WO2012108102A1 - Microporous crystalline polymer membrane, production method therefor and filtration filter - Google Patents

Microporous crystalline polymer membrane, production method therefor and filtration filter Download PDF

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WO2012108102A1
WO2012108102A1 PCT/JP2011/079147 JP2011079147W WO2012108102A1 WO 2012108102 A1 WO2012108102 A1 WO 2012108102A1 JP 2011079147 W JP2011079147 W JP 2011079147W WO 2012108102 A1 WO2012108102 A1 WO 2012108102A1
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crystalline polymer
surface
microporous membrane
polymer microporous
film
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PCT/JP2011/079147
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French (fr)
Japanese (ja)
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憲一 石塚
一樹 山崎
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富士フイルム株式会社
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Abstract

[Problem] To provide: a microporous crystalline polymer membrane that has excellent water resistance and ion adsorption capacity, is highly hydrophilic, has a long filtration life, and an excellent permeation flow rate; a microporous crystalline polymer membrane production method capable of producing said microporous crystalline polymer membranes efficiently; and a filtration filter using said microporous crystalline polymer membrane. [Solution] A microporous crystalline polymer membrane with an asymmetric pore structure, wherein: at least a portion of the exposed surface of the microporous crystalline polymer membrane is covered with a radical polymer obtained by polymerizing a composition comprising a radical-polymerizable monomer; a functional compound comprising at least one of ion-exchanging groups or chelating groups has undergone an addition reaction with at least a portion of the radical polymer; and the radical-polymerizable monomer is at least one selected from acrylate, methacrylate, acrylamide and derivatives thereof.

Description

Crystalline polymer microporous membrane and a production method thereof as well filtration filter,

The present invention is a gas, a method of manufacturing a filtration-efficient crystalline polymer microporous membrane and the crystalline polymer microporous membranes used in the microfiltration of liquids, and the like, as well as the crystalline polymer microporous membrane is used on the filtration filter.

Microporous membranes have been known for a long time, it is widely used for filtration filters and the like. Such microporous films, for example those produced cellulose ester as a raw material (see Patent Document 1), a microporous membrane using aliphatic polyamide as a raw material (see Patent Document 2), a raw material polyfluorocarbon those produced as (see Patent Document 3), polypropylene which a raw material (see Patent Document 4), and the like.
These microporous membranes are electronic industrial cleaning water, semiconductor manufacturing chemical, pharmaceutical water, pharmaceutical manufacturing process water, filtration of food water or the like is used for sterilization, in recent years, has expanded its application and usage, microporous membrane having high reliability is noted in terms of particle capture. Among them, microporous membrane according to crystalline polymers are superior in chemical resistance, particularly microporous membrane of polytetrafluoroethylene (PTFE) as a raw material is excellent in heat resistance and chemical resistance , significant growth in the demand.

Generally, filterable amount per unit area of ​​the microporous membrane is small (i.e., filtration life is short). Therefore, when used industrially, to increase the membrane area has been forced to be used in parallel a number of filtration units, from the viewpoint of the cost of the filtration process, to increase the filtration life there is a need. For example as an effective microporous membrane flow rate reduction due to clogging, the asymmetric porous membrane having an average pore diameter toward the inlet side to the outlet side becomes gradually smaller is proposed.
For example, larger than the average pore size of the average pore diameter of the surface backside of the film, and an average pore diameter from the surface toward the rear surface microporous film of the crystalline polymer continuously changes has been proposed (Patent Document 5 reference). According to this proposal, by performing the filtering surface having the larger average pore diameter (surface) as an inlet side, can be captured efficiently fine particles, it is possible to improve the filtration life.

Further, as the hydrophilic treatment method of a crystalline polymer microporous membrane having an asymmetric pore, for example, in Patent Document 6, the exposed surface of the microporous membrane of the crystalline polymer of the asymmetric pore structure, hydrogen peroxide or a water-soluble solvent aqueous impregnating solution of, laser irradiation, be hydrophilic treatment with such chemical etching are proposed.
However, in the crystalline polymer microporous membrane having an asymmetric pore, heated surface, unheated surface, and has its interior, since the crystallinity of the crystalline polymer is different at each site of the proposed hydrophilicity the treatment method can not uniform hydrophilic for the entire film, and if you try to hydrophilic treatment, it is necessary to perform a hydrophilic treatment separately in several times for each condition according to the degree of crystallinity, efficiency it is a bad thing. Also not sufficiently satisfactory hydrophilicity of the produced hydrophilic treatment film. Further, in the method of the hydrophilic treatment by irradiation with ultraviolet laser and ArF laser, the irradiation of the ultraviolet laser and ArF laser, may damage the film, there is a problem that deteriorates the film strength.

Further, as the hydrophilic treatment method of a crystalline polymer microporous membrane, a cationic polymerizable monomer, and a cationic polymerization initiator, to polymerize the cationically polymerizable monomer, at least a part of the surface of the porous membrane method of modifying is proposed, it has been proposed that further optionally contain, functional monomers containing a quaternary ammonium salt or the like (see Patent Document 7).
However, in this proposal, it is impossible to improve the filtration rate and filtration life of the porous membrane to a level sufficiently satisfactory.

In recent years, in semiconductor manufacture, because the purity that can be used therewith to obtain a very high ultra pure water or the like, the appearance of the filter which can capture simultaneously the metal ions present in small concentrations of less than simultaneously ppm and diesel particulate It is desired. Sequestering capability have, acid, less fine filter of alkali and resistance strongly eluted into the drug solution such oxidizing agent has as particularly determined. Conventional for such purpose, the microporous film itself attempts to impart ion exchange functionality to the ion adsorption function have been made.
As a crystalline polymer microporous membranes provided with ion adsorption function, for example, Patent Document 8 contains a functional group which is reactive with activated polar group from the membrane, optionally with an affinity for a specific ion porous membrane ligand was applied have been proposed.
However, in this proposal, it is used a porous membrane having a symmetrical pore structure, when functioning of such a porous membrane, a problem that the filtration flow rate are not necessarily greatly improved, and also not improved filtration life there is.

US Pat. No. 1,421,341 US Pat. No. 2,783,894 US Pat. No. 4,196,070 West German Pat. No. 3,003,400 JP 2007-332342 JP JP 2009-119412 JP JP 2007-503862 JP Hei 9-511948 JP

The present invention is to solve the various problems in the art, and achieving the following object. Specifically, the present invention provides water resistance, and excellent in ion adsorption capacity, high hydrophilicity, filtration life is long and excellent crystalline polymer microporous membrane permeation flow rate, and the crystalline polymer microporous membrane efficiency good method for producing a crystalline polymer microporous film can be produced, as well as an object to provide a filtration filter using the crystalline polymer microporous membrane.

The means for solving the problems are as follows. In other words,
A crystalline polymer microporous membrane having a <1> asymmetric pore structure,
At least a portion of the exposed surface of the crystalline polymer microporous film is coated with a radical polymer obtained by polymerizing a composition containing a radical polymerizable monomer, at least in part on, the ion-exchange groups of the radical polymer and functional compounds is an addition reaction including at least one chelating group, wherein the radical polymerizable monomer is an acrylate, methacrylate, acrylamide, is at least one selected from acrylic acid and derivatives thereof is a crystalline polymer microporous membrane to be.
<2> radical-polymerizable monomer, a carboxyl group, an amino group, a hydroxyl group, an epoxy group, an acrylamide group, isocyanate group, and the crystalline polymer microporous according to <1> having at least one of acid chloride groups it is a membrane.
<3> functional compound is a crystalline polymer microporous membrane according to any one of <2> wherein a compound having a reactive group with the radical polymer from <1>.
<4> The average pore diameter of the first surface of the two exposed surfaces, larger than the average pore diameter in the second surface opposite the first surface, and wherein the said first face first the average pore diameter toward the second surface is a crystalline polymer microporous membrane according to any one of <3> above <1> having a plurality of holes which varies continuously.
<5> by heating one surface of a film containing a crystalline polymer constituting the crystalline polymer microporous membrane wherein a film has been stretched semi-sintered film provided with a temperature gradient in the thickness direction of the film < 4 is a crystalline polymer microporous membrane according to>.
<6> The crystalline polymer microporous membrane according to any one of <5>, wherein the <4> to the second surface and the heating surface.
<7> The ratio of before coating the radical polymerizable monomer polymer on the exposed surface, the average pore diameter d 3 at the first surface of the crystalline polymer microporous film, the average pore diameter d 4 of the second surface ( and d 3 / d 4),
After coating the fluorine-based surfactant to the exposed surface, the average pore diameter in the first surface of the crystalline polymer microporous membrane 'with an average pore diameter d 4 of the second surface' d 3 ratio of (d 3 '/ d 4') and although the following formula, (d 3 '/ d 4 ') / (d 3 / d 4)> 1, the satisfying <1 from> according to any one of <6> crystalline a sex polymer microporous membrane.
<8> crystalline polymer is polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene, chlorotrifluoroethylene-ethylene copolymer, polyethylene, polypropylene, nylon, polyacetal, polybutylene terephthalate, polyethylene terephthalate, syndiotactic polystyrene, polyphenylene sulfide, polyether ether ketone, wholly aromatic family polyamide, wholly aromatic polyester, and at least one selected from polyether nitrile of <1> to <7> It is a crystalline polymer microporous membrane according to any one.
<9> crystalline polymer is a crystalline polymer microporous membrane according polytetrafluoroethylene to any one of <1> to <7>.
The exposed surface of the crystalline polymer microporous film having a <10> asymmetric pore structure imparts a composition comprising a radical polymerizable monomer, a hydrophilic treatment step of polymerizing the radical polymerizable monomer,
Wherein a part of the radical polymer, and a addition reaction treatment step of addition reaction of functional compounds containing at least one ion-exchange group and a chelating group,
The radical polymerizable monomer is an acrylate, methacrylate, acrylamide, method for producing a crystalline polymer microporous membrane, characterized in that at least one selected from acrylic acid and derivatives thereof.
<11> by heating one producing a crystalline polymer microporous film, the asymmetric heating step of forming a semi-baked film with a temperature gradient in the thickness direction of the film,
Wherein a method for producing a crystalline polymer microporous membrane according to the semi-sintering and stretching process of the film by stretching to form a crystalline polymer microporous membrane having an asymmetric pore structure, the further comprising a <10>.
<12> radical-polymerizable monomer, a carboxyl group, an amino group, a hydroxyl group, an epoxy group, an acrylamide group, wherein an isocyanate group, and the including at least one of the acid chloride group from the <10> to any one of <11> which is a method for producing a crystalline polymer microporous membrane.
<13> functional compound is a method for producing a crystalline polymer microporous membrane according a compound having a reactive group with a radical polymer from <10> to any one of <12>.
<14> The filtration filter characterized by having a crystalline polymer microporous membrane according to any one of <1> to <9>.

According to the present invention, to solve the various problems in the art, the can achieve the purpose, water resistance, and excellent in ion adsorption capacity, high hydrophilicity, filtration life is long and excellent permeation flux crystal sex polymer microporous membrane, and method for producing a crystalline polymer microporous film of the crystalline polymer microporous film can be efficiently produced and filtration filter using the crystalline polymer microporous membrane, it is possible to provide a.

Figure 1 is a diagram showing a general structure of a pleated filter element before mounted in a housing. Figure 2 is a diagram representing the architecture of a typical filter element before mounted in a housing of a capsule-type filter cartridge. Figure 3 is a diagram representing the architecture of a filter cartridge of the general capsule-type integrated with the housing. 4A is a diagram schematically showing a cut surface of the crystalline polymer microporous membrane having symmetric pores before functionalization process in Comparative Example 2 (hydrophilic treatment and addition reactions pretreatment). Figure 4B is a diagram schematically showing a cut surface of the crystalline polymer microporous membrane having symmetric pores after functionalization treatment in Comparative Example 2 (after hydrophilization and addition reaction process). Figure 5A is a diagram schematically showing a cut surface of the crystalline polymer microporous asymmetric membrane having functionalized pretreatment in Example 1 (after hydrophilization and addition reaction process). 5B is a diagram schematically showing a cut surface of the crystalline polymer microporous film having an asymmetric pore after functionalization process in Example 1 (after hydrophilization and addition reaction process).

(Method for producing a crystalline polymer microporous membrane and the crystalline polymer microporous membrane)
Crystalline polymer microporous membrane of the present invention is a crystalline polymer microporous membrane having an asymmetric pore structure, at least a portion of the exposed surface of the crystalline polymer microporous membrane, the radical polymerizable monomer coated with a radical polymer obtained by polymerizing a composition comprising, at least a portion of the radical polymer, functional compound formed by addition reaction including at least one ion-exchange group and a chelating group.
Method for producing a crystalline polymer microporous membrane of the present invention, a hydrophilization treatment step, and a addition reaction step, an asymmetric heating step, drawing step, the crystalline polymer film producing step, other if necessary comprising the step.
The method for manufacturing a crystalline polymer microporous membrane and the crystalline polymer microporous membrane of the present invention will be described in detail.

Microporous membrane of the crystalline polymer of the present invention is a crystalline polymer microporous membrane having an asymmetric pore structure, as described below the crystalline polymer microporous membrane, the composition comprising a radical polymerizable monomer coated with a radical polymer obtained by polymerizing an object, at least a portion of the radical polymer, functional compound formed by addition reaction including at least one ion-exchange group and a chelating group.
Further, the crystalline polymer microporous film, by heating one surface of a film composed of crystalline polymer is preferably obtained by stretching a semi-sintered film having a temperature gradient in the thickness direction of the film .
In this case, the side surface having the larger average pore diameter of the two exposed surfaces of the crystalline polymer microporous membrane obtained by stretching a first surface, opposite the first surface If the surface has a second surface, it is preferable that the heating surface of the second surface.
The hole has a continuous hole from the first surface to the second surface (both ends are opened) has become.
Hereinafter, the first surface of the average pore diameter is larger side as "non-heated surface" describes the second surface of the average pore size smaller side as "heated surface". This is not just a designation wearing for the sake of convenience in order to facilitate understanding of the description of the present invention. Therefore, it may be in the "heated surface" by heating the one surface of the crystalline polymer film of the green after semi-baked.

- crystalline polymer -
Examples of the "crystalline polymer" is not particularly limited and regularly aligned crystalline region is long-chain molecules into the molecular structure, as long as it is a polymer amorphous regions are mixed not regularly arranged in it can be appropriately selected depending on the purpose. Such polymers are physical treatment, crystallinity is expressed. For example, when stretched by an external force polyethylene film, initially observed a phenomenon that a transparent film becomes cloudy. This by molecular arrangement in the polymer is aligned in one direction by the external force, from the crystallinity is expressed.

The crystalline polymer is not particularly limited and may be appropriately selected depending on the intended purpose, for example, polyalkylenes, polyesters, polyamides, polyethers, and liquid crystalline polymers. Specifically, polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene, chlorotrifluoroethylene-ethylene copolymer, polyethylene, polypropylene, nylon, polyacetal, polybutylene terephthalate, polyethylene terephthalate, syndiotactic polystyrene, polyphenylene sulfide, polyether ether ketone, wholly aromatic polyamides, wholly aromatic polyester, fluororesin, polyether nitriles. These may be used alone or in combination of two or more thereof.
Among these, from the viewpoints of handling properties and chemical resistance, polyalkylenes (e.g., polyethylene and polypropylene) are preferable, a fluorine-based polyalkylenes hydrogen atom of the alkylene group in polyalkylene is partially or entirely by fluorine atoms are substituted still more preferably, polytetrafluoroethylene (PTFE) is particularly preferred.
The polyethylene, the density is varied by the degree of branching, many branching degree, what crystallinity is low low density polyethylene (LDPE), degree of branching less, a high degree of crystallinity is high density polyethylene (HDPE) classified as both can be used. Among these, from the viewpoint of crystallinity control, HDPE is particularly preferable.

The crystalline polymer is its glass transition temperature, preferably 40 ° C. ~ 400 ° C., more preferably from 50 ℃ ~ 350 ℃. Further, the weight average molecular weight of the crystalline polymer is preferably 1,000 to 100,000,000. The number average molecular weight of the crystalline polymer is preferably 500 to 50,000,000, more preferably 1,000 to 10,000,000.

Crystalline polymer microporous membrane of the present invention has an average pore diameter of the first surface is greater than the average pore diameter in the second surface, and an average pore diameter toward the second surface from said first surface having a plurality of holes which continuously changes, i.e., greater than the average diameter of the average pore diameter heating surface of the non-heated surface (first surface) (the second surface).
Further, the crystalline polymer microporous membrane, the membrane thickness is "10", the average pore size of pores at a portion with a thickness in the depth direction from the surface "1" and P1, and the average pore size of pores at a portion with a thickness of "9" P2 when, P1 / P2 is preferably 2 to 10,000, more preferably 3-100.
Further, the crystalline polymer microporous membrane, the ratio of the average pore size (non-heated surface / heated surface ratio) is preferably from 5 to 30 times the non-heated surface heated surface, and more preferably from 10 times to 25 times, 15 to 20 times being particularly preferred.
The average pore size of pores in the non-heated surface of the crystalline polymer microporous film (first surface) is not particularly limited and may be appropriately selected depending on the intended purpose, is 0.1 [mu] m ~ 500 [mu] m preferably, more preferably 0.25μm ~ 250μm, 0.50μm ~ 100μm is particularly preferred.
When the average pore diameter is less than 0.1 [mu] m, there is a possibility that the flow rate is reduced, when it exceeds 500 [mu] m, efficiently there is a possibility that can not capture fine particles. On the other hand, when it is in the more preferable range, it is advantageous in terms of flow rate and particulate trapping properties.
The average pore size of pores in the heating surface of the crystalline polymer microporous film (second surface) is not particularly limited and may be appropriately selected depending on the purpose, 0.01 [mu] m ~ 5.0 .mu.m It is preferred, more preferably 0.025 .mu.m ~ 2.5 [mu] m, particularly preferably from 0.05 .mu.m ~ 1.0 .mu.m.
When the average pore diameter is less than 0.01 [mu] m, there is a possibility that the flow rate is reduced, when it exceeds 5.0 .mu.m, efficiently there is a possibility that can not capture fine particles. On the other hand, when it is in the more preferable range, it is advantageous in terms of flow rate and particulate trapping properties.

Here, the average pore size, for example, a scanning electron microscope (Hitachi S-4000 type, deposition Hitachi E1030 type, both manufactured by Hitachi, Ltd.) photograph of the film surface (SEM photograph, 000 magnifications - take a 5,000-fold), and the resulting photographic image processing apparatus (body name: Nippon avionics Co., Ltd., TV image processor TVIP-4100II, control software name: RATOC system engineering Co., Ltd., TV image processor image command 4198 ) to and takes in to obtain an image composed of only crystalline polymer fibers, a pore diameter in the image to a predetermined number determined by calculating process it can determine the average pore diameter.

The crystalline polymer microporous membrane of the present invention, in addition to the above features, the average pore diameter continuously changes toward a further unheated surface (first surface) heating surface (second surface) and in that embodiment (first embodiment) include both still a single-layer structure embodiment in addition to the above feature (second aspect). By adding these additional features can be further effectively improved filtration life.

The term "average pore diameter toward the heated surface from the non-heated surface is continuously changed" a first aspect, the horizontal axis to the depth of the thickness direction of the distance t (the surface from the non-heated surface takes considerable), the vertical axis when taking the average pore diameter D, and means that the graph is drawn with one continuous line. It non graph of the heating surface from (t = 0) up to the heating surface (t = film thickness) may be one inclination becomes only negative region (dD / dt <0), the slope is negative it may be those regions and the slope is zero region (dD / dt = 0) are mixed, may be one slope negative region and a positive region (dD / dt> 0) are mixed . Preferred are either those inclination becomes only negative region (dD / dt <0), in which the inclination is negative region and the slope is zero region (dD / dt = 0) are mixed. Further preferred are those inclination becomes only negative region (dD / dt <0).

The inclination is to include non-heated surface of the at least film into negative region is preferred. In slope negative region (dD / dt <0), it may tilt always different be constant. For example, dD the heating surface of the film than dD / dt when the crystalline polymer microporous membrane are those inclination becomes only negative region (dD / dt <0), in the non-heated surface of the film of the present invention / dt can take a large aspect. Further, it is possible to take a gradual dD / dt increases manner toward the heated surface from the non-heated surface of the crystalline polymer microporous membrane (aspects absolute value decreases).

From the "single-layer structure" is used in the second aspect, a multilayer structure formed by or or laminated bonding two or more layers are excluded. In other words, the term "single-layer structure" used in the second aspect means a structure having no boundary between layers existing in the multilayer structure. In a second aspect, in the film, it is preferable than the average pore size of the small and the heating surface than the average pore size of the non-heated surface there is a surface having a large average pore size.

Crystalline polymer microporous membrane of the present invention is preferably one that also has both features of the first aspect and the features of the second aspect. That is, the average pore diameter of the non-heated surface of the crystalline polymer microporous membrane is larger than the average pore size of the heating surface, the average pore diameter toward the heated surface from the non-heated surface are continuously changing, and the monolayer a is are preferred structure. With such a crystalline polymer microporous membrane may further efficiently when subjected to filtration from the non-heated surface side can be captured particulates, it is possible to greatly improve filtration life, easy and inexpensive It can also be prepared to.

Thickness of the crystalline polymer microporous film is preferably 1 [mu] m ~ 300 [mu] m, more preferably 5 [mu] m ~ 100 [mu] m, particularly preferably 10 [mu] m ~ 80 [mu] m.

In the present invention, at least a portion of the exposed surface of the crystalline polymer microporous membrane is coated by a radical polymer obtained by polymerizing a composition containing a radical-polymerizable monomer (hydrophilic treatment), the radical polymer At least a part of the functional compound containing at least one ion-exchange group and a chelating group has been added (addition reaction process).
Here, the exposed surface, in addition to the surface (first surface and second surface) which is exposed in the crystalline polymer microporous membrane includes around the hole portion, and the interior of the hole.

Composition containing the radically polymerizable monomers are acrylates, methacrylates, acrylamides, comprising at least one radical polymerizable monomer selected from acrylic acid and derivatives thereof, and if necessary, other radically polymerizable sex monomers, solvents, radical polymerization initiators, photosensitizers, include other components such as antioxidants.

<Radical polymerizable monomer>
As the radical polymerizable monomers, acrylates, methacrylates, acrylamides, not particularly as long as at least one limit selected from acrylic acid and derivatives thereof, can be appropriately selected depending on the purpose, for example, 1- hydroxy-2-propyl acrylate, 2-hydroxy-1-propyl acrylate, hydroxypropyl methacrylate, 2,3-dihydroxypropyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, alkyl (meth) acrylates such as hydroxyethyl methacrylate; 4- hydroxybutyl acrylate glycidyl ether, glycidyl such as glycidyl acrylate (meth) acrylates; aminoethyl methacrylate, dimethylaminoethyl methacrylate click relay , Primary amines, such as diethylaminoethyl methacrylate (meth) acrylates; urethane (meth) acrylate; acrylamide, methacrylamide, ethacrylamide, N, acrylamides such as N- dimethylacrylamide, acrylic acid, acrylic acids such as methacrylic acid; acrylic acid chloride, and the like (meth) acrylic acid chloride such as methacrylic acid chloride. These may be used alone or in combination of two or more thereof.
Among these, from the viewpoint reactivity with the reactive compound is good, glycidyl (meth) acrylates, acrylic acids are preferred.

The radical polymerizable monomer, a carboxyl group, an amino group, a hydroxyl group, an epoxy group, an acrylamide group, isocyanate group, and preferably contains at least one of acid chloride groups.
Examples of the radical polymerizable monomer containing a carboxyl group include acrylic acid, methacrylic acid, and carboxymethyl ethyl acrylate. Examples of the radical polymerizable monomer containing an amino group, for example, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate. Examples of the radical polymerizable monomer containing the hydroxyl group, for example, 4-hydroxybutyl acrylate and hydroxyethyl methacrylate. Examples of the radical polymerizable monomer containing the epoxy group, for example, 4-hydroxybutyl acrylate glycidyl ether, and glycidyl acrylate. Examples of the radical polymerizable monomer containing the acrylamide groups, for example, acrylamide, N, etc. N- dimethyl acrylamide. Examples of the radical polymerizable monomer containing an isocyanate group include, for example, urethane (meth) acrylates. Examples of the radical polymerizable monomer containing the acid chloride group include, for example, acrylic acid chloride.
Examples of the urethane (meth) acrylates are not particularly limited and may be appropriately selected depending on the purpose, a commercially available product can be used. Examples of the commercially available products, for example, Desmodur HL (Bayer AG, manufactured Leverkusen), Roskydal UA VP LS 2265 (Bayer AG, manufactured Leverkusen) and the like.

The content of the composition of the radical polymerizable monomer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 mass% to 30 mass%, 0.2 mass% more preferably 25% by weight, particularly preferably 0.3 mass% to 20 mass%.
When the content is less than 0.1 wt%, there may not be able to hydrophilizing the entire microporous film of the crystalline polymer, when it exceeds 30 wt%, the microporous of the crystalline polymer It would block the holes of the sex film, which may lower the transmission rate.

<< radical polymerization initiator >>
As the radical polymerization initiator, any of photo-radical polymerization initiator and the thermal radical polymerization initiator can be preferably used.

- photo-radical polymerization initiator -
As the photo-radical polymerization initiator is not particularly limited and may be appropriately selected depending on the purpose, for example, Irgacure commercially available from BASF Japan Co., Ltd. (Irgacure) series (e.g., Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 819, etc.), Darocure (Darocure) series (for example, Darocure TPO, Darocure 1173, etc.), Quanta cure (Quantacure) PDO, commercially available from Sartomer (Sartomer), Inc. has been and Esacure (Specialty Chemicals; and EZACURE) series (e.g., Ezacure TZM, Esacure TZT, etc.) and the like.

- thermal radical polymerization initiator -
As the heat radical polymerization initiator is not particularly limited and may be appropriately selected depending on the purpose, for example, alpha,. Alpha .'- azobisisobutyronitrile, three SI series commercially available from Shin Chemical Co. (e.g., SI-100, etc.) and the like.

The additive amount of the radical polymerization initiator, particularly, without limitation, with respect to the radical polymerizable monomer 100 parts by weight, preferably 0.1 parts by mass to 20 parts by weight, 0.5 parts by mass to 15 parts by weight and particularly preferably from 1.0 parts by mass to 10 parts by weight.
When the amount is less than 0.1 part by weight, the polymerization reaction is slow, and when it exceeds 20 parts by mass, the film strength becomes brittle.

<< solvent >>
The solvent is not particularly limited and may be appropriately selected depending on the purpose, for example, water; methanol, ethanol, isopropanol, alcohols such as ethylene glycol; ketones such as acetone and methyl ethyl ketone (MEK); tetrahydrofuran , ethers such as dioxane and propylene glycol monomethyl ether acetate; dimethylformamide, and dimethyl sulfoxide.

<< photosensitizer >>
The composition may be used in combination photosensitizer as needed. The use of the photosensitizer, the reactivity improved and mechanical strength and adhesive strength of the cured product can be improved.
As the photosensitizer is not particularly limited and may be appropriately selected depending on the purpose, for example, carbonyl compounds, organic sulfur compounds, peroxides, redox compounds, azo and diazo compounds, halogen compounds, photoreduction such as sexual dyes can be mentioned, specifically, benzoin methyl ether, benzoin isopropyl ether, alpha, benzoin derivatives such as α- dimethoxy -α- phenyl acetophenone; benzophenone, 2,4-dichlorobenzophenone, o- benzoyl benzoate benzophenone derivatives such as 4,4'-bis (diethylamino) benzophenone; 2-chloro-thioxanthone, 2-isopropyl thioxanthone derivatives such as thioxanthone; 2-chloro-anthraquinone, anthraquinone derivatives such as 2-methyl anthraquinone; N- Mechiruaku Pyrrolidone, acridone derivatives such as N- butyl acridone; Other, alpha, alpha-diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compounds, and the like. These may be used alone or in combination of two or more thereof.
Examples of commercially available products of the photosensitizer, for example, ANTHRACURE (registered trademark) UVS-1331 (Kawasaki Kasei Chemicals Ltd.), KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) and the like.

<< Antioxidant >>
The composition, as long as they do not impair the effects of the present invention may be contain other additives such as an antioxidant.
Examples of commercially available products of antioxidants, for example, dibutylhydroxytoluene (BHT); Irganox 1010, Irganox 1035FF, (manufactured by both BASF Japan Ltd.) Irganox 565, and the like.

In the crystalline polymer microporous membrane of the present invention, at least part of the exposed surface of the crystalline polymer microporous membrane is coated with a radical polymer obtained by polymerizing a composition containing a radical-polymerizable monomer includes a film before coating, finely respectively the film after coating, methanol the crystalline polymer microporous membrane, water, and extracted with a solvent such as DMF, the components of the extract NMR, IR, etc. it can be confirmed by measuring and analyzed using.
Further, when it is impossible to extract the crystalline polymer microporous membrane in the solvent, minced each film, in a state where dusted with KBr, making measurements and analyzed by IR, and using supercritical methanol while decomposing the polymer, the component MASS, NMR, it can be confirmed by measuring and analysis by IR or the like.

Further, the functional compound to be described later to the radical polymer is addition reactions, minced each film, in a state where crusted KBr, making measurements and analyzed by IR, and using supercritical methanol, while decomposing the polymer, the component MASS, NMR, it can be confirmed by measuring and analysis by IR or the like.

Crystalline polymer microporous membrane of the present invention, at least a portion of the exposed surface of the crystalline polymer microporous membrane is coated with a radical polymer obtained by polymerizing a composition containing a radical-polymerizable monomer since, in addition to the surface (first surface and second surface) which is exposed in the crystalline polymer microporous membrane, around the hole portion, and the internal bore is uniformly coated, thus, hydrophilic high, filtration life is long and excellent permeation rate.
On the other hand, at least a portion of the exposed surface of the crystalline polymer microporous membrane, previously when polymerized are covered by radical polymers, coating the exposed surface, particularly around the hole portion, and coating the inside of the hole There may become nonuniform, thus, sufficient hydrophilicity can be obtained, as compared with the crystalline polymer microporous membrane of the present invention, can not be improved filtration life, and the flux.
Distribution and the degree of coating of the radical polymer, for example, energy dispersive X-ray - elemental analysis by scanning electron microscopy spectroscopy (EDX-SEM), can be identified by examining the element distribution in the exposed surface .

Further, the crystalline polymer microporous membrane of the present invention, at least a portion of the exposed surface of the crystalline polymer microporous membrane is coated by a radical polymer obtained by polymerizing a composition containing a radical-polymerizable monomer since it is, it is possible to impart hydrophilicity, can form a significant asymmetric structure in the asymmetric membrane, thereby improving further filtration life. This said radical polymer, toward the second surface dense portion (heating surface) of the crystalline polymer microporous film, thicker than coarse filtration portion of the first surface (unheated surface) can be attached, is considered an average particle diameter from the first surface toward the second surface is because it forms a pronounced asymmetric structure degree increases continuously varies.
This is evidenced by satisfying the relationship shown below.
As shown in FIG. 5A, the crystalline polymer before coating the crystalline polymer microporous membrane radical polymer obtained by polymerizing a composition containing the radical polymerizable monomer to the exposed surface of the (hydrophilic treatment before) Fine the average pore diameter d 3 at the first surface of the membranes, the ratio between the average pore diameter d 4 of the second surface (d 3 / d 4),
As shown in FIG. 5B, the crystalline polymer after coating the crystalline polymer microporous membrane radical polymer obtained by polymerizing a composition containing the radical polymerizable monomer to the exposed surface of the (after hydrophilization) Fine the average pore diameter in the first surface of the membranes' with an average pore diameter d 4 of the second surface 'd 3 and the ratio of the (d 3' / d 4 ' ) , but the formula, (d 3' / d 4 ') / (d 3 / d 4)> 1, preferably satisfies, (d 3' / d 4 ') / (d 3 / d 4)> 1.005 , more preferably, (d 3' / d 4 ') / (d 3 / d 4)> 1.01 is particularly preferred. Wherein if there is one or less (d 3 '/ d 4' ) / (d 3 / d 4), by clogging of particles, sometimes life is extremely short.

The coverage of the radical polymer, if at least part of the exposed surface of the crystalline polymer microporous film is coated is not particularly limited, depending on the surface area of ​​the crystalline polymer microporous membrane can be appropriately adjusted Te, for example, it can be appropriately adjusted based on the porosity described in JP-a-8-283447. That is, the surface area has a correlation with the porosity of the crystalline polymer microporous membrane can be in relation to the porosity to optimize the coverage of the radical polymer, specifically can be calculated using the following equation (1) and the following formula (2).
As the porosity is not particularly limited and may be appropriately selected depending on the intended purpose, preferably 60% or more, more preferably 60% to 95%. The porosity is less than 60%, the hydrophilicity is low, in the crystalline polymer microporous membrane may not be able to obtain the desired transmission rate exceeds 95%, the crystalline polymer the strength of the microporous membrane is lowered.
Higher porosity of the crystalline polymer microporous membrane is low, the less radical polymerization of coverage, conversely, as the porosity becomes higher, but the coverage is increased, the range, the following equation (1) and formula may be in the range defined by (2).
The coverage is less than the range defined by the following formula (1) and the following formula (2), high hydrophilicity, it may be impossible to obtain a long crystalline polymer microporous membrane of the filtration life, and greater than the range, it may cause clogging.
(C / 5) -11.5 ≦ D ≦ (C / 5) -9.5 ··· Equation (1)
D = (coating weight / crystalline polymer microporous membrane weight of radical polymerizable monomer) × 100 · · · formula (2)
(In the formula (1), "C" represents the porosity of the crystalline polymer microporous membrane (%).)

<Functional compounds>
Examples of the functional compound, as long as it contains at least one ion-exchange group and a chelating group is not particularly limited and may be appropriately selected depending on the purpose, the reactive group of the radical polymer, if necessary and further contains other components Te.

- ion-exchange group -
The ion exchange group is a functional group that captured by ionic bonding metal ion.
Examples of the ion-exchange group, as long as it is a functional group which ionic bond with a metal ion such is not particularly limited and may be appropriately selected depending on the purpose, for example, a sulfonic acid group, a phosphoric acid group, such as a carboxyl group cation exchange groups, primary amino groups, secondary amino groups, tertiary amino groups, quaternary amino groups, and anion-exchange groups such as quaternary ammonium bases.

- chelating group -
The chelating group is a functional group which captures a metal ion and chelating (coordination) by bonding.
Examples of the chelating group, as long as it is a functional group that metal ion chelates (coordination) bonds is not particularly limited and may be appropriately selected depending on the purpose, for example, nitrilotriacetic acid derivatives (NTA) group, iminodiacetic acid group, iminodiethanol group, amino polycarboxylic acids, amino polyphosphonic acids, porphyrin skeleton, a phthalocyanine skeleton, cyclic ethers, cyclic amines, phenols and lysine derivatives, phenanthroline group, terpyridine group, bipyridine group, triethylenetetramine group, diethylenetriamine group, tris (carboxymethyl) ethylenediamine group, diethylenetriaminepentaacetic acid groups, poly pyrazolyl borate acid, 1,4,7-triazolium triazacyclononane group, dimethylglyoxime group, polydentate ligand such as diphenyl glyoxime group It is like .

- reactive groups of the radical polymer -
The reactive groups of the radical polymer is not particularly limited and may be appropriately selected depending on the purpose, for example, an amino group, a hydroxyl group, an epoxy group, or their derivatives groups. Among these, amino group, a hydroxyl group are preferred.
Specific examples of the functional compound having a reactive group, the reactive group is an amino group, pentaethylenehexamine, aminoethanesulfonic acid, phosphoryl ethanolamine; reactive group is a hydroxyl group, hydroxy diamine triacetic acetate, choline, hydroxypropane sulfonic acid, glycerophosphate disodium pentahydrate, and the like; other, ethylene sulfide, and the like oxetane compounds and cyclic compounds.

- membrane anchor functional compound -
Was coated a radical polymerizable monomer in the hole wall surface of the crystalline polymer microporous film (film of crystalline polymer), for immobilizing by polymerizing, the functional compound is present in the side chain of the radical polymer by addition reaction to a reactive group in a non-covalent bond state, it is fixed to the crystalline polymer microporous membrane.
Further, the functional compound is fixed to the crystalline polymer microporous membrane by, for instance, reverse titration method described in JP-A-2005-131482 can be confirmed.

By film fixing the functional compound, it is possible to achieve high flow rates of.
Flow rate is generally such that the following equation, hole diameter (D), pressure loss (△ P), the number of holes (n), is determined by the thickness (L), liquid viscosity (eta). By fixing the functional compound to the membrane, although the pore size was expected that the downward flow rate decreases, in fact, it has Hakare high flow rate of. The reason for this is estimated that because hydrophilic is improved.

Figure JPOXMLDOC01-appb-M000001

(Method for producing a crystalline polymer microporous membrane)
Method for producing a crystalline polymer microporous membrane of the present invention, hydrophilic treatment step, the addition reaction treatment step includes at least a crystalline polymer film producing step, an asymmetric heating step, drawing step, other if necessary comprising the step.
The hydrophilic treatment, and also to the addition reaction process, referred to as a functional process.

<Crystalline Polymer Film Preparation Step>
The type of the crystalline polymer materials used in producing the unbaked crystalline film composed of crystalline polymer is not particularly limited, may be preferably used crystalline polymer described above. Among them, polyethylene, or a crystalline polymer preferably substituted with the hydrogen atoms fluorine atom, for example, polytetrafluoroethylene (PTFE) is preferred. Wherein the poly as tetrafluoroethylene, usually, it is possible to use a polytetrafluoroethylene produced by emulsion polymerization, preferably finely powdered obtained by coagulating the resulting aqueous dispersion by emulsion polymerization it can be used polytetrafluoroethylene.
The number average molecular weight of the crystalline polymer used as a raw material is preferably 500 to 50,000,000, more preferably 1,000 to 10,000,000.
The number average molecular weight of polytetrafluoroethylene to be used as a starting material, preferably from 2,500,000 to 10,000,000, more preferably from 3,000,000 to 8,000,000.
Examples of the polytetrafluoroethylene material is not particularly limited, it may be used appropriately selected and polytetrafluoroethylene materials sold in the market. For example, such as manufactured by Daikin Industries, Ltd. "POLYFLON fine powder F104U" is preferably used.

The polytetrafluoroethylene starting material was prepared mixture was mixed with extrusion aid, which it is preferred to prepare a film by rolling Te paste extrusion. The extrusion aid, it is preferable to use a liquid lubricant, in particular solvent naphtha, and the like can be exemplified white oil. As the extrusion aid, it is possible to use a hydrocarbon oil such as manufactured by Esso Sekiyu KK "Isopar" sold in the market. The amount of the extrusion aid, based on 100 parts by weight of the crystalline polymer, preferably 20 to 30 parts by mass.

Paste extrusion is preferably carried out at usually 50 ℃ ~ 80 ℃. The extruded shape is not particularly limited and may be appropriately selected depending on the purpose, usually preferably a rod. The extrudate is then stretched into a film by rolling. Rolling, for example, it can be performed by calendering at 50 m / min by a calender roll. The stretching temperature is generally set to 50 ℃ ~ 70 ℃. Thereafter, it is preferable that the unbaked crystalline polymer film to remove the extrusion aid by heating the film. This heating temperature time may be determined depending on the type of the crystalline polymer to be used is preferably from 40 ° C. ~ 400 ° C., more preferably from 60 ℃ ~ 350 ℃. For example, in the case of using a polytetrafluoroethylene is preferably 0.99 ° C. ~ 280 ° C., more preferably from 200 ℃ ~ 255 ℃. The heating can be carried out by passing the film through a hot air drying oven. The thickness of the unbaked crystalline polymer film this way is produced can be adjusted appropriately according to the thickness of the crystalline polymer microporous membrane to be finally produced, subjected to the stretching in a later step in this case, it is preferably adjusted in consideration of reduction in thickness by stretching.
When producing the unbaked crystalline polymer film, "Polyflon Handbook" (published by DAIKIN INDUSTRIES, LTD, 1983 revised edition) may be suitably employed the matters stated in.

<Asymmetric heating step>
The asymmetric heating step is heating one surface of a film composed of crystalline polymer is a step of forming a semi-baked film with a temperature gradient in the thickness direction of the film.
Here, the semi-sintering, the crystalline polymer is at least the melting point of the sintered body, and means to heat treatment at the melting point + 15 ° C. below the temperature of the green body.
Further, in the present invention, the green body of the crystalline polymer is one which has not been heat treatment sintering. Further, the melting point of the crystalline polymer means the temperature of the peak of the endothermic curve appearing the unbaked crystalline polymer material as measured by differential scanning calorimetry. The melting points and the green body of the sintered body may vary depending on the type and the average molecular weight and the like of the crystalline polymer, preferably from 50 ° C. ~ 450 ° C., more preferably from 80 ℃ ~ 400 ℃.
Such temperatures can be considered as follows. For example, when the crystalline polymer is polytetrafluoroethylene, the melting point of the green body melting of the sintered body is at about 324 ° C. is about 345 ° C.. Thus, a semi-sintered body in the case of polytetrafluoroethylene film, 327 ° C. ~ 360 ° C., more preferably 335 ° C. ~ 350 ° C., is heated to a temperature of for example 345 ° C.. Semi-baked body is a state in which those having a melting point of about 324 ° C. and that of the melting point of about 345 ° C. are mixed.

The semi-baking is performed by heating one surface of a film consisting of crystalline polymer (heating surface). Thus, it is possible to control the heating temperature asymmetrically in the thickness direction, the crystalline polymer microporous membrane of the present invention can be easily produced.
As the temperature gradient in the thickness direction of the made of a crystalline polymer film, the temperature difference between the heating surface and the unheated surface is preferably 30 ° C. or higher, more preferably at least 50 ° C..

Examples heating method, a method of blowing hot air, a method of contacting a heat medium, a method of contacting the heated material, a method of irradiating infrared rays, various methods, such as microwave heating or the like electromagnetic radiation can be used.
Examples heating method is not particularly limited, a method of contacting a heated on the surface of the film, the infrared radiation is particularly preferred. The heated, it is particularly preferable to select the heating roll. If heated rolls, industrial can be performed continuously semi-baked in an assembly-line operation to control the temperature and maintain the device is easy. The temperature of the heating roll can be set to a temperature at which a semi-sintered body of the above. Contact time of the film on the heating roll is the time required for semi-sintered sufficiently proceeds of interest, preferably from 30 seconds to 120 seconds, more preferably from 45 seconds to 90 seconds, 60 seconds and 80 seconds There further preferred.

As the infrared ray irradiation is not particularly limited and may be appropriately selected depending on the purpose.
General definition of the infrared can be "practical infrared" (human beings and history, Inc., issued in 1992) to the reference. In the present invention, the infrared ray has a wavelength refers to electromagnetic waves 0.74 [mu] m ~ 1,000 .mu.m, of which wavelength is a near-infrared range of 0.74 [mu] m ~ 3 [mu] m, the far range wavelength of 3 [mu] m ~ 1,000 .mu.m an infrared.

In the present invention, since Write temperature difference between the heating surface and the unheated surface of the semi-baked film is preferred, is advantageous far infrared to the surface of the heating is preferably used.
As the type of device that performs infrared radiation is not particularly limited as long irradiation infrared wavelength of interest, can be appropriately selected depending on the purpose, as the heating element used in the infrared radiation, in general, near infrared the bulb (halogen lamp), far infrared rays may be used ceramics, quartz, a heating element such as a metal oxide surface.
Furthermore, if infrared radiation, industrially it can be performed continuously semi-baked in an assembly-line operation to control the temperature and maintain the device is easy. Since a non-contact, never clean, and defects such as fuzz occurs.
Film surface temperature by the infrared radiation, the output of the infrared radiator, the distance of the infrared irradiation device and the film surface, irradiation time (conveyance speed), can be controlled by the ambient temperature is set to temperature at which a semi-sintered body of the can, but preferably 327 ° C. ~ 380 ° C., more preferably from 335 ℃ ~ 360 ℃. When the surface temperature is less than 327 ° C., without crystalline state changes, it may not be able to control the pore size exceeds 380 ° C., or deformed excessively shape by the entire film is melted, the polymer there is the decomposition of the heat.
The infrared irradiation time is not particularly limited, a time required for the semi-sintered of interest sufficiently proceeds, preferably from 30 seconds to 120 seconds, more preferably from 45 seconds to 90 seconds, 60 seconds to more preferably 80 seconds.

Heating in the asymmetric heating step may be performed continuously, or may be performed intermittently by dividing into several times.
In case of heating the heating surface of the continuous film, in order to maintain the temperature gradient between the heated surface and the unheated surface of the film, it is preferable to cool the heated and at the same time non-heated surface of the heating surface.
The method as a method of cooling the non-heated surface is not particularly limited and may be appropriately selected depending on the purpose of contacting example method of blowing cold air, a method of contacting the refrigerant, the cooled material, by cooling various cooling methods and the like can be used, preferably, carried out by contacting the cooled product to a non-heated surface of the film. The cooled product, the cooled product, it is particularly preferable to select a cooling roll. If the cooling roll, similarly to the heating of the heating surfaces, industrially can be performed continuously semi-baked in an assembly-line operation to control the temperature and maintain the device is easy. Temperature of the cooling roll can be set to produce a temperature and difference in time of the semi-sintered body of the above. Time of contacting the film with a cooling roll is a time required for the semi-sintered sufficiently proceeds of interest, given that performing the heating step and simultaneously, is usually 30 seconds to 120 seconds, preferably 45 seconds to 90 seconds, more preferably from 60 seconds to 80 seconds.
Surface material of the heating roll and the cooling roll, generally can be stainless steel having excellent durability, in particular can be mentioned SUS316. In the production method of the present invention, it is preferred to contact the non-heated surface of the film to heating and cooling roll, may be a roller which is set at a lower temperature than the heating and cooling roll into contact with the heating surface of the film Absent. For example, by pressing a roller which is maintained at room temperature from film heating surface, it may be caused to fit the film to the heat roll. Further, before or after contacting the heating roll, it may be brought into contact with the heating surface of the film guide roll.
Further, even when intermittently performing the asymmetric heating step, the heating surface of the film is cooled intermittently heated and non-heated surface, it is preferable to suppress an increase in the temperature of the unheated surface.

<Stretching step>
The stretching step is a step of stretching the semi-baked film.
As the stretching, the is preferably performed for both the longitudinal direction and the width direction of the semi-baked film. At this time, the longitudinal direction and the width direction, may be sequentially performed stretching, respectively, may be biaxially stretched simultaneously.
The longitudinal direction and the width direction, sequentially in the case of performing the stretching, respectively, first, it is preferable to carry out the stretching in the width direction after performing stretching in the longitudinal direction.
Draw ratio of the longitudinal direction is preferably 4 to 100 times, more preferably 8 times to 90 times, still more preferably 10 times to 80 times. Longitudinal stretching temperature is preferably 100 ° C. ~ 300 ° C., more preferably from 200 ° C. ~ 290 ° C., particularly preferably from 250 ℃ ~ 280 ℃.
Stretch ratio in the width direction is preferably 10 to 100 times, more preferably 12 times to 90 times, more preferably 15 times to 70 times, particularly preferably 20 to 40 times. The temperature for widthwise stretching is preferably 100 ° C. ~ 300 ° C., more preferably from 200 ° C. ~ 290 ° C., particularly preferably from 250 ℃ ~ 280 ℃.
Areal draw ratio is preferably from 50 times to 300 times, more preferably 75 times to 280 times, still more preferably 100 times to 260 times.
Upon stretching, it may have been pre-heating the film in advance stretching temperature or lower.

Incidentally, after the stretching, heat can be fixed if needed. The temperature of the thermal fixing, usually, it is preferably carried out below the melting point of the crystalline polymer sintered body above the stretching temperature.

<Hydrophilic treatment process>
The hydrophilization treatment step, the exposed surface of the film, imparting a composition comprising at least a radically polymerizable monomer, a step of polymerizing the radical polymerizable monomer.

As the application method of a composition comprising at least a radically polymerizable monomer in the hydrophilic treatment step is not particularly limited and may be appropriately selected depending on the purpose, for example, a method of immersing the film, the composition , the film, and a method of applying said composition.

Then, by applying the composition (immersion or coating) film with ultraviolet irradiation treatment or heat treatment after (annealing), to polymerize the radical-polymerizable monomer contained in said composition.
Composition wherein comprising at least a radically polymerizable monomer, if they contain a photoradical polymerization initiator, the ultraviolet irradiation treatment, the radical polymerizable monomer by radical polymerization, the polymer is coated on the exposed surface of the film .
The light conditions of the ultraviolet irradiation treatment is preferably 1.0 × 10 2 mJ / cm 2 ~ 1.0 × 10 5 mJ / cm 2, 5.0 × 10 2 mJ / cm 2 ~ 5.0 × 10 4 mJ / cm 2 is more preferable.

It said composition containing at least a radical polymerizable monomer, if they contain a thermal radical polymerization initiator, by heat treatment, the radical polymerizable monomer by radical polymerization, the polymer to the exposed surface of the film is coated.
The temperature in the heating treatment is preferably 50 ° C. ~ 200 ° C., more preferably from 60 ° C. ~ 180 ° C., particularly preferably from 70 ℃ ~ 160 ℃.
Wherein as the time in the heat treatment is preferably 1 minute to 120 minutes, more preferably from 1 minute to 100 minutes, particularly preferably 1 minute to 80 minutes.
When the annealing temperature is to the time less than 50 ° C. treatment is less than 1 minute, no hydrophilic treatment promotes a polymerization reaction does not proceed, there is the water resistance, and hydrophilicity is lost, the annealing treatment When the temperature is 200 ° C. greater than or time exceeds between 80 minutes and may radically polymerizable monomer is decomposed.

- addition reaction process -
The addition reaction step, at least a portion of the radical polymer is a step of addition reaction of functional compounds containing at least one ion-exchange group and a chelating group.

In the addition reaction step, as a method of addition reaction of functional compounds in at least part of the radical polymer is not particularly limited and may be appropriately selected depending on the purpose, for example, (i) a film ( the porous membrane) is impregnated with a mixed solution containing at least a radical polymerizable monomer and functional compounds, and heat treatment (thermal annealing), the reaction for coating by polymerizing a radical polymerizable monomer and (hydrophilic treatment), the method of causing at the same time an addition reaction with at least a portion functional compound radical polymer, impregnated with a mixed solution containing (ii) a film (porous film) at least a radical polymerizable monomer and functional compounds, ultraviolet irradiation treatment to, by coating by polymerizing a radical polymerizable monomer, followed by heat treatment (thermal annealing), the radical polymerization Method of addition reaction and at least a portion the functional compound (sequential reaction with the addition reaction with the hydrophilic treatment), impregnated into a composition comprising at least a radical polymerizable monomer (iii) a film (porous film) ultraviolet irradiation treatment or heat treatment with (thermal annealing), was coated by polymerizing a radical polymerizable monomer, followed by impregnating the solution containing the functional compound, and heating treatment (thermal annealing), the radical polymer method of addition reaction and at least a portion the functional compound (sequential reaction with the addition reaction with the hydrophilic treatment), and the like.
The light conditions of the ultraviolet irradiation treatment is preferably 1.0 × 10 2 mJ / cm 2 ~ 1.0 × 10 5 mJ / cm 2, 5.0 × 10 2 mJ / cm 2 ~ 5.0 × 10 4 mJ / cm 2 is more preferable.
The temperature in the heating treatment (thermal annealing) is preferably from 50 ° C. ~ 200 ° C., more preferably from 50 ° C. ~ 180 ° C., particularly preferably from 50 ℃ ~ 160 ℃.
Wherein as the time in the heat treatment is preferably 0.5 minutes to 300 minutes, more preferably from 0.75 minutes to 200 minutes, particularly preferably 1 minute to 100 minutes.

Crystalline polymer microporous membrane of the present invention is not particularly limited and may be used in a variety of applications, it can be suitably used as a filtration filter described below.

(Filtration filter)
Filtration filter of the present invention is characterized by having a crystalline polymer microporous membrane of the present invention.
When the crystalline polymer microporous membrane of the present invention as a filtration filter performs filtering the unheated surface (the surface having the larger average pore diameter) as the inlet side. That is, using the large surface side of the pore size in the filter surface of the filter. Thus, by performing a filtering surface having the larger average pore diameter (the unheated surface) as the inlet side, it is possible to efficiently trap fine particles.
Further, the crystalline polymer microporous membrane of the present invention, because a large specific surface area are removed by adsorption or adhesion before the fine particles introduced from the surface to reach pores of minimum diameters. Accordingly, clogging hardly occurs and it is possible to maintain high filtration efficiency for a long period of time.

The filtration filter of the present invention, when a differential pressure of 0.1 kg / cm 2 was filtered, can be capable of at least 5ml / cm 2 · min or more filters.
The shape of the filtration filter of the present invention, the pleated to pleated filtration membrane, spiral of the filtration membrane to glue wound shape, a frame-and-plate type of laminating disc-shaped filtration membrane, the filtration membrane and the like tube of the tubular. Among these, from the viewpoint of capable of increasing the effective surface area used for filtration of per cartridge filters, pleated is particularly preferred.
Furthermore, the classification and the element exchange type filter cartridge to replace only the filter element when replacing the filtration membrane degraded, to a capsule-type filter cartridge of the type of disposable each housing by processing a filter element integral with the filtering housing, the filtration filter of the invention can be suitably used as either.

Here, FIG. 1 is a development view showing a structure of a pleated filter cartridge element of the element replaceable. Microfiltration membrane 103 is corrugated and that Sandwiched between two membrane supports 102 and 104, are wound around a core 105 having multiple liquid-collecting port. The outside has an outer peripheral cover 101 to protect the microfiltration membrane. End plate 106a at both ends of the cylinder, by 106b, microfiltration membrane is sealed. End plates in contact with the sealing portion of the filter housing (not shown) via a gasket 107. Filtered liquid is collected from the liquid collecting ports of the core, it is discharged from the fluid outlet 108.

The capsule-type pleated filter cartridges are shown in FIGS.
Figure 2 is a developed view showing the overall structure of a microfiltration membrane filter element before being incorporated in a housing of a capsule-type filter cartridge. Microfiltration membrane 2 is corrugated and sandwiched by two support 1,3, and wound around a filter element core 7 having multiple liquid-collecting port. Its outside has a filter element cover 6, so as to protect the microfiltration membrane. At both ends of the cylindrical upper end plate 4 and a lower end plate 5, and microfiltration membrane is sealed.
Figure 3 shows the structure of a pleated filter cartridge of the capsule type filter element is integrally incorporated in a housing. Filter element 10 is incorporated in a housing consisting of housing base 12 and housing cover 11. Lower end plate 5 is sealed to the water collecting pipe in the housing base 12 center via the O-ring 8 (not shown). Liquid enters the liquid inlet nozzle 13 into the housing, pass through the filter medium 9, collected from liquid collecting ports of a filter element core 7 and discharged from a liquid outlet nozzle 14. The housing base 12 and housing cover 11 are thermally fused in a liquid-tight in a conventional welded portion 17. Air vents 15 in the housing upper part, has a drain 16 in the lower housing.

2 and 3, there is shown an example in which a seal with the lower end plate 5 and the housing base 12 through the O-ring 8, the sealing of the lower end plate 5 and the housing base 12 is thermally fused or bonded also it is performed by the agent. Or sealing the housing base 12 and housing cover 11 to other thermal fusion, a method using an adhesive is also possible. 1 to 3, a specific example of a microfiltration filter cartridges, the present invention is not limited to these figures.

Filtration filter using the crystalline polymer microporous membrane of the present invention is thus high filtration function since it has a feature of a long life, it can be summarized filtration device compact. In conventional filtration devices, which had to deal with shortness of multiple filtration units in parallel use by filtration life, the number of filtration units in parallel using the use of the filtration filter of the present invention greatly it can be reduced. In addition, since it is possible to extend significantly also exchange the period of time for which the filter can cut costs and time necessary for maintenance.

The filtration filter of the present invention, filtration can be used in a variety of contexts that are required, gas, suitably used for microfiltration of liquids such as, for example, electronic industrial cleaning water, pharmaceutical water, pharmaceutical manufacturing process water, filtration of food water or the like, used for sterilization. In particular, filtration filter of the present invention is excellent in ion adsorption capacity, as an ion exchange membrane or an ion adsorption film, for example, it can be effectively used for the production of ultrapure water.

EXAMPLES The following explains Examples of the present invention, the present invention is not intended to be limited to these Examples.

(Example 1)
<Production of Crystalline Polymer Microporous Film (1)>
- Production of semi-baked film -
The number average molecular weight of 6,200,000 polytetrafluoroethylene fine powder (Daikin Industries, Ltd., "POLYFLON fine powder F104U") to 100 parts by weight of a hydrocarbon oil as an extrusion aid (Esso Sekiyu Co., "Isopar" ) 27 parts by mass were added thereto to carry out a paste extruded round bar. This, the calender roll heated to 70 ° C. and calendered at 50 m / min, to produce a polytetrafluoroethylene film. The film extrusion aid was removed by drying through a hot air drying oven at 250 ° C., to produce an average thickness 100 [mu] m, average width 150 mm, an unbaked polytetrafluoroethylene film having a specific gravity of 1.55.
Obtained unbaked polytetrafluoroethylene roll heated one face (heating surface) 345 ° C. of the film (surface material: SUS316) was heated for 1 minute at, to produce a semi-baked film.

Semi-baked film obtained was stretched between rolls to 12.5 times in the longitudinal direction at a 270 ° C., it was wound up once the take-up roll. Then, after pre-heated to 305 ° C. film sandwiched at both ends with clips, and stretched to 30 times in the width direction at 270 ° C.. This was followed by heat-set at 380 ° C.. Areal draw ratio of the resulting crystalline polymer microporous film was 260 times in terms of the elongated areal ratio.

- function of processing -
5 mass% as glycidyl acrylate 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Chemical Co., Ltd.), 5 wt% as a functional compound having a chelating group N-(2-hydroxyethyl) ethylenediamine triacetic acid (Dojindo and Research Laboratory), methanol · MEK mixed solution containing 0.1 wt% Irgacure 907 (manufactured by BASF Japan Ltd.) as a photo-radical polymerization initiator, and immersing the crystalline polymer microporous membrane, pulling the crystalline the polymer microporous membrane, and UV radiation, followed by, 0.99 ° C. in air was carried out annealing for 10 minutes. After that, washing was immersed in methanol for 30 minutes, followed by drying, to prepare a functionalized crystalline polymer microporous membrane (1).

(Example 2)
<Preparation of the crystalline polymer microporous membrane (2)>
The functional process of Example 1, except that instead of the function processing of the following, in the same manner as in Example 1 to prepare a functionalized crystalline polymer microporous membrane (2).

- function of processing -
5 wt% of acrylic acid (manufactured by TCI, Inc.), 0.1 wt% as a photo-radical polymerization initiator Irgacure907 (manufactured by BASF Japan Ltd.), a methanol · MEK mixed solution, immersing the crystalline polymer microporous membrane the crystalline polymer microporous film was pulled, and UV irradiation. Subsequently, after the thionyl chloride treatment was immersed in methanol solution of 5.0 wt% pentaethylenehexamine, the crystalline polymer microporous film was pulled, 0.99 ° C. in air was carried out annealing for 10 minutes. Subsequently, soaked 10 wt% ethylene sulfide to (Tokyo Kasei Kogyo Co., Ltd.) in toluene, the crystalline polymer microporous film was pulled, 100 ° C. in air was carried out annealing for 10 minutes. After that, washing was immersed in methanol for 30 minutes, followed by drying, to prepare a functionalized crystalline polymer microporous membrane (2).
Incidentally, reacting the compound of the pentaethylenehexamine and the ethylene sulfide functions as a functional compound having a chelating group.

(Example 3)
<Preparation of the crystalline polymer microporous membrane (3)>
In Example 1, 5 wt% in methanol · MEK mixed solution of N- (2-hydroxyethyl) ethylenediamine triacetic acid (Co. Dojin Chemical Laboratory), instead of the addition as a functional compound having a chelating group Te, 5 wt% of 3-hydroxy propane sulfonic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.), except that the reactive group is added as a functional compound having an ion exchange group is a hydroxyl group, in the same manner as in example 1 crystalline polymer microporous film (3) was prepared.

(Comparative Example 1)
<Preparation of the crystalline polymer microporous membrane (4)>
In Example 1, but for the functionalization process, in the same manner as in Example 1, an asymmetric membrane of polytetrafluoroethylene comprising the crystalline polymer microporous membrane of Comparative Example 1 Crystalline Polymer membranes (4) was prepared.

(Comparative Example 2)
<Preparation of the crystalline polymer microporous membrane (5)>
In Example 2, instead of using the crystalline polymer microporous membrane, a polytetrafluoroethylene microporous membrane: except for using (Nippon Gore Co. symmetric membranes), in the same manner as in Example 2 Te, to prepare a crystalline polymer microporous membrane of Comparative example 2 (5).

(Comparative Example 3)
<Preparation of the crystalline polymer microporous membrane (6)>
The functional process of Example 1, except that instead of the function processing of the following, in the same manner as in Example 1, to prepare a crystalline polymer microporous membrane of Comparative Example 3 (6). That is, coated with a radical polymer obtained by polymerizing a composition containing a radical polymerizable monomer, instead of addition reaction of functional compounds in at least part of the radical polymer include radical polymers were pre-polymerized (polymer coated with), and addition reaction of functional compounds in at least part of the radical polymer.

- function of processing -
To 5% by weight of 4-hydroxybutyl acrylate MEK solution of the radical polymerization of the glycidyl ether, immersing the crystalline polymer microporous membrane, and dried, followed by 5 wt% N-(2-hydroxyethyl) ethylenediamine triacetic acid was immersed in methanol solution (manufactured Dojin chemical Laboratory), the crystalline polymer microporous film was pulled, 0.99 ° C. in air was carried out annealing for 10 minutes.
Thus, to produce a functionalized crystalline polymer microporous membrane (6).

<Evaluation>
For the crystalline polymer microporous film in Examples 1-3 and Comparative Examples 1 to 3 prepared and evaluated as follows.

<< Measurement of Average pore diameter, and pore shape evaluation >>
Each crystalline polymer microporous film in Examples 1-3 and Comparative Examples 1-3 was cut along the longitudinal direction of the crystalline polymer microporous membrane, in the thickness direction of the crystalline polymer microporous membrane the cut surface, scanning electron microscope (Hitachi S-4000 type, deposition Hitachi E1030 type, both manufactured by Hitachi, Ltd.) photograph of the film surface at (SEM photograph, magnification of 1,000 times to 5,000 times) take, resulting photographic image processing apparatus (body name: Nippon avionics Co., Ltd., TV image processor TVIP-4100II, control software name: RATOC system engineering Co., Ltd., TV image processor image command 4198) crystalline incorporated into to obtain an image consisting only of polymer fibers. The resulting measured 100 pore size for the image, by arithmetic processing to determine the average pore size.

For easy understanding of the hole shape of the cut surface in the thickness direction of the crystalline polymer microporous film it will be described with reference to schematic diagrams.
4A is a diagram schematically showing a cut surface of the crystalline polymer microporous membrane having symmetric pores before functionalization process in Comparative Example 2 (hydrophilic treatment and addition reactions pretreatment).
The average pore diameter in the first surface of the crystalline polymer microporous membrane 40 having symmetric pores of the functionalized pretreatment in FIG 4A (hydrophilic treatment and addition reactions pretreatment) and d 1, the average of the second surface when the pore size was d 2, the ratio of d 1 and d 2 in the observed SEM images (d 1 / d 2) was 1.0.
Figure 4B is a diagram schematically showing a cut surface of the crystalline polymer microporous membrane having symmetric pores after functionalization treatment in Comparative Example 2 (after hydrophilization and addition reaction process).
(After hydrophilization and addition reaction treatment, the covering portion 45) After this functionalization process in Figure 4B an average pore diameter in the first surface of the crystalline polymer microporous membrane 40 having symmetric pores of the d 1 ', the 'when a, d 1 in the observed SEM images' average pore diameter in the second surface d 2' ratio of (d 1 'and d 2 / d 2') was 1.0.
Therefore in Comparative Example 2 (d 1 '/ d 2 ') / (d 1 / d 2) was 1.0. Thus, in the crystalline polymer microporous membrane having symmetric pores of Comparative Example 2 not subjected to asymmetric heating treatment, function processing (hydrophilic treatment and addition reaction treatment) ratio before and after (d 1 / d 2) it was found that no change in the ratio and (d 1 '/ d 2' ).

Next, FIG. 5A is a diagram schematically showing a cut surface of the crystalline polymer microporous asymmetric membrane having functionalized pretreatment in Example 1 (hydrophilized and addition reactions pretreatment).
The average pore diameter in the first surface of the crystalline polymer microporous membrane 50 having asymmetric pores before functionalization process in FIG. 5A (hydrophilic treatment and addition reactions pretreatment) and d 3, the average of the second surface when the pore size was d 4, the ratio of d 3 and d 4 in the observed SEM images (d 3 / d 4) was 15.
5B is a diagram schematically showing a cut surface of the crystalline polymer microporous film having an asymmetric pore after functionalization process in Example 1 (after hydrophilization and addition reaction process).
(After hydrophilization and addition reaction treatment, the covering portion 55) After this functionalization process in Figure 5B the average pore diameter in the first surface of the crystalline polymer microporous membrane 50 having asymmetric pores of the d 3 ', the 'when a, d 3 in the SEM image observed' an average pore diameter in the second surface d 4 'ratio of (d 3' and d 4 / d 4 ') was 15.9.
Thus in Example 1 (d 3 '/ d 4 ') / (d 3 / d 4) was 1.06.

After functionalization process in the first embodiment the ratio of the crystalline polymer microporous membrane of (after hydrophilization and addition reaction treatment) (d 3 '/ d 4 '), functionalized pretreatment in Example 1 (Hydrophilic comparison of the ratio (d 3 / d 4) in the crystalline polymer microporous membrane of the process and the addition reaction pretreatment), the functionalized pretreatment (hydrophilic treatment and addition reactions pretreatment), the first surface and average pore diameter in the (non-heated surface), it has been found that it is possible to increase the ratio between the average pore diameter in the second surface (heated surface).
This result is contrary to expectations of the prior SEM image observation, in addition to average pore size average pore diameter of the crystalline polymer microporous membrane 50 toward the second surface from the first surface changes continuously, crystalline the thickness of the covering portion 55 after the functionalization process using sex polymer, is based on the thickness from the first surface toward the second surface continuously changes in the direction of increasing. This causes the covering portion 55, toward the second surface dense portion (heating surface) of the crystalline polymer microporous membrane, thicker deposition over coarse filtration portion of the first surface (unheated surface) is to be able, degree to which the mean particle diameter from the first surface toward the second surface changes continuously is large, presumably because that can form a significant asymmetric structure.
Ratio from these results, in the crystalline polymer microporous membrane of Example 1 (1), in addition to excellent hydrophilicity, and an average pore diameter of the first surface, and the average pore diameter of the second surface it is possible to take a large revealed that filtration life until clogging (filtration flow rate) can be greatly improved.

Similarly, in Example 2, the asymmetric membrane having d 3 / d 4 = 15, after function processing (hydrophilic treatment and after the addition reaction treatment), d 3 '/ d 4 ' = 15. next 6 was (d 3 '/ d 4' ) / (d 3 / d 4) = 1.04.
Likewise, in Example 3, the asymmetric membrane having d 3 / d 4 = 15, after function processing (hydrophilic treatment and after the addition reaction treatment), d 3 '/ d 4 ' = 15. next 9 were (d 3 '/ d 4' ) / (d 3 / d 4) = 1.06.
Similarly, in Comparative Example 1, the asymmetric membrane having d 3 / d 4 = 15, since not subjected to function processing (hydrophilic treatment), there was no hole diameter changes.
Similarly, in Comparative Example 3, the asymmetric membrane having d 3 / d 4 = 15, after function processing (after hydrophilization and addition reaction treatment), d 3 '/ d 4 ' = 15. 3 next, it was (d 3 '/ d 4' ) / (d 3 / d 4) = 1.02.

<< hydrophilic evaluation >>
Next, the crystalline polymer microporous membranes of Examples 1 to 3 and Comparative Examples 1 to 3 prepared and evaluated hydrophilicity.
Hydrophilic the crystalline polymer microporous film was evaluated by the Japanese Patent No. 3075421 as a reference. Specifically, it was evaluated in the following manner.
The initial hydrophilicity, dropped from at a height 5cm water drops on the sample surface, whether water droplets are absorbed and evaluated by the following criteria. The results are shown in Table 1.
〔Evaluation criteria〕
A: immediately absorbed B: C was naturally absorbed: pressurizing only absorbed or not absorbed but contact angle decreased D: not absorbed. In other words, springing the water. The D evaluation is unique to a porous fluororesin material

<< filtration test >>
For the crystalline polymer microporous membranes of Examples 1 to 3 and Comparative Examples 1 to 3 were filtered test. First, an aqueous solution of polystyrene latex (average particle size 1.5 [mu] m) containing 0.01 wt%, a differential pressure of 10 kPa, filtered, indicating the permeation amount of up clogged eyes in Table 1.

<< flow rate test >>
For the crystalline polymer microporous membranes of Examples 1 to 3 and Comparative Examples 1 to 3 were flow test as follows.
Flow rate measurements were carried out under the following conditions in accordance with JIS K3831. Type of test method using "pressure filtration test method", the sample is cut into a circle having a diameter of 13 mm, the measurement was carried out was set in a stainless steel holder. The test solution using ion exchange water, measure the time required to filter test liquid 100mL at a pressure 10 kPa, was calculated flow rate (L / min · m 2) . The results are shown in Table 1.

Figure JPOXMLDOC01-appb-T000002

From the results of Table 1, Examples 1 to 3 and Comparative Examples 2 and 3, there is hydrophilic, Comparative Example 1, it can be seen that there is no hydrophilic.
In the filtration tests, the crystalline polymer microporous membrane of Comparative Example 1 has no hydrophilicity, could not be measured. Further, Comparative Examples 2 and 3 did not exceed 100 mL / cm 2.
In contrast, the crystalline polymer microporous membranes of Examples 1-3, pre-hydrophilization treatment by isopropanol which has been conventionally required is unnecessary, and is capable of filtration until 100 mL / cm 2 or more, the the crystalline polymer microporous membrane of the invention it has been found that filtration life can be improved by using.
Also in the flow test, the crystalline polymer microporous membrane of Comparative Example 1 has no hydrophilicity is not measurable Comparative Example 2-3 did not exceed 100L / min · m 2. In contrast, the crystalline polymer microporous membranes of Examples 1 to 3, in 100L / min · m 2 or more, by using the crystalline polymer microporous membrane of the present invention, greatly improved flow it has been found.
The reason why the filtration life and flow is improved, and improved bubble permeability, clogging caused by the foams is believed to be due to a decrease.

<< water resistance of the evaluation >>
To the crystalline polymer microporous film in Examples 1-3 and Comparative Examples 1-3 was repeated 5 times a process of passing water 200mL under pressure conditions of 100 kPa. Drying was carried out for every single pass through.
Water resistance evaluation, for each crystalline polymer microporous membrane of Example 1 to 3 and Comparative Examples 1 to 3 through the above process, evaluation based on the criteria (A ~ D) determined in the evaluation of the hydrophilic It was carried out by. The results are shown in Table 2.

Figure JPOXMLDOC01-appb-T000003
In Table 2, "unmeasurable" because poor hydrophilicity, indicating that could not be evaluated.

Evaluation of << ion adsorption performance >>
Evaluation of the ion adsorption performance, for the crystalline polymer microporous membranes of Examples 1 to 3 and Comparative Examples 1 to 3 were the Hei 2-187136 discloses as a reference. Specifically, 10 ppm each of metal ions (silver, sodium) of the aqueous solution containing was 1L prepared, in the crystalline polymer microporous membrane of Example 1 to 3 and Comparative Examples 1 to 3, is transmitted through the aqueous solution 10mL , it was carried out by measuring the metal ion concentration in the aqueous solution after permeation. The results are shown in Table 3.

Figure JPOXMLDOC01-appb-T000004
In Table 3, "unmeasurable" because poor hydrophilicity, indicating that could not be evaluated.

(Example 4)
- filter cartridge -
Between two polypropylene nonwoven, across the crystalline polymer microporous membrane prepared in Example 1 was pleated to Hidahaba 10.5 mm, rounded into a cylindrical shape by taking the 138-peak amount of folds, combined the eye was welding an impulse sealer. Cut off by two ends 2mm cylindrical, finished with element replaceable filter cartridge by thermal welding the cut surface in a polypropylene of the end plates.
Filter cartridge of the present invention produced, since the crystalline polymer microporous membrane to be built is hydrophilic, it is unnecessary complicated pre-hydrophilization treatment in the process of water. Also, excellent solvent resistance due to the use of crystalline polymers. Further, since the hole has an asymmetric structure, it was long-lived, it causes less large flow Katsume clogging.

Filtration filter using the crystalline polymer microporous membrane and its invention is excellent in heat resistance and chemical resistance, can be used in a variety of situations where filtration is required, a gas, suitably used for microfiltration of liquids such as, for example, electronic industrial cleaning water, pharmaceutical water, pharmaceutical manufacturing process water, filtration of food such as aqueous, sterile, can be widely used in such high-temperature filtration.

1 primary support 2 microfiltration membrane 3 secondary side support 4 top end plate 5 the lower end plate 6 filter element cover 7 filter element core 8 O-ring 9 filter media 10 filter element 11 a housing cover 12 housing base 13 liquid inlet nozzle 14 solution outlet nozzle 15 air vent 16 drain 17 welded portion 101 outer circumferential cover 102 film support 103 microfiltration membranes 104 membrane support 105 core 106a, 106b end plate 107 gasket 108 liquid outlet

Claims (11)

  1. A crystalline polymer microporous membrane having an asymmetric pore structure,
    At least a portion of the exposed surface of the crystalline polymer microporous film is coated with a radical polymer obtained by polymerizing a composition containing a radical polymerizable monomer, at least in part on, the ion-exchange groups of the radical polymer and functional compounds is an addition reaction including at least one chelating group, wherein the radical polymerizable monomer is an acrylate, methacrylate, acrylamide, is at least one selected from acrylic acid and derivatives thereof crystalline polymer microporous membrane to be.
  2. Radically polymerizable monomer, a carboxyl group, an amino group, a hydroxyl group, an epoxy group, an acrylamide group, isocyanate group, and the crystalline polymer microporous membrane according to claim 1 comprising at least one of acid chloride groups.
  3. Functional compound, crystalline polymer microporous membrane according to any one of claims 1 2, which is a compound having a reactive group with the radical polymer.
  4. The average pore diameter of the first surface is greater than the average pore diameter in the second plane, and wherein having a plurality of holes having an average pore diameter continuously changes toward from said first surface to said second surface crystalline polymer microporous membrane according to any one of claim 1 3.
  5. The ratio between the average pore diameter d 3 at the first surface of the crystalline polymer microporous film before coating the radical polymerizable monomer polymer on the exposed surface, the average pore diameter d 4 of the second surface (d 3 / d 4 )When,
    The average pore diameter in the first surface of the crystalline polymer microporous film after coating a fluorine-based surfactant to the exposed surface 'and the average pore diameter d 4 of the second surface' d 3 ratio of (d 3 ' / d 4 ') and although the following formula, (d 3' / d 4 ') / (d 3 / d 4)> 1, the crystalline polymer microporous according to any one of claims 1 to 4 satisfying film.
  6. Crystalline polymer, crystalline polymer microporous membrane according to claims 1, which is a polytetrafluoroethylene either 5.
  7. The exposed surface of the crystalline polymer microporous membrane having an asymmetric pore structure, the hydrophilizing step of imparting a composition comprising a radical polymerizable monomer, thereby polymerizing the radical polymerizable monomer,
    Wherein a part of the radical polymer, and a addition reaction treatment step of addition reaction of functional compounds containing at least one ion-exchange group and a chelating group,
    The radical polymerizable monomer is an acrylate, methacrylate, acrylamide, method for producing a crystalline polymer microporous membrane, characterized in that at least one selected from acrylic acid and derivatives thereof.
  8. Heating the one producing a crystalline polymer microporous film, the asymmetric heating step of forming a semi-baked film with a temperature gradient in the thickness direction of the film,
    Method for producing a crystalline polymer microporous membrane according to claim 7 in which the stretching step, further comprising a forming a crystalline polymer microporous membrane having an asymmetric pore structure by stretching the semi-baked film.
  9. Radically polymerizable monomer, a carboxyl group, an amino group, a hydroxyl group, an epoxy group, an acrylamide group, crystalline polymer microporous according to any one of the isocyanate groups, and from the claims 7 comprises at least one of acid chloride groups 8 method of manufacturing a sex film.
  10. Functional compound, method for producing a crystalline polymer microporous membrane according to any one of claims 7 to 9 which is a compound having a reactive group with the radical polymer.
  11. Filtration filter characterized by having a crystalline polymer microporous membrane according to any one of claims 1 to 6.
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