WO2017038898A1 - 多孔質膜及びその製造方法 - Google Patents
多孔質膜及びその製造方法 Download PDFInfo
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- WO2017038898A1 WO2017038898A1 PCT/JP2016/075571 JP2016075571W WO2017038898A1 WO 2017038898 A1 WO2017038898 A1 WO 2017038898A1 JP 2016075571 W JP2016075571 W JP 2016075571W WO 2017038898 A1 WO2017038898 A1 WO 2017038898A1
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- film
- porous membrane
- varnish
- polyimide
- fine particles
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/06—Polysulfones; Polyethersulfones
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a porous membrane and a method for producing the same.
- porous membranes have been used for applications such as filters.
- the porous membrane has also been applied to separator applications for secondary batteries such as lithium batteries.
- a varnish in which silica particles are dispersed in a solution of polyamic acid or polyimide is applied onto a substrate, and then the polyimide containing silica particles by heating the coating film as necessary.
- a method is known in which a membrane is obtained, and then silica in the polyimide membrane is eluted and removed with hydrogen fluoride water to make it porous (see Patent Document 1).
- a porous film having a smooth surface is required.
- battery performance is improved by making the separator and the electrode adhere well. If the surface of the porous membrane used as the separator is smooth, the separator and the electrode are in good contact.
- a filter that is a gas or liquid separation membrane it is desired that the porous membrane and the support that supports the porous membrane have good adhesion. If the porous membrane and the support are in good contact with each other, the separation performance and handleability of the filter are improved. If the surface of the porous membrane is smooth, the permeability (liquid permeability) of the porous membrane is improved and the handling is good.
- the present invention has been made in view of the above circumstances, and an object thereof is to provide a porous film having excellent surface smoothness and a method for producing the same.
- the inventors of the present invention have intensively studied to solve the above problems. As a result, it was found that a porous film excellent in surface smoothness can be obtained by adjusting conditions such as kneading time for the production conditions of the varnish used when producing the porous film, and the present invention It came to be completed.
- the first aspect of the present invention is a porous film of polyvinylidene fluoride, polyethersulfone, polyimide and / or polyamideimide, and has a surface roughness Ra of 30,000 mm or less.
- a second aspect of the present invention is a porous membrane of polyvinylidene fluoride, polyethersulfone, polyimide and / or polyamideimide, Including a structure in which spherical holes communicate with each other; There is no undulation deeper than the dent formed by the opening on the surface, A porous membrane having an opening with a diameter of 100 nm to 5000 nm.
- a third aspect of the present invention is an unfired composite film comprising fine particles and at least one resin selected from the group consisting of polyvinylidene fluoride, polyethersulfone, polyamic acid, polyimide, polyamideimide precursor, and polyamideimide
- a varnish containing fine particles and at least one resin selected from the group consisting of polyvinylidene fluoride, polyethersulfone, polyamic acid, polyimide, polyamideimide precursor, and polyamideimide is kneaded.
- the varnish has a viscosity at 25 ° C. of 0.1 to 3 Pa ⁇ s, a solid content concentration of 10 to 50% by mass, and an average particle size of fine particles of 10 to 5000 nm.
- the kneading is a method for producing a porous membrane, which is carried out for 2 minutes to 10 hours.
- a porous film having excellent surface smoothness and a method for producing the same can be provided.
- FIG. 2 is an electron microscopic image of the porous film obtained in Example 1.
- FIG. 4 is a diagram showing an electron microscopic image of a porous film obtained in Comparative Example 1.
- the porous membrane is made of polyvinylidene fluoride, polyethersulfone, polyimide and / or polyamideimide.
- the surface roughness Ra of the porous membrane is 30,000 mm or less, preferably 10,000 mm or less, more preferably 5000 mm or less, and further preferably 3500 mm or less. For this reason, the porous membrane is excellent in smoothness.
- the surface roughness Ra of the porous film is more than 30,000 mm
- convection occurs in the unfired composite film containing the fine particles and the resin, thereby increasing the surface roughness value of the unfired composite film.
- uneven distribution of fine particles tends to occur in the unfired composite film.
- the fine particles are dense in the thin valley portions, while the fine particles are sparse in the thick mountain portions, or the fine particles are sparse in the mountain portions.
- the fine particles are dense in the part.
- the porous film adheres well to the electrode when the porous film is used as a battery separator. Furthermore, when the surface roughness Ra is within the above range, the permeability of the porous membrane is improved when the porous membrane is used as a filter.
- the porous membrane which is a filter, is in close contact with the support, peeling of the filter from the support during filtering is suppressed, and along with this, breakage such as breakage of the filter is suppressed, and handling is also good.
- the surface roughness Ra is a value measured according to the following conditions using a stylus type surface roughness meter.
- a stylus type surface roughness meter Dektak150 manufactured by Asbach Corporation can be used.
- Stylus radius 12.5 ⁇ m
- Measuring distance 10000 ⁇ m
- Measurement time 120 seconds
- Horizontal resolution 0.278 ⁇ m / sample
- Stylus pressure 5.00mg
- the porous film includes a structure in which spherical holes communicate with each other (hereinafter referred to simply as “communication holes”).
- This porous film is manufactured by being formed on a substrate as will be described later.
- the surface of the porous membrane is the surface opposite to the surface facing the substrate at the time of manufacture.
- the opening in the porous membrane is a portion where the communication hole opens on the surface of the porous membrane.
- the porous membrane preferably has no waviness on its surface.
- the waviness refers to “a recess deeper than the recess formed by the opening” on the surface where the surface roughness is measured.
- the recess formed by the opening corresponds to a spherical hole formed on the surface of the film when the porous film is manufactured, and a recess deeper than the depth of the spherical hole from the film surface corresponds to the undulation.
- the spherical shape related to the shape of the hole is a concept including a true spherical shape, but is not necessarily limited to a true spherical shape.
- the spherical shape may be a substantially spherical shape, and a shape that can be recognized as a substantially spherical shape when an enlarged image of the hole is visually confirmed is also included in the spherical shape.
- the surface that defines the hole portion is a curved surface, and it is only necessary that the spherical surface defines a spherical hole or a substantially spherical hole.
- the individual spherical holes are typically holes formed by removing individual fine particles present in the resin-fine particle composite film described later in a later step.
- the communication hole is formed by removing a plurality of fine particles present in contact with each other in the resin-fine particle composite film in a later step in the porous film production method described later.
- the part where the spherical hole communicates in the communication hole is derived from the place where the plurality of fine particles before being removed contact each other.
- the diameter of the opening of the porous membrane may be changed as appropriate according to the intended use of the porous membrane, for example, in the range of 100 nm to 5000 nm. In the case of a separator, 100 to 2000 nm is preferable, 200 to 1000 nm is more preferable, and 300 to 900 nm is more preferable.
- the diameter of the opening is the same as or approximately the same as the diameter of the spherical hole constituting the communication hole.
- the communication holes formed by connecting the spherical holes having such diameters allow the fluid to pass through well in the porous membrane.
- the porous membrane has a communication hole penetrating the porous membrane in the thickness direction as a fluid flow path.
- the fluid can permeate from one main surface of the porous membrane to the other main surface.
- the fluid passes through the inside of a porous membrane, contacting the curved surface which defines each spherical hole.
- the contact area of the fluid inside the porous membrane is considerably wide due to the provision of communication holes made up of spherical holes. For this reason, when a fluid is passed through a laminate including a porous membrane, it is considered that minute substances existing in the fluid are easily adsorbed to the spherical holes in the porous membrane.
- Varnish for porous membrane production
- a varnish for producing a porous film (hereinafter, simply referred to as “varnish”) containing predetermined fine particles, a resin, and a solvent, respectively, in which the resin is dissolved in the solvent. ) Is used. Varnish is typically.
- the varnish preferably has a viscosity at 25 ° C. of 0.1 to 3 Pa ⁇ s or more, a solid content concentration of 10 to 50% by mass, and an average particle size of fine particles of 10 to 5000 nm.
- the varnish is preferably produced by kneading for 2 minutes to 10 hours, more preferably 2 to 60 minutes.
- the varnish viscosity is measured with an E-type viscometer.
- a rotation / revolution mixer (trade name: Awatori Rentaro, manufactured by Shinky Co., Ltd.), a planetary mixer, a bead mill, or the like can be used.
- the viscosity and solid content concentration of the production varnish for porous membrane are adjusted to the above ranges, it is easy to form a porous membrane having the desired smoothness.
- the varnish is kneaded for an appropriate time, a smooth porous film can be easily formed using the varnish.
- the kneading time is 2 minutes or longer, the desired smoothness with a surface roughness Ra of 30,000 mm or less is easily achieved for the porous film formed using varnish. From the viewpoint of throughput, the varnish kneading time preferably does not exceed 10 hours.
- an opening having a desired size can be formed on the surface of the porous film, and a desired large-sized spherical hole is formed inside the porous film.
- a continuous communication hole can be formed.
- the varnish includes at least one resin selected from the group consisting of polyvinylidene fluoride, polyethersulfone, polyamic acid, polyimide, polyamideimide precursor, and polyamideimide.
- resins will be described.
- the polyvinylidene fluoride is not particularly limited as long as it is soluble in the solvent used for varnish formation.
- the polyvinylidene fluoride may be a homopolymer or a copolymer (copolymer).
- Examples of the structural unit to be copolymerized include ethylene, trifluorochloroethylene, tetrafluoroethylene, and hexafluoropropylene, and the mass average molecular weight is, for example, about 10,000 to 5,000,000.
- the polyether sulfone is not particularly limited as long as it is soluble in the solvent used for varnish formation.
- the polyethersulfone can be appropriately selected according to the use of the porous membrane to be produced, and may be hydrophilic or hydrophobic. Further, it may be an aliphatic polyether sulfone or an aromatic polyether sulfone.
- the weight average molecular weight is, for example, 5000 to 1,000,000, preferably 10,000 to 300,000.
- polyamic acid a product obtained by polymerizing any tetracarboxylic dianhydride and diamine can be used without any particular limitation.
- the amount of tetracarboxylic dianhydride and diamine used is not particularly limited, but 0.50 to 1.50 mol of diamine is preferably used relative to 1 mol of tetracarboxylic dianhydride, and 0.60 to 1. It is more preferable to use 30 mol, and it is particularly preferable to use 0.70 to 1.20 mol.
- the tetracarboxylic dianhydride can be appropriately selected from tetracarboxylic dianhydrides conventionally used as raw materials for polyamic acid synthesis.
- the tetracarboxylic dianhydride may be an aromatic tetracarboxylic dianhydride or an aliphatic tetracarboxylic dianhydride. From the viewpoint of the heat resistance of the resulting polyimide resin, the aromatic tetracarboxylic dianhydride may be used. Preference is given to using carboxylic dianhydrides.
- a tetracarboxylic dianhydride may be used individually by 1 type, and may be used in combination of 2 or more type.
- aromatic tetracarboxylic dianhydride examples include pyromellitic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxy Phenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′- Biphenyltetracarboxylic dianhydride, 2,2,6,6-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2 , 3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-
- aliphatic tetracarboxylic dianhydride examples include, for example, ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, 1, 2, Examples include 4,5-cyclohexanetetracarboxylic dianhydride and 1,2,3,4-cyclohexanetetracarboxylic dianhydride. Among these, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are preferable from the viewpoints of price and availability. Moreover, these tetracarboxylic dianhydrides can also be used individually by 1 type or in mixture of 2 or more types.
- the diamine can be appropriately selected from diamines conventionally used as a raw material for synthesizing polyamic acid.
- the diamine may be an aromatic diamine or an aliphatic diamine, but an aromatic diamine is preferred from the viewpoint of the heat resistance of the resulting polyimide resin. These diamines may be used alone or in combination of two or more.
- aromatic diamines include diamino compounds in which one or about 2 to 10 phenyl groups are bonded. Specifically, phenylenediamine and derivatives thereof, diaminobiphenyl compounds and derivatives thereof, diaminodiphenyl compounds and derivatives thereof, diaminotriphenyl compounds and derivatives thereof, diaminonaphthalene and derivatives thereof, aminophenylaminoindane and derivatives thereof, diaminotetraphenyl Compounds and derivatives thereof, diaminohexaphenyl compounds and derivatives thereof, and cardo-type fluorenediamine derivatives.
- Phenylenediamine is m-phenylenediamine, p-phenylenediamine, etc., and phenylenediamine derivatives include diamines to which alkyl groups such as methyl group and ethyl group are bonded, such as 2,4-diaminotoluene, 2,4-triphenylene. Diamines and the like.
- diaminobiphenyl compound two aminophenyl groups are bonded to each other.
- diaminobiphenyl compound two aminophenyl groups are bonded to each other.
- a diaminodiphenyl compound is a compound in which two aminophenyl groups are bonded to each other via other groups.
- the bond is an ether bond, a sulfonyl bond, a thioether bond, a bond by alkylene or a derivative group thereof, an imino bond, an azo bond, a phosphine oxide bond, an amide bond, a ureylene bond, or the like.
- the number of carbon atoms of the alkylene bond is about 1 to 6.
- the derivative group of an alkylene group is an alkylene group substituted with one or more halogen atoms and the like.
- diaminodiphenyl compounds include 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone 3,4′-diaminodiphenyl ketone, 2,2-bis (p-aminophenyl) propane, 2,2′-bis (p-aminophenyl) hexafluor
- p-phenylenediamine p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, and 4,4'-diaminodiphenyl ether are preferable from the viewpoint of price and availability.
- a diaminotriphenyl compound is a compound in which two aminophenyl groups and one phenylene group are bonded via another group. As other groups, the same groups as in the diaminodiphenyl compound are selected. Examples of diaminotriphenyl compounds include 1,3-bis (m-aminophenoxy) benzene, 1,3-bis (p-aminophenoxy) benzene, 1,4-bis (p-aminophenoxy) benzene, and the like. be able to.
- diaminonaphthalene examples include 1,5-diaminonaphthalene and 2,6-diaminonaphthalene.
- aminophenylaminoindane examples include 5 or 6-amino-1- (p-aminophenyl) -1,3,3-trimethylindane.
- diaminotetraphenyl compounds examples include 4,4′-bis (p-aminophenoxy) biphenyl, 2,2′-bis [p- (p′-aminophenoxy) phenyl] propane, 2,2′-bis [ and p- (p′-aminophenoxy) biphenyl] propane, 2,2′-bis [p- (m-aminophenoxy) phenyl] benzophenone, and the like.
- cardo-type fluorenediamine derivatives include 9,9-bisaniline fluorene.
- the number of carbon atoms in the aliphatic diamine is preferably about 2 to 15, for example.
- Specific examples of the aliphatic diamine include pentamethylene diamine, hexamethylene diamine, and heptamethylene diamine.
- a compound in which the hydrogen atom of these diamines is substituted with at least one substituent selected from the group such as a halogen atom, a methyl group, a methoxy group, a cyano group, and a phenyl group may be used.
- the means for producing the polyamic acid is not particularly limited, and for example, a known method such as a method of reacting an acid and a diamine component in a solvent can be used.
- the reaction between tetracarboxylic dianhydride and diamine is usually carried out in a solvent.
- the solvent used for the reaction of tetracarboxylic dianhydride and diamine is particularly limited as long as it can dissolve tetracarboxylic dianhydride and diamine and does not react with tetracarboxylic dianhydride and diamine. Not.
- a solvent may be used individually by 1 type and may be used in combination of 2 or more type.
- Examples of the solvent used for the reaction of tetracarboxylic dianhydride and diamine include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, Nitrogen-containing polar solvents such as N-diethylformamide, N-methylcaprolactam, N, N, N ′, N′-tetramethylurea; ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, Lactone polar solvents such as ⁇ -caprolactone and ⁇ -caprolactone; dimethyl sulfoxide; acetonitrile; fatty acid esters such as ethyl lactate and butyl lactate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, tetrahydrofuran, methyl cellosolve acetate
- N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethyl are considered because of the solubility of the resulting polyamic acid.
- Nitrogen-containing polar solvents such as formamide, N-methylcaprolactam, N, N, N ′, N′-tetramethylurea are preferred.
- the polymerization temperature is generally ⁇ 10 to 120 ° C., preferably 5 to 30 ° C.
- the polymerization time varies depending on the raw material composition used, but is usually 3 to 24 Hr (hour).
- a polyamic acid may be used individually by 1 type, and may be used in combination of 2 or more type.
- Polyimide The structure and molecular weight of the polyimide are not limited, and known ones can be used. About a polyimide, you may have a functional group which accelerates
- ethylenediamine hexamethylenediamine, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane
- 4 Aliphatic diamines such as 2,4'-diaminodicyclohexylmethane; 2-methyl-1,4-phenylenediamine, o-tolidine, m-tolidine, 3,3'-dimethoxybenzidine, 4,4'-diaminobenzanilide, etc.
- Aromatic diamines such as polyoxyethylene diamine, polyoxypropylene diamine and polyoxybutylene diamine; polysiloxane diamines; 2,3,3 ′, 4′-oxydiphthalic anhydride, 3,4,3 ′, 4'-oxydiphthalic anhydride, 2,2-bis (4-hydroxypheny E) Use of propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride is effective.
- a monomer having a functional group that improves solubility in a solvent such as 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2-trifluoromethyl-1,4- It is also effective to use a fluorinated diamine such as phenylenediamine.
- the same monomer as the monomer described in the column of the polyamic acid can be used in combination as long as the solubility is not inhibited.
- Each of the polyimide and its monomer may be used alone or in combination of two or more.
- a polyimide there is no restriction
- known methods such as a method of chemically imidizing or heat imidizing polyamic acid can be used.
- polyimide include aliphatic polyimide (total aliphatic polyimide), aromatic polyimide and the like, and aromatic polyimide is preferable.
- aromatic polyimide include those obtained by subjecting a polyamic acid having a repeating unit represented by the formula (1) to a ring-closing reaction by heat or chemical means, or a polyimide having a repeating unit represented by the formula (2). It is done.
- Ar represents an aryl group.
- Polyamideimide and polyamideimide precursor Polyamideimide is not limited to its structure and molecular weight, and known ones can be used.
- the polyamideimide may have a functional group capable of condensing such as a carboxy group in the side chain or a functional group that promotes a crosslinking reaction or the like during firing.
- a varnish contains a solvent
- dissolved in the solvent to be used is preferable.
- Polyamideimide is usually (i) a resin obtained by reacting an acid having a carboxyl group and an acid anhydride group in one molecule such as trimellitic anhydride and diisocyanate, (ii) trimellitic anhydride chloride, etc.
- a resin obtained by imidizing a precursor polymer (polyamideimide precursor) obtained by reacting a reactive derivative of the above acid with a diamine can be used without any particular limitation.
- trimellitic anhydride halides such as trimellitic anhydride and trimellitic anhydride chloride, trimellitic anhydride ester, and the like.
- diamines exemplified in the above description of polyamic acid can be mentioned.
- a diaminopyridine compound can also be used.
- the arbitrary diisocyanate is not particularly limited, and examples thereof include diisocyanate compounds corresponding to the arbitrary diamines, and specific examples thereof include metaphenylene diisocyanate, p-phenylene diisocyanate, o-tolidine diisocyanate, and p-phenylene.
- raw material monomers for polyamideimide in addition to the above, compounds described in general formulas in JP-A-63-283705 and JP-A-2-198619 can also be used.
- imidation in the method (ii) may be either thermal imidization or chemical imidization.
- chemical imidization a method of immersing an unfired composite film formed using a varnish containing a polyamideimide precursor or the like in acetic anhydride or a mixed solvent of acetic anhydride and isoquinoline can be used.
- the polyamideimide precursor can also be said to be a polyimide precursor in terms of a precursor before imidization.
- the polyamideimide to be contained in the varnish (1) a polymer obtained by reacting an acid such as trimellitic anhydride with diisocyanate, and (2) a reactive derivative of the above acid such as trimellitic anhydride and diamine. It may be a polymer obtained by imidizing a precursor polymer obtained by the reaction.
- the “polyamideimide precursor” means a polymer (precursor polymer) before imidization.
- Each of the polyamideimide and the polyamideimide precursor may be used alone or in combination of two or more.
- each of the said polymer, raw material monomer, and oligomer may be used individually by 1 type, and may be used in combination of 2 or more type.
- the material of the fine particles is not particularly limited as long as it is insoluble in the solvent contained in the varnish and can be removed from the resin-fine particle composite film later.
- inorganic materials include metal oxides such as silica (silicon dioxide), titanium oxide, and alumina (Al 2 O 3 ), and organic materials include high molecular weight olefins (polypropylene, polyethylene, etc.), polystyrene, epoxy resins, and cellulose.
- Organic polymer fine particles such as polyvinyl alcohol, polyvinyl butyral, polyester, and polyether.
- the fine particles include colloidal silica.
- colloidal silica when monodispersed spherical silica particles are selected, it is preferable because uniform pores can be formed.
- the fine particles preferably have a high sphericity and a small particle size distribution index.
- the fine particles having these conditions are excellent in dispersibility in the varnish and can be used in a state where they do not aggregate with each other.
- the average particle size of the fine particles used is preferably 100 to 5000 nm, for example. By satisfying these conditions, the pore diameters of the porous film obtained by removing the fine particles can be made uniform. In the case of a separator, it is preferable to use fine particles having an average particle diameter of 100 to 2000 nm because the electric field applied to the resulting porous film can be made uniform.
- the fine particles may be used alone or in combination of two or more.
- the solvent is not particularly limited as long as it can dissolve a resin made of polyvinylidene fluoride, polyethersulfone, polyamic acid and / or polyimide, and does not dissolve fine particles.
- a solvent the solvent illustrated as a solvent used for reaction with tetracarboxylic dianhydride and diamine is mentioned.
- a solvent may be used independently and may be used in combination of 2 or more type.
- examples of the solvent include the above nitrogen-containing polar solvents, lower alkyl ketones such as methyl ethyl ketone, acetone, and tetrahydrofuran, and trimethyl phosphate.
- a dispersant For the purpose of uniformly dispersing the fine particles in the varnish, a dispersant may be further added together with the fine particles.
- the fine particles By adding the dispersant, the fine particles can be mixed more uniformly in the varnish, and furthermore, the fine particles can be uniformly distributed in the film in which the varnish is formed.
- the drying property of the varnish is easily improved, and the peelability of the formed unfired composite film from the substrate or the like is easily improved.
- the dispersing agent is not particularly limited, and known ones can be used.
- Anionic surfactants such as nate salt, isopropyl phosphate, polyoxyethylene alkyl ether phosphate salt, polyoxyethylene allyl phenyl ether phosphate salt; oleylamine acetate, lauryl pyridinium chloride, cetyl pyridinium chloride, lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride , Behenyltrimethylammonium chloride, did
- the content of the dispersant is, for example, preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass with respect to the mass of the fine particles from the viewpoint of film formability. Preferably, it is 0.1 to 0.5% by mass.
- a typical method for producing a porous film includes an unfired composite film forming step for forming an unfired composite film using varnish, and a firing for obtaining a resin-fine particle composite film by firing the unfired composite film. And a fine particle removal step of removing fine particles from the resin-fine particle composite film.
- an unfired composite film is formed using varnish.
- the unfired composite film may be directly formed on the substrate, or may be formed on a lower layer film different from the unfired composite film.
- an upper layer film different from the unfired composite film may be further formed on the upper layer.
- the method of providing the lower layer film on the substrate also forms an unfired composite film using the aforementioned varnish, and then forms an upper layer film different from the unfired composite film on the upper layer.
- the method is also included in the method for forming the unfired composite film on the substrate.
- the resin component contained in the varnish is a polyamic acid or polyamideimide precursor and a material that does not require a baking step is used for the upper layer film
- the upper layer film is formed on the resin-fine particle composite film after baking. It may be formed.
- the unfired composite film made of the varnish is formed as a single layer film on the substrate, or an upper layer film on a lower layer film It is preferable to be formed as The unfired composite film is formed, for example, by applying a varnish on the substrate or the lower layer film and drying at 0 to 100 ° C., preferably 10 to 100 ° C. under normal pressure or vacuum. Can do.
- the substrate include a PET film, a SUS substrate, and a glass substrate.
- the lower layer film includes, for example, a resin made of polyvinylidene fluoride, polyethersulfone, polyamic acid and / or polyimide, fine particles, and a solvent, and the content of the fine particles is the same as that of the resin.
- a lower (or upper) unfired composite film formed using a varnish for a lower layer (or upper layer) that is more than 40% by volume and not more than 81% by volume with respect to the total of the fine particles.
- the lower (or upper) unfired composite film may be formed on the substrate. When the content of the fine particles is more than 40% by volume, the particles are uniformly dispersed.
- the particles When the content of the fine particles is 81% by volume or less, the particles are dispersed without agglomeration.
- the pores can be formed uniformly in the membrane. Further, when the content of the fine particles is within the above range, when the lower layer (or upper layer) unfired composite film is formed on the substrate, even if a release layer is not provided on the substrate in advance, Easy to ensure releasability.
- the fine particles used for the lower layer (or upper layer) film varnish and the fine particles used for the porous film production varnish may be the same or different from each other.
- do the fine particles used in the lower (or upper) membrane varnish have a smaller particle size distribution index than the fine particles used in the porous membrane varnish?
- the fine particles used for the lower layer (or upper layer) film varnish preferably have a smaller or equal sphericity than the fine particles used for the porous film production varnish.
- the average particle diameter of the fine particles used in the varnish for the lower layer (or upper layer) may be the same as or different from the average particle diameter of the fine particles in the varnish for producing the porous film.
- the average particle diameter may be appropriately set in the range of 10 to 5000 nm according to the application.
- the varnish for manufacturing a porous film according to the present invention is used as an upper layer, and varnishes for lower layer films having different average particle diameters or particle size distribution indices are combined. Are preferably used.
- the content of fine particles in the varnish for forming a lower layer (or upper layer) may be more or less than that of the varnish described above.
- Suitable examples of components such as a resin component, fine particles, and a solvent contained in the lower layer (or upper layer) film-forming varnish are the same as those of the aforementioned varnish.
- the varnish for forming a lower layer (or upper layer) can be prepared by the same method as that for the varnish described above.
- the lower unfired composite film is formed, for example, by applying the lower film forming varnish on a substrate and drying at 0 to 100 ° C., preferably 10 to 100 ° C. under normal pressure or vacuum. be able to.
- the film forming conditions for the upper unfired composite film are the same.
- the lower layer (or upper layer) film is a lower layer made of a fiber material such as, for example, a cellulose-based resin, a nonwoven fabric (for example, a polyimide nonwoven fabric, etc., and a fiber diameter is, for example, about 50 nm to about 3000 nm).
- membrane and a polyimide film are also mentioned.
- the unfired composite film or a laminated film of the unfired composite film and the lower layer (or upper layer) film is fired to enter a firing step for obtaining a polyimide-fine particle composite film.
- the unfired composite film or the lower unfired composite film is formed on the substrate, it may be fired as it is, or before entering the firing step, the unfired composite film or the unfired composite film and the lower unfired film.
- the laminated film with the fired composite film may be peeled off from the substrate.
- the lower layer (or upper layer) film in the laminated film is a lower layer (or upper layer) unfired composite film formed using a lower layer (or upper layer) film varnish, and the lower layer (or upper layer) film varnish.
- the laminated film of the unfired composite film and the lower layer (or upper layer) is substantially 1 Although it becomes a layer (single layer), it is called a laminated film in this specification.
- a substrate provided with a release layer in advance is used to further enhance the peelability of the film. You can also When a release layer is provided on the substrate in advance, a release agent is applied on the substrate and dried or baked before application of the varnish.
- a release agent such as an alkyl ammonium phosphate salt type, fluorine type, or silicon can be used without any particular limitation.
- a cleaning process for cleaning the unfired composite film peeled from the substrate or the laminated film of the unfired composite film and the lower unfired composite film using an organic solvent may be introduced.
- the release layer forming step and the cleaning step can be omitted.
- an immersion step in a solvent containing water, a pressing step, and a drying step after the immersion step may be provided as optional steps before the firing step described later.
- the underlayer film is also fired together with the unfired composite film in the firing step.
- the firing temperature in the firing step is preferably from 120 to 450 ° C., more preferably from 150 to 400 ° C., although it varies depending on the structure of the unfired composite film and the lower layer film and the presence or absence of a condensing agent. Further, when an organic material is used for the fine particles, it is necessary to set the temperature to be lower than the thermal decomposition temperature. When the resin component contained in the varnish is polyamic acid, it is preferable to complete imidization in the firing step.
- the firing conditions are, for example, a method in which the temperature is raised from room temperature to 400 ° C. in 3 hours and then held at 400 ° C. for 20 minutes, or the temperature is gradually raised from room temperature to 400 ° C. in increments of 50 ° C. (holding 20 minutes for each step) And a stepwise drying-thermal imidization method such as a final holding at 400 ° C. for 20 minutes can also be used.
- a method is adopted in which the end of the unfired composite film is fixed to a SUS mold or the like to prevent deformation. You can also
- the film thickness of the completed resin-fine particle composite film can be obtained by measuring and averaging the thickness of a plurality of locations with a micrometer, for example. What average film thickness is preferable depends on the use of the porous film, but for example, when used for a separator or the like, it is preferably 5 to 500 ⁇ m, more preferably 10 to 100 ⁇ m, 15 More preferably, it is ⁇ 30 ⁇ m. When used for a filter or the like, the thickness is preferably 5 to 500 ⁇ m, more preferably 10 to 300 ⁇ m, and still more preferably 20 to 150 ⁇ m.
- silica is used as the material of the fine particles
- An organic material can also be selected as the material of the fine particles. Any organic material can be used without particular limitation as long as it decomposes at a lower temperature than the resin contained in the resin-fine particle composite film.
- resin fine particles made of a linear polymer or a known depolymerizable polymer can be mentioned.
- a normal linear polymer is a polymer in which a polymer molecular chain is randomly cleaved during thermal decomposition
- a depolymerizable polymer is a polymer in which the polymer is decomposed into monomers during thermal decomposition. All of them disappear from the porous membrane by decomposing into low molecular weight substances or CO 2 .
- the decomposition temperature of the resin fine particles used is preferably 200 to 320 ° C., more preferably 230 to 260 ° C.
- the decomposition temperature is 200 ° C. or higher, film formation can be performed even when a high boiling point solvent is used for the varnish, and the range of selection of the firing conditions for the resin-fine particle composite film is widened. If the decomposition temperature is less than 320 ° C., only the resin fine particles can be lost without causing thermal damage to the resin contained in the resin-fine particle composite film.
- the total film thickness of the porous film is not particularly limited, but for example, when used for a separator or the like, it is preferably 5 to 500 ⁇ m, more preferably 10 to 100 ⁇ m, and 15 to 30 ⁇ m. More preferably. When used for a filter or the like, the thickness is preferably 5 to 500 ⁇ m, more preferably 10 to 300 ⁇ m, and still more preferably 20 to 150 ⁇ m.
- the film thickness can be obtained by measuring and averaging the thickness at a plurality of locations with a micrometer or the like, for example, as in the measurement of the resin-fine particle composite film.
- the ratio in the thickness direction of the region formed by each composition for producing a porous membrane may be appropriately set according to the use of the porous membrane.
- the ratio in the thickness direction of each region ((I) :( II)) is, for example, 1:99 to 99: 1, preferably 5:95 to 95: 5. .
- the thickness of each layer can be calculated by observing a plurality of locations on the cross section of the porous membrane with a scanning electron microscope (SEM) or the like and averaging them.
- SEM scanning electron microscope
- the method for producing a porous membrane includes a resin removal step of removing at least a part of the resin portion of the resin-particle composite membrane before the fine particle removal step, or removing at least a portion of the porous membrane after the fine particle removal step. You may have. By removing at least a part of the resin part of the resin-particulate composite film before the fine particle removal process, when the fine particles are removed and pores are formed in the subsequent fine particle removal process, at least a part of the resin part is removed. It is possible to improve the open area ratio and surface smoothness of the porous film of the final product as compared with those not removed.
- the porosity of the porous film of the final product can be improved as compared with the case where at least a part of the porous film is not removed. It becomes possible.
- the step of removing at least a part of the resin part or the step of removing at least a part of the porous film may be performed by a normal chemical etching method, a physical removal method, or a combination thereof. it can.
- Examples of the chemical etching method include treatment with a chemical etching solution such as an inorganic alkali solution or an organic alkali solution.
- a chemical etching solution such as an inorganic alkali solution or an organic alkali solution.
- Inorganic alkaline solutions are preferred.
- the inorganic alkaline solution include, for example, a hydrazine solution containing hydrazine hydrate and ethylenediamine, a solution of an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide, sodium carbonate, sodium silicate, and sodium metasilicate, an ammonia solution, and a hydroxide.
- Examples thereof include an etchant containing alkali, hydrazine and 1,3-dimethyl-2-imidazolidinone as main components.
- Organic alkaline solutions include primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; dimethylethanolamine And alcohol amines such as triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; and alkaline solutions such as cyclic amines such as pyrrole and pihelidine.
- primary amines such as ethylamine and n-propylamine
- secondary amines such as diethylamine and di-n-butylamine
- tertiary amines such as triethylamine and methyldiethylamine
- dimethylethanolamine And alcohol amines such as triethanolamine
- quaternary ammonium salts such as tetra
- the solvent of each solution pure water and alcohols can be selected as appropriate. Moreover, what added a suitable amount of surfactant can also be used.
- the alkali concentration is, for example, 0.01 to 20% by mass.
- a physical method for example, plasma (oxygen, argon, etc.), dry etching by corona discharge, etc., an abrasive (eg, alumina (hardness 9), etc.) is dispersed in a liquid, and this is applied to the film surface.
- plasma oxygen, argon, etc.
- an abrasive eg, alumina (hardness 9), etc.
- a method of surface treatment by irradiating at a speed of 30 to 100 m / s can be used.
- the above-described method is preferable because it can be applied to any resin removal step before or after the fine particle removal step.
- a mount film for example, a polyester film such as a PET film
- a method of peeling the porous film from the mount film can also be adopted. Due to the surface tension or electrostatic adhesion force of the liquid, the porous film is peeled off from the mount film with only the surface layer of the porous film remaining on the mount film.
- the porous membrane described above can be used as a separator of a lithium ion battery, a fuel cell electrolyte membrane, a gas or liquid separation membrane, or a low dielectric constant material.
- the porous membrane can be used as a separator for secondary batteries such as nickel cadmium, nickel metal hydride batteries, lithium ion secondary batteries, etc., but particularly used as a porous separator for lithium ion secondary batteries. preferable.
- the unfired composite film forming step when used as a separator for a lithium ion battery, in the unfired composite film forming step, the unfired composite film is formed on a lower layer film different from the unfired composite film, Battery performance can be improved by using what was formed using the varnish for lower layer films, and making the surface of the said lower layer film side into the negative electrode surface side of a lithium ion battery.
- a secondary battery In a secondary battery, an electrolytic solution and a separator made of the porous film described above are disposed between a negative electrode and a positive electrode.
- the type and configuration of the secondary battery are not limited at all.
- a battery element in which a positive electrode, a separator, and a negative electrode are sequentially laminated so as to satisfy the above conditions is impregnated with an electrolytic solution, and if this is a structure enclosed in an exterior, a nickel cadmium, nickel metal hydride battery, lithium ion It can use without limitation especially for well-known secondary batteries, such as a secondary battery.
- the negative electrode of the secondary battery can have a structure in which a negative electrode mixture composed of a negative electrode active material, a conductive additive and a binder is formed on a current collector.
- a negative electrode active material cadmium hydroxide can be used in the case of a nickel cadmium battery, and a hydrogen storage alloy can be used in the case of a nickel metal hydride battery.
- a material capable of electrochemically doping lithium can be employed. Examples of such an active material include a carbon material, silicon, aluminum, tin, and a wood alloy.
- Examples of the conductive additive constituting the negative electrode include carbon materials such as acetylene black and ketjen black.
- the binder is made of an organic polymer, and examples thereof include polyvinylidene fluoride and carboxymethyl cellulose.
- copper foil, stainless steel foil, nickel foil, or the like can be used.
- the positive electrode can have a structure in which a positive electrode mixture comprising a positive electrode active material, a conductive additive and a binder is formed on a current collector.
- a positive electrode active material nickel hydroxide can be used in the case of a nickel cadmium battery, and nickel hydroxide or nickel oxyhydroxide can be used in the case of a nickel hydrogen battery.
- examples of the positive electrode active material include lithium-containing transition metal oxides.
- the conductive assistant include carbon materials such as acetylene black and ketjen black.
- the binder is made of an organic polymer, and examples thereof include polyvinylidene fluoride.
- aluminum foil, stainless steel foil, titanium foil, or the like can be used.
- the electrolytic solution for example, in the case of a nickel cadmium battery or a nickel metal hydride battery, an aqueous potassium hydroxide solution is used.
- the electrolyte solution of the lithium ion secondary battery has a structure in which a lithium salt is dissolved in a non-aqueous solvent.
- the lithium salt include LiPF 6 , LiBF 4 , LiClO 4 and the like.
- the non-aqueous solvent include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ⁇ -butyrolactone, and vinylene carbonate. These may be used alone or in combination.
- Examples of exterior materials include metal cans or aluminum laminate packs.
- the shape of the battery includes a square shape, a cylindrical shape, a coin shape, and the like, but the above-described separator made of a porous film can be suitably applied to any shape.
- Example 1 After being added to a rotating / revolving mixer (trade name: manufactured by Awatori Nertaro Co., Ltd., Sinky), Example 1 kneaded for 5 minutes at a rotational speed of 2000 rpm and Comparative Example 1 for 1 minute at a rotational speed of 2000 rpm for solid content concentration.
- a varnish for producing a porous membrane of 30% by mass was prepared.
- the ratio of polyamic acid and silica (polyamic acid: silica) in the obtained varnish composition was 28:72 as a volume ratio and 20:80 as a mass ratio.
- the following polyamic acid solution, organic solvent, dispersant, and fine particles were used.
- Polyamic acid solution reaction product of pyromellitic dianhydride and 4,4′-diaminodiphenyl ether (solid content 20% by mass (organic solvent: N, N-dimethylacetamide)) Organic solvent (1): N, N-dimethylacetamide (DMAc) Organic solvent (2): gamma butyrolactone Dispersant: Polyoxyethylene secondary alkyl ether dispersant Fine particle: Silica: Silica having an average particle size of 700 nm
- the obtained varnish for producing a porous membrane was applied on a polyethylene terephthalate (PET) film as a base material using an applicator to form an unfired composite membrane.
- PET polyethylene terephthalate
- This unfired composite film was put in an oven and baked at 380 ° C. for 15 minutes to complete imidization to obtain a resin-fine particle composite film. Thereafter, the resin-fine particle composite film was peeled from the substrate.
- the resin-fine particle composite film was immersed in hydrogen fluoride (HF) for 10 minutes to remove silica fine particles contained in the film, and then washed with water and dried to obtain a film thickness of 40 ⁇ m.
- HF hydrogen fluoride
- the surface roughness of the obtained polyimide porous membrane of Example 1 and Comparative Example 1 was measured according to the following method. First, the porous film wetted with water was spread on a flat glass substrate so that the surface of the porous film in contact with the PET film was in contact with the glass substrate. At that time, by using the PET film, air between the glass substrate and the porous membrane was removed to stretch the wrinkles generated in the porous membrane. Next, the porous film on the glass substrate was heated at 70 ° C. for 2 minutes. In this way, the surface roughness of the porous film laid flat on the glass substrate was measured. The surface roughness was measured according to the following conditions using a stylus type surface roughness meter Dektak 150 manufactured by Asbach. Stylus radius: 12.5 ⁇ m Measuring distance: 10000 ⁇ m Measurement time: 120 seconds Horizontal resolution: 0.278 ⁇ m / sample Stylus pressure: 5.00mg
- the surface roughness Ra of the polyimide porous film of Example 1 was 3069 mm
- the surface roughness Ra of the polyimide porous film of Comparative Example 1 was 30454 mm.
- the result of having observed the porous membrane surface with the scanning electron microscope (SEM) is shown in FIG.1 and FIG.2. From the measurement results of FIG. 1 and the surface roughness, it is confirmed that no striped undulation is observed on the surface of the polyimide porous film of Example 1, and the polyimide porous film of Example 1 has excellent surface smoothness. I understand.
- FIG. 2 and the measurement result of the surface roughness it can be seen that the surface of the polyimide porous film of Comparative Example 1 has a large difference in height, and striped waviness is observed.
- Example 2 to 4 Changing the polyamic acid to polyethersulfone, changing the solid content concentration of the varnish from 30% by mass to 42% by mass, and further adding 5% by mass phosphoric acid-based dispersant to the silica dispersion. Adding only DMAc as an organic solvent, and changing the ratio of resin to silica (resin: silica) in the obtained varnish from 20:80 to 30:70 as a mass ratio. Otherwise, a varnish for producing a porous membrane was prepared in the same manner as in Example 1.
- the obtained varnish for producing a porous membrane is coated on a polyethylene terephthalate (PET) film as a base material using an applicator, and then the coated membrane is baked at 50 ° C. for 5 minutes to form a resin-fine particle composite membrane. did.
- the resin-fine particle composite membrane was immersed in water for 3 minutes. Thereafter, the resin-fine particle composite film was peeled from the substrate.
- the resin-fine particle composite film is immersed in hydrogen fluoride (HF) for 10 minutes to remove silica fine particles contained in the film, and then washed with water and dried to obtain the polyether of Example 2 having a film thickness of 40 ⁇ m.
- HF hydrogen fluoride
- a sulfone porous membrane was obtained.
- the polyethersulfone porous membrane when the baking temperature of a coating film was changed from 50 degreeC to 70 degreeC (Example 3) and 90 degreeC (Example 4), respectively was obtained.
- the surface roughness of the obtained polyethersulfone porous membrane of Example 2 was measured in the same manner as in Example 1. As a result of measurement with a stylus type surface roughness meter, the surface roughness Ra of the polyethersulfone porous membrane of Example 2 was 11,000 mm. The surface roughness Ra of the polyethersulfone porous membranes of Examples 3 and 4 was also an equivalent value.
- Example 5 Changing the polyamic acid to polyethersulfone, changing the solid content concentration of the varnish from 30% by mass to 35% by mass, and further adding 5% by mass of a phosphoric acid dispersant to the silica dispersion. Adding only DMAc as an organic solvent, and changing the ratio of resin to silica (resin: silica) in the obtained varnish from 20:80 to 30:70 as a mass ratio. Otherwise, a varnish for producing a porous membrane was prepared in the same manner as in Example 1.
- a polyethersulfone porous membrane of Example 5 having a thickness of 40 ⁇ m was obtained in the same manner as Example 2 using the obtained varnish for producing a porous membrane.
- the surface roughness of the resulting polyethersulfone porous membrane of Example 5 was measured in the same manner as in Example 1.
- the surface roughness Ra of the polyethersulfone porous membrane of Example 5 was 8000 mm.
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Abstract
Description
また、ガス又は液体の分離用膜であるフィルタにおいては、多孔質膜とこれを支持する支持体とを良好に密着性させることが望まれている。多孔質膜と支持体とが良好に密着すれば、フィルタの分離性能及び取扱性が向上する。多孔質膜の表面が平滑であれば、多孔質膜の透過性(通液性)が向上し、取り扱いも良好である。
球状孔が相互に連通した構造を含み、
表面の開口部が形成する凹みよりも深いうねりがなく、
開口部の直径が100nm~5000nmである、多孔質膜である。
ワニスは、25℃における粘度が0.1~3Pa・s、固形分濃度が10~50質量%、微粒子の平均粒子径が10~5000nmであり、
混練は2分~10時間行う、多孔質膜の製造方法である。
多孔質膜は、ポリフッ化ビニリデン、ポリエーテルスルホン、ポリイミド及び/又はポリアミドイミドからなる。多孔質膜の表面粗さRaは3万Å以下であり、好ましくは10000Å以下であり、より好ましくは5000Å以下であり、さらに好ましくは3500Å以下である。このため、多孔質膜は平滑性に優れる。
未焼成複合膜中で対流が生じると、未焼成複合膜中で微粒子の分布にむらが生じやすい。例えば、未焼成複合膜中の膜厚の薄い谷の部分で微粒子が密である一方で膜厚の厚い山の部分で微粒子が疎であったり、山の部分で微粒子が疎である一方で谷の部分で微粒子が密であったりする。
この場合、未焼成複合膜から微粒子を除去して多孔質膜を形成した結果、開口の分布にばらつきのある多孔質膜が得られることになる。
対して、多孔質膜の表面粗さが3万Å以下である場合、微粒子と樹脂とを含む未焼成副膜中で対流が起きていないか、穏やかな対流しか生じていない場合が多い。その結果、多孔質膜の表面粗さが3万Å以下である場合、表面における開口の分布が均一である多孔質膜を得やすい。
さらに、表面粗さRaが上記範囲内であることにより、多孔質膜をフィルタとして用いる場合に、多孔質膜の透過性が向上する。フィルタである多孔質膜が支持体と密着すると、フィルタリングを行う際のフィルタの支持体からの剥離が抑制され、これに伴い、フィルタの破れ等の破損も抑制され、取扱も良好である。
触針半径:12.5μm
測定距離:10000μm
測定時間:120秒
水平分解能:0.278μm/sample
触針圧:5.00mg
多孔質膜における開口部とは、多孔質膜の表面において上記の連通孔が開口する部分である。
多孔質膜は、その表面において好ましくはうねりを有さない。うねりとは、表面粗さが測定される面における、「開口部が形成する凹みよりも深い凹部」を言う。開口部が形成する凹みとは、多孔質膜を製造する際に膜の表面に形成される球状孔に相当し、当該球状孔の膜表面からの深さよりも深い凹部が、うねりに相当する。
具体的には球状孔では、孔部を規定する面が曲面であり、当該曲面により真球状又は略真球上の空孔が規定されていればよい。
開口部の直径は、連通孔を構成する球状孔の直径と同等又は略同等である。かかる直径の球状孔が連なって構成される連通孔は、多孔質膜内において、流体を良好に通過させる。
多孔質膜は、多孔質膜を厚さ方向に貫通する、連通孔を流体の流路として内部に有する。これにより流体は、多孔質膜の一方の主面から、他方の主面へと透過できる。
また、積層体をフィルタとして用いる場合、流体は個々の球状孔を規定する曲面に接触しながら多孔質膜の内部を通過する。多孔質膜の内部における流体の接触面積は、球状孔からなる連通孔を備えることに起因してかなり広い。このため、流体を多孔質膜を含む積層体を通過させると、多孔質膜内の球状孔に、流体内に存在する微小な物質が吸着しやすいと考えられる。
前述の多孔質膜の製造には、それぞれ所定の微粒子と、樹脂と、溶剤とを含有し、樹脂が溶剤に溶解している多孔質膜製造用ワニス(以下、単に「ワニス」とも記載する。)を用いる。
ワニスは、典型的には。微粒子を溶剤に分散させる、微粒子分散液調製工程と、ポリフッ化ビニリデン、ポリエーテルスルホン、ポリアミド酸、ポリイミド、ポリアミドイミド前駆体となるポリアミド酸、及びポリアミドイミドよりなる群から選択される少なくとも1つの樹脂を含む樹脂溶液を調製する工程と、これら微粒子分散液と樹脂溶液とを合わせて混錬し濃度調製を行う混錬工程とにより製造される。
なお、ワニスの粘度はE型粘度計により測定される。
ワニスの混錬には、自転・公転ミキサー(商品名:あわとり錬太郎、(株)シンキー製)、プラネタリミキサー、ビーズミル等を用いることができる。
多孔質膜用製造用ワニスの粘度、及び固形分濃度を、上記範囲に調製すると、所望する平滑性を有する多孔質膜を形成しやすい。
ワニスが適切な範囲内の時間混練されると、ワニスを用いて平滑な多孔質膜を形成しやすい。混錬時間が2分以上であると、ワニスを用いて形成される多孔質膜について、表面粗さRaが3万Å以下の所望する平滑性を達成しやすい。スループットの観点からワニスの混練時間は10時間を超えないことが好ましい。
また、上記範囲内の平均粒径を有する微粒子を用いることにより、多孔質膜の表面に、所望の大きさの開口部を形成でき、多孔質膜の内部に、所望の大記載の球状孔が連なった連通孔を形成することができる。
前述の通り、ワニスは、ポリフッ化ビニリデン、ポリエーテルスルホン、ポリアミド酸、ポリイミド、ポリアミドイミド前駆体、及びポリアミドイミドからなる群より選択される少なくとも1種の樹脂を含む。以下、これらの樹脂について説明する。
ポリフッ化ビニリデンとしては、ワニス形成に用いられる溶剤に可溶なものであれば特に限定されない。ポリフッ化ビニリデンとしては、ホモポリマーであってもよいし、コポリマー(共重合体)であってもよい。共重合する構成単位としては、エチレン、三フッ化塩化エチレン、四フッ化エチレン又は六フッ化プロピレン等が挙げられ、質量平均分子量は、例えば1万~500万程度である。
ポリエーテルスルホンとしては、ワニス形成に用いられる溶剤に可溶なものであれば特に限定されない。ポリエーテルスルホンとしては、製造する多孔質膜の用途に応じて適宜選択することができ、親水性でも疎水性であってもよい。また脂肪族ポリエーテルスルホンであっても芳香族ポリエーテルスルホンであってもよい。質量平均分子量は、例えば、5000~1,000,000であり、好ましくは10,000~300,000である。
ポリアミド酸としては、任意のテトラカルボン酸二無水物とジアミンとを重合して得られる生成物が、特に限定されることなく使用できる。テトラカルボン酸二無水物及びジアミンの使用量は特に限定されないが、テトラカルボン酸二無水物1モルに対して、ジアミンを0.50~1.50モル用いるのが好ましく、0.60~1.30モル用いるのがより好ましく、0.70~1.20モル用いるのが特に好ましい。
これらの溶剤は1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。溶剤の使用量に特に制限はないが、生成するポリアミド酸の含有量が5~50質量%とするのが望ましい。
ポリアミド酸は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
ポリイミドは、その構造や分子量が限定されることはなく、公知のものが使用できる。ポリイミドについて、側鎖にカルボキシ基等の縮合可能な官能基又は焼成時に架橋反応等を促進させる官能基を有していてもよい。また、ワニスが溶剤を含有する場合、使用する溶剤に溶解可能な可溶性ポリイミドが好ましい。
ポリイミド及びそのモノマーの各々は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
ポリアミドイミドは、その構造や分子量に限定されることなく、公知のものが使用できる。ポリアミドイミドについて、側鎖にカルボキシ基等の縮合可能な官能基又は焼成時に架橋反応等を促進させる官能基を有していてもよい。また、ワニスが溶剤を含有する場合、使用する溶剤に溶解可能な可溶性ポリアミドイミドが好ましい。
ポリアミドイミド及びポリアミドイミド前駆体の各々は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。また、ポリアミドイミドについて、上記ポリマー、原料モノマー、及びオリゴマーの各々は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
微粒子の材質は、ワニスに含まれる溶剤に不溶で、後に樹脂-微粒子複合膜から除去可能であれば、特に限定されることなく公知の材質を採用可能である。例えば、無機材料としては、シリカ(二酸化珪素)、酸化チタン、アルミナ(Al2O3)等の金属酸化物、有機材料としては、高分子量オレフィン(ポリプロピレン,ポリエチレン等)、ポリスチレン、エポキシ樹脂、セルロース、ポリビニルアルコール、ポリビニルブチラール、ポリエステル、ポリエーテル等の有機高分子微粒子が挙げられる。
微粒子は、単独で用いてもよく、2種以上を組み合わせて用いてもよい。
溶剤は、ポリフッ化ビニリデン、ポリエーテルスルホン、ポリアミド酸及び/又はポリイミドからなる樹脂を溶解することができ、微粒子を溶解しなければ、特に限定されない。溶剤の例としては、テトラカルボン酸二無水物とジアミンとの反応に用いる溶剤として例示した溶剤が挙げられる。溶剤は、単独で用いてもよく、2種以上を組み合わせて用いてもよい。
ポリフッ化ビニリデンの場合、溶剤としては、上記含窒素極性溶剤の他、メチルエチルケトン、アセトン、テトラヒドロフラン等の低級アルキルケトンや、リン酸トリメチル等が挙げられる。
ポリエーテルスルホンの場合、溶剤としては、上記含窒素極性溶剤の他、ジフェニルスルホン、ジメチルスルホン、ジメチルスルホキシド、ベンゾフェノン、テトラヒドロチオフェン-1,1-ジオキシド、1,3-ジメチル-2-イミダゾリジノン等の極性溶媒が挙げられる。
ワニス中の微粒子を均一に分散することを目的に、微粒子とともにさらに分散剤を添加してもよい。分散剤を添加することにより、微粒子をワニス中に一層均一に混合でき、さらには、ワニスを成膜した膜中で、微粒子を均一に分布させることができる。その結果、最終的に得られる多孔質膜の表面に稠密な開口を設け、かつ、表裏面を効率よく連通させることが可能となり、多孔質膜の透気度が向上する。さらに、分散剤を添加することにより、ワニスの乾燥性が向上しやすく、また、形成された未焼成複合膜の基板等からの剥離性が向上しやすい。
多孔質膜の典型的な製造方法は、ワニスを用いて、未焼成複合膜を成膜する未焼成複合膜成膜工程と、上記未焼成複合膜を焼成して樹脂-微粒子複合膜を得る焼成工程と、上記樹脂-微粒子複合膜から微粒子を取り除く微粒子除去工程と、を有する。
以下、未焼成複合膜の成膜方法について説明する。未焼成複合膜成膜工程においては、ワニスを用いて、未焼成複合膜を成膜する。その際、未焼成複合膜は、基板上に直接成膜してもよいし、上記未焼成複合膜とは異なる下層膜上に成膜してもよい。また、前述のワニス(多孔質膜製造用組成物)を用いて、未焼成複合膜を成膜した後に、さらに上層に上記未焼成複合膜とは異なる上層膜を成膜してもよい。なお、本出願において、基板上に下層膜を設ける方法も、前述のワニスを用いて、未焼成複合膜を成膜した後に、さらに上層に上記未焼成複合膜とは異なる上層膜を成膜する方法も、基板上に未焼成複合膜を形成する方法に含める。ただし、前述のワニスに含まれる樹脂成分が、ポリアミド酸又はポリアミドイミド前駆体であって、上層膜に焼成工程不要の材料を用いる場合は、焼成後の樹脂-微粒子複合膜に対し、上層膜を形成してもよい。
表面粗さの小さい平滑な表面を備える多孔質膜を形成しやすいことから、前述のワニスからなる未焼成複合膜は、基板上に単層の膜として形成されるか、下層膜上に上層膜として形成されるのが好ましい。
未焼成複合膜は、例えば、基板上又は上記下層膜上に、ワニスを塗布し、常圧又は真空下で0~100℃、好ましくは常圧10~100℃で乾燥することにより、形成することができる。
基板としては、例えば、PETフィルム、SUS基板、ガラス基板等が挙げられる。
ワニスに含まれる樹脂成分が、ポリアミド酸又はポリアミドイミド前駆体の場合、上記未焼成複合膜に加熱による後処理(焼成)を行って、ポリイミド及び/又はポリアミドイミドからなる樹脂と、微粒子と、からなる複合膜(樹脂-微粒子複合膜)とする。
なお、ワニスに含まれる樹脂成分が、ポリイミド、ポリアミドイミド又はポリエーテルスルホンである場合は、焼成工程を省いてもよい。上記未焼成複合膜成膜工程において、上記未焼成複合膜とは異なる下層膜上に上記未焼成複合膜を成膜した場合には、焼成工程において、上記未焼成複合膜とともに上記下層膜も焼成する。焼成工程における焼成温度は、未焼成複合膜及び下層膜の構造や縮合剤の有無によっても異なるが、120~450℃であることが好ましく、さらに好ましくは150~400℃である。また、微粒子に、有機材料を使用するときは、その熱分解温度よりも低い温度に設定する必要がある。ワニスに含まれる樹脂成分が、ポリアミド酸の場合、焼成工程においてはイミド化を完結させることが好ましい。
樹脂-微粒子複合膜から、微粒子を適切な方法を選択して除去することにより、多孔質膜を再現性よく製造することができる。
多孔質膜の製造方法は、微粒子除去工程前に、樹脂-微粒子複合膜の樹脂部分の少なくとも一部を除去するか、又は、微粒子除去工程後に多孔質膜の少なくとも一部を除去する樹脂除去工程を有していてもよい。微粒子除去工程前に、樹脂-微粒子複合膜の樹脂部分の少なくとも一部を除去することにより、続く微粒子除去工程で微粒子が取り除かれ空孔が形成された場合に、上記樹脂部分の少なくとも一部を除去しないものに比べて、最終製品の多孔質膜の開孔率及び表面平滑性を向上させることが可能となる。また、微粒子除去工程後に多孔質膜の少なくとも一部を除去することにより、上記多孔質膜の少なくとも一部を除去しないものに比べて、最終製品の多孔質膜の開孔率を向上させることが可能となる。
以上説明した多孔質膜は、リチウムイオン電池のセパレータや燃料電池電解質膜、ガス又は液体の分離用膜、低誘電率材料として使用することが可能である。上記多孔質膜は、ニッケルカドミウム、ニッケル水素電池、リチウムイオン二次電池等の二次電池用セパレータとして使用することが可能であるが、リチウムイオン二次電池用多孔質セパレータとして使用することが特に好ましい。特に、リチウムイオン電池のセパレータとして使用する場合、上記未焼成複合膜成膜工程において、上記未焼成複合膜とは異なる下層膜上に上記未焼成複合膜を成膜し、上記下層膜として、上記下層膜用ワニスを用いて成膜したものを用い、上記下層膜側の面をリチウムイオン電池の負極面側とすることにより、電池性能を向上させることができる。
二次電池では、負極と正極との間に、電解液と前述の多孔質膜からなるセパレータとが配置される。
二次電池の種類や構成は、何ら限定されるものではない。正極とセパレータと負極とが順に上記条件を満たすように積層された電池要素に電解液が含浸され、これが外装に封入された構造となった構成であれば、ニッケルカドミウム、ニッケル水素電池、リチウムイオン二次電池等の公知の二次電池に、特に限定されることなく使用することができる。
ポリアミド酸溶液に、ポリアミド酸の質量とシリカの質量との合計に対して、ポリアミド酸の量が20質量%であり、シリカの質量が80質量%であるように、シリカ分散液(シリカに対し0.5質量%の分散剤を含む)を添加した。さらに有機溶剤(1)及び(2)を最終組成物全体における溶剤組成が有機溶剤(1):有機溶剤(2)=90:10となるようにそれぞれ追加した。自転・公転ミキサー(商品名:あわとり練太郎(株)シンキー製)に加えた後、実施例1では回転数2000rpmで5分間、比較例1では回転数2000rpmで1分間混練し、固形分濃度30質量%の多孔質膜製造用ワニスを調製した。なお、得られたワニス組成物におけるポリアミド酸とシリカとの比率(ポリアミド酸:シリカ)は体積比として28:72、質量比として20:80であった。
なお、以下に示すポリアミド酸溶液、有機溶剤、分散剤、及び微粒子を用いた。
・ポリアミド酸溶液:ピロメリット酸二無水物と4,4’-ジアミノジフェニルエーテルとの反応物(固形分20質量%(有機溶剤:N,N-ジメチルアセトアミド))
・有機溶剤(1):N,N-ジメチルアセトアミド(DMAc)
・有機溶剤(2):ガンマブチロラクトン
・分散剤:ポリオキシエチレン二級アルキルエーテル系分散剤
・微粒子:シリカ:平均粒径700nmのシリカ
まず、多孔質膜のPETフィルムと接触していた側の面がガラス基板と接するように、水で濡れた多孔質膜を平坦なガラス基板上に広げた。その際、PETフィルムを用いて、ガラス基板と多孔質膜との間の空気を抜くことにより、多孔質膜に生じた皺を伸ばした。次いで、ガラス基板上の多孔質膜を70℃で2分間加熱した。
このようにして、ガラス基板上に平たく敷かれた多孔質フィルムについて表面粗さの測定を行った。
表面粗さの測定は、アスバック社製の触針式表面粗さ計Dektak150を用い、下記の条件に従って行った。
触針半径:12.5μm
測定距離:10000μm
測定時間:120秒
水平分解能:0.278μm/sample
触針圧:5.00mg
また、多孔質膜表面を走査型電子顕微鏡(SEM)により観察した結果を図1及び図2に示す。図1と表面粗さの測定結果とから、実施例1のポリイミド多孔質膜の表面では縞状のうねりが観察されず実施例1のポリイミド多孔質膜が表面の平滑性に優れていることが分かる。
これに対し、図2と、表面粗さの測定結果とから、比較例1のポリイミド多孔質膜の表面では高低差が大きく、縞状のうねりが観察されることが分かる。
ポリアミド酸をポリエーテルスルホンに変更することと、ワニスの固形分濃度を30質量%から42質量%に変更することと、シリカ分散液中にさらにシリカに対し5質量%のリン酸系分散剤を添加したことと、有機溶剤としてDMAcのみを用いることと、得られたワニスにおける樹脂とシリカとの比率(樹脂:シリカ)を、質量比として20:80から、30:70に変更することとの他は、実施例1と同様にして、多孔質膜製造用ワニスを調製した。
また、塗布膜のベーク温度を50℃から70℃(実施例3)、90℃(実施例4)にそれぞれ変更した場合のポリエーテルスルホン多孔質膜を得た。
触針式表面粗さ計による測定の結果、実施例2のポリエーテルスルホン多孔質膜の表面粗さRaは11000Åであった。実施例3、4のポリエーテルスルホン多孔質膜の表面粗さRaも同等の値であった。
ポリアミド酸をポリエーテルスルホンに変更することと、ワニスの固形分濃度を30質量%から35質量%に変更することと、シリカ分散液中にさらにシリカに対し5質量%のリン酸系分散剤を添加したことと、有機溶剤としてDMAcのみを用いることと、得られたワニスにおける樹脂とシリカとの比率(樹脂:シリカ)を、質量比として20:80から、30:70に変更することとの他は、実施例1と同様にして、多孔質膜製造用ワニスを調製した。
得られた実施例5のポリエーテルスルホン多孔質膜の表面粗さを、実施例1と同様に測定した。
触針式表面粗さ計による測定の結果、実施例5のポリエーテルスルホン多孔質膜の表面粗さRaは8000Åであった。
Claims (6)
- ポリフッ化ビニリデン、ポリエーテルスルホン、ポリイミド及び/又はポリアミドイミドの多孔質膜であって、
表面粗さRaが3万Å以下である、多孔質膜。 - 表面における開口直径が10nm~5000nmである、請求項1に記載の多孔質膜。
- 前記表面粗さRaは、製造時に基板に面していた面と反対側の面における表面粗さRaである、請求項1又は2に記載の多孔質膜。
- ポリフッ化ビニリデン、ポリエーテルスルホン、ポリイミド及び/又はポリアミドイミドの多孔質膜であって、
球状孔が相互に連通した構造を含み、
表面の開口部が形成する凹みよりも深いうねりがなく、
前記開口部の直径が10nm~5000nmである、多孔質膜。 - 微粒子とポリフッ化ビニリデン、ポリエーテルスルホン、ポリアミド酸、ポリイミド、ポリアミドイミド前駆体及びポリアミドイミドよりなる群から選択される少なくとも1つの樹脂とを含有する未焼成複合膜の表面粗さRaが3万Å以下となるように前記微粒子と前記樹脂とを含有するワニスを混練する工程を含む、ポリフッ化ビニリデン、ポリエーテルスルホン、ポリイミド及び/又はポリアミドイミドの多孔質膜の製造方法。
- 微粒子とポリフッ化ビニリデン、ポリエーテルスルホン、ポリアミド酸、ポリイミド、ポリアミドイミド前駆体及びポリアミドイミドよりなる群から選択される少なくとも1つの樹脂とを含有するワニスを混練する工程を含む、ポリフッ化ビニリデン、ポリエーテルスルホン、ポリイミド及び/又はポリアミドイミドの多孔質膜の製造方法であって、
前記ワニスは、25℃における粘度が0.1~3Pa・s、固形分濃度が10~50質量%、微粒子の平均粒子径が10~5000nmであり、
前記混練は2分~10時間行う、多孔質膜の製造方法。
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WO2022091915A1 (ja) * | 2020-10-30 | 2022-05-05 | 東京応化工業株式会社 | ポリイミド多孔質膜製造用ワニス |
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US20200346169A1 (en) | 2020-11-05 |
US20180250640A1 (en) | 2018-09-06 |
CN107922664A (zh) | 2018-04-17 |
US11344848B2 (en) | 2022-05-31 |
KR20180050350A (ko) | 2018-05-14 |
JP7018100B2 (ja) | 2022-02-09 |
KR102157364B1 (ko) | 2020-09-18 |
JP2020203283A (ja) | 2020-12-24 |
JPWO2017038898A1 (ja) | 2018-08-09 |
JP6807318B2 (ja) | 2021-01-06 |
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