WO2016171121A1 - Resin dispersion, fine particles, and production processes therefor - Google Patents

Resin dispersion, fine particles, and production processes therefor Download PDF

Info

Publication number
WO2016171121A1
WO2016171121A1 PCT/JP2016/062351 JP2016062351W WO2016171121A1 WO 2016171121 A1 WO2016171121 A1 WO 2016171121A1 JP 2016062351 W JP2016062351 W JP 2016062351W WO 2016171121 A1 WO2016171121 A1 WO 2016171121A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
organic polymer
anionic group
containing organic
dispersion
Prior art date
Application number
PCT/JP2016/062351
Other languages
French (fr)
Japanese (ja)
Inventor
早織 奈良
勇也 榎本
高橋　誠治
Original Assignee
Dic株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2017514126A priority Critical patent/JPWO2016171121A1/en
Publication of WO2016171121A1 publication Critical patent/WO2016171121A1/en

Links

Classifications

    • 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
    • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
    • 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
    • C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/14—Powdering or granulating by precipitation from solutions
    • 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
    • C08J2400/00—Characterised by the use of unspecified polymers
    • C08J2400/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08J2400/104—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C08J2400/105—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms containing carboxyl groups

Definitions

  • the present invention relates to resin powder particles (fine particles) coated with an anionic group-containing organic polymer compound, a resin dispersion comprising the particles, and methods for producing them.
  • Engineering plastics excel in heat resistance, mechanical strength, and wear resistance, replacing metal materials in core parts that require high performance, durability, and safety, such as mechanical parts, automotive parts, and electronic equipment parts. Realizes light weight and low cost.
  • Patent Document 1 when a polymer A, a polymer B, and an organic solvent are dissolved and mixed, a system that phase-separates into two phases, a solution phase mainly composed of the polymer A and a solution phase mainly composed of the polymer B.
  • a method for producing polymer fine particles in which an emulsion is formed and then contacted with a poor solvent for polymer A to precipitate polymer A is proposed. The method is characterized in that the emulsion is formed at a temperature of 100 ° C. or higher. Has been.
  • Patent Document 2 a specific polysulfone is freeze-pulverized to 8 to 24 ⁇ m with an impact-type mechanical pulverizer, and then the pulverized polysulfone, pure water, and a surfactant are mixed, stirred and ultrasonically dispersed, and dispersed in water. Liquid has been proposed.
  • Patent Document 2 water is dispersed from a paint using an organic solvent as a dispersion medium as described in Patent Document 1 from the viewpoint of improving the working environment at the time of preparation and coating, discarding the organic solvent, and reducing the recovery cost.
  • a water-based paint as a medium is preferable, but engineering plastics are difficult to dissolve in water and are not easy to produce.
  • Patent Document 2 in which an aqueous dispersion of a thermoplastic resin is produced, in this method, the resin is dispersed using a surfactant after mechanical pulverization. There is a problem that the particle size at the time of dispersion is large and is not sufficient from the viewpoint of maintaining dispersion stability.
  • an object of the present invention is to provide an aqueous dispersion of engineering plastics, in which resin particles are less likely to settle for a longer period of time and have excellent dispersion stability.
  • the present inventors have achieved dispersion stability by coating particles of a specific resin classified as engineering plastic with an anionic group-containing organic polymer compound by an acid precipitation method. A highly water-based resin dispersion was obtained, and it was found that the above problems could be solved, and the present invention was completed.
  • the present invention [Section 1. Resin dispersion comprising at least one resin particle selected from the group consisting of resins having a glass transition temperature of 100 ° C. or higher, an anionic group-containing organic polymer compound, a base, and an aqueous medium A dispersion in which the resin particles are coated with an anionic group-containing organic polymer compound.
  • the anionic group of the anionic group-containing organic polymer compound is at least one anionic group selected from the group consisting of a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group, and a phosphoric acid group.
  • Item 2. The dispersion according to Item 1.
  • Item 3 The main skeleton of the anionic group-containing organic polymer compound is a (meth) acrylic ester resin, (meth) acrylic ester-styrene resin, (meth) acrylic ester-epoxy resin, vinyl resin, urethane resin, and polyamideimide.
  • Item 3 The dispersion according to Item 1 or 2, wherein the dispersion is at least one organic polymer compound selected from the group consisting of resins.
  • Item 4. The dispersion according to any one of Items 1 to 3, wherein the acid value of the anionic group-containing organic polymer compound is 10 to 300 mgKOH / g.
  • Item 5 Item 5. Item 1-4, wherein in the anionic group-containing organic polymer compound, the base used for neutralization of the anionic group is at least one base selected from the group consisting of metal hydroxides and organic amines. The dispersion according to any one of the above.
  • Item 6 The dispersion according to any one of Items 1 to 5, wherein the dispersion particle diameter of the resin particles in the dispersion is less than 1 ⁇ m.
  • Item 7-1 Item 7. Powder particles (fine particles) obtained by drying the dispersion according to any one of Items 1 to 6.
  • Item 7-2. 7. Powder particles (fine particles), which are a dried product of the dispersion according to any one of items 1 to 6.
  • Item 7-3 A fine particle of a resin having a glass transition temperature of 100 ° C. or more, wherein the fine particle is coated with an anionic group-containing organic polymer compound.
  • Step (A) in which at least one resin solution selected from the group consisting of resins having a glass transition temperature of 100 ° C. or higher and an anionic group-containing organic polymer compound aqueous solution are mixed to form resin fine particles
  • a dispersion comprising resin particles coated with an anionic group-containing organic polymer compound obtained by reacting the resin particle wet cake coated with the water-containing anionic group-containing organic polymer obtained in the step (C) with a base. And a step (D) for obtaining a resin dispersion.
  • Step (A) in which at least one resin solution selected from the group consisting of resins having a glass transition temperature of 100 ° C. or higher and an anionic group-containing organic polymer compound aqueous solution are mixed to form resin fine particles
  • Step (A) in which at least one resin solution selected from the group consisting of resins having a glass transition temperature of 100 ° C. or higher and an anionic group-containing organic polymer compound aqueous solution are mixed to form resin fine particles
  • a dispersion comprising resin particles coated with an anionic group-containing organic polymer compound obtained by reacting the resin particle wet cake coated with the water-containing anionic group-containing organic polymer obtained in the step (C) with a base.
  • Item 11 The method for producing a resin dispersion according to Item 8, wherein after the step (A), the resin fine particle dispersion obtained in the step (A) is mechanically pulverized.
  • Item 12 The method for producing resin powder particles according to Item 9 or 10, wherein mechanical pulverization is performed on the dispersion of resin fine particles obtained in Step (A) after Step (A).
  • Item 13-1 A paint comprising the dispersion according to any one of items 1 to 6.
  • Item 13-2 A coating film obtained using the polyarylene sulfide dispersion according to any one of Items 1 to 6. About].
  • the present invention also provides: [Section 14. Item 2. The dispersion according to Item 1, wherein the resin is at least one resin selected from the group consisting of polysulfone, polyetheretherketone, polyethersulfone, polycarbonate, polyphenylene ether, and polyphenylsulfone. Item 15. Item 2. The dispersion according to Item 1, wherein the resin is at least one resin selected from the group consisting of polysulfone, polyetheretherketone, polyethersulfone, and polyphenylsulfone. Item 16. Item 2.
  • the dispersion according to Item 1, wherein the resin is at least one resin selected from the group consisting of polysulfone, polyethersulfone, and polyphenylsulfone.
  • Item 17. The dispersion according to Item 1, wherein the resin is polyethersulfone.
  • Item 18. The dispersion according to Item 1, wherein the resin is polyphenylsulfone. ] About.
  • At least one resin particle selected from the group consisting of resins having a glass transition temperature of 100 ° C. or higher is coated with an anionic group-containing organic polymer compound, and has excellent long-term dispersion
  • An aqueous dispersion of the resin exhibiting stability can be provided.
  • the dispersion of the present invention can contain resin particles at a high concentration.
  • the dispersion of the present invention having such an effect can be suitably used for coating applications.
  • the particles contained in the resin dispersion of the present invention have a glass transition temperature of 100 ° C. or higher and are dispersed as fine particles in an aqueous medium using an anionic group-containing organic polymer compound. It is a thing. Details of the resin fine particle dispersion method will be described later.
  • the aqueous medium may be water alone or a mixed solvent composed of water and a water-soluble solvent.
  • the resin usable in the present invention is a resin having a glass transition temperature of 100 ° C. or higher (hereinafter sometimes referred to as “resin (X)”). These resins may be commercially available products or may be synthesized by a known method.
  • Examples of such resin (X) include polysulfone (PSF), polyetheretherketone (PEEK), polyethersulfone (PES), polycarbonate, polyphenylene ether (PPE), polyphenylsulfone (PPSU), and the like. Of these, more preferred are polysulfone, polyetheretherketone, polyethersulfone, and polyphenylsulfone, and still more preferred are polysulfone, polyethersulfone, and polyphenylsulfone.
  • PSF polysulfone
  • PEEK polyetheretherketone
  • PES polyethersulfone
  • PPE polyphenylsulfone
  • PPSU polyphenylsulfone
  • Polysulfone has a sulfonyl group in the structural unit and has the following formula:
  • Polyetheretherketone has a structural unit in which a benzene ring is connected via an ether bond and a ketone bond, and has the following formula:
  • Polyethersulfone has a sulfonyl group in the structural unit and has the following formula:
  • PES resin represented by these.
  • Commercially available PES products include Udel (registered trademark) series P-1700 manufactured by Solvay Advanced Polymer, Radel A series (RADEL (registered trademark) A series) manufactured by Solvay Advanced Polymer, and Ultra Zone (registered by BASF).
  • Trademarks) E series Ultrason E-1010 etc.
  • Sumika Excel series manufactured by Sumitomo Chemical Co., Ltd. (Sumika Excel 5003P, Sumika Excel 4100P etc.) and the like.
  • Polyphenylsulfone has a sulfonyl group in the structural unit and has the following formula:
  • Polycarbonate has a carbonate group and has the following formula:
  • polycarbonate products include Panlite (registered trademark) manufactured by Teijin Chemicals Ltd., Iupilon (registered trademark) manufactured by Mitsubishi Engineering Plastics Co., Ltd., SD Polyca (registered trademark) manufactured by Sumitomo Dow Co., Ltd., Dow Examples include Caliber (registered trademark) manufactured by Chemical Corporation.
  • PPE Polyphenylene ether
  • PPE can form a polymer alloy (modified PPE) with other resins, and m-PPE that is a polymer alloy with polystyrene can also be used in the present invention.
  • modified PPE polymer alloy
  • m-PPE polymer alloy with polystyrene
  • Examples of commercially available PPE include Noryl (registered trademark, modified PPE) series such as Noryl N1250 manufactured by GE, and Zylon (registered trademark, modified PPE) X 9102 manufactured by Asahi Kasei.
  • the resin dispersion in the present invention is a step (A) in which a resin solution in which the resin (X) is dissolved and an aqueous solution of an anionic group-containing organic polymer compound are mixed to form fine particles of the resin (X).
  • the obtained resin (X) particles are filtered off, washed with water to obtain a wet anionic group-containing organic polymer compound-coated resin (X) particle wet cake (C) (wet cake preparation step), and the obtained wet It is a resin (X) dispersion obtained by neutralizing a cake with a base and redispersing and adjusting (step (D): dispersion preparation step).
  • Resin (X) used is one dissolved in a solvent.
  • an inorganic salt described later may be added, but it may not be added in particular.
  • the form of the resin (X) that can be used in the present invention is not particularly limited, and specific examples include powders, granules, pellets, fibers, films, molded products, and the like. From the viewpoint of shortening the time required for operability and dissolution, powders, granules and pellets are desirable. Among these, powder resin (X) is particularly preferably used. Usually, the resin (X) and the solvent are introduced into the container and then dissolved, but the order of introduction into the container is not limited.
  • the atmosphere in the container may be either an air atmosphere or an inert gas atmosphere, but an inert atmosphere that reacts with the resin (X) or deteriorates the resin (X) itself should be avoided.
  • a gas atmosphere is preferred.
  • the inert gas includes nitrogen gas, carbon dioxide, helium gas, argon gas, neon gas, krypton gas, xenon gas, etc. Nitrogen gas, argon gas in consideration of economy and availability Carbon dioxide gas is desirable, and nitrogen gas or argon gas is more preferably used.
  • chlorides, bromides, carbonates, sulfates, etc. such as an alkali metal, alkaline earth metal, and ammonia are used.
  • chlorides such as sodium chloride, lithium chloride, potassium chloride, calcium chloride, magnesium chloride, ammonium chloride, sodium bromide, lithium bromide, potassium bromide, calcium bromide, magnesium bromide, ammonium bromide
  • bromide such as sodium carbonate, potassium carbonate, lithium carbonate, calcium carbonate, magnesium carbonate, ammonium carbonate
  • sulfate such as calcium sulfate, sodium sulfate, potassium sulfate, lithium sulfate, magnesium sulfate, ammonium sulfate, etc.
  • the weight ratio of the inorganic salt to the resin (X) is in the range of 0.1 to 10 parts by mass, preferably in the range of 0.5 to 5 parts by mass with respect to 1 part by mass of the resin (X). It is.
  • the solvent used in the present invention is not particularly limited as long as it dissolves the resin (X), and the dispersion of the present invention can be obtained.
  • At least one solvent selected is at least one solvent selected from N-methyl-2-pyrrolidone, 1-chloronaphthalene, o-dichlorobenzene, and 1,3-dimethyl-2-imidazolidinone.
  • N-methyl-2-pyrrolidone, 1-chloronaphthalene, and 1,3-dimethyl-2-imidazolidinone are preferably used in consideration of workability and water solubility.
  • the weight ratio of the resin (X) to the solvent is not particularly limited as long as the resin (X) is dissolved in the solvent, but can be exemplified as a range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the solvent.
  • the amount is preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass.
  • the mixed reaction solution can be heated.
  • reaction solution may or may not be stirred, but it is preferable that the reaction solution is stirred, thereby shortening the time required for dissolution.
  • an anionic group-containing organic polymer compound aqueous solution is prepared in advance.
  • the anionic group in the anionic group-containing organic polymer compound used here for example, a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group, a phosphoric acid group, and the like can be used. It is preferable to use a carboxylate group or sulfonate group in which a part or all of the carboxyl group or sulfonic acid group is neutralized with a basic compound or the like in order to impart good water dispersion stability.
  • the main skeleton of the anionic group-containing organic polymer compound includes (meth) acrylic acid ester resin, (meth) acrylic acid ester-styrene resin, (meth) acrylic acid ester-epoxy resin, vinyl resin, urethane resin, Polyamideimide resin.
  • the anionic group-containing organic polymer compound used in the present invention may be a single substance or a mixture of one or more of the above anionic group-containing organic polymer compounds, and if dissolved in a basic state, the present invention.
  • the resin (X) dispersion and resin (X) powder particles can be used.
  • the anionic group-containing organic polymer compound is completely dissolved in a basic aqueous solution.
  • the base used here include ammonia, inorganic metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, methylamine, ethylamine, n-butylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, triethylamine, and the like.
  • Alkylamines such as n-butylamine; hydroxylamines such as N-methylaminoethanol, N, N-dimethylaminoethanol, N, N-diethylaminoethanol, 2-amino-2-methylpropanol, diethanolamine and triethanolamine
  • Organic organic amines such as polyamines such as ethylenediamine and diethylenetriamine are preferred. These can be used alone or in combination of two or more.
  • the base amount for dissolving the anionic group-containing organic polymer compound is more preferably 70 to 300% with respect to the acid value of the anionic group-containing organic polymer compound in order to completely dissolve the resin. preferable.
  • an anionic group-containing organic polymer compound having an acid value of 10 to 300 mgKOH / g it is preferable to use an anionic group-containing organic polymer compound having an acid value of 10 to 300 mgKOH / g.
  • Use of an anionic group-containing organic polymer compound having an acid value lower than this range is not preferable because the dispersion stability becomes insufficient.
  • Such an anionic group-containing organic polymer compound may be synthesized and used by the method described in the production examples described later, or a commercially available product may be used. Specific examples of commercially available products include ACRIDIC WML-542 (manufactured by DIC Corporation), UNIDIC EMG-1015 (manufactured by DIC Corporation), and the like.
  • the present invention even if a part or the entire surface of the resin (X) particles is coated with the anionic group-containing organic polymer compound, an effect on dispersion stability can be obtained. Therefore, it is preferable to use 1 part by mass to 200 parts by mass with respect to 100 parts by mass of the resin (X). Of these, the use of 5 parts by mass to 150 parts by mass is preferable because the dispersion stability is the highest.
  • the resin (X) dispersion (crystallization solution) can be obtained by pouring the prepared resin (X) solution into the prepared anionic group-containing organic polymer compound aqueous solution. At this time, it is different from the “dispersion of resin (X) particles coated with an anionic group-containing organic polymer compound” which is the object of the present invention.
  • the particle state of the resin (X) in this crystallization step is as described later.
  • the prepared anionic group-containing organic polymer compound aqueous solution is preferably prepared as a water stream stirred at high speed with a stirrer such as a stirring blade. Either turbulent flow or laminar flow may be used, but higher peripheral speed is preferable because the crystallized particle size can be made finer.
  • a water injection method there is a method in which water is directly injected into a solution obtained by strongly stirring the prepared anionic group-containing organic polymer compound solution.
  • the stirring of the anionic group-containing organic polymer compound solution is preferably strong stirring in order to form fine resin particles.
  • it can also pass through the process [dispersion process] which disperse
  • the mechanical pulverization include a method using the apparatus described in the item of the mechanical pulverization apparatus described later.
  • the particle state of the resin (X) in this crystallization step is considered not to be a state in which the anionic group-containing organic polymer compound is present on the surface layer of the resin (X) particles and is still firmly fixed. . This is because the acidic group at the end of the anionic group-containing organic polymer compound is in an ion-bonded state with an alkali metal, so that it is presumed that the anionic group is present flexibly on the surface layer of the resin (X) particles.
  • a salt exchange reaction of the functional group of the anionic group-containing organic polymer compound is caused by an acid in a subsequent acid precipitation step, and is fixed to the surface of the resin (X).
  • Step B Resin (X) particles in which the water-soluble resin obtained in the above step is present on the surface layer are acid precipitated with an acid, and a slurry in which resin (X) particles coated with an anionic group-containing organic polymer compound are precipitated It is a manufacturing process.
  • Examples of the acid used for acid precipitation include hydrochloric acid, sulfuric acid, acetic acid, nitric acid, and hydrochloric acid is preferable.
  • the acid concentration depends on the various anionic group-containing organic polymer compounds and various resins (X), but it is necessary to set the number of terminal substituents of the anionic group-containing organic polymer compound. Adjust to ⁇ 5.
  • the resin (X) particles coated with the anionic group-containing polymer compound are filtered from the slurry obtained by precipitating the resin (X) particles coated with the anionic group-containing polymer compound obtained in the acid precipitation step. And a wet cake process.
  • any method may be used as long as particles and liquid can be separated, such as filtration and centrifugation.
  • the moisture content in the filtered wet cake is preferably in the range of 15 to 55%. If the moisture content is too low, it becomes difficult to be loosened by redispersion in the subsequent process, and the redispersibility becomes poor. 20-45%.
  • the wet cake is washed with ion-exchanged water, distilled water, pure water, tap water or the like in order to wash the remaining organic solvent and undeposited resin.
  • the wet cake may be filtered and washed with a washing solvent, or the wet cake may be washed again by peptizing with a washing solvent.
  • Step D The wet cake obtained in the above wet cake preparation step is re-peptized with water using a bead mill or an ultrasonic disperser, and the pH is adjusted to 6 to 10 with an inorganic base or an organic base as described above. ) A dispersion can be obtained. The nonvolatile content in the resulting dispersion is 15 to 40%.
  • the resin (X) powder particles in the present invention are obtained by removing moisture from the wet cake obtained in the above step C or the resin (X) dispersion obtained in the step D and then drying. Resin (X) powder particles coated with an anionic group-containing organic polymer compound. After drying, it can be pulverized by various pulverizers and adjusted to a desired particle size for use.
  • the resin (X) coarse particle suspension in which the resin (X) coarse particles are dispersed is mechanically pulverized until the dispersed particle size in the measurement method described below becomes less than 1 ⁇ m.
  • mechanical pulverization is performed until the dispersed particle diameter is less than 500 nm.
  • mechanical pulverizer include commercially available mechanical pulverizers.
  • a ball mill apparatus suitable for efficiently dispersing and pulverizing resin (X) coarse particles and preparing a dispersion of resin (X) fine particles having a small particle diameter
  • a ball mill apparatus suitable for efficiently dispersing and pulverizing resin (X) coarse particles and preparing a dispersion of resin (X) fine particles having a small particle diameter
  • a ball mill apparatus suitable for efficiently dispersing and pulverizing resin (X) coarse particles and preparing a dispersion of resin (X) fine particles having a small particle diameter
  • a ball mill apparatus suitable for efficiently dispersing and pulverizing resin (X) coarse particles and preparing a dispersion of resin (X) fine particles having a small particle diameter
  • a ball mill apparatus suitable for efficiently dispersing and pulverizing resin (X) coarse particles and preparing a dispersion of resin (X) fine particles having a small particle diameter
  • a ball mill apparatus for efficiently dispersing and pulverizing resin (X) coarse particles and preparing a dispersion
  • a bead mill can be controlled by selecting the bead diameter and the bead amount and adjusting the peripheral speed.
  • the resin (X) fine particle dispersion may also contain a precipitate in some cases.
  • the precipitation part and the dispersion part may be used separately.
  • the precipitation part and the dispersion part may be separated.
  • decantation, filtration, or the like may be performed.
  • centrifugation or the like is performed to completely settle the larger particle size, and decantation or filtration is performed to remove the precipitated portion.
  • the fine particles and the anionic group-containing organic polymer compound aqueous solution are not separated even after standing for 24 hours.
  • the resin (X) fine particle dispersion obtained in this way is a useful additive in the fields of paint, adhesion and polymer compounds because of its characteristics.
  • the obtained resin dispersion was defined as D50 particle size measured using “MT-3300EXII” (Laser Doppler particle size distribution meter manufactured by Nikkiso Co., Ltd.) as the dispersed particle size.
  • anionic group-containing organic polymer compound As an example of a method for producing an anionic group-containing organic polymer compound used in the present specification, examples of producing a styrene (meth) acrylic copolymer and an alcohol-modified polyamideimide resin are described below.
  • the functional group-containing organic polymer compound can also be produced by the same method.
  • This resin solution is an anionic group-containing organic polymer compound (alcohol-modified polyamideimide resin (abbreviated as R-2)).
  • Example 1 [crystallization process] Mix an aqueous solution of anionic group-containing organic polymer compound (anionic group-containing organic polymer compound (containing R-1, 55% IPA): 2.22 g), 0.66 g of 25% KOH aqueous solution, and 2500 g of water.
  • PPSU BASF Ultrason P-3010
  • 10 g dissolved in N-methyl-2-pyrrolidone 500 g at 180 ° C. and coarse particles with a metal mesh (aperture 45 ⁇ m) was removed to obtain a dispersion liquid (crystallization liquid) containing PPSU fine particles. This operation was repeated 5 times.
  • Step (D) [Fine particle dispersion preparation step] 110 g of the wet cake obtained in the step (C) and 2.1 g of 50% dimethylethanolamine aqueous solution were ultrasonically irradiated for 60 minutes with an ultrasonic disperser (UP400S manufactured by Hielscher), and a PPSU dispersion having a nonvolatile content of 31% was obtained. Obtained.
  • Example 4 An anionic group was obtained in the same manner as in Example 1 except that polyethersulfone (PES) (Ultrason E-1010 manufactured by BASF) was used instead of PPSU used in Example 1. R-1 was used as the containing organic polymer compound), and a PES dispersion having a nonvolatile content of 31% was obtained.
  • PES polyethersulfone
  • R-1 was used as the containing organic polymer compound
  • D 50 162 nm.
  • the precipitation by visual observation was not seen (no solid-liquid separation).
  • Example 7 Anionic group-containing organic as in Example 1, except that polysulfone (PSF) (Ultrason S-2010 manufactured by BASF) was used instead of PPSU used in Example 1 above. R-1 was used as the polymer compound), and a PES dispersion having a nonvolatile content of 30% was obtained.
  • PES polysulfone
  • R-1 was used as the polymer compound
  • D 50 173 nm.
  • the precipitation by visual observation was not seen (no solid-liquid separation).
  • Example 1 In Example 1, instead of the anionic group-containing organic polymer compound aqueous solution, the same operation as in Example 1 was used, except that an aqueous solution obtained by mixing 0.66 g of 25% KOH aqueous solution and 2500 g of water was used. Although implemented, acid precipitation did not occur and an anionic group-containing organic polymer compound-coated PPSU wet cake could not be produced. (Dispersion cannot be produced)
  • Example 2 (Comparative Example 2) In Example 1, instead of 2.22 g of the anionic group-containing organic polymer compound (R-1), Surfynol 465 (produced by Air Products and Chemicals), which is an acetylene glycol-based nonionic surfactant, is 1 Except for using 0.0 g, the same operation as in Example 1 was performed, but acid precipitation did not occur, and an anionic group-containing organic polymer compound-coated PPSU wet cake could not be produced. (Dispersion cannot be produced)
  • Surfynol 465 produced by Air Products and Chemicals
  • Example 4 In Example 4, the same operation as in Example 4 was used except that an aqueous solution obtained by mixing 0.66 g of 25% KOH aqueous solution and 2500 g of water was used instead of the anionic group-containing organic polymer compound aqueous solution. Although implemented, acid precipitation did not occur and an anionic group-containing organic polymer compound-coated PES wet cake could not be produced. (PES dispersion cannot be produced)
  • Example 4 (Comparative Example 4) In Example 4, instead of 2.22 g of the anionic group-containing organic polymer compound (R-1), Surfynol 465 (produced by Air Products and Chemicals), which is an acetylene glycol-based nonionic surfactant, is 1 Except for using 0.0 g, the same operation as in Example 4 was performed, but acid precipitation did not occur, and an anionic group-containing organic polymer compound-coated PES wet cake could not be produced. (PES dispersion cannot be produced)
  • Surfynol 465 produced by Air Products and Chemicals
  • the resin powder particles coated with the anionic group-containing organic polymer compound of the present invention and the dispersion comprising the particles are excellent in dispersion stability over a long period of time and further contain resin particles at a high concentration. Also, it can be suitably used in paint applications.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention addresses the problem of providing an aqueous dispersion of at least one resin selected from the group consisting of resins each characterized by having a glass transition temperature of 100ºC or higher, the resin particles in the dispersion being less apt to sediment over a longer period. The present invention solves the above-mentioned problem by coating particles of at least one resin selected from the group consisting of resins each characterized by having a glass transition temperature of 100ºC or higher, with an anionic-group-containing organic polymer by an acid precipitation method, thereby providing both a dispersion of the particles which has high dispersion stability even in a high concentration and powder particles (fine particles) obtained from the dispersion.

Description

樹脂分散体、微粒子、及びそれらの製造方法Resin dispersion, fine particles, and production method thereof
　本発明は、アニオン性基含有有機高分子化合物により被覆された樹脂粉体粒子（微粒子）及び該粒子からなる樹脂分散体、並びにそれらの製造方法に関する。 The present invention relates to resin powder particles (fine particles) coated with an anionic group-containing organic polymer compound, a resin dispersion comprising the particles, and methods for producing them.
　エンジニアリングプラスチックは、耐熱性、機械的強度、耐摩耗性に優れ、機械部品、自動車用部品、電子機器部品など、高性能と耐久性、安全性が求められる基幹部品においても金属材料を代替し、軽量化、低コスト化を実現している。 Engineering plastics excel in heat resistance, mechanical strength, and wear resistance, replacing metal materials in core parts that require high performance, durability, and safety, such as mechanical parts, automotive parts, and electronic equipment parts. Realizes light weight and low cost.
　一方で、エンジニアリングプラスチックは、粉体塗料及び水性塗料用途としての展開が注目されており、樹脂微粒子、分散液を得る手段として、いくつかの手法が提案されている。 On the other hand, engineering plastics are attracting attention for use as powder paints and water-based paints, and several methods have been proposed as means for obtaining resin fine particles and dispersions.
　特許文献１では、ポリマーＡとポリマーＢと有機溶媒とを溶解混合した際に、ポリマーＡを主成分とする溶液相と、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、エマルションを形成させた後、ポリマーＡの貧溶媒を接触させて、ポリマーＡを析出させるポリマー微粒子の製造方法において、エマルションの形成を１００℃以上の温度で実施することを特徴とする方法が提案されている。 In Patent Document 1, when a polymer A, a polymer B, and an organic solvent are dissolved and mixed, a system that phase-separates into two phases, a solution phase mainly composed of the polymer A and a solution phase mainly composed of the polymer B. A method for producing polymer fine particles in which an emulsion is formed and then contacted with a poor solvent for polymer A to precipitate polymer A is proposed. The method is characterized in that the emulsion is formed at a temperature of 100 ° C. or higher. Has been.
　特許文献２では、特定のポリスルホンを衝撃型機械粉砕機にて８～２４μｍに凍結粉砕し、その後、粉砕した該ポリスルホンと純水、界面活性剤を混合し攪拌及び超音波分散して、水分散液が提案されている。 In Patent Document 2, a specific polysulfone is freeze-pulverized to 8 to 24 μm with an impact-type mechanical pulverizer, and then the pulverized polysulfone, pure water, and a surfactant are mixed, stirred and ultrasonically dispersed, and dispersed in water. Liquid has been proposed.
国際公開２０１２／０４３５０９号公報International Publication 2012/043509 特開２０１１－０６８８６２号公報JP 2011-068862 A
　しかしながら、塗料用途としては、調製時や塗工時の作業環境改善、有機溶剤の廃棄及び回収コスト削減の点から、前記特許文献１のような有機溶媒を分散媒とする塗料より、水を分散媒とする水性塗料が好ましいが、エンジニアリングプラスチックは水に溶解し難くその作製は容易でない。
　また、いくつかの熱可塑性樹脂の水分散体を作製した例（前記特許文献２）があるものの、この方法では、樹脂を機械的粉砕後に、界面活性剤を使用して分散体化しているため、分散時の粒径が大きく、分散安定性の維持の観点から十分でないという問題があった。
　さらに、これら塗料用途においては、分散体中の樹脂粒子を高濃度で含有する分散体を得ることが要求されている。
　そこで、本発明の課題は、エンジニアリングプラスチックの水分散体であって、より長期に樹脂粒子が沈降し難い、分散安定性に優れた分散体を提供することにある。 However, as a paint application, water is dispersed from a paint using an organic solvent as a dispersion medium as described in Patent Document 1 from the viewpoint of improving the working environment at the time of preparation and coating, discarding the organic solvent, and reducing the recovery cost. A water-based paint as a medium is preferable, but engineering plastics are difficult to dissolve in water and are not easy to produce.
In addition, although there are some examples (Patent Document 2) in which an aqueous dispersion of a thermoplastic resin is produced, in this method, the resin is dispersed using a surfactant after mechanical pulverization. There is a problem that the particle size at the time of dispersion is large and is not sufficient from the viewpoint of maintaining dispersion stability.
Furthermore, in these coating applications, it is required to obtain a dispersion containing a high concentration of resin particles in the dispersion.
Accordingly, an object of the present invention is to provide an aqueous dispersion of engineering plastics, in which resin particles are less likely to settle for a longer period of time and have excellent dispersion stability.
　本発明者らは上記課題を解決するために鋭意研究した結果、酸析法により、エンジニアリングプラスチックに分類される特定の樹脂の粒子をアニオン性基含有有機高分子化合物により被覆することで、分散安定性の高い、水媒体の樹脂分散体が得られ、上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above-mentioned problems, the present inventors have achieved dispersion stability by coating particles of a specific resin classified as engineering plastic with an anionic group-containing organic polymer compound by an acid precipitation method. A highly water-based resin dispersion was obtained, and it was found that the above problems could be solved, and the present invention was completed.
　すなわち、本発明は、
『項１．ガラス転移温度が１００℃以上であることを特徴とする樹脂からなる群より選ばれる少なくとも一種の樹脂粒子と、アニオン性基含有有機高分子化合物と、塩基と、水性媒体とを含んでなる樹脂分散体において、前記樹脂粒子がアニオン性基含有有機高分子化合物により被覆されていることを特徴とする分散体。 That is, the present invention
[Section 1. Resin dispersion comprising at least one resin particle selected from the group consisting of resins having a glass transition temperature of 100 ° C. or higher, an anionic group-containing organic polymer compound, a base, and an aqueous medium A dispersion in which the resin particles are coated with an anionic group-containing organic polymer compound.
項２．前記アニオン性基含有有機高分子化合物のアニオン性基が、カルボキシル基、カルボキシレート基、スルホン酸基、スルホネート基及びリン酸基からなる群より選ばれる少なくとも一種のアニオン性基であることを特徴とする項１に記載の分散体。 Item 2. The anionic group of the anionic group-containing organic polymer compound is at least one anionic group selected from the group consisting of a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group, and a phosphoric acid group. Item 2. The dispersion according to Item 1.
項３．前記アニオン性基含有有機高分子化合物の主骨格が、（メタ）アクリル酸エステル樹脂、（メタ）アクリル酸エステル－スチレン樹脂、（メタ）アクリル酸エステル－エポキシ樹脂、ビニル樹脂、ウレタン樹脂及びポリアミドイミド樹脂からなる群より選ばれる少なくとも一種の有機高分子化合物であることを特徴とする項１又は項２に記載の分散体。 Item 3. The main skeleton of the anionic group-containing organic polymer compound is a (meth) acrylic ester resin, (meth) acrylic ester-styrene resin, (meth) acrylic ester-epoxy resin, vinyl resin, urethane resin, and polyamideimide. Item 3. The dispersion according to Item 1 or 2, wherein the dispersion is at least one organic polymer compound selected from the group consisting of resins.
項４．前記アニオン性基含有有機高分子化合物の酸価が１０～３００ｍｇＫＯＨ／ｇであることを特徴とする項１～３いずれか一項に記載の分散体。 Item 4. Item 4. The dispersion according to any one of Items 1 to 3, wherein the acid value of the anionic group-containing organic polymer compound is 10 to 300 mgKOH / g.
項５．前記アニオン性基含有有機高分子化合物において、アニオン性基の中和に用いられる塩基が金属水酸化物及び有機アミンからなる群より選ばれる少なくとも一種の塩基であることを特徴とする項１～４いずれか一項に記載の分散体。 Item 5. Item 1-4, wherein in the anionic group-containing organic polymer compound, the base used for neutralization of the anionic group is at least one base selected from the group consisting of metal hydroxides and organic amines. The dispersion according to any one of the above.
項６．前記分散体中の樹脂粒子の分散粒径が１μｍ未満であることを特徴とする項１～項５いずれか一項に記載の分散体。 Item 6. Item 6. The dispersion according to any one of Items 1 to 5, wherein the dispersion particle diameter of the resin particles in the dispersion is less than 1 μm.
項７－１．前記項１～６いずれか一項に記載の分散体を、乾燥させて得られる粉体粒子（微粒子）。
項７－２．前記項１～６いずれか一項に記載の分散体の乾燥物である粉体粒子（微粒子）。
項７－３．ガラス転移温度が１００℃以上である樹脂の微粒子であって、該微粒子がアニオン性基含有有機高分子化合物で被覆されていることを特徴とする粉体粒子（微粒子）。 Item 7-1. Item 7. Powder particles (fine particles) obtained by drying the dispersion according to any one of Items 1 to 6.
Item 7-2. 7. Powder particles (fine particles), which are a dried product of the dispersion according to any one of items 1 to 6.
Item 7-3. A fine particle of a resin having a glass transition temperature of 100 ° C. or more, wherein the fine particle is coated with an anionic group-containing organic polymer compound.
項８．ガラス転移温度が１００℃以上であることを特徴とする樹脂からなる群より選ばれる少なくとも一種の樹脂溶液とアニオン性基含有有機高分子化合物水溶液とを混合し、樹脂微粒子を形成させる工程（Ａ）と、
工程（Ａ）で得られた樹脂微粒子と酸とを反応させて樹脂微粒子表面にアニオン性基含有有機高分子化合物を析出させてアニオン性基含有有機高分子により被覆された樹脂粒子を沈殿させる工程（Ｂ）と、
工程（Ｂ）で得られたアニオン性基含有有機高分子により被覆された樹脂粒子をろ別、洗浄し、含水アニオン性基含有有機高分子により被覆された樹脂粒子ウェットケーキを得る工程（Ｃ）と、
工程（Ｃ）で得られた含水アニオン性基含有有機高分子により被覆された樹脂粒子ウェットケーキと塩基とを反応させてアニオン性基含有有機高分子化合物により被覆された樹脂粒子からなる分散体を得る工程（Ｄ）と、を含む樹脂分散体の製造方法。 Item 8. Step (A) in which at least one resin solution selected from the group consisting of resins having a glass transition temperature of 100 ° C. or higher and an anionic group-containing organic polymer compound aqueous solution are mixed to form resin fine particles When,
A step of causing the resin fine particles obtained in the step (A) to react with an acid to precipitate an anionic group-containing organic polymer compound on the surface of the resin fine particles to precipitate resin particles coated with the anionic group-containing organic polymer. (B) and
The step (C) of obtaining the resin particle wet cake coated with the water-containing anionic group-containing organic polymer by filtering and washing the resin particles coated with the anionic group-containing organic polymer obtained in the step (B). When,
A dispersion comprising resin particles coated with an anionic group-containing organic polymer compound obtained by reacting the resin particle wet cake coated with the water-containing anionic group-containing organic polymer obtained in the step (C) with a base. And a step (D) for obtaining a resin dispersion.
項９．ガラス転移温度が１００℃以上であることを特徴とする樹脂からなる群より選ばれる少なくとも一種の樹脂溶液とアニオン性基含有有機高分子化合物水溶液とを混合し、樹脂微粒子を形成させる工程（Ａ）と、
工程（Ａ）で得られた樹脂微粒子と酸とを反応させて樹脂微粒子表面にアニオン性基含有有機高分子化合物を析出させてアニオン性基含有有機高分子により被覆された樹脂粒子を沈殿させる工程（Ｂ）と、
工程（Ｂ）で得られたアニオン性基含有有機高分子により被覆された樹脂粒子をろ別、洗浄し、含水アニオン性基含有有機高分子により被覆された樹脂粒子ウェットケーキを得る工程（Ｃ）と、
工程（Ｃ）で得られた含水アニオン性基含有有機高分子により被覆された樹脂粒子ウェットケーキを乾燥してアニオン性基含有有機高分子により被覆された樹脂粉体粒子を得る工程（Ｅ１）と、を含む樹脂粉体粒子の製造方法。 Item 9. Step (A) in which at least one resin solution selected from the group consisting of resins having a glass transition temperature of 100 ° C. or higher and an anionic group-containing organic polymer compound aqueous solution are mixed to form resin fine particles When,
A step of causing the resin fine particles obtained in the step (A) to react with an acid to precipitate an anionic group-containing organic polymer compound on the surface of the resin fine particles to precipitate resin particles coated with the anionic group-containing organic polymer. (B) and
The step (C) of obtaining the resin particle wet cake coated with the water-containing anionic group-containing organic polymer by filtering and washing the resin particles coated with the anionic group-containing organic polymer obtained in the step (B). When,
A step (E1) of obtaining resin powder particles coated with the anionic group-containing organic polymer by drying the resin particle wet cake coated with the water-containing anionic group-containing organic polymer obtained in the step (C); A method for producing resin powder particles.
項１０．ガラス転移温度が１００℃以上であることを特徴とする樹脂からなる群より選ばれる少なくとも一種の樹脂溶液とアニオン性基含有有機高分子化合物水溶液とを混合し、樹脂微粒子を形成させる工程（Ａ）と、
工程（Ａ）で得られた樹脂微粒子と酸とを反応させて樹脂微粒子表面にアニオン性基含有有機高分子化合物を析出させてアニオン性基含有有機高分子により被覆された樹脂粒子を沈殿させる工程（Ｂ）と、
工程（Ｂ）で得られたアニオン性基含有有機高分子により被覆された樹脂粒子をろ別、洗浄し、含水アニオン性基含有有機高分子により被覆された樹脂粒子ウェットケーキを得る工程（Ｃ）と、
工程（Ｃ）で得られた含水アニオン性基含有有機高分子により被覆された樹脂粒子ウェットケーキと塩基とを反応させてアニオン性基含有有機高分子化合物により被覆された樹脂粒子からなる分散体を得る工程（Ｄ）と、
工程（Ｄ）で得られたアニオン性基含有有機高分子化合物により被覆された樹脂粒子からなる分散体を乾燥してアニオン性基含有有機高分子により被覆された樹脂粉体粒子を得る工程（Ｅ２）と、を含む樹脂粉体粒子の製造方法。 Item 10. Step (A) in which at least one resin solution selected from the group consisting of resins having a glass transition temperature of 100 ° C. or higher and an anionic group-containing organic polymer compound aqueous solution are mixed to form resin fine particles When,
A step of causing the resin fine particles obtained in the step (A) to react with an acid to precipitate an anionic group-containing organic polymer compound on the surface of the resin fine particles to precipitate resin particles coated with the anionic group-containing organic polymer. (B) and
The step (C) of obtaining the resin particle wet cake coated with the water-containing anionic group-containing organic polymer by filtering and washing the resin particles coated with the anionic group-containing organic polymer obtained in the step (B). When,
A dispersion comprising resin particles coated with an anionic group-containing organic polymer compound obtained by reacting the resin particle wet cake coated with the water-containing anionic group-containing organic polymer obtained in the step (C) with a base. Obtaining step (D);
A step of drying the dispersion composed of the resin particles coated with the anionic group-containing organic polymer compound obtained in the step (D) to obtain resin powder particles coated with the anionic group-containing organic polymer (E2 And a method for producing resin powder particles.
項１１．前記工程（Ａ）の後に、工程（Ａ）で得られた樹脂微粒子の分散液に対し、機械的粉砕を行うことを特徴とする項８に記載の樹脂分散体の製造方法。 Item 11. Item 9. The method for producing a resin dispersion according to Item 8, wherein after the step (A), the resin fine particle dispersion obtained in the step (A) is mechanically pulverized.
項１２．前記工程（Ａ）の後に、工程（Ａ）で得られた樹脂微粒子の分散液に対し、機械的粉砕を行うことを特徴とする項９又は項１０に記載の樹脂粉体粒子の製造方法。 Item 12. Item 11. The method for producing resin powder particles according to Item 9 or 10, wherein mechanical pulverization is performed on the dispersion of resin fine particles obtained in Step (A) after Step (A).
項１３－１．前記項１～６のいずれか一項に記載の分散体を用いてなる塗料。
項１３－２．前記項１～６のいずれか一項に記載のポリアリーレンスルフィド分散体を用いて得られた塗膜。』に関する。 Item 13-1. A paint comprising the dispersion according to any one of items 1 to 6.
Item 13-2. A coating film obtained using the polyarylene sulfide dispersion according to any one of Items 1 to 6. About].
　また、本発明は、
『項１４．前記樹脂が、ポリスルホン、ポリエーテルエーテルケトン、ポリエーテルスルホン、ポリカーボネート、ポリフェニレンエーテル及びポリフェニルスルホンからなる群から選ばれる少なくとも一種の樹脂である、前記項１に記載の分散体。
項１５．前記樹脂が、ポリスルホン、ポリエーテルエーテルケトン、ポリエーテルスルホン及びポリフェニルスルホンからなる群から選ばれる少なくとも一種の樹脂である、前記項１に記載の分散体。
項１６．前記樹脂が、ポリスルホン、ポリエーテルスルホン及びポリフェニルスルホンからなる群から選ばれる少なくとも一種の樹脂である、前記項１に記載の分散体。
項１７．前記樹脂が、ポリエーテルスルホンである、前記項１に記載の分散体。
項１８．前記樹脂が、ポリフェニルスルホンである、前記項１に記載の分散体。』
に関する。 The present invention also provides:
[Section 14. Item 2. The dispersion according to Item 1, wherein the resin is at least one resin selected from the group consisting of polysulfone, polyetheretherketone, polyethersulfone, polycarbonate, polyphenylene ether, and polyphenylsulfone.
Item 15. Item 2. The dispersion according to Item 1, wherein the resin is at least one resin selected from the group consisting of polysulfone, polyetheretherketone, polyethersulfone, and polyphenylsulfone.
Item 16. Item 2. The dispersion according to Item 1, wherein the resin is at least one resin selected from the group consisting of polysulfone, polyethersulfone, and polyphenylsulfone.
Item 17. Item 2. The dispersion according to Item 1, wherein the resin is polyethersulfone.
Item 18. Item 2. The dispersion according to Item 1, wherein the resin is polyphenylsulfone. ]
About.
　本発明により、ガラス転移温度が１００℃以上であることを特徴とする樹脂からなる群より選ばれる少なくとも一種の樹脂粒子がアニオン性基含有有機高分子化合物で被覆されており、長期に優れた分散安定性を示す前記樹脂の水分散体を提供することができる。
　また、本発明の分散体は、樹脂粒子を高濃度で含有させることが可能である。
　このような効果を有する本発明の分散体は、塗料用途として好適に用いることができる。 According to the present invention, at least one resin particle selected from the group consisting of resins having a glass transition temperature of 100 ° C. or higher is coated with an anionic group-containing organic polymer compound, and has excellent long-term dispersion An aqueous dispersion of the resin exhibiting stability can be provided.
The dispersion of the present invention can contain resin particles at a high concentration.
The dispersion of the present invention having such an effect can be suitably used for coating applications.
　以下、本発明の実施の形態について詳細に説明する。
　本発明の樹脂分散液に含有される粒子は、ガラス転移温度が１００℃以上であることを特徴とする樹脂が、アニオン性基含有有機高分子化合物を用いて、水性媒体中に微粒子として分散されたものである。樹脂微粒子の分散方法の詳細については後述する。
　ここで、水性媒体としては、水単独であってもよく、水と水溶性溶媒からなる混合溶媒でもよい。 Hereinafter, embodiments of the present invention will be described in detail.
The particles contained in the resin dispersion of the present invention have a glass transition temperature of 100 ° C. or higher and are dispersed as fine particles in an aqueous medium using an anionic group-containing organic polymer compound. It is a thing. Details of the resin fine particle dispersion method will be described later.
Here, the aqueous medium may be water alone or a mixed solvent composed of water and a water-soluble solvent.
　本発明に使用可能な樹脂は、ガラス転移温度が１００℃以上であることを特徴とする樹脂（以下、樹脂（Ｘ）と表記する場合がある）である。これらの樹脂は、市販品を用いてもよいし、公知の方法で合成して用いてもよい。 The resin usable in the present invention is a resin having a glass transition temperature of 100 ° C. or higher (hereinafter sometimes referred to as “resin (X)”). These resins may be commercially available products or may be synthesized by a known method.
　このような樹脂（Ｘ）として、たとえば、ポリスルホン（ＰＳＦ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、ポリエーテルスルホン（ＰＥＳ）、ポリカーボネート、ポリフェニレンエーテル（ＰＰＥ）、ポリフェニルスルホン（ＰＰＳＵ）などが挙げられる。なかでも、より好ましくは、ポリスルホン、ポリエーテルエーテルケトン、ポリエーテルスルホン、ポリフェニルスルホンが挙げられ、さらに好ましくは、ポリスルホン、ポリエーテルスルホン、ポリフェニルスルホンが挙げられる。 Examples of such resin (X) include polysulfone (PSF), polyetheretherketone (PEEK), polyethersulfone (PES), polycarbonate, polyphenylene ether (PPE), polyphenylsulfone (PPSU), and the like. Of these, more preferred are polysulfone, polyetheretherketone, polyethersulfone, and polyphenylsulfone, and still more preferred are polysulfone, polyethersulfone, and polyphenylsulfone.
　本発明を詳述するために、本発明で用いる樹脂の具体例を以下説明するが、これらの説明は、本発明を限定する目的で記載されるものではない。 In order to describe the present invention in detail, specific examples of the resin used in the present invention will be described below. However, these descriptions are not described for the purpose of limiting the present invention.
　ポリスルホン（ＰＳＦ）は、構成単位中にスルホニル基を有し、下記式： Polysulfone (PSF) has a sulfonyl group in the structural unit and has the following formula:
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
で表される樹脂である。ＰＳＦの市販品としては、ＢＡＳＦ社製のウルトラゾーン（登録商標）　Ｓ－２０１０（Ｕｌｔｒａｓｏｎ　Ｓ－２０１０）、ウルトラゾーン（登録商標）　Ｓ－３０１０（Ｕｌｔｒａｓｏｎ　Ｓ－３０１０）、ウルトラゾーン（登録商標）　Ｓ－６０１０（Ｕｌｔｒａｓｏｎ　Ｓ－６０１０）などが挙げられる。 It is resin represented by these. As commercial products of PSF, Ultra Zone (registered trademark) S-2010 (Ultrason S-2010), Ultra Zone (registered trademark) S-3010 (Ultrason S-3010), Ultra Zone (registered trademark) S manufactured by BASF -6010 (Ultrason S-6010).
ポリエーテルエーテルケトン（ＰＥＥＫ）は、ベンゼン環がエーテル結合とケトン結合を介して繋がる構成単位を有することを特徴とする、下記式： Polyetheretherketone (PEEK) has a structural unit in which a benzene ring is connected via an ether bond and a ketone bond, and has the following formula:
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
で表される樹脂である。ＰＥＥＫの市販品としては、ビクトレックス社製のものなどが挙げられる。 It is resin represented by these. Examples of commercially available PEEK include those manufactured by Victrex.
ポリエーテルスルホン（ＰＥＳ）は、構成単位中にスルホニル基を有し、下記式： Polyethersulfone (PES) has a sulfonyl group in the structural unit and has the following formula:
で表される樹脂である。ＰＥＳの市販品としては、ソルベイアドバンストポリマー社製のユーデル（登録商標）シリーズ　Ｐ－１７００、ソルベイアドバンストポリマー社製のレーデルＡシリーズ（ＲＡＤＥＬ（登録商標）Ａシリーズ）、ＢＡＳＦ社製のウルトラゾーン（登録商標）　Ｅシリーズ（Ｕｌｔｒａｓｏｎ　Ｅ－１０１０など）、住友化学社製のスミカエクセルシリーズ（スミカエクセル５００３Ｐ、スミカエクセル４１００Ｐなど）などが挙げられる。 It is resin represented by these. Commercially available PES products include Udel (registered trademark) series P-1700 manufactured by Solvay Advanced Polymer, Radel A series (RADEL (registered trademark) A series) manufactured by Solvay Advanced Polymer, and Ultra Zone (registered by BASF). Trademarks) E series (Ultrason E-1010 etc.), Sumika Excel series manufactured by Sumitomo Chemical Co., Ltd. (Sumika Excel 5003P, Sumika Excel 4100P etc.) and the like.
ポリフェニルスルホン（ＰＰＳＵ）は、構成単位中にスルホニル基を有し、下記式： Polyphenylsulfone (PPSU) has a sulfonyl group in the structural unit and has the following formula:
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
で表される樹脂である。ＰＰＳＵの市販品としては、ソルベイアドバンストポリマー社製のレーデルＲシリーズ（ＲＡＤＥＬ（登録商標）Ｒシリーズ）、ＢＡＳＦ社製のウルトラゾーン（登録商標）　Ｐ－３０１０（Ｕｌｔｒａｓｏｎ　Ｐ－３０１０）等が挙げられる。 It is resin represented by these. As commercial products of PPSU, Radel R series (RADEL (registered trademark) R series) manufactured by Solvay Advanced Polymer, Ultrason (registered trademark) P-3010 (Ultrason P-3010) manufactured by BASF, and the like can be mentioned.
ポリカーボネートは、カーボネート基を有し、下記式： Polycarbonate has a carbonate group and has the following formula:
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
で表される樹脂である。ポリカーボネートの市販品としては、帝人化成（株）製のパンライト（登録商標）、三菱エンジニアリングプラスチック（株）製のユーピロン（登録商標）、住友ダウ（株）製のＳＤポリカ（登録商標）、ダウケミカル（株）製のカリバー（登録商標）等が挙げられる。 It is resin represented by these. Commercially available polycarbonate products include Panlite (registered trademark) manufactured by Teijin Chemicals Ltd., Iupilon (registered trademark) manufactured by Mitsubishi Engineering Plastics Co., Ltd., SD Polyca (registered trademark) manufactured by Sumitomo Dow Co., Ltd., Dow Examples include Caliber (registered trademark) manufactured by Chemical Corporation.
ポリフェニレンエーテル（ＰＰＥ）は、下記式： Polyphenylene ether (PPE) has the following formula:
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
で表される樹脂である。ＰＰＥは他の樹脂とポリマーアロイを形成（変性ＰＰＥ）することができ、本発明においてはポリスチレンとのポリマーアロイであるｍ－ＰＰＥ等を用いることもできる。ＰＰＥの市販品としては、ＧＥ社製のノリル　Ｎ１２５０等のノリル（登録商標、変性ＰＰＥ）シリーズ、旭化成社製のザイロン（登録商標、変性ＰＰＥ）　Ｘ　９１０２等が挙げられる。 It is resin represented by these. PPE can form a polymer alloy (modified PPE) with other resins, and m-PPE that is a polymer alloy with polystyrene can also be used in the present invention. Examples of commercially available PPE include Noryl (registered trademark, modified PPE) series such as Noryl N1250 manufactured by GE, and Zylon (registered trademark, modified PPE) X 9102 manufactured by Asahi Kasei.
　これらは、いずれもエンジニアリングプラスチックに分類される樹脂である。 These are all resins classified as engineering plastics.
　［樹脂分散体の作製］
　次に、本発明の樹脂分散体について詳細に説明する。本発明における樹脂分散体とは、上記樹脂（Ｘ）を溶解させた樹脂溶液と、アニオン性基含有有機高分子化合物の水溶液とを混合して樹脂（Ｘ）の微粒子を形成させる工程（Ａ）（晶析工程）と、酸によりアニオン性基含有有機高分子化合物を樹脂（Ｘ）微粒子の表面に析出させ被覆させる工程（Ｂ）（酸析工程）と、アニオン性基含有有機高分子化合物被覆された樹脂（Ｘ）粒子をろ別し、水洗して含水アニオン性基含有有機高分子化合物被覆樹脂（Ｘ）粒子ウェットケーキを得る工程（Ｃ）（ウェットケーキ作製工程）と、得られたウェットケーキを塩基により中和して再分散、調整（工程（Ｄ）：分散体作製工程）して得られる樹脂（Ｘ）分散体のことである。 [Preparation of resin dispersion]
Next, the resin dispersion of the present invention will be described in detail. The resin dispersion in the present invention is a step (A) in which a resin solution in which the resin (X) is dissolved and an aqueous solution of an anionic group-containing organic polymer compound are mixed to form fine particles of the resin (X). (Crystallization step), an anionic group-containing organic polymer compound deposited on the surface of the resin (X) fine particles with an acid (B) (acidification step), and an anionic group-containing organic polymer compound coating The obtained resin (X) particles are filtered off, washed with water to obtain a wet anionic group-containing organic polymer compound-coated resin (X) particle wet cake (C) (wet cake preparation step), and the obtained wet It is a resin (X) dispersion obtained by neutralizing a cake with a base and redispersing and adjusting (step (D): dispersion preparation step).
　樹脂（Ｘ）は、溶媒に溶解させたものを用いる。ここで後述する無機塩を加える場合もあるが、特に加えなくても良い。本発明に用いることのできる樹脂（Ｘ）の形態は特に問わないが、具体的に例示するならば粉体、顆粒、ペレット、繊維、フィルム、成形品等が挙げられる。操作性及び溶解に要する時間を短縮させる観点から、粉末、顆粒、ペレットが望ましい。これらの中でも特に粉体の樹脂（Ｘ）が好ましく用いられる。通常、樹脂（Ｘ）、溶媒を容器中に投入した後、溶解を行うが、容器へ投入する順序は問わない。 Resin (X) used is one dissolved in a solvent. Here, an inorganic salt described later may be added, but it may not be added in particular. The form of the resin (X) that can be used in the present invention is not particularly limited, and specific examples include powders, granules, pellets, fibers, films, molded products, and the like. From the viewpoint of shortening the time required for operability and dissolution, powders, granules and pellets are desirable. Among these, powder resin (X) is particularly preferably used. Usually, the resin (X) and the solvent are introduced into the container and then dissolved, but the order of introduction into the container is not limited.
　容器は、高温下で使用する場合には、耐圧製容器を用いる方が好ましい。容器中の雰囲気は、空気雰囲気下、不活性ガス雰囲気下のいずれでも良いが、樹脂（Ｘ）と反応したり、樹脂（Ｘ）自身を劣化させるような雰囲気を避けるべきであるため、不活性ガス雰囲気下が好ましい。
　ここでいう、不活性ガスとは、窒素ガス、二酸化炭素、ヘリウムガス、アルゴンガス、ネオンガス、クリプトンガス、キセノンガスなどが挙げられ、経済性、入手容易性を勘案して、窒素ガス、アルゴンガス、二酸化炭素ガスが望ましく、より好ましくは窒素ガス或いはアルゴンガスが用いられる。 When the container is used at a high temperature, it is preferable to use a pressure-resistant container. The atmosphere in the container may be either an air atmosphere or an inert gas atmosphere, but an inert atmosphere that reacts with the resin (X) or deteriorates the resin (X) itself should be avoided. A gas atmosphere is preferred.
As used herein, the inert gas includes nitrogen gas, carbon dioxide, helium gas, argon gas, neon gas, krypton gas, xenon gas, etc. Nitrogen gas, argon gas in consideration of economy and availability Carbon dioxide gas is desirable, and nitrogen gas or argon gas is more preferably used.
　無機塩として、特に制限はないが、通常、アルカリ金属、アルカリ土類金属、アンモニアなどの塩化物、臭化物、炭酸塩、硫酸塩等が用いられる。具体的には、塩化ナトリウム、塩化リチウム、塩化カリウム、塩化カルシウム、塩化マグネシウム、塩化アンモニウム等の塩化塩、臭化ナトリウム、臭化リチウム、臭化カリウム、臭化カルシウム、臭化マグネシウム、臭化アンモニウム等の臭化物、炭酸ナトリウム、炭酸カリウム、炭酸リチウム、炭酸カルシウム、炭酸マグネシウム、炭酸アンモニウム等の炭酸塩、硫酸カルシウム、硫酸ナトリウム、硫酸カリウム、硫酸リチウム、硫酸マグネシウム、硫酸アンモニウム等の硫酸塩等が用いられるが、塩化ナトリウム、塩化リチウム、塩化カリウム、塩化カルシウム、塩化マグネシウム、塩化アンモニウム等の塩化物が好ましい。これらは一種または二種以上で用いることができる。
　無機塩を加える場合の樹脂（Ｘ）に対する無機塩の重量比率は、樹脂（Ｘ）　１質量部に対して０．１～１０質量部の範囲、好ましくは、０．５～５質量部の範囲である。 Although there is no restriction | limiting in particular as an inorganic salt, Usually, chlorides, bromides, carbonates, sulfates, etc., such as an alkali metal, alkaline earth metal, and ammonia are used. Specifically, chlorides such as sodium chloride, lithium chloride, potassium chloride, calcium chloride, magnesium chloride, ammonium chloride, sodium bromide, lithium bromide, potassium bromide, calcium bromide, magnesium bromide, ammonium bromide Such as bromide such as sodium carbonate, potassium carbonate, lithium carbonate, calcium carbonate, magnesium carbonate, ammonium carbonate, sulfate such as calcium sulfate, sodium sulfate, potassium sulfate, lithium sulfate, magnesium sulfate, ammonium sulfate, etc. However, chlorides such as sodium chloride, lithium chloride, potassium chloride, calcium chloride, magnesium chloride, and ammonium chloride are preferable. These can be used alone or in combination of two or more.
When the inorganic salt is added, the weight ratio of the inorganic salt to the resin (X) is in the range of 0.1 to 10 parts by mass, preferably in the range of 0.5 to 5 parts by mass with respect to 1 part by mass of the resin (X). It is.
　本発明で用いられる溶媒としては、樹脂（Ｘ）を溶解するものであれば特に制限はなく本発明の分散体を得ることができる。例えば、クロロホルム、ブロモホルム、塩化メチレン、１，２－ジクロロエタン、１，１，１－トリクロロエタン、クロロベンゼン、ｏ－ジクロロベンゼン、ｐ－ジクロロベンゼン、２，６－ジクロロトルエン、１－クロロナフタレン、ヘキサフルオロイソプロパノール等のハロゲン系溶媒、Ｎ－メチル－２－ピロリジノン、Ｎ－エチル－２－ピロリジノン等のＮ－アルキルピロリジノン系溶媒、Ｎ－メチル－ε－カプロラクタム、Ｎ－エチル－ε－カプロラクタム等のＮ－アルキルカプロラクタム系溶媒、１，３－ジメチル－２－イミダゾリジノン、Ｎ、Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、ヘキサメチルリン酸トリアミド、ジメチルスルホキシド、ジメチルスルホン、テトラメチレンスルホン等の極性溶媒の中から選ばれる少なくとも一種の溶媒が挙げられる。好ましくは、Ｎ－メチル－２－ピロリドン、１－クロロナフタレン、ｏ－ジクロロベンゼン、１，３－ジメチル－２－イミダゾリジノンの中から選ばれる少なくとも一種の溶媒である。これらの中でも特に、作業性、水溶性を考慮するとＮ－メチル－２－ピロリドン、１－クロロナフタレン、１，３－ジメチル－２－イミダゾリジノンが好ましく用いられる。 The solvent used in the present invention is not particularly limited as long as it dissolves the resin (X), and the dispersion of the present invention can be obtained. For example, chloroform, bromoform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, chlorobenzene, o-dichlorobenzene, p-dichlorobenzene, 2,6-dichlorotoluene, 1-chloronaphthalene, hexafluoroisopropanol Halogen solvents such as N-methyl-2-pyrrolidinone, N-alkylpyrrolidinone solvents such as N-ethyl-2-pyrrolidinone, N-alkyl such as N-methyl-ε-caprolactam and N-ethyl-ε-caprolactam Polar solvents such as caprolactam solvents, 1,3-dimethyl-2-imidazolidinone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, dimethyl sulfoxide, dimethyl sulfone, tetramethylene sulfone, etc. From inside There may be mentioned at least one solvent selected. Preferably, it is at least one solvent selected from N-methyl-2-pyrrolidone, 1-chloronaphthalene, o-dichlorobenzene, and 1,3-dimethyl-2-imidazolidinone. Among these, N-methyl-2-pyrrolidone, 1-chloronaphthalene, and 1,3-dimethyl-2-imidazolidinone are preferably used in consideration of workability and water solubility.
　溶媒に対する樹脂（Ｘ）の重量比率は、溶媒に樹脂（Ｘ）が溶解する限り特に制限はないが、溶媒１００質量部に対して０．１～２０質量部の範囲を例示することができ、好ましくは、０．１～１０質量部であり、より好ましくは、０．１～５質量部である。ここで、樹脂（Ｘ）をより良く溶解させるために、混合した反応液を昇温させて行うこともできる。 The weight ratio of the resin (X) to the solvent is not particularly limited as long as the resin (X) is dissolved in the solvent, but can be exemplified as a range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the solvent. The amount is preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass. Here, in order to dissolve the resin (X) better, the mixed reaction solution can be heated.
　また、反応液を攪拌してもしなくても良いが、好ましくは攪拌したほうが良く、これにより溶解に要する時間を短くすることができる。 In addition, the reaction solution may or may not be stirred, but it is preferable that the reaction solution is stirred, thereby shortening the time required for dissolution.
　次に上記で得られた樹脂（Ｘ）溶解液を基に、本発明である樹脂（Ｘ）分散体及びそれから得られる粉体粒子の製造方法を、製造工程順に詳細に説明する。 Next, based on the resin (X) solution obtained above, the production method of the resin (X) dispersion according to the present invention and the powder particles obtained therefrom will be described in detail in the order of the production steps.
　［晶析工程］（工程Ａ）
　まず、予めアニオン性基含有有機高分子化合物水溶液を調整する。ここで使用されるアニオン性基含有有機高分子化合物中のアニオン性基としては、例えば、カルボキシル基、カルボキシレート基、スルホン酸基、スルホネート基、リン酸基などを使用することができ、なかでも、前記カルボキシル基やスルホン酸基の一部または全部が塩基性化合物等によって中和されたカルボキシレート基やスルホネート基を使用することが、良好な水分散安定性を付与するうえで好ましい。 [Crystalling Step] (Step A)
First, an anionic group-containing organic polymer compound aqueous solution is prepared in advance. As the anionic group in the anionic group-containing organic polymer compound used here, for example, a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group, a phosphoric acid group, and the like can be used. It is preferable to use a carboxylate group or sulfonate group in which a part or all of the carboxyl group or sulfonic acid group is neutralized with a basic compound or the like in order to impart good water dispersion stability.
　また、前記アニオン性基含有有機高分子化合物の主骨格は、（メタ）アクリル酸エステル樹脂、（メタ）アクリル酸エステル－スチレン樹脂、（メタ）アクリル酸エステル－エポキシ樹脂、ビニル樹脂、ウレタン樹脂、ポリアミドイミド樹脂である。また、本発明で使用されるアニオン性基含有有機高分子化合物は、単体でも上記アニオン性基含有有機高分子化合物を１種類以上混合してもよく、塩基性の状態で溶解すれば、本発明の樹脂（Ｘ）分散体、樹脂（Ｘ）粉体粒子に使用することができる。 The main skeleton of the anionic group-containing organic polymer compound includes (meth) acrylic acid ester resin, (meth) acrylic acid ester-styrene resin, (meth) acrylic acid ester-epoxy resin, vinyl resin, urethane resin, Polyamideimide resin. The anionic group-containing organic polymer compound used in the present invention may be a single substance or a mixture of one or more of the above anionic group-containing organic polymer compounds, and if dissolved in a basic state, the present invention. The resin (X) dispersion and resin (X) powder particles can be used.
　アニオン性基含有有機高分子化合物は、塩基性水溶液中で完全に溶解させる。ここで使用する塩基としては、アンモニアや、水酸化リチウム、水酸化ナトリウム、水酸化カリウム等の無機の金属水酸化物、メチルアミン、エチルアミン、ｎ－ブチルアミン、ジメチルアミン、ジエチルアミン、トリメチルアミン、トリエチルアミン、トリ－ｎ－ブチルアミンの如きアルキルアミン類；Ｎ－メチルアミノエタノール、Ｎ，Ｎ－ジメチルアミノエタノール、Ｎ，Ｎ－ジエチルアミノエタノール、２－アミノ－２－メチルプロパノール、ジエタノールアミン、トリエタノールアミンの如きヒドロキシルアミン類；エチレンジアミン、ジエチレントリアミンの如き多価アミン類等の有機アミン等が好ましい。これらは一種または二種以上で用いることができる。また、アニオン性基含有有機高分子化合物を溶解するための塩基量としては、樹脂を完全に溶解させるために、アニオン性基含有有機高分子化合物の酸価に対して、７０～３００％がより好ましい。
　また、アニオン性基含有有機高分子化合物の酸価が１０～３００ｍｇＫＯＨ／ｇのものを使用することが好ましい。この範囲よりも低い酸価を有するアニオン性基含有有機高分子化合物を使用すると分散安定性が不十分となってしまうために好ましくない。中でも５０～２４０ｍｇＫＯＨ／ｇとなるアニオン性基含有有機高分子化合物を使用することが、最も分散安定性が高くなるためにより好ましい。
　このようなアニオン性基含有有機高分子化合物は後述の製造例に記載の方法等で合成して用いても良いし、市販品を用いても良い。市販品の具体例としては、アクリディックＷＭＬ－５４２（ＤＩＣ株式会社製）、ユニディックＥＭＧ－１０１５（ＤＩＣ株式会社製）等が挙げられる。 The anionic group-containing organic polymer compound is completely dissolved in a basic aqueous solution. Examples of the base used here include ammonia, inorganic metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, methylamine, ethylamine, n-butylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, triethylamine, and the like. Alkylamines such as n-butylamine; hydroxylamines such as N-methylaminoethanol, N, N-dimethylaminoethanol, N, N-diethylaminoethanol, 2-amino-2-methylpropanol, diethanolamine and triethanolamine Organic organic amines such as polyamines such as ethylenediamine and diethylenetriamine are preferred. These can be used alone or in combination of two or more. In addition, the base amount for dissolving the anionic group-containing organic polymer compound is more preferably 70 to 300% with respect to the acid value of the anionic group-containing organic polymer compound in order to completely dissolve the resin. preferable.
Further, it is preferable to use an anionic group-containing organic polymer compound having an acid value of 10 to 300 mgKOH / g. Use of an anionic group-containing organic polymer compound having an acid value lower than this range is not preferable because the dispersion stability becomes insufficient. Among them, it is more preferable to use an anionic group-containing organic polymer compound of 50 to 240 mgKOH / g because the dispersion stability is the highest.
Such an anionic group-containing organic polymer compound may be synthesized and used by the method described in the production examples described later, or a commercially available product may be used. Specific examples of commercially available products include ACRIDIC WML-542 (manufactured by DIC Corporation), UNIDIC EMG-1015 (manufactured by DIC Corporation), and the like.
　さらに、本発明では、アニオン性基含有有機高分子化合物により、樹脂（Ｘ）の粒子の一部または表面全体を被覆しても、分散安定性に効果が得られる。そのため、樹脂（Ｘ）１００質量部に対して、１質量部～２００質量部を使用することが好ましい。中でも５質量部～１５０質量部になるように使用するのが、最も分散安定性が高くなるため好ましい。 Furthermore, in the present invention, even if a part or the entire surface of the resin (X) particles is coated with the anionic group-containing organic polymer compound, an effect on dispersion stability can be obtained. Therefore, it is preferable to use 1 part by mass to 200 parts by mass with respect to 100 parts by mass of the resin (X). Of these, the use of 5 parts by mass to 150 parts by mass is preferable because the dispersion stability is the highest.
　次に、調整したアニオン性基含有有機高分子化合物水溶液に上記で調整した樹脂（Ｘ）溶解液を注ぐことで、樹脂（Ｘ）分散液（晶析液）を得ることができる。この時点では本発明の目的物である「アニオン性基含有有機高分子化合物により被覆された樹脂（Ｘ）粒子の分散体」とは異なるものである。この晶析工程にける樹脂（Ｘ）の粒子状態については後述の通りである。 Next, the resin (X) dispersion (crystallization solution) can be obtained by pouring the prepared resin (X) solution into the prepared anionic group-containing organic polymer compound aqueous solution. At this time, it is different from the “dispersion of resin (X) particles coated with an anionic group-containing organic polymer compound” which is the object of the present invention. The particle state of the resin (X) in this crystallization step is as described later.
　調整したアニオン性基含有有機高分子化合物水溶液は、撹拌羽根等の撹拌機で高速撹拌された水流を作製することが好ましい。乱流、層流いずれでも構わないが、周速は速い方が晶析した粒子サイズを細かく出来るため好ましい。 The prepared anionic group-containing organic polymer compound aqueous solution is preferably prepared as a water stream stirred at high speed with a stirrer such as a stirring blade. Either turbulent flow or laminar flow may be used, but higher peripheral speed is preferable because the crystallized particle size can be made finer.
　樹脂（Ｘ）の溶解液の注水速度は、遅いほど細かい粒子を形成し得る上で好適である。注水方法としては、調整したアニオン性基含有有機高分子化合物溶液を強撹拌した溶液に、直接注水する方法がある。ここで、アニオン性基含有有機高分子化合物溶液の撹拌は、微細な樹脂粒子を形成するために、強撹拌が好ましい。
　また、樹脂（Ｘ）の溶解液を注ぎ終えた後に得られた樹脂（Ｘ）分散液（晶析液）に対して機械的粉砕を行うことにより分散させる工程［分散工程］を経ることもできる。これにより、より良好な分散安定性を保持することができる。ここで、機械的粉砕としては、後述する機械的粉砕装置の項目で述べた装置を用いる方法などが挙げられる。 The slower the water injection rate of the resin (X) solution, the better the fine particles can be formed. As a water injection method, there is a method in which water is directly injected into a solution obtained by strongly stirring the prepared anionic group-containing organic polymer compound solution. Here, the stirring of the anionic group-containing organic polymer compound solution is preferably strong stirring in order to form fine resin particles.
Moreover, it can also pass through the process [dispersion process] which disperse | distributes by performing mechanical grinding | pulverization with respect to resin (X) dispersion liquid (crystallization liquid) obtained after finishing pouring the solution of resin (X). . Thereby, better dispersion stability can be maintained. Here, examples of the mechanical pulverization include a method using the apparatus described in the item of the mechanical pulverization apparatus described later.
　この晶析工程にける樹脂（Ｘ）の粒子状態は、アニオン性基含有有機高分子化合物が樹脂（Ｘ）粒子の表層に存在しており、まだ強固に固着している状態ではないと思われる。アニオン性基含有有機高分子化合物末端の酸性基がアルカリ金属とのイオン結合状態であるため、柔軟に樹脂（Ｘ）粒子の表層上に存在していると推測されるためである。後工程の酸析工程で酸により、アニオン性基含有有機高分子化合物の官能基の塩交換反応がおき、樹脂（Ｘ）表面に固着されるものである。 The particle state of the resin (X) in this crystallization step is considered not to be a state in which the anionic group-containing organic polymer compound is present on the surface layer of the resin (X) particles and is still firmly fixed. . This is because the acidic group at the end of the anionic group-containing organic polymer compound is in an ion-bonded state with an alkali metal, so that it is presumed that the anionic group is present flexibly on the surface layer of the resin (X) particles. A salt exchange reaction of the functional group of the anionic group-containing organic polymer compound is caused by an acid in a subsequent acid precipitation step, and is fixed to the surface of the resin (X).
　［酸析工程］（工程Ｂ）
　上記工程で得られた水溶性樹脂が表層に存在する樹脂（Ｘ）粒子を、酸によって酸析出させ、アニオン性基含有有機高分子化合物により被覆された樹脂（Ｘ）粒子を沈殿させたスラリーを作製する工程である。 [Acid deposition step] (Step B)
Resin (X) particles in which the water-soluble resin obtained in the above step is present on the surface layer are acid precipitated with an acid, and a slurry in which resin (X) particles coated with an anionic group-containing organic polymer compound are precipitated It is a manufacturing process.
　酸析出に使用される酸としては、塩酸、硫酸、酢酸、硝酸等が挙げられ、中でも塩酸が好ましい。 Examples of the acid used for acid precipitation include hydrochloric acid, sulfuric acid, acetic acid, nitric acid, and hydrochloric acid is preferable.
　酸濃度は、各種アニオン性基含有有機高分子化合物、各種樹脂（Ｘ）にもよるが、アニオン性基含有有機高分子化合物の末端置換基数による設定が必要で、酸により系内のｐＨを２～５に調整する。 The acid concentration depends on the various anionic group-containing organic polymer compounds and various resins (X), but it is necessary to set the number of terminal substituents of the anionic group-containing organic polymer compound. Adjust to ~ 5.
　［ウェットケーキ作製工程］（工程Ｃ）
　上記酸析工程で得られたアニオン性基含有高分子化合物により被覆された樹脂（Ｘ）粒子を沈殿させたスラリーから、アニオン性基含有高分子化合物により被覆された樹脂（Ｘ）粒子をろ別し、ウェットケーキにする工程である。ろ別する方法としては、ろ過や遠心分離等、粒子と液体が分離可能であれば如何なる方法でも構わない。ろ別されたウェットケーキ中の水分量は、１５～５５％の範囲が好ましく、水分量が低すぎると後工程での再分散でほぐれにくくなり、再分散性が悪くなるため、好ましい水分量は、２０～４５％である。ウェットケーキは、残存する有機溶媒や、未析出の樹脂を洗浄するため、イオン交換水、蒸留水、純水、水道水等で洗浄を行う。洗浄方法は、ウェットケーキ上から、洗浄溶媒をかけてろ過洗浄してもよいし、ウェットケーキを洗浄溶媒に再解膠して洗浄してもよい。 [Wet cake preparation process] (Process C)
The resin (X) particles coated with the anionic group-containing polymer compound are filtered from the slurry obtained by precipitating the resin (X) particles coated with the anionic group-containing polymer compound obtained in the acid precipitation step. And a wet cake process. As a method for filtering, any method may be used as long as particles and liquid can be separated, such as filtration and centrifugation. The moisture content in the filtered wet cake is preferably in the range of 15 to 55%. If the moisture content is too low, it becomes difficult to be loosened by redispersion in the subsequent process, and the redispersibility becomes poor. 20-45%. The wet cake is washed with ion-exchanged water, distilled water, pure water, tap water or the like in order to wash the remaining organic solvent and undeposited resin. As the washing method, the wet cake may be filtered and washed with a washing solvent, or the wet cake may be washed again by peptizing with a washing solvent.
　［分散体作製工程］（工程Ｄ）
　上記ウェットケーキ作製工程で得られたウェットケーキを水にビーズミルや超音波分散機等で、再解膠し、前述した、無機塩基、有機塩基でｐＨを６～１０に調整して、樹脂（Ｘ）分散体を得ることができる。得られる分散体中の不揮発分は、１５～４０％である。 [Dispersion Preparation Step] (Step D)
The wet cake obtained in the above wet cake preparation step is re-peptized with water using a bead mill or an ultrasonic disperser, and the pH is adjusted to 6 to 10 with an inorganic base or an organic base as described above. ) A dispersion can be obtained. The nonvolatile content in the resulting dispersion is 15 to 40%.
　［樹脂（Ｘ）粉体粒子の作製］（工程Ｅ１及び工程Ｅ２）
　さらに、本発明における樹脂（Ｘ）粉体粒子とは、上記工程Ｃで得られたウェットケーキあるいは、工程Ｄで得られた樹脂（Ｘ）分散体から水分を除去し、その後乾燥して得られるアニオン性基含有有機高分子化合物で被覆された樹脂（Ｘ）粉体粒子のことである。乾燥した後、各種粉砕装置で粉砕して、所望の粒子サイズに調整して使用することが可能である。 [Preparation of Resin (X) Powder Particles] (Step E1 and Step E2)
Furthermore, the resin (X) powder particles in the present invention are obtained by removing moisture from the wet cake obtained in the above step C or the resin (X) dispersion obtained in the step D and then drying. Resin (X) powder particles coated with an anionic group-containing organic polymer compound. After drying, it can be pulverized by various pulverizers and adjusted to a desired particle size for use.
　後述の測定方法における分散粒径が１μｍ未満になるまで上記樹脂（Ｘ）粗粒子を分散させた樹脂（Ｘ）粗粒子懸濁液の機械的粉砕を行う。好ましくは分散粒径が５００ｎｍ未満となるまで機械的粉砕を行う。
［機械的粉砕装置］
　機械的粉砕装置として、市販の機械的粉砕装置を挙げることができる。特に樹脂（Ｘ）粗粒子を効率よく分散、粉砕し、粒径の小さな樹脂（Ｘ）微粒子の分散液を作製するために好適な機械的粉砕装置として、ボールミル装置、ビーズミル装置、サンドミル装置、コロイドミル装置、ディスパー分散攪拌装置、湿式微粒化装置（例えば、スギノマシン製のアルティマイザー、Ｈｉｅｌｓｃｈｅｒ社製の超音波分散機等）が挙げられるが、なかでもボールミル装置、ビーズミル装置、サンドミル装置、湿式微粒化装置、から選択される装置が好ましい。機械的粉砕の際の粉砕の力は一般に大きくなるほど、また粉砕時間が長くなるほど得られる微粒子の分散粒径は、小さくなる方向にあるが、これらが過度になると凝集が生じやすくなるので、適切な範囲に制御される。例えばビーズミルではビーズ径やビーズ量の選択、周速の調整で、その制御が可能である。 The resin (X) coarse particle suspension in which the resin (X) coarse particles are dispersed is mechanically pulverized until the dispersed particle size in the measurement method described below becomes less than 1 μm. Preferably, mechanical pulverization is performed until the dispersed particle diameter is less than 500 nm.
[Mechanical grinding equipment]
Examples of the mechanical pulverizer include commercially available mechanical pulverizers. In particular, as a mechanical pulverization apparatus suitable for efficiently dispersing and pulverizing resin (X) coarse particles and preparing a dispersion of resin (X) fine particles having a small particle diameter, a ball mill apparatus, a bead mill apparatus, a sand mill apparatus, a colloid Examples thereof include a mill device, a disper dispersion stirrer, and a wet atomization device (for example, an optimizer manufactured by Sugino Machine, an ultrasonic disperser manufactured by Hielscher, etc.), among others, a ball mill device, a bead mill device, a sand mill device, a wet fine particle An apparatus selected from the converters is preferred. In general, the larger the pulverization force in mechanical pulverization and the longer the pulverization time, the smaller the dispersed particle size of the fine particles obtained. However, when these are excessive, aggregation tends to occur. Controlled to range. For example, a bead mill can be controlled by selecting the bead diameter and the bead amount and adjusting the peripheral speed.
　樹脂（Ｘ）微粒子分散液においても、場合によっては沈殿物を含む場合もある。その際には、沈殿部と分散部を分離して利用してもよい。分散液のみを得る場合には、沈殿部と分散部の分離を行えばよく、そのためには、デカンテーション、ろ過などを行えば良い。また、より粒径の細かい粒子まで必要な場合には、遠心分離などを行い、粒径の大きなものを完全に沈降させ、デカンテーションやろ過を行い、沈殿部分を除去すればよい。 The resin (X) fine particle dispersion may also contain a precipitate in some cases. In that case, the precipitation part and the dispersion part may be used separately. When only the dispersion liquid is obtained, the precipitation part and the dispersion part may be separated. For this purpose, decantation, filtration, or the like may be performed. In addition, when particles having a finer particle size are required, centrifugation or the like is performed to completely settle the larger particle size, and decantation or filtration is performed to remove the precipitated portion.
　本発明で得られた樹脂（Ｘ）微粒子分散液は、通常２４時間静置しても微粒子とアニオン性基含有有機高分子化合物水溶液とが分離しない。 In the resin (X) fine particle dispersion obtained in the present invention, the fine particles and the anionic group-containing organic polymer compound aqueous solution are not separated even after standing for 24 hours.
　このようにして得られた樹脂（Ｘ）微粒子分散液は、その特性から塗料、接着、ポリマーコンパウンド分野における有用な添加剤となる。 The resin (X) fine particle dispersion obtained in this way is a useful additive in the fields of paint, adhesion and polymer compounds because of its characteristics.
　以下、実施例を挙げることにより、本発明をより詳細に説明する。しかし、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail by giving examples. However, the present invention is not limited to these.
　後記する実施例、比較実施例で得た樹脂分散体の分散粒径及び沈降性の測定方法を記載する。 The methods for measuring the dispersed particle size and sedimentation of the resin dispersions obtained in the examples and comparative examples described below are described.
　［分散粒径の測定］
　得られた樹脂分散液を、「ＭＴ－３３００ＥＸＩＩ」（日機装社製のレーザードップラー式粒度分布計）を用いて測定したＤ５０粒径を分散粒径とした。 [Measurement of dispersed particle size]
The obtained resin dispersion was defined as D50 particle size measured using “MT-3300EXII” (Laser Doppler particle size distribution meter manufactured by Nikkiso Co., Ltd.) as the dispersed particle size.
　［目視による沈降の確認］
　得られた樹脂分散体を２４時間静置させた際の上澄みを確認した。上澄みが透明である場合は「沈降あり」、上澄みが確認されない場合は「沈降なし」と判断した。 [Confirmation of settling visually]
The supernatant was confirmed when the obtained resin dispersion was allowed to stand for 24 hours. When the supernatant was transparent, it was judged as “with sedimentation”, and when the supernatant was not confirmed, it was judged as “no sedimentation”.
　［アニオン性基含有有機高分子化合物の製造］
　本明細書で用いられるアニオン性基含有有機高分子化合物の製造方法の一例として、スチレン（メタ）アクリル系共重合体、アルコール変性ポリアミドイミド樹脂の製造例を以下に記載するが、これら以外のアニオン性基含有有機高分子化合物についても同様の方法で製造することができる。 [Production of anionic group-containing organic polymer compound]
As an example of a method for producing an anionic group-containing organic polymer compound used in the present specification, examples of producing a styrene (meth) acrylic copolymer and an alcohol-modified polyamideimide resin are described below. The functional group-containing organic polymer compound can also be produced by the same method.
（製造例１）アニオン性基含有有機高分子化合物（Ｒ－１）の製造
　攪拌装置、滴下装置、温度センサー、および上部に窒素導入装置を有する還流装置を取り付けた反応容器を有する自動重合反応装置（重合試験機ＤＳＬ－２ＡＳ型、轟産業（株）製）の反応容器に重合溶剤として２－プロパノール（以下、ＩＰＡと表記する）７２０部を仕込み、攪拌しながら反応容器内を窒素置換した。反応容器内を窒素雰囲気に保ちながら８０℃に昇温させた後、滴下装置よりメタクリル酸ベンジル　１２０部、メタクリル酸２－ヒドロキシエチル　４９．８部、メタクリル酸　１５３．７２部、スチレン　１８０部、メタクリル酸グリシジル　０．６部、メタクリル酸ｎ－ブチル　３４．６２部、アクリル酸ブチル　６０．６６部、メタクリル酸メチル　０．６部および「パーブチル（登録商標）Ｏ」（有効成分ペルオキシ２－エチルヘキサン酸ｔ－ブチル、日油（株）製）４８部、チオグリセロール　２４部の混合液を４時間かけて滴下した。滴下終了後、さらに同温度で１５時間反応を継続させた後、樹脂分濃度を４５％に調整し、実測酸価　１５７ｍｇＫＯＨ／ｇのアニオン性基含有高分子化合物である、スチレン（メタ）アクリル系共重合体（Ｒ－１）のＩＰＡ溶液を得た。 (Production Example 1) Production of anionic group-containing organic polymer compound (R-1) Automatic polymerization reaction device having a reaction vessel equipped with a stirring device, a dropping device, a temperature sensor, and a reflux device having a nitrogen introduction device at the top 720 parts of 2-propanol (hereinafter referred to as IPA) as a polymerization solvent was charged into a reaction vessel (polymerization tester DSL-2AS type, manufactured by Sakai Sangyo Co., Ltd.), and the inside of the reaction vessel was purged with nitrogen while stirring. The temperature inside the reaction vessel was raised to 80 ° C. while maintaining a nitrogen atmosphere, and then 120 parts by weight of benzyl methacrylate, 49.8 parts of 2-hydroxyethyl methacrylate, 153.72 parts of methacrylic acid, 180 parts of styrene, methacrylic acid from the dropping device. Glycidyl acid 0.6 parts, n-butyl methacrylate 34.62 parts, butyl acrylate 60.66 parts, methyl methacrylate 0.6 parts and “Perbutyl® O” (active ingredient peroxy 2-ethylhexanoic acid) A mixed solution of 48 parts of t-butyl (manufactured by NOF Corporation) and 24 parts of thioglycerol was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was further continued for 15 hours at the same temperature, and then the resin concentration was adjusted to 45%. An IPA solution of copolymer (R-1) was obtained.
（製造例２）アニオン性基含有有機高分子化合物（Ｒ－２）の製造
　撹拌装置、温度計、コンデンサを付けたフラスコにＰＧＭＡｃ（プロピレングリコールモノメチルエーテルアセテート）１０８６ｇ、ＩＰＤＩ３Ｎ（イソホロンジイソシアネートから合成されたイソシアヌレート型トリイソシアネート：ＮＣＯ％＝１７．２）５８７．３ｇ（０．８０ｍｏｌ）及びシクロヘキサン－１，３，４－トリカルボン酸－３，４－無水物　４９９．１ｇ（２．５２ｍｏｌ）を加え、１４０℃まで昇温した。反応は、発泡とともに進行した。この温度で８時間反応させた。系内は淡黄色の液体となり、赤外スペクトルにて特性吸収を測定した結果、イソシアネート基の特性吸収である２２７０ｃｍ－１が完全に消滅し、１７８０ｃｍ－１、１７２０ｃｍ－１にイミド基の吸収が確認された。酸価は、固形分換算で２１２ｍｇＫＯＨ／ｇで、分子量はポリスチレン換算で数平均分子量４７００であった。酸無水物基の濃度は、固形分換算で１．１４ｍｍｏｌ／ｇであった。また、樹脂分の濃度は４７．４質量％であった。この樹脂の溶液をイミド樹脂の溶液と略記する。続いて、得られたイミド樹脂の溶液にｎ－ブタノール　９６．３ｇ（１．３ｍｏｌ）を加え、１２０℃にて２時間反応させた。赤外スペクトルにて特性吸収を測定した結果、酸無水物基の特性吸収である１８６０ｃｍ－１の質量吸収が完全に消失した。酸価は、固形分換算で、１４８ｍｇＫＯＨ／ｇで、分子量はポリスチレン換算で数平均分子量４８００であった。また、樹脂分の濃度は４９．２質量％であった。この樹脂の溶液がアニオン性基含有有機高分子化合物（アルコール変性ポリアミドイミド樹脂（Ｒ－２と略す））である。 (Production Example 2) Production of anionic group-containing organic polymer compound (R-2) A flask equipped with a stirrer, thermometer and condenser was synthesized from 1086 g of PGMAc (propylene glycol monomethyl ether acetate) and IPDI3N (isophorone diisocyanate). Isocyanurate type triisocyanate: NCO% = 17.2) 587.3 g (0.80 mol) and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 499.1 g (2.52 mol) were added, The temperature was raised to 140 ° C. The reaction proceeded with foaming. The reaction was carried out at this temperature for 8 hours. As a result of measuring the characteristic absorption in the infrared spectrum, 2270 cm −1, which is the characteristic absorption of the isocyanate group, disappeared completely, and imide group absorption was observed at 1780 cm −1 and 1720 cm −1. confirmed. The acid value was 212 mgKOH / g in terms of solid content, and the molecular weight was a number average molecular weight of 4700 in terms of polystyrene. The concentration of the acid anhydride group was 1.14 mmol / g in terms of solid content. Moreover, the density | concentration of the resin part was 47.4 mass%. This resin solution is abbreviated as an imide resin solution. Subsequently, 96.3 g (1.3 mol) of n-butanol was added to the resulting imide resin solution and reacted at 120 ° C. for 2 hours. As a result of measuring the characteristic absorption in the infrared spectrum, the mass absorption at 1860 cm −1 , which is the characteristic absorption of the acid anhydride group, completely disappeared. The acid value was 148 mgKOH / g in terms of solid content, and the molecular weight was a number average molecular weight of 4800 in terms of polystyrene. Moreover, the density | concentration of the resin part was 49.2 mass%. This resin solution is an anionic group-containing organic polymer compound (alcohol-modified polyamideimide resin (abbreviated as R-2)).
（実施例１）
・工程（Ａ）［晶析工程］
　激しく攪拌させたアニオン性基含有有機高分子化合物水溶液（アニオン性基含有有機高分子化合物（Ｒ－１、ＩＰＡ　５５％含有）２．２２ｇと、２５％ＫＯＨ水溶液　０．６６ｇと、水　２５００ｇを混合したもの）に、ＰＰＳＵ（ＢＡＳＦ社製　Ｕｌｔｒａｓｏｎ　Ｐ－３０１０）　１０ｇをＮ－メチル－２－ピロリドン　５００ｇに１８０℃にて溶解させたＰＰＳＵ溶液を投入し、金属メッシュ（目開き４５μｍ）にて粗大粒子を除去することで、ＰＰＳＵ微粒子を含む分散液（晶析液）を得た。この操作を５回繰り返し行なった。 (Example 1)
-Process (A) [crystallization process]
Mix an aqueous solution of anionic group-containing organic polymer compound (anionic group-containing organic polymer compound (containing R-1, 55% IPA): 2.22 g), 0.66 g of 25% KOH aqueous solution, and 2500 g of water. PPSU (BASF Ultrason P-3010) 10 g dissolved in N-methyl-2-pyrrolidone 500 g at 180 ° C. and coarse particles with a metal mesh (aperture 45 μm) Was removed to obtain a dispersion liquid (crystallization liquid) containing PPSU fine particles. This operation was repeated 5 times.
・工程（Ｂ）［酸析工程］
　前記工程（Ａ）で得られたＰＰＳＵ微粒子分散液に２％塩酸を１３０ｇ添加し、アニオン性基含有有機高分子化合物をＰＰＳＵ粒子表面に析出させて、酸析スラリー（ＰＰＳＵ微粒子－アニオン性樹脂粒子）を得た。 -Process (B) [acid precipitation process]
130 g of 2% hydrochloric acid is added to the PPSU fine particle dispersion obtained in the step (A), and an anionic group-containing organic polymer compound is precipitated on the surface of the PPSU particles, so that an acid precipitation slurry (PPSU fine particles-anionic resin particles) is obtained. )
・工程（Ｃ）［ウェットケーキ作製工程］
　前記工程（Ｂ）で得られた酸析スラリーより水性媒体を吸引ろ過し、ろ集し、水洗・搾汁することで、不揮発分３０％のアニオン性基含有有機高分子化合物被覆ＰＰＳＵウェットケーキを得た。 -Process (C) [wet cake preparation process]
An aqueous medium is suction-filtered from the acid precipitation slurry obtained in the step (B), collected, washed and squeezed to obtain an anionic group-containing organic polymer compound-coated PPSU wet cake having a nonvolatile content of 30%. Obtained.
・工程（Ｄ）［微粒子分散体作製工程］
　前記工程（Ｃ）で得られたウェットケーキ１１０ｇと５０％ジメチルエタノールアミン水溶液２．１ｇを超音波分散機（ｈｉｅｌｓｃｈｅｒ製　ＵＰ４００Ｓ）にて６０分間超音波照射し、不揮発分３１％のＰＰＳＵ分散体を得た。得られた分散体の分散粒径を、Ｍｉｃｒｏｔｒａｃ－ＭＴ３３００ＥＸ　ＩＩ（日機装株式会社製）で測定したところ、Ｄ５０＝１６０ｎｍであった。また、一晩静置しても目視での沈殿はみられなかった（固液分離なし）。 Step (D) [Fine particle dispersion preparation step]
110 g of the wet cake obtained in the step (C) and 2.1 g of 50% dimethylethanolamine aqueous solution were ultrasonically irradiated for 60 minutes with an ultrasonic disperser (UP400S manufactured by Hielscher), and a PPSU dispersion having a nonvolatile content of 31% was obtained. Obtained. When the dispersed particle diameter of the obtained dispersion was measured by Microtrac-MT3300EX II (manufactured by Nikkiso Co., Ltd.), D 50 = 160 nm. Moreover, even if it left still overnight, the precipitation by visual observation was not seen (no solid-liquid separation).
（実施例２）
　前記実施例１で用いたアニオン性基含有有機高分子化合物　Ｒ－１に代えて、アニオン性基含有有機高分子化合物Ｒ－２　２．２７ｇを用い、また、２５％ＫＯＨの量を０．５９ｇに代えた以外は、実施例１と同条件にてＰＰＳＵ分散体を得た。得られた分散体の分散粒径をＭｉｃｒｏｔｒａｃ－ＭＴ３３００ＥＸ　ＩＩ（日機装株式会社製）で測定したところ、Ｄ５０＝１８２ｎｍであった。また、一晩静置しても目視での沈殿はみられなかった（固液分離なし）。 (Example 2)
Instead of the anionic group-containing organic polymer compound R-1 used in Example 1, 2.27 g of the anionic group-containing organic polymer compound R-2 was used, and the amount of 25% KOH was 0.59 g. A PPSU dispersion was obtained under the same conditions as in Example 1 except that. When the dispersed particle diameter of the obtained dispersion was measured by Microtrac-MT3300EX II (manufactured by Nikkiso Co., Ltd.), D 50 = 182 nm. Moreover, even if it left still overnight, the precipitation by visual observation was not seen (no solid-liquid separation).
（実施例３）
　前記実施例１で用いたアニオン性基含有有機高分子化合物　Ｒ－１に代えて、スチレン－アクリル系樹脂（ジョンクリル６８３、ＢＡＳＦ社製、酸価：１６０ｍｇＫＯＨ／ｇ）　１ｇを用い、また、２５％ＫＯＨの量を０．６４ｇに代えた以外は、実施例１と同条件にてＰＰＳＵ分散体を得た。得られた分散体の分散粒径をＭｉｃｒｏｔｒａｃ－ＭＴ３３００ＥＸ　ＩＩ（日機装株式会社製）で測定したところ、Ｄ５０＝８５ｎｍであった。また、一晩静置しても目視での沈殿はみられなかった（固液分離なし）。 (Example 3)
Instead of the anionic group-containing organic polymer compound R-1 used in Example 1, 1 g of a styrene-acrylic resin (John Clyl 683, manufactured by BASF, acid value: 160 mgKOH / g) was used. A PPSU dispersion was obtained under the same conditions as in Example 1 except that the amount of% KOH was changed to 0.64 g. When the dispersed particle diameter of the obtained dispersion was measured by Microtrac-MT3300EX II (manufactured by Nikkiso Co., Ltd.), D 50 = 85 nm. Moreover, even if it left still overnight, the precipitation by visual observation was not seen (no solid-liquid separation).
（実施例４）
　前記実施例１で用いたＰＰＳＵに代えて、ポリエーテルスルホン（ＰＥＳ）（ＢＡＳＦ社製　Ｕｌｔｒａｓｏｎ　Ｅ－１０１０）を用いた以外は、実施例１と同様にして（実施例１と同様にアニオン性基含有有機高分子化合物としてはＲ－１を使用）、不揮発分３１％のＰＥＳ分散体を得た。得られた分散体の分散粒径を、Ｍｉｃｒｏｔｒａｃ－ＭＴ３３００ＥＸ　ＩＩ（日機装株式会社製）で測定したところ、Ｄ５０＝１６２ｎｍであった。また、一晩静置しても目視での沈殿はみられなかった（固液分離なし）。 Example 4
An anionic group was obtained in the same manner as in Example 1 except that polyethersulfone (PES) (Ultrason E-1010 manufactured by BASF) was used instead of PPSU used in Example 1. R-1 was used as the containing organic polymer compound), and a PES dispersion having a nonvolatile content of 31% was obtained. When the dispersed particle diameter of the obtained dispersion was measured by Microtrac-MT3300EX II (manufactured by Nikkiso Co., Ltd.), it was D 50 = 162 nm. Moreover, even if it left still overnight, the precipitation by visual observation was not seen (no solid-liquid separation).
（実施例５）
　前記実施例４で用いたアニオン性基含有有機高分子化合物　Ｒ－１に代えて、アニオン性基含有有機高分子化合物Ｒ－２　２．２７ｇを用い、また、２５％ＫＯＨの量を０．５９ｇに代えた以外は、実施例４と同条件にてＰＥＳ分散体を得た。得られた分散体の分散粒径をＭｉｃｒｏｔｒａｃ－ＭＴ３３００ＥＸ　ＩＩ（日機装株式会社製）で測定したところ、Ｄ５０＝１８６ｎｍであった。また、一晩静置しても目視での沈殿はみられなかった（固液分離なし）。 (Example 5)
Instead of the anionic group-containing organic polymer compound R-1 used in Example 4, 2.27 g of the anionic group-containing organic polymer compound R-2 was used, and the amount of 25% KOH was 0.59 g. A PES dispersion was obtained under the same conditions as in Example 4 except that. When the dispersed particle diameter of the obtained dispersion was measured with Microtrac-MT3300EX II (manufactured by Nikkiso Co., Ltd.), D 50 = 186 nm. Moreover, even if it left still overnight, the precipitation by visual observation was not seen (no solid-liquid separation).
（実施例６）
　前記実施例４で用いたアニオン性基含有有機高分子化合物　Ｒ－１に代えて、スチレン－アクリル系樹脂（ジョンクリル６８３、ＢＡＳＦ社製、酸価：１６０ｍｇＫＯＨ／ｇ）　１ｇを用い、また、２５％ＫＯＨの量を０．６４ｇに代えた以外は、実施例４と同条件にてＰＥＳ分散体を得た。得られた分散体の分散粒径をＭｉｃｒｏｔｒａｃ－ＭＴ３３００ＥＸ　ＩＩ（日機装株式会社製）で測定したところ、Ｄ５０＝５５ｎｍであった。また、一晩静置しても目視での沈殿はみられなかった（固液分離なし）。 (Example 6)
Instead of the anionic group-containing organic polymer compound R-1 used in Example 4, 1 g of a styrene-acrylic resin (John Clyl 683, manufactured by BASF, acid value: 160 mgKOH / g) was used. A PES dispersion was obtained under the same conditions as in Example 4 except that the amount of% KOH was changed to 0.64 g. When the dispersed particle diameter of the obtained dispersion was measured by Microtrac-MT3300EX II (manufactured by Nikkiso Co., Ltd.), D 50 = 55 nm. Moreover, even if it left still overnight, the precipitation by visual observation was not seen (no solid-liquid separation).
（実施例７）
　前記実施例１で用いたＰＰＳＵに代えて、ポリスルホン（ＰＳＦ）（ＢＡＳＦ社製　Ｕｌｔｒａｓｏｎ　Ｓ－２０１０）を用いた以外は、実施例１と同様にして（実施例１と同様にアニオン性基含有有機高分子化合物としてはＲ－１を使用）、不揮発分３０％のＰＥＳ分散体を得た。得られた分散体の分散粒径を、Ｍｉｃｒｏｔｒａｃ－ＭＴ３３００ＥＸ　ＩＩ（日機装株式会社製）で測定したところ、Ｄ５０＝１７３ｎｍであった。また、一晩静置しても目視での沈殿はみられなかった（固液分離なし）。 (Example 7)
Anionic group-containing organic as in Example 1, except that polysulfone (PSF) (Ultrason S-2010 manufactured by BASF) was used instead of PPSU used in Example 1 above. R-1 was used as the polymer compound), and a PES dispersion having a nonvolatile content of 30% was obtained. When the dispersed particle diameter of the obtained dispersion was measured by Microtrac-MT3300EX II (manufactured by Nikkiso Co., Ltd.), D 50 = 173 nm. Moreover, even if it left still overnight, the precipitation by visual observation was not seen (no solid-liquid separation).
（比較例１）
　前記実施例１において、アニオン性基含有有機高分子化合物水溶液の代わりに、２５％ＫＯＨ水溶液　０．６６ｇと、水　２５００ｇとを混合した水溶液を用いたこと以外は、実施例１と同様の操作を実施したが、酸析出せず、アニオン性基含有有機高分子化合物被覆ＰＰＳＵウェットケーキを作製することができなかった。（分散体作製不可能） (Comparative Example 1)
In Example 1, instead of the anionic group-containing organic polymer compound aqueous solution, the same operation as in Example 1 was used, except that an aqueous solution obtained by mixing 0.66 g of 25% KOH aqueous solution and 2500 g of water was used. Although implemented, acid precipitation did not occur and an anionic group-containing organic polymer compound-coated PPSU wet cake could not be produced. (Dispersion cannot be produced)
（比較例２）
　前記実施例１において、アニオン性基含有有機高分子化合物（Ｒ－１）　２．２２ｇの代わりに、アセチレングリコール系非イオン性界面活性剤であるサーフィノール４６５（エアープロダクツアンドケミカルズ社製）を１．０ｇ使用した以外は、実施例１と同様の操作を実施したが、酸析出せず、アニオン性基含有有機高分子化合物被覆ＰＰＳＵウェットケーキを作製することができなかった。（分散体作製不可能） (Comparative Example 2)
In Example 1, instead of 2.22 g of the anionic group-containing organic polymer compound (R-1), Surfynol 465 (produced by Air Products and Chemicals), which is an acetylene glycol-based nonionic surfactant, is 1 Except for using 0.0 g, the same operation as in Example 1 was performed, but acid precipitation did not occur, and an anionic group-containing organic polymer compound-coated PPSU wet cake could not be produced. (Dispersion cannot be produced)
（比較例３）
　前記実施例４において、アニオン性基含有有機高分子化合物水溶液の代わりに、２５％ＫＯＨ水溶液　０．６６ｇと、水　２５００ｇとを混合した水溶液を用いたこと以外は、実施例４と同様の操作を実施したが、酸析出せず、アニオン性基含有有機高分子化合物被覆ＰＥＳウェットケーキを作製することができなかった。（ＰＥＳ分散体作製不可能） (Comparative Example 3)
In Example 4, the same operation as in Example 4 was used except that an aqueous solution obtained by mixing 0.66 g of 25% KOH aqueous solution and 2500 g of water was used instead of the anionic group-containing organic polymer compound aqueous solution. Although implemented, acid precipitation did not occur and an anionic group-containing organic polymer compound-coated PES wet cake could not be produced. (PES dispersion cannot be produced)
（比較例４）
　前記実施例４において、アニオン性基含有有機高分子化合物（Ｒ－１）　２．２２ｇの代わりに、アセチレングリコール系非イオン性界面活性剤であるサーフィノール４６５（エアープロダクツアンドケミカルズ社製）を１．０ｇ使用した以外は、実施例４と同様の操作を実施したが、酸析出せず、アニオン性基含有有機高分子化合物被覆ＰＥＳウェットケーキを作製することができなかった。（ＰＥＳ分散体作製不可能） (Comparative Example 4)
In Example 4, instead of 2.22 g of the anionic group-containing organic polymer compound (R-1), Surfynol 465 (produced by Air Products and Chemicals), which is an acetylene glycol-based nonionic surfactant, is 1 Except for using 0.0 g, the same operation as in Example 4 was performed, but acid precipitation did not occur, and an anionic group-containing organic polymer compound-coated PES wet cake could not be produced. (PES dispersion cannot be produced)
　本発明のアニオン性基含有有機高分子化合物で被覆された樹脂の粉体粒子及び該粒子からなる分散体は、長期に分散安定性に優れ、さらに樹脂粒子を高濃度に含有するものであるから、塗料用途などにおいても好適に利用可能である。 Since the resin powder particles coated with the anionic group-containing organic polymer compound of the present invention and the dispersion comprising the particles are excellent in dispersion stability over a long period of time and further contain resin particles at a high concentration. Also, it can be suitably used in paint applications.

Claims (13)

  1. ガラス転移温度が１００℃以上であることを特徴とする樹脂からなる群より選ばれる少なくとも一種の樹脂粒子と、アニオン性基含有有機高分子化合物と、塩基と、水性媒体とを含んでなる樹脂分散体において、前記樹脂粒子がアニオン性基含有有機高分子化合物により被覆されていることを特徴とする樹脂分散体。 Resin dispersion comprising at least one resin particle selected from the group consisting of resins having a glass transition temperature of 100 ° C. or higher, an anionic group-containing organic polymer compound, a base, and an aqueous medium A resin dispersion, wherein the resin particles are coated with an anionic group-containing organic polymer compound.
  2. 前記アニオン性基含有有機高分子化合物のアニオン性基が、カルボキシル基、カルボキシレート基、スルホン酸基、スルホネート基及びリン酸基からなる群より選ばれる少なくとも一種のアニオン性基であることを特徴とする請求項１に記載の分散体。 The anionic group of the anionic group-containing organic polymer compound is at least one anionic group selected from the group consisting of a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group, and a phosphoric acid group. The dispersion according to claim 1.
  3. 前記アニオン性基含有有機高分子化合物の主骨格が、（メタ）アクリル酸エステル樹脂、（メタ）アクリル酸エステル－スチレン樹脂、（メタ）アクリル酸エステル－エポキシ樹脂、ビニル樹脂、ウレタン樹脂及びポリアミドイミド樹脂からなる群より選ばれる少なくとも一種の有機高分子化合物であることを特徴とする請求項１または２に記載の分散体。 The main skeleton of the anionic group-containing organic polymer compound is a (meth) acrylic ester resin, (meth) acrylic ester-styrene resin, (meth) acrylic ester-epoxy resin, vinyl resin, urethane resin, and polyamideimide. The dispersion according to claim 1 or 2, which is at least one organic polymer compound selected from the group consisting of resins.
  4. 前記アニオン性基含有有機高分子化合物の酸価が１０～３００ｍｇＫＯＨ／ｇであることを特徴とする請求項１～３いずれか一項に記載の分散体。 The dispersion according to any one of claims 1 to 3, wherein the acid value of the anionic group-containing organic polymer compound is 10 to 300 mgKOH / g.
  5. 前記アニオン性基含有有機高分子化合物において、アニオン性基の中和に用いられる塩基が金属水酸化物及び有機アミンからなる群より選ばれる少なくとも一種の塩基であることを特徴とする請求項１～４いずれか一項に記載の分散体。 In the anionic group-containing organic polymer compound, the base used for neutralization of the anionic group is at least one base selected from the group consisting of metal hydroxides and organic amines. 4. The dispersion according to any one of 4 above.
  6. 前記分散体中の樹脂粒子の分散粒径が１μｍ未満であることを特徴とする請求項１～５いずれか一項に記載の分散体。 The dispersion according to any one of claims 1 to 5, wherein the dispersion particle diameter of the resin particles in the dispersion is less than 1 µm.
  7. ガラス転移温度が１００℃以上である樹脂の微粒子であって、該微粒子がアニオン性基含有有機高分子化合物で被覆されていることを特徴とする微粒子。 A fine particle of a resin having a glass transition temperature of 100 ° C. or more, wherein the fine particle is coated with an anionic group-containing organic polymer compound.
  8. ガラス転移温度が１００℃以上であることを特徴とする樹脂からなる群より選ばれる少なくとも一種の樹脂溶液とアニオン性基含有有機高分子化合物水溶液とを混合し、樹脂微粒子を形成させる工程（Ａ）と、
    工程（Ａ）で得られた樹脂微粒子と酸とを反応させて樹脂微粒子表面にアニオン性基含有有機高分子化合物を析出させてアニオン性基含有有機高分子により被覆された樹脂粒子を沈殿させる工程（Ｂ）と、
    工程（Ｂ）で得られたアニオン性基含有有機高分子により被覆された樹脂粒子をろ別、洗浄し、含水アニオン性基含有有機高分子により被覆された樹脂粒子ウェットケーキを得る工程（Ｃ）と、
    工程（Ｃ）で得られた含水アニオン性基含有有機高分子により被覆された樹脂粒子ウェットケーキと塩基とを反応させてアニオン性基含有有機高分子化合物により被覆された樹脂粒子からなる分散体を得る工程（Ｄ）と、を含む樹脂分散体の製造方法。     Step (A) in which at least one resin solution selected from the group consisting of resins having a glass transition temperature of 100 ° C. or higher and an anionic group-containing organic polymer compound aqueous solution are mixed to form resin fine particles When,
    A step of causing the resin fine particles obtained in the step (A) to react with an acid to precipitate an anionic group-containing organic polymer compound on the surface of the resin fine particles to precipitate resin particles coated with the anionic group-containing organic polymer. (B) and
    The step (C) of obtaining the resin particle wet cake coated with the water-containing anionic group-containing organic polymer by filtering and washing the resin particles coated with the anionic group-containing organic polymer obtained in the step (B). When,
    A dispersion comprising resin particles coated with an anionic group-containing organic polymer compound obtained by reacting the resin particle wet cake coated with the water-containing anionic group-containing organic polymer obtained in the step (C) with a base. And a step (D) for obtaining a resin dispersion.
  9. ガラス転移温度が１００℃以上であることを特徴とする樹脂からなる群より選ばれる少なくとも一種の樹脂溶液とアニオン性基含有有機高分子化合物水溶液とを混合し、樹脂微粒子を形成させる工程（Ａ）と、
    工程（Ａ）で得られた樹脂微粒子と酸とを反応させて樹脂微粒子表面にアニオン性基含有有機高分子化合物を析出させてアニオン性基含有有機高分子により被覆された樹脂粒子を沈殿させる工程（Ｂ）と、
    工程（Ｂ）で得られたアニオン性基含有有機高分子により被覆された樹脂粒子をろ別、洗浄し、含水アニオン性基含有有機高分子により被覆された樹脂粒子ウェットケーキを得る工程（Ｃ）と、
    工程（Ｃ）で得られた含水アニオン性基含有有機高分子により被覆された樹脂粒子ウェットケーキを乾燥してアニオン性基含有有機高分子により被覆された樹脂粉体粒子を得る工程（Ｅ１）と、を含む樹脂粉体粒子の製造方法。     Step (A) in which at least one resin solution selected from the group consisting of resins having a glass transition temperature of 100 ° C. or higher and an anionic group-containing organic polymer compound aqueous solution are mixed to form resin fine particles When,
    A step of causing the resin fine particles obtained in the step (A) to react with an acid to precipitate an anionic group-containing organic polymer compound on the surface of the resin fine particles to precipitate resin particles coated with the anionic group-containing organic polymer. (B) and
    The step (C) of obtaining the resin particle wet cake coated with the water-containing anionic group-containing organic polymer by filtering and washing the resin particles coated with the anionic group-containing organic polymer obtained in the step (B). When,
    A step (E1) of obtaining resin powder particles coated with the anionic group-containing organic polymer by drying the resin particle wet cake coated with the water-containing anionic group-containing organic polymer obtained in the step (C); A method for producing resin powder particles.
  10. ガラス転移温度が１００℃以上であることを特徴とする樹脂からなる群より選ばれる少なくとも一種の樹脂溶液とアニオン性基含有有機高分子化合物水溶液とを混合し、樹脂微粒子を形成させる工程（Ａ）と、
    工程（Ａ）で得られた樹脂微粒子と酸とを反応させて樹脂微粒子表面にアニオン性基含有有機高分子化合物を析出させてアニオン性基含有有機高分子により被覆された樹脂粒子を沈殿させる工程（Ｂ）と、
    工程（Ｂ）で得られたアニオン性基含有有機高分子により被覆された樹脂粒子をろ別、洗浄し、含水アニオン性基含有有機高分子により被覆された樹脂粒子ウェットケーキを得る工程（Ｃ）と、
    工程（Ｃ）で得られた含水アニオン性基含有有機高分子により被覆された樹脂粒子ウェットケーキと塩基とを反応させてアニオン性基含有有機高分子化合物により被覆された樹脂粒子からなる分散体を得る工程（Ｄ）と、
    工程（Ｄ）で得られたアニオン性基含有有機高分子化合物により被覆された樹脂粒子からなる分散体を乾燥してアニオン性基含有有機高分子により被覆された樹脂粉体粒子を得る工程（Ｅ２）と、を含む樹脂粉体粒子の製造方法。     Step (A) in which at least one resin solution selected from the group consisting of resins having a glass transition temperature of 100 ° C. or higher and an anionic group-containing organic polymer compound aqueous solution are mixed to form resin fine particles When,
    A step of causing the resin fine particles obtained in the step (A) to react with an acid to precipitate an anionic group-containing organic polymer compound on the surface of the resin fine particles to precipitate resin particles coated with the anionic group-containing organic polymer. (B) and
    The step (C) of obtaining the resin particle wet cake coated with the water-containing anionic group-containing organic polymer by filtering and washing the resin particles coated with the anionic group-containing organic polymer obtained in the step (B). When,
    A dispersion comprising resin particles coated with an anionic group-containing organic polymer compound obtained by reacting the resin particle wet cake coated with the water-containing anionic group-containing organic polymer obtained in the step (C) with a base. Obtaining step (D);
    A step of drying the dispersion composed of the resin particles coated with the anionic group-containing organic polymer compound obtained in the step (D) to obtain resin powder particles coated with the anionic group-containing organic polymer (E2 And a method for producing resin powder particles.
  11. 前記工程（Ａ）の後に、工程（Ａ）で得られた樹脂微粒子の分散液に対し、機械的粉砕を行うことを特徴とする請求項８に記載の樹脂分散体の製造方法。 9. The method for producing a resin dispersion according to claim 8, wherein after the step (A), the resin fine particle dispersion obtained in the step (A) is mechanically pulverized.
  12. 前記工程（Ａ）の後に、工程（Ａ）で得られた樹脂微粒子の分散液に対し、機械的粉砕を行うことを特徴とする請求項９又は１０に記載の樹脂粉体粒子の製造方法。 The method for producing resin powder particles according to claim 9 or 10, wherein after the step (A), the dispersion of resin fine particles obtained in the step (A) is mechanically pulverized.
  13. 請求項１～６いずれか一項に記載の分散体を用いてなる塗料。 A paint comprising the dispersion according to any one of claims 1 to 6.
PCT/JP2016/062351 2015-04-22 2016-04-19 Resin dispersion, fine particles, and production processes therefor WO2016171121A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2017514126A JPWO2016171121A1 (en) 2015-04-22 2016-04-19 Resin dispersion, fine particles, and production method thereof

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2015-087553 2015-04-22
JP2015-087554 2015-04-22
JP2015087553 2015-04-22
JP2015087554 2015-04-22
JP2015227754 2015-11-20
JP2015-227754 2015-11-20

Publications (1)

Publication Number Publication Date
WO2016171121A1 true WO2016171121A1 (en) 2016-10-27

Family

ID=57143859

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/062351 WO2016171121A1 (en) 2015-04-22 2016-04-19 Resin dispersion, fine particles, and production processes therefor

Country Status (2)

Country Link
JP (1) JPWO2016171121A1 (en)
WO (1) WO2016171121A1 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004010653A (en) * 2002-06-04 2004-01-15 Osaka Prefecture Composite fine particle and method for producing the same
JP2005266317A (en) * 2004-03-18 2005-09-29 Fuji Xerox Co Ltd Electrostatic charge image developing toner, method for manufacturing toner for electrostatic charge image developing toner, electrostatic charge image developer, and image forming method
JP2010006995A (en) * 2008-06-27 2010-01-14 Toray Ind Inc Method for preparing aqueous dispersion liquid of polyphenylene sulfide fine particle
WO2015178105A1 (en) * 2014-05-22 2015-11-26 Dic株式会社 Polyarylene sulfide dispersion, powder particles, method for producing polyarylene sulfide dispersion, and method for producing powder particles

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0977871A (en) * 1995-09-11 1997-03-25 Japan Synthetic Rubber Co Ltd Crystalline polyimide
JP2001323061A (en) * 2000-05-12 2001-11-20 Toray Ind Inc Low-dielectric constant polyimide composition
JP2011014890A (en) * 2009-06-02 2011-01-20 Mitsubishi Chemicals Corp Metal substrate and light source device
JP2011132287A (en) * 2009-12-22 2011-07-07 Dic Corp Method for lowering glass transition temperature of polyarylene sulfide resin and method for producing molded article of polyarylene sulfide resin
JP5843506B2 (en) * 2011-07-13 2016-01-13 ダイセルパックシステムズ株式会社 Manufacturing method of integrally molded body and integrally molded body

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004010653A (en) * 2002-06-04 2004-01-15 Osaka Prefecture Composite fine particle and method for producing the same
JP2005266317A (en) * 2004-03-18 2005-09-29 Fuji Xerox Co Ltd Electrostatic charge image developing toner, method for manufacturing toner for electrostatic charge image developing toner, electrostatic charge image developer, and image forming method
JP2010006995A (en) * 2008-06-27 2010-01-14 Toray Ind Inc Method for preparing aqueous dispersion liquid of polyphenylene sulfide fine particle
WO2015178105A1 (en) * 2014-05-22 2015-11-26 Dic株式会社 Polyarylene sulfide dispersion, powder particles, method for producing polyarylene sulfide dispersion, and method for producing powder particles

Also Published As

Publication number Publication date
JPWO2016171121A1 (en) 2018-03-01

Similar Documents

Publication Publication Date Title
JP6090639B2 (en) Polyarylene sulfide dispersion and powder particles, and production method thereof
KR101643990B1 (en) Process for production of polyamideimide resin microparticles, and polyamideimide resin microparticles
US8563681B2 (en) Process for producing fine polyphenylene sulfide resin particles, fine polyphenylene sulfide resin particles, and dispersion thereof
JP6007992B2 (en) Polyvinylidene fluoride resin particles and method for producing the same
JP5156764B2 (en) Method for producing transparent pigment violet 23
JP5369645B2 (en) Polyphenylene sulfide fine particles, dispersion thereof, and production method thereof
JP5821213B2 (en) Method for producing polyphenylene sulfide resin fine particle dispersion
KR20170097030A (en) Composite phthalocyanine microparticles and method for producing same
WO2016171121A1 (en) Resin dispersion, fine particles, and production processes therefor
JP6274548B2 (en) Polyarylene sulfide dispersion and fine particles, and production method thereof
JP5589373B2 (en) Polyphenylene sulfide resin fine particle dispersion and method for producing the same
WO2016185857A1 (en) Resin dispersion, fine particles and methods for producing same
JP2014005409A (en) Coagulation method of polyphenylene sulfide resin fine particle dispersion
JP2009242498A (en) Coarse particle of polyphenylene sulfide and method of manufacturing fine particle using the same
JPWO2015111546A1 (en) Polyphenylene sulfide resin fine particles, production method thereof and dispersion
JP2017095564A (en) Composite particle dispersed body made of polyarylene sulfide and wholly aromatic linear polymer, powder particle, and methods for producing them
JP2017095563A (en) Composite particle dispersed body made of polyarylene sulfide and wholly aromatic linear polymer, powder particle, and method for producing them
JP2009242499A (en) Manufacturing method of dispersion of polyphenylene sulfide fine particle
JP6977712B2 (en) Polyarylene sulfide composition, its production method and coating film
JP6187273B2 (en) Polyamideimide resin fine particle dispersion and method for producing polyamideimide resin fine particle dispersion
JP2017186391A (en) Electrodeposition coating composition, production process therefor, and electrodeposition coating film
JP2015137324A (en) Method of collecting polyphenylene sulphide resin microparticles by heat concentration

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16783142

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017514126

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16783142

Country of ref document: EP

Kind code of ref document: A1