WO2018025790A1 - 液体の精製方法、及び多孔質膜の製造方法 - Google Patents

液体の精製方法、及び多孔質膜の製造方法 Download PDF

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Publication number
WO2018025790A1
WO2018025790A1 PCT/JP2017/027618 JP2017027618W WO2018025790A1 WO 2018025790 A1 WO2018025790 A1 WO 2018025790A1 JP 2017027618 W JP2017027618 W JP 2017027618W WO 2018025790 A1 WO2018025790 A1 WO 2018025790A1
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WIPO (PCT)
Prior art keywords
porous membrane
particles
liquid
filter
viscous liquid
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PCT/JP2017/027618
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English (en)
French (fr)
Japanese (ja)
Inventor
司 菅原
中田　明彦
永恭 橋本
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東京応化工業株式会社
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Application filed by 東京応化工業株式会社 filed Critical 東京応化工業株式会社
Priority to KR1020227032524A priority Critical patent/KR102508570B1/ko
Priority to KR1020197004287A priority patent/KR102447053B1/ko
Priority to CN201780047301.1A priority patent/CN109562323B/zh
Priority to JP2018531875A priority patent/JP6835848B2/ja
Publication of WO2018025790A1 publication Critical patent/WO2018025790A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/0031—Degasification of liquids by filtration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B01D67/00793—Dispersing a component, e.g. as particles or powder, in another component
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B01D71/027—Silicium oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/06—Specific viscosities of materials involved
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/219—Specific solvent system
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/0283—Pore size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/20—Specific permeability or cut-off range

Definitions

  • the present invention relates to a liquid purification method for purifying a viscous liquid and a method for producing a porous membrane that can be suitably used in the purification method.
  • the viscous liquid is a photoresist composition
  • bubbles contained in the photoresist composition may cause uneven coating or defects in a patterned film formed using the photoresist composition. It becomes.
  • a method for satisfactorily removing bubbles in a viscous liquid such as a photoresist composition is required.
  • Patent Document 1 As a method for removing bubbles from a viscous liquid such as a photoresist composition, there has been proposed a method in which a viscous liquid is supplied to a substrate after passing through a filter for removing foreign substances and bubbles (Patent Document 1). ).
  • Patent Document 1 does not specifically describe the material, shape, opening diameter, etc. of the filter.
  • a known filter such as a non-woven fabric made of PTFE (polytetrafluoroethylene) fiber is applied to remove bubbles, depending on the viscosity of the liquid and the method of passing through the filter, the bubbles in the liquid to be treated It may increase.
  • PTFE polytetrafluoroethylene
  • the present invention has been made in view of the above problems, and is a method for purifying a viscous liquid that can favorably reduce the number of bubbles in the viscous liquid, and a porous material suitably used as a filter in the production method. It is an object of the present invention to provide a method for producing a membrane.
  • the inventors apply a varnish containing a resin component (A), particles (B), and a solvent (S) on a substrate, and a composite comprising the resin component (A) and particles (B).
  • the present inventors have found that the above-mentioned problems can be solved by filtering a viscous liquid having a viscosity of 0.1 Pa ⁇ s or more using a filter including a porous film having the above.
  • the present invention provides the following.
  • a first aspect of the present invention is a liquid purification method comprising filtering a viscous liquid having a viscosity of 0.1 Pa ⁇ s or more with a filter, The filter Coating a varnish containing a resin component (A), particles (B) and a solvent (S) on a substrate to form a composite film comprising the resin component (A) and particles (B); , Removing the particles (B) in the composite membrane, and a method comprising a porous membrane obtained by a production method.
  • a second aspect of the present invention is a method for purifying a liquid, comprising filtering a viscous liquid having a viscosity of 0.1 Pa ⁇ s or more with a filter,
  • the filter includes a porous film having a communication hole including a structure in which spherical holes or substantially spherical holes communicate with each other.
  • the third aspect of the present invention is: Coating a varnish containing a resin component (A), particles (B) and a solvent (S) on a substrate to form a composite film comprising the resin component (A) and particles (B); , Removing the particles (B) in the composite membrane, and a method for producing a porous membrane comprising:
  • the viscosity of the varnish is 2.0 Pa ⁇ s or more.
  • a method for purifying a viscous liquid that can favorably reduce the number of bubbles in the viscous liquid, and a method for producing a porous membrane suitably used as a filter in the production method. Can do.
  • a liquid purification method described below is referred to as a “first purification method”.
  • a liquid purification method comprising filtering a viscous liquid having a viscosity of 0.1 Pa ⁇ s or more with a filter, The filter Coating a varnish containing a resin component (A), particles (B) and a solvent (S) on a substrate to form a composite film comprising the resin component (A) and particles (B); , Removing the particles (B) in the composite membrane, and a method comprising a porous membrane obtained by a production method.
  • the viscosity of the viscous liquid is a value measured at 25 ° C. using an E-type viscometer.
  • a viscous liquid having a predetermined viscosity is filtered while reducing the number of bubbles contained in the viscous liquid by using a filter including a porous membrane obtained through the predetermined process.
  • the porous membrane used in the first purification method has pores corresponding to the shape of the particles (B).
  • communication holes in which a large number of holes communicate with each other are formed.
  • the opening on the surface (first main surface) of the porous membrane and the back surface (second main surface opposite to the first main surface) of the porous membrane are provided.
  • Surface is communicated with a communication hole.
  • Such a communication hole functions as a flow path for allowing fluid to flow from the first main surface to the second main surface of the porous membrane when the porous membrane is used as a filter.
  • the inclusion of the characteristic-shaped communication holes in the porous membrane prevents the bubbles from passing through the porous membrane, and the bubbles when the viscous liquid passes through the porous membrane. And the growth of bubbles dissolved in the viscous liquid is prevented, and as a result, the number of bubbles contained in the viscous liquid is reduced by filtering the viscous liquid using the porous membrane as a filter. It is done.
  • the porous membrane also has a function of removing solid minute foreign matters. For this reason, according to the first purification method, not only the number of bubbles in the viscous liquid but also the number of solid foreign substances is reduced.
  • the porous membrane used as the filter preferably has a communication hole including a structure in which spherical holes or substantially spherical holes communicate with each other. That is, it is preferable that substantially the entire inner surface of the pores in the porous membrane in the present invention is a curved surface.
  • a hole having a shape substantially close to a true sphere may be referred to as a “spherical hole”, and a hole having a shape close to a true sphere is referred to as a “substantially spherical hole”. It may be noted.
  • substantially spherical is defined by the sphericity expressed by a value obtained by dividing the major axis of spherical particles or pores by the minor axis.
  • a shape that has a sphericity of 1 ⁇ 0.3 or less and is not a sphere is a substantially spherical shape.
  • the sphericity of the spherical pores or substantially spherical pores contained in the porous membrane used in the first purification method is preferably 0.90 or more and 1.10 or less, more preferably 0.95 or more and 1.05 or less.
  • the Gurley permeability of the porous membrane is preferably, for example, within 1000 seconds, more preferably within 100 seconds, further preferably within 50 seconds, and most preferably within 20 seconds.
  • the lower limit is not particularly set since it is preferably as low as possible. However, for example, 1 second or more is preferable in that the number of bubbles can be easily reduced while maintaining the flow rate of the viscous liquid passing through the porous membrane to a certain degree.
  • the porous membrane used as a filter in the first purification method is Coating a varnish containing a resin component (A), particles (B) and a solvent (S) on a substrate to form a composite film comprising the resin component (A) and particles (B); , It is manufactured by a method including a porous film obtained by a manufacturing method including removing particles (B) in the composite film.
  • the step of forming the composite film is also referred to as “composite film forming step”
  • the step of removing the particles (B) from the composite film is also referred to as “removal step”.
  • a varnish containing a resin component (A), particles (B), and a solvent (S) is applied onto a substrate to form a coating film, and then the solvent (S) is removed from the coating film.
  • grains (B) is removed by removing.
  • the resin component (A) is not particularly limited as long as it has sufficient mechanical strength and chemical resistance for use as a filter.
  • the resin suitably used as the resin component (A) includes at least one resin selected from the group consisting of polyvinylidene fluoride, polyethersulfone, polyamic acid, polyimide, polyamideimide precursor, and polyamideimide. .
  • the resin component (A) contains a polyamic acid or a polyamideimide precursor, imidization treatment is performed on the composite membrane or the porous membrane after removing the particles (B), and polyamide It is preferred to convert the acid or polyamideimide precursor to polyimide or polyamideimide, respectively.
  • these 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 polyethersulfone 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 mass average molecular weight is, for example, from 5,000 to 1,000,000, preferably from 10,000 to 300,000.
  • polyamide acid As the polyamic acid, a product obtained by polymerizing any tetracarboxylic dianhydride and diamine can be used without any particular limitation.
  • the usage-amount of tetracarboxylic dianhydride and diamine is not specifically limited, It is preferable to use 0.50 mol or more and 1.50 mol or less of diamine with respect to 1 mol of tetracarboxylic dianhydrides, and 0.60 mol More preferably, it is used in an amount of 1.30 mol or less, particularly preferably 0.70 mol or more and 1.20 mol or less.
  • 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 about 1 or 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 or more and 6 or less.
  • 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 from ⁇ 10 ° C. to 120 ° C., preferably from 5 ° C. to 30 ° C.
  • the polymerization time varies depending on the raw material composition used.
  • the polymerization time is usually 3 Hr (hour) or more and 24 Hr or less.
  • a polyamic acid may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Polyimide resin The structure and molecular weight of the polyimide resin are not limited, and a known polyimide resin can be used. About a polyimide, you may have a functional group which accelerates
  • a monomer to introduce a flexible bending structure into the main chain in order to obtain a polyimide resin soluble in a solvent, such as ethylenediamine, hexamethylenediamine, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, Aliphatic diamines such as 4,4'-diaminodicyclohexylmethane; 2-methyl-1,4-phenylenediamine, o-tolidine, m-tolidine, 3,3'-dimethoxybenzidine, 4,4'-diaminobenzanilide, etc.
  • a solvent such as ethylenediamine, hexamethylenediamine, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, Aliphatic diamines such as 4,4'-diaminodicyclohexylmethane; 2-methyl-1,4-phenylenediamine
  • 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-hydroxyphenyl) It is effective to use a phenyl) propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride.
  • 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 resin and its monomer may be used alone or in combination of two or more.
  • polyimide resin there is no restriction
  • known methods such as a method of chemically imidizing or heat imidizing polyamic acid can be used.
  • polyimide resins include aliphatic polyimide resins (total aliphatic polyimide resins) and aromatic polyimide resins, and aromatic polyimide resins are preferred.
  • aromatic polyimide resin a polyimide resin obtained by subjecting a polyamic acid having a repeating unit represented by formula (1) to a ring-closing reaction by heat or chemical means, or a polyimide resin having a repeating unit represented by formula (2) Etc.
  • Ar represents an aryl group.
  • the polyamide-imide resin is not limited to its structure and molecular weight, and a known polyamide-imide resin can be used.
  • the polyamide-imide resin may have a condensable functional group such as a carboxy group on 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 resin is usually (i) a resin obtained by reacting a diisocyanate with an acid having a carboxy group and an acid anhydride group in one molecule such as trimellitic anhydride, and (ii) trimellitic anhydride chloride.
  • a resin obtained by imidizing a precursor polymer (polyamideimide resin precursor) obtained by reacting a reactive derivative of the above acid with a diamine can be used without 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.
  • the raw material monomer for the polyamide-imide resin compounds described in general formulas in JP-A-63-283705 and JP-A-2-198619 can also be used in addition to the above.
  • 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 resin 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 chloride; It may be a polymer obtained by imidizing a precursor polymer obtained by reaction with diamine.
  • the “polyamideimide precursor” means a polymer (precursor polymer) before imidization.
  • Each of the polyamideimide resin 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 particles (B) is not particularly limited as long as it is insoluble in the solvent contained in the varnish and can be removed from the composite film composed of the resin component (A) and the particles (B) later. It can be adopted.
  • 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, acrylic resins ( Examples thereof include organic polymer fine particles such as methyl methacrylate, isobutyl methacrylate, polymethyl methacrylate (PMMA), epoxy resin, cellulose, polyvinyl alcohol, polyvinyl butyral, polyester, and polyether.
  • silica such as colloidal silica is preferable as the inorganic material, and acrylic resin, particularly PMMA is preferable as the organic material. It is preferable to use spherical particles made of such a material as the particles (B) because it is easy to form fine pores having a curved surface on the inner surface in the porous membrane.
  • grains (B) may be suitably selected according to the objective from a normal linear polymer or a well-known depolymerizable polymer, for example.
  • a normal linear polymer is a polymer in which polymer molecular chains are randomly cut during thermal decomposition
  • a depolymerizable polymer is a polymer in which the polymer is decomposed into monomers during thermal decomposition. Any of them can be removed from the composite membrane by decomposing into monomers, low molecular weight substances, or CO 2 upon heating.
  • the decomposition temperature of the resin used as the material of the particles (B) is preferably 200 ° C. or higher and 320 ° C. or lower, and more preferably 230 ° C.
  • decomposition temperature is 200 ° C. or higher, film formation can be performed even when a high-boiling solvent is used for the varnish, and there is a wide range of selection of baking conditions when a polyimide resin or a polyamideimide resin is generated by baking. Moreover, if decomposition temperature is 320 degrees C or less, particle
  • the thermal decomposition temperature is low and the handling at the time of pore formation is easy, so a homopolymer of methyl methacrylate or isobutyl methacrylate (polymethyl methacrylate or polyisobutyl methacrylate), or methyl methacrylate
  • a copolymer mainly composed of units derived from isobutyl methacrylate is preferable.
  • the particle diameter (average diameter) of the particles (B) is, for example, preferably 800 nm or more and 3500 nm or less, more preferably 900 nm or more and 3000 nm or less, and particularly preferably more than 2000 nm and 2500 nm or less.
  • the particle size distribution index (d25 / 75) of the particles (B) may be 1 or more and 6 or less, preferably 1.1 or more and 5 or less, and more preferably 1.2 or more and 4 or less.
  • the composite film can be efficiently filled with the particles (B), and therefore, the communication hole that is a flow path for the viscous liquid is formed well.
  • d25 and d75 are values of particle diameters where the cumulative frequency of particle size distribution is 25% and 75%, respectively. In this specification, d25 is the larger particle diameter.
  • the particles (B1) used for the first varnish and the particles (B2) used for the second varnish are the same, May be different.
  • the particle size distribution index of the particles (B1) is preferably equal to or less than the particle size distribution index of the particles (B2).
  • the sphericity of the particles (B1) is preferably equal to or less than the sphericity of the particles (B2).
  • the particle diameter (average diameter) of the particles (B1) is preferably smaller than the particle diameter of the particles (B2). In this case, it is easy to increase the strength of the porous film while making the opening ratio on the surface of the porous film high and uniform.
  • the varnish may further contain a dispersant together with the particles (B) for the purpose of uniform dispersion of the particles (B).
  • the varnish contains a dispersant, the resin component (A) and the particles (B) can be mixed more uniformly. Further, the particles (B) can be uniformly distributed in the coating film formed using the varnish. Can be distributed. As a result, it is possible to form a communication hole that efficiently communicates the front and back surfaces of the porous membrane so as to provide a dense opening on the surface of the finally obtained porous membrane and improve the air permeability of the porous membrane. .
  • the dispersant is not particularly limited, and can be appropriately selected from known dispersants.
  • suitable dispersants include palm fatty acid salt, castor sulfated oil salt, lauryl sulfate salt, polyoxyalkylene allyl phenyl ether sulfate salt, alkylbenzene sulfonic acid, alkylbenzene sulfonate, alkyl diphenyl ether disulfonate, alkyl Anionic surfactants such as naphthalene sulfonate, dialkyl sulfosuccinate, isopropyl phosphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene allyl phenyl ether phosphate; oleylamine acetate, lauryl pyridinium chloride, cetyl pyridinium chloride, lauryl Trimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride And
  • Nonionic surfactants Fatty acid alkyl esters such as octyl stearate and trimethylolpropane tridecanoate; Polyether polyols such as polyoxyalkylene butyl ether, polyoxyalkylene oleyl ether and trimethylolpropane tris (polyoxyalkylene) ether .
  • the dispersant is not limited to these.
  • the said dispersing agent can also be used in mixture of 2 or more types.
  • solvent (S) The type of the solvent (S) is not particularly limited as long as it can dissolve the resin component (A) and does not dissolve the particles (B).
  • examples of the solvent (S) include the solvents exemplified as the solvent used for the reaction between tetracarboxylic dianhydride and diamine.
  • a solvent (S) 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.
  • the solvent includes, in addition to the above nitrogen-containing polar solvent, diphenylsulfone, dimethylsulfone, dimethylsulfoxide, benzophenone, tetrahydrothiophene-1,1-dioxide, 1,3-dimethyl- Examples include polar solvents such as 2-imidazolidinone.
  • the varnish is an antistatic agent, a flame retardant, a chemical imidizing agent, a condensing agent, for the purpose of antistatic, imparting flame retardancy, low temperature baking, imparting releasability, improving coatability, etc.
  • Known components such as a release agent and a surface conditioner may be appropriately included as necessary.
  • the varnish contains the resin component (A), the particles (B), and the solvent (S).
  • the method for producing the varnish is not particularly limited as long as the method can produce a varnish in which the resin component (A) is dissolved in the solvent (S) and the particles (B) are dispersed in the solvent (S).
  • the monomer may be polymerized in the solvent (S) to produce the resin component (A), or the resin component (A) may be dissolved in the solvent (S).
  • the polymerization reaction may be performed in the presence of the particles (B) or in the absence of the particles (B).
  • the viscosity of the varnish is preferably 2.0 Pa ⁇ s or more. This viscosity is a value measured at 25 ° C. using an E-type viscometer.
  • the viscosity of the varnish has some influence on the dispersion state of the particles (B) in the coating film formed using the varnish, and a porous film having communication holes in a shape that can easily remove bubbles is formed. It is guessed.
  • the viscosity of the varnish is more preferably 2.0 Pa ⁇ s or more, and particularly preferably 2.3 Pa ⁇ s or more and 4.9 Pa ⁇ s or less. Further, the viscosity of the varnish is preferably 2.0 Pa ⁇ s or more, more preferably 2.3 Pa ⁇ s or more, and 2.5 Pa or more from the viewpoints of applicability and uniformity of the thickness of the porous film to be formed. -S or more is particularly preferable.
  • the method for adjusting the viscosity of the varnish is not particularly limited, but the content of the resin component (A), the type of the resin component (A), the content of the particles (B), the particle diameter of the particles (B), the solvent (S) It is preferable to adjust by changing at least one of the content and the type of the solvent (S).
  • the solid content concentration of the varnish is preferably 25% by mass or more.
  • the solid content concentration of the varnish is particularly preferably 40% by mass or less.
  • a varnish having a solid content concentration of 25% by mass or more it is particularly easy to form a porous film that easily removes bubbles in a viscous liquid.
  • the solid content concentration of the varnish is 40% by mass or less, it is easy to apply the varnish to the substrate, and it is easy to form a porous film having a uniform film thickness.
  • the ratio V A of the volume V B of particles (B): is V B, 15: 85 ⁇ 40 : 60 is preferred.
  • the resin component (A) and the particles (B) are blended in the varnish at such a ratio, it is easy to disperse the particles (B) uniformly in the varnish while preventing aggregation of the particles (B). It is easy to form a porous film having a uniform opening on the surface.
  • the coating film thickness is, for example, from 1 ⁇ m to 500 ⁇ m, preferably from 5 ⁇ m to 100 ⁇ m, and preferably from 10 ⁇ m to 50 ⁇ m.
  • a release layer may be provided on the substrate as necessary. Further, in the production of the composite film, 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 release layer can be produced by applying a release agent on a substrate and then drying or baking.
  • a known mold release agent such as an ammonium alkylphosphate salt, a fluorine-based resin, or silicone can be used without particular limitation.
  • the release agent remains slightly on the peeled surface of the composite film. Since this remaining mold release agent can affect the wettability of the porous membrane surface and contamination with impurities, it is preferable to remove this.
  • the composite film peeled from the substrate is preferably washed using an organic solvent or the like.
  • the cleaning method can be selected from known methods such as a method of removing the composite membrane after immersing it in a cleaning solution, and a method of spraying a cleaning solution on the composite membrane and performing shower cleaning. Further, the washed composite membrane is dried.
  • a drying method a known method such as air-drying the washed composite membrane at room temperature or heating the composite membrane to an appropriate set temperature in a thermostatic bath can be applied without limitation. At the time of drying, for example, a method can be adopted in which the end of the composite film is fixed to a SUS mold or the like to prevent deformation.
  • the step of forming the release layer and the cleaning process of the unfired composite film can be omitted.
  • the first varnish is applied as it is on a substrate such as a glass substrate, and the temperature is from 0 ° C. to 120 ° C. (preferably 0 ° C. under normal pressure or vacuum).
  • the first composite film is formed by drying at a normal pressure of 10 ° C. or higher and 100 ° C. or lower (more preferably 10 ° C. or higher and 90 ° C. or lower).
  • the film thickness of the first composite film is preferably 1 ⁇ m or more and 5 ⁇ m or less.
  • a second varnish is applied on the first composite film, and similarly, 0 ° C. or higher and 80 ° C. or lower (preferably 0 ° C. or higher and 50 ° C. or lower), more preferably normal pressure of 10 ° C. or higher and 80 ° C. or lower. Drying is performed (more preferably 10 ° C. or more and 30 ° C. or less) to form a second composite film, thereby obtaining a composite film that is a two-layer laminated film.
  • the film thickness of the second composite film is preferably 5 ⁇ m or more and 50 ⁇ m or less.
  • the composite membrane obtained according to the above method is then subjected to a removal step described later.
  • the resin component (A) contains polyamic acid, a polyamideimide precursor, or the like
  • the composite film is fired before removing the fine particles (B), if necessary, and included in the resin component (A).
  • the polyamic acid or the polyamideimide precursor may be converted into a polyimide resin or a polyamideimide resin, respectively.
  • Calcination temperature varies depending on the structure of the polyamic acid or polyamideimide precursor contained in the composite film and the presence or absence of a condensing agent.
  • the firing temperature is usually preferably 120 ° C. or higher and 400 ° C. or lower, more preferably 150 ° C. or higher and 375 ° C. or lower.
  • Calcination does not necessarily have to be clearly separated from the drying process.
  • the temperature is raised from room temperature to 375 ° C. in 3 hours and then held at 375 ° C. for 20 minutes, or from room temperature to 375 ° C. in steps of 50 ° C. (each A stepwise drying-thermal imidization method can be used, such as holding for 20 minutes) and finally holding at 375 ° C. for 20 minutes.
  • a method may be employed in which the end of the unfired composite film is fixed to a SUS mold or the like to prevent deformation.
  • the thickness of the composite film can be obtained by measuring and averaging the thickness of a plurality of locations with a micrometer or the like.
  • the average thickness is preferably thinner, for example, may be 1 ⁇ m or more, preferably 5 ⁇ m or more and 500 ⁇ m or less, and more preferably 8 ⁇ m or more and 100 ⁇ m or less.
  • a porous membrane having micropores By removing the particles (B) from the composite membrane by selecting an appropriate method, a porous membrane having micropores can be produced with good reproducibility.
  • the porous membrane can be obtained by treating the composite membrane with low-concentration hydrogen fluoride water (HF) or the like and dissolving and removing silica from the composite membrane.
  • HF hydrogen fluoride water
  • the particles (B) are resin fine particles
  • the composite film is heated to a temperature not lower than the thermal decomposition temperature of the resin fine particles and lower than the thermal decomposition temperature of the resin component (A). Can be removed and removed from the composite membrane.
  • the porous film obtained after the removal step contains a polyamic acid or a polyamideimide precursor as the resin component (A), an imide ring is generated by ring-closing the polyamic acid or the polyamideimide precursor to the porous film.
  • Examples of such treatment include the above-described firing treatment.
  • Chemical etching may be further performed on the composite film or the porous film formed as described above. By performing chemical etching, the aperture ratio of the porous membrane surface can be increased. In particular, when chemical etching is performed on the porous film, a plurality of holes derived from the particles (B) are communicated well, and a communication hole having a preferable shape is easily formed. It does not specifically limit as a chemical etching method, For example, a conventionally well-known method can be used.
  • 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.
  • examples of inorganic alkaline solutions include hydrazine solutions containing hydrazine hydrate and ethylenediamine, solutions of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia solutions, alkali hydroxides And an etching solution mainly containing hydrazine and 1,3-dimethyl-2-imidazolidinone.
  • 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
  • pure water and alcohols can be selected as appropriate.
  • a solvent to which an appropriate amount of a surfactant is added can also be used.
  • the alkali concentration is, for example, 0.01% by mass or more and 20% by mass or less.
  • the composite film or the porous film formed as described above may be physically removed separately from or together with the chemical etching.
  • the physical removal method include dry etching using plasma (oxygen, argon, etc.), corona discharge, or the like. By this method, the resin component (A) in the porous film is partially removed, and the same curing as the above chemical etching is obtained.
  • the obtained porous film has spherical pores having an average diameter of 800 nm or more and 3500 nm or less (preferably 900 nm or more and 3000 nm or less, more preferably more than 2000 nm and 2500 nm or less).
  • a hole diameter of a portion (communication hole) where spherical holes are connected it is preferable to include a communication hole of 50 nm or more and 2000 nm or less, more preferably 500 nm or more and 1800 nm or less, and a communication hole of more than 1000 nm and 1300 nm or less. It is particularly preferable that it is included.
  • the average pore diameter of the communication holes measured by a porosimeter is preferably 500 nm or more and 2000 nm or less, more preferably 900 nm or more and 1800 nm or less, and further preferably 1000 nm or more and 1500 nm or less.
  • the porosity of the obtained porous film is, for example, 50% or more and 90% or less, and preferably 60% or more and 85% or less.
  • a viscous liquid is a liquid whose viscosity measured at 25 ° C. using an E-type viscometer is 0.1 Pa ⁇ s or more and does not dissolve or deteriorate the filter when contacted for several minutes to 1 hour. If it does not specifically limit.
  • gas is not easily released from the liquid naturally due to the viscosity, and bubbles are present stably.
  • bubbles may be generated in the viscous liquid if a flow that entrains the gas occurs.
  • the viscous liquid is filtered using the porous film formed by the above-described method, the number of bubbles in the viscous liquid can be effectively reduced.
  • the viscosity measured by an E-type viscometer at 25 ° C. is 0.15 Pa ⁇ s or more, preferably 0.7 Pa ⁇ s or more, more preferably 1 Pa ⁇ s or more, and further preferably This is particularly effective for reducing the number of bubbles in a viscous liquid of 1.5 Pa ⁇ s or more.
  • the upper limit of the viscosity of the viscous liquid is not particularly limited as long as it can be filtered by a filter, but is preferably 8.0 Pa ⁇ s or less, and more preferably 7.0 Pa ⁇ s or less. If the viscosity is excessively high, filtration with a filter may be difficult in the first place.
  • the first purification method is preferably used for purification of a liquid curable material used for forming an insulating film, an antireflection film, an adhesive layer, and a hard coat, for example.
  • a liquid curable material used for forming an insulating film, an antireflection film, an adhesive layer, and a hard coat, for example.
  • bubbles are included in such a liquid curable material, defects in appearance occur in the formed insulating film, antireflection film, adhesive layer, hard coat, and the like.
  • the insulating layer, the antireflection film, the adhesive layer, the hard coat, etc. are transparent layers, in the display device or optical device including these layers, bubbles cause unwanted light scattering or refraction, May degrade performance.
  • a photoresist composition is also preferable as an object to be purified by the first purification method. Bubbles in the photoresist composition become defects in the patterned film formed using the photoresist composition. In addition, if bubbles exist in the photoresist composition, when the photoresist composition is applied to the substrate, the bubble portion remains in the coating film, resulting in coating unevenness such as a reduction in the thickness of the portion. Cheap.
  • the composition of the photoresist composition is not particularly limited, and may be a negative type or a positive type.
  • a raw material chemical solution such as a resin solution used for the curable material, the photoresist composition or the like is also preferable.
  • a raw chemical solution having a high concentration and a high viscosity can be purified to effectively reduce the number of bubbles in the liquid.
  • the viscous liquid is filtered using a filter including a porous membrane produced by the method described above.
  • the viscous liquid is transmitted from one side of the filter to the other side. Such permeation is typically performed by creating a differential pressure between one side of the filter and the other side.
  • Examples of the method of using the porous membrane as a filter in the first purification method include a method using a planar porous membrane and a method using a porous membrane processed into a pipe shape. It is preferable that the pipe-like porous membrane has a pleated shape because the contact area between the viscous liquid and the filter increases. As will be described later, the porous membrane is appropriately sealed so that the supply liquid and the filtrate are not mixed.
  • the purification of the viscous liquid can be performed by using the above-described porous membrane without differential pressure, that is, by natural filtration by gravity, but is preferably performed by differential pressure.
  • the method for generating the differential pressure is not particularly limited as long as a pressure difference is provided between one side and the other side of the porous membrane.
  • a method for generating the differential pressure normally, one side of the porous membrane (supply liquid side) is pressurized (positive pressure), and one side of the porous membrane (filtrate side) is negative pressure Reduced pressure (negative pressure) and the like, and pressurization is preferred.
  • Pressurization is the application of pressure to the polyimide resin porous membrane side (supply liquid side) where there is a liquid before passing through the porous film (sometimes referred to as “supply liquid” in this specification). is there.
  • the fluid flow pressure can be generated by an active fluid pressure application method such as a pump (liquid feed pump, circulation pump, etc.).
  • the pump include a rotary pump, a diaphragm pump, a metering pump, a chemical pump, a plunger pump, a bellows pump, a gear pump, a vacuum pump, an air pump, and a liquid pump.
  • the flowing liquid pressure may be, for example, a pressure applied to the porous film by the liquid when the liquid is allowed to permeate the porous film only according to gravity. It is preferable that pressure is applied by the above-described positive fluid pressure application method.
  • the gas used for pressurization is preferably a gas that is inert or non-reactive with respect to the supply liquid, and specifically includes nitrogen or a rare gas such as helium or argon.
  • pressurization is preferred. In that case, the side that collects the liquid that has permeated through the porous membrane may be at atmospheric pressure without decompression.
  • a positive pressure by gas is preferable.
  • the pressurization may be performed via a pressurization valve or a valve such as a pressurization valve or a three-way valve.
  • the reduced pressure is a reduced pressure on the side (filtrate side) collecting the liquid that has passed through the polyimide resin porous membrane.
  • the reduced pressure may be reduced by a pump, for example. It is preferable to reduce the pressure to a vacuum.
  • the pump is usually disposed between the supply liquid tank (or the circulation tank) and the porous membrane.
  • the pressurization may utilize both the flowing liquid pressure and the positive pressure of the gas.
  • the differential pressure may be a combination of pressurization and reduced pressure.
  • the pressurization may use, for example, both the flowing liquid pressure and the reduced pressure, may use both the positive pressure and the reduced pressure of the gas, or uses the flowing liquid pressure and the positive pressure and the reduced pressure of the gas. May be.
  • the combination of the flowing fluid pressure and the positive pressure of the gas and the combination of the flowing fluid pressure and the reduced pressure are preferable from the viewpoint of simplification of production.
  • the pressure difference applied before and after the porous membrane by providing the differential pressure is the thickness, porosity or average pore diameter of the porous membrane to be used, or the desired degree of purification, flow rate, flow rate, or concentration of the supply liquid What is necessary is just to set suitably by a viscosity etc.
  • the differential pressure is preferably 3 MPa or less, for example.
  • the differential pressure is preferably 1 MPa or less, for example. If the differential pressure is excessively high, bubbles may be generated in the viscous liquid during filtration. When the differential pressure is within the above range, it is easy to filter viscous liquid without generating bubbles.
  • the lower limit of the differential pressure is not particularly limited, and is, for example, 10 Pa.
  • the temperature during filtration may be set as appropriate, for example, in the range of 0 ° C. to 30 ° C., preferably 25 ° C.
  • About filtration temperature you may provide a temperature gradient by the time difference of filtration, and you may provide a temperature difference by the supply liquid side and a filtrate side.
  • the porous membrane pre-wet the porous membrane with a liquid different from the viscous liquid before supplying the viscous liquid to the porous membrane.
  • a liquid different from the viscous liquid By pre-wetting, the wettability between the viscous liquid and the porous membrane is improved, the filtration speed of the viscous liquid is expected to be improved, and the effect of reducing bubbles is increased.
  • the liquid used for prewetting include alcohols such as methanol, ethanol, and isopropyl alcohol, or ketones such as acetone and methyl ethyl ketone, and water.
  • the liquid used for pre-wetting may be another organic solvent, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono -N-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol mono Ethyl ether, propylene glycol mono-n-propyl ether, propylene glycol Non-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-n
  • (Poly) alkylene Recall monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate; Lactic acid alkyl esters such as ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ethyl, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutylacetate Tate, 3-methyl-3-methoxybutylpropionate
  • the liquid used for prewetting can be used individually or in combination of 2 or more types.
  • the liquid used for prewetting is preferably a solvent containing one or more of the solvents contained in the viscous liquid, and more preferably the same solvent as the solvent contained in the viscous liquid.
  • the method for contacting the pre-wetting liquid and the porous membrane before allowing the supply liquid to permeate is not particularly limited as long as the pre-wetting liquid and the porous membrane can be brought into contact with each other.
  • a method of impregnating the porous film with the pre-wetting liquid by immersing the porous film in the pre-wetting liquid can be mentioned.
  • the contact between the prewetting liquid and the porous film before allowing the viscous liquid to permeate may be performed by the above-described differential pressure.
  • the range of the differential pressure is, for example, about 1 KPa or more and 0.25 MPa or less.
  • the prewetting may be performed under pressure. When pressurizing, it is preferable to carry out in the range of 0.01 MPa or more and 0.25 MPa or less.
  • the bubbles in the viscous liquid can be removed while preventing the generation of bubbles during the filtration.
  • the porous membrane can be used as, for example, filter media or other filter media.
  • the porous membrane may be used alone or as a filter media and used as another functional layer (membrane). May be given.
  • the porous membrane may be used as a membrane to be combined with other filter media.
  • the porous membrane can be used as a membrane used in a filter device or the like.
  • the functional layer that can be used in combination with the porous membrane is not particularly limited.
  • nylon membrane polytetrafluoroethylene (PTFE) membrane, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA) membrane, or these
  • a film having a chemical or physicochemical function such as a film modified with.
  • the second purification method is a liquid purification method including filtering a viscous liquid having a viscosity of 0.1 Pa ⁇ s or more through a filter,
  • the filter includes a porous membrane having communication holes including a structure in which spherical holes or substantially spherical holes communicate with each other.
  • the method for producing a porous membrane used as a filter in the second purification method is not particularly limited.
  • the porous film including the predetermined structure is manufactured by the method described for the first manufacturing method.
  • the second purification method while the viscous liquid is filtered using a porous membrane having a communication hole including a structure in which spherical holes or substantially spherical holes are connected to each other as a filter, generation of bubbles during filtration is prevented.
  • the number of bubbles in the viscous liquid can be reduced.
  • the viscous liquid to be purified by the second purification method is the same as the method described for the first purification method.
  • the viscous liquid filtration method in the second purification method is also the same as the method described for the first purification method.
  • silica (1) is about 1.5 and silica (2) is 1.6 or more.
  • -Polyamic acid solution Reaction product of pyromellitic dianhydride and 4,4'-diaminodiphenyl ether (organic solvent: N, N-dimethylacetamide) Organic solvent (1): N, N-dimethylacetamide (DMAc) Organic solvent (2): gamma butyrolactone Dispersant: polyoxyethylene secondary alkyl ether dispersant Dispersion: silica (1): silica with an average particle diameter of 2500 nm Silica (2): silica etching with an average particle diameter of 3500 nm Liquid: Tetramethylammonium hydroxide (TMAH) 5 mass% solution in a mixed solution of isopropyl alcohol: water (mass ratio 6: 4)
  • TMAH Tetramethylammonium hydroxide
  • the volume ratio of the polyamic acid and silica in the obtained varnish is 40:60 (mass ratio is 30:70), and solid content concentration (concentration of polyamic acid and silica) is 33 mass%.
  • the viscosity was 4.0 Pa ⁇ s.
  • the unfired composite film is peeled from the substrate to obtain an unfired composite film, and subjected to heat treatment (firing) at 400 ° C. for 15 minutes.
  • heat treatment firing
  • imidization was performed to obtain a polyimide-fine particle composite film.
  • the obtained polyimide-fine particle composite film was immersed in a 20% HF solution to remove fine particles contained in the film, and then washed with water and dried to obtain a polyimide porous film. Further, the opening diameter and the communication holes on the surface of the polyimide porous membrane were expanded using an etching solution, washed with water and dried, and then heat-treated again at 350 ° C. for 15 minutes.
  • a polyimide porous membrane 1 having a film thickness of about 40 ⁇ m, an air permeability of 20 seconds or less, a porosity of about 70%, and an average pore diameter of 2500 nm was obtained.
  • the average diameter of the communication holes confirmed by the porosimeter was 1000 nm.
  • Example 2 A polyimide porous membrane 2 was obtained in the same manner as in Example 1 except that silica (2) was used instead of silica (1).
  • the final varnish viscosity was 4.1 Pa ⁇ s.
  • the polyimide porous membrane 2 had a thickness of about 40 ⁇ m, an air permeability of 20 seconds or less, a porosity of about 70%, and an average pore diameter of 3500 nm.
  • the polyimide porous membrane 2 had a communication hole exceeding 1000 nm.
  • Example 1 A varnish was prepared in the same manner as in Example 1 except that the final varnish viscosity was adjusted to about 1.5 Pa ⁇ s.
  • the varnish of Comparative Example 1 since a sea island was generated after pre-baking, a polyimide porous film could not be formed.
  • Example 3 Using a filter device provided with the polyimide porous membrane 1 obtained in Example 1 as a filter, at room temperature and under the conditions shown in Table 1, the resist composition for the plating process (viscosity (25 ° C., E-type viscometer ): 3.9 Pa ⁇ s, manufactured by Tokyo Ohka Kogyo Co., Ltd., containing propylene glycol monomethyl ether acetate (PGMEA)).
  • the resist composition for the plating process viscosity (25 ° C., E-type viscometer ): 3.9 Pa ⁇ s, manufactured by Tokyo Ohka Kogyo Co., Ltd., containing propylene glycol monomethyl ether acetate (PGMEA)
  • PGMEA propylene glycol monomethyl ether acetate
  • a filter device comprising a filter.
  • Discharge solution piping connecting the discharge port of the filter device and the resist solution tank.
  • a three-way valve for sampling provided in the middle of the discharge liquid piping. Filtration conditions are as described in Table 1. Before starting filtration, the filter was pre-wet by passing about 4 L of PGMEA through the filter under a pressure of 0.02 MPa.
  • Sample 1 and sample 2 were evaluated for reduction of the number of foreign substances and reduction of the number of bubbles according to the following method.
  • the coating film was pre-baked at 140 ° C. for 300 seconds, and a film having a thickness of about 38 ⁇ m was observed with NSX-220 (manufactured by Rudolf). The number of foreign matters and the number of bubbles per unit area were counted. The same evaluation was performed on the resist composition before filtration.
  • Example 2 The resist composition was filtered in the same manner as in Example 3 except that the filter was changed to a filter made of PTFE fibers having an average pore diameter of 1 ⁇ m (1000 nm) and the filtration conditions were changed to the conditions shown in Table 1. Processed. When the number of bubbles in the resist composition obtained after filtration was confirmed by the same method as in Example 3, it was confirmed that Sample 1 and Sample 2 were reduced in the number of foreign substances. However, in sample 1, a reduction in the number of bubbles from the resist composition before filtration could not be confirmed, and in sample 2, the number of bubbles increased to about 100 times the number of bubbles before filtration.
  • Example 4 Using a filter device provided with the polyimide porous membrane 1 obtained in Example 1 as a filter, at room temperature and under the conditions shown in Table 2, a resist composition (viscosity (25 ° C., E-type viscometer) ): 1.0 Pa ⁇ s, Tokyo Ohka Kogyo Co., Ltd., containing propylene glycol monomethyl ether acetate (PGMEA) and 3-methoxybutyl acetate (MA)) was filtered. As a test apparatus, an apparatus having the following configurations 1) to 6) was used. 1) Resist solution tank. 2) A liquid supply pipe connecting the resist liquid tank and the liquid supply port of the filter device.
  • a resist composition viscosity (25 ° C., E-type viscometer)
  • PMEA propylene glycol monomethyl ether acetate
  • MA 3-methoxybutyl acetate
  • a liquid supply pump provided in the middle of the liquid supply pipe for supplying liquid to the filter while generating a differential pressure (filtration pressure).
  • a filter device comprising a filter.
  • Discharge solution piping connecting the discharge port of the filter device and the resist solution tank.
  • a three-way valve for sampling provided in the middle of the discharge liquid piping. Filtration conditions are as described in Table 2.
  • the resist composition 12L was supplied to the filter device while circulating a part of the resist composition through a circulation system including a resist solution tank, a solution supply pipe, a filter device, and a discharge liquid pipe.
  • a 100 mL sample of the filtrate at the time of 12 L supply was collected from the three-way valve. This sample was designated as sample 3.
  • Sample 3 was evaluated for the reduction in the number of foreign substances and the reduction in the number of bubbles in the same manner as in Example 3.
  • the number of foreign matters and the number of bubbles were evaluated in the same manner as in Example 3.
  • a decrease in the number of foreign matters was observed in Sample 3.
  • the number of bubbles in sample 3 was reduced to about 6% of the number of bubbles in the resist composition before filtration, and the number of foreign matters was reduced to about 2% of the number of bubbles in the resist composition before filtration.
  • Example 3 Evaluation was performed in the same manner as in Example 4 except that the filter in the test apparatus was changed to PTFE nonwoven fabric. Unlike Example 3, the number of bubbles in the sample was not reduced (about 80% of the number of bubbles in the resist composition before filtration remained), and the number of foreign matters was also about 41% of the number of foreign matters in the resist composition before filtration. It was only reduced to.

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  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
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