WO2015098654A1 - ポリフェニレンサルファイド微粒子 - Google Patents
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- WO2015098654A1 WO2015098654A1 PCT/JP2014/083423 JP2014083423W WO2015098654A1 WO 2015098654 A1 WO2015098654 A1 WO 2015098654A1 JP 2014083423 W JP2014083423 W JP 2014083423W WO 2015098654 A1 WO2015098654 A1 WO 2015098654A1
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- C08J3/00—Processes of treating or compounding macromolecular substances
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- C08J3/16—Powdering or granulating by coagulating dispersions
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- C08J9/16—Making expandable particles
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/096—Nitrogen containing compounds
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/11—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids from solid polymers
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
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- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/054—Precipitating the polymer by adding a non-solvent or a different solvent
- C08J2201/0542—Precipitating the polymer by adding a non-solvent or a different solvent from an organic solvent-based polymer composition
- C08J2201/0544—Precipitating the polymer by adding a non-solvent or a different solvent from an organic solvent-based polymer composition the non-solvent being aqueous
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- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
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- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/05—Open cells, i.e. more than 50% of the pores are open
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- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/02—Polyalkylene oxides
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- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/04—Polysulfides
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- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/06—Polysulfones; Polyethersulfones
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- C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2481/06—Polysulfones; Polyethersulfones
Definitions
- the present invention relates to porous polyphenylene sulfide fine particles.
- the spherical polymer fine particles having a high specific surface area are used as additives for molding various polymers and modifying / improving materials. Specific applications include coating processing consisting of coating film formation of polymer fine particles, use for various molding processes such as films and sheets, cosmetic modifiers, toner additives, paint additives, molding Use as an additive to a product, a light diffusing agent of a film, and the like.
- the polymer fine particles are fused together by applying thermal energy to them to form the polymer in the desired form
- a method of forming is known. In such an application, if the specific surface area of the polymer fine particles is large, the fusion of the particles is promoted, and coating and molding can be performed at a lower temperature and in a shorter time.
- polymer fine particles are added to paints and the like, and are also used as additives for changing the appearance and texture of paints.
- polymer fine particles are added as a matting agent for paints.
- Inorganic particles such as silica particles are known as additives for paints, but inorganic particles have a large specific gravity and are more likely to separate from the paint because they are more likely to settle by gravity compared to polymer fine particles, which is not practically preferable. .
- Polyphenylene sulfide (hereinafter abbreviated as PPS) resin has excellent properties as engineering plastics such as excellent heat resistance, chemical resistance, solvent resistance, and electrical insulation, and is suitable for injection molding and extrusion. Mainly for molding applications, it is used as an additive to modifiers for various electrical parts, mechanical parts, automobile parts, and various sliding parts such as oil and grease.
- Patent Document 1 PPS and other thermoplastic polymers are melt-kneaded, and after forming a sea-island structure resin composition with PPS as an island and other thermoplastic polymers as the sea, the sea phase is dissolved and washed. Spherical PPS resin particles are obtained.
- Patent Document 2 PPS is taken out as a powder by cooling a reaction vessel after polymerization of PPS resin.
- dissolved PPS resin is made into a heating and pressurization state, the solution is ejected in a solvent through a nozzle, and PPS microparticles
- Patent Document 1 forms a sea island structure by melting and kneading a PPS resin and another thermoplastic resin to form an island that is a source of PPS fine particles. Therefore, only PPS fine particles having a smooth surface can be produced by the action of surface tension.
- the precipitation method disclosed in Patent Document 2 it is difficult to prevent the PPS powders from fusing with each other in the precipitation step, so that the PPS powder is deformed or the particle size distribution is widened. Even in the method described in Patent Document 3, since the droplets formed by the action of surface tension are cooled and deposited in the ejection step, only PPS fine particles having a smooth surface can be obtained.
- porous PPS fine particles are expected to have high operability in molding and high delustering effect as a paint additive.
- porous PPS fine particles having a spherical shape and a uniform particle size are desired, but the PPS fine particles obtained by the conventional technique do not satisfy these characteristics.
- An object of the present invention is to provide porous polyphenylene sulfide fine particles having a practically usable level.
- the present invention relates to polyphenylene sulfide fine particles having a linseed oil absorption of 40 to 1000 mL / 100 g and a number average particle diameter of 1 to 200 ⁇ m.
- the present invention also includes a dispersion containing the polyphenylene sulfide fine particles.
- the polyphenylene sulfide resin (A) is a main component.
- the polyphenylene sulfide resin (A), the polymer (B) and the organic solvent (C) are heated at a temperature Td (° C.).
- a step of mixing and dissolving a step of forming an emulsion by applying a shearing force to the obtained solution, and a polyphenylene sulfide resin (A) by contacting the emulsion with a poor solvent of the polyphenylene sulfide resin (A) at a temperature Tp (° C.).
- Method for producing polyphenylene sulfide fine particles including a step of depositing sulfide resin (A) A is, the temperature Tp (° C.) includes a manufacturing method of the temperature Td (° C.) than 10 ° C. or more lower polyphenylene sulfide particles.
- the present invention it is possible to obtain porous PPS fine particles having a practically usable level, which has been difficult to produce by the conventional technology. Since the PPS fine particles of the present invention have a large specific surface area, for example, when processing into various shaped bodies by applying thermal energy, the fusion of the particles is promoted, and the particle coating layer can be formed at a lower temperature and in a shorter time. Can be formed and processed. In addition, since the PPS fine particles of the present invention have a porous shape, they can scatter light in multiple directions and can suppress specific reflection of reflected light in a specific direction. When this is done, a blurring effect and a matting effect can be imparted.
- FIG. 2 is a scanning electron microscope image (magnification: 3,000) of porous PPS fine particles obtained in Example 1.
- FIG. 1 is a scanning electron microscope image (magnification: 3,000) of porous PPS fine particles obtained in Example 1.
- the polyphenylene sulfide in the present invention is a homopolymer or copolymer having a repeating unit represented by the formula (1) as a main structural unit.
- Ar in the general formula (1) is an aromatic group.
- Ar include aromatic groups represented by the following formulas (2) to (4).
- R 1 and R 2 are each independently a group selected from hydrogen, an alkyl group, an alkoxyl group, and a halogen group.
- a copolymer component represented by the formulas (6) to (14) may also be included.
- R 1 and R 2 are each independently a substituent selected from hydrogen, an alkyl group, an alkoxyl group, and a halogen group.
- PPS is a copolymer of a p-phenylene sulfide unit, an m-phenylene sulfide unit and / or an o-phenylene sulfide unit represented by the formula (15) as the main structural unit of the polymer.
- the copolymerization ratio of p-phenylene sulfide units, m-phenylene sulfide units and / or o-phenylene sulfide units greatly affects the melting point (Tm) of the PPS resin.
- Tm melting point
- the melting point of the PPS resin affects the porosity of the PPS fine particles. Furthermore, the melting point of the PPS resin affects the sphericity and particle size distribution of the PPS fine particles. Therefore, it is preferable that the copolymerization ratio is in the range described later. If the melting point of the PPS resin is too low, the porosity of the PPS fine particles becomes small or the PPS fine particles become amorphous, and it is difficult to obtain PPS fine particles having a stable porosity.
- the melting point of the PPS resin is too low, the sphericity of the PPS fine particles is lowered, and the particle size distribution becomes wide. Even if the melting point of the PPS resin is too high, the sphericity of the PPS fine particles is lowered, so that the particle size distribution is widened.
- the PPS resin used as a raw material for producing the PPS fine particles of the present invention preferably has a melting point of 210 ° C. to 270 ° C., more preferably 220 ° C. to 260 ° C., A temperature of 230 ° C. to 250 ° C. is particularly preferable.
- the obtained PPS fine particles By setting the melting point of the raw material PPS resin in such a range, the obtained PPS fine particles easily have a porous form and have a particle size with good powder handling properties. Furthermore, by setting the melting point of the raw material PPS resin in such a range, the obtained PPS fine particles have a high sphericity and a narrow particle size distribution.
- the melting point of the PPS resin here means that the temperature is increased to 300 ° C. under a temperature increase rate of 20 ° C./min by differential scanning calorimetry (DSC), and then the temperature is decreased to 20 ° C. at a temperature decrease rate of 20 ° C./min. Again, the temperature is raised at a temperature rising rate of 20 ° C./min, and the temperature at the peak apex indicating the heat of fusion when measured.
- DSC differential scanning calorimetry
- the copolymerization ratio of p-phenylene sulfide units to m-phenylene sulfide units and / or o-phenylene sulfide units is m-phenylene sulfide units and / or o-phenylene sulfide.
- the unit is preferably contained in an amount of 1 to 50% by mass, more preferably 2 to 40% by mass, particularly preferably 3 to 30% by mass based on the total phenylene sulfide unit.
- the melting point of the obtained porous PPS particles is preferably 210 ° C. to It becomes 270 ° C., more preferably 220 ° C. to 260 ° C., particularly preferably 230 ° C. to 250 ° C.
- a resin synthesized by a commonly used method from a dihalogen aromatic compound and an alkyl metal sulfide in an N-alkylamide solvent can be used.
- linseed oil absorption which is a pigment test method defined in the gas adsorption amount per unit weight by BET etc. and Japanese Industrial Standards etc.
- JIS Japanese Industrial Standard
- the PPS fine particles of the present invention have a linseed oil absorption of 40 to 1000 mL / 100 g.
- the lower limit is preferably 45 ml / 100 g or more, more preferably 50 ml / 100 g or more, still more preferably 55 ml / 100 g or more, particularly preferably 80 ml / 100 g or more, and most preferably 100 ml / 100 g. That's it.
- the upper limit of the linseed oil absorption is preferably 800 ml / 100 g or less, more preferably 700 ml / 100 g or less, further preferably 600 ml / 100 g or less, particularly preferably 500 ml / 100 g or less, and particularly preferably 400 ml. / 100g or less.
- the linseed oil absorption is less than 40 mL / 100 g, the effect of improving moldability during molding cannot be greatly expected.
- the linseed oil absorption exceeds 1000 mL / 100 g, the fine particles become bulky, and at the same time, when the fine particles are used for forming a coating film, the viscosity of the coating liquid becomes high, resulting in poor handling. .
- the PPS fine particles of the present invention have a number average particle size of 1 to 200 ⁇ m as measured from an image observed with a scanning electron microscope.
- the upper limit of the number average particle diameter is preferably 180 ⁇ m or less, more preferably 150 ⁇ m or less, further preferably 125 ⁇ m or less, particularly preferably 100 ⁇ m or less, and most preferably 75 ⁇ m or less, most preferably 50 ⁇ m or less.
- the lower limit of the number average particle diameter is preferably more than 1 ⁇ m, more preferably 3 ⁇ m or more, further preferably 5 ⁇ m or more, particularly preferably 8 ⁇ m or more, and particularly preferably 10 ⁇ m or more.
- the number average particle diameter is less than 1 ⁇ m, the fine particles are scattered during handling, which deteriorates the working environment and makes it difficult to control the thickness of the molded body during molding, for example, it is difficult to increase the thickness. Further, when the number average particle diameter exceeds 200 ⁇ m, the specific surface area of the fine particles becomes small, so that not only the molding time becomes long, but also the dispersion stability deteriorates when the fine particles are used as a coating liquid. Will settle down significantly.
- the particle size of the PPS fine particles is determined by observing the PPS fine particles at a magnification of 100 to 500 times using a scanning electron microscope (for example, a scanning electron microscope JSM-6301NF manufactured by JEOL Ltd.). Measure (particle diameter). Subsequently, the number average particle diameter is calculated by obtaining the arithmetic average of 100 particle diameters according to the following formula. In addition, when the particles are not in a perfect circle shape on the image (for example, in the case of an elliptical shape, or when the particles form an aggregate in which the particles are irregularly gathered), the longest diameter is measured as the particle diameter. .
- Ri particle size of each particle
- n number of measurements 100
- Dn number average particle size.
- the sphericity of the porous PPS fine particles is preferably 80 or more, more preferably 85 or more, particularly preferably 90 or more, and most preferably 98 or more.
- PPS fine particles When the sphericity is high, PPS fine particles not only have excellent fluidity and adhesion, but when heat energy is applied during molding, the heat is uniformly transferred to the fine particles, and the fine particles are dissolved more efficiently and uniformly. Therefore, the molding operation can be simplified.
- the sphericity of the porous PPS fine particles is an arithmetic average value of the sphericity of 30 particles randomly selected with a scanning electron microscope, and was calculated according to the following formula.
- the sphericity of each particle is the ratio of the major axis of each particle to the minor axis perpendicular to it, and was calculated according to the following formula.
- Sm average sphericity (%)
- Si sphericity of each particle
- ai minor diameter of each particle
- bi major diameter of each particle
- n number of measurements 30.
- the particle size distribution index which is an index indicating the breadth of the particle size distribution of the porous PPS fine particles, is preferably 1 to 3, more preferably 1 to 2.5, still more preferably 1 to 2.0, and more preferably. Is 1 to 1.75, particularly preferably 1 to 1.5.
- the lower limit of the particle size distribution index is theoretically 1. If the particle size distribution index is small, the particle size is more uniform and the difference in dissolution or melting rate between particles is less likely to occur. This is advantageous in the molding process, such as being capable of forming a smooth surface with less surface roughness.
- the particle size distribution index of the porous PPS fine particles is calculated by the following formula using the particle size length measurement result performed when calculating the number average particle size.
- Ri particle size of each particle
- n number of measurements 100
- Dn number average particle size
- Dv volume average particle size
- PDI particle size distribution index.
- the PPS fine particles of the present invention can be dispersed in a desired dispersion medium to form a dispersion.
- the dispersion medium is not particularly limited, but aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, ester solvents, halogen solvents, ketone solvents, alcohol solvents, aprotic polar solvents, carboxylic acid solvents, Examples include ether solvents, ionic liquids, and water.
- Examples of the aliphatic hydrocarbon solvent include pentane, hexane, heptane, octane, nonane, n-decane, n-dodecane, n-tridecane, tetradecane, cyclohexane and cyclopentane.
- Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and 2-methylnaphthalene.
- Examples of the ester solvent include ethyl acetate, methyl acetate, butyl acetate, butyl propionate, and butyl butyrate.
- halogenated hydrocarbon solvent examples include chloroform, bromoform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, chlorobenzene, 2,6-dichlorotoluene, hexafluoroisopropanol and the like.
- ketone solvent examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl butyl ketone.
- alcohol solvents examples include methanol, ethanol, 1-propanol, 2-propanol and the like.
- Examples of aprotic polar solvents include N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), propylene carbonate, trimethyl phosphorus Acid, 1,3-dimethyl-2-imidazolidinone, sulfolane and the like.
- Examples of the carboxylic acid solvent include formic acid, acetic acid, propionic acid, butyric acid, and lactic acid.
- Examples of the ether solvent include anisole, diethyl ether, tetrahydrofuran, diisopropyl ether, dioxane, diglyme, dimethoxyethane and the like.
- ionic liquids examples include 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium hydrogen sulfate, 1-ethyl-3-imidazolium acetate, 1-ethyl-3-methylimidazolium thiocyanate Etc.
- preferable dispersion media among these include aromatic hydrocarbon solvents, alcohol solvents, ketone solvents. And a dispersion medium selected from water, more preferably a dispersion medium selected from alcohol solvents, ketone solvents and water, and more preferably selected from alcohol solvents and water. It is a dispersion medium.
- Specific examples of the preferable dispersion medium include a dispersion medium selected from toluene, methyl ethyl ketone, ethanol, isopropanol, and water. In addition, you may use these dispersion media in mixture of multiple types.
- the dispersion of PPS fine particles of the present invention forms a coating layer at a lower temperature and in a shorter time because of the good moldability expressed by the unique form of PPS fine particles. Can do.
- the method for producing porous PPS fine particles includes, for example, a quench method in which a PPS resin is gradually cooled after polymerization to form granules, a flash method in which a solvent is rapidly scattered after polymerization, a ball mill, a bead mill, a jet mill, a mortar, etc.
- a mechanical pulverization method in which a PPS resin is gradually cooled after polymerization to form granules
- a flash method in which a solvent is rapidly scattered after polymerization
- a ball mill a bead mill, a jet mill, a mortar, etc.
- a mechanical pulverization method a forced melt kneading method
- a spray drying method a precipitation method by cooling.
- the following method using the phase separation phenomenon of the polymer solution is most preferable.
- the particle formation method using the phase separation phenomenon of a polymer solution is a method in which a PPS resin (A), a polymer (B) different from the PPS resin, and an organic solvent (C) are dissolved and mixed together.
- the solution phase mainly comprising the PPS resin (A) is a disperse phase, a polymer.
- PPS fine particles are precipitated by bringing the emulsion into contact with a poor solvent of a PPS resin.
- the solution phase containing PPS resin (A) as a main component is a solution phase in which the PPS resin is more distributed between the PPS resin and the polymer (B).
- the solution phase containing polymer (B) as a main component is a solution phase in which polymer (B) is more distributed between PPS resin and polymer (B). It is.
- a solution phase containing the PPS resin (A) as a main component and the polymer (B ) Is a system that phase-separates into two phases of a solution phase mainly composed of PPS resin (A), polymer (B), and organic solvent (C) when the PPS resin solution phase and polymer ( B) A system that is divided into two phases of solution phase.
- the polymer (B) may be a thermoplastic resin or a thermosetting resin among polymers different from the PPS resin, but a thermoplastic resin is preferable from the viewpoint of being easily dissolved in the organic solvent (C).
- a thermoplastic resin is preferable from the viewpoint of being easily dissolved in the organic solvent (C).
- Specific examples include polyethylene oxide, polyethylene glycol, polyvinyl alcohol (which may be a completely saponified or partially saponified polyvinyl alcohol), hydroxypropyl cellulose, and the like. Since the particle size distribution of the obtained PPS particles becomes narrow, it is preferably a resin selected from polyethylene oxide, polyethylene glycol and polyvinyl alcohol (may be completely saponified or partially saponified polyvinyl alcohol). .
- the molecular weight of the polymer (B) it is preferable to use a polymer having a weight average molecular weight of 1,000 or more.
- phase separation into two phases of a solution phase mainly composed of PPS resin and a solution phase mainly composed of polymer (B) is easily induced. It is easy to obtain porous PPS fine particles having a sphericity of 80 or more.
- the molecular weight of the polymer (B) is preferably in the range of 1,000 to 10,000,000 in terms of weight average molecular weight.
- the more preferred upper limit of the molecular weight is 5,000,000 or less, more preferably 2,000,000 or less, and the particularly preferred upper limit is 1,000,000 or less.
- the more preferable lower limit of the molecular weight is 1,000 or more, more preferably 10,000 or more, and the particularly preferable lower limit is 20,000 or more.
- the weight average molecular weight refers to a weight average molecular weight measured by gel permeation chromatography (GPC) using water as a solvent and converted using polyethylene glycol as a standard material.
- GPC gel permeation chromatography
- dimethylformamide is used when water cannot be used
- tetrahydrofuran is used when water cannot be measured
- hexafluoroisopropanol is used when water cannot be measured.
- Organic solvent (C) is a solvent that dissolves the PPS resin (A) and the polymer (B).
- the solvent that dissolves the polymer refers to the PPS resin and the polymer with respect to the organic solvent (C) at the temperature at which the PPS resin (A) and the polymer (B) are dissolved and mixed.
- (B) means a solvent capable of dissolving more than 1% by mass. It is preferable that the organic solvent (C) can metastable the PPS resin metastable at a temperature Tp in the step of obtaining porous PPS fine particles by contacting with a poor solvent.
- the organic solvent (C) in the PPS resin solution phase and the organic solvent (C) in the polymer (B) solution phase may be the same or different, but are preferably substantially the same solvent.
- Preferred solvents are organic amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and N-methylcaprolactam. These solvents may be used alone or in combination. N-methyl-2-pyrrolidone is more preferable from the viewpoint of the solubility of the PPS resin and the dissolution stability at Tp.
- the poor solvent of the PPS resin refers to a solvent having a solubility of the PPS resin in the solvent of 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.1% by mass or less.
- the poor solvent is preferably a poor solvent for the PPS resin and a solvent that dissolves the polymer (B). Thereby, the porous PPS microparticles
- the said organic solvent (C) and poor solvent are the solvents mixed uniformly.
- poor solvents vary depending on the type of PPS resin and polymer (B), but include pentane, hexane, heptane, octane, nonane, n-decane, n-dodecane, n-tridecane, cyclohexane, cyclopentane, etc.
- An aliphatic hydrocarbon solvent such as benzene, toluene and xylene; an alcohol solvent such as methanol, ethanol, 1-propanol and 2-propanol; and a solvent selected from water It is done.
- a solvent selected from an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, an alcohol solvent and water preferably a solvent selected from alcohol solvents and water, and most preferably water.
- the difference in SP value between the PPS resin (A) and the polymer (B) is 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 upper limit of the difference in SP value is preferably 20 (J / cm 3 ) 1 / It is 2 or less, more preferably 15 (J / cm 3 ) 1/2 or less, and further preferably 10 (J / cm 3 ) 1/2 or less.
- the SP value here is calculated based on the Fedor's estimation method, and is calculated based on the cohesive energy density and molar molecular volume (hereinafter also referred to as the calculation method).
- the SP value basics / applications and calculation methods by Hideki Yamamoto, Information Organization Co., Ltd., published on March 31, 2005.
- the SP value is calculated by an experimental method (hereinafter also referred to as an experimental method) by determining whether or not the solubility parameter is dissolved in a known solvent, and is used instead.
- an experimental method hereinafter also referred to as an experimental method
- the phase diagram is prepared by determining whether or not an interface is formed when the PPS resin (A), the polymer (B), and the organic solvent (C) are mixed and dissolved in an arbitrary ratio and left standing. It is possible to determine the conditions for phase separation by distinguishing the region that separates into two phases and the region that becomes one phase by performing the measurement at a point or more, preferably 5 points or more, more preferably 10 points or more. It becomes like this.
- the PPS resin (A), the polymer (B), and the organic solvent (C) are arbitrarily mixed at the temperature and pressure when the emulsion is actually formed.
- the PPS resin (A) and the polymer (B) are completely dissolved, sufficiently stirred, and left to stand for 3 days, and then whether or not the phase separation is macroscopically confirmed.
- macroscopic phase separation may not occur even if left for 3 days. In that case, the phase separation is discriminated based on whether or not the phase separation is microscopically using an optical microscope or a phase contrast microscope.
- the concentration of the PPS resin (A) and the polymer (B) with respect to the organic solvent (C) is premised on being within a range that dissolves in the organic solvent (C), but the lower limit is set for each of the total mass of the mixture. Is preferably more than 1% by mass, more preferably 2% by mass or more, further preferably 3% by mass or more, and more preferably 5% by mass or more. Further, the upper limit of the concentration of the PPS resin (A) and the polymer (B) is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass with respect to the total mass of the mixture. % Or less.
- the interfacial tension between the two phases of the PPS resin solution phase obtained by phase separation and the polymer (B) solution phase is an organic solvent, so that the interfacial tension is small. Due to its properties, the emulsion to be produced is stable, and an emulsion having a very narrow droplet size distribution can be obtained. Therefore, the particle size distribution of the obtained PPS fine particles is considered to be small. This tendency is remarkable when both a PPS resin (A) and a polymer (B) are dissolved using a single solvent as the organic solvent (C).
- the interfacial tension between the two separated phases cannot be measured directly by the hanging drop method in which a different kind of solution is added to a commonly used solution because the interfacial tension is too small.
- the interfacial tension can be estimated.
- the surface tension of each phase with air is r 1 and r 2
- the preferable upper limit of r 1/2 is 10 mN / m or less, more preferably 5 mN / m or less, further preferably 3 mN / m or less, and particularly preferably 2 mN / m or less.
- the preferred lower limit is more than 0 mN / m.
- the viscosity ratio of the two phases separated by phase affects the number average particle size and particle size distribution of the resulting PPS fine particles.
- the lower limit thereof is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, more preferably 0.5 or more, and remarkably Preferred is 0.8 or more.
- the upper limit of the viscosity ratio is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less, particularly preferably 1.5 or less, and particularly preferably 1.2 or less.
- the viscosity ratio of the two phases here is defined as the viscosity of the PPS resin solution phase / the viscosity of the polymer (B) solution phase under the temperature condition to be actually carried out.
- Such PPS resin (A), polymer (B) and organic solvent (C) are mixed, and PPS resin (A) and polymer (B) are completely dissolved.
- the temperature at this time is Td (° C.).
- Td varies depending on the copolymerization ratio of the PPS resin to be used and the type of organic solvent (C), and therefore cannot be uniquely determined, but is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, and still more preferably It is 220 ° C. or higher, particularly preferably 230 ° C. or higher, and particularly preferably 240 ° C. or higher.
- the upper limit is not particularly limited, but is preferably 300 ° C. or less from the viewpoint of industrial feasibility.
- An emulsion is formed by applying a shearing force to the obtained solution using the phase separation system.
- the temperature of the emulsion forming step is equal to or higher than the temperature at which the PPS resin and the polymer (B) are dissolved in the organic solvent (C).
- the temperature range is not particularly limited, but is preferably 0 ° C. to 300 ° C. from the viewpoint of industrial feasibility.
- the upper limit of the temperature range is a balance with the temperature Td at which the PPS resin is dissolved, but is preferably 290 ° C. or less, more preferably 280 ° C. or less, further preferably 270 ° C. or less, and particularly preferably 260 It is below °C.
- the lower limit of the temperature range cannot be determined uniquely because the appropriate temperature varies depending on the copolymerization ratio of the PPS resin and the type of the organic solvent (C), but is particularly limited if it is higher than the temperature at which the PPS resin is precipitated.
- the lower limit of the temperature of the emulsion forming step is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, further preferably 220 ° C. or higher, particularly preferably 230 ° C. or higher, and particularly preferably 240 ° C. or higher. It is.
- the pressure in the emulsion forming step is preferably in the range of normal pressure to 100 atm (10.1 MPa) from the viewpoint of industrial feasibility.
- the preferred upper limit of the pressure is 75 atm (7.5 MPa) or less, more preferably 50 atm (5.0 MPa) or less, and particularly preferably 30 atm. (3.0 MPa) or less.
- the minimum with a preferable pressure is more than the saturated vapor pressure of the solvent in Td and Tp.
- the emulsion forming step is preferably performed in an inert gas atmosphere.
- the inert gas nitrogen, helium, argon or carbon dioxide is preferable, and nitrogen or argon is more preferable.
- 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 300 rpm to 600 rpm. is there.
- stirring blades examples include propeller type, paddle type, flat paddle type, turbine type, double cone type, single cone type, single ribbon type, double ribbon type, screw type, helical ribbon type, etc. As long as a sufficient shearing force can be applied, there is no particular limitation thereto. Moreover, in order to perform efficient stirring, you may install a baffle plate etc. in a tank.
- a stirrer in order to generate an emulsion, it is not always necessary to use a stirrer, and an apparatus such as an emulsifier or a disperser may be used.
- an apparatus such as an emulsifier or a disperser may be used.
- batch emulsification such as a homogenizer (manufactured by IKA Japan), Polytron (registered trademark) (manufactured by Kinematica), TK auto homomixer (manufactured by Special Machine Industries Co., Ltd.), etc.
- the emulsion thus obtained is subsequently subjected to a step of precipitating fine particles.
- PPS fine particles are deposited with a diameter corresponding to the droplet diameter of the emulsion.
- the temperature Tp in the reaction tank when the poor solvent is brought into contact is preferably 10 ° C. or lower than the temperature Td at which the PPS resin (A) is dissolved in the organic solvent (C). PPS fine particles can be obtained in a porous form.
- the solubility of the PPS resin is lowered by lowering the temperature Tp at which the poor solvent is brought into contact by 10 ° C. or more than Td, the PPS fine particles can be precipitated more rapidly. Growth can be controlled, and porous PPS fine particles can be obtained in a form with a high sphericity and a narrow particle size distribution.
- the temperature difference between Tp and Td is more preferably in the range of 10 ° C. to 80 ° C., more preferably 10 ° C. to 70 ° C., particularly preferably 20 ° C. to 60 ° C., and most preferably 30 ° C. to 50 ° C. is there. It is preferable to set the temperature difference between Tp and Td in such a range because porous PPS fine particles can be obtained in a form having a higher sphericity and a smaller particle size distribution index.
- 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 more preferable.
- the method for introducing the poor solvent is not particularly limited as long as the PPS fine particles of the present invention are obtained, and any of a continuous dropping method, a divided addition method and a batch addition method may be used.
- a continuous dropping method preferably the continuous dropping method or splitting
- the continuous dropping method is the most preferred for the industrially efficient implementation.
- the time for adding the poor solvent is preferably 5 minutes or more and 50 hours or less. More preferably, it is 10 minutes or more and 10 hours or less, More preferably, it is 30 minutes or more and 5 hours or less, Most preferably, they are 1 hour or more and 5 hours or less.
- the poor solvent within this time range, when the PPS fine particles are precipitated from the emulsion, aggregation between the particles can be suppressed, and PPS fine particles having a uniform particle size and a narrow particle size distribution are obtained. be able to.
- the poor solvent is added in a time shorter than this range, the particle size distribution of the resulting PPS fine particles becomes wider or a lump is generated due to the cohesive fusion or coalescence of emulsion droplets. There is. Moreover, it is industrially disadvantageous when it is carried out for a longer time.
- the amount of the poor solvent to be added varies depending on the molecular weight of the polymer (B) and the solubility of the PPS resin (A) in the organic solvent (C). In general, it is preferably 0.1 to 10 parts by mass. As a more preferable upper limit, it is 5 parts by mass or less, more preferably 3 parts by mass or less, particularly preferably 2 parts by mass or less, and most preferably 1 part by mass or less. Moreover, a preferable minimum is 0.1 mass part or more, More preferably, it is 0.5 mass part or more.
- the contact time between the poor solvent and the emulsion may be sufficient time for the fine particles to precipitate, but in order to cause sufficient precipitation and to obtain efficient productivity, 5 minutes or more after the addition of the poor solvent is completed. 50 hours or less is preferable, more preferably 5 minutes or more and 10 hours or less, still more preferably 10 minutes or more and 5 hours or less, particularly preferably 20 minutes or more and 4 hours or less, and most preferably 30 minutes or more and 3 hours or less. It is as follows.
- the PPS fine particle dispersion prepared in this way can be recovered as fine particles by solid-liquid separation by a generally known method such as filtration, vacuum filtration, pressure filtration, centrifugal separation, centrifugal filtration, spray drying and the like. it can.
- Solid-liquid separated fine particles are purified with a solvent or the like as necessary to remove attached or contained impurities.
- the solvent separated in the solid-liquid separation step is a mixture of the polymer (B), the organic solvent (C) and the poor solvent.
- the poor solvent By removing the poor solvent from this solvent, it can be reused as a solvent for forming an emulsion.
- 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. A method by simple distillation, vacuum distillation or precision distillation is preferred.
- the system When performing distillation operations such as simple distillation and vacuum distillation, the system is heated similarly to the production of PPS microparticles, and there is a possibility of promoting the thermal decomposition of the polymer (B) and the organic solvent (C). It is preferable to carry out in a state free of oxygen as much as possible, more preferably in an inert atmosphere. Specifically, it is preferably carried out in an atmosphere of nitrogen, helium, argon or carbon dioxide. Moreover, when performing distillation operation, you may add a phenolic compound as antioxidant.
- the residual amount of the poor solvent is 10% by mass or less, preferably 5% by mass or less, more preferably based on the total amount of the organic solvent (C) and the polymer (B). Is 3% by mass or less, particularly preferably 1% by mass or less.
- the amount of the poor solvent in the solvent to be recycled can be measured by a known method such as a gas chromatography method or a Karl Fischer method.
- the organic solvent (C) or the polymer (B) may actually be lost. Therefore, when the recovered solvent is reused, it is necessary to adjust the composition as appropriate. preferable.
- the PPS fine particles of the present invention thus obtained have a porous particle surface, and therefore, when processed into various shaped bodies by applying thermal energy, the fusion of the particles is promoted, and the temperature is lower. In addition, it is possible to form and form a particle coating layer in a shorter time.
- the PPS fine particles of the present invention since the PPS fine particles of the present invention have a porous shape, they can scatter light in multiple directions and reduce the reflection intensity of light. Therefore, when added to a medium, the blur effect and the matte effect Can be granted.
- the porous PPS fine particles are spherical, and the particle diameter is uniform, thereby improving the handling of the porous PPS fine particles during the molding processing operation and the obtained molded product. Improves smoothness and suppresses unevenness.
- porous PPS fine particles are spherical and the particle diameter is uniform, when the particles are added to the paint, the particles are aggregated or separated in the paint without impairing the quality of the paint, Demonstrates the effect of a paint delustering agent.
- the PPS fine particles of the present invention can be practically used for various applications.
- molding materials represented by injection molding, microfabrication, etc .; and electronic / electrical material component parts, electronics product housing parts members obtained using the materials; thickeners during various molding processes; Additives such as molding dimension stabilizers; coatings in the form of dispersions, coating liquids, paints, coating materials; rapid prototyping, rapid manufacturing and additive manufacturing materials; flow as powders Property improvers, lubricants, abrasives and thickeners; plastic films, sheet slipperiness improvers, antiblocking agents, gloss modifiers and matte finishes; plastic films, sheets, lens light diffusers, Various modifiers such as surface hardness improvers and toughness improvers; various inks; toner gloss modifiers, matte finishes, etc.
- Additives as uses Additives as uses for gloss control agents for various paints, matte finishes, etc .; Spacers for liquid crystal display operations; Fillers for chromatography; Base materials and additives for cosmetics; Catalysts for chemical reactions And can be used for applications such as a gas adsorbent.
- the particle diameter of the porous PPS fine particles in the present invention is a number average particle diameter.
- a scanning electron microscope scanning electron microscope JSM-6301NF manufactured by JEOL Ltd.
- the PPS fine particles were observed at a magnification of 100 to 500 times, and the diameter (particle diameter) of 100 PPS fine particles was measured.
- the number average particle diameter was calculated by obtaining the arithmetic average of 100 particle diameters according to the following formula.
- the longest diameter is measured as the particle diameter. .
- Ri particle size of each particle
- n number of measurements 100
- Dn number average particle size.
- the sphericity of the porous PPS fine particles is an arithmetic average value of the sphericity of 30 particles randomly selected by a scanning electron microscope, and was calculated according to the following formula.
- the sphericity is a ratio of the major axis of each particle to the minor axis perpendicular to it, and was calculated according to the following formula.
- Sm average sphericity
- Si sphericity of each particle
- ai minor diameter of each particle
- bi major diameter of each particle
- n number of measurements 30.
- the particle size distribution index of the porous PPS fine particles is calculated by the following equation using the particle size length measurement result performed when calculating the number average particle size.
- Ri particle size of each particle
- n number of measurements 100
- Dn number average particle size
- Dv volume average particle size
- PDI particle size distribution index.
- the melting points of the raw material PPS resin and the PPS fine particles were raised to 300 ° C. under a temperature rising rate of 20 ° C./min using differential scanning calorimetry (TA Instruments Co., Ltd. differential scanning calorimeter Q20). Peak temperature indicating the heat capacity of fusion in the second temperature increase process when the temperature is decreased to 20 ° C. at a temperature decrease rate of 20 ° C./min and the temperature is increased and measured again at a temperature increase rate of 20 ° C./min. It was measured by calculating.
- Thermogravimetry Using a differential thermal and thermogravimetric simultaneous measurement device (TG-DTA, DTG-60 manufactured by Shimadzu Corporation), the temperature was raised from 20 ° C. to 500 ° C. at a rate of temperature increase of 10 ° C./min. The amount of decrease was measured.
- TG-DTA differential thermal and thermogravimetric simultaneous measurement device
- the powder handling properties of the porous PPS fine particles are as follows. It was evaluated as follows. A: Fine particles are excellent in fluidity and can be weighed without problems, and fine particles can be spread on the film without gaps B: Fine particles are excellent in fluidity and can be weighed without problems, but filling characteristics when fine particles are spread on the film Low C: Adhesion of fine particles is strong, handling at the time of weighing is difficult, and it is difficult to spread thinly on a film.
- the porous PPS fine particles were comprehensively evaluated according to the following criteria in response to the results of the film formability evaluation and the powder handleability evaluation at the above four stages of temperature.
- the particle has no specific reflection in a specific direction and can scatter light in multiple directions regardless of the angle. However, it can be said that the blur effect is exhibited.
- the blur effect of the porous PPS fine particles produced by the method of the present invention was evaluated as follows based on the PPS resin powder used as the raw material. A: Both the standard deviation and the maximum deviation of the reflection intensity are small compared to the raw material powder. B: Either the standard deviation or the maximum deviation of the reflection intensity is small compared to the raw material powder, but the other is compared to the raw material powder. Large C: Both the standard deviation and the maximum deviation of the reflection intensity are large compared to the raw material powder.
- Ii reflection intensity at each angle
- Im average value of reflection intensity
- ⁇ standard deviation
- Imax maximum value of reflection intensity
- Tmax maximum deviation.
- PPS fine particles are added to a two-component urethane paint (black, Retan (registered trademark) PG60, manufactured by Kansai Paint Co., Ltd.) at a concentration of 2 wt%, and then the paint is applied to a plastic plate with an air brush to disperse the particles into the paint.
- a two-component urethane paint black, Retan (registered trademark) PG60, manufactured by Kansai Paint Co., Ltd.
- the properties and the matting effect of the paint were evaluated as follows.
- the amount of residual water in the system per mole of the alkali metal sulfide charged was 1.1 mol including the water consumed for hydrolysis of N-methyl-2-pyrrolidone.
- the amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.
- Example 1 In a 1 liter autoclave, 5 parts by mass of PPS (melting point: 239 ° C.) obtained in Reference Example 2 as PPS resin (A), and polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., G-type “Gosenol” (registered) Trademark) 'GM-14, weight average molecular weight 29,000) 15 parts by mass, N-methyl-2-pyrrolidone 80 parts by mass as the organic solvent (C), and stirring at a rotational speed of 555 rpm using a paddle blade as a stirring blade The temperature was raised to 250 ° C. over about 1 hour, and the mixture was stirred for 1 hour while being kept at 250 ° C.
- PPS resin (A) PPS resin
- polyvinyl alcohol manufactured by Nippon Synthetic Chemical Industry Co., Ltd., G-type “Gosenol” (registered) Trademark
- a fine white powder was obtained, and the obtained PPS fine particle had a linseed oil absorption of 126 mL / 100 g, a number average particle size of 22.4 ⁇ m, a sphericity of 95%, and a particle size distribution index of 1.4.
- the resulting porous PPS fine particles had a melting point of 242 ° C., and the thermal weight loss at 300 ° C. was 0.64%. It is shown in Table 2.
- Example 2 5 parts by mass of PPS (melting point: 239 ° C.) obtained in Reference Example 2 as the PPS resin (A), polyvinyl alcohol as the polymer (B) (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., G type “GOHSENOL (registered trademark)” GM- 14. Particle formation was carried out in the same manner as in Example 1 except that 10 parts by mass of the weight average molecular weight 29,000) and 85 parts by mass of N-methyl-2-pyrrolidone as the organic solvent (C) were used.
- the obtained linseed oil absorption of the obtained PPS fine particles was 70 mL / 100 g, the number average particle size was 37.0 ⁇ m, the sphericity was 98%, and the particle size distribution index was 1.4.
- the resulting porous PPS fine particles had a melting point of 248 ° C., and the thermal weight loss at 300 ° C. was 0.53%.
- Table 2 shows the film formability and powder handling properties of the obtained PPS fine particles.
- formation of the emulsion with the said composition was confirmed separately.
- Example 3 3 parts by weight of PPS (melting point: 239 ° C.) obtained in Reference Example 2 as the PPS resin (A), polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., G-type “Gosenol (registered trademark)” GM- 14. Particle formation was carried out in the same manner as in Example 1 except that 10 parts by mass of weight average molecular weight 29,000) and 87 parts by mass of N-methyl-2-pyrrolidone as the organic solvent (C) were used.
- the obtained PPS fine particles had a linseed oil absorption of 90 mL / 100 g, a number average particle size of 30.3 ⁇ m, a sphericity of 99%, and a particle size distribution index of 1.3.
- the melting point of the obtained porous PPS fine particles was 245 ° C., and the thermal weight loss at 300 ° C. was 0.66%.
- Table 2 shows the film formability and powder handling properties of the obtained PPS fine particles.
- formation of the emulsion with the said composition was confirmed separately.
- Example 4 5 parts by mass of PPS (melting point: 239 ° C.) obtained in Reference Example 2 as the PPS resin (A), polyethylene oxide (manufactured by Meisei Chemical Co., Ltd., “Alcox (registered trademark)” E-60, Particleization was carried out in the same manner as in Example 1 except that 5 parts by weight of the weight average molecular weight 600,000) and 90 parts by weight of N-methyl-2-pyrrolidone as the organic solvent (C) were used.
- the obtained linseed oil absorption of the obtained PPS fine particles was 80 mL / 100 g, the number average particle size was 8.1 ⁇ m, the sphericity was 95%, and the particle size distribution index was 1.5.
- the melting point of the obtained porous PPS fine particles was 245 ° C., and the thermal weight loss at 300 ° C. was 0.72%.
- Table 2 shows the film formability and powder handling properties of the obtained PPS fine particles.
- formation of the emulsion with the said composition was confirmed separately.
- Example 5 5 parts by mass of PPS (melting point: 239 ° C.) obtained in Reference Example 2 as the PPS resin (A), polyvinyl alcohol as the polymer (B) (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., G type “GOHSENOL (registered trademark)” GM- 14, weight average molecular weight 29,000) 5 parts by mass, organic solvent (C) N-methyl-2-pyrrolidone 90 parts by mass, poor solvent (D) 82 parts by mass ion-exchanged water, and poor solvent dropped Particleization was carried out in the same manner as in Example 1 except that the temperature Tp when the temperature was changed to 230 ° C.
- the obtained linseed oil absorption of the obtained PPS fine particles was 61 mL / 100 g, the number average particle size was 5.6 ⁇ m, the sphericity was 81%, and the particle size distribution index was 3.0.
- the melting point of the obtained porous PPS fine particles was 239 ° C., and the thermogravimetric loss at 300 ° C. was 0.74%.
- Table 2 shows the film formability and powder handling properties of the obtained PPS fine particles.
- formation of the emulsion with the said composition was confirmed separately.
- Example 6 5 parts by mass of PPS (melting point: 239 ° C.) obtained in Reference Example 2 as the PPS resin (A), polyethylene oxide (manufactured by Meisei Chemical Co., Ltd., “Alcox (registered trademark)” E-30, Particleization was carried out in the same manner as in Example 1 except that 10 parts by weight of the weight average molecular weight 400,000) and 85 parts by weight of N-methyl-2-pyrrolidone as the organic solvent (C) were used.
- the linseed oil absorption of the obtained PPS fine particles was 60 mL / 100 g, the number average particle size was 8.7 ⁇ m, the sphericity was 92%, and the particle size distribution index was 3.2.
- the resulting porous PPS fine particles had a melting point of 244 ° C., and the thermal weight loss at 300 ° C. was 0.45%.
- Table 2 shows the film formability and powder handling properties of the obtained PPS fine particles.
- formation of the emulsion with the said composition was confirmed separately.
- Example 7 5 parts by mass of PPS (melting point 281 ° C.) obtained in Reference Example 1 as the PPS resin (A), polyethylene oxide (manufactured by Meisei Chemical Industry Co., Ltd., “Alcox (registered trademark)” E-60, Particleization was carried out in the same manner as in Example 1 except that 5 parts by weight of the weight average molecular weight 600,000) and 90 parts by weight of N-methyl-2-pyrrolidone as the organic solvent (C) were used.
- the obtained linseed oil absorption amount of the fine PPS particles was 128 mL / 100 g, the number average particle size was 77.0 ⁇ m, the sphericity was 71%, and the particle size distribution index was 1.7.
- the resulting porous PPS fine particles had a melting point of 280 ° C., and the thermogravimetric loss at 300 ° C. was 0.62%.
- Table 2 shows the film formability and powder handling properties of the obtained PPS fine particles.
- formation of the emulsion with the said composition was confirmed separately.
- the porous PPS fine particles obtained in Example 1 and Example 6 were evaluated for the blurring effect performance of the particles, the dispersibility in the paint, and the delustering effect when added to the paint, and the evaluation results are shown in Table 3. Indicated. In addition, the same evaluation was implemented about the PPS powder (comparative example 2) obtained by the reference example 2 as a comparative example.
- the porous PPS fine particles of the present invention have a blur effect that suppresses reflection of light due to its porous form, and the blur effect is evenly expressed in a wide range of angles without depending on the angle, and dispersed in the paint. The properties were also good and an excellent paint matting effect was exhibited.
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Abstract
Description
すなわち、本発明は、アマニ油吸油量が40~1000mL/100gであり、かつ、数平均粒子径が1~200μmであるポリフェニレンサルファイド微粒子である。
また、本発明は、上記のポリフェニレンサルファイド微粒子を含有する分散液を含む。
また、本発明は、ポリフェニレンサルファイド樹脂(A)とポリフェニレンサルファイド樹脂とは異なるポリマー(B)と有機溶媒(C)とを混合し溶解させたときに、ポリフェニレンサルファイド樹脂(A)を主成分とする溶液相と、前記ポリマー(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、ポリフェニレンサルファイド樹脂(A)、ポリマー(B)および有機溶媒(C)を温度Td(℃)で混合して溶解させる工程、得られた溶液に剪断力を加えることによりエマルションを形成させる工程、および該エマルションに温度Tp(℃)でポリフェニレンサルファイド樹脂(A)の貧溶媒を接触させることにより、ポリフェニレンサルファイド樹脂(A)を析出させる工程を含むポリフェニレンサルファイド微粒子の製造方法であって、前記温度Tp(℃)が、前記温度Td(℃)より10℃以上低いポリフェニレンサルファイド微粒子の製造方法を含む。
本発明におけるポリフェニレンサルファイドとは、式(1)に示す繰り返し単位を主要構成単位とするホモポリマーまたはコポリマーである。
日本工業規格(JIS)K5101-13-1:2004に記載の方法に準拠してアマニ油吸油量を測定した。
本発明における多孔質PPS微粒子の粒子径は、数平均粒子径である。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)を用いてPPS微粒子を100倍~500倍で観察し、100個のPPS微粒子についてその直径(粒子径)を測長した。続いて、下記式により100個の粒子の粒子径につき、その算術平均を求めることで数平均粒子径を算出した。なお、画像上で粒子が真円状でない場合(例えば楕円状のような場合や、粒子が不規則に寄せ集まった凝集体を形成している場合)は、その最長径を粒子径として測定した。
多孔質PPS微粒子の真球度は、走査型電子顕微鏡にて、無作為に選択した粒子30個の真球度の算術平均値であり、下記式に従い算出した。真球度は、個々の粒子の長径と、それと垂直に交わる短径の比であり、下記式に従い算出した。
多孔質PPS微粒子の粒子径分布指数は、数平均粒子径の算出時に行った粒子径の測長結果を用いて、次の式により算出される。
原料PPS樹脂およびPPS微粒子の融点は、示差走査熱量測定(TAインスツルメント株式会社製示差走査熱量計Q20)を用いて、昇温速度20℃/分の条件で300℃まで昇温した後、20℃まで20℃/分の降温速度で降温し、再度、昇温速度20℃/分の条件で昇温して測定した際の、2回目の昇温過程における融解熱容量を示すピークの頂点温度を算出することで測定した。
示差熱・熱重量同時測定装置(TG-DTA、株式会社島津製作所製DTG-60)にて、昇温速度10℃/分の条件で、20℃から500℃まで昇温し、300℃における重量減少量を測定した。
多孔質PPS微粒子0.3gを不融性のポリイミドフイルムで挟み、ホットプレス機に挿入し、異なるサンプルについて、230℃、250℃、290℃および340℃の各温度で、それぞれ2分間プレスを行った後、水中に浸漬して急冷し、フイルムを得た。フイルム成形性の評価基準は次のとおりである。
A:表面平滑で透明度の高いフイルムを成形できた
B:フイルム状に成形できたが透明度が低い、微粒子の溶け残りが見られた
C:微粒子が圧着もしくは融着したのみでフイルム状にならなかった。
多孔質PPS微粒子の重量を計測するときの取扱性、および上記フイルム成形性評価でポリイミドフイルムに微粒子を挟み込む操作をするときの取扱性に基づいて、多孔質PPS微粒子の粉体取扱性を、次のように評価した。
A:微粒子は流動性に優れ、問題なく秤量でき、微粒子をフイルム上に間隙なく敷き詰めることができる
B:微粒子は流動性に優れ、問題なく秤量できるが、微粒子をフイルム上に敷き詰めるときの充填特性が低い
C:微粒子の付着性が強く、秤量時の取り扱いが困難であり、フイルム上に薄く広げるのが困難である。
上記4段階の温度におけるフイルム成形性の評価および粉体取扱性の評価の結果を受け、多孔質PPS微粒子を以下の基準で総合評価した。
A:A評価が4つ以上で、かつC評価がない
B:A評価が3つ以下で、かつC評価がない
C:C評価が1つ以上。
三次元変角分光測色システム(村上色彩技術研究所社製GCMS-4型)を用いて、D65光源、入射角45度、受光角-80度~80度(2度ピッチ)、あおり角0度の測定条件で粒子の反射強度の角度依存性を測定し、粒子の反射分布図を得た。測定サンプルは、透明粘着テープの粘着面にPPS微粒子が単層となるように均一に塗布することで調製した。測定結果より、下記式を用いて、反射強度の平均値、標準偏差および最大偏差を算出した。当該粒子の反射強度の標準偏差および最大偏差の値がそれぞれ小さければ、粒子は特定方向への特異的な反射を有さず、角度に依存せず光を多方向に散乱させることができていると言え、ボカシ効果を発現していると言える。本発明の方法により製造した多孔質PPS微粒子のボカシ効果につき、その原料として用いたPPS樹脂粉体を基準として、次のように評価した。
A:反射強度の標準偏差と最大偏差がともに原料粉体と比べて小さい
B:反射強度の標準偏差または最大偏差のどちらか一方は原料粉体と比べて小さいが、他方は原料粉体と比べて大きい
C:反射強度の標準偏差と最大偏差がともに原料粉体と比べて大きい
PPS微粒子を二液ウレタン系塗料(関西ペイント社製、黒色、レタン(登録商標)PG60)に2wt%の濃度で投入した後、塗料をプラスチック板にエアーブラシで塗装し、粒子の塗料への分散性および塗料のツヤ消し効果を次のように評価した。
ツヤ消し効果:塗装面のツヤ消し効果を、目視で次のように5段階評価した(5:非常に優れている~1:効果がない)。
(脱水工程)
攪拌機および底栓弁付きの70リットルオートクレーブに、47.5%水硫化ナトリウム8.3kg、96%水酸化ナトリウム2.9kg、N-メチル-2-ピロリドン11.5kg、酢酸ナトリウム1.9kg、およびイオン交換水5.5kgを仕込み、常圧で窒素を通じながら245℃まで約3時間かけて徐々に加熱し、水9.8kgおよびN-メチル-2-ピロリドン0.3kgを留出した後、反応容器を200℃に冷却した。仕込みアルカリ金属硫化物1モル当たりの系内残存水分量は、N-メチル-2-ピロリドンの加水分解に消費された水分を含めて1.1モルであった。また、硫化水素の飛散量は、仕込みアルカリ金属硫化物1モル当たり0.02モルであった。
次に、p-ジクロロベンゼン10.4kg、N-メチル-2-ピロリドン9.4kgを加え、反応容器を窒素ガス下に密封し、240rpmで攪拌しながら0.6℃/分の速度で200℃から270℃まで昇温し、270℃で140分反応した。その後、270℃から250℃まで15分かけて冷却しながら水2.4kgを圧入した。ついで250℃から220℃まで75分かけて徐々に冷却した後、室温近傍まで急冷し、内容物を取り出した。
取り出した内容物を約35リットルのN-メチル-2-ピロリドンで希釈し、スラリーとした。得られたスラリーを、85℃で30分攪拌後、80メッシュ金網(目開き0.175mm)で濾別して固形物を得た。得られた固形物を70リットルのイオン交換水で希釈し、70℃で30分攪拌後、80メッシュ金網で濾過して固形物を回収する操作を合計3回繰り返した。このようにして得られた固形物を窒素気流下、120℃で乾燥することにより、乾燥PPS粉体を得た。得られたPPSの融点は281℃であった。また、300℃における熱重量減少量は0.66%であった。
(脱水工程)
攪拌機付きの1リットルオートクレーブに、47%水硫化ナトリウム118g、96%水酸化ナトリウム42.4g、N-メチル-2-ピロリドン163g、酢酸ナトリウム32.0g、およびイオン交換水150gを仕込み、常圧で窒素を通じながら225℃まで約3時間かけて徐々に加熱し、水210gおよびN-メチル-2-ピロリドン4gを留出した後、反応容器を150℃に冷却した。硫化水素の飛散量は1.8モル%であった。
次に、p-ジクロロベンゼン125g、m-ジクロロベンゼン22.1g、N-メチル-2-ピロリドン131gを加え、反応容器を窒素ガス下に密封し、400rpmで攪拌しながら、227℃まで0.8℃/分の速度で昇温し、その後270℃/分まで0.6℃/分の速度で昇温し、270℃で170分保持した。その間、270℃に到達後30分経過した時点から水14.4gを10分かけて添加した。その後180℃まで0.4℃/分の速度で冷却し、次に室温近傍まで急冷した。
内容物を取り出し、0.5リットルのN-メチル-2-ピロリドンで希釈し、スラリーとした。得られたスラリーを85℃で30分攪拌後、80メッシュ金網(目開き0.175mm)で濾別して固形物を得た。得られた固形物を1リットルのイオン交換水で希釈し、70℃で30分攪拌後、80メッシュ金網で濾過して固形物を回収する操作を合計3回繰り返した。このようにして得られた固形物を窒素気流下、120℃で乾燥することにより、乾燥PPS粉体を得た。得られたPPSの融点は239℃であった。また、300℃における熱重量減少量は0.58%であった。
1リットルオートクレーブに、PPS樹脂(A)として参考例2で得られたPPS(融点239℃)5質量部、ポリマー(B)としてポリビニルアルコール(日本合成化学工業株式会社製、G型‘ゴーセノール(登録商標)’GM-14、重量平均分子量29,000)15質量部、有機溶媒(C)としてN-メチル-2-ピロリドン80質量部を入れ、攪拌羽としてパドル翼を用いて回転数555rpmで攪拌しながら250℃まで約1時間かけて昇温し、250℃で保持したまま1時間攪拌を行い、PPS樹脂(A)およびポリマー(B)を溶解させた。続いて、オートクレーブ系内の温度を210℃にし、555rpmで攪拌しながら、貧溶媒(D)として100質量部のイオン交換水を、送液ポンプを経由して、0.83質量部/分のスピードで滴下し(、懸濁液を得た。得られた懸濁液を濾過し、イオン交換水100質量部で洗浄し、濾別した固形物を、80℃で真空乾燥することで、PPS微粒子の白色粉体を得た。得られたPPS微粒子のアマニ油吸油量は126mL/100g、数平均粒子径は22.4μm、真球度は95%、粒子径分布指数は1.4であった。得られた多孔質PPS微粒子の融点は242℃であり、300℃における熱重量減少量は0.64%であった。また、得られたPPS微粒子のフイルム成形性および粉体取扱性を表2に示した。
PPS樹脂(A)として参考例2で得られたPPS(融点239℃)5質量部、ポリマー(B)としてポリビニルアルコール(日本合成化学工業株式会社製、G型‘ゴーセノール(登録商標)’GM-14、重量平均分子量29,000)10質量部、有機溶媒(C)としてN-メチル-2-ピロリドン85質量部とした以外は実施例1と同様に粒子化を行った。得られたPPS微粒子のアマニ油吸油量は70mL/100g、数平均粒子径は37.0μm、真球度は98%、粒子径分布指数は1.4であった。得られた多孔質PPS微粒子の融点は248℃であり、300℃における熱重量減少量は0.53%であった。また、得られたPPS微粒子のフイルム成形性および粉体取扱性を表2に示した。なお、実施例1と同様に耐圧試験管を用いた試験で、上記組成でのエマルションの形成を別途確認した。
PPS樹脂(A)として参考例2で得られたPPS(融点239℃)3質量部、ポリマー(B)としてポリビニルアルコール(日本合成化学工業株式会社製、G型‘ゴーセノール(登録商標)’GM-14、重量平均分子量29,000)10質量部、有機溶媒(C)としてN-メチル-2-ピロリドン87質量部とした以外は実施例1と同様に粒子化を行った。得られたPPS微粒子のアマニ油吸油量は90mL/100g、数平均粒子径は30.3μm、真球度は99%、粒子径分布指数は1.3であった。得られた多孔質PPS微粒子の融点は245℃であり、300℃における熱重量減少量は0.66%であった。また、得られたPPS微粒子のフイルム成形性および粉体取扱性を表2に示した。なお、実施例1と同様に耐圧試験管を用いた試験で、上記組成でのエマルションの形成を別途確認した。
PPS樹脂(A)として参考例2で得られたPPS(融点239℃)5質量部、ポリマー(B)としてポリエチレンオキサイド(明成化学工業株式会社製、‘アルコックス(登録商標)’E-60、重量平均分子量600,000)5質量部、有機溶媒(C)としてN-メチル-2-ピロリドン90量部とした以外は実施例1と同様に粒子化を行った。得られたPPS微粒子のアマニ油吸油量は80mL/100g、数平均粒子径は8.1μm、真球度は95%、粒子径分布指数は1.5であった。得られた多孔質PPS微粒子の融点は245℃であり、300℃における熱重量減少量は0.72%であった。また、得られたPPS微粒子のフイルム成形性および粉体取扱性を表2に示した。なお、実施例1と同様に耐圧試験管を用いた試験で、上記組成でのエマルションの形成を別途確認した。
PPS樹脂(A)として参考例2で得られたPPS(融点239℃)5質量部、ポリマー(B)としてポリビニルアルコール(日本合成化学工業株式会社製、G型‘ゴーセノール(登録商標)’GM-14、重量平均分子量29,000)5質量部、有機溶媒(C)としてN-メチル-2-ピロリドン90質量部とし、貧溶媒(D)として82質量部のイオン交換水とし、貧溶媒を滴下するときの温度Tpを230℃とした以外は実施例1と同様に粒子化を行った。得られたPPS微粒子のアマニ油吸油量は61mL/100g、数平均粒子径は5.6μm、真球度は81%、粒子径分布指数は3.0であった。得られた多孔質PPS微粒子の融点は239℃であり、300℃における熱重量減少量は0.74%であった。また、得られたPPS微粒子のフイルム成形性および粉体取扱性を表2に示した。なお、実施例1と同様に耐圧試験管を用いた試験で、上記組成でのエマルションの形成を別途確認した。
PPS樹脂(A)として参考例2で得られたPPS(融点239℃)5質量部、ポリマー(B)としてポリエチレンオキサイド(明成化学工業株式会社製、‘アルコックス(登録商標)’E-30、重量平均分子量400,000)10質量部、有機溶媒(C)としてN-メチル-2-ピロリドン85量部とした以外は実施例1と同様に粒子化を行った。得られたPPS微粒子のアマニ油吸油量は60mL/100g、数平均粒子径は8.7μm、真球度は92%、粒子径分布指数は3.2であった。得られた多孔質PPS微粒子の融点は244℃であり、300℃における熱重量減少量は0.45%であった。また、得られたPPS微粒子のフイルム成形性および粉体取扱性を表2に示した。なお、実施例1と同様に耐圧試験管を用いた試験で、上記組成でのエマルションの形成を別途確認した。
PPS樹脂(A)として参考例1で得られたPPS(融点281℃)5質量部、ポリマー(B)としてポリエチレンオキサイド(明成化学工業株式会社製、‘アルコックス(登録商標)’E-60、重量平均分子量600,000)5質量部、有機溶媒(C)としてN-メチル-2-ピロリドン90量部とした以外は実施例1と同様に粒子化を行った。得られたPPS微粒子のアマニ油吸油量は128mL/100g、数平均粒子径は77.0μm、真球度は71%、粒子径分布指数は1.7であった。得られた多孔質PPS微粒子の融点は280℃であり、300℃における熱重量減少量は0.62%であった。また、得られたPPS微粒子のフイルム成形性および粉体取扱性を表2に示した。なお、実施例1と同様に耐圧試験管を用いた試験で、上記組成でのエマルションの形成を別途確認した。
参考例1で得られたPPS粉体(融点281℃)について、アマニ油吸油量、数平均粒子径、真球度、および粒子径分布指数を測定した。その結果、アマニ油吸油量は36mL/100g、数平均粒子径は119.2μm、真球度は64%、粒子径分布指数は4.4であった。また、参考例1で得られたPPS粉体のフイルム成形性および粉体取扱性を表2に示した。
参考例2で得られたPPS粉体(融点239℃)について、アマニ油吸油量、数平均粒子径、真球度、および粒子径分布指数を測定した。その結果、アマニ油吸油量は27mL/100g、数平均粒子径は259.9μm、真球度は60%、粒子径分布指数は4.8であった。また、参考例2で得られたPPS粉体のフイルム成形性および粉体取扱性を表2に示した。
Claims (9)
- アマニ油吸油量が40~1000mL/100gであり、かつ、数平均粒子径が1~200μmであるポリフェニレンサルファイド微粒子。
- 真球度が80以上である請求項1に記載のポリフェニレンサルファイド微粒子。
- 粒子径分布指数が1~3である請求項1または2に記載のポリフェニレンサルファイド微粒子。
- 融点が210℃~270℃である請求項1~3のいずれかに記載のポリフェニレンサルファイド微粒子。
- ポリフェニレンサルファイド樹脂が、p-フェニレンサルファイド単位とm-フェニレンサルファイド単位および/またはo-フェニレンサルファイド単位の共重合体であり、m-フェニレンサルファイド単位および/またはo-フェニレンサルファイド単位を、全フェニレンサルファイド単位を基準として3~30質量%含む請求項1~4のいずれかに記載のポリフェニレンサルファイド微粒子。
- 請求項1~5項のいずれかに記載のポリフェニレンサルファイド微粒子を含有する分散液。
- ポリフェニレンサルファイド樹脂(A)とポリフェニレンサルファイド樹脂とは異なるポリマー(B)と有機溶媒(C)とを混合し溶解させたときに、ポリフェニレンサルファイド樹脂(A)を主成分とする溶液相と、前記ポリマー(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、ポリフェニレンサルファイド樹脂(A)、ポリマー(B)および有機溶媒(C)を温度Td(℃)で混合して溶解させる工程、得られた溶液に剪断力を加えることによりエマルションを形成させる工程、および該エマルションに温度Tp(℃)でポリフェニレンサルファイド樹脂(A)の貧溶媒を接触させることにより、ポリフェニレンサルファイド樹脂(A)を析出させる工程を含むポリフェニレンサルファイド微粒子の製造方法であって、前記温度Tp(℃)が、前記温度Td(℃)より10℃以上低いポリフェニレンサルファイド微粒子の製造方法。
- ポリフェニレンサルファイド樹脂(A)の融点が210℃~270℃である請求項7に記載のポリフェニレンサルファイド微粒子の製造方法。
- ポリフェニレンサルファイド樹脂(A)が、p-フェニレンサルファイド単位とm-フェニレンサルファイド単位および/またはo-フェニレンサルファイド単位の共重合体であり、m-フェニレンサルファイド単位および/またはo-フェニレンサルファイド単位を、全フェニレンサルファイド単位を基準として3~30質量%含む請求項7または8に記載のポリフェニレンサルファイド微粒子の製造方法。
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