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WO2012043510A1 - Dispersion aqueuse de fines particules de résine - Google Patents

Dispersion aqueuse de fines particules de résine Download PDF

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Publication number
WO2012043510A1
WO2012043510A1 PCT/JP2011/071955 JP2011071955W WO2012043510A1 WO 2012043510 A1 WO2012043510 A1 WO 2012043510A1 JP 2011071955 W JP2011071955 W JP 2011071955W WO 2012043510 A1 WO2012043510 A1 WO 2012043510A1
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WO
WIPO (PCT)
Prior art keywords
polymer
resin fine
mass
aqueous dispersion
water
Prior art date
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Ceased
Application number
PCT/JP2011/071955
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English (en)
Japanese (ja)
Inventor
浅野到
竹崎宏
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Toray Industries Inc
Original Assignee
Toray Industries Inc
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Publication date
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Priority to CN201180043786.XA priority Critical patent/CN103119101B/zh
Priority to KR1020137009486A priority patent/KR101372054B1/ko
Priority to JP2011543029A priority patent/JP5440611B2/ja
Publication of WO2012043510A1 publication Critical patent/WO2012043510A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
    • 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
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers

Definitions

  • the present invention relates to an aqueous dispersion of resin fine particles having heat resistance and suitable as a binder and coating material for paints, adhesives and the like.
  • a dispersion of resin particles with high heat resistance is used as a high-performance dispersion in the field of paints, adhesives, binders or coating agents.
  • Resins with high heat resistance such as polyarylene sulfide and polyamideimide generally tend to have a low affinity with water, and in order to obtain these dispersions, an organic solvent is used as a medium or a surfactant.
  • a method of dispersing in water using a dispersing agent such as is proposed (Patent Documents 1 and 2).
  • thermoplastic elastomer such as an ether ester block copolymer
  • Patent Document 4 discloses a resin fine particle dispersion for forming a film. This Patent Document 4 discloses fine particles particularly suitable from the viewpoints of coating film appearance and storage stability, and an appropriate particle size is 250 nm or less as an average particle size.
  • a surfactant is used for dispersion.
  • the surfactant is used when mixing.
  • the agent is in a mixture state, the dispersibility may be deteriorated, or the function of the mixture may not be sufficiently exhibited. It is better that the dispersion of resin fine particles as much as possible does not contain a surfactant or the like.
  • an object of the present invention is to provide an aqueous dispersion of resin fine particles having excellent practicality in which resin fine particles having high heat resistance are dispersed in an aqueous medium with good dispersibility.
  • the present inventors have found that the above object can be achieved by the heat-resistant resin fine particles copolymerized with aliphatic polyether units, and have completed the present invention.
  • the present invention has the following configuration.
  • Resin fine particles comprising a resin fine particle comprising a copolymer containing 10 to 90% by mass of an aliphatic polyether unit, having a melting point of 120 ° C. or higher and an average particle diameter of 1 ⁇ m to 100 ⁇ m.
  • Aqueous dispersion [2] The resin fine particle aqueous dispersion according to [1], wherein the resin fine particle aqueous dispersion does not contain a dispersant, or even if contained, the amount is less than 1 part by mass with respect to 100 parts by mass of the copolymer.
  • the copolymer containing 10 to 90% by mass of an aliphatic polyether unit is a copolymer comprising an aliphatic polyether unit and a crystalline polyester unit [1] to [3] The resin fine particle water dispersion according to any one of the above.
  • the present invention it is possible to obtain an extremely practical aqueous dispersion containing resin fine particles comprising a highly heat-resistant copolymer containing an aliphatic polyether unit.
  • the resin fine particles comprising the copolymer used in the present invention are well dispersed in water without containing a dispersant. Therefore, an aqueous dispersion having excellent dispersibility can be obtained without using a dispersant. It becomes possible.
  • the resin fine particle aqueous dispersion obtained by the present invention can be used in the field of paints, adhesives, binders or coating agents, and cosmetics applications, and can be applied to aqueousization aimed at reducing the environmental burden of these applications. .
  • aqueous dispersion having good dispersibility can be obtained without using a dispersant, in that case, a highly heat-resistant resin fine particle aqueous dispersion in which coloring and water absorption by the dispersant are suppressed is provided. Is also possible.
  • the resin in the resin fine particle aqueous dispersion in the present invention is characterized by being a copolymer having a melting point of 120 ° C. or higher and containing an aliphatic polyether unit.
  • a copolymer having a melting point of 120 ° C. or higher and containing an aliphatic polyether unit.
  • aliphatic polyether units it has been found that even in heat-resistant resins having a low affinity for water, dispersibility in water is better than in organic solvents. It was found that a dispersion was obtained. Since the dispersion medium is water, the organic solvent can be avoided, which is preferable in terms of environmental conservation, and it is possible to improve the working environment in terms of occupational safety.
  • the aqueous dispersion of the present invention is excellent in dispersibility in water despite having high heat resistance, and therefore has good dispersibility without using a dispersant. Therefore, when a dispersant is not used, it is extremely practical to suppress coloring by the dispersant, deterioration of heat resistance, deterioration of water resistance, adhesion to a substrate, bleeding out to the surface, and occurrence of stickiness. It is also possible to use a simple aqueous dispersion.
  • the copolymer used in the present invention is a copolymer containing an aliphatic polyether unit and having a melting point of 120 ° C. or higher.
  • the copolymerization state of the aliphatic polyether unit may be any form such as random copolymerization, block copolymerization, and graft copolymerization, but the block copolymer can suppress a decrease in heat resistance. preferable.
  • the aliphatic polyether unit of the present invention is represented by the following general formula (1).
  • R represents a divalent aliphatic hydrocarbon group, and specific examples include a linear saturated hydrocarbon group, a branched saturated hydrocarbon group, a linear unsaturated hydrocarbon group, and a branched unsaturated hydrocarbon group.
  • n is the number of repeating units and indicates a positive number.
  • the linear saturated hydrocarbon group, branched saturated hydrocarbon group, linear unsaturated hydrocarbon group, branched unsaturated hydrocarbon group preferably has 1 to 20 carbon atoms from the viewpoint of excellent dispersibility in water, In particular, the number of carbon atoms is preferably 1 to 10.
  • the aliphatic polyether unit to be copolymerized include polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, polyhexamethylene glycol, a copolymer of ethylene oxide and propylene oxide, and ethylene oxide addition of polypropylene glycol. And a copolymer of ethylene oxide and tetrahydrofuran.
  • R has 1 to 10 carbon atoms, such as polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, because it imparts hydrophilicity and facilitates dispersion in water.
  • the amount of the aliphatic polyether unit is in the range of 10 to 90% by mass in the copolymer, preferably 15 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 20 to 70% by mass. is there. If the aliphatic polyether unit is less than 10% by mass, the dispersibility of the resin in water deteriorates, which is not preferable. If it exceeds 90% by mass, the heat resistance of the resin is lowered, which is not preferable.
  • the weight average molecular weight of the aliphatic polyether is not particularly limited, but is usually 500 to 20,000, preferably 500 to 10,000.
  • the weight average molecular weight is a weight average molecular weight measured by gel permeation chromatography (GPC) using dimethylformamide as a solvent and converted to standard polystyrene.
  • the resin in the present invention has a melting point of 120 ° C. or higher, preferably 140 ° C. or higher, more preferably 150 ° C. or higher, and particularly preferably 160 ° C. or higher.
  • a melting point of less than 120 ° C. is not preferable because the heat resistance of the coating film and the like is lowered.
  • limiting in particular as an upper limit It is preferable that it is 300 degrees C or less from the point of the dispersibility to water, and it is more preferable that it is 280 degrees C or less.
  • fusing point is melting
  • the copolymer of the aliphatic polyether unit in the present invention may be copolymerized with other copolymer components without particular limitation as long as the melting point is 120 ° C. or higher.
  • Specific examples of other copolymer components that may be copolymerized include polyester units, polyamide units, polycarbonate units, polyarylene sulfide units, polyether ether ketone units, polyimide units, and monomer units constituting these polymers. Etc. Of these, a block copolymer is preferable, and a unit constituting the block copolymer is preferably a polyester unit or a polyamide unit.
  • a polyester unit is preferable because the heat resistance is maintained even when the ratio of the polyether unit is increased, and a polyester unit that is a polymer unit of an aromatic dicarboxylic acid and a diol is particularly preferable.
  • the polyester unit is not particularly limited as long as it has an ester bond in the main chain or side chain, and can be obtained by polycondensation from an acid component and a glycol component.
  • the acid component constituting the polyester unit includes terephthalic acid, isophthalic acid, phthalic acid, 2,5-dimethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2 -Bisphenoxyethane-p, p'-dicarboxylic acid, phenylindanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, dimer acid, 1,3-cyclopentanedicarboxylic acid, 1,2- Cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like, and ester-forming derivatives thereof, and acid components containing a sulfonic acid group and its base include, for example, sulfoterephthalic acid, 5-sulfoisophthalic
  • glycol component constituting the polyester unit examples include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentane.
  • glycol polycondensates of aromatic dicarboxylic acids are preferred from the viewpoint of the heat resistance of the resin.
  • polyethylene terephthalate, polybutylene terephthalate and the like are preferable from the viewpoint of strength.
  • the weight average molecular weight of the copolymer containing the aliphatic polyether of the present invention is not particularly limited, but is usually 1,000 to 100,000, preferably 10,000 to 80,000, more preferably. 10,000 to 50,000.
  • the weight average molecular weight is a weight average molecular weight measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent and converted to standard polystyrene.
  • the above-mentioned copolymer containing an aliphatic polyether can be produced by a known method.
  • Specific examples include, for example, a method of subjecting a lower alcohol diester of a dicarboxylic acid, an excessive amount of a low molecular weight glycol and a low melting point polymer segment component to a transesterification reaction in the presence of a catalyst, and polycondensing the resulting reaction product, Any method such as a method in which an acid, an excessive amount of glycol and a low melting point polymer segment component are esterified in the presence of a catalyst and the resulting reaction product is polycondensed may be used.
  • the resin fine particle aqueous dispersion in the present invention refers to a resin fine particle present in a dispersion medium containing water as a medium.
  • the resin fine particle aqueous dispersion is in the best condition in which the fine resin particles are constantly suspended in water as a dispersion medium.
  • the resin fine particles may settle with time, but in the resin fine particle aqueous dispersion in the present invention, the resin fine particles settled by performing mechanical redispersion treatment, Those that can be easily redispersed are also included in the resin fine particle dispersion.
  • the number average particle diameter of the resin fine particles in the resin fine particle dispersion is usually 1 to 100 ⁇ m, preferably 1 to 50 ⁇ m, more preferably 1 to 20 ⁇ m. If the number average particle diameter is less than 1 ⁇ m, the fine particles are likely to aggregate, and if it exceeds 100 ⁇ m, it is not preferable because it settles in water.
  • the number average particle diameter of the resin fine particles is calculated from the following formula (1) by observing 100 arbitrary particles in a scanning electron micrograph and measuring the diameter. When the particle is not a perfect circle, the major axis is measured.
  • the particle size distribution index of the resin fine particles is in the range of 1.0 to 3.0, preferably 1.0 to 2.0, more preferably 1.0 to 1.5.
  • the particle size distribution index is calculated by the ratio of the volume average particle size to the number average particle size according to the following formula (3).
  • the volume average particle diameter is calculated from the following formula (2) by observing 100 arbitrary particles in a scanning electron micrograph, measuring the diameter. When the particle is not a perfect circle, the major axis is measured.
  • Di particle diameter of individual particles
  • n number of measurement 100
  • Dn number average particle diameter
  • Dv volume average particle diameter
  • PDI particle diameter distribution index
  • the shape of the resin fine particles is preferably true spherical, but may be oval.
  • any known method may be used. Among them, a method for obtaining fine particles by phase-separating a polymer solution, forming an emulsion, and adding a poor solvent (International Publication No. 2009). / 142231) is preferred.
  • polymer A the above resin to be microparticulated
  • polymer B dissolved in a poor solvent of polymer A and an organic solvent
  • polymer A solution phase a solution phase containing polymer A as a main component
  • polymer B solution phase a solution phase containing polymer A as a main component
  • an emulsion is formed, By contacting with a poor solvent, the polymer A can be obtained by such a method.
  • a system in which polymer A, polymer B, and an organic solvent are dissolved and mixed and phase-separated into two phases of a solution phase mainly composed of polymer A and a solution phase mainly composed of polymer B means a polymer When A, polymer B, and an organic solvent are mixed, the system is divided into two phases, a solution phase mainly containing polymer A and a solution phase mainly containing polymer B.
  • phase-separating system By using such a phase-separating system, it can be mixed and emulsified under the phase-separating conditions to form an emulsion.
  • This emulsion has a polymer A solution phase as a dispersed phase and a polymer B solution phase as a continuous phase.
  • a polymer A poor solvent By contacting the emulsion with a polymer A poor solvent, the polymer A solution phase from the polymer A solution phase in the emulsion is polymerized. A precipitates, and resin fine particles composed of the polymer A can be obtained.
  • polymer A refers to a high molecular weight polymer, preferably a synthetic polymer that does not exist in nature, and more preferably a water-insoluble polymer.
  • the polymer A is preferably insoluble in the poor solvent, since the present method is intended to precipitate fine particles when contacting with the poor solvent, and a polymer that does not dissolve in the poor solvent described later is used.
  • a water-insoluble polymer is particularly preferable.
  • the water-insoluble polymer is a polymer having a water solubility of 1% by mass or less, preferably 0.5% by mass or less, and more preferably 0.1% by mass or less.
  • Examples of the polymer B include thermoplastic resins and thermosetting resins, but those that are soluble in an organic solvent that dissolves the polymer A used in the present method and a poor solvent for the polymer A are preferable. And what dissolve
  • polymer B examples include poly (vinyl alcohol) (which may be a fully saponified or partially saponified poly (vinyl alcohol)), a poly (vinyl alcohol-ethylene) copolymer ( Fully saponified or partially saponified poly (vinyl alcohol-ethylene) copolymer), polyvinylpyrrolidone, poly (ethylene glycol), 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, polystyrene sulfonic acid, poly Sodium restyrenesulfonate, polyvinylpyrrolidinium chloride, poly (styrene-maleic acid) copolymer, aminopoly (acrylamide), poly (paravinylphenol),
  • the molecular weight of the polymer B is preferably 1,000 to 100,000,000, more preferably 1,000 to 10,000,000, still more preferably 5,000 to 1,000,000 in terms of weight average molecular weight. 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 refers to a weight average molecular weight measured by gel permeation chromatography (GPC) using water as a solvent and converted into polyethylene glycol.
  • dimethylformamide is used. If it cannot be measured, tetrahydrofuran is used. If it cannot be measured, hexafluoroisopropanol is used.
  • the organic solvent for dissolving the polymer A and the polymer B is an organic solvent capable of dissolving the polymer A and the polymer B to be used, and is selected according to the type of each polymer.
  • aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, n-decane, n-dodecane, n-tridecane, tetradecane, cyclohexane, cyclopentane, benzene, toluene, xylene, 2- Aromatic hydrocarbon solvents such as methylnaphthalene, ester solvents such as ethyl acetate, methyl acetate, butyl acetate, butyl propionate, butyl butyrate, chloroform, bromoform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, 1 Halogenated hydrocarbon solvents such as 1,1,1-trichloroethane, chlorobenzene, 2,6-dichlorotoluene, hexafluoroisopropanol, ketone solvents
  • an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, a halogenated hydrocarbon solvent, an alcohol solvent, an ether solvent, an aprotic polar solvent, a carboxylic acid solvent Preferable ones are alcohol solvents, aprotic polar solvents and carboxylic acid solvents which are water-soluble solvents, and extremely preferred are aprotic polar solvents and carboxylic acid solvents, which are easily available and have a wide range.
  • N is most preferable because it can be dissolved in a wide range of polymers, and can be uniformly mixed with a solvent that can be preferably used as a poor solvent to be described later, such as water and alcohol-based solvents.
  • organic solvents may be used in a plurality of types, or may be used in combination. However, particles having a relatively small particle size and a small particle size distribution can be obtained, and when used solvents are recycled. From the standpoint of reducing the process load in manufacturing, avoiding the troublesome separation step, it is preferable to use a single organic solvent, and it should be a single organic solvent that dissolves both polymer A and polymer B. Is preferred.
  • the poor solvent for polymer A refers to a solvent that does not dissolve polymer A.
  • the solubility of the polymer A in the poor solvent is 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.1% by mass or less.
  • a poor solvent for polymer A is used, and the poor solvent is preferably a poor solvent for polymer A and a solvent that dissolves polymer B.
  • the solvent for dissolving the polymer A and the polymer B and the poor solvent for the polymer A are solvents that are uniformly mixed.
  • the poor solvent in this method varies depending on the type of polymer A to be used, desirably both types of polymers A and B to be used.
  • n -Aliphatic hydrocarbon solvents such as decane, n-dodecane, n-tridecane, tetradecane, cyclohexane, cyclopentane, etc.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, 2-methylnaphthalene, ethyl acetate, methyl acetate Ester solvents such as butyl acetate, butyl propionate and butyl butyrate, chloroform, bromoform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, chlorobenzene, 2,
  • Examples include carboxylic acid solvents, ether solvents such as anisole, diethyl ether, tetrahydrofuran, diisopropyl ether, dioxane, diglyme, and dimethoxyethane, and a solvent selected from at least one of water.
  • ether solvents such as anisole, diethyl ether, tetrahydrofuran, diisopropyl ether, dioxane, diglyme, and dimethoxyethane
  • an aromatic hydrocarbon solvent an aliphatic hydrocarbon solvent, an alcohol solvent, an ether solvent, and water are preferable, and an alcohol solvent, water is most preferable. Particularly preferred is water.
  • polymer A can be efficiently precipitated and resin fine particles can be obtained by appropriately selecting and combining polymer A, polymer B, an organic solvent for dissolving them, and a poor solvent for polymer A.
  • the liquid obtained by mixing and dissolving the polymers A and B and the organic solvent for dissolving them is phase-separated into two phases, a solution phase mainly composed of the polymer A and a solution phase mainly composed of the polymer B. is required.
  • the solution-phase organic solvent containing polymer A as a main component and the organic solvent containing polymer B as a main component may be the same or different, but are preferably substantially the same solvent.
  • Conditions for generating a state of two-phase separation vary depending on the types of polymers A and B, the molecular weights of polymers A and B, the types of organic solvents, the concentrations of polymers A and B, the temperature and pressure at which this method is performed. come.
  • the difference between the solubility parameters of the polymer A and the polymer B (hereinafter also referred to as SP values) 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 very preferably 8 (J / cm 3 ) 1/2 or more.
  • the SP value is within this range, phase separation is easily performed.
  • both polymer A and polymer B can be dissolved in an organic solvent, but the upper limit of the difference in SP value is preferably 20 (J / cm 3 ) 1/2 or less, more preferably 15 (J / Cm 3 ) 1/2 or less, more preferably 10 (J / cm 3 ) 1/2 or less.
  • the SP value is calculated based on the Fedor's estimation method, and is calculated based on the cohesive energy density and the molar molecular volume (hereinafter also referred to as a calculation method).
  • 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 by determining whether or not the solubility parameter is dissolved in a known solvent (hereinafter also referred to as an experimental method).
  • a three-component phase diagram can be prepared by a simple preliminary experiment by observing a state in which the ratio of the three components of the polymer A, the polymer B, and the organic solvent in which they are dissolved is changed. Can be distinguished.
  • the phase diagram is prepared by mixing and dissolving the polymers A and B and the solvent at an arbitrary ratio and determining whether or not an interface is formed when allowed to stand at least 3 points, preferably 5 points or more.
  • the measurement is performed at 10 points or more, and by separating the region that separates into two phases and the region that becomes one phase, the conditions for achieving the phase separation state can be determined.
  • the polymers A and B are adjusted to any ratio of the polymers A and B and the solvent at the temperature and pressure at which the present invention is to be carried out. Then, the polymers A and B are completely dissolved, and after the dissolution, the mixture is sufficiently stirred and left for 3 days to confirm whether or not the phase separation is performed macroscopically.
  • phase separation may not occur even if left for 3 days.
  • an optical microscope, a phase contrast microscope, or the like is used to determine the phase separation based on whether or not the phase separation is microscopically.
  • the phase separation is formed by separating a polymer A solution phase mainly containing polymer A and a polymer B solution phase mainly containing polymer B in an organic solvent.
  • the polymer A solution phase is a phase in which the polymer A is mainly distributed
  • the polymer B solution phase is a phase in which the polymer B is mainly distributed.
  • the polymer A solution phase and the polymer B solution phase seem to have a volume ratio corresponding to the types and amounts of the polymers A and B used.
  • the concentration of the polymers A and B with respect to the organic solvent is premised on being within a possible range that can be dissolved in the organic solvent. Is more than 1% by mass to 50% by mass, more preferably more than 1% by mass to 30% by mass, and still more preferably 2% by mass to 20% by mass.
  • the interfacial tension between the two phases of the polymer A solution phase and the polymer B solution phase is an organic solvent in both phases, the interfacial tension is small, and the resulting emulsion can be stably maintained due to its properties.
  • the particle size distribution seems to be smaller.
  • the organic solvents of the polymer A phase and the polymer B phase are the same, the effect is remarkable.
  • the interfacial tension can be estimated by estimating from the surface tension.
  • the surface tension of each phase with air is r 1 and r 2
  • a preferable range of r 12 is more than 0 to 10 mN / m, more preferably more than 0 to 5 mN / m, still more preferably more than 0 to 3 mN / m, and particularly preferably 0. Ultra to 2 mN / m.
  • the viscosity between the two phases in the present method affects the average particle size and the particle size distribution, and the smaller the viscosity ratio, the smaller the particle size distribution.
  • a preferable range is 0.1 or more and 10 or less, and a more preferable range is 0.1. 2 or more and 5 or less, more preferably 0.3 or more and 3 or less, particularly preferably 0.5 or more and 1.5 or less, and remarkably preferable range is 0.8 or more and 1.2 or less. is there.
  • the temperature suitable for carrying out the present invention is in the range of ⁇ 50 ° C. to 200 ° C., preferably ⁇ 20 ° C. to 150 ° C., more preferably 0 ° C. to 120 ° C. from the viewpoint of industrial feasibility. More preferably, it is 10 ° C. to 100 ° C., particularly preferably 20 ° C. to 80 ° C., and most preferably in the range of 20 ° C. to 50 ° C.
  • the pressure suitable for carrying out the present invention is in the range of 100 atm from the reduced pressure state, preferably in the range of 1 to 5 atm, and more preferably in the range of 1 to 2 atm.
  • Atmospheric pressure particularly preferably atmospheric pressure.
  • an emulsion is formed by mixing the phase separation system state.
  • an emulsion is formed by applying a shearing force to the phase separation solution obtained above.
  • the emulsion is formed so that the polymer A solution phase becomes particulate droplets.
  • the volume of the polymer B solution phase is larger than the volume of the polymer A solution phase after phase separation.
  • the emulsion in such a form tends to be easily formed.
  • the volume ratio of the polymer A solution phase is preferably 0.4 or less with respect to the total volume 1 of both phases, 0.4 to 0.1 It is preferable to be between.
  • the resin 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 that dissolves both the polymers A and B is used. For this reason, in order to obtain a sufficient shearing force to form an emulsion, it is sufficient to use stirring by a conventionally known method, such as a liquid phase stirring method using a stirring blade, a stirring method using a continuous biaxial mixer, or a homogenizer. They can be mixed by a generally known method such as a mixing method or ultrasonic irradiation.
  • the stirring speed is preferably 50 rpm to 1200 rpm, more preferably 100 rpm to 1000 rpm, still more preferably 200 rpm to 800 rpm, and particularly preferably 300 rpm to 600 rpm.
  • 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.
  • 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.
  • a paddle type a flat paddle type
  • a turbine type a double cone type
  • a single cone type a single cone type
  • a single ribbon type a double ribbon type
  • screw type and a helical ribbon type
  • 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 step of precipitating target fine particles.
  • the desired resin fine particles are deposited with a diameter corresponding to the emulsion diameter by bringing a poor solvent for the polymer A into contact with the emulsion produced in the above-described step.
  • 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 the resin fine particles produced in the present invention can be obtained, and any of a continuous dropping method, a divided addition method, and a batch addition method may be used.
  • the continuous dropping method and the divided dropping method are preferable.
  • the continuous dropping method is most preferred.
  • the time for adding the poor solvent is 10 minutes or more and 50 hours or less, more preferably 30 minutes or more and 10 hours or less, and further preferably 1 hour or more and 5 hours or less.
  • the particle size distribution may increase with the aggregation, fusion and coalescence of the emulsion, and a lump may be generated. Moreover, when it implements in the time longer than this, when industrial implementation is considered, it is unrealistic.
  • the amount of the poor solvent to be added depends on the state of the emulsion, but is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and still more preferably, with respect to 1 part by weight of the total emulsion. Is 0.2 to 3 parts by weight, particularly preferably 0.2 to 1 part by weight, and most preferably 0.2 to 0.5 parts by weight.
  • the contact time between the poor solvent and the emulsion may be a time sufficient for the fine particles to precipitate, but in order to cause sufficient precipitation and to obtain efficient productivity, 5 minutes to 50 minutes after completion of the addition of the poor solvent. Time, 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 particularly preferably 30 minutes or more and 3 hours or less. Within hours.
  • the resin fine particle dispersion thus prepared is usually known in the art such as filtration, decantation, vacuum filtration, pressure filtration, centrifugation, centrifugal filtration, spray drying, acid precipitation method, salting out method, freeze coagulation method and the like.
  • the fine particle powder By performing solid-liquid separation by the method, the fine particle powder can be recovered.
  • the resin fine particles separated by solid-liquid separation are washed with a solvent or the like, if necessary, to remove attached or contained impurities, etc., and then purified.
  • the preferred solvent is the above poor solvent, and more preferably one or more mixed solvents selected from water, methanol, and ethanol.
  • the obtained resin fine particles can be dried to remove the residual solvent.
  • the drying method include air drying, heat drying, reduced pressure drying, and freeze drying.
  • the temperature for heating is preferably lower than the glass transition temperature, specifically, 50 to 150 ° C. is preferable.
  • the organic solvent and the polymer B separated in the solid-liquid separation step performed when the resin fine particles are obtained can be used for recycling.
  • the solvent obtained by solid-liquid separation is a mixture of polymer B, organic solvent and poor solvent.
  • the method for removing the poor solvent is usually performed by a known method, and specific examples include simple distillation, vacuum distillation, precision distillation, thin film distillation, extraction, membrane separation, and the like. This is a method by distillation or precision distillation.
  • distillation operations such as simple distillation and vacuum distillation
  • it is preferable to carry out in a state free from oxygen as much as possible because heat is applied to the system and the thermal decomposition of the polymer B and the organic solvent may be accelerated.
  • it is performed under an inert atmosphere. Specifically, it is carried out under nitrogen, helium, argon, carbon dioxide conditions.
  • the resin fine particles obtained by the above method are dispersed in water as a dispersion medium by using a conventional mixing and dispersing machine (for example, a planetary mixer, three rolls, a mechanical stirrer, a self-revolving mixer, a homomixer, a ball mill, Any of the methods of a bead mill, a sand mill, a roll mill, a homogenizer, an attritor, a resolver, a paint shaker, etc. can be used, and several methods may be combined and adjusted. Moreover, you may perform heating and pressure increase / decrease as needed.
  • a conventional mixing and dispersing machine for example, a planetary mixer, three rolls, a mechanical stirrer, a self-revolving mixer, a homomixer, a ball mill, Any of the methods of a bead mill, a sand mill, a roll mill, a homogenizer, an attritor, a resolver, a paint shaker, etc. can be used,
  • the amount of the resin fine particles added to the water in the present invention is preferably adjusted according to the use for which the resin fine particle aqueous dispersion is used, but is preferably 80% by mass or less, more preferably 50% by mass or less. Yes, more preferably 30% by mass or less, particularly preferably 20% by mass or less. If it exceeds 80% by mass, the resin fine particles tend to be difficult to disperse, and it is necessary to disperse with a dispersant or the like.
  • the lower limit is not particularly limited and may be set according to the purpose.
  • the resin fine particles used in the present invention are excellent in dispersibility in water, the resin fine particles can be dispersed in water without using a dispersant as long as it is in the above preferred range.
  • a dispersion of resin fine particles can be obtained substantially without using a dispersant, the occurrence of coloring, a decrease in heat resistance, a deterioration in water resistance, a base material due to the influence of the dispersant itself. It can also be used practically when there is a problem of reduced adhesion to the surface, bleed-out to the surface, stickiness, or the like.
  • the aqueous dispersion containing the dispersant is usually used in the case of using the heat-resistant resin fine particles as in the present invention, and the heat treatment condition is usually high, so that coloring caused by the decomposition of the dispersant, etc. May become even more prominent, and adverse effects such as deterioration in design may become very large. Therefore, substantially not containing a dispersant is a great advantage in using the resin fine particle aqueous dispersion.
  • the content of the dispersing agent is less than 1 part by weight, preferably less than 0.2 parts by weight, and most preferably not used with respect to 100 parts by weight of the resin fine particles.
  • the dispersant is not particularly limited as long as the resin fine particles are dispersed in water.
  • a polymer dispersant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant are exemplified. Agents and the like.
  • polymer dispersant examples include poly (vinyl alcohol) (which may be completely saponified or partially saponified poly (vinyl alcohol)), poly (vinyl alcohol-ethylene) copolymer (completely Saponified or partially saponified poly (vinyl alcohol-ethylene) copolymer), polyvinylpyrrolidone, poly (ethylene glycol), 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, polysodium methacrylate , Polystyrene sulfonic acid, polystyrene Sodium sulfonate, polyvinylpyrrolidinium chloride, poly (styrene-maleic acid) copolymer, aminopoly (acrylamide), poly (paravinyl
  • Poly (vinyl alcohol-ethylene) copolymer (fully saponified or partially saponified poly (vinyl alcohol-ethylene) copolymer Body), polyethylene glycol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, cellulose derivatives such as cellulose esters, and polyvinyl pyrrolidone.
  • anionic surfactants include fatty acid sodium, fatty acid potassium, sodium alkylbenzene sulfonate, sodium alkyl naphthalene sulfonate, sodium alkyl sulfate, sodium alkyl sulfonate, sodium alkyl ether sulfate, monoalkyl phosphate, Examples include sodium polyoxyethylene alkyl ether phosphate, sodium fatty acid ester sulfonate, sodium fatty acid ester sulfate, sodium fatty acid alkylose amide sulfate, sodium fatty acid amide sulfonate, and the like.
  • cationic surfactant examples include alkylmethylammonium chloride, alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, alkyldimethylbenzylammonium chloride, and alkylpyridinium chloride.
  • the zwitterionic surfactant include alkylaminocarboxylates, carboxybetaines, alkylbetaines, sulfobetaines, phosphobetaines, and the like.
  • specific examples of the nonionic surfactant include sucrose fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene lanolin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycol monofatty acid ester, polyoxyethylene alkylphenyl Ether, polyoxyethylene monobenzyl phenyl ether, polyoxyethylene dibenzyl phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene monostyryl phenyl ether, polyoxyethylene distyryl phenyl ether, polyoxyethylene tristyryl phenyl ether, Polyoxyethylene biphenyl ether, polyoxyethylene phenoxyphenyl ether, polyoxyethylene cumylf Vinyl ether, polyoxyethylene al
  • alkyl here is illustrated, a C1-C30 linear saturated hydrocarbon group or a branched saturated hydrocarbon group will be mentioned.
  • a linear unsaturated hydrocarbon group or a branched unsaturated hydrocarbon group may be used instead of alkyl.
  • various agents such as a leveling agent, an antifoaming agent, an anti-waxing agent, a pigment dispersant, an ultraviolet absorber and the like, and titanium oxide, as long as the purpose is not impaired
  • pigments or dyes such as zinc and carbon black may be added.
  • the resin fine particle water dispersion of the present invention is well dispersed in water even though it has high heat resistance, so that it can be dispersed well in water.
  • High heat resistance can be imparted in paint applications such as adhesives, ink applications, binder or coating agent applications, and water-based cosmetic applications.
  • coloring by a dispersant and a decrease in heat resistance, deterioration of water resistance, adhesion to a base material, bleeding out to the surface, and the occurrence of stickiness can be suppressed.
  • the dispersion medium is water, the organic solvent can be avoided, so that deterioration of the base material, environmental conservation, improvement of the workplace environment, and the like are possible.
  • weight average molecular weight was calculated by using a gel permeation chromatography method and comparing it with a calibration curve using polystyrene.
  • Apparatus LC-10A series manufactured by Shimadzu Corporation Column: HFIP-806M ⁇ 2 manufactured by Showa Denko KK Mobile phase: hexafluoroisopropanol Flow rate: 0.5 ml / min Detection: differential refractometer column temperature: 25 ° C.
  • the number average particle diameter (Dn) and volume average particle diameter (Dv) were calculated according to the formulas (1) and (2) from the average of 100 arbitrary particles.
  • the particle size distribution index (PDI) was calculated according to Equation (3).
  • Di particle diameter of individual particles
  • n number of measurement 100
  • Dn number average particle diameter
  • Dv volume average particle diameter
  • PDI particle diameter distribution index
  • Robot DSC RDC220 manufactured by Seiko Instruments Inc. was used to measure the top temperature of the melting peak when heated at a heating rate of 10 ° C./min in a nitrogen stream atmosphere.
  • Coating evaluation 1 The appearance of the coating film was evaluated according to the following criteria. A: Coloring is not recognized. ⁇ : Slight coloring is observed. X: Coloring is recognized. (Coating evaluation 2) Moreover, the coating film was formed simultaneously and the external appearance was evaluated as follows. 5 g of the resin fine particle aqueous dispersion obtained above was applied to a polyester film (210 mm ⁇ 297 mm ⁇ 0.1 mm, manufactured by Toray Industries, Inc.) with a bar coater, and then dried with an air dryer at 150 ° C. for 30 minutes. A membrane was obtained. The appearance of the obtained coating film was visually confirmed. Good ones were marked with ⁇ , and poor ones with x.
  • the obtained powder was a spherical fine particle, and was a polyether-polyester copolymer fine particle having a volume average particle size of 15.4 ⁇ m and a particle size distribution index of 1.17.
  • Polyester elastomer “Hytrel” (registered trademark) 7247 (manufactured by Toray DuPont Co., Ltd.), which is an aliphatic polyether-polyester copolymer, in a 1000 ml pressure-resistant glass autoclave (pressure-resistant glass industry, HyperGlaster TEM-V1000N) , Weight average molecular weight 29,000) 28 g, N-methyl-2-pyrrolidone (Kanto Chemical Co., Ltd.) 304.5 g, polyvinyl alcohol (Wako Pure Chemical Industries, Ltd.
  • PVA-1500 weight average molecular weight 29,000: methanol 17.5 g of the sodium acetate content reduced to 0.05 mass% by washing with (2), and after nitrogen substitution, the mixture was heated to 180 ° C. and stirred for 4 hours until the polymer was dissolved. Thereafter, 350 g of ion-exchanged water as a poor solvent was dropped at a speed of 2.92 g / min via a liquid feed pump. After the entire amount of water has been added, the temperature is lowered while stirring, and the resulting suspension is filtered, washed with 700 g of ion exchange water and reslurried, and the filtered product is vacuum dried at 80 ° C. for 10 hours. 26.5 g of a white solid was obtained.
  • this white solid When this white solid was observed with a scanning electron microscope, it had an average particle size of 5.5 ⁇ m and a particle size distribution index of 1.12. At the same time, this white solid was analyzed with a laser particle size distribution analyzer (SALD-2100, manufactured by Shimadzu Corporation). As a result, a polyether-polyester copolymer having a volume average particle size of 5.5 ⁇ m and a particle size distribution index of 1.12. It was fine particles.
  • SALD-2100 laser particle size distribution analyzer
  • Polyester elastomer “Hytrel” (registered trademark) 7247 (manufactured by Toray DuPont Co., Ltd.), which is an aliphatic polyether-polyester copolymer, in a 1000 ml pressure-resistant glass autoclave (pressure-resistant glass industry, HyperGlaster TEM-V1000N) , 28 g of weight average molecular weight 29,000, 308 g of N-methyl-2-pyrrolidone (manufactured by Kanto Chemical Co., Ltd.), polyvinyl alcohol (PVA-1500, manufactured by Wako Pure Chemical Industries, Ltd.), weight average molecular weight of 29,000 in methanol After washing, 14 g of the sodium acetate content reduced to 0.05% by mass was replaced with nitrogen, heated to 180 ° C., and stirred for 4 hours until the polymer was dissolved.
  • Polyester elastomer “Hytrel” (registered trademark) 7247 (manufactured by Toray DuPont Co., Ltd.), which is an aliphatic polyether-polyester copolymer, in a 1000 ml pressure-resistant glass autoclave (pressure-resistant glass industry, HyperGlaster TEM-V1000N) , 28 g of weight average molecular weight 29,000, 301 g of N-methyl-2-pyrrolidone (manufactured by Kanto Chemical Co., Ltd.), polyvinyl alcohol (PVA-1500, manufactured by Wako Pure Chemical Industries, Ltd.), weight average molecular weight of 29,000 in methanol After washing, 10.5 g of the sodium acetate content reduced to 0.05% by mass was replaced with nitrogen, heated to 180 ° C., and stirred for 4 hours until the polymer was dissolved.
  • Polyester elastomer “Hytrel (registered trademark)” 8238 (made by DuPont Co., Ltd., weight), which is an aliphatic polyether-polyester copolymer, in a 1000 ml pressure glass autoclave (Hyperglaster TEM-V1000N). (Average molecular weight 27,000) 17.5 g, N-methyl-2-pyrrolidone (Kanto Chemical Co., Ltd.) 315 g, polyvinyl alcohol (Wako Pure Chemical Industries, Ltd.
  • PVA-1500 weight average molecular weight 29,000 in methanol 17.5 g) (sodium acetate content was reduced to 0.05% by washing) was replaced with nitrogen, heated to 180 ° C., and stirred for 4 hours until the polymer was dissolved. Thereafter, 350 g of ion-exchanged water as a poor solvent was dropped at a speed of 2.92 g / min via a liquid feed pump. After the entire amount of water has been added, the temperature is lowered while stirring, and the resulting suspension is filtered, washed with 700 g of ion exchange water and reslurried, and the filtered product is vacuum dried at 80 ° C. for 10 hours. 14.9 g of a white solid was obtained.
  • Polyester elastomer “Hytrel (registered trademark)” 8238 (made by DuPont Co., Ltd., weight), which is an aliphatic polyether-polyester copolymer, in a 1000 ml pressure glass autoclave (Hyperglaster TEM-V1000N). (Average molecular weight 27,000) 33.25 g, N-methyl-2-pyrrolidone (Kanto Chemical Co., Ltd.) 299.25 g, polyvinyl alcohol (Wako Pure Chemical Industries, Ltd.
  • PVA-1500 weight average molecular weight 29,000: methanol 17.5 g of the sodium acetate content reduced to 0.05 mass% by washing with (2), and after nitrogen substitution, the mixture was heated to 180 ° C. and stirred for 4 hours until the polymer was dissolved. Thereafter, 350 g of ion-exchanged water as a poor solvent was dropped at a speed of 2.92 g / min via a liquid feed pump. After the entire amount of water has been added, the temperature is lowered while stirring, and the resulting suspension is filtered, washed with 700 g of ion exchange water and reslurried, and the filtered product is vacuum dried at 80 ° C. for 10 hours.
  • a resin fine particle dispersion was prepared using the resin fine particles shown below, and compared with the dispersion obtained in the examples.
  • Resin fine particles used for comparison Nylon 12 fine particles (Orgasol, melting point 170 ° C by Arkema)
  • Example 1 20 parts by mass of the polyether-polyester block copolymer resin fine particles prepared in Production Example 1 were put into 80 parts by mass of water, and subjected to ultrasonic treatment at 25 KHz for 1 minute to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was observed.
  • Example 2 20 parts by mass of the polyether-polyester block copolymer resin fine particles prepared in Production Example 1 were added to 80 parts by mass of water, and 0.15 parts by mass of Triton X-100 (Aldrich) was added as a dispersant. Ultrasonic treatment was performed in the same manner as in Example 1 to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was observed.
  • Example 3 When a 40% by mass aqueous dispersion of the polyether-polyester block copolymer resin fine particles prepared in Production Example 2 was prepared, it was well dispersed. To 50 parts by mass of this aqueous dispersion, 50 parts by mass of water was added, and 25 KHz ultrasonic treatment was performed for 1 minute to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was observed.
  • Example 4 When a 40% by mass aqueous dispersion of the polyether-polyester block copolymer resin fine particles prepared in Production Example 3 was prepared, it was well dispersed. To 50 parts by mass of this aqueous dispersion, 50 parts by mass of water was added, and 25 KHz ultrasonic treatment was performed for 1 minute to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was observed.
  • Example 5 A 40% by mass aqueous dispersion of the polyether-polyester block copolymer resin fine particles prepared in Production Example 4 was prepared and dispersed. To 50 parts by mass of this aqueous dispersion, 50 parts by mass of water was added, and 25 KHz ultrasonic treatment was performed for 1 minute to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was observed.
  • Example 6 A 40% by mass aqueous dispersion of the polyether-polyester block copolymer resin fine particles prepared in Production Example 5 was prepared and dispersed. To 50 parts by mass of this aqueous dispersion, 50 parts by mass of water was added, and 25 KHz ultrasonic treatment was performed for 1 minute to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was observed.
  • Example 7 A 40% by mass aqueous dispersion of the polyether-polyester block copolymer resin fine particles prepared in Production Example 6 was prepared and dispersed. To 50 parts by mass of this aqueous dispersion, 50 parts by mass of water was added, and 25 KHz ultrasonic treatment was performed for 1 minute to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was observed.
  • Example 8 A 40% by mass aqueous dispersion of the polyether-polyester block copolymer resin fine particles produced in Production Example 7 was prepared and dispersed. To 50 parts by mass of this aqueous dispersion, 50 parts by mass of water was added, and 25 KHz ultrasonic treatment was performed for 1 minute to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was observed.
  • Example 9 A 40% by mass aqueous dispersion of the polyether-polyester block copolymer resin fine particles produced in Production Example 8 was prepared and dispersed. To 50 parts by mass of this aqueous dispersion, 50 parts by mass of water was added, and 25 KHz ultrasonic treatment was performed for 1 minute to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was observed.
  • Example 10 A 40% by mass aqueous dispersion of the polyether-polyester block copolymer resin fine particles produced in Production Example 9 was prepared and dispersed. To 50 parts by mass of this aqueous dispersion, 50 parts by mass of water was added, and 25 KHz ultrasonic treatment was performed for 1 minute to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was observed.
  • Comparative Example 1 ethyl acetate was used as a dispersion medium, but it was not dispersed and the dispersibility was poor.
  • Comparative Example 2 the resin does not have an aliphatic polyether unit, but the resin fine particles were not dispersed.

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Abstract

L'invention concerne une dispersion aqueuse de fines particules de résine, qui se caractérise en ce qu'elle contient de fines particules de résine qui sont formées d'un copolymère contenant 10-90 % en masse d'un motif polyéther aliphatique et qui ont un point de fusion qui n'est pas inférieur à 120 °C et un diamètre moyen de particules de 1-100 μm (inclus). La dispersion aqueuse de fines particules de résine est particulièrement efficace dans les cas où moins de 1 partie en masse d'un dispersant est contenue pour 100 parties en masse du copolymère, ou qu'aucun dispersant n'est contenu. En outre, il est préférable que les particules fines aient un indice de distribution de tailles de particule de 1-3. La présente invention permet d'obtenir une dispersion aqueuse extrêmement pratique qui contient des particules fines de résine qui sont formées d'un copolymère très résistant à la chaleur qui contient un motif polyéther aliphatique.
PCT/JP2011/071955 2010-09-29 2011-09-27 Dispersion aqueuse de fines particules de résine Ceased WO2012043510A1 (fr)

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JP2017527646A (ja) * 2014-07-01 2017-09-21 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ ポリエーテルを主体とした反応生成物、および前記反応生成物を含む水性ベースコート材料
WO2025037601A1 (fr) * 2023-08-14 2025-02-20 信越化学工業株式会社 Particules composites élastomères, leur procédé de production et procédé de production de particules sphériques élastomères

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WO2025037601A1 (fr) * 2023-08-14 2025-02-20 信越化学工業株式会社 Particules composites élastomères, leur procédé de production et procédé de production de particules sphériques élastomères

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TW201219491A (en) 2012-05-16
KR101372054B1 (ko) 2014-03-07
KR20130114659A (ko) 2013-10-18
CN103119101B (zh) 2015-04-01
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