WO2011062006A1 - ポリアミドイミド樹脂微粒子の製造方法、ポリアミドイミド樹脂微粒子 - Google Patents
ポリアミドイミド樹脂微粒子の製造方法、ポリアミドイミド樹脂微粒子 Download PDFInfo
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- WO2011062006A1 WO2011062006A1 PCT/JP2010/067514 JP2010067514W WO2011062006A1 WO 2011062006 A1 WO2011062006 A1 WO 2011062006A1 JP 2010067514 W JP2010067514 W JP 2010067514W WO 2011062006 A1 WO2011062006 A1 WO 2011062006A1
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- polyamideimide resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/14—Powdering or granulating by precipitation from solutions
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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
- C08G73/14—Polyamide-imides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the present invention relates to a method for producing polyamideimide resin fine particles and polyamideimide resin fine particles.
- Polyamideimide resin is excellent in heat resistance, chemical resistance, wear resistance, etc., and is used in industrial equipment parts, films, electrical / electronic parts, automobile parts, aerospace related members. Moreover, when apply
- One of the methods is a means for pulverizing polyamideimide. By pulverizing, it is possible to directly spray the member or apply the aqueous dispersion to the member, and then remove the water to perform coating. Polyamideimide resin fine particles are mixed with other resins and composite materials and used for imparting thixotropy and improving impact resistance, or mixed with other resins and used for disc brake shims, etc. ing.
- Polyimide amide resin fine particles are used in many applications and are expected to be used in various applications. To bring out the properties of polyamide-imide resin by mixing with water or resin, it is uniformly dispersed in water or resin. It is important to let For this purpose, it is desirable that the average primary particle size of the fine particles is 300 nm or less, particularly 200 nm or less, and the particle size is uniform.
- a method for synthesizing polyamideimide resin fine particles for example, a first solution containing an acid chloride such as trimellitic anhydride chloride and a second solution containing a diamine compound such as 4,4′-diaminodiphenyl ether are used.
- a method is known in which polyamideimide resin fine particles are obtained by stirring with ultrasonic waves in the presence of a solvent soluble in both the solution and the second solution (Patent Documents 1, 2, and 3).
- Patent Documents 1, 2, and 3 Patent Documents 1, 2, and 3
- this method requires a special device such as an ultrasonic generator, and there are various manufacturing problems in industrially producing polyamideimide fine particles.
- the above-mentioned patent document only describes the production of polyamide fine particles using dicarboxylic acid chloride as the acid chloride as a specific production example, and a specific production example of polyamideimide resin fine particles is disclosed. Not.
- Patent Document 4 a method for producing polyamideimide resin fine particles by a spray drying method is disclosed (Patent Document 4).
- polyamideimide resin dissolved in N-methyl-2-pyrrolidinone is spray-dried by mobile minor type spray drying to obtain polyamideimide fine particles having an average particle size of 4.5 ⁇ m.
- a method for producing polyamideimide resin fine particles having an average particle diameter of 3 ⁇ m from polymerization of 4,4′-diphenylmethane diisocyanate and trimellitic anhydride is disclosed (Patent Documents 5 and 6).
- these methods cannot produce polyamideimide resin fine particles of 1 ⁇ m or less.
- Patent Document 7 Also disclosed is a method of adding polyamideimide resin dissolved in 1,3-dimethyl-2-imidazolidinone to an aqueous surfactant solution having a phenyl group to precipitate polyamideimide resin fine particles.
- polyamideimide resin fine particles of 1 ⁇ m or less can be obtained, but the particle size greatly varies depending on the surfactant concentration, the stirring rotation speed, and the time until the polyamideimide resin solution is dropped into the surfactant aqueous solution. The reproducibility is poor, and polyamideimide resin fine particles of 1 ⁇ m or less are not always obtained.
- the solvent for dissolving the PAI resin is limited to 1,3-dimethyl-2-imidazolidinone, and high agitation at 1,000 to 4,000 rpm is necessary. There is a problem.
- an object of the present invention is to provide a method for producing polyamideimide resin fine particles (hereinafter, polyamideimide may be abbreviated as PAI) which can be industrially implemented and can be easily operated.
- PAI polyamideimide resin fine particles
- the present inventors have surprisingly used an organic solvent solution having a PAI resin concentration of less than 5% by mass, and this is used as a PAI resin substantially free from a surfactant. It has been found that fine PAI resin fine particles can be stably obtained by adding to a solvent for precipitating the fine particles, and in the case of flash crystallization of an organic solvent solution, the solution is adjusted to a PAI resin concentration of 10 It has been found that fine PAI resin particles can be stably obtained when the content is less than mass%, and the present invention has been achieved.
- this invention is a manufacturing method of the polyamideimide resin microparticles
- Step (a1) selected from the following (a1) and (b1)
- Step (b1) Polyamideimide in which a polyamideimide resin is dissolved in an organic solvent to obtain a polyamideimide resin solution A1 having a polyamideimide resin concentration of less than 5% by mass
- precipitation step] A2) Polyamideimide resin solution A1 is added to a solvent for precipitating polyamideimide resin particles substantially free of surfactant to precipitate polyamideimide resin particles (b2) Polyamideimide resin solution B1 For precipitating fine particles of polyamideimide resin by flash crystallization
- PAI resin fine particles having an average primary particle size of 300 nm or less, particularly 200 nm or less, which has been difficult to obtain industrially stably, can be easily and stably produced. Industrially useful materials can be provided.
- FIG. 2 is a scanning electron micrograph of PAI fine particles produced in Example 1.
- FIG. 2 is a scanning electron micrograph of PAI fine particles produced in Example 14.
- FIG. 2 is a scanning electron micrograph of PAI particles produced in Comparative Example 1.
- the polyamideimide resin used in the present invention is obtained by polymerizing an acid component such as trimellitic anhydride or trimellitic anhydride monochloride and an amine component.
- an isocyanate method using trimellitic anhydride and diisocyanate as raw materials for example, Japanese Patent Publication No. 50-33120
- trimellitic anhydride chloride and diamine are polymerized in N, N-dimethylacetamide.
- Acid chloride method for example, Japanese Patent Publication No. 42-15637
- a direct polymerization method for example, Japanese Patent Publication No. 49-4077
- the PAI resin in the present invention can be produced by any method.
- polyamideimide resin can be appropriately selected from commercially available ones, and specifically, polyamideimide resin TI-5013P manufactured by Toray Industries, Inc., Torlon manufactured by Solvay Co., Ltd., and the like can be used.
- the PAI resin fine particles in the present invention can be produced through the steps including the following dissolution step and precipitation step.
- Step (a1) selected from the following (a1) and (b1)
- Step (b1) Polyamideimide in which a polyamideimide resin is dissolved in an organic solvent to obtain a polyamideimide resin solution A1 having a polyamideimide resin concentration of less than 5% by mass
- Precipitation step] A2
- Polyamideimide resin solution A1 is added to a solvent for precipitating polyamideimide resin particles substantially free of surfactant to precipitate polyamideimide resin particles
- Polyamideimide resin solution B1 In the above, when the dissolution step (a1) is selected, the precipitation step (a2) is performed, and the dissolution step (b1) is selected.
- (B2) is performed. That is, when the concentration of the PAI resin is less than 5% by mass (a1), fine particles can be obtained by simply adding the PAI resin to the poor solvent (a2), but when the concentration is 5% by mass or more, coarse particles or agglomerates are obtained. . In contrast, in the flash crystallization method (b2), it is possible to produce fine particles with a PAI resin concentration of less than 10% by mass.
- the dissolution step in the present invention is selected from the above (a1) and (a2).
- the PAI resin in the dissolving step, is dissolved in an organic solvent.
- the form of the PAI resin used in the present invention is not particularly limited, and examples thereof include powders, granules, pellets, films, and molded articles. From the viewpoint of shortening the operability and the time required for dissolution, powders, granules and pellets are desirable, and powdered PAI resin is particularly preferable.
- powder, granules, and pellets of PAI that do not contain inorganic ions Resins are particularly preferred.
- any organic solvent can be used in this step as long as the PAI resin is soluble.
- N-alkylpyrrolidones such as N-methyl-2-pyrrolidinone (hereinafter abbreviated as NMP)
- N-alkylcaprolactams such as N-methyl- ⁇ -caprolactam
- 1,3-dimethyl-2 -Ureas such as imidazolidinone (hereinafter abbreviated as DMI)
- chain amides such as N, N-dimethylacetamide (hereinafter abbreviated as DMAc), N, N-dimethylformamide (hereinafter abbreviated as DMF)
- the solvent include at least one solvent selected from sulfur oxide polar solvents such as a solvent, dimethyl sulfoxide (hereinafter abbreviated as DMSO), dimethyl sulfone, and tetramethylene sulfone.
- the solvent used is not limited to DMI but also has problems such as reproducibility.
- PAI If the resin concentration is controlled to be equal to or lower than a predetermined concentration, not only DMI but also the above-mentioned various solvents can be used, and a solvent according to the purpose can be selected.
- the atmosphere of the tank in the dissolution process may be any of an air atmosphere, an inert gas atmosphere, or a solvent vapor atmosphere, but in order to suppress the decomposition and deterioration of the PAI resin, and to proceed more safely It is preferable to reduce the oxygen gas concentration.
- the inert gas include nitrogen gas, carbon dioxide gas, helium gas, argon gas, etc.
- nitrogen gas, argon gas, carbon dioxide gas is preferable, Particularly preferably, nitrogen gas or argon gas is used.
- (1) a method in which the reaction tank is depressurized or vacuumed to remove air and then the temperature of the reaction tank is increased, and (2) while sucking air in the reaction tank, (3) A method of stopping the suction when the solvent vapor is filled while sucking the air in the reaction tank while the temperature is raised and the solvent vapor is filled, (3) 4) A method of blowing the same kind of vapor as the solvent into the reaction vessel while sucking the air in the reaction vessel, or a combination of these methods, and thereby making the inside of the dissolution vessel a vaporized solvent vapor atmosphere. Can do.
- the methods (2) to (4) it is desirable to know the amount of solvent in the dissolution tank.
- the dissolution method is not particularly limited, but PAI resin and solvent are put in a predetermined container and dissolved while stirring. If not dissolved at room temperature, dissolve by heating.
- a method in which the PAI resin is completely dissolved in a solvent and then added, or is precipitated by flash crystallization, but undissolved PAI resin may be present.
- the dissolution temperature varies depending on the type of solvent used and the concentration of the PAI resin, but is usually room temperature to 250 ° C., preferably room temperature to 100 ° C.
- the dissolution time varies depending on the type of solvent, the concentration of the PAI resin, and the dissolution temperature, but is usually 5 minutes to 5 hours, preferably 10 minutes to 4 hours.
- the PAI resin can be dissolved by the above operation.
- the PAI resin concentration is set to a PAI resin solution A1 having a concentration of less than 5% by mass (hereinafter sometimes referred to as a solution A1).
- the viscosity of the PAI resin with respect to the organic solvent increases rapidly as the concentration of the PAI resin increases.
- the solution viscosity is 11 mPa ⁇ s
- 10% by mass solution is 54 mPa ⁇ s
- 15% by mass is 225 mPa ⁇ s
- 20% by mass is 837 mPa ⁇ s (described later). Measured by viscosity measurement method).
- the PAI resin solution is added to a solvent for precipitating the fine particles of the PAI resin. Fine particles having a small diameter or a uniform particle diameter cannot be obtained.
- the amount of PAI resin used is usually 5 parts by mass of PAI resin with respect to a total of 100 parts by mass of the organic solvent and PAI resin. Less than 5 parts by weight, preferably 0.1 parts by weight or more and less than 5 parts by weight, more preferably 0.5 to 4 parts by weight.
- the PAI resin concentration is set to a PAI resin solution B1 having a concentration of less than 10% by mass (hereinafter, sometimes referred to as a solution B1).
- the PAI resin fine particles are produced using flash crystallization as in the precipitation step (b2) described later, if the PAI resin concentration is less than 10% by mass, the PAI fine particles can be produced stably.
- the amount of the PAI resin used in the solution B1 in the step (b1) is less than 10 parts by weight of the PAI resin and the organic solvent in total of 100 parts by weight, preferably 0.1 parts by weight or more to 10 to 10 parts by weight. The amount is less than mass parts, more preferably 0.5 parts by mass to 7 parts by mass.
- a PAI resin is charged in the solvent and dissolved at room temperature or heated, and then the PAI resin solution is subjected to a precipitation step described later.
- Step (a2) the PAI resin solution A1 dissolved in the dissolving step (a1) is added to a solvent for precipitating PAI resin fine particles not containing a surfactant to precipitate the PAI resin fine particles.
- the PAI resin solution A1 dissolved under normal pressure conditions may be pressurized conditions
- the above addition means simply putting the PAI resin solution A1 into a solvent for precipitating the PAI resin, and it may be continuously injected from the container containing the PAI resin solution into the container containing the solvent for precipitating the PAI resin. And may be dripped.
- the solvent for precipitating the PAI resin fine particles is not particularly limited, but is preferably a solvent that is uniformly mixed with the organic solvent used in the dissolving step from the viewpoint of being uniformly dispersed in the solvent.
- uniform mixing means that when two or more solvents are mixed, the interface does not appear even if the mixture is allowed to stand for one day, and is mixed uniformly.
- NMP, DMF, DMAc, acetone, DMSO, tetrahydrofuran, methanol, ethanol and the like can be mentioned as a solvent in which they are uniformly mixed.
- the fine PAI resin fine particles are obtained and that the particle diameters are easily uniform, so that the PAI resin is poorly mixed with the solvent used in the dissolution step and contains a poor solvent for the PAI resin.
- the poor solvent is a solvent which does not dissolve PAI resin at the temperature when adding PAI resin solution, that is, addition Any solvent capable of precipitating the PAI resin dissolved in the dissolving solution can be used as a poor solvent. Therefore, even if it is an organic solvent which can be used for a solution, it can be used as a poor solvent if it is an organic solvent in which the solubility of the PAI resin is lowered by lowering the temperature.
- NMP NMP
- alcohols, acetones, water, etc. can be used, and the solvent to be precipitated can be selected according to the purpose.
- water it is preferable to use water from the viewpoint of easily obtaining fine PAI resin particles having a uniform particle diameter.
- the solvent for precipitating the PAI resin fine particles may be a single solvent or a mixture of two or more solvents as long as it is uniformly mixed with the organic solvent used in the dissolving step.
- the amount of the solvent for precipitating the PAI resin fine particles is not particularly limited, but can be exemplified by a range of 0.3 to 100 parts by mass, preferably 0.4 to 50 parts by mass with respect to 1 part by mass of the solvent in the dissolution step. Part, more preferably 0.4 to 10 parts by weight.
- the solvent for precipitating the PAI resin fine particles is substantially free of surfactant.
- the surfactant is added, the solvent for precipitating the PAI resin fine particles tends to foam, and the stability of the system is impaired when the solution A is added, so that the reproducibility is deteriorated. Therefore, it is most preferable that the surfactant is not contained at all, but may be mixed as long as the effect of the present invention is not impaired. Specifically, it should be limited to about 3% by mass or less with respect to the mass of the PAI resin, and should be less than 1% by mass as much as possible.
- the receiving tank When added to the solvent for precipitating the PAI resin fine particles, the receiving tank may or may not be cooled.
- PAI resin fine particles are precipitated from the PAI resin solution, and a liquid in which the PAI resin fine particles are dispersed or suspended is obtained.
- the receiving tank When the receiving tank is cooled, it is cooled with a refrigerant or ice water.
- the cooling temperature of the receiving tank varies depending on the solvent for precipitating the PAI resin fine particles to be placed in the receiving tank, but the temperature at which the solvent for precipitating the PAI resin fine particles does not solidify is 15 to 15 ° C. Specifically, in the case of water, 0 to 40 ° C. is preferable, and 0 to 30 ° C. is more preferable.
- Step (b2) In the step (b2), the PAI resin solution B1 dissolved in the dissolution step (b1) is flash crystallized to precipitate a solvent.
- Flash crystallization means heating / pressurization, or the above-mentioned solution under pressure, below the boiling point of the organic solvent used in the dissolution step (may be under cooling) / under pressure under pressure (may be under reduced pressure) ), Or jetted through a nozzle into another container (hereinafter also referred to as a receiving tank) below the pressure being applied (may be under reduced pressure) and transferred, thereby crystallizing fine particles
- a receiving tank another container below the pressure being applied (may be under reduced pressure) and transferred, thereby crystallizing fine particles
- the nozzle tip is separated from the solvent and flushed into the solvent via the gas phase even when the tip of the nozzle from which the solution B is ejected is placed in the solvent on the receiving tank side.
- the former is preferable.
- fine particles having an average primary particle size of 300 nm or less, particularly 200 nm or less can be obtained by controlling the concentration of the PAI resin to a predetermined concentration or less.
- the PAI resin is extruded all at once at a high pressure, so that the solution in the dissolving tank diffuses into the solvent in the receiving tank in a shorter time, and spherical or nearly spherical fine particles are generated. Therefore, when obtaining spherical or nearly spherical fine particles, it is more preferable to use flash crystallization that flashes in a solvent.
- the flash crystallization will be specifically described.
- the flash crystallization is performed by flash crystallization of a solution of PAI resin from a container held under pressure under heating or pressurization into a receiving tank under atmospheric pressure (or under reduced pressure).
- a pressure resistant container such as an autoclave
- the inside of the container is pressurized by a self-made pressure by heating (may be further pressurized with an inert gas such as nitrogen).
- an inert gas such as nitrogen
- dissolves at normal temperature PAI resin microparticles
- the solvent for depositing the PAI resin fine particles used for flash crystallization in the solvent is not particularly limited, and the same solvent as described in the step (a2) can be used.
- the amount of the solvent for precipitating the PAI resin fine particles is not particularly limited, but can be exemplified by a range of 0.3 to 100 parts by mass, preferably 0.4 to 50 parts by mass with respect to 1 part by mass of the solvent in the dissolution step. Part, more preferably 0.4 to 10 parts by weight.
- the solvent for precipitating the PAI resin fine particles during flash crystallization may or may not contain a surfactant, but it contains a surfactant because it is necessary to remove excess surfactant. Preferably not.
- the flash crystallization method is not particularly limited, but is usually a method of flash crystallization in a single stage in a vessel under a pressurized pressure or a pressure of a solution at room temperature to 250 ° C., preferably from room temperature to 100 ° C.
- a method of performing flash crystallization in multiple stages in a container having a lower pressure than the inside of the tank in which the solution is placed can be employed.
- the melting step when heated and dissolved in a pressure-resistant vessel such as an autoclave, the inside of the vessel is pressurized by a self-made pressure by heating (even if further pressurized with an inert gas such as nitrogen) Good).
- the solution in a pressurized state is flushed in an atmospheric pressure receiving tank containing a solvent for precipitating PAI resin fine particles, or is flushed in a receiving tank under reduced pressure.
- the dissolved solution pressurized to an arbitrary pressure is flushed in an atmospheric pressure receiving tank containing a solvent for precipitating PAI resin fine particles. Or flush into a receiving tank under reduced pressure.
- the pressure (gauge pressure) of the solution for flash crystallization is preferably 0.2 to 4 MPa. From this environment, it is preferable to perform flash crystallization, preferably flash crystallization in a receiving tank under atmospheric pressure, more preferably under atmospheric pressure.
- the receiving tank may or may not be cooled.
- PAI resin fine particles are precipitated from the solution of the PAI resin by flash crystallization, and a liquid in which the PAI resin fine particles are dispersed or suspended is obtained.
- the receiving tank is cooled, it is cooled with a refrigerant or ice water.
- the cooling temperature of the receiving tank varies depending on the solvent in which the PAI resin fine particles to be deposited in the receiving tank are precipitated, but the temperature at which the solvent for precipitating the PAI resin fine particles does not solidify to 15 ° C. Specifically, in the case of water, the temperature immediately before the flash crystallization 0 to 40 ° C is preferable, and 0 to 30 ° C is more preferable.
- the flash crystallization method there is a method in which the outlet of the connecting pipe from the dissolution tank is placed in the atmosphere of the receiving tank or in a solvent for precipitating PAI resin fine particles, and flash crystallization is performed.
- PAI resin fine particles are preferable because they are obtained.
- the PAI resin fine particles obtained by the step (b2) can be obtained in the state of a dispersion or suspension (hereinafter, the dispersion or suspension in this state may be referred to as a flash solution). At this time, when coarse particles such as an undissolved portion of the charged PAI resin are included, it can be removed by filtration or the like.
- the PAI resin fine particles thus obtained are fine particles having an average primary particle size of 300 nm or less, and in a more preferred embodiment, 200 nm or less.
- the lower limit is about 90 nm.
- fine particles having a uniform particle size can be obtained, and polyamideimide resin fine particles having a coefficient of variation of usually 70% or less, and in a preferred embodiment 60% or less are obtained.
- salting out is used.
- the method is preferable in that the aggregate can be obtained in a short time and that a large aggregate can be obtained.
- a coagulation method by salting out an aggregate having a large particle size suitable for an industrial solid-liquid separation method can be obtained.
- the average particle size of the aggregates at this time is preferably 5 to 100 ⁇ m (particle size by the measurement method described later).
- an inorganic salt such as sodium chloride is added in an amount of 0.01 to 1000 parts by mass, preferably about 0.05 to 500 parts by mass with respect to 1 part by mass of PAI resin fine particles. Aggregates having a large diameter can be obtained.
- a method such as adding an inorganic salt directly into the dispersion or suspension, or adding a 0.1 to 20% by mass solution of the inorganic salt can be used.
- Inorganic salts include sodium chloride, magnesium chloride, calcium chloride, lithium chloride, potassium chloride, sodium acetate, magnesium acetate, calcium acetate, sodium oxalate, magnesium oxalate, calcium oxalate, sodium citrate, magnesium citrate, citric acid
- examples thereof include inorganic salts such as calcium acid.
- a solvent for dissolving the inorganic salt water is preferable.
- the inorganic salt can be added in advance or dissolved in a solvent for precipitating the PAI resin fine particles in the receiving tank when flash crystallization is performed.
- the solvent for precipitating the PAI resin fine particles at this time is preferably water.
- the amount of the inorganic salt to be added is preferably 0.05 parts by mass or more with respect to 1 part by mass of the PAI resin fine particles and less than or equal to the saturated dissolution amount in the solvent in which the PAI resin fine particles are precipitated.
- the PAI resin fine particles obtained by addition or flash crystallization as in the present invention can be easily solid-liquid separated by agglomeration by such a method. Further, PAI resin fine particles that are extremely easily redispersed can be obtained even if they are aggregated by such a method.
- Examples of the solid-liquid separation method include methods such as filtration and centrifugation.
- a membrane filter filtration or centrifugation
- a filter cloth filtration, centrifugation
- the opening of the filter is appropriately determined according to the particle size of the PAI resin fine particles to be obtained.
- a membrane filter it is usually about 0.1 to 50 ⁇ m.
- the air permeability is 5 cm 3 / cm. Those of 2 ⁇ sec at 124.5 Pa or less can be used.
- the PAI fine particles thus obtained can be used as they are, or dispersed in a desired solvent to form a dispersion, or re-dispersed in another medium to form a composite, which can be used for various applications.
- the average particle size of the PAI resin fine particles is Nikkiso Laser Diffraction / Scattering Particle Size Distribution Measuring Device MT3300EXII. It measured using 0.5 mass% aqueous solution. Specifically, the cumulative curve is obtained by setting the total volume of fine particles obtained by analyzing the scattered light of the laser by the microtrack method to 100%, and the particle diameter (median diameter: d50) at which the cumulative curve becomes 50% is obtained. The average particle size of the fine particles was used.
- the average primary particle size in the present invention is an arbitrary 100 particles selected from an image (magnification: 30,000 times) obtained with a scanning electron microscope JEOL JMS-6700F manufactured by JEOL. The particle size was measured and the average value was defined as the average primary particle size.
- the coefficient of variation (CV) of the average primary particle size in the present invention is a value of the particle size distribution obtained by measuring arbitrary 100 particle sizes from an image obtained with a scanning electron microscope JEOL JMS-6700F manufactured by JEOL. Was obtained by the following formulas (1) to (3).
- Example 1 [Dissolution process] (b1) A 1,000 ml autoclave in the dissolution tank was equipped with a stirrer, a temperature measurement device, and an internal dissolution liquid extraction tube. A connecting pipe that can be opened and closed is attached to the extraction pipe. As a receiving tank for flash crystallization, a 1,000 ml autoclave is placed in a position where the stirrer, condenser, gas vent pipe, and the other end of the connecting pipe from the dissolution tank (flash crystal precipitation port) enter the receiving tank liquid. Installed.
- PAI resin (TI-5013P, manufactured by Toray Industries, Inc., this powder was used in the following examples) 12 g, NMP (manufactured by Kanto Chemical Co.) 388 g (PAI resin concentration: 3% by mass) was charged into the dissolution tank, and nitrogen was added. The inner temperature was raised to 240 ° C. while stirring, and the mixture was further stirred for 1 hour. The internal pressure (gauge pressure) at this time was 0.15 MPa. Further, the pressure was increased to 0.5 MPa with nitrogen gas.
- Precipitation step (b2) The receiving tank containing 400 g of water was ice-cooled, and a small amount of nitrogen gas was aerated while stirring. The valve of the internal connection pipe of the dissolution tank was opened, the dissolved solution was transferred to a receiving tank under atmospheric pressure, stirring was stopped after confirming that the liquid temperature was 40 ° C. or lower, and the receiving tank was opened. .
- the average particle size of the flash solution of the PAI resin fine particles in the receiving tank was 8.7 ⁇ m.
- the flash solution was added to 400 g of 4% saline, stirred at 1400 rpm for 30 minutes, and then allowed to stand for 5 hours.
- the salted out suspension was filtered and washed to obtain a PAI resin fine particle wet cake.
- the average primary particle size was 109 nm and the coefficient of variation was 32%.
- SEM scanning electron microscope
- the average primary particle size of the PAI fine particles was 102 nm and the coefficient of variation was 28%, confirming that the PAI fine particles were reproducible.
- Example 2 (dissolution step: b1, precipitation step: b2) The same operation as in Example 1 was performed except that the dissolution tank temperature of Example 1 was 50 ° C. and the pressure was increased to 0.5 MPa with nitrogen gas.
- the average particle size of the flash solution was 12.4 ⁇ m.
- the average primary particle size of the PAI fine particles was 110 nm and the coefficient of variation was 40%. When observed with a scanning electron microscope (SEM) at 30,000 times, the particles were almost spherical.
- SEM scanning electron microscope
- the average primary particle size of the PAI fine particles was 112 nm and the coefficient of variation was 38%, confirming that the PAI fine particles were reproducible.
- Example 3 (dissolution step: b1, precipitation step: b2) The same operation as in Example 1 was performed except that the dissolution tank temperature of Example 1 was normal temperature (21 ° C.) and the pressure was increased to 0.5 MPa with nitrogen gas.
- the average particle size of the flash solution was 18.6 ⁇ m.
- the average primary particle size of the PAI fine particles was 110 nm and the coefficient of variation was 40%. When observed with a scanning electron microscope (SEM) at 30,000 times, the particles were almost spherical.
- the average primary particle diameter of the PAI fine particles was 110 nm, and the coefficient of variation was 39%, confirming reproducibility.
- Example 4 (dissolution step: b1, precipitation step: b2)
- Example 1 was the same as Example 1 except that the dissolution tank temperature was normal temperature (21 ° C.), pressurized to 0.5 MPa with nitrogen gas, and the ratio of dissolution tank NMP mass to the amount of water received in the tank was 1 / 0.6. Carried out.
- the average particle size of the flash solution was 20.2 ⁇ m.
- the average primary particle size of the PAI fine particles was 157 nm and the variation coefficient was 44%. When observed with a scanning electron microscope (SEM) at 30,000 times, the particles were almost spherical.
- SEM scanning electron microscope
- the average primary particle size of the PAI fine particles was 160 nm and the coefficient of variation was 41%, confirming reproducibility.
- Example 5 (dissolution step: b1, precipitation step: b2)
- Example 1 was the same as Example 1 except that the dissolution tank temperature was normal temperature (21 ° C.), pressurized to 0.5 MPa with nitrogen gas, and the ratio of dissolution tank NMP mass to the amount of receiving water was set to 1/4. Carried out.
- the average particle size of the flash solution was 22.4 ⁇ m.
- the average primary particle size of the PAI fine particles was 155 nm and the variation coefficient was 51%. When observed with a scanning electron microscope (SEM) at 30,000 times, the particles were almost spherical.
- SEM scanning electron microscope
- Example 6 (dissolution step: b1, precipitation step: b2) Except that the dissolution tank temperature of Example 1 was normal temperature (21 ° C.), pressurized with nitrogen gas to 0.5 MPa, the amount of PPS charged to the dissolution tank was 14 g, and NMP 386 g (PAI resin concentration: 3.5 mass%). This was carried out in the same manner as in Example 1.
- the average particle size of the flash solution was 19.6 ⁇ m.
- the average primary particle size of the PAI fine particles was 167 nm and the coefficient of variation was 46%. When observed with a scanning electron microscope (SEM) at 30,000 times, the particles were almost spherical.
- the average primary particle size of the PAI fine particles was 160 nm, and the coefficient of variation was 47%, confirming reproducibility.
- Example 7 (dissolution step: b1, precipitation step: b2) Except that the dissolution tank temperature of Example 1 was normal temperature (21 ° C.), pressurized to 0.5 MPa with nitrogen gas, the amount of PPS charged to the dissolution tank was 16 g, and NMP 384 g (PAI resin concentration: 4 mass%). Performed as in Example 1.
- the average particle size of the flash solution was 19.2 ⁇ m.
- the average primary particle size of the PAI fine particles was 175 nm and the coefficient of variation was 62%. When observed with a scanning electron microscope (SEM) at 30,000 times, the particles were almost spherical.
- SEM scanning electron microscope
- the average primary particle size of the PAI fine particles was 170 nm, and the coefficient of variation was 60%, confirming reproducibility.
- Example 8 (dissolution step: b1, precipitation step: b2) Except that the dissolution tank temperature of Example 1 was normal temperature (21 ° C.), pressurized to 0.5 MPa with nitrogen gas, the amount of PPS charged to the dissolution tank was 20 g, and NMP 380 g (PAI resin concentration: 5 mass%). Performed as in Example 1.
- the average particle size of the flash solution was 24.5 ⁇ m.
- the average primary particle size of the PAI fine particles was 249 nm and the coefficient of variation was 52%. When observed with a scanning electron microscope (SEM) at 30,000 times, the particles were almost spherical.
- SEM scanning electron microscope
- the average primary particle size of the PAI fine particles was 252 nm and the coefficient of variation was 55%.
- Example 9 (dissolution step: b1, precipitation step: b2) The same operation as in Example 1 was performed except that the dissolution tank temperature of Example 1 was normal temperature (21 ° C.) and the pressure was increased to 1 MPa with nitrogen gas.
- the average particle size of the flash solution was 17.2 ⁇ m.
- the average primary particle size of the PAI resin fine particles was 143 nm and the coefficient of variation was 58%. When observed with a scanning electron microscope (SEM) at 30,000 times, the particles were almost spherical.
- the average primary particle size of the PAI fine particles was 140 nm and the coefficient of variation was 55%, confirming that the PAI fine particles were reproducible.
- Example 10 (dissolution step: b1, precipitation step: b2) The same operation as in Example 1 was performed except that the dissolution tank temperature in Example 1 was normal temperature (21 ° C.) and the pressure was increased to 0.25 MPa with nitrogen gas.
- the average particle size of the flash solution was 20.2 ⁇ m.
- the average primary particle size of the PAI resin fine particles was 161 nm and the coefficient of variation was 43%. When observed with a scanning electron microscope (SEM) at 30,000 times, the particles were almost spherical.
- SEM scanning electron microscope
- the average primary particle diameter of the PAI fine particles was 160 nm and the coefficient of variation was 45%, confirming that the PAI fine particles were reproducible.
- Example 11 (dissolution step: b1, precipitation step: b2) The same procedure as in Example 1 was performed except that the dissolution tank temperature of Example 1 was normal temperature (21 ° C.), pressurized to 0.5 MPa with nitrogen gas, and the solvent of the dissolution tank was DMF.
- the average particle size of the flash solution was 16.3 ⁇ m.
- the average primary particle size of the PAI resin fine particles was 91 nm and the coefficient of variation was 46%. When observed with a scanning electron microscope (SEM) at 30,000 times, the particles were almost spherical.
- the average primary particle size of the PAI fine particles was 95 nm and the coefficient of variation was 43%, confirming reproducibility.
- Example 12 (dissolution step: b1, precipitation step: b2) The same operation as in Example 1 was performed except that the dissolution tank temperature of Example 1 was normal temperature (21 ° C.), pressurized to 0.5 MPa with nitrogen gas, and the solvent of the dissolution tank was DMAc.
- the average particle size of the flash solution was 21.6 ⁇ m.
- the average primary particle size of the PAI resin fine particles was 130 nm and the coefficient of variation was 39%. When observed with a scanning electron microscope (SEM) at 30,000 times, the particles were almost spherical.
- the average primary particle size of the PAI fine particles was 125 nm and the coefficient of variation was 38%, confirming reproducibility.
- Example 13 (dissolution step: b1, precipitation step: b2) The same procedure as in Example 1 was performed except that the dissolution tank temperature of Example 1 was normal temperature (21 ° C.), pressurized to 0.5 MPa with nitrogen gas, and the solvent of the dissolution tank was DMSO.
- the average particle size of the flash solution was 23.1 ⁇ m.
- the average primary particle size of the PAI resin fine particles was 163 nm and the coefficient of variation was 48%. When observed with a scanning electron microscope (SEM) at 30,000 times, the particles were almost spherical.
- the average primary particle size of the PAI fine particles was 158 nm and the coefficient of variation was 50%, confirming reproducibility.
- Example 14 (dissolution step: a1, precipitation step: a2) Dissolve 1.5 g of PAI resin in 48.5 g of NMP (PAI resin concentration: 3% by mass), drop the solution at room temperature (21 ° C.) into 50 g of stirring water with a pipette and suspend the fine PAI resin particles. A liquid was obtained. The average particle size of the suspension was 17.6 ⁇ m. The suspension was added to 50 g of 4% saline, stirred at 1400 rpm for 30 minutes, and then allowed to stand for 3 hours. The salted out suspension was filtered and washed to obtain a PAI resin fine particle wet cake. The average primary particle diameter of the PAI resin fine particles was 140 nm and the coefficient of variation was 36%. When observed with a scanning electron microscope (SEM) at 30,000 times, the particles were observed to have a bowl-like shape in which the particles were partially fused (FIG. 2).
- SEM scanning electron microscope
- the average primary particle diameter of the PAI fine particles was 139 nm and the coefficient of variation was 39%, confirming that the PAI fine particles were reproducible.
- Example 15 (dissolution step: a1, precipitation step: a2) The same operation as in Example 14 was performed except that 1.75 g of PAI resin and 48.25 g of NMP (PAI resin concentration: 3.5% by mass) were used.
- the average particle size of the suspension was 21.7 ⁇ m.
- the average primary particle diameter of the PAI resin fine particles was 159 nm and the coefficient of variation was 58%.
- SEM scanning electron microscope
- the average primary particle size of the PAI fine particles was 163 nm and the coefficient of variation was 57%, confirming that the PAI fine particles were reproducible.
- Example 16 (dissolution step: a1, precipitation step: a2) The same operation as in Example 14 was carried out except that 2 g of PAI resin and 48 g of NMP (PAI resin concentration: 4% by mass) were used.
- the average particle size of the suspension was 20.4 ⁇ m.
- the average primary particle diameter of the PAI resin fine particles was 183 nm and the coefficient of variation was 48%.
- SEM scanning electron microscope
- the same operation as described above was performed to confirm reproducibility.
- the average primary particle size of the PAI fine particles was 177 nm, and the coefficient of variation was 48%, confirming reproducibility.
- Comparative Example 1 (dissolution step: a1, precipitation step: a2) The same operation as in Example 14 was carried out except that 2.5 g of PAI resin and 47.5 g of NMP (PAI resin concentration: 5 mass%) were used. Non-spherical coarse particles were formed (FIG. 3).
- Example 1 was the same as Example 1 except that the dissolution tank temperature was room temperature (21 ° C.), pressurized to 0.5 MPa with nitrogen gas, and the ratio of the dissolution tank NMP mass to the amount of water received was 1 / 0.2. Carried out. It became non-spherical coarse particles.
- Comparative Example 3 (dissolution step: b1, precipitation step: b2) Except that the dissolution tank temperature of Example 1 was normal temperature (21 ° C.), pressurized to 0.5 MPa with nitrogen gas, the amount of PAI charged to the dissolution tank was 40 g, and NMP 360 g (PAI resin concentration: 10% by mass). Performed as in Example 1. It became a big lump.
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Abstract
Description
[溶解工程]
下記(a1)および(b1)から選択される工程
(a1)ポリアミドイミド樹脂を有機溶媒に溶解させ、ポリアミドイミド樹脂濃度が5質量%未満のポリアミドイミド樹脂溶解液A1とする工程
(b1)ポリアミドイミド樹脂を有機溶媒に溶解させ、ポリアミドイミド樹脂濃度が10質量%未満のポリアミドイミド樹脂溶解液B1とする工程
[析出工程]
(a2)ポリアミドイミド樹脂溶解液A1を界面活性剤を実質的に含まないポリアミドイミド樹脂の微粒子を析出させる溶媒へ添加してポリアミドイミド樹脂の微粒子を析出させる工程
(b2)ポリアミドイミド樹脂溶解液B1をフラッシュ晶析してポリアミドイミド樹脂の微粒子を析出させる工程
本発明で用いるポリアミドイミド樹脂は、無水トリメリット酸、トリメリット酸無水物モノクロリド等の酸成分とアミン成分を重合させて得られるものである。
本発明におけるPAI樹脂微粒子は、上記PAI樹脂を下記の溶解工程と析出工程を含む工程を経て製造することができる。
[溶解工程]
下記(a1)および(b1)から選択される工程
(a1)ポリアミドイミド樹脂を有機溶媒に溶解させ、ポリアミドイミド樹脂濃度が5質量%未満のポリアミドイミド樹脂溶解液A1とする工程
(b1)ポリアミドイミド樹脂を有機溶媒に溶解させ、ポリアミドイミド樹脂濃度が10質量%未満のポリアミドイミド樹脂溶解液B1とする工程
[析出工程]
(a2)ポリアミドイミド樹脂溶解液A1を界面活性剤を実質的に含まないポリアミドイミド樹脂の微粒子を析出させる溶媒へ添加してポリアミドイミド樹脂の微粒子を析出させる工程
(b2)ポリアミドイミド樹脂溶解液B1をフラッシュ晶析してポリアミドイミド樹脂の微粒子を析出させる工程
すなわち、上記において、(a1)の溶解工程を選択した場合、(a2)の析出工程を行い、(b1)の溶解工程を選択した場合、(b2)の析出工程を行うものである。すなわち、PAI樹脂の濃度が5質量%未満の場合(a1)、PAI樹脂を単に貧溶媒へ添加する(a2)ことにより微粒子が得られるが、5質量%以上では粗大粒子、もしくは塊状物となる。これに対してフラッシュ晶析法(b2)では、PAI樹脂の濃度が10質量%未満で微粒子を作製することが可能である。
本発明における溶解工程は、上記(a1)および(a2)から選択されるものである。
[工程(a2)]
工程(a2)では、上記溶解工程(a1)によって溶解させたPAI樹脂溶解液A1を、界面活性剤を含まないPAI樹脂微粒子を析出させる溶媒中に添加してPAI樹脂微粒子を析出させる。工程(a2)では、常圧条件下(加圧条件下でも良い)で溶解させたPAI樹脂溶解液A1を、常圧条件下でPAI樹脂を析出させる溶媒中へ添加する。
工程(b2)では、上記溶解工程(b1)によって溶解させたPAI樹脂溶解液B1を、フラッシュ晶析して溶媒を析出させる。
PAI樹脂微粒子を単離する方法としては、ろ過、遠心分離、遠心ろ過等の従来公知の固液分離方法で行うことができるが、平均1次粒径300nm以下のような微細なPAI樹脂微粒子を固液分離操作で効率よく単離するためには、凝集によって粒径を増大させた後、ろ過や遠心分離等の固液分離操作を行うことが望ましい。凝集によって粒径を増大させる方法としては、経時的に凝集させる自然凝集法、塩析等の凝集剤を用いた凝集法などを用いることができるが、これらの凝集法のうち、塩析を用いる方法が短時間で凝集体を得ることができること、および大きな凝集体が得られる点から好ましい。塩析による凝集法を用いることにより、工業的な固液分離方法に適した粒径の大きな凝集体を得ることができる。このときの凝集体の平均粒径としては5~100μm(後述の測定方法による粒径)であることが好ましい。
PAI樹脂微粒子の平均粒径は日機装製レーザー回折・散乱方式粒度分布測定装置MT3300EXIIを用い、分散媒としてポリオキシエチレンクミルフェニルエーテル(商品名ノナール912A 東邦化学工業製 以後、ノナール912Aと称す)の0.5質量%水溶液を用いて測定した。具体的にはマイクロトラック法によるレーザーの散乱光を解析して得られる微粒子の総体積を100%として累積カーブを求め、その累積カーブが50%となる点の粒径(メジアン径:d50)を微粒子の平均粒径とした。
本発明での平均一次粒径は日本電子製走査型電子顕微鏡JEOL JMS-6700Fで得られた画像(倍率:30,000倍)から任意の100個の粒子を選び、その最大長さを粒径として粒径を測長し、その平均値を平均一次粒径とした。
[平均一次粒径の変動係数の算出]
本発明における平均一次粒径の変動係数(CV)は、日本電子製走査型電子顕微鏡JEOL JMS-6700Fで得られた画像から任意の100個の粒径を測長して求めた粒度分布の値を用いて下記の式(1)~式(3)により求めた。
東機産業製TVB-10M型粘度計、ローターとしてL/Adpを用い、例えば、粘度が10m~20Pa・sの場合は、ローターの回転数を30rpm、粘度が50~100Pa・sの場合は、ローターの回転数を6rpmとした。それ以外の粘度範囲になるでも場合、測定粘度に合わせたローター回転数を選択し、粘度を測定した。
〔溶解工程〕(b1)
溶解槽の1,000mlのオートクレーブに撹拌機、温度測定器、およびインターナルの溶解液抜き出し管を装着した。抜き出し管にはバルブ開閉ができる連結管を装着した。また、フラッシュ晶析の受槽として、1,000mlのオートクレーブに撹拌機、コンデンサー、ガス通気管、および前記溶解槽からの連結管の他端(フラッシュ晶析出口)を受槽液の中に入る位置に装着した。
水400gを入れた受槽を氷冷し、撹拌しながら窒素ガスを微量通気しておいた。前記溶解槽のインターナル連結管のバルブを開き、溶解液を大気圧下の受槽に移液し、液温が40℃以下になったのを確認してから撹拌を停止し、受槽を開封した。受槽中のPAI樹脂微粒子のフラッシュ液の平均粒径は8.7μmであった。
実施例1の溶解槽温度を50℃とし、窒素ガスで0.5MPaまで加圧した以外は、実施例1と同様に実施した。フラッシュ液の平均粒径は、12.4μmであった。また、PAI微粒子の平均1次粒径は、110nm、変動係数40%であった。30,000倍の走査型電子顕微鏡(SEM)で観察したところ、粒子はほぼ球状であった。
実施例1の溶解槽温度を常温(21℃)とし、窒素ガスで0.5MPaまで加圧した以外は、実施例1と同様に実施した。フラッシュ液の平均粒径は、18.6μmであった。また、PAI微粒子の平均1次粒径は、110nm、変動係数40%であった。30,000倍の走査型電子顕微鏡(SEM)で観察したところ、粒子はほぼ球状であった。
実施例1の溶解槽温度を常温(21℃)、窒素ガスで0.5MPaまで加圧、溶解槽NMP質量と受槽水量の比を1/0.6とした以外は、実施例1と同様に実施した。フラッシュ液の平均粒径は、20.2μmであった。また、PAI微粒子の平均1次粒径は、157nm、変動係数44%であった。30,000倍の走査型電子顕微鏡(SEM)で観察したところ、粒子はほぼ球状であった。
実施例1の溶解槽温度を常温(21℃)、窒素ガスで0.5MPaまで加圧、溶解槽NMP質量と受槽水量の比を1/0.4とした以外は、実施例1と同様に実施した。フラッシュ液の平均粒径は、22.4μmであった。また、PAI微粒子の平均1次粒径は、155nm、変動係数51%であった。30,000倍の走査型電子顕微鏡(SEM)で観察したところ、粒子はほぼ球状であった。
実施例1の溶解槽温度を常温(21℃)、窒素ガスで0.5MPaまで加圧、溶解槽へのPPS仕込み量を14g、NMP386g(PAI樹脂濃度:3.5質量%)とした以外は、実施例1と同様に実施した。フラッシュ液の平均粒径は、19.6μmであった。また、PAI微粒子の平均1次粒径は、167nm、変動係数46%であった。30,000倍の走査型電子顕微鏡(SEM)で観察したところ、粒子はほぼ球状であった。
実施例1の溶解槽温度を常温(21℃)、窒素ガスで0.5MPaまで加圧、溶解槽へのPPS仕込み量を16g、NMP384g(PAI樹脂濃度:4質量%)とした以外は、実施例1と同様に実施した。フラッシュ液の平均粒径は、19.2μmであった。また、PAI微粒子の平均1次粒径は、175nm、変動係数62%であった。30,000倍の走査型電子顕微鏡(SEM)で観察したところ、粒子はほぼ球状であった。
実施例1の溶解槽温度を常温(21℃)、窒素ガスで0.5MPaまで加圧、溶解槽へのPPS仕込み量を20g、NMP380g(PAI樹脂濃度:5質量%)とした以外は、実施例1と同様に実施した。フラッシュ液の平均粒径は、24.5μmであった。また、PAI微粒子の平均1次粒径は、249nm、変動係数52%であった。30,000倍の走査型電子顕微鏡(SEM)で観察したところ、粒子はほぼ球状であった。
実施例1の溶解槽温度を常温(21℃)、窒素ガスで1MPaまで加圧をとした以外は、実施例1と同様に実施した。フラッシュ液の平均粒径は、17.2μmであった。また、PAI樹脂微粒子の平均1次粒径は、143nm、変動係数58%であった。30,000倍の走査型電子顕微鏡(SEM)で観察したところ、粒子はほぼ球状であった。
実施例1の溶解槽温度を常温(21℃)、窒素ガスで0.25MPaまで加圧をとした以外は、実施例1と同様に実施した。フラッシュ液の平均粒径は、20.2μmであった。また、PAI樹脂微粒子の平均1次粒径は、161nm、変動係数43%であった。30,000倍の走査型電子顕微鏡(SEM)で観察したところ、粒子はほぼ球状であった。
実施例1の溶解槽温度を常温(21℃)、窒素ガスで0.5MPaまで加圧、溶解槽の溶媒をDMFとした以外は、実施例1と同様に実施した。フラッシュ液の平均粒径は、16.3μmであった。また、PAI樹脂微粒子の平均1次粒径は、91nm、変動係数46%であった。30,000倍の走査型電子顕微鏡(SEM)で観察したところ、粒子はほぼ球状であった。
実施例1の溶解槽温度を常温(21℃)、窒素ガスで0.5MPaまで加圧、溶解槽の溶媒をDMAcとした以外は、実施例1と同様に実施した。フラッシュ液の平均粒径は、21.6μmであった。また、PAI樹脂微粒子の平均1次粒径は、130nm、変動係数39%であった。30,000倍の走査型電子顕微鏡(SEM)で観察したところ、粒子はほぼ球状であった。
実施例1の溶解槽温度を常温(21℃)、窒素ガスで0.5MPaまで加圧、溶解槽の溶媒をDMSOとした以外は、実施例1と同様に実施した。フラッシュ液の平均粒径は、23.1μmであった。また、PAI樹脂微粒子の平均1次粒径は、163nm、変動係数48%であった。30,000倍の走査型電子顕微鏡(SEM)で観察したところ、粒子はほぼ球状であった。
PAI樹脂1.5gをNMP48.5g(PAI樹脂濃度:3質量%)に溶かし、その溶解液を常温(21℃)にて、撹拌している水50gへピペットで滴下してPAI樹脂微粒子懸濁液を得た。懸濁液の平均粒径は、17.6μmであった。その懸濁液を4%食塩水50gへ加え、1400rpmで30分間撹拌した後、3時間静置した。塩析した懸濁液をろ過、洗浄してPAI樹脂微粒子ウエットケークを得た。PAI樹脂微粒子の平均1次粒径は、140nm、変動係数36%であった。30,000倍の走査型電子顕微鏡(SEM)で観察したところ、粒子は一部に粒子が融着したような繭型形状のものが観察された(図2)。
PAI樹脂1.75g、NMP48.25g(PAI樹脂濃度:3.5質量%)とした以外は、実施例14と同様に実施した。懸濁液のの平均粒径は、21.7μmであった。PAI樹脂微粒子の平均1次粒径は、159nm、変動係数58%であった。30,000倍の走査型電子顕微鏡(SEM)で観察したところ、粒子の一部に粒子が融着したような繭型形状のものが観察された。
PAI樹脂2g、NMP48g(PAI樹脂濃度:4質量%)とした以外は、実施例14と同様に実施した。懸濁液の平均粒径は、20.4μmであった。PAI樹脂微粒子の平均1次粒径は、183nm、変動係数48%であった。30,000倍の走査型電子顕微鏡(SEM)で観察したところ、粒子の一部に粒子が融着したような繭型形状のものが観察された。
PAI樹脂2.5g、NMP47.5g(PAI樹脂濃度:5質量%)とした以外は、実施例14と同様に実施した。非真球状の粗大粒子となった(図3)。
実施例1の溶解槽温度を常温(21℃)、窒素ガスで0.5MPaまで加圧、溶解槽NMP質量と受槽水量の比を1/0.2とした以外は、実施例1と同様に実施した。非真球状の粗大粒子となった。
実施例1の溶解槽温度を常温(21℃)、窒素ガスで0.5MPaまで加圧、溶解槽へのPAI仕込み量を40g、NMP360g(PAI樹脂濃度:10質量%)とした以外は、実施例1と同様に実施した。大きな塊状物となった。
Claims (7)
- 下記の溶解工程と析出工程を含むことを特徴とするポリアミドイミド樹脂微粒子の製造方法。
[溶解工程]
下記(a1)および(b1)から選択される工程
(a1)ポリアミドイミド樹脂を有機溶媒に溶解させ、ポリアミドイミド樹脂濃度が5質量%未満のポリアミドイミド樹脂溶解液A1とする工程
(b1)ポリアミドイミド樹脂を有機溶媒に溶解させ、ポリアミドイミド樹脂濃度が10質量%未満のポリアミドイミド樹脂溶解液B1とする工程
[析出工程]
(a2)ポリアミドイミド樹脂溶解液A1を、界面活性剤を実質的に含まないポリアミドイミド樹脂の微粒子を析出させる溶媒へ添加してポリアミドイミド樹脂の微粒子を析出させる工程
(b2)ポリアミドイミド樹脂溶解液B1をフラッシュ晶析してポリアミドイミド樹脂の微粒子を析出させる工程 - 前記析出工程(b2)のフラッシュ晶析において、0.2~4MPaの圧力(ゲージ圧)下にある溶解液をフラッシュ晶析する請求項1に記載のポリアミドイミド樹脂微粒子の製造方法。
- 前記溶解工程において、用いる有機溶媒が、N-メチル-2-ピロリジノン、ジメチホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド、1,3-ジメチル-2-イミダゾリジノンから選ばれる少なくとも一種である請求項1または2に記載のポリアミドイミド樹脂微粒子の製造方法。
- 前記析出工程(a2)、(b2)において、ポリアミドイミド樹脂微粒子を析出させる溶媒が水である請求項1から3のいずれかに記載のポリアミドイミド樹脂微粒子の製造方法。
- 請求項1から4のいずれかの製造方法によって得られるポリアミドイミド樹脂微粒子であって、平均一次粒径が300nm以下であるポリアミドイミド樹脂微粒子。
- 平均一次粒径が200nm以下である請求項5に記載のポリアミドイミド樹脂微粒子。
- 平均一次粒径が200nm以下、かつ、変動係数が70%以下であることを特徴とするポリアミドイミド樹脂微粒子。
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JP2015515501A (ja) * | 2012-08-02 | 2015-05-28 | 東レ・ダウコーニング株式会社 | ポリミドイミド樹脂を含む塗料組成物 |
JP2015531813A (ja) * | 2012-09-12 | 2015-11-05 | ヴァルレック オイル アンド ガスフランス | 発がん性、突然変異性、または生殖毒性物質を含まない、ポリアミド−イミドの安定な水性分散液を調製するプロセスと、塗膜への応用 |
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US20120237771A1 (en) | 2012-09-20 |
EP2502952A4 (en) | 2014-07-02 |
JPWO2011062006A1 (ja) | 2013-04-04 |
EP2502952B1 (en) | 2018-06-13 |
US9193836B2 (en) | 2015-11-24 |
KR20120117738A (ko) | 2012-10-24 |
EP2502952A1 (en) | 2012-09-26 |
KR101643990B1 (ko) | 2016-07-29 |
JP5477300B2 (ja) | 2014-04-23 |
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