) was performed on the separation membrane, and the separation performance of the obtained separation membrane was similarly evaluated. The results are shown in Table 3.

Comparative Example 5
A separation membrane was obtained in the same manner as in Example 1 except that the substrate was changed to a SUS mesh (# 50, opening diameter 400 μm, indicated as “SUS # 50” in the table). Further, as in Example 1, the separation performance was evaluated, and the separation performance after the durability test was also evaluated. The results are shown in Table 3.

  As shown to Tables 1-3, it turned out that the separation membrane of each Example has hydrophilicity and oil repellency, is excellent in durability, and does not need high temperature processing or UV processing.

  The separation membrane according to the present invention has the possibility of being used as an oil / water separation treatment material for factory drainage, household drainage, drainage at the time of resource digging, and the like.

Claims (4)

A substrate and a coating located on the surface of the substrate;
The opening diameter of the substrate is 0.1 μm or more and 200 μm or less,
The coating viewing contains a condensate of a non-fluorinated hydrophilic resin, and a hydrolyzate of a hydrolyzable silicon compound which produces a hydroxyl group by hydrolysis,
The non-fluorinated hydrophilic resin is at least one non-fluorinated hydrophilic resin selected from the group consisting of acrylic emulsion particles, acrylic styrene emulsion particles, acrylic silicone emulsion particles, and urethane resin emulsion particles,
A separation membrane , wherein the weight average molecular weight of the condensate is 8,000 or more and less than 500,000 .   The separation membrane according to claim 1, wherein an opening diameter of the separation membrane is 20 μm or more and 120 μm or less. It said coating further comprises a metal oxide fine particles, the separation membrane according to claim 1 or 2. The separation membrane according to any one of claims 1 to 3 , which is used for oil-water separation.