WO2014034581A1 - フッ化ビニリデン樹脂微粒子の製造方法、およびフッ化ビニリデン樹脂微粒子 - Google Patents
フッ化ビニリデン樹脂微粒子の製造方法、およびフッ化ビニリデン樹脂微粒子 Download PDFInfo
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- WO2014034581A1 WO2014034581A1 PCT/JP2013/072650 JP2013072650W WO2014034581A1 WO 2014034581 A1 WO2014034581 A1 WO 2014034581A1 JP 2013072650 W JP2013072650 W JP 2013072650W WO 2014034581 A1 WO2014034581 A1 WO 2014034581A1
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- vinylidene fluoride
- fluoride resin
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/18—Monomers containing fluorine
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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
- C08J3/124—Treatment for improving the free-flowing characteristics
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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
- C08J3/16—Powdering or granulating by coagulating dispersions
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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
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/26—Cellulose ethers
- C08L1/28—Alkyl ethers
- C08L1/284—Alkyl ethers with hydroxylated hydrocarbon radicals
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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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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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 vinylidene fluoride resin fine particles and vinylidene fluoride resin fine particles.
- polymer fine particles are used to modify and improve various materials by utilizing the large specific surface area and the structure of fine particles.
- Major applications include additives for toner, binder materials such as paint, additives such as powder coating materials, additives for metal coating materials, water-repellent coating materials, automotive materials, building materials, and other molded products. Can be mentioned.
- Vinylidene fluoride resin fine particles have excellent weather resistance, stain resistance, solvent resistance, water resistance, moisture resistance, etc., and are used for antifouling materials in printing presses, toner applications, weather resistance and water resistant paints. It is suitably used as a resin.
- An object of the present invention is to provide a method for producing vinylidene fluoride resin fine particles, and vinylidene fluoride resin fine particles suitable for coating and coating applications.
- the vinylidene fluoride resin fine particles according to the present invention have the configurations shown in the following [1] to [4].
- [1] Vinylidene fluoride resin fine particles having an average particle size of 0.3 ⁇ m or more and less than 100 ⁇ m and a particle size distribution index of 1 to 2,
- [2] The vinylidene fluoride resin fine particles according to the above [1], wherein the angle of repose is less than 40 degrees
- the vinylidene fluoride resin fine particles according to the above [1] or [2] having an average sphericity of 80 or more
- [4] The vinylidene fluoride resin fine particles according to any one of the above [1] to [3], wherein the particles are solid.
- the method for producing vinylidene fluoride resin fine particles according to the present invention includes the following [5] to [12]. It has the structure shown in FIG. [5] An organic solvent composed of at least one selected from the group consisting of a ketone organic solvent, a nitrile organic solvent, and an ether organic solvent as a vinylidene fluoride resin (A) and a polymer (B) different from the vinylidene fluoride resin When dissolved and mixed in (C), phase separation into two phases, a solution phase mainly composed of vinylidene fluoride resin (A) and a solution phase mainly composed of polymer (B) different from vinylidene fluoride resin
- the emulsion forming step of forming an emulsion of the polymer (B) and the organic solvent (C) different from the vinylidene fluoride resin (A) and the vinylidene fluoride resin, and the solubility of the vinylidene fluoride resin (A) is organic.
- Vinylidene fluoride resin fine particles are precipitated by bringing the poor solvent of vinylidene fluoride resin smaller than the solvent (C) into contact with the emulsion.
- the method of producing a vinylidene fluoride resin fine particles; and a that micronization step [6] The method for producing fine vinylidene fluoride resin particles according to [5] above, wherein the solvent of each phase is the same when phase-separated into two phases, [7] The method for producing fine vinylidene fluoride resin particles according to [5] or [6] above, wherein the polymer (B) different from the vinylidene fluoride resin is a thermoplastic resin, [8] The method for producing vinylidene fluoride resin fine particles according to any one of the above [5] to [7], wherein the polymer (B) different from the vinylidene fluoride resin is dissolved in a poor solvent for the vinylidene fluoride resin.
- the vinylidene fluoride resin fine particle production method of the present invention makes it possible to easily produce vinylidene fluoride resin fine particles. Furthermore, it is a spherical shape that is slippery, slippery, uniformly dispersed, and capable of processing without coating unevenness. It becomes possible to produce desired vinylidene fluoride resin fine particles such as vinylidene fluoride resin fine particles according to the application.
- the vinylidene fluoride resin fine particles obtained by the present invention include a slush molding material, a rapid prototyping / rapid manufacturing material, a plastic sol paste resin, a powder blocking material, a powder flowability improving material, a lubricant, Rubber compounding agents, abrasives, thickeners, filter agents and filter aids, gelling agents, flocculants, paint additives, oil absorbents, mold release agents, plastic film / sheet slipperiness improvers, antiblocking agents , Gloss modifier, matte finish agent, light diffusing agent, surface high hardness improver, binder material, adhesive, coating agent, valves and caps for semiconductor and liquid crystal manufacturing equipment, guide rails, rollers, bolts, linings, toughness improvers Various modifiers such as, spacers for liquid crystal display devices, chromatographic fillers, fragrances and pesticide retention agents, chemical reaction catalyst And its support, gas adsorbent, sintered material for ceramic processing, standard particles for measurement and analysis, particles for food industry, powder coating
- FIG. 3 is an observation view of vinylidene fluoride resin fine particles produced in Example 1 using a scanning electron microscope.
- FIG. 5 is an observation view of vinylidene fluoride resin fine particles produced in Example 2 using a scanning electron microscope.
- the method for producing vinylidene fluoride resin fine particles according to the present invention includes a vinylidene fluoride resin (A) and a polymer (B) different from vinylidene fluoride resin, a ketone organic solvent, a nitrile organic solvent, and an ether organic solvent (C ) And a polymer (B) different from the vinylidene fluoride resin and the solution phase mainly composed of the vinylidene fluoride resin (A) when dissolved and mixed in the organic solvent (C) consisting of at least one of the group consisting of Forming step of forming an emulsion of polymer (B) and organic solvent (C) different from vinylidene fluoride resin (A) and vinylidene fluoride resin in a system in which the phase is separated into two phases of a solution phase mainly composed of And the poor solvent of the vinylidene fluoride resin (A) having a lower solubility than the organic solvent (C) in contact with the emulsion And a fine step of
- the vinylidene fluoride resin in the present invention refers to a resin obtained by polymerizing vinylidene fluoride, which is represented by the following general formula (1).
- a commercially available product can be used as the vinylidene fluoride resin (A) in the present invention.
- Specific examples of commercially available vinylidene fluoride resins include KF polymers W # 1100, # 1300, # 1700, # 7200, # 7300, # 9100, # 9200, # 9300 (made by Kureha), Kyner 721, 741, 761, 461, 301F, HSV900, Kyner Flex 2851, 2801, 2821 (made by Arkema), Solef 1013, 1015 21216, 31508, 6020 (manufactured by Solvay Solexis), reagents manufactured by Aldrich, and the like.
- the vinylidene fluoride resin (A) in the present invention may be a homopolymer of vinylidene fluoride, or another unit not containing vinylidene fluoride as long as the characteristics of the vinylidene fluoride resin are not impaired.
- a copolymer with a monomer component may be included.
- examples of other monomer components that do not contain vinylidene fluoride include hydrocarbon vinyl monomers such as ethylene, propylene, isobutene, and butadiene, ethylene fluoride, ethylene trifluoride, and ethylene tetrafluoride.
- Fluorine vinyl monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl maleate, ethyl maleate, butyl maleate, 2-carboxyethyl acrylate Containing carboxyl ester groups such as 2-carboxyethyl melacrylate, acryloyloxyethyl succinic acid, methacryloyloxyethyl succinic acid, acryloyloxyethyl phthalic acid, methacryloyloxyethyl phthalic acid, trifluoromethyl acrylic acid, etc.
- the amount of the copolymer is not particularly limited as long as it does not impair the properties of the vinylidene fluoride resin (A), but the total of the structural units of the vinylidene fluoride resin (A) is 100 mol%. In this case, it is usually 30 mol% or less, preferably 25 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less, and particularly preferably 5 mol% or less.
- the lower limit of the weight average molecular weight is 1,000 or more, preferably 5,000 or more, more preferably 10,000 or more, and still more preferably. Is 50,000 or more, particularly preferably 100,000 or more, and extremely preferably 500,000 or more.
- the upper limit of the molecular weight is 10,000,000 or less, preferably 5,000,000 or less, 2,000,000 or less, and more preferably 1,000,000 as the weight average molecular weight. 000 or less.
- the molecular weight of the vinylidene fluoride resin (A) in the present invention refers to a weight average molecular weight measured by gel permeation chromatography (GPC) using dimethylformamide as a solvent and converted to polystyrene.
- thermoplastic resins examples include thermoplastic resins and thermosetting resins. From the viewpoint of being easily dissolved in the organic solvent (C) described later, the thermoplastic resin is used. Is preferred. Specifically, poly (vinyl alcohol) (which may be fully saponified or partially saponified poly (vinyl alcohol)), poly (vinyl alcohol-ethylene) copolymer (fully saponified or partially saponified) Saponified poly (vinyl alcohol-ethylene) copolymer), polyvinyl pyrrolidone, poly (ethylene glycol), poly (ethylene oxide), sucrose fatty acid ester, poly (oxyethylene fatty acid ester), poly (Oxyethylene laurin fatty acid ester), poly (oxyethylene glycol monofatty acid ester), poly (oxyethylene alkylphenyl ether), poly (oxyalkyl ether), polyacrylic acid, sodium polyacrylate, polymethacrylic acid, polymethacrylic acid Sodium, polystyren
- poly (vinyl alcohol) (fully saponified or partially saponified poly (May be vinyl alcohol)), poly (vinyl alcohol-ethylene) copolymer (may be fully saponified or partially saponified poly (vinyl alcohol-ethylene) copolymer) , Poly (ethylene glycol), poly (ethylene oxide), sucrose fatty acid ester, poly (oxyethylene alkylphenyl ether), poly (oxyalkyl ether), poly (acrylic acid), poly (methacrylic acid), carboxymethylcellulose, hydroxy Cellulose derivatives such as ethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, ethyl hydroxy cellulose, carboxymethyl ethyl cellulose, carboxymethyl cellulose, carboxymethyl cellulose sodium, cellulose ester, polyvinyl pyrrolidone, and more preferably poly (vinyl alcohol) (fully saponified) Type (partially saponified poly (vinyl alcohol)) and poly (vinyl alcohol
- the molecular weight of the polymer (B) different from the vinylidene fluoride resin is preferably 1,000 to 100,000,000, more preferably 1,000 to 10,000,000, still more preferably in terms of weight average molecular weight. 5,000 to 1,000,000, particularly preferably in the range of 10,000 to 500,000, and most preferably in the range of 10,000 to 100,000.
- the weight average molecular weight here refers to a weight average molecular weight measured by gel permeation chromatography (GPC) using water as a solvent and converted into polyethylene glycol.
- GPC gel permeation chromatography
- Organic solvent (C) consisting of at least one selected from the group consisting of ketone organic solvents, nitrile organic solvents and ether organic solvents used in the present invention (hereinafter also simply referred to as “organic solvent (C)”) Is a pure solvent or mixed solvent containing at least one ketone organic solvent, nitrile organic solvent or ether organic solvent.
- ketone organic solvent acetone, methyl ethyl ketone (2-butanone) , 3-pentanone, 3-pentanone, methyl isopropyl ketone, diisopropyl ketone, methyl isobutyl ketone, diisobutyl ketone and other aliphatic ketones, acetophenone, phenyl ethyl ketone, diphenyl ketone and other aromatic ketones.
- Aromatic chain ethers such as dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, dihexyl ether, dioctyl ether, diisoamyl ether, tert-amyl methyl ether, tert-butyl ethyl ether, butyl methyl ether , Butyl ethyl ether, 1-methoxyethane (monoglyme), 1-ethoxyethane, diethylene glycol dimethyl ether (di Lime), ethylene glycol diethyl ether, 2-methoxyethyl ether, di (ethylene glycol) diethyl ether, di (ethylene glycol) dibutyl ether, triethylene glycol dimethyl ether, aliphatic cyclic ether tetrahydrofuran, 2-methyltetrahydrofuran, 2, 5-dimethyltetrahydro
- the ketone organic solvent is preferably acetone, methyl ethyl ketone, methyl isobutyl ketone, or diethyl ketone
- the nitrile organic solvent is preferably acetonitrile or propionitrile, and is an ether type.
- organic solvents examples include dipropyl ether, diisopropyl ether, dibutyl ether, 1-ethoxyethane, diethylene glycol dimethyl ether (diglyme), ethylene glycol diethyl ether, 2-methoxyethyl ether, di (ethylene glycol) diethyl ether, tetrahydrofuran, 2-methyl Tetrahydrofuran, tetrahydropyran, 1,4-dioxane and anisole are preferred.
- the ketone organic solvent is more preferably acetone or methyl ethyl ketone
- the nitrile organic solvent is more preferably acetonitrile
- the ether organic solvent is dipropyl ether, diisopropyl ether, 1-ethoxyethane, diethylene glycol dimethyl ether (diglyme). ) Is more preferable.
- the organic solvent (C) is more preferably an ether-based organic solvent having a boiling point of 100 ° C. or higher.
- a solvent for example, diethylene glycol dimethyl ether ( Diglyme) and 1,4-dioxane.
- an organic solvent having a boiling point lower than 100 ° C. which is the boiling point of water
- examples of such solvents include acetone, methyl ethyl ketone, and 3-methylbutanone as ketone organic solvents.
- nitrile organic solvent examples include acetonitrile and propionitrile
- ether organic solvent examples include diethyl ether, dipropyl ether, diisopropyl ether, tetrahydrofuran, and tetrahydropyran.
- a system that separates into two phases, a solution phase mainly composed of vinylidene fluoride resin (A) and a solution phase mainly composed of a polymer (B) different from vinylidene fluoride resin means vinylidene fluoride.
- Resin (A) is a system in which a polymer (B) different from vinylidene fluoride resin is dissolved in an organic solvent (C), and when these are mixed, mainly contains vinylidene fluoride resin (A) 2 of a solution phase (hereinafter also referred to as a vinylidene fluoride resin solution phase) and a solution phase mainly containing a polymer (B) different from the vinylidene fluoride resin (hereinafter also referred to as a polymer B solution phase)
- a system that divides into phases. By mixing and emulsifying such a system under conditions for phase separation, an emulsion is formed.
- the polymer (A) and the polymer (B) different from the vinylidene fluoride resin are dissolved in the organic solvent (C). Whether the polymer (B) different from the vinylidene fluoride resin (A) and the vinylidene fluoride resin is dissolved by more than 1% by mass in the organic solvent (C) is determined.
- the vinylidene fluoride resin solution phase becomes a dispersed phase and the polymer B solution phase becomes a continuous phase.
- fine-particles precipitate from the vinylidene fluoride resin solution phase in an emulsion, and are comprised with a vinylidene fluoride resin (A). Polymer fine particles can be obtained.
- the poor solvent for the vinylidene fluoride resin refers to a solvent in which the solubility of the vinylidene fluoride resin (A) is smaller than that of the organic solvent (C) and hardly dissolves the vinylidene fluoride resin (A).
- the solubility of the vinylidene fluoride resin (A) is 1% by mass or less.
- the upper limit of the solubility of the vinylidene fluoride resin (A) in the poor solvent is more preferably 0.5% by mass or less, and further preferably 0.1% by mass or less.
- the poor solvent for the vinylidene fluoride resin used in the above-described production method is a poor solvent for the vinylidene fluoride resin (A) and a solvent that dissolves the polymer (B) different from the vinylidene fluoride resin. preferable. Thereby, the vinylidene fluoride resin fine particle comprised with a vinylidene fluoride resin (A) can be precipitated efficiently.
- the poor solvent of the vinylidene fluoride resin is a solvent that is uniformly mixed with the organic solvent (C), which is a solvent for dissolving the vinylidene fluoride resin (A) and the polymer (B) different from the vinylidene fluoride resin. Is preferred.
- the type of the vinylidene fluoride resin (A) to be used preferably the vinylidene fluoride resin (A) to be used and the polymer (B) different from the vinylidene fluoride resin to be used as appropriate.
- Specific examples include pentane, hexane, heptane, octane, nonane, n-decane, n-dodecane, n-tridecane, cyclohexane, cyclopentane and other aliphatic hydrocarbon solvents, benzene And an aromatic hydrocarbon solvent such as toluene and xylene, an alcohol solvent such as methanol, ethanol, 1-propanol and 2-propanol, and a solvent selected from at least one of water.
- an aromatic hydrocarbon solvent an aliphatic hydrocarbon solvent, an alcohol solvent, and water are preferable, and an alcohol is more preferable.
- the polymer fine particles can be obtained by efficiently depositing vinylidene fluoride resin.
- a solution in which a vinylidene fluoride resin (A) and a polymer (B) different from the vinylidene fluoride resin are mixed and dissolved in an organic solvent (C) is mixed with a solution phase containing the vinylidene fluoride resin (A) as a main component and a fluorine. It is necessary to phase-separate into two solution phases mainly composed of a polymer (B) different from the vinylidene chloride resin.
- a solution phase organic solvent (C) mainly composed of vinylidene fluoride resin (A) and a solution phase organic solvent (C) mainly composed of a polymer (B) different from vinylidene fluoride resin May be the same or different, but are preferably the same solvent. Note that the same solvent as used herein permits substantially the same type of solvent.
- the conditions for generating the two-phase separation state are the types of the polymer (B) different from the vinylidene fluoride resin (A) or the vinylidene fluoride resin, the polymer different from the vinylidene fluoride resin (A) or the vinylidene fluoride resin ( It varies depending on the molecular weight of B), the type of organic solvent (C), the concentration of polymer (B) different from vinylidene fluoride resin (A) or vinylidene fluoride resin, the temperature at which the invention is carried out, the pressure, and the like.
- the difference in solubility parameter (hereinafter also referred to as SP value) of polymer (B) different from vinylidene fluoride resin (A) and vinylidene fluoride resin. are preferably separated.
- the difference in SP value is 1 (J / cm 3 ) 1/2 or more, more preferably 2 (J / cm 3 ) 1/2 or more, and further preferably 3 (J / cm 3 ) 1/2 or more. Particularly preferably, it is 5 (J / cm 3 ) 1/2 or more, and most preferably 8 (J / cm 3 ) 1/2 or more.
- the SP value is within this range, phase separation is easily performed and phase separation is facilitated, so that vinylidene fluoride resin fine particles having a higher vinylidene fluoride resin component content can be obtained.
- the upper limit of the SP value difference is preferably 20 ( J / cm 3 ) 1/2 or less, more preferably 15 (J / cm 3 ) 1/2 or less, and even more preferably 10 (J / cm 3 ) 1/2 or less.
- the SP value referred to here is calculated based on the Fedor's estimation method, and is specifically calculated based on the cohesive energy density and molar molecular volume (written by Hideki Yamamoto, “SP Value Basics”). ⁇ Application and calculation method ”, Information Organization Co., Ltd., published on March 31, 2005). In addition, in the case where the calculation cannot be performed by this method, the SP value is calculated based on the determination as to whether or not it dissolves in a known solvent, and is substituted (J. Brand, “Polymer Handbook No. 1 4th Edition (Polymer Handbook Fourth Edition), Wiley, 1998).
- the conditions for the phase separation state can be discriminated by the three-component phase diagram of the vinylidene fluoride resin (A), the polymer (B) different from the vinylidene fluoride resin, and the organic solvent (C) for dissolving them,
- This three-component phase diagram can be created by a simple preliminary experiment by observing a state in which the ratio of each component is changed. Specifically, first, the vinylidene fluoride resin (A), the polymer (B) different from the vinylidene fluoride resin, and the organic solvent (C) are mixed and dissolved at a predetermined ratio, and left to stand for a predetermined time. Determine whether it occurs.
- this determination is performed with at least 3 points, preferably 5 points or more, more preferably 10 points or more, and a phase diagram is created based on the determination results.
- this phase diagram By using this phase diagram to distinguish the two-phase separation region and the one-phase region, the conditions for the phase separation state can be determined.
- the vinylidene fluoride resin (A), the polymer (B) different from the vinylidene fluoride resin, and the organic solvent (C) are adjusted to a predetermined ratio, and then the present invention.
- the polymer (B) different from the vinylidene fluoride resin (A) and the vinylidene fluoride resin is completely dissolved in the organic solvent (C) under sufficient temperature and pressure conditions, and sufficient stirring is performed. And after leaving still for 3 days, it confirms whether a phase separation is carried out macroscopically. However, when a sufficiently stable emulsion is obtained, macroscopic phase separation may not occur even after standing for 3 days. In this case, phase separation is determined by using an optical microscope, a phase contrast microscope, or the like based on whether the phase is microscopically separated.
- the phase separation state includes a vinylidene fluoride resin solution phase mainly composed of vinylidene fluoride resin (A) in an organic solvent (C) and a polymer B composed mainly of a polymer (B) different from vinylidene fluoride resin. Formed by separation into solution phase.
- the vinylidene fluoride resin solution phase is a phase in which the vinylidene fluoride resin (A) is mainly distributed
- the polymer B solution phase is a phase in which the polymer (B) different from the vinylidene fluoride resin is mainly distributed. It is.
- the vinylidene fluoride resin solution phase and the polymer B solution phase have a volume ratio according to the type and amount of the polymer (B) different from the vinylidene fluoride resin (A) and vinylidene fluoride resin.
- the concentration of each of the vinylidene fluoride resin (A) and the polymer (B) different from the vinylidene fluoride resin relative to the organic solvent (C) is particularly limited as long as it is within the possible range of dissolution in the organic solvent (C).
- the lower limit of each concentration is preferably more than 1% by mass, more preferably 2% by mass. %, Further preferably 3% by mass, and more preferably 5% by mass.
- the upper limit of each concentration is preferably 50% by mass, more preferably 30% by mass, and still more preferably 20% by mass.
- the interfacial tension is reduced. As a result, the resulting emulsion is stably maintained, and the particle size distribution Is estimated to be small. Since the interfacial tension between these two phases is very small, it cannot be directly measured by a commonly used method such as the hanging drop method in which different solutions are added to the solution, but from the surface tension of each phase with air. By estimating, the interfacial tension can be estimated.
- the upper limit of r 1/2 is preferably 10 mN / m, more preferably 5 mN / m, still more preferably 3 mN / m, and particularly preferably 2 mN / m.
- the lower limit is more than 0 mN / m.
- the viscosity between the two phases affects the average particle size and particle size distribution, and the smaller the viscosity ratio, the smaller the particle size distribution.
- the lower limit of the viscosity ratio between the two phases is preferably 0.1 or more, more preferably 0.2 or more, further preferably 0.3 or more, more preferably 0.5 or more, and is extremely preferable. Is 0.8 or more.
- the upper limit is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less, particularly preferably 1.5 or less, and extremely preferably 1.2 or less.
- the viscosity ratio between the two phases is defined as “viscosity of the vinylidene fluoride resin solution phase / viscosity of the polymer B solution phase” under the temperature conditions for carrying out the present invention.
- an emulsion forming step of mixing the phase-separated system thus obtained that is, applying a shearing force to the solution comprising the phase-separated system) to emulsify, and the poor vinylidene fluoride resin
- a fine particle forming step of bringing a solvent into contact with the emulsion to precipitate vinylidene fluoride resin fine particles makes the vinylidene fluoride resin fine particles to produce polymer fine particles.
- the emulsion forming step may be performed after the step of dissolving the vinylidene fluoride resin (A) and the polymer (B) different from the vinylidene fluoride resin in the organic solvent (C), or the vinylidene fluoride resin (You may implement simultaneously with the process of melt
- the emulsion formation step and the micronization step can be performed in a normal reaction tank.
- the temperature at which the emulsion formation step and the micronization step are performed is a temperature at which the vinylidene fluoride resin (A) and the polymer (B) different from the vinylidene fluoride resin are dissolved and phase-separated, and desired microparticles are obtained.
- the lower limit is usually 0 ° C. or higher, preferably 10 ° C. or higher, more preferably 20 ° C. or higher.
- the upper limit is preferably 300 ° C. or lower, more preferably 200 ° C. or lower, more preferably 160 ° C. or lower, particularly preferably 140 ° C. or lower, and particularly preferably 100 ° C. or lower. It is below °C.
- the pressure suitable for carrying out the emulsion formation step and the micronization step is in the range of normal pressure to 10 atm.
- a preferable lower limit is 1 atm or more.
- As a preferable upper limit it is 5 atmospheres or less, More preferably, it is 3 atmospheres or less, More preferably, it is 2 atmospheres or less.
- an inert gas for the reaction tank.
- nitrogen, helium, argon, and carbon dioxide are preferable, and nitrogen and argon are preferable.
- an emulsion is formed by mixing the above-described system for phase separation. That is, an emulsion is formed by applying a shearing force to the solution as a phase separation system obtained above.
- the emulsion is formed so that the vinylidene fluoride resin solution phase becomes particulate droplets.
- the volume of the polymer B solution phase is the volume of the vinylidene fluoride resin solution phase.
- the volume ratio of the vinylidene fluoride resin solution phase is preferably less than 0.5 and more preferably between 0.4 and 0.1 with respect to the total volume 1 of both phases. For example, when preparing the phase diagram, it is possible to set an appropriate volume ratio range by simultaneously measuring the volume ratio in the concentration of each component.
- the fine particles obtained by this production method become fine particles having a small particle size distribution, because a very uniform emulsion can be obtained at the stage of emulsion formation. This tendency is remarkable when a single solvent capable of dissolving both the vinylidene fluoride resin (A) and the polymer (B) different from the vinylidene fluoride resin is used.
- the emulsion formation step in order to obtain a sufficient shearing force to form an emulsion, it is sufficient to use stirring by a conventionally known method, a liquid phase stirring method using a stirring blade, a stirring method using a continuous biaxial mixer, It can mix by well-known methods, such as the mixing method by a homogenizer, and an ultrasonic irradiation method.
- the stirring speed is preferably 50 rpm to 1,200 rpm, more preferably 100 rpm to 1,000 rpm, still more preferably 200 rpm to 800 rpm, and particularly preferably. Is 300 to 600 rpm.
- Specific examples of the stirring blade include a propeller type, a paddle type, a flat paddle type, a turbine type, a double cone type, a single cone type, a single ribbon type, a double ribbon type, a screw type, and a helical ribbon type. As long as a sufficient shearing force can be applied to the system, it is not particularly limited thereto.
- a stirrer In order to generate an emulsion, not only a stirrer but also a widely known device such as an emulsifier and a disperser may be used.
- a batch emulsifier such as a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), Ebara Milder (manufactured by Ebara Seisakusho) , TK fill mix, TK pipeline homomixer (manufactured by Koki Kogyo Co., Ltd.), colloid mill (manufactured by Shinko Pantech Co., Ltd.), slasher, trigonal wet pulverizer (manufactured by Mitsui Miike Chemical Co., Ltd.), ultrasonic homogenizer, static For example, a mixer.
- a homogenizer manufactured by IKA
- polytron
- the emulsion thus obtained is subsequently subjected to a micronization step for precipitating microparticles.
- a poor solvent of vinylidene fluoride resin hereinafter sometimes simply referred to as a poor solvent
- Fine particles are deposited with a diameter corresponding to the emulsion diameter.
- the contact method of the poor solvent and the emulsion may be a method of putting the emulsion in the poor solvent or a method of putting the poor solvent in the emulsion, but a method of putting the poor solvent in the emulsion is preferable.
- the method for introducing the poor solvent is not particularly limited as long as desired polymer fine particles can be obtained, and any of a continuous dropping method, a divided addition method, and a batch addition method may be used. In order to prevent the particle size distribution from becoming unity and the formation of a mass exceeding 1000 ⁇ m, it is preferable to use a continuous dropping method or a divided dropping method, and to implement industrially efficiently. Is most preferably a continuous dropping method.
- the temperature at which the poor solvent is brought into contact is not particularly limited as long as the vinylidene fluoride resin fine particles are precipitated, and the lower limit is 0 ° C. or more and the upper limit is 300 ° C. or less. If the temperature is too low, the poor solvent is solidified and cannot be used, so the lower limit is preferably 10 ° C. or higher, more preferably 20 ° C. or higher. Further, if the temperature is too high, thermal degradation of the vinylidene fluoride resin (A) or the polymer (B) different from the vinylidene fluoride resin is likely to proceed, so the upper limit is preferably 200 ° C. or less, more preferably Is 100 ° C. or lower, more preferably 90 ° C. or lower.
- time to add a poor solvent Preferably it is 10 minutes or more and less than 50 hours, More preferably, it is 15 minutes or more and less than 10 hours, More preferably, it is 30 minutes or more and less than 5 hours. If it is carried out in a time shorter than this range, the particle size distribution may increase or a lump may be generated with the aggregation, fusion, and coalescence of the emulsion. Moreover, when it implements in the time longer than this, when industrial implementation is considered, it is unrealistic. By carrying out within this time range, when converting from emulsion to polymer fine particles, aggregation between particles can be suppressed, and polymer fine particles having a small particle size distribution can be obtained.
- the amount of the poor solvent to be added depends on the state of the emulsion, it is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 1 part by mass of the total emulsion. Parts, more preferably 0.2 parts by weight to 3 parts by weight, particularly preferably 0.2 parts by weight to 2 parts by weight, and most preferably 0.2 parts by weight to 1.0 parts by weight. is there. *
- the contact time between the poor solvent and the emulsion may be a time sufficient for the fine particles to precipitate. However, in order to cause sufficient precipitation and to obtain efficient productivity, it is preferably 5 after the end of the addition of the poor solvent. Minutes to 50 hours, more preferably 5 minutes to 10 hours, even more preferably 10 minutes to 5 hours, particularly preferably 20 minutes to 4 hours, and most preferably 30 minutes. This is within 3 hours.
- the fine particle powder is recovered by subjecting the polymer fine particle dispersion thus prepared to solid-liquid separation by a known method such as filtration, vacuum filtration, pressure filtration, centrifugal separation, centrifugal filtration, and spray drying. I can do it.
- the polymer fine particles separated by solid-liquid separation are washed with a solvent or the like, if necessary, to remove impurities attached or contained therein, and then purified.
- the solvent obtained by solid-liquid separation is a mixture of a polymer (B), an organic solvent (C), and a poor solvent different from the vinylidene fluoride resin.
- a known method can be used. Specifically, simple distillation, vacuum distillation, precision distillation, thin film distillation, extraction, membrane separation, and the like can be mentioned. This is a method by distillation or precision distillation.
- the system When performing distillation operations such as simple distillation and vacuum distillation, the system is heated, and there is a possibility of promoting thermal decomposition of a polymer different from vinylidene fluoride resin (B) and an organic solvent (C), As in the above-described production of the polymer fine particles, it is preferably performed in a state free of oxygen as much as possible, and more preferably in an inert atmosphere. Specifically, it is preferable to carry out under nitrogen, helium, argon, carbon dioxide conditions. Moreover, you may re-add a phenol type compound as antioxidant.
- the residual amount of the poor solvent is 10% by mass or less, preferably 5% by mass or less, based on the total amount of the organic solvent (C) to be recycled and the polymer (B) different from the vinylidene fluoride resin. More preferably, it is 3 mass% or less, Most preferably, it is 1 mass% or less. If it exceeds this range, the particle size distribution of the fine particles may be widened or the particles may be aggregated.
- the amount of the poor solvent in the solvent used for recycling can be measured by a known method, such as a gas chromatography method or a Karl Fischer method.
- the organic solvent (C), the polymer (B) different from the vinylidene fluoride resin, etc. may be lost. Is preferred.
- the vinylidene fluoride resin fine particles of the present invention will be described in detail.
- an appropriate particle diameter range can be determined according to the application. For example, in applications such as paint, the smaller the particle diameter, the smoother it can be, so the upper limit of the number average particle diameter is usually less than 100 ⁇ m, and according to a preferred embodiment, it is 80 ⁇ m or less, and more According to a preferred embodiment, it is 50 ⁇ m or less, according to a further preferred embodiment, it is 30 ⁇ m or less, and according to a most preferred embodiment, it is 20 ⁇ m or less.
- the lower limit is usually 0.3 ⁇ m or more, preferably 0.5 ⁇ m or more, more preferably 0. 0.7 ⁇ m or more, more preferably 0.8 ⁇ m or more, particularly preferably 1 ⁇ m or more, particularly preferably more than 1 ⁇ m, particularly preferably 2 ⁇ m or more, and most preferably 3 ⁇ m or more. Yes, and most preferably 5 ⁇ m or more.
- the particle size distribution index indicating the particle size distribution of the vinylidene fluoride resin fine particles of the present invention is 2 or less, the flow of the particles is improved when used in a paint or the like, and it becomes more uniform and smooth.
- the particle size distribution index is preferably 1.8 or less, more preferably 1.7 or less, further preferably 1.5 or less, particularly preferably 1.3 or less, and according to the most preferred embodiment, 1.2 or less. .
- the lower limit is theoretically 1.
- the number average particle diameter of the vinylidene fluoride resin fine particles referred to herein can be calculated by measuring the diameter of 100 particles randomly selected from a scanning electron micrograph and calculating the arithmetic average thereof. I can do it.
- the maximum particle diameter is taken as the particle diameter.
- it is measured at a magnification of at least 1000 times, preferably 5000 times or more.
- the particle size distribution index is calculated based on the following numerical conversion formula using the measured value of the particle diameter obtained by the above measurement.
- Ri particle diameter of individual particles
- Dn number average particle diameter
- Dv volume average particle diameter
- PDI particle diameter distribution index.
- the vinylidene fluoride resin fine particles of the present invention have an angle of repose of less than 40 degrees.
- the upper limit of the angle of repose is usually less than 40 degrees, preferably 39 degrees or less, more preferably 38 degrees, and still more preferably 37 degrees or less.
- the lower limit of the angle of repose is usually 25 degrees or more, preferably 26 degrees or more, more preferably 27 degrees or more, and particularly preferably 28 degrees or more.
- the angle of repose is measured by the measurement method described in “JIS R 9301-2-2 Alumina powder—Part 2: Physical property measurement method-2: Angle of repose”. The angle of repose.
- the average sphericity of the vinylidene fluoride resin fine particles is preferably 80 or more, more preferably 85 or more, still more preferably 90 or more, particularly preferably 92 or more, and most preferably 95 or more.
- the upper limit is 100.
- the average sphericity is determined by observing particles with a scanning electron microscope, measuring the short diameter and long diameter of 30 randomly selected particles, and calculating the true sphere of each particle from the following formula (2b). After obtaining the degree, the sphericity of each obtained particle is calculated by substituting it into the following formula (2a).
- S average sphericity
- S i sphericity of each particle
- D S minor axis of particle
- D L major axis of particle.
- the vinylidene fluoride resin fine particles of the present invention may be solid or hollow, but are preferably solid from the viewpoint of industrial use. Moreover, in order to confirm that the vinylidene fluoride resin fine particles of the present invention are solid, it can be carried out by observation of the fine particle cross section with a transmission electron microscope.
- the feature of the vinylidene fluoride resin fine particles in the present invention is that it has a smooth and true spherical shape and a narrow particle size distribution.
- effects such as improved fluidity, improved texture such as slipperiness, and ease of viscosity control when added to a paint or the like can be obtained.
- vinylidene fluoride resin particles flow easily on the surface of the substrate and have a narrow particle size distribution and are uniformly fused to the substrate, especially high fluidity and low-temperature fusion properties such as toners. Is suitably used in the field where is required.
- the vinylidene fluoride resin fine particles having a spherical shape and a smooth surface having a narrow particle size distribution can be used extremely usefully and practically in various industrial applications.
- additives for toners, rheology modifiers such as paints, medical diagnostic inspection agents, mechanical property improvers for molded products such as automobile materials and building materials, mechanical property improvers such as films and fibers
- Raw materials for resin moldings such as rapid prototyping and rapid manufacturing, flash molding materials, paste resins for plastic sols, powder blocking materials, powder flowability improvers, lubricants, rubber compounding agents, abrasives, increases Sticky agent, filter agent and filter aid, gelling agent, flocculant, paint additive, oil absorbent, mold release agent, plastic film / sheet slipperiness improver, anti-blocking agent, gloss control agent, matte finish agent , Light diffusing agent, surface high hardness improver, various modifiers such as toughness improver, liquid crystal display spacer, chromatographic filler,
- the individual particle size of the fine particles was measured by observing the fine particles at 1000 times with a scanning electron microscope (JEM-6301NF, manufactured by JEOL Ltd.). It was long. When the particles were not perfect circles, the maximum particle diameter was measured as the particle diameter.
- the average particle diameter was calculated by measuring the diameter of 100 particles randomly selected from the photograph and obtaining the arithmetic average thereof.
- the particle size distribution index indicating the particle size distribution was calculated based on the following numerical conversion formula using the measured values of the individual particle diameters obtained in the above measurement.
- Ri particle diameter of individual particles
- Dn number average particle diameter
- Dv volume average particle diameter
- PDI particle diameter distribution index.
- Average sphericity is determined by observing particles with a scanning electron microscope, measuring the short diameter and long diameter of 30 randomly selected particles, and using the following formula (4b). After obtaining the sphericity of each particle, the sphericity of each obtained particle is calculated by substituting into the following formula (4a).
- S average sphericity
- S i sphericity of each particle
- D S minor axis of particle
- D L major axis of particle.
- Example 1 Polyvinylidene fluoride (manufactured by Aldrich, reagent, CAS No. 24937-79-9, weight average molecular weight 354,000, SP value 15) in a 1000 ml pressure-resistant glass autoclave (Hyperglaster TEM-V1000N).
- FIG. 1 shows an observation view of the polyvinylidene fluoride fine particles by a scanning electron microscope. Since the polyvinylidene fluoride fine particles of this example had a high average sphericity, they were smooth and excellent in powder flowability.
- Example 2 Polyvinylidene fluoride (manufactured by Aldrich, reagent, CAS No. 24937-79-9, weight average molecular weight 354,000, SP value 15) in a 1000 ml pressure-resistant glass autoclave (Hyperglaster TEM-V1000N).
- FIG. 2 shows an observation view of the polyvinylidene fluoride fine particles by a scanning electron microscope. Since the polyvinylidene fluoride fine particles of this example had a high average sphericity, they were smooth and excellent in powder flowability.
- Example 3 In a 200-ml separable flask equipped with a helical ribbon type stirring blade and a cooling tube, polyvinylidene fluoride (Kureha Co., Ltd. # 9300, weight average molecular weight 2,161,000, SP value 15.4 (J / Cm 3 ) 1/2 ) 1.5 g, hydroxypropylcellulose (2-15% viscosity 6-15 mPa ⁇ s product) 7.5 g, and acetone 41 g were added and stirred at 50 ° C. and 450 rpm. The inside became cloudy and an emulsion was formed.
- the angle of repose was 32 degrees, and it was solid as a result of cross-sectional observation with a transmission electron microscope. Since the polyvinylidene fluoride fine particles of this example had a high average sphericity, they were smooth and excellent in powder flowability.
- Example 4 In a 200-ml separable flask equipped with a helical ribbon type stirring blade and a cooling tube, polyvinylidene fluoride (Kureha Co., Ltd. # 9300, weight average molecular weight 2,161,000, SP value 15.4 (J / Cm 3 ) 1/2 ) 1.5 g, hydroxypropylcellulose (2% aqueous solution viscosity 6-15 mPa ⁇ s product) 3.5 g, and acetonitrile 45 g were added and stirred at 50 ° C. and 450 rpm. The inside became cloudy and an emulsion was formed.
- the angle of repose was 33 degrees, and it was solid as a result of cross-sectional observation with a transmission electron microscope. Since the polyvinylidene fluoride fine particles of this example had a high average sphericity, they were smooth and excellent in powder flowability.
- Example 5 In a 200-ml separable flask equipped with a helical ribbon type stirring blade and a cooling tube, polyvinylidene fluoride (Kureha Co., Ltd. # 9300, weight average molecular weight 2,161,000, SP value 15.4 (J / Cm 3 ) 1/2 ) 1.5 g, hydroxypropylcellulose (2% aqueous solution viscosity 6-15 mPa ⁇ s product) 5 g, and acetonitrile 43.5 g were added and stirred at 50 ° C. and 450 rpm. The inside became cloudy and an emulsion was formed.
- the angle of repose was 30 degrees, and it was solid as a result of cross-sectional observation with a transmission electron microscope. Since the polyvinylidene fluoride fine particles of this example had a high average sphericity, they were smooth and excellent in powder flowability.
- Example 6 In a 1000 ml glass pressure vessel equipped with a helical ribbon type stirring blade, polyvinylidene fluoride (Kureha Co., Ltd. # 9300, weight average molecular weight 2,161,000, SP value 15.4 (J / cm 3 ) 1 / 2 ) 10.5 g, 52.5 g of polyethylene oxide (Meiko Chemical Co., Ltd. Alcox R-1000 weight average molecular weight 259,000) and 287 g of acetonitrile were added and stirred at 140 ° C. and 350 rpm. The inside became cloudy and an emulsion was formed.
- the angle of repose was 36 degrees and it was solid as a result of cross-sectional observation with a transmission electron microscope. Since the polyvinylidene fluoride fine particles of this example had a high average sphericity, they were smooth and excellent in powder flowability.
- the obtained powder When the obtained powder was observed with a scanning electron microscope, it was found to be a powder having a mean sphericity of 53, a number average particle size of 128 ⁇ m, and a particle size distribution index of 2.15. Moreover, although it was solid as a result of cross-sectional observation with a transmission electron microscope, the angle of repose was 45 degrees, and the obtained powder was indefinite, rough, and inferior in powder flowability. there were.
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Abstract
Description
即ち、本発明に係るフッ化ビニリデン樹脂微粒子は、下記[1]~[4]に示す
構成を有する。
[1]平均粒子径が0.3μm以上、100μm未満であり、粒子径分布指数が1~2であることを特徴とするフッ化ビニリデン樹脂微粒子、
[2]安息角が40度未満であることを特徴とする上記[1]に記載のフッ化ビニリデン樹脂微粒子、
[3]平均真球度が80以上である、上記[1]または[2]に記載のフッ化ビニリデン樹脂微粒子、
[4]粒子が中実である、上記[1]~[3]のいずれかに記載のフッ化ビニリデン樹脂微粒子。
また、本発明に係るフッ化ビニリデン樹脂微粒子の製造方法は、下記[5]~[12]
に示す構成を有する。
[5]フッ化ビニリデン樹脂(A)およびフッ化ビニリデン樹脂とは異なるポリマー(B)を、ケトン系有機溶媒、ニトリル系有機溶媒およびエーテル系有機溶媒からなる群のうち少なくとも1種からなる有機溶媒(C)に溶解混合したときに、フッ化ビニリデン樹脂(A)を主成分とする溶液相と、フッ化ビニリデン樹脂とは異なるポリマー(B)を主成分とする溶液相の2相に相分離する系において、フッ化ビニリデン樹脂(A)とフッ化ビニリデン樹脂とは異なるポリマー(B)と有機溶媒(C)のエマルションを形成するエマルション形成工程と、フッ化ビニリデン樹脂(A)の溶解度が有機溶媒(C)よりも小さいフッ化ビニリデン樹脂の貧溶媒を前記エマルションに接触させることによってフッ化ビニリデン樹脂微粒子を析出させる微粒子化工程とを有することを特徴とするフッ化ビニリデン樹脂微粒子の製造方法、
[6]2相に相分離したときの各相の溶媒が同じである、上記[5]に記載のフッ化ビニリデン樹脂微粒子の製造方法、
[7]フッ化ビニリデン樹脂とは異なるポリマー(B)が熱可塑性樹脂である、上記[5]または[6]に記載のフッ化ビニリデン樹脂微粒子の製造方法、
[8]フッ化ビニリデン樹脂とは異なるポリマー(B)がフッ化ビニリデン樹脂の貧溶媒に溶解する、上記[5]~[7]のいずれかに記載のフッ化ビニリデン樹脂微粒子の製造方法、
[9]フッ化ビニリデン樹脂とは異なるポリマー(B)が、ポリビニルアルコール、ヒドロキシプロピルセルロース、ポリエチレンオキサイドまたはポリエチレングリコールのいずれかである、上記[5]~[8]のいずれかに記載のフッ化ビニリデン樹脂微粒子の製造方法、
[10]前記フッ化ビニリデン樹脂の貧溶媒が水である、上記[5]~[9]のいずれかに記載のフッ化ビニリデン樹脂微粒子の製造方法、
[11]前記エーテル系有機溶媒の沸点が100℃以上である、上記[5]~[10]に記載のフッ化ビニリデン樹脂微粒子の製造方法、
[12]前記エーテル系有機溶媒がジエチレングリコールジメチルエーテルである、上記[11]に記載のフッ化ビニリデン樹脂微粒子の製造方法。
なお、本発明におけるフッ化ビニリデン樹脂(A)の分子量とは、溶媒としてジメチルホルムアミドを溶媒に用いたゲルパーミエーションクロマトグラフィー(GPC)で測定し、ポリスチレンで換算した重量平均分子量を指す。
具体的には、ポリ(ビニルアルコール)(完全ケン化型や部分ケン化型のポリ(ビニルアルコール)であってもよい)、ポリ(ビニルアルコール-エチレン)共重合体(完全ケン化型や部分ケン化型のポリ(ビニルアルコール-エチレン)共重合体であってもよい)、ポリビニルピロリドン、ポリ(エチレングリコール)、ポリ(エチレンオキサイド)、ショ糖脂肪酸エステル、ポリ(オキシエチレン脂肪酸エステル)、ポリ(オキシエチレンラウリン脂肪酸エステル)、ポリ(オキシエチレングリコールモノ脂肪酸エステル)、ポリ(オキシエチレンアルキルフェニルエーテル)、ポリ(オキシアルキルエーテル)、ポリアクリル酸、ポリアクリル酸ナトリウム、ポリメタクリル酸、ポリメタクリル酸ナトリウム、ポリスチレンスルホン酸、ポリスチレンスルホン酸ナトリウム、ポリビニルピロリジニウムクロライド、ポリ(スチレン-マレイン酸)共重合体、アミノポリ(アクリルアミド)、ポリ(パラビニルフェノール)、ポリアリルアミン、ポリビニルエーテル、ポリビニルホルマール、ポリ(アクリルアミド)、ポリ(メタクリルアミド)、ポリ(オキシエチレンアミン)、ポリ(ビニルピロリドン)、ポリ(ビニルピリジン)、ポリアミノスルホン、ポリエチレンイミン等の合成樹脂、マルトース、セルビオース、ラクトース、スクロースなどの二糖類、セルロース、キトサン、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、メチルセルロース、エチルセルロース、エチルヒドロキシセルロース、カルボキシメチルエチルセルロース、カルボキシメチルセルロース、カルボキシメチルセルロースナトリウム、セルロースエステル等のセルロース誘導体、アミロースおよびその誘導体、デンプンおよびその誘導体、デキストリン、シクロデキストリン、アルギン酸ナトリウムおよびその誘導体等の多糖類またはその誘導体、ゼラチン、カゼイン、コラーゲン、アルブミン、フィブロイン、ケラチン、フィブリン、カラギーナン、コンドロイチン硫酸、アラビアゴム、寒天、たんぱく質等が挙げられ、粒子径分布が狭くなることから、好ましくは、ポリ(ビニルアルコール)(完全ケン化型や部分ケン化型のポリ(ビニルアルコール)であってもよい)、ポリ(ビニルアルコールーエチレン)共重合体(完全ケン化型や部分ケン化型のポリ(ビニルアルコールーエチレン)共重合体であってよい)、ポリ(エチレングリコール)、ポリ(エチレンオキサイド)、ショ糖脂肪酸エステル、ポリ(オキシエチレンアルキルフェニルエーテル)、ポリ(オキシアルキルエーテル)、ポリ(アクリル酸)、ポリ(メタクリル酸)、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、メチルセルロース、エチルセルロース、エチルヒドロキシセルロース、カルボキシメチルエチルセルロース、カルボキシメチルセルロース、カルボキシメチルセルロースナトリウム、セルロースエステル等のセルロース誘導体、ポリビニルピロリドンであり、より好ましくは、ポリ(ビニルアルコール)(完全ケン化型や部分ケン化型のポリ(ビニルアルコール)であってよい)、ポリ(ビニルアルコールーエチレン)共重合体(完全ケン化型や部分ケン化型のポリ(ビニルアルコールーエチレン)共重合体)、ポリ(エチレングリコール)、ポリ(エチレンオキサイド)、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、メチルセルロース、エチルセルロース、エチルヒドロキシセルロース、カルボキシメチルエチルセルロース、カルボキシメチルセルロース、カルボキシメチルセルロースナトリウム、セルロースエステル等のセルロース誘導体、ポリビニルピロリドンであり、特に好ましくは、ポリ(ビニルアルコール)(完全ケン化型や部分ケン化型のポリ(ビニルアルコール)であってよい)、ポリ(エチレングリコール)、ポリ(エチレンオキサイド)、ヒドロキシプロピルセルロースである。
ここでいう重量平均分子量とは、溶媒として水を用いたゲルパーミエーションクロマトグラフィー(GPC)で測定し、ポリエチレングリコールで換算した重量平均分子量を指す。
なお、水で測定できない場合においては、ジメチルホルムアミドを用い、それでも測定できない場合においては、テトラヒドロフランを用い、さらに測定できない場合においては、ヘキサフルオロイソプロパノールを用いる。
このような系を、相分離する条件下で混合して、乳化させることにより、エマルションが形成される。
なお、フッ化ビニリデン樹脂(A)を効率的に粒子化させる観点から、好ましくは、芳香族炭化水素系溶媒、脂肪族炭化水素系溶媒、アルコール系溶媒、水であり、より好ましいのは、アルコール系溶媒、水であり、最も好ましくは、水である。
そこで、相分離状態になりやすい条件を得るためには、フッ化ビニリデン樹脂(A)とフッ化ビニリデン樹脂とは異なるポリマー(B)の溶解度パラメーター(以下、SP値と称することもある)の差が離れていた方が好ましい。
この際、SP値の差としては1(J/cm3)1/2以上、より好ましくは2(J/cm3)1/2以上、さらに好ましくは3(J/cm3)1/2以上、特に好ましくは5(J/cm3)1/2以上、最も好ましくは8(J/cm3)1/2以上である。SP値がこの範囲であれば、容易に相分離しやすくなり、また相分離がしやすくなることから、よりフッ化ビニリデン樹脂成分の含有率の高いフッ化ビニリデン樹脂微粒子を得ることができる。フッ化ビニリデン樹脂(A)とフッ化ビニリデン樹脂とは異なるポリマー(B)の両者が有機溶媒(C)に溶けるのであれば、特に制限はないが、SP値の差の上限として好ましくは20(J/cm3)1/2以下、より好ましくは、15(J/cm3)1/2以下であり、さらに好ましくは10(J/cm3)1/2以下である。
具体的には、まず、フッ化ビニリデン樹脂(A)、フッ化ビニリデン樹脂とは異なるポリマー(B)および有機溶媒(C)を所定の割合で混合溶解させ、一定時間静置した後に、界面が生じるか否かの判定を行う。そして、この判定を少なくとも3点以上、好ましくは5点以上、より好ましくは10点以上の点で実施し、それらの判定結果に基づいて相図を作成する。この相図を用いて2相に分離する領域および1相になる領域を峻別することで、相分離状態になる条件を見極めることが出来る。
安定に維持され、粒子径分布が小さくなると推定される。
この2相間の界面張力は微小であるため、溶液に異種の溶液を加えて測定する懸滴法などの通常用いられる方法では直接測定することは出来ないが、各相の空気との表面張力から推算することにより、界面張力を見積もることが出来る。各相の空気との表面張力をr1、r2とすると、2相間の界面張力r1/2は、r1/2=|r1-r2|(r1-r2の絶対値)で推算することができる。
粒子径分布を小さくするという観点から、このr1/2の上限は、好ましくは10mN/mであり、より好ましくは5mN/mであり、さらに好ましくは、3mN/mであり、特に好ましくは、2mN/mである。また、その下限は0mN/m超である。
2相間の粘度比の下限としては、0.1以上が好ましく、より好ましくは0.2以上であり、さらに好ましくは0.3以上であり、より好ましくは0.5以上であり、著しく好ましいのは0.8以上である。またその上限としては10以下が好ましく、より好ましくは5以下であり、さらに好ましくは、3以下であり、特に好ましくは、1.5以下であり、著しく好ましくは、1.2以下である。なお、ここでいう2相間の粘度比は、本発明を実施しようとする温度条件下における「フッ化ビニリデン樹脂溶液相の粘度/ポリマーB溶液相の粘度」と定義することとする。
エマルションの形成に際しては、フッ化ビニリデン樹脂溶液相が粒子状の液滴になるようにエマルションを形成させるが、一般に相分離させた際、ポリマーB溶液相の体積が
フッ化ビニリデン樹脂溶液相の体積より大きい場合に、このような形態のエマルションを形成させやすい傾向にある。特に、フッ化ビニリデン樹脂溶液相の体積比としては、両相の合計体積1に対して0.5未満であることが好ましく、0.4~0.1の間にあることがより好ましい。
例えば、上記相図を作成する際に、各成分の濃度における体積比を同時に測定しておくことにより、適切な体積比の範囲を設定することが可能である。
攪拌羽としては、具体的には、プロペラ型、パドル型、フラットパドル型、タービン型、ダブルコーン型、シングルコーン型、シングルリボン型、ダブルリボン型、スクリュー型、ヘリカルリボン型などが挙げられるが、系に対して十分に剪断力をかけられるものであれば、これらに特に限定されるものではない。また、効率的な攪拌を行うために、槽内に邪魔板等を設置してもよい。
フッ化ビニリデン樹脂(A)の微粒子を得るためには、フッ化ビニリデン樹脂の貧溶媒(以下、単に貧溶媒と称することもある)を、前記エマルション形成工程で製造したエマルションに接触させることにより、エマルション径に応じた径で微粒子を析出させる。
貧溶媒を投入する方法としては、所望のポリマー微粒子が得られる限り特に制限はなく、連続滴下法、分割添加法、一括添加法のいずれでも良いが、貧溶媒添加時にエマルションが凝集・融着・合一し、粒子径分布が大きくなったり、1000μmを超える塊状物が生成しやすくならないようにするために、好ましくは連続滴下法、分割滴下法であり、工業的に効率的に実施するためには、最も好ましいのは、連続滴下法である。
この範囲よりも短い時間で実施すると、エマルションの凝集・融着・合一に伴い、粒子径分布が大きくなったり、塊状物が生成したりする場合がある。また、これ以上長い時間で実施する場合は、工業的な実施を考えた場合、非現実的である。
この時間の範囲内で行うことにより、エマルションからポリマー微粒子に転換する際に、粒子間の凝集を抑制することができ、粒子径分布の小さいポリマー微粒子を得ることができる。
固液分離したポリマー微粒子は、必要に応じて、溶媒等で洗浄を行うことにより、付着または含有している不純物等の除去を行い、精製を行う。
フッ化ビニリデン樹脂微粒子の数平均粒子径に関しては、用途に応じて、適正な粒子径の範囲を決定することができる。例えば、塗料などの用途においては、粒子径が小さいほうが滑らかさを付与することができるため、数平均粒子径の上限としては通常100μm未満であり、好ましい態様によれば、80μm以下であり、より好ましい態様によれば、50μm以下であり、さらに好ましい態様によれば、30μm以下であり、最も好ましい態様によれば、20μm以下である。また、潤滑剤などに使用する場合、粒子径が小さすぎると粒子同士の凝集が起こりやすくなるため、下限としては通常0.3μm以上であり、好ましくは0.5μm以上であり、より好ましくは0.7μm以上であり、さらに好ましくは、0.8μm以上であり、特に好ましくは、1μm以上であり、著しく好ましくは、1μm超であり、格別に好ましくは2μm以上であり、極めて好ましくは3μm以上であり、最も好ましくは、5μm以上である。
また、安息角の下限としては、通常は25度以上であり、好ましくは26度以上であり、より好ましくは27度以上であり、特に好ましくは28度以上である。安息角が25度未満の場合または40度を超える場合は、粉体流動性が低下する。
なお、本発明において安息角とは、フッ化ビニリデン樹脂微粒子を、「JIS R 9301-2-2 アルミナ粉末-第2部:物性測定方法-2:安息角」に記載の測定方法において測定される安息角である。
また、本発明のフッ化ビニリデン樹脂微粒子が中実であることを確認するためには、透過型電子顕微鏡の微粒子断面観察にて行うことができる。
微粒子の個々の粒子径は、走査型電子顕微鏡(日本電子株式会社製走査型電子顕微鏡JSM-6301NF)にて、微粒子を1000倍で観察し、測長した。尚、粒子が真円でない場合は、粒子の最大径をその粒子径として測定した。
平均粒子径は、写真から無作為に選ばれた100個の粒子直径を測長し、その算術平均を求めることにより算出した。
粒子径分布を示す粒子径分布指数は、上記測定で得られた個々の粒子直径の測定値を用いて、下記数値変換式に基づき算出した。
フッ化ビニリデン樹脂微粒子の安息角は、80℃で16時間以上真空乾燥させた微粒子を「JIS R 9301-2-2 アルミナ粉末-第2部:物性測定方法-2:安息角」に準じて測定した。
平均真球度は、走査型電子顕微鏡にて粒子を観察し、無作為に選択された粒子30個について短径と長径を測定して下記数式(4b)より粒子個々の真球度を求めた後、得られた粒子個々の真球度を下記数式(4a)に代入して算出する。
粒子が中実であるかの確認を行うために、微粒子を電子顕微鏡用エポキシ樹脂で固めたのち、透過型電子顕微鏡用試料として切削して得た超薄切片の観察用試料として、透過型電子顕微鏡(日立製作所株式会社製H-7100)を用いて観察を行った。
フッ化ビニリデン樹脂の重量平均分子量は、ゲルパーミエーションクロマトグラフィー法を用い、ポリスチレンによる校正曲線と対比させて分子量を算出した。
装置 :株式会社島津製作所製 LC-10Aシリーズ
カラム:昭和電工株式会社製 KD-806M × 2本
移動相:ジメチルホルムアミド
流量 :1.0ml/min
検出 :示差屈折率計
カラム温度:40℃
ポリマーBの重量平均分子量は、ゲルパーミエーションクロマトグラフィー法を用い、ポリエチレングリコールによる校正曲線と対比させて分子量を算出した。
装置:株式会社島津製作所製 LC-10Aシリーズ
カラム:昭和電工株式会社製 GF-7MHQ × 2本
移動相:10mmol/L 臭化リチウム水溶液
流量 :1.0ml/min
検出 :示差屈折率計
カラム温度:40℃
1000mlの耐圧ガラスオートクレーブ(耐圧硝子工業(株)ハイパーグラスターTEM-V1000N)の中に、ポリフッ化ビニリデン(アルドリッチ社製、試薬、CASNo.24937-79-9、重量平均分子量 354,000、SP値 15.4(J/cm3)1/2)を17.5g、ポリフッ化ビニリデンとは異なるポリマーとしてヒドロキシプロピルセルロース(東京化成工業株式会社製、重量平均分子量118,000 、SP値29.0(J/cm3)1/2)を17.5g、エーテル系有機溶媒としてジエチレングリコールジメチルエーテル(ジグライム)315gを加え、99体積%以上の窒素置換を行った後、140℃に加熱し、ポリマーが溶解するまで2時間ヘリカルリボン型攪拌翼にて攪拌を行った。その後、貧溶媒として350gのイオン交換水を、送液ポンプを経由して、2.92g/分のスピードで滴下した。全量の水を入れ終わった後に、攪拌したまま室温まで降温させ、得られた懸濁液を、ろ過し、イオン交換水700gで洗浄し、濾別したものを、80℃ 10時間真空乾燥を行い、粉体状の白色固体を15g得た。
得られた粉体を走査型電子顕微鏡にて観察したところ、平均真球度92の真球状微粒子形状であり、数平均粒子径は、13.4μm、粒子径分布指数は、1.29、のポリフッ化ビニリデン微粒子であった。また、安息角は31度であり、透過型電子顕微鏡での断面観察の結果、中実であった。このポリフッ化ビニリデン微粒子の走査型電子顕微鏡による観察図を図1に示す。本実施例のポリフッ化ビニリデン微粒子は平均真球度が高いため、滑らかで、粉体流動性に優れるものであった。
1000mlの耐圧ガラスオートクレーブ(耐圧硝子工業(株)ハイパーグラスターTEM-V1000N)の中に、ポリフッ化ビニリデン(アルドリッチ社製、試薬、CASNo.24937-79-9、重量平均分子量 354,000、SP値 15.4(J/cm3)1/2)を17.5g、ポリフッ化ビニリデンとは異なるポリマーとしてヒドロキシプロピルセルロース(東京化成工業株式会社製、重量平均分子量118,000 、SP値29.0(J/cm3)1/2)を17.5g、エーテル系有機溶媒としてジエチレングリコールジメチルエーテル(ジグライム)315gを加え、99体積%以上の窒素置換を行った後、160℃に加熱し、ポリマーが溶解するまで2時間ヘリカルリボン型攪拌翼にて攪拌を行った。その後、貧溶媒として350gのイオン交換水を、送液ポンプを経由して、2.92g/分のスピードで滴下した。全量の水を入れ終わった後に、攪拌したまま室温まで降温させ、得られた懸濁液を、ろ過し、イオン交換水700gで洗浄し、濾別したものを、80℃ 10時間真空乾燥を行い、粉体状の白色固体を15g得た。
得られた粉体を走査型電子顕微鏡にて観察したところ、平均真球度87の真球状微粒子形状であり、数平均粒子径は、8.9μm、粒子径分布指数は、1.68、のポリフッ化ビニリデン微粒子であった。また、安息角は34度であり、透過型電子顕微鏡での断面観察の結果、中実であった。このポリフッ化ビニリデン微粒子の走査型電子顕微鏡による観察図を図2に示す。本実施例のポリフッ化ビニリデン微粒子は平均真球度が高いため、滑らかで、粉体流動性に優れるものであった。
ヘリカルリボン型攪拌羽および冷却管が取り付けられた200mlのセパラブルフラスコの中に、ポリフッ化ビニリデン(クレハ(株)社製 #9300、重量平均分子量 2,161,000、SP値 15.4(J/cm3)1/2)1.5g、ヒドロキシプロピルセルロース(2%水溶液時粘度6-15mPa・s品)7.5g、アセトン41gを加え、50℃下、450rpmの速度で攪拌を行った。内部が白濁化し、エマルションが形成されていた。引き続き、水100gを0.41g/分のスピードで加え、全量の水を入れ終わった後に、攪拌したまま室温まで降温させ、得られた懸濁液を、ろ過し、イオン交換水100gで洗浄し、濾別したものを、80℃ 10時間真空乾燥を行い、粉体状の白色固体を1.45g得た。
得られた粉体を走査型電子顕微鏡にて観察したところ、平均真球度89の真球状微粒子形状であり、数平均粒子径 6.1μm、粒子径分布指数 1.75のポリフッ化ビニリデン粒子であった。また、安息角は32度であり、透過型電子顕微鏡での断面観察の結果、中実であった。本実施例のポリフッ化ビニリデン微粒子は平均真球度が高いため、滑らかで、粉体流動性に優れるものであった。
ヘリカルリボン型攪拌羽および冷却管が取り付けられた200mlのセパラブルフラスコの中に、ポリフッ化ビニリデン(クレハ(株)社製 #9300、重量平均分子量 2,161,000、SP値 15.4(J/cm3)1/2)1.5g、ヒドロキシプロピルセルロース(2%水溶液時粘度6-15mPa・s品)3.5g、アセトニトリル45gを加え、50℃下、450rpmの速度で攪拌を行った。内部が白濁化し、エマルションが形成されていた。引き続き、水50gを0.41g/分のスピードで加え、全量の水を入れ終わった後に、攪拌したまま室温まで降温させ、得られた懸濁液を、ろ過し、イオン交換水100gで洗浄し、濾別したものを、80℃ 10時間真空乾燥を行い、粉体状の白色固体を1.47g得た。
得られた粉体を走査型電子顕微鏡にて観察したところ、平均真球度90の真球状微粒子形状であり、数平均粒子径 6.3μm、粒子径分布指数 1.27のポリフッ化ビニリデン粒子であった。また、安息角は33度であり、透過型電子顕微鏡での断面観察の結果、中実であった。本実施例のポリフッ化ビニリデン微粒子は平均真球度が高いため、滑らかで、粉体流動性に優れるものであった。
ヘリカルリボン型攪拌羽および冷却管が取り付けられた200mlのセパラブルフラスコの中に、ポリフッ化ビニリデン(クレハ(株)社製 #9300、重量平均分子量 2,161,000、SP値 15.4(J/cm3)1/2)1.5g、ヒドロキシプロピルセルロース(2%水溶液時粘度6-15mPa・s品)5g、アセトニトリル 43.5gを加え、50℃下、450rpmの速度で攪拌を行った。内部が白濁化し、エマルションが形成されていた。引き続き、水50gを0.41g/分のスピードで加え、全量の水を入れ終わった後に、攪拌したまま室温まで降温させ、得られた懸濁液を、ろ過し、イオン交換水100gで洗浄し、濾別したものを、80℃ 10時間真空乾燥を行い、粉体状の白色固体を1.44g得た。
得られた粉体を走査型電子顕微鏡にて観察したところ、平均真球度90の真球状微粒子形状であり、数平均粒子径 7.0μm、粒子径分布指数 1.21のポリフッ化ビニリデン粒子であった。また、安息角は30度であり、透過型電子顕微鏡での断面観察の結果、中実であった。本実施例のポリフッ化ビニリデン微粒子は平均真球度が高いため、滑らかで、粉体流動性に優れるものであった。
ヘリカルリボン型攪拌羽を備えた1000mlガラス製耐圧容器に、ポリフッ化ビニリデン(クレハ(株)社製 #9300、重量平均分子量 2,161,000、SP値 15.4(J/cm3)1/2)10.5g、ポリエチレンオキサイド(明成化学工業(株) アルコックス R-1000 重量平均分子量 259,000)52.5g、アセトニトリル287gを加え、140℃下、350rpmの速度で攪拌を行った。内部が白濁化し、エマルションが形成されていた。引き続き、水350gを2.92g/分のスピードで加え、全量の水を入れ終わった後に、攪拌したまま室温まで降温させ、得られた懸濁液を、ろ過し、イオン交換水300gで洗浄し、濾別したものを、80℃ 10時間真空乾燥を行い、粉体状の白色固体を9.7g得た。
得られた粉体を走査型電子顕微鏡にて観察したところ、平均真球度91の真球状微粒子形状であり、数平均粒子径 1.8μm、粒子径分布指数 1.32のポリフッ化ビニリデン粒子であった。また、安息角は36度であり、透過型電子顕微鏡での断面観察の結果、中実であった。本実施例のポリフッ化ビニリデン微粒子は平均真球度が高いため、滑らかで、粉体流動性に優れるものであった。
SPEX社製 フリーザーミル6750を用いて、ポリフッ化ビニリデン(アルドリッチ社製、試薬、CASNo.24937-79-9、重量平均分子量 354,000、SP値 15.4(J/cm3)1/2)15gを液体窒素中で、粉砕時間2分、インパクター回数20回/秒、粉砕回数3回の条件で凍結粉砕し、ポリフッ化ビニリデンの粉体を得た。
得られた粉体を走査型電子顕微鏡にて観察したところ、平均真球度53のばらついた形状の粉体であり、数平均粒子径は128μm、粒子径分布指数2.15であった。また、透過型電子顕微鏡での断面観察の結果、中実であったものの、安息角は45度であり、得られた粉体は不定形で、ざらつきが大きく、粉体流動性が劣るものであった。
Claims (12)
- 平均粒子径が0.3μm以上、100μm未満であり、粒子径分布指数が1~2であることを特徴とするフッ化ビニリデン樹脂微粒子。
- 安息角が40度未満である、請求項1に記載のフッ化ビニリデン樹脂微粒子。
- 平均真球度が80以上である、請求項1または2に記載のフッ化ビニリデン樹脂微粒子。
- 粒子が中実である、請求項1~3のいずれかに記載のフッ化ビニリデン樹脂微粒子。
- フッ化ビニリデン樹脂(A)およびフッ化ビニリデン樹脂とは異なるポリマー(B)を、ケトン系有機溶媒、ニトリル系有機溶媒およびエーテル系有機溶媒からなる群のうち少なくとも1種からなる有機溶媒(C)に溶解混合したときに、フッ化ビニリデン樹脂(A)を主成分とする溶液相と、フッ化ビニリデン樹脂とは異なるポリマー(B)を主成分とする溶液相の2相に相分離する系において、
フッ化ビニリデン樹脂(A)とフッ化ビニリデン樹脂とは異なるポリマー(B)と有機溶媒(C)のエマルションを形成するエマルション形成工程と、
フッ化ビニリデン樹脂(A)の溶解度が有機溶媒(C)よりも小さいフッ化ビニリデン樹脂の貧溶媒を前記エマルションに接触させることによってフッ化ビニリデン樹脂微粒子を析出させる微粒子化工程と
を有することを特徴とするフッ化ビニリデン樹脂微粒子の製造方法。 - 2相に相分離したときの各相の溶媒が同じである、請求項5に記載のフッ化ビニリデン樹脂微粒子の製造方法。
- フッ化ビニリデン樹脂とは異なるポリマー(B)が熱可塑性樹脂である、請求項5または6に記載のフッ化ビニリデン樹脂微粒子の製造方法。
- フッ化ビニリデン樹脂とは異なるポリマー(B)がフッ化ビニリデン樹脂の貧溶媒に溶解する、請求項5~7のいずれかに記載のフッ化ビニリデン樹脂微粒子の製造方法。
- フッ化ビニリデン樹脂とは異なるポリマー(B)が、ポリビニルアルコール、ヒドロキシプロピルセルロース、ポリエチレンオキサイドまたはポリエチレングリコールのいずれかである、請求項5~8のいずれかに記載のフッ化ビニリデン樹脂微粒子の製造方法。
- 前記フッ化ビニリデン樹脂の貧溶媒が水である、請求項5~9のいずれかに記載のフッ化ビニリデン樹脂微粒子の製造方法。
- 有機溶媒(C)が、沸点100℃以上のエーテル系有機溶媒である、請求項5~10のいずれかに記載のフッ化ビニリデン樹脂微粒子の製造方法。
- 有機溶媒(C)がジエチレングリコールジメチルエーテルである、請求項11に記載のフッ化ビニリデン樹脂微粒子の製造方法。
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US14/421,304 US9920193B2 (en) | 2012-08-30 | 2013-08-26 | Method for producing polyvinylidene difluoride particles, and polyvinylidene difluoride particles |
EP13833331.5A EP2891676B1 (en) | 2012-08-30 | 2013-08-26 | Method for producing fine vinylidene fluoride resin particles, and fine vinylidene fluoride resin particles |
JP2013540565A JP5904209B2 (ja) | 2012-08-30 | 2013-08-26 | フッ化ビニリデン樹脂微粒子の製造方法、およびフッ化ビニリデン樹脂微粒子 |
KR1020147035462A KR20150051940A (ko) | 2012-08-30 | 2013-08-26 | 플루오르화 비닐리덴 수지 미립자의 제조 방법, 및 플루오르화 비닐리덴 수지 미립자 |
CN201380037389.0A CN104428349B (zh) | 2012-08-30 | 2013-08-26 | 1,1-二氟乙烯树脂微粒的制造方法及1,1-二氟乙烯树脂微粒 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016093146A1 (ja) * | 2014-12-09 | 2016-06-16 | 東レ株式会社 | 二次電池用セパレータ、二次電池用セパレータの製造方法および二次電池 |
JP2018162416A (ja) * | 2017-03-27 | 2018-10-18 | Agc株式会社 | 粉体塗料 |
JP2021519369A (ja) * | 2018-03-27 | 2021-08-10 | フリードリヒ−アレクサンダー−ウニベルジテート・エアランゲン−ニュルンベルク | ポリ二フッ化ビニリデンの粒子の、またはポリ二フッ化ビニリデンを含むコポリマーの粒子の集団を生産するための方法。 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3825336A4 (en) * | 2018-07-20 | 2021-06-16 | Kureha Corporation | PARTICULATE POLYMER BASED ON VINYLIDEN FLUORIDE AND A PROCESS FOR PRODUCING A PARTICULATE POLYMER BASED ON VINYLIDEN FLUORIDE |
US11807702B2 (en) | 2018-09-28 | 2023-11-07 | Tosoh Corporation | Fluororesin, fluororesin particles, and methods for producing these |
EP3640281A1 (en) * | 2018-10-19 | 2020-04-22 | 3M Innovative Properties Company | Sprayable powder of fluoropolymer particles |
Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0790153A (ja) | 1993-09-20 | 1995-04-04 | Daikin Ind Ltd | ビニリデンフルオライド系重合体の水性分散液およびその製法 |
JPH09165535A (ja) | 1995-12-18 | 1997-06-24 | Daikin Ind Ltd | 粉体塗料用組成物 |
WO1997040089A1 (fr) * | 1996-04-24 | 1997-10-30 | Daikin Industries, Ltd. | Fluoropolymere en poudre et procede de preparation |
JPH11184164A (ja) | 1997-12-25 | 1999-07-09 | Toray Ind Inc | 電子写真用現像剤組成物 |
JP2000103865A (ja) * | 1998-09-30 | 2000-04-11 | Asahi Glass Co Ltd | 含フッ素重合体粉末の製造方法 |
JP2001114901A (ja) * | 1999-10-22 | 2001-04-24 | Technology Resources Incorporated:Kk | 球状複合粉体の製造方法 |
WO2002088227A1 (fr) * | 2001-04-26 | 2002-11-07 | Daikin Industries, Ltd. | Poudre de polymere contenant du fluor, procede de production associe et article revetu |
JP2003082295A (ja) | 2001-09-11 | 2003-03-19 | Dainippon Ink & Chem Inc | 粉体塗料及び塗膜形成方法 |
JP2003306551A (ja) * | 2002-02-15 | 2003-10-31 | Daikin Ind Ltd | Ptfe造粒ゲル化粉砕品、ptfe造粒半ゲル化粉砕品、ptfe粉体、ptfe造粒ゲル化粉砕品製造方法及び成形体 |
JP2005213507A (ja) * | 2004-01-28 | 2005-08-11 | Xerox Corp | 硬化可能な粉体塗装組成物の製造方法、硬化可能な粉体塗装組成物、及びその使用法 |
JP2006152060A (ja) * | 2004-11-26 | 2006-06-15 | Seiko Epson Corp | 樹脂微粒子の製造方法および樹脂微粒子 |
JP2007308811A (ja) | 2006-05-16 | 2007-11-29 | Nicca Chemical Co Ltd | 防水導電性布帛及びその製造方法 |
JP2009083437A (ja) | 2007-10-03 | 2009-04-23 | Fuji Xerox Co Ltd | 記録装置、インク受容性粒子 |
WO2011052669A1 (ja) * | 2009-10-30 | 2011-05-05 | 株式会社クレハ | 熱処理済フッ化ビニリデン系重合体粉末の製造方法およびフッ化ビニリデン系重合体溶液の製造方法 |
JP2011177614A (ja) | 2010-02-26 | 2011-09-15 | Kyocera Chemical Corp | 触媒担持体とその製造方法 |
JP2011231273A (ja) | 2010-04-30 | 2011-11-17 | Mitsubishi Rayon Co Ltd | フッ素系艶消しフィルム用樹脂組成物及びフッ素系艶消しフィルム |
JP2012511074A (ja) | 2008-12-05 | 2012-05-17 | ソルヴェイ・スペシャルティ・ポリマーズ・イタリー・エッセ・ピ・ア | 加硫(パー)フルオロエラストマーシール物品 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0551495A (ja) * | 1991-08-21 | 1993-03-02 | Idemitsu Petrochem Co Ltd | オレフイン重合体組成物及び該組成物を用いたフイルム又はシート |
JP2002030263A (ja) * | 2000-07-18 | 2002-01-31 | Atofina Japan Kk | フッ素系接着性樹脂組成物 |
CN1160398C (zh) * | 2001-11-21 | 2004-08-04 | 中国科学院生态环境研究中心 | 颗粒度均匀的高分子微球、针状微粒及成形方法 |
FR2833267A1 (fr) * | 2001-12-11 | 2003-06-13 | Solvay | Procede de recuperation d'un polymere en solution |
JP5015413B2 (ja) * | 2003-02-27 | 2012-08-29 | ローム・アンド・ハース・エレクトロニック・マテリアルズ,エル.エル.シー. | ポリマーの分別方法 |
FR2868782B1 (fr) | 2004-04-13 | 2006-06-16 | Solvay Sa Sa Belge | Procede de recuperation d'un polymere en solution |
WO2006043609A1 (ja) * | 2004-10-20 | 2006-04-27 | Kureha Corporation | 溶融成形用ポリフッ化ビニリデン樹脂粉末及び該樹脂粉末を用いた成形体の製造方法 |
JP4822257B2 (ja) * | 2005-10-28 | 2011-11-24 | 独立行政法人産業技術総合研究所 | 芳香族カルボン酸イミドの製造方法 |
KR20090008202A (ko) * | 2006-03-20 | 2009-01-21 | 니혼 이타가라스 가부시키가이샤 | 인편 형상 유리가 배합된 화장료 |
JP4836723B2 (ja) * | 2006-09-14 | 2011-12-14 | 株式会社リコー | 静電荷像現像用トナー、画像形成方法及びその製造方法 |
JP5224799B2 (ja) * | 2007-12-17 | 2013-07-03 | ユニバーサルエンジニアリング株式会社 | 有機性排水処理の遠隔制御による循環型再生水利用方法 |
AU2009250453B2 (en) * | 2008-05-21 | 2014-07-10 | Toray Industries, Inc. | Method for producing polymer fine particle |
CN103140540B (zh) | 2010-09-28 | 2014-07-23 | 东丽株式会社 | 聚合物微粒的制造方法 |
ES2528961T3 (es) * | 2011-01-31 | 2015-02-13 | Toray Industries, Inc. | Método de producción de micropartículas de resina a base de ácido poliláctico, micropartículas de resina a base de ácido poliláctico y cosmético que las usa |
US10023748B2 (en) * | 2011-08-29 | 2018-07-17 | Daikin Industries, Ltd. | Fluorine-containing polymer powder, film, and method for producing fluorine-containing polymer powder |
CN102580576A (zh) * | 2012-03-20 | 2012-07-18 | 江苏英超环保有限公司 | 一种聚偏氟乙烯超滤膜及其制备方法 |
-
2013
- 2013-08-26 CN CN201380037389.0A patent/CN104428349B/zh not_active Expired - Fee Related
- 2013-08-26 JP JP2013540565A patent/JP5904209B2/ja not_active Expired - Fee Related
- 2013-08-26 EP EP13833331.5A patent/EP2891676B1/en not_active Not-in-force
- 2013-08-26 US US14/421,304 patent/US9920193B2/en not_active Expired - Fee Related
- 2013-08-26 WO PCT/JP2013/072650 patent/WO2014034581A1/ja active Application Filing
- 2013-08-26 KR KR1020147035462A patent/KR20150051940A/ko not_active Application Discontinuation
- 2013-08-26 HU HUE13833331A patent/HUE043422T2/hu unknown
- 2013-08-28 TW TW102130728A patent/TW201414754A/zh unknown
Patent Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0790153A (ja) | 1993-09-20 | 1995-04-04 | Daikin Ind Ltd | ビニリデンフルオライド系重合体の水性分散液およびその製法 |
JPH09165535A (ja) | 1995-12-18 | 1997-06-24 | Daikin Ind Ltd | 粉体塗料用組成物 |
WO1997040089A1 (fr) * | 1996-04-24 | 1997-10-30 | Daikin Industries, Ltd. | Fluoropolymere en poudre et procede de preparation |
JPH11184164A (ja) | 1997-12-25 | 1999-07-09 | Toray Ind Inc | 電子写真用現像剤組成物 |
JP2000103865A (ja) * | 1998-09-30 | 2000-04-11 | Asahi Glass Co Ltd | 含フッ素重合体粉末の製造方法 |
JP2001114901A (ja) * | 1999-10-22 | 2001-04-24 | Technology Resources Incorporated:Kk | 球状複合粉体の製造方法 |
WO2002088227A1 (fr) * | 2001-04-26 | 2002-11-07 | Daikin Industries, Ltd. | Poudre de polymere contenant du fluor, procede de production associe et article revetu |
JP2003082295A (ja) | 2001-09-11 | 2003-03-19 | Dainippon Ink & Chem Inc | 粉体塗料及び塗膜形成方法 |
JP2003306551A (ja) * | 2002-02-15 | 2003-10-31 | Daikin Ind Ltd | Ptfe造粒ゲル化粉砕品、ptfe造粒半ゲル化粉砕品、ptfe粉体、ptfe造粒ゲル化粉砕品製造方法及び成形体 |
JP2005213507A (ja) * | 2004-01-28 | 2005-08-11 | Xerox Corp | 硬化可能な粉体塗装組成物の製造方法、硬化可能な粉体塗装組成物、及びその使用法 |
JP2006152060A (ja) * | 2004-11-26 | 2006-06-15 | Seiko Epson Corp | 樹脂微粒子の製造方法および樹脂微粒子 |
JP2007308811A (ja) | 2006-05-16 | 2007-11-29 | Nicca Chemical Co Ltd | 防水導電性布帛及びその製造方法 |
JP2009083437A (ja) | 2007-10-03 | 2009-04-23 | Fuji Xerox Co Ltd | 記録装置、インク受容性粒子 |
JP2012511074A (ja) | 2008-12-05 | 2012-05-17 | ソルヴェイ・スペシャルティ・ポリマーズ・イタリー・エッセ・ピ・ア | 加硫(パー)フルオロエラストマーシール物品 |
WO2011052669A1 (ja) * | 2009-10-30 | 2011-05-05 | 株式会社クレハ | 熱処理済フッ化ビニリデン系重合体粉末の製造方法およびフッ化ビニリデン系重合体溶液の製造方法 |
JP2011177614A (ja) | 2010-02-26 | 2011-09-15 | Kyocera Chemical Corp | 触媒担持体とその製造方法 |
JP2011231273A (ja) | 2010-04-30 | 2011-11-17 | Mitsubishi Rayon Co Ltd | フッ素系艶消しフィルム用樹脂組成物及びフッ素系艶消しフィルム |
Non-Patent Citations (3)
Title |
---|
HIDEKI YAMAMOTO: "SP value, base, application and calculation method", 31 March 2005, JOHOKIKO CO., LTD. |
J. BRAND: "Polymer Handbook", 1998, WILEY |
See also references of EP2891676A4 |
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KR102480759B1 (ko) * | 2014-12-09 | 2022-12-23 | 도레이 카부시키가이샤 | 이차 전지용 세퍼레이터, 이차 전지용 세퍼레이터의 제조 방법 및 이차 전지 |
JP2018162416A (ja) * | 2017-03-27 | 2018-10-18 | Agc株式会社 | 粉体塗料 |
JP2021519369A (ja) * | 2018-03-27 | 2021-08-10 | フリードリヒ−アレクサンダー−ウニベルジテート・エアランゲン−ニュルンベルク | ポリ二フッ化ビニリデンの粒子の、またはポリ二フッ化ビニリデンを含むコポリマーの粒子の集団を生産するための方法。 |
US11945919B2 (en) | 2018-03-27 | 2024-04-02 | Evonik Operations Gmbh | Method for producing a population of particles of polyvinylidene difluoride or of particles of a copolymer comprising polyvinylidene difluoride |
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EP2891676A1 (en) | 2015-07-08 |
JP5904209B2 (ja) | 2016-04-13 |
EP2891676A4 (en) | 2016-04-06 |
US9920193B2 (en) | 2018-03-20 |
JPWO2014034581A1 (ja) | 2016-08-08 |
US20150218359A1 (en) | 2015-08-06 |
KR20150051940A (ko) | 2015-05-13 |
EP2891676B1 (en) | 2018-11-28 |
CN104428349A (zh) | 2015-03-18 |
TW201414754A (zh) | 2014-04-16 |
HUE043422T2 (hu) | 2019-08-28 |
CN104428349B (zh) | 2016-10-12 |
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