WO2016056480A1 - ポリイミド溶液、耐熱性不織布およびその製造方法 - Google Patents
ポリイミド溶液、耐熱性不織布およびその製造方法 Download PDFInfo
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- WO2016056480A1 WO2016056480A1 PCT/JP2015/078028 JP2015078028W WO2016056480A1 WO 2016056480 A1 WO2016056480 A1 WO 2016056480A1 JP 2015078028 W JP2015078028 W JP 2015078028W WO 2016056480 A1 WO2016056480 A1 WO 2016056480A1
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- polyimide solution
- nonwoven fabric
- polyimide
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- 0 CC(C)(N*=C)N*=C Chemical compound CC(C)(N*=C)N*=C 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N c1ccccc1 Chemical compound c1ccccc1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- 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 is used for base materials of low dielectric constant substrates, sound absorbing materials such as aircraft, electromagnetic wave shielding materials, separation filters, heat-resistant bag filters, electrodes and separators of lithium ion secondary batteries, electrodes and separators of electric double layer capacitors, etc.
- the present invention relates to a heat-resistant non-woven fabric and a method for producing the same. More specifically, the present invention relates to a nonwoven fabric that is not easily affected by humidity during yarn production and has excellent heat resistance, and a method for producing the same.
- heat-resistant materials having voids are required.
- a heat-resistant nonwoven fabric that can withstand the solder process as a base material of such a material is one of the promising candidates.
- heat-resistant non-woven fabrics are attracting attention as materials having excellent ion permeability and high mechanical strength and heat resistance by metal plating.
- Specific applications include lightweight and excellent electromagnetic shielding materials, electrode materials for light and high capacity lithium ion secondary batteries and electric double layer capacitors, and heat-resistant bag filters that remove dust from combustion gases emitted from factories, etc. And separators for gas separation membranes, water separation membranes, lithium ion secondary batteries and electric double layer capacitors.
- Patent Document 1 discloses a polyimide composition having a specific structure suitable for an electrospinning method (ESP method) and a method for producing a nonwoven fabric for a bag filter used at a high temperature.
- ESP method electrospinning method
- Patent Document 2 a polyimide solution is obtained by discharging a polyimide solution from a nozzle and applying a high-speed air flow intersecting with the nozzle, and applied to a heat-resistant bag filter, a heat-absorbing sound-absorbing material, heat-resistant clothing, and the like. It is disclosed.
- Patent Document 3 discloses a separator for a lithium ion secondary battery using a resin solution obtained by reacting a polyamic acid and an alkoxysilane partial condensate containing an epoxy group.
- Patent Document 4 discloses a separator obtained by applying a highly branched polymer to a porous structure material such as a nonwoven fabric.
- Patent Document 5 discloses a non-woven fabric made of polyimide short fibers by beating a foam using a polyimide having a specific structure.
- Patent Document 6 discloses a separator having a high insulating property while increasing the liquid absorption rate by using a separator in which a porous film and a nonwoven fabric are laminated on a lithium ion secondary battery.
- Patent Document 7 describes a thin and tough material suitable for the production of capacitors with high energy density and low internal resistance using aliphatic polyketone non-woven fabrics, with heat resistance, dimensional stability, electrical insulation, chemical resistance, and low water absorption.
- Patent Document 8 discloses a high-performance oleophobic polyimide film obtained by electrospinning a polyimide fiber having a diameter of 10 nm to 50 ⁇ m to form a nonwoven fabric composed of a plurality of polyimide fibers and treating the nonwoven fabric with a perfluoropolymer.
- Patent Document 9 discloses that an electrospinning method can be obtained by using a polyimide solution having a specific structure of nano-sized fine fibers.
- Patent Document 10 discloses that heat resistance and solubility are both achieved by using an assembly including polyimide fibers for a lithium ion battery separator, a bag filter, and a fuel exhaust gas filter.
- Patent Document 11 discloses that a decrease in capacity of a lithium ion battery can be suppressed by using polyamideimide, polyamide, or polyimide for a separator including an organic fiber layer produced by an electrospinning method (ESP method).
- ESP method electrospinning method
- JP 2011-132611 A (Claims) JP 2011-9769 A (Claims) International Publication No. 2009/054349 (Claims) JP 2012-134145 A (Claims) International Publication No. 2011-074641 JP 2011-210680 A JP 2006-351733 A JP 2013-217008 A JP 2011-132651 A Japanese Patent Laid-Open No. 2015-74866 JP 2014-41817 A
- the polyimides disclosed in Patent Documents 1 and 10 have a problem that the water absorption is high and the swelling due to the electrolytic solution or water is large, so that the opening size of the obtained nonwoven fabric is easily changed.
- the spinning method disclosed in Patent Document 3 requires a high-temperature air flow to be constantly applied to the yarn, which increases energy consumption.
- clogging is likely to occur when the temperature of the base increases and the solvent evaporates.
- the present invention does not require a high-temperature ring-closing step to obtain a heat-resistant polyimide nonwoven fabric, and is not easily affected by atmospheric humidity during yarn production by the electrospinning method. It aims at providing the polyimide resin composition which can be obtained, a heat resistant nonwoven fabric using the same, and its manufacturing method.
- the present invention (A) a resin containing the structural unit represented by the general formula (1) at 50% mol or more of the whole resin, and (b) a polyimide solution containing a solvent.
- R 1 and R 2 each independently represents an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a cyano group, or a nitro group
- Z represents a hydroxyl group or a carboxyl group
- Y represents a carbon number.
- 4 represents a tetravalent organic group of 4 to 30.
- X is a structure represented by the following structure, and p, q, r, and s are integers of 0 to 4, provided that p + q> 1 N represents an integer of 0 to 4.
- R 3 and R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group, or a phenyl group
- R 5 to R 11 Represents an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group, or a phenyl group, all of which may be the same or different
- t is an integer of 0 to 3.
- the present invention is a nonwoven fabric formed using the polyimide solution of the present invention. Moreover, this invention is a manufacturing method of the nonwoven fabric which spins a polyimide on a board
- a polyimide having a water-soluble substituent can be obtained although the hygroscopicity of the polyimide itself is low. Therefore, even if the amount of water in the polyimide solution increases, it is possible to obtain a polyimide solution in which the solubility of the polyimide in the polyimide solution is not lowered and the solution is not whitened.
- this polyimide solution it is possible to form a yarn having a stable shape even if the temperature and humidity at the time of yarn production change somewhat. As a result, it is not necessary to put the apparatus in a booth where large-scale temperature / humidity management is possible, and the desired nonwoven fabric can be obtained.
- the polyimide solution of the present invention is a polyimide solution containing a resin containing the structural unit represented by the general formula (1) in an amount of 50 mol% or more of the total resin and (b) a solvent.
- the polyimide structure it is essential that the structure be soluble in a solvent, and the relative dielectric constant is preferably 3.2 or more from the viewpoint of forming a yarn having a stable shape.
- the nonwoven fabric of the present invention is obtained by spinning a polyimide solution by an electrospinning method.
- the structure represented by the general formula (1) is a structural unit of polyimide.
- the structural unit represented by the general formula (1) contains highly polar components such as a sulfone group, a ketone group, and a hydroxyl group, and even if water is mixed in the solvent of the polyimide solution, the polyimide is difficult to precipitate from the solvent. Has characteristics. In addition, it increases the solubility in aprotic organic solvents such as N-methylpyrrolidone and dimethylacetamide.
- aprotic organic solvents such as N-methylpyrrolidone and dimethylacetamide.
- the electrospinning method is particularly suitable for obtaining a thin yarn having a diameter of ⁇ m or less.
- the humidity of the atmosphere in which a voltage is applied to the polyimide solution to be blown is high, water enters the polyimide solution. As a result, the polyimide is precipitated from the polyimide solution on the way, and a white brittle film-like solid is generated. In order to suppress this, it has been generally necessary to control the humidity of the atmosphere in which electrospinning is performed.
- the polyimide used in the polyimide solution of the present invention is less likely to be whitened due to the highly polar component introduced into the polyimide even when moisture enters the solvent.
- X is any structure represented by the structure shown below
- Z represents a hydroxyl group or a carboxyl group
- p and q are 0 to It is an integer of 4. From the viewpoint of forming a stable finely shaped yarn, p + q> 1 due to the introduction of a hydroxyl group or a carboxyl group that contributes to an increase in dielectric constant.
- R 3 and R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group, or a phenyl group. From the viewpoint of suppressing moisture absorption of the resulting polyimide solution and forming a more stable fine-shaped yarn, R 3 and R 4 are preferably an alkyl group having 1 to 4 carbon atoms or a fluoroalkyl group, and preferably an isopropyl group or hexafluoride group. An isopropyl group is more preferable.
- R 5 to R 11 represent an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group, or a phenyl group, and may be all the same or different.
- t is an integer of 0 to 3.
- diamine having a hydroxyl group or a carboxyl group examples include 2,2-bis (aminohydroxyphenyl) hexafluoropropane and bis (aminohydroxyphenyl) fluorene.
- preferred diamines include 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, and 4,4'-diamino. Examples thereof include diphenyl sulfone, 3,4'-diaminodiphenyl ketone, 3,3'-diaminodiphenyl ketone, and 4,4'-diaminodiphenyl ketone.
- the structure represented by the general formula (1) in the present invention is a structure in which an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a cyano group, or a nitro group represented by R 1 and R 2 is bonded to a benzene ring.
- R 1 and R 2 each have at least one methyl group, ethyl group, propyl group, butyl group, trifluoromethyl group, pentafluoroethyl group, perfluoropropyl group, or perfluorobutyl group bonded to the benzene ring. It preferably includes a structure.
- Examples include diaminotoluene, diaminotrifluoromethylbenzene, diaminoxylene, bis (trifluoromethyl) diaminobiphenyl, diaminodimethylbiphenyl, bis (trifluoromethyl) diaminobiphenyl, diaminodiethylbiphenyl, bis (tripentafluoro And ethyl) diaminobiphenyl.
- hydrogen atoms added to an aromatic ring contained in 2,2-bis (aminohydroxyphenyl) hexafluoropropane, bis (aminohydroxyphenyl) fluorene, etc. are represented by R 1 and R 2.
- the structure represented by (a) general formula (1) in the present invention is a structural unit of polyimide.
- Polyimide can be obtained by reacting diamine and tetracarboxylic acid.
- tetracarboxylic dianhydride in particular, in order to facilitate the reaction, it is preferable to react tetracarboxylic dianhydride with diamine. It can also be obtained by reacting a tetracarboxylic acid dichloride or diester with a diamine.
- the tetracarboxylic acid residue corresponds to a moiety represented by Y, and Y represents a tetravalent organic group having 4 to 30 carbon atoms.
- the tetracarboxylic acid residue represented by Y is benzene, cyclobutane, cycloheptane, cyclohexane, naphthalene, biphenyl, terphenyl, diphenyl ether, triphenyl ether, diphenylmethane, or diphenylhexafluoropropane, diphenylsulfone, diphenylketone. It preferably contains an organic group.
- tetracarboxylic acids containing such a structure include pyromellitic acid, naphthalenetetracarboxylic acid, biphenyltetracarboxylic acid, terphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, triphenylethertetracarboxylic acid, diphenylmethanetetracarboxylic acid, Aromatic tetracarboxylic acids such as diphenylhexafluoropropanetetracarboxylic acid, diphenylsulfonetetracarboxylic acid, diphenylketonetetracarboxylic acid, monocyclic tetramers such as cyclobutanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid Examples thereof include carboxylic acid.
- perfluoropentanetetracarboxylic acid bis (trifluoromethyl) pyromellitic acid, bis (perfluoroethyl) pyromellitic acid, cyclopropanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclooctanetetracarboxylic acid, Bicyclic [2] having a monocyclic tetracarboxylic acid such as cyclononanetetracarboxylic acid, cyclodecanetetracarboxylic acid, cycloundecanetetracarboxylic acid, cyclododecanetetracarboxylic acid, aromatic benzophenonetetracarboxylic acid, condensed ring structure .2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid, pentacyclo [8.2.1.1 4,7 0 2,9.
- tricarboxylic acid such as trimellitic acid, terephthalic acid, isophthalic acid, maleic acid, succinic acid, adipic acid, pentanedicarboxylic acid, decanedicarboxylic acid and other dicarboxylic acids such as 50 mol of acid component are used. % Or less can be copolymerized.
- tetracarboxylic acid residue represented by Y include diphenylsulfonetetracarboxylic acid and diphenylketone having a large proportion of polar groups contributing to high dielectric constant. Tetracarboxylic acid. Further, it is more preferable that these residues are 40 mol% or more of Y.
- Y is a residue of diphenylsulfone tetracarboxylic acid and / or diphenyl ketone tetracarboxylic acid, and at the same time 5 to 50 mol% of Y is pyromellitic acid. Most preferred are residues of When the above residues are not included in this range, thread formation tends to become unstable.
- the resin used in the present invention is a solution in the form of a polyamic acid or polyamic acid ester which is a polyimide precursor, it is necessary to heat and close the ring after electrospinning to form a polyimide, so it is desirable to use polyimide.
- the component (a) used in the present invention may contain a polyimide precursor structure as long as it contains 50 mol% or more of the structural unit of polyimide represented by the general formula (1) in the whole resin.
- the polyimide solution of the present invention is a polyimide solution that contains a resin represented by the general formula (2) and (b) a solvent and is used for forming a nonwoven fabric.
- R 12 represents a diamine residue.
- R 12 is a divalent organic group having at least 2 carbon atoms, and among them, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferable.
- diamines include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl ketone, 3,3′-diaminodiphenyl ketone, 4,4′-diaminodiphenyl ketone, 3,4′- Diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, benzidine, m-phenylenediamine, p-phenylenediamine,
- preferred specific examples include 9,9-bis (aminohydroxyphenyl) fluorene and 2,2-bis (aminohydroxyphenyl), which have a large proportion of polar groups contributing to high dielectric constant.
- R 13 represents an acid dianhydride residue.
- R 13 is a tetravalent organic group having at least 2 carbon atoms, and among them, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferable.
- the acid dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic Acid dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3 ′ -Benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1
- Bonn dianhydride, butane tetracarboxylic dianhydride, and the like aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-cyclopentane tetracarboxylic dianhydride. Two or more of these may be used.
- preferred specific examples include pyromellitic dianhydride and 3,3 ′, 4,4′-benzophenonetetracarboxylic acid having a large proportion of polar groups contributing to high dielectric constant. Examples thereof include dianhydrides, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, and the like.
- the polyimide precursor and polyimide used in the present invention can be obtained by reacting an acid anhydride and a diamine in a generally known aprotic solvent such as N-methylpyrrolidone or dimethylacetamide.
- aprotic solvent such as N-methylpyrrolidone or dimethylacetamide.
- polyamic acid is obtained at 60 ° C. or lower
- polyimide is obtained at a temperature higher than 60 ° C.
- an acid anhydride and an alcohol are reacted in the presence of a catalyst such as pyridine or triethylamine, and then the dicarboxylic acid is acid chloride with sulfonyl chloride, succinic chloride, thionyl chloride or the like.
- a condensing agent such as dicyclohexylcarbodiimide.
- the organic solvent used as the reaction solvent can be used as long as it is a solvent in which the polyimide of the present invention is dissolved.
- aprotic polar solvents are preferred.
- diphenyl sulfone, dimethyl sulfoxide, sulfolane, dimethyl sulfone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, diethyl sulfone, diethyl sulfoxide, 1,4-dimethylbenzazolidinone examples include hexamethyltriamide and 1,3-dimethylimidazolidinone.
- high boiling ketone solvents such as cyclohexanone, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol methyl ethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene
- glycol solvents such as glycol methyl ethyl ether and dipropylene glycol diethyl ether, and aromatic hydrocarbon solvents such as toluene and xylene, and ester solvents such as propylene glycol monomethyl ether acetate and methyl-methoxybutanol acetate. You can also.
- the amount of the solvent used in the polycondensation is preferably 50 parts by weight or more and more preferably 200 parts by weight or more with respect to 100 parts by weight of the total monomers.
- an operation such as stirring becomes easy and the polycondensation reaction easily proceeds smoothly.
- 2000 parts by weight or less is preferable, and 800 parts by weight or less is more preferable.
- the solvent used as the reaction solvent for the resin can be used as it is as the solvent for the polyimide solution.
- the weight average molecular weight of the resin in the present invention is preferably in the range of 5,000 to 100,000, particularly preferably in the range of 10,000 to 100,000.
- the weight average molecular weight in the present invention by gel permeation chromatography (GPC) method, measuring the molecular weight of the polyimide resin using the solvent was added lithium chloride concentration of 1M in a mixed solvent of NMP / H 3 PO 4 And a value calculated using a calibration curve of standard polystyrene.
- a surfactant can be added to the polyimide solution of the present invention. It is also possible to add a photodegradable diazonaphthoquinone compound, a coumarin compound in order to improve the decomposability, a silane coupling agent, a titanium chelate, an aluminum chelate or the like in order to improve the adhesiveness. Furthermore, a bifunctional or higher functional epoxy compound, an oxetane compound, a methylol compound, an alkoxymethylol compound, or the like, which is a crosslinkable compound, can be added for the purpose of improving chemical resistance. Also, fine particles such as silica can be added to increase the hardness. These additive components can be added from 1 ppm to about 30% by weight with respect to the polyimide component.
- the non-woven fabric formed using the polyimide solution of the present invention will be described.
- the nonwoven fabric manufactured using the polyimide solution of the present invention is manufactured by an electrospinning method.
- the electrospinning method is a method in which a high voltage is applied to a polyimide solution to collect charges in the droplets at the tip of the nozzle, the droplets repel each other and spread, and the solution flow is stretched to perform spinning. .
- This method it is possible to obtain a thin yarn. Therefore, according to the electrospinning method, a thin yarn having a diameter of several tens nm to several ⁇ m can be obtained, and as a result, a thin nonwoven fabric having a thickness of 10 ⁇ m can be formed.
- this nonwoven fabric is spun from a polyimide solution that has already been imidized, no heat treatment for imidization is required after spinning, and a nonwoven fabric excellent in heat resistance and mechanical properties can be obtained very simply. .
- the polyimide solution of the present invention is characterized by containing a highly polar sulfone group, ketone group, hydroxyl group or carboxyl group. Therefore, even if water is mixed in the solvent of the polyimide solution, the solubility of the polyimide itself can be kept high, so that the polyimide hardly deposits from the solvent. Therefore, until now, when the electrospinning process was performed in a high humidity atmosphere, water entered the polyimide solution, and the polymer precipitated in the polyimide solution during the spinning process, resulting in a white brittle film-like solid. There was a problem that occurred.
- the nonwoven fabric can be stably obtained in a simple booth without having to put the electrospinning apparatus in a booth capable of managing temperature and humidity at a large scale.
- the highly polar polyimide structure since the highly polar polyimide structure has a strong intermolecular force of the polymer, it exhibits a high glass transition point in the solvent removal state after electrospinning. From the viewpoint of application to a heat resistant nonwoven fabric, the glass transition point is preferably 200 ° C. or higher. If it is lower than this, the structure of the non-woven fabric is modified by heat softening, so that there is a possibility that the performance will deteriorate due to changes over time.
- the non-woven fabric of the present invention can be used as a high-order processed product for a heat-resistant bag filter, an electromagnetic shielding material, a core material for a low dielectric constant substrate, a gas separation membrane, a battery or capacitor electrode, a separator, a heat insulating sound absorbing material, or the like.
- batteries and electric double layer capacitors using the nonwoven fabric of the present invention as a separator have a high heat resistance and a small thickness. Therefore, the porosity is increased, and a battery and a capacitor excellent in short-time charging and discharging characteristics can be obtained.
- the polyimide solution was spin-coated on a 6-inch silicon wafer so that the film thickness after drying at 120 ° C. for 4 minutes was about 15 ⁇ m. After spin coating, 120 minutes at 120 ° C., dried on a hot plate attached to a coating and developing apparatus SCW-636 manufactured by Dainippon Screen, and then used for 1 hour at 300 ° C. using an inert oven INH-9CD manufactured by Koyo Thermo Systems Heat treatment was performed to obtain a polyimide film.
- the wafer on which this film was formed was immersed in a 45% aqueous hydrofluoric acid solution at room temperature for 3 minutes, washed with deionized water for 10 minutes, and peeled off from the wafer.
- the film was weighed and then dried at 200 ° C. for 1 hour to determine the absolute dry weight.
- the water absorption was determined from the weight at the time of water absorption and the absolute dry weight using the following formula.
- Water absorption rate (water absorption weight ⁇ absolute dry weight) / absolute dry weight ⁇ 100 (%). ⁇ Measurement of relative permittivity>
- a polyimide solution was spin-coated on an aluminum substrate.
- the wafer on which this film was formed was immersed in a 45% aqueous hydrofluoric acid solution at room temperature for 3 minutes, washed with deionized water for 10 minutes, and peeled off from the wafer.
- the membrane was dried at 120 ° C. for 2 hours, dehydrated, and cut into a weight of 5 mg to obtain a sample.
- This sample was heated from room temperature to 400 ° C. using a DSC-50 manufactured by Shimadzu Corporation at a heating rate of 10 ° C./min, and the glass transition point was measured.
- Example 1 In a 500 mL three-necked flask equipped with a nitrogen inlet tube, a stir bar, and a thermometer, 3.66 g (0.01 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane under a dry nitrogen stream AZ Materials), 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl 3.20 g (0.01 mol, manufactured by Wakayama Seika) was added to N-methyl-2-pyrrolidone (NMP). , Manufactured by Mitsubishi Chemical Co., Ltd.) and 30 g of toluene (manufactured by Tokyo Chemical Industry) at 40 ° C. or lower.
- NMP N-methyl-2-pyrrolidone
- the resin solution thus obtained was filtered through a 2 ⁇ m polytetrafluoroethylene membrane filter to obtain a polyimide solution.
- this polyimide solution was spin-coated on a 4-inch silicon wafer in an atmosphere of room temperature and 50% humidity, the solution did not whiten even if left for 120 seconds after coating.
- the water absorption was 1.9%, the relative dielectric constant was 2.9, and the glass transition point was 170 ° C.
- Example 2 22.8 g of bis (3-amino-4-hydroxyphenyl) fluorene (0.06 mol, manufactured by AZ Materials) in a 500 mL three-necked flask equipped with a nitrogen inlet tube, a stir bar, and a thermometer under a dry nitrogen stream Then, it was dissolved in 2.88 g of 2,4-diaminotoluene (0.04 mol, manufactured by Tokyo Chemical Industry) NMP235 g and 10 g of toluene (produced by Tokyo Chemical Industry) at 40 ° C. or lower.
- the resin solution thus obtained was filtered through a 2 ⁇ m polytetrafluoroethylene membrane filter to obtain a polyimide solution.
- this polyimide solution was spin-coated on a 4-inch silicon wafer in an atmosphere of room temperature and 50% humidity, the solution did not whiten even if left for 120 seconds after coating.
- the water absorption was 1.5%
- the relative dielectric constant was 3.2
- the glass transition point was 200 ° C.
- Example 3 In a 500 mL three-necked flask equipped with a nitrogen inlet tube, a stir bar, and a thermometer, 11.5 g of 2,2-bis (3-carboxyl-4-aminophenyl) methane (made by Wakayama Seika, 0 .05 mol), 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl 12.8 g (manufactured by Wakayama Seika, 0.04 mol), 1,3-bis (3-aminopropyl) 2.48 g of tetramethyldisiloxane (manufactured by Shin-Etsu Chemical Co., 0.01 mol) was dissolved in 240 g of NMP at 40 ° C.
- the resin solution thus obtained was filtered through a 2 ⁇ m polytetrafluoroethylene membrane filter to obtain a polyimide solution.
- this polyimide solution was spin-coated on a 4-inch silicon wafer in an atmosphere of room temperature and 50% humidity, the solution did not whiten even if left for 120 seconds after coating.
- the water absorption was 2.5%
- the relative dielectric constant was 3.0
- the glass transition point was 180 ° C.
- Example 4 25.0 g of bis (3-amino-4-hydroxyphenyl) sulfone (0.1 mol, manufactured by AZ Materials) in a 500 mL three-necked flask equipped with a nitrogen introduction tube, a stirring rod, and a thermometer under a dry nitrogen stream was dissolved in 10 g of NMP 230 g toluene at 40 ° C.
- pyromellitic dianhydride 10.9 g (0.05 mol, manufactured by Daicel Chemical Industries), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride 17.9 g (0.05 mol, New Nippon Rika Co., Ltd.) is added and stirred at 40 ° C for 2 hours, then the temperature of the solution is raised to 180 ° C and further stirred for 4 hours to carry out the reaction while removing distilled toluene and water. It was. The resin solution thus obtained was filtered through a 2 ⁇ m polytetrafluoroethylene membrane filter to obtain a polyimide solution.
- Example 5 In a 500 mL three-necked flask equipped with a nitrogen introduction tube, a stirring rod, and a thermometer, 14.9 g of bis (3-amino-4-hydroxyphenyl) cyclohexane (0.05 mol, manufactured by Tokyo Chemical Industry) under a dry nitrogen stream, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl 12.8 g (0.04 mol, manufactured by Wakayama Seika), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 2 .48 g (0.01 mol, manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 205 g of NMP at 40 ° C.
- the resin solution thus obtained was filtered through a 2 ⁇ m polytetrafluoroethylene membrane filter to obtain a polyimide solution.
- this polyimide solution was spin-coated on a 4-inch silicon wafer in an atmosphere of room temperature and 50% humidity, the solution did not whiten even if left for 120 seconds after coating.
- the water absorption was 1.4%
- the relative dielectric constant was 2.9
- the glass transition point was 190 ° C.
- the resin solution thus obtained was filtered through a 2 ⁇ m polytetrafluoroethylene membrane filter to obtain a polyimide solution.
- this polyimide solution was spin-coated on a 4-inch silicon wafer in an atmosphere of room temperature and 50% humidity, the solution did not whiten even if left for 120 seconds after coating.
- Comparative Example 1 In a 500 mL three-necked flask equipped with a nitrogen inlet tube, a stirring rod, and a thermometer, 2.8 g (0.05 mol, manufactured by Wakayama Seika), 2,2 ′ under a dry nitrogen stream -Bis (trifluoromethyl) -4,4'-diaminobiphenyl 1.60 g (0.05 mol, manufactured by Wakayama Seika) was dissolved in 40 g of NMP 40 g toluene (manufactured by Tokyo Chemical Industry Co., Ltd.) at 40 ° C.
- NMP 40 g toluene manufactured by Tokyo Chemical Industry Co., Ltd.
- the resin solution thus obtained was filtered through a 2 ⁇ m polytetrafluoroethylene membrane filter to obtain a polyimide solution.
- this polyimide solution was spin-coated on a 4-inch silicon wafer in an atmosphere of room temperature and 50% humidity, the entire coating film was whitened due to moisture absorption in 30 seconds after coating.
- the water absorption was 1.0%, the relative dielectric constant was 2.6, and the glass transition point was 170 ° C.
- Example 7 The polyimide solution obtained in Example 1 was diluted to a concentration of 12%, and the inner diameter of the nozzle was 0.84 mm on an earthed aluminum foil using an electrospray coater in an environment of a temperature of 24 ° C. and a humidity of 50% ( Using the needle of G18), the distance between the nozzle and the aluminum foil was 250 mm, and the solution was fed at a total liquid volume of 20 ⁇ L / min and applied at a voltage of 15 kV. As a result, a polyimide nonwoven fabric was obtained on the aluminum foil.
- Comparative Example 2 A polyimide nonwoven fabric was prepared from the polyimide solution obtained in Comparative Example 1 in the same manner as in Example 7. However, moisture absorption occurred, a white fragile film was formed, and a tough nonwoven fabric was not formed. Examples 8 to 25, Comparative Example 3 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 3.66 g (0.01 mol, manufactured by AZ Materials), 2,2′-bis (trifluoromethyl) -4,4′- 3.20 g of diaminobiphenyl (0.01 mol, manufactured by Wakayama Seika), 30 g of N-methyl-2-pyrrolidone (NMP, manufactured by Mitsubishi Chemical) and 4.36 g of pyromellitic dianhydride (0.02 mol, A polyimide solution was obtained in the same manner as in Example 1 except that the diamine, NMP amount, and acid dianhydride shown in Tables 1 and 2 were used instead of Daicel Chemical Industries).
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Abstract
Description
特許文献2には、ポリイミド溶液をノズルから吐出させ、これと交差する高速の気流をあてることでポリイミド繊維を得て、それを用いた耐熱バグフィルター、断熱吸音材、耐熱服などへの適用が開示されている。
特許文献3には、ポリアミド酸とエポキシ基を含有するアルコキシシラン部分縮合物を反応させた樹脂溶液を用いたリチウムイオン二次電池用のセパレーターが開示されている。
特許文献4には、高分枝ポリマーを不織布などの多孔質構造材料に塗布したセパレーターが開示されている。
特許文献5には、特定の構造のポリイミドを用いた発泡体を叩解することで、ポリイミド短繊維からなる不織布が開示されている。
特許文献6には、リチウムイオン二次電池に多孔質フィルムと不織布を積層したセパレーターを用いることで、電解液の吸液速度が高まるとともに、高い絶縁性を有したセパレーターが開示されている。
特許文献7には、脂肪族ポリケトン不織布を用いた高エネルギー密度で内部抵抗の低いコンデンサーの生産に適した薄く強靱で、耐熱性、寸法安定性、電気絶縁性、耐薬品性、低吸水性に優れ、均一で多孔性のコンデンサー用電極セパレーターが開示されている。
特許文献8には、10nm~50μmの直径を有するポリイミド繊維を電気紡績して、複数のポリイミド繊維よりなる不織布を形成し、この不織布をパーフルオロポリマーで処理した高性能疎油性ポリイミド膜が開示されている。
特許文献9には、ナノサイズの微細繊維を特定の構造を有するポリイミド溶液を用いることで、電界紡糸法が得られることが開示されている。
特許文献10には、ポリイミド繊維を含む集合体をリチウムイオン電池セパレーター、バグフィルター、燃料排ガスフィルターに用いることで、耐熱性と可溶性の両立を図ることが開示されている。
特許文献11には電界紡糸法(ESP法)で作製した有機繊維の層を含むセパレーターにポリアミドイミド、ポリアミド、ポリイミドを使用することで、リチウムイオン電池の容量低下を抑制できることが開示されている。
(a)一般式(1)で表される構造単位を樹脂全体の50%モル以上含む樹脂、および(b)溶剤を含むポリイミド溶液である。
ポリイミド構造については、溶剤に可溶な構造であることが必須であり、安定な形状の糸を形成させる観点から好ましくは比誘電率が3.2以上であることが好ましい。
また、本発明の不織布は、ポリイミド溶液を電界紡糸法で紡糸することによって得ることを特徴とする。
得られるポリイミド溶液の吸湿を押さえ、さらに安定な微細形状の糸を形成させる観点から、R3およびR4は、炭素数1~4のアルキル基、フルオロアルキル基が好ましく、イソプロピル基、6フッ化イソプロピル基がより好ましい。
R5~R11は、炭素数1~4のアルキル基、フルオロアルキル基、またはフェニル基を表し、全てが同一でも異なっていても良い。tは0~3の整数である。
r、sは0~4の整数である。得られるポリイミド不織布の強度の点からr=s=0であることが好ましい。
Xの構造としてより好ましいのは、5~50モル%が下記に示すいずれかの構造であることである。この範囲より小さいと、吸湿抑制による安定な微細形状の糸を形成させる効果がなく、この範囲より大きいと吸湿抑制よりも極性低下による糸の不安定化の寄与が大きくなる。
特に反応を容易に進行させるためには、テトラカルボン酸二無水物とジアミンを反応させるのが良い。また、テトラカルボン酸のジクロリドやジエステルとジアミンを反応させて得ることもできる。
一般式(1)で表される構造のうち、テトラカルボン酸の残基は、Yで示された部分に該当し、Yは炭素数4~30の4価の有機基を表す。また、Yで示されるテトラカルボン酸の残基は、ベンゼン、シクロブタン、シクロヘプタン、シクロヘキサン、ナフタレン、ビフェニル、ターフェニル、ジフェニルエーテル、トリフェニルエーテル、ジフェニルメタン、またはジフェニルヘキサフルオロプロパン、ジフェニルスルホン、ジフェニルケトンを含む有機基を含むことが好ましい。
このような構造を含むテトラカルボン酸の例として、ピロメリット酸、ナフタレンテトラカルボン酸、ビフェニルテトラカルボン酸、ターフェニルテトラカルボン酸、ジフェニルエーテルテトラカルボン酸、トリフェニルエーテルテトラカルボン酸、ジフェニルメタンテトラカルボン酸、ジフェニルヘキサフルオロプロパンテトラカルボン酸、ジフェニルスルホンテトラカルボン酸、ジフェニルケトンテトラカルボン酸などの芳香族系のテトラカルボン酸、シクロブタンテトラカルボン酸、シクロヘキサンテトラカルボン酸、シクロヘプタンテトラカルボン酸などの単環状のテトラカルボン酸などが挙げられる。
この他にも、パーフルオロペンタンテトラカルボン酸、ビス(トリフルオロメチル)ピロメリット酸、ビス(パーフルオロエチル)ピロメリット酸、シクロプロパンテトラカルボン酸、シクロペンタンテトラカルボン酸、シクロオクタンテトラカルボン酸、シクロノナンテトラカルボン酸、シクロデカンテトラカルボン酸、シクロウンデカンテトラカルボン酸、シクドデカンテトラカルボン酸などの単環状のテトラカルボン酸、芳香族系のベンゾフェノンテトラカルボン酸、縮合環構造を有する、ビシクロ[2.2.2]オクタ-7-エン-2,3,5,6-テトラカルボン酸、ペンタシクロ[8.2.1.14,702,9.03,8]テトラデカン-5,6,11,12-テトラカルボン酸、ビシクロ[2.2.2]オクタ-7-エン-2,3,5,6-テトラカルボン酸、ペンタシクロ[8.2.1.14,702,9.03,8]テトラデカン-5,6,11,12-テトラカルボン酸、ペンタシクロ[8.2.1.14,7.02,9.03,8]テトラデカン-5,6,11,12-テトラカルボン酸、ビシクロ[2.2.2]オクト-7-エン-2,3,5,6-テトラカルボン酸、ペンタシクロ[8.2.1.14,7.02,9.03,8]テトラデカン-5,6,11,12-テトラカルボン酸、1,2,4,5-ビシクロヘキセンテトラカルボン酸などのテトラカルボン酸、これらのエステル化合物、酸クロリド化合物、アミド化合物などを組み合わせて用いることができる。
R13は酸二無水物の残基を表す。R13は少なくとも2個以上の炭素原子を有する4価の有機基であり、なかでも芳香族環または環状脂肪族基を含有する炭素原子数5~40の有機基が好ましい。
酸二無水物の具体的な例としては、ピロメリット酸二無水物、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、2,3,3’,4’-ビフェニルテトラカルボン酸二無水物、2,2’,3,3’-ビフェニルテトラカルボン酸二無水物、3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物、2,2’,3,3’-ベンゾフェノンテトラカルボン酸二無水物、2,2-ビス(3,4-ジカルボキシフェニル)プロパン二無水物、2,2-ビス(2,3-ジカルボキシフェニル)プロパン二無水物、1,1-ビス(3,4-ジカルボキシフェニル)エタン二無水物、1,1-ビス(2,3-ジカルボキシフェニル)エタン二無水物、ビス(3,4-ジカルボキシフェニル)メタン二無水物、ビス(2,3-ジカルボキシフェニル)メタン二無水物、ビス(3,4-ジカルボキシフェニル)スルホン二無水物、ビス(3,4-ジカルボキシフェニル)エーテル二無水物、1,2,5,6-ナフタレンテトラカルボン酸二無水物、9,9-ビス(3,4-ジカルボキシフェニル)フルオレン酸二無水物、9,9-ビス{4-(3,4-ジカルボキシフェノキシ)フェニル}フルオレン酸二無水物、2,3,6,7-ナフタレンテトラカルボン酸二無水物、2,3,5,6-ピリジンテトラカルボン酸二無水物、3,4,9,10-ペリレンテトラカルボン酸二無水物、2,2-ビス(3,4-ジカルボキシフェニル)ヘキサフルオロプロパン二無水物、3,3’,4,4’-ジフェニルスルホンテトラカルボン酸二無水物および下記に示した構造の酸二無水物などの芳香族テトラカルボン酸二無水物や、ブタンテトラカルボン酸二無水物、1,2,3,4-シクロペンタンテトラカルボン酸二無水物などの脂肪族のテトラカルボン酸二無水物などを挙げることができる。これらを2種以上用いてもよい。
安定な形状の糸を形成させる観点から、好ましい具体例としては高誘電率化に寄与する極性基の割合の多いピロメリット酸二無水物、3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物、2,2’,3,3’-ベンゾフェノンテトラカルボン酸二無水物、ビス(3,4-ジカルボキシフェニル)スルホン二無水物などが挙げられる。
また、シクロヘキサノンなどの高沸点のケトン系溶媒、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールジメチルエーテル、プロピレングリコールメチルエチルエーテル、プロピレングリコールジエチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールメチルエチルエーテル、ジプロピレングリコールジエチルエーテルなどのグリコール系溶媒、およびこれらにトルエン、キシレンなどの芳香族炭化水素系溶媒、プロピレングリコールモノメチルエーテルアセテート、メチル-メトキシブタノールアセテートなどのエステル系溶媒などを加えることもできる。
<吸水率の測定>
ポリイミド溶液を6インチのシリコンウェハーに、120℃で4分乾燥後の膜厚が約15μmになるようにスピン塗布した。スピン塗布後に120℃で4分、大日本スクリーン製造製の塗布現像装置SCW-636に付随しているホットプレートで乾燥後、光陽サーモシステム社製イナートオーブン INH-9CDを用いて300℃で1時間加熱処理を行い、ポリイミドフィルムを得た。このフィルムを形成したウェハーを45%のフッ化水素酸水溶液に室温で3分浸漬し、脱イオン水で10分間水洗し、ウェハーから剥がした。このフィルムの重量を測定し、その後、200℃で1時間乾燥させて、絶乾重量を求めた。吸水時の重量と絶乾重量から下記式を用いて吸水率を求めた。
吸水率=(吸水重量-絶乾重量)/絶乾重量×100(%)。
<比誘電率の測定>
アルミ基板にポリイミド溶液をスピン塗布した。スピン塗布後に120℃で4分、大日本スクリーン製造製の塗布現像装置SCW-636に付随しているホットプレートで乾燥後、光陽サーモシステム社製イナートオーブン INH-9CDを用いて300℃で1時間加熱処理を行い、厚み5μmのポリイミドフィルムを得た。この膜の上に上部アルミ電極を日本真空技術(株)製真空蒸着機EBH-6を用いて蒸着し測定サンプルとした。
次いで1MHzにおける静電容量を横川ヒューレットパッカード製のLCRメーター4284Aを用いて測定し、下記式により比誘電率(ε)を求めた。
ε=C・d/ε0・S(但し、Cは静電容量(単位:F)、dは試料膜厚(単位:m)、
ε0は真空中の誘電率、Sは上部電極面積(単位:m2)である。)
<ガラス転移点の測定>
シリコン基板にポリイミド溶液をスピン塗布した。スピン塗布後に120℃で4分、大日本スクリーン製造製の塗布現像装置SCW-636に付随しているホットプレートで乾燥後、光陽サーモシステム社製イナートオーブン INH-9CDを用いて300℃で1時間加熱処理を行い、厚み10μmのポリイミドフィルムを得た。このフィルムを形成したウェハーを45%のフッ化水素酸水溶液に室温で3分浸漬し、脱イオン水で10分間水洗し、ウェハーから剥がした。この膜を120℃で2時間乾燥して脱水し、5mgの重さになるよう切り出しサンプルとした。このサンプルについて島津製作所製DSC-50を用いて、昇温速度10℃/minで室温から400℃まで加熱し、ガラス転移点の測定を行った。
窒素導入管、撹拌棒、温度計を取り付けた500mLの3つ口フラスコに乾燥窒素気流下、2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン 3.66g(0.01モル、AZマテリアルズ製)、2,2’-ビス(トリフルオロメチル)-4,4’-ジアミノビフェニル 3.20g(0.01モル、和歌山精化製)をN-メチル-2-ピロリドン(NMP、三菱化学製)30g、トルエン(東京化成製)10gに40℃以下で溶解させた。ここにピロメリット酸二無水物4.36g(0.02モル、ダイセル化学工業製)を添加し、40℃で2時間撹拌を行い、その後、液温を180℃に昇温し、さらに4時間撹拌を行ない、留出するトルエンと水を除去しながら反応を行った。
また、吸水率は1.9%、比誘電率は2.9、ガラス転移点は170℃であった。
窒素導入管、撹拌棒、温度計を取り付けた500mLの3つ口フラスコに乾燥窒素気流下、ビス(3-アミノ-4-ヒドロキシフェニル)フルオレン22.8g(0.06モル、AZマテリアルズ製)と、2,4-ジアミノトルエン4.88g(0.04モル、東京化成製)NMP235g、トルエン(東京化成製)10gに40℃以下で溶解させた。ここに3,3‘,4,4’-ジフェニルエーテルテトラカルボン酸二無水物31.0g(0.1モル、マナック製)、を添加し、40℃で1時間、その後溶液の温度を180℃にして6時間撹拌を行った。
また、吸水率は1.5%、比誘電率は3.2、ガラス転移点は200℃であった。
窒素導入管、撹拌棒、温度計を取り付けた500mLの3つ口フラスコに乾燥窒素気流下、2,2-ビス(3-カルボキシル-4-アミノフェニル)メタン11.5g(和歌山精化製、0.05モル)、2,2’-ビス(トリフルオロメチル)-4,4’-ジアミノビフェニル12.8g (和歌山精化製、0.04モル)、1,3-ビス(3-アミノプロピル)テトラメチルジシロキサン2.48g(信越化学製、0.01モル)をNMP、240gに40℃以下で溶解させた。ここにピロメリット酸二無水物10.9(ダイセル化学工業製0.05モル)、2,2-ビス(ヘキサフルオロプロパン)フタル酸無水物22.2g(0.05モル、ダイキン工業製)を添加し、40℃で2時間撹拌を行い、その後、液温を180℃に昇温し、さらに4時間撹拌を行ない、留出するトルエンと水を除去しながら反応を行った。
また、吸水率は2.5%、比誘電率は3.0、ガラス転移点は180℃であった。
窒素導入管、撹拌棒、温度計を取り付けた500mLの3つ口フラスコに乾燥窒素気流下、ビス(3-アミノ-4-ヒドロキシフェニル)スルホン28.0g(0.1モル、AZマテリアルズ製)をNMP230gトルエン10gに40℃で溶解させた。ここにピロメリット酸二無水物 10.9g(0.05モル、ダイセル化学工業製)、3,3’,4,4’-ジフェニルスルホンテトラカルボン酸二無水物17.9g (0.05モル、新日本理化製)を添加し、40℃で2時間撹拌を行い、その後、液温を180℃に昇温し、さらに4時間撹拌を行ない、留出するトルエンと水を除去しながら反応を行った。
このようにして得られた樹脂溶液を2μmのポリテトラフルオロエチレン製のメンブレンフィルターでろ過を行い、ポリイミド溶液を得た。このポリイミド溶液を室温、湿度50%の雰囲気で4インチシリコンウェハー上にスピンコートしたところ、コート後、120秒放置しても溶液が白化することはなかったが、吸水率は9.0%、比誘電率は3.6、ガラス転移点は220℃であった。
窒素導入管、撹拌棒、温度計を取り付けた500mLの3つ口フラスコに乾燥窒素気流下、ビス(3-アミノ-4-ヒドロキシフェニル)シクロヘキサン14.9g(0.05モル、東京化成製)、2,2’-ビス(トリフルオロメチル)-4,4’-ジアミノビフェニル 12.8g (0.04モル、和歌山精化製)、1,3-ビス(3-アミノプロピル)テトラメチルジシロキサン2.48g(0.01モル、、信越化学製)をNMP205gに40℃以下で溶解させた。ここにピロメリット酸二無水物10.9(0.05モル、ダイセル化学工業製)、シクロブタン酸二無水物9.8g(0.05モル、東京化成製)を添加し、40℃で2時間撹拌を行い、その後、液温を180℃に昇温し、さらに4時間撹拌を行ない、留出するトルエンと水を除去しながら反応を行った。
また、吸水率は1.4%、比誘電率は2.9、ガラス転移点は190℃であった。
窒素導入管、撹拌棒、温度計を取り付けた500mLの3つ口フラスコに乾燥窒素気流下、ビス(3-アミノ-4-ヒドロキシフェニル)シクロペンタン1.04g(0.05モル、東京化成製)、2,2’-ビス(トリフルオロメチル)-4,4’-ジアミノビフェニル (0.05モル、和歌山精化製)をN-メチル-2-ピロリドン(NMP、三菱化学(株)製)40gに40℃以下で溶解させた。ここにピロメリット酸二無水物10.9(0.05モル、ダイセル化学工業製)、シクロブタン酸二無水物22.2g(0.05モル、東京化成製)を添加し、40℃で2時間撹拌を行い、その後、液温を180℃に昇温し、さらに4時間撹拌を行ない、留出するトルエンと水を除去しながら反応を行った。
窒素導入管、撹拌棒、温度計を取り付けた500mLの3つ口フラスコに乾燥窒素気流下、4,4’-ジアミノジフェニルエーテル 2.8g(0.05モル、和歌山精化製)、2,2’-ビス(トリフルオロメチル)-4,4’-ジアミノビフェニル1.60g(0.05モル、和歌山精化製)をNMP40gトルエン(東京化成(株)製)10gに40℃で溶解させた。ここに2,2-ビス(ヘキサフルオロイソプロピリデン)フタル酸無水物 22.2g(0.05モル、ダイキン工業製)を添加し、40℃で2時間撹拌を行い、その後、液温を180℃に昇温し、さらに4時間撹拌を行ない、留出するトルエンと水を除去しながら反応を行った。
実施例1で得たポリイミド溶液を濃度12%に希釈して、エレクトロスプレーコーターを用いて、アースしたアルミ箔上に、温度24℃、湿度50%の環境下、ノズルの内径が0.84mm(G18)のニードルを用いて、ノズルとアルミ箔の距離を250mmとして、溶液を20μL/minの総液量で送り、電圧15kVで塗布した。この結果、ポリイミドの不織布がアルミ箔上に得られた。
比較例1で得られたポリイミド溶液を実施例7と同じようにしてポリイミドの不織布を作成したが、吸湿が起こり、白色のもろい膜が形成され、強靱な不織布にならなかった。
実施例8~25、比較例3
2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン 3.66g(0.01モル、AZマテリアルズ製)、2,2’-ビス(トリフルオロメチル)-4,4’-ジアミノビフェニル 3.20g(0.01モル、和歌山精化製)をN-メチル-2-ピロリドン(NMP、三菱化学製)30g、および、ピロメリット酸二無水物4.36g(0.02モル、ダイセル化学工業製)の代わりに表1および表2に示したジアミン、NMP量、酸二無水物を使用する以外は実施例1と同様にしてポリイミド溶液を得た。このポリイミド溶液を室温、湿度50%の雰囲気で4インチシリコンウェハー上にスピンコートし塗膜全体の白化の有無、吸水率、比誘電率、ガラス転移点を測定した。
実施例26~48、比較例4
実施例2~6、実施例8~25、比較例3で得られたポリイミド溶液を実施例7と同様の方法で不織布形成テストを実施し、不織布形成状態、不織布を形成している繊維直径の平均値を測定した。
実施例および比較例の結果を表1、表2および表3に示す。
Claims (17)
- (a)一般式(1)で表される構造単位を樹脂全体の50モル%以上含む樹脂、および(b)溶剤を含むポリイミド溶液。
- 前記樹脂の比誘電率が3.2以上である、請求項1に記載のポリイミド溶液。
- 前記一般式(1)において、Yがジフェニルスルホンまたはジフェニルケトンを含む有機基を表す請求項1または2に記載のポリイミド溶液。
- 前記一般式(1)において、Yはベンゼン、シクロブタン、シクロヘプタン、シクロヘキサン、ナフタレン、ビフェニル、ターフェニル、ジフェニルエーテル、トリフェニルエーテル、ジフェニルメタン、またはジフェニルヘキサフルオロプロパンを含む有機基を表す請求項1または2に記載のポリイミド溶液。
- 前記一般式(1)に記載のXがスルホン基、またはケトン基のいずれかであって、p=q=0である、請求項1~4のいずれかに記載のポリイミド溶液。
- Yの40モル%以上がジフェニルスルホンまたはジフェニルケトンである、請求項3に記載のポリイミド溶液。
- Yの5~50モル%がベンゼンである、請求項4に記載のポリイミド溶液。
- 請求項1~9のいずれかに記載のポリイミド溶液を用いて形成される不織布。
- 請求項11に記載の不織布を製造する方法であって、電界紡糸法により前記不織布を形成する、不織布の製造方法。
- 電界紡糸法により形成される請求項11に記載の不織布。
- ガラス転移点が200℃以上である請求項11に記載の不織布。
- 請求項11、13、14のいずれかに記載の不織布を用いる高次加工品。
- 電池用セパレーター、吸音材、電磁波シールド材、分離フィルター、または耐熱バグフィルターに用いられる請求項15に記載の高次加工品。
- 請求項11、13、14のいずれかに記載の不織布を用いる電気二重層キャパシター用セパレーター。
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WO2019009037A1 (ja) | 2017-07-03 | 2019-01-10 | 東レ株式会社 | 樹脂、樹脂組成物、および、これらを用いた不織布、繊維製品、セパレーター、二次電池、および、電気二重層キャパシターならびに不織布の製造方法 |
JP2019039096A (ja) * | 2017-08-24 | 2019-03-14 | 宇部興産株式会社 | ポリイミド繊維およびその製造方法 |
KR20190070322A (ko) * | 2016-10-28 | 2019-06-20 | 도레이 카부시키가이샤 | 비수 전해질 전지용 세퍼레이터 및 비수 전해질 전지 |
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KR20200026200A (ko) | 2017-07-03 | 2020-03-10 | 도레이 카부시키가이샤 | 수지, 수지 조성물, 및 이들을 사용한 부직포, 섬유 제품, 세퍼레이터, 이차 전지, 및 전기 이중층 커패시터 그리고 부직포의 제조 방법 |
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JP7246182B2 (ja) | 2018-02-01 | 2023-03-27 | 東京応化工業株式会社 | 二次電池、及び二次電池用多孔質セパレータ |
JP2020033460A (ja) * | 2018-08-30 | 2020-03-05 | サムソン エレクトロ−メカニックス カンパニーリミテッド. | ポリイミド樹脂、感光性樹脂組成物、及び、硬化物 |
JP7167402B2 (ja) | 2018-08-30 | 2022-11-09 | サムソン エレクトロ-メカニックス カンパニーリミテッド. | ポリイミド樹脂、感光性樹脂組成物、及び、硬化物 |
WO2022097547A1 (ja) * | 2020-11-04 | 2022-05-12 | 東レ株式会社 | 樹脂組成物、不織布ならびにそれを用いた繊維製品、蓄電素子用セパレーター、二次電池および電気二重層キャパシター |
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US20170342214A1 (en) | 2017-11-30 |
JP6728680B2 (ja) | 2020-07-22 |
CN106795285A (zh) | 2017-05-31 |
EP3216819A4 (en) | 2018-09-05 |
KR102339152B1 (ko) | 2021-12-15 |
CN106795285B (zh) | 2020-06-05 |
US10669377B2 (en) | 2020-06-02 |
JPWO2016056480A1 (ja) | 2017-07-20 |
TW201623445A (zh) | 2016-07-01 |
EP3216819A1 (en) | 2017-09-13 |
KR20170067749A (ko) | 2017-06-16 |
TWI732745B (zh) | 2021-07-11 |
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