JP5440611B2 - Resin fine particle water dispersion - Google Patents

Description

  The present invention relates to an aqueous resin fine particle dispersion having heat resistance and suitable as a binder and coating material for paints, adhesives and the like.

  The dispersion of resin fine particles having high heat resistance is used as a highly functional dispersion in the field of paints, adhesives, binders or coating agents.

  Resins with high heat resistance such as polyarylene sulfide and polyamideimide generally tend to have a low affinity with water, and in order to obtain these dispersions, an organic solvent is used as a medium or a surfactant. A method of dispersing in water using a dispersing agent such as is proposed (Patent Documents 1 and 2).

  In recent years, there has been an increasing demand to change the organic solvent conventionally used in the dispersion medium to highly safe water from the viewpoint of environmental protection and occupational safety.

  On the other hand, resin particles made of a thermoplastic elastomer such as an ether ester block copolymer are disclosed in Patent Document 3, which describes use as a thermosetting resin, a photocurable resin, or a varnish.

  Patent Document 4 discloses a resin fine particle dispersion for forming a film. This Patent Document 4 discloses fine particles particularly suitable from the viewpoints of coating film appearance and storage stability, and an appropriate particle size is 250 nm or less as an average particle size.

JP 2007-154166 A JP 2009-67880 A JP 2008-239638 A JP 2007-277497 A

  In aqueous dispersions of resin fine particles, a surfactant is used for dispersion. However, when mixing with paint or varnish, which is the next step in which the dispersion is used, the surfactant is used when mixing. When the agent is in a mixture state, the dispersibility may be deteriorated, or the function of the mixture may not be sufficiently exhibited. It is better that the dispersion of resin fine particles as much as possible does not contain a surfactant or the like.

  In addition, although depending on the use environment, when the particle size is small, dispersibility is ensured, but due to the small particle size, the specific surface area increases and the viscosity of the dispersion increases. In order to reduce the influence, an aqueous dispersion of resin fine particles having a particle diameter of 500 nm or more, further 1 μm or more and good dispersibility is required. In recent years, improvement in heat resistance of resin fine particles has played an important role in the development of new materials in various fields, and further improvement of the dispersion liquid is one of the important issues.

  Under such circumstances, an object of the present invention is to provide an aqueous dispersion of resin fine particles having excellent practicality in which resin fine particles having high heat resistance are dispersed in an aqueous medium with good dispersibility.

  As a result of intensive studies, the present inventors have found that the above object can be achieved by heat-resistant resin fine particles copolymerized with aliphatic polyether units, and have completed the present invention.

That is, the present invention has the following configuration.
[1] Resin fine particles comprising a copolymer containing 10 to 90% by mass of an aliphatic polyether unit, having a melting point of 120 ° C. or higher, a number average particle size of 1 μm to 100 μm, and a particle size distribution index of 1 to 3. A resin fine particle aqueous dispersion characterized by containing
[2] The resin fine particle aqueous dispersion according to [1], wherein the resin fine particle aqueous dispersion does not contain a dispersant, or even if contained, the amount is less than 1 part by mass with respect to 100 parts by mass of the copolymer. ,
[3] The copolymer containing 10 to 90% by mass of an aliphatic polyether unit is a copolymer composed of an aliphatic polyether unit and a crystalline polyester unit [1] or [2] The resin fine particle aqueous dispersion described in 1.

  According to the present invention, it is possible to obtain a very practical aqueous dispersion containing resin fine particles comprising a highly heat-resistant copolymer containing an aliphatic polyether unit. In addition, the resin fine particles comprising the copolymer used in the present invention are well dispersed in water without containing a dispersant. Therefore, an aqueous dispersion having excellent dispersibility can be obtained without using a dispersant. It becomes possible. The resin fine particle aqueous dispersion obtained by the present invention can be used in the field of paints, adhesives, binders or coating agents, and cosmetics applications, and can be applied to aqueousization aimed at reducing the environmental burden of these applications. . In addition, since an aqueous dispersion having good dispersibility can be obtained without using a dispersant, in that case, a highly heat-resistant resin fine particle aqueous dispersion in which coloring and water absorption by the dispersant are suppressed is provided. Is also possible.

The present invention will be described in more detail below.
The resin in the resin fine particle aqueous dispersion in the present invention is characterized by being a copolymer having a melting point of 120 ° C. or higher and containing an aliphatic polyether unit. In particular, by copolymerizing aliphatic polyether units, it has been found that even in heat-resistant resins having a low affinity for water, dispersibility in water is better than in organic solvents. It has been found that a dispersion can be obtained. Since the dispersion medium is water, the organic solvent can be avoided, which is preferable in terms of environmental conservation, and it is possible to improve the working environment in terms of occupational safety. In addition, the aqueous dispersion of the present invention is excellent in dispersibility in water despite having high heat resistance, and therefore has good dispersibility without using a dispersant. Therefore, when a dispersant is not used, it is extremely practical to suppress coloring by the dispersant, deterioration of heat resistance, deterioration of water resistance, adhesion to a substrate, bleeding out to the surface, and occurrence of stickiness. It is also possible to use a simple aqueous dispersion.

  The copolymer used in the present invention is a copolymer containing an aliphatic polyether unit and having a melting point of 120 ° C. or higher. The copolymerization state of the aliphatic polyether unit may be any form such as random copolymerization, block copolymerization, and graft copolymerization, but the block copolymer can suppress a decrease in heat resistance. preferable.

  The aliphatic polyether unit of the present invention is represented by the following general formula (1).

  R represents a divalent aliphatic hydrocarbon group, and specific examples include a linear saturated hydrocarbon group, a branched saturated hydrocarbon group, a linear unsaturated hydrocarbon group, and a branched unsaturated hydrocarbon group. n is the number of repeating units and indicates a positive number. The linear saturated hydrocarbon group, branched saturated hydrocarbon group, linear unsaturated hydrocarbon group, and branched unsaturated hydrocarbon group preferably have 1 to 20 carbon atoms from the viewpoint of excellent dispersibility in water, In particular, it is preferably 1 to 10 carbon atoms.

  Specific examples of the aliphatic polyether unit to be copolymerized include polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, polyhexamethylene glycol, a copolymer of ethylene oxide and propylene oxide, and ethylene oxide addition of polypropylene glycol. And a copolymer of ethylene oxide and tetrahydrofuran. Particularly, it is particularly preferable that R has 1 to 10 carbon atoms, such as polyethylene glycol, polypropylene glycol, polytrimethylene glycol, and polytetramethylene glycol, because it imparts hydrophilicity and facilitates dispersion in water.

  The amount of the aliphatic polyether unit is in the range of 10 to 90% by mass in the copolymer, preferably 15 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 20 to 70% by mass. is there. If the aliphatic polyether unit is less than 10% by mass, the dispersibility of the resin in water deteriorates, which is not preferable. If it exceeds 90% by mass, the heat resistance of the resin is lowered, which is not preferable.

  Although there is no restriction | limiting in particular as a weight average molecular weight of aliphatic polyether, Usually, 500-20,000, Preferably, it is 500-10,000. The weight average molecular weight is a weight average molecular weight measured by gel permeation chromatography (GPC) using dimethylformamide as a solvent and converted to standard polystyrene.

  The resin in the present invention has a melting point of 120 ° C. or higher, preferably 140 ° C. or higher, more preferably 150 ° C. or higher, and particularly preferably 160 ° C. or higher. A melting point of less than 120 ° C. is not preferable because the heat resistance of the coating film and the like is lowered. Although there is no restriction | limiting in particular as an upper limit, It is preferable that it is 300 degrees C or less from the point of the dispersibility to water, and it is more preferable that it is 280 degrees C or less. In addition, melting | fusing point is melting | fusing point measured with the temperature increase rate of 10 degree-C / min using the differential scanning calorimeter.

  The copolymer of the aliphatic polyether unit in the present invention may be copolymerized with other copolymer components without particular limitation as long as the melting point is 120 ° C. or higher. Specific examples of other copolymer components that may be copolymerized include polyester units, polyamide units, polycarbonate units, polyarylene sulfide units, polyether ether ketone units, polyimide units, and monomer units constituting these polymers. Etc. Of these, a block copolymer is preferable, and a unit constituting the block copolymer is preferably a polyester unit or a polyamide unit. A polyester unit is preferable because the heat resistance is maintained even when the ratio of the polyether unit is increased, and a polyester unit that is a polymer unit of an aromatic dicarboxylic acid and a diol is particularly preferable.

  The polyester unit is not particularly limited as long as it has an ester bond in the main chain or side chain, and can be obtained by polycondensation from an acid component and a glycol component.

  Examples of the acid component constituting the polyester unit include terephthalic acid, isophthalic acid, phthalic acid, 2,5-dimethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2 -Bisphenoxyethane-p, p'-dicarboxylic acid, phenylindanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, dimer acid, 1,3-cyclopentanedicarboxylic acid, 1,2- Examples of acid components containing cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof, and sulfonic acid groups and their bases include, for example, sulfoterephthalic acid, 5-sulfoisophthalic acid, 4- Sulfoisophthalic acid, 4-sulfonaphthalene-2, Alkali metal salts such as dicarboxylic acid, sulfo-p-xylylene glycol, 2-sulfo-1,4-bis (hydroxyethoxy) benzene, alkaline earth metal salts, ammonium salts and the like can be used. Two or more types are copolymerized.

Examples of the glycol component constituting the polyester unit include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentane. Diol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4-dimethyl-2-ethylhexane-1, 3-diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2 , 2,4-trimethyl-1,6-hexanediol, 1 , 2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4′-thiodiphenol, Bisphenol A, 4,4′-methylenediphenol, 4,4 ′-(2-norbornylidene) diphenol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, and cyclohexane-1,4-diol Etc. can be used, and these are copolymerized using 1 type, or 2 or more types. These resins can be used alone or in combination of two or more.
In the present invention, among the above, glycol polycondensates of aromatic dicarboxylic acids are preferred from the viewpoint of the heat resistance of the resin. Of these, polyethylene terephthalate, polybutylene terephthalate and the like are preferable from the viewpoint of strength.

  The weight average molecular weight of the copolymer containing the aliphatic polyether of the present invention is not particularly limited, but is usually 1,000 to 100,000, preferably 10,000 to 80,000, more preferably 10,000 to 50,000. The weight average molecular weight is a weight average molecular weight measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent and converted to standard polystyrene.

  The above copolymer containing an aliphatic polyether can be produced by a known method.

  Specific examples include, for example, a method of subjecting a lower alcohol diester of a dicarboxylic acid, an excessive amount of a low molecular weight glycol and a low melting point polymer segment component to a transesterification reaction in the presence of a catalyst, and polycondensing the resulting reaction product, Any method such as a method in which an acid, an excessive amount of glycol and a low melting point polymer segment component are esterified in the presence of a catalyst and the resulting reaction product is polycondensed may be used.

Next, the resin fine particles in the resin fine particle aqueous dispersion of the present invention will be described.
The resin fine particle aqueous dispersion in the present invention refers to a resin fine particle present in a dispersion medium containing water as a medium.

  In this case, the resin fine particle aqueous dispersion is best in a state where the resin fine particles are constantly suspended in the water as the dispersion medium. However, in some cases, the resin fine particles may settle with time, but in the resin fine particle aqueous dispersion in the present invention, the resin fine particles settled by performing mechanical redispersion treatment, Those that can be easily redispersed are also included in the resin fine particle dispersion.

  The number average particle diameter of the resin fine particles in the resin fine particle dispersion is usually 1 to 100 μm, preferably 1 to 50 μm, more preferably 1 to 20 μm. If the number average particle diameter is less than 1 μm, the fine particles are likely to aggregate, and if it exceeds 100 μm, it is not preferable because it settles in water. The number average particle diameter of the resin fine particles is calculated from the following formula (1) by observing 100 arbitrary particles in a scanning electron micrograph and measuring the diameter. When the particle is not a perfect circle, the major axis is measured. The particle size distribution index of the resin fine particles is in the range of 1.0 to 3.0, preferably 1.0 to 2.0, more preferably 1.0 to 1.5. When the particle size distribution index exceeds 3.0, the coating properties when used as a coating agent deteriorate, which is not preferable. The particle size distribution index is calculated by the ratio of the volume average particle size to the number average particle size according to the following formula (3). The volume average particle diameter is calculated from the following formula (2) by observing 100 arbitrary particles in a scanning electron micrograph, measuring the diameter. When the particle is not a perfect circle, the major axis is measured.

  Here, Di: particle size of each particle, n: number of measurement 100, Dn: number average particle size, Dv: volume average particle size, PDI: particle size distribution index.

  The shape of the resin fine particles is preferably a true sphere, but may be an oval sphere.

  As a method for obtaining resin fine particles, any known method may be used. Among them, a method for obtaining fine particles by phase-separating a polymer solution, forming an emulsion, and adding a poor solvent (International Publication No. 2009). / 142231) is preferred.

  For example, the above resin to be microparticulated (hereinafter referred to as polymer A), polymer B dissolved in a poor solvent of polymer A and an organic solvent are dissolved and mixed, and a solution phase containing polymer A as a main component (hereinafter referred to as polymer A solution phase). In a system in which phase separation into two phases of a polymer B as a main component (hereinafter also referred to as a polymer B solution phase), an emulsion is formed, By contacting with a poor solvent, the polymer A can be obtained by such a method.

The above method will be described more specifically.
In the above, “a system in which polymer A, polymer B, and an organic solvent are dissolved and mixed and phase-separated into two phases of a solution phase mainly composed of polymer A and a solution phase mainly composed of polymer B” means a polymer When A, polymer B, and an organic solvent are mixed, the system is divided into two phases, a solution phase mainly containing polymer A and a solution phase mainly containing polymer B.

  By using such a phase-separating system, it is possible to mix and emulsify under a phase-separating condition to form an emulsion.

  In the above, whether or not the polymer is dissolved is more than 1% by mass with respect to the organic solvent at the temperature at which this method is carried out, that is, the temperature at which the polymer A and the polymer B are dissolved and mixed to separate into two phases Judged by whether or not to dissolve.

  This emulsion has a polymer A solution phase as a dispersed phase and a polymer B solution phase as a continuous phase. By contacting the emulsion with a polymer A poor solvent, the polymer A solution phase from the polymer A solution phase in the emulsion is polymerized. A precipitates, and resin fine particles composed of the polymer A can be obtained.

  In this method, polymer A, polymer B, an organic solvent for dissolving them, and a poor solvent for polymer A are used, and the combination thereof is not particularly limited as long as the resin fine particles of this method can be obtained. A refers to a high molecular weight polymer, preferably a synthetic polymer that does not exist in nature, and more preferably a water-insoluble polymer.

  In the present method, the polymer A is preferably insoluble in the poor solvent, since the present method is intended to precipitate fine particles when contacting with the poor solvent, and a polymer that does not dissolve in the poor solvent described later is used. A water-insoluble polymer is particularly preferable.

  Here, the water-insoluble polymer is a polymer having a solubility in water of 1% by mass or less, preferably 0.5% by mass or less, and more preferably 0.1% by mass or less.

  Examples of the polymer B include thermoplastic resins and thermosetting resins, but those that are soluble in an organic solvent that dissolves the polymer A used in the present method and a poor solvent for the polymer A are preferable. And what dissolve | melts in an alcohol solvent or water is more preferable at the point which is excellent in industrial handleability, and also what melt | dissolves in an organic solvent and melt | dissolves in methanol, ethanol, or water is especially preferable.

  If the polymer B is specifically exemplified, poly (vinyl alcohol) (which may be completely saponified or partially saponified poly (vinyl alcohol)), poly (vinyl alcohol-ethylene) copolymer ( Fully saponified or partially saponified poly (vinyl alcohol-ethylene) copolymer), polyvinylpyrrolidone, poly (ethylene glycol), sucrose fatty acid ester, poly (oxyethylene fatty acid ester), poly (Oxyethylene laurin fatty acid ester), poly (oxyethylene glycol monofatty acid ester), poly (oxyethylene alkylphenyl ether), poly (oxyalkyl ether), polyacrylic acid, sodium polyacrylate, polymethacrylic acid, polymethacrylic acid Sodium, polystyrenesulfonic acid, poly Sodium styrenesulfonate, polyvinylpyrrolidinium chloride, poly (styrene-maleic acid) copolymer, aminopoly (acrylamide), poly (paravinylphenol), polyallylamine, polyvinyl ether, polyvinyl formal, poly (acrylamide), poly ( Methacrylamide), poly (oxyethyleneamine), poly (vinyl pyrrolidone), poly (vinyl pyridine), polyaminosulfone, polyethyleneimine, and other synthetic resins, disaccharides such as maltose, cellobiose, lactose, sucrose, cellulose, chitosan, hydroxy Ethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, ethyl hydroxy cellulose, carboxymethyl ethyl cellulose, carboxymethyl cell Cellulose, cellulose derivatives such as sodium carboxymethylcellulose, cellulose ester, amylose and derivatives thereof, starch and derivatives thereof, polysaccharides or derivatives thereof such as dextrin, cyclodextrin, sodium alginate and derivatives thereof, gelatin, casein, collagen, albumin, Examples include fibroin, keratin, fibrin, carrageenan, chondroitin sulfate, gum arabic, agar, protein, etc., preferably poly (vinyl alcohol) (fully saponified or partially saponified poly (vinyl alcohol)) Good), poly (vinyl alcohol-ethylene) copolymer (may be fully saponified or partially saponified poly (vinyl alcohol-ethylene) copolymer), polyethylene glycol, sucrose fatty acid Ester, poly (oxyethylene alkylphenyl ether), poly (oxyalkyl ether), poly (acrylic acid), poly (methacrylic acid), carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, ethylhydroxycellulose, carboxymethyl Cellulose derivatives such as ethyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, cellulose ester, and polyvinyl pyrrolidone, and more preferably poly (vinyl alcohol) (fully saponified or partially saponified poly (vinyl alcohol)). ), Poly (vinyl alcohol-ethylene) copolymer (fully saponified or partially saponified poly (vinyl alcohol-ethylene) Polymer), polyethylene glycol, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, ethylhydroxycellulose, carboxymethylethylcellulose, carboxymethylcellulose, carboxymethylcellulose sodium, cellulose ester, and the like, and polyvinylpyrrolidone, particularly preferred Is poly (vinyl alcohol) (may be fully saponified or partially saponified poly (vinyl alcohol)), poly (ethylene glycol), carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, ethyl Cellulose derivatives such as hydroxycellulose, poly Is Nirupiroridon.

  The molecular weight of the polymer B is preferably 1,000 to 100,000,000, more preferably 1,000 to 10,000,000, and still more preferably 5,000 to 1,000,000 in terms of weight average molecular weight. 000, particularly preferably in the range of 10,000 to 500,000, and most preferably in the range of 10,000 to 100,000.

  The weight average molecular weight here refers to a weight average molecular weight measured by gel permeation chromatography (GPC) using water as a solvent and converted into polyethylene glycol.

  Use dimethylformamide when it cannot be measured with water, use tetrahydrofuran when it cannot be measured with water, and use hexafluoroisopropanol when it cannot be measured with water.

  The organic solvent that dissolves the polymer A and the polymer B is an organic solvent that can dissolve the polymer A and the polymer B to be used, and is selected according to the type of each polymer.

  Specific examples include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, n-decane, n-dodecane, n-tridecane, tetradecane, cyclohexane, cyclopentane, benzene, toluene, xylene, 2- Aromatic hydrocarbon solvents such as methylnaphthalene, ester solvents such as ethyl acetate, methyl acetate, butyl acetate, butyl propionate, butyl butyrate, chloroform, bromoform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, 1 , 1,1-trichloroethane, chlorobenzene, 2,6-dichlorotoluene, halogenated hydrocarbon solvents such as hexafluoroisopropanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl butyl ketone, methanol, ethanol, 1 − Alcohol solvents such as propanol, 2-propanol, N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), propylene carbonate , Aprotic polar solvents such as trimethyl phosphoric acid, 1,3-dimethyl-2-imidazolidinone, sulfolane, carboxylic acid solvents such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, anisole, diethyl ether, tetrahydrofuran, diisopropyl Ether solvents such as ether, dioxane, diglyme, dimethoxyethane, 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium hydrogen sulfate, 1-ethyl-3-imidazolium acetate Ionic liquids or mixtures thereof, such as 1-ethyl-3-methylimidazolium thiocyanate, and the like, the polymer component A to be used is appropriately selected depending on the type of polymer B component. Preferably, an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, a halogenated hydrocarbon solvent, an alcohol solvent, an ether solvent, an aprotic polar solvent, a carboxylic acid solvent, Preferable ones are alcohol solvents, aprotic polar solvents and carboxylic acid solvents which are water-soluble solvents, and extremely preferred are aprotic polar solvents and carboxylic acid solvents, which are easily available and have a wide range. N is most preferable because it can be dissolved in a wide range of polymers, and can be uniformly mixed with a solvent that can be preferably used as a poor solvent to be described later, such as water and alcohol-based solvents. -Methyl-2-pyrrolidone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, propylene carbonate Boneto, formic acid, acetic acid.

  These organic solvents may be used in a plurality of types, or may be used in combination. However, particles having a relatively small particle size and a small particle size distribution can be obtained, and when used solvents are recycled. From the standpoint of reducing the process load in manufacturing, avoiding the troublesome separation step, it is preferable to use a single organic solvent, and it should be a single organic solvent that dissolves both polymer A and polymer B. Is preferred.

  The poor solvent for polymer A in this method refers to a solvent that does not dissolve polymer A. When the solvent is not dissolved, the solubility of the polymer A in the poor solvent is 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.1% by mass or less.

  In this method, a poor solvent for polymer A is used, and the poor solvent is preferably a poor solvent for polymer A and a solvent that dissolves polymer B. Thereby, the polymer fine particle comprised with the polymer A can be precipitated efficiently. Moreover, it is preferable that the solvent for dissolving the polymer A and the polymer B and the poor solvent for the polymer A are solvents that are uniformly mixed.

  The poor solvent in this method varies depending on the type of polymer A to be used, desirably both types of polymers A and B to be used. Specifically, for example, pentane, hexane, heptane, octane, nonane, n -Aliphatic hydrocarbon solvents such as decane, n-dodecane, n-tridecane, tetradecane, cyclohexane, cyclopentane, etc., aromatic hydrocarbon solvents such as benzene, toluene, xylene, 2-methylnaphthalene, ethyl acetate, methyl acetate Ester solvents such as butyl acetate, butyl propionate and butyl butyrate, chloroform, bromoform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, chlorobenzene, 2,6-dichlorotoluene, Halogenated hydrocarbons such as hexafluoroisopropanol Solvent, ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl butyl ketone, alcohol solvent such as methanol, ethanol, 1-propanol, 2-propanol, dimethyl sulfoxide, N, N-dimethylformamide, N, N -Aprotic polar solvents such as dimethylacetamide, trimethylphosphoric acid, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, sulfolane, carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid Examples include acid solvents, ether solvents such as anisole, diethyl ether, tetrahydrofuran, diisopropyl ether, dioxane, diglyme and dimethoxyethane, and a solvent selected from at least one of water.

  From the viewpoint of efficiently atomizing the polymer A, an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, an alcohol solvent, an ether solvent, and water are preferable, and an alcohol solvent, water is most preferable. Particularly preferred is water.

  In this method, polymer A can be efficiently precipitated and resin fine particles can be obtained by appropriately selecting and combining polymer A, polymer B, an organic solvent for dissolving them, and a poor solvent for polymer A.

  At this time, the liquid obtained by mixing and dissolving the polymers A and B and the organic solvent for dissolving them is phase-separated into two phases, a solution phase mainly composed of the polymer A and a solution phase mainly composed of the polymer B. is necessary.

  At this time, the solution-phase organic solvent containing polymer A as the main component and the organic solvent containing polymer B as the main component may be the same or different, but are preferably substantially the same solvent.

  Conditions for generating a state of two-phase separation vary depending on the types of polymers A and B, the molecular weights of polymers A and B, the types of organic solvents, the concentrations of polymers A and B, the temperature and pressure at which this method is performed. come.

  In order to obtain conditions that are likely to cause a phase separation state, it is preferable that the difference between the solubility parameters of the polymer A and the polymer B (hereinafter also referred to as SP values) is separated.

At this time, the difference in SP value is 1 (J / cm ³ ) ^1/2 or more, more preferably 2 (J / cm ³ ) ^1/2 or more, and further preferably 3 (J / cm ³ ) ^1/2 or more. Particularly preferably, it is 5 (J / cm ³ ) ^1/2 or more, and very preferably 8 (J / cm ³ ) ^1/2 or more. When the SP value is within this range, phase separation is easily performed.

There is no particular limitation as long as both polymer A and polymer B can be dissolved in an organic solvent, but the upper limit of the difference in SP value is preferably 20 (J / cm ³ ) ^1/2 or less, more preferably 15 (J / Cm ³ ) ^1/2 or less, more preferably 10 (J / cm ³ ) ^1/2 or less.

  Here, the SP value is calculated based on the Fedor's estimation method, and is calculated based on the cohesive energy density and the molar molecular volume (hereinafter also referred to as a calculation method). ("SP Value Basics / Applications and Calculation Methods" by Hideki Yamamoto, Information Organization Co., Ltd., published on March 31, 2005).

  When the calculation cannot be performed by this estimation method, the SP value is calculated by an experimental method by determining whether or not the solubility parameter is dissolved in a known solvent (hereinafter also referred to as an experimental method). ("Polymer Handbook Fourth Edition" by J. Brand, published in Wiley 1998).

  In order to select the conditions for the phase separation state, a three-component phase diagram can be prepared by a simple preliminary experiment by observing a state in which the ratio of the three components of the polymer A, the polymer B, and the organic solvent in which they are dissolved is changed. Can be distinguished.

  The phase diagram is prepared by mixing and dissolving the polymers A and B and the solvent at an arbitrary ratio and determining whether or not an interface is formed when allowed to stand at least 3 points, preferably 5 points or more. Preferably, the measurement is performed at 10 points or more, and by separating the region that separates into two phases and the region that becomes one phase, the conditions for achieving the phase separation state can be determined.

  At this time, in order to determine whether or not it is in a phase-separated state, the polymers A and B are adjusted to any ratio of the polymers A and B and the solvent at the temperature and pressure at which the present invention is to be carried out. Then, the polymers A and B are completely dissolved, and after the dissolution, the mixture is sufficiently stirred and left for 3 days to confirm whether or not the phase separation is performed macroscopically.

  However, in the case of a sufficiently stable emulsion, macroscopic phase separation may not occur even if left for 3 days. In that case, an optical microscope, a phase contrast microscope, or the like is used to determine the phase separation based on whether or not the phase separation is microscopically.

  The phase separation is formed by separating into a polymer A solution phase mainly composed of polymer A and a polymer B solution phase mainly composed of polymer B in an organic solvent. At this time, the polymer A solution phase is a phase in which the polymer A is mainly distributed, and the polymer B solution phase is a phase in which the polymer B is mainly distributed. At this time, the polymer A solution phase and the polymer B solution phase seem to have a volume ratio corresponding to the types and amounts of the polymers A and B used.

  The concentration of the polymers A and B with respect to the organic solvent is premised on being within a possible range that can be dissolved in the organic solvent. Is more than 1% by mass to 50% by mass, more preferably more than 1% by mass to 30% by mass, and still more preferably 2% by mass to 20% by mass.

  In this method, since the interfacial tension between the two phases of the polymer A solution phase and the polymer B solution phase is an organic solvent in both phases, the interfacial tension is small, and the resulting emulsion can be stably maintained due to its properties. The particle size distribution seems to be smaller. In particular, when the organic solvents of the polymer A phase and the polymer B phase are the same, the effect is remarkable.

Since the interfacial tension between the two phases in this method is too small, it cannot be measured directly by the hanging drop method in which a different kind of solution is added to a commonly used solution. The interfacial tension can be estimated by estimating from the surface tension. When the surface tension of each phase with air is r ₁ and r ₂ , the interfacial tension r ₁₂ can be estimated by an absolute value of r ₁₂ = r ₁ −r ₂ . At this time, a preferable range of r ₁₂ is more than 0 to 10 mN / m, more preferably more than 0 to 5 mN / m, still more preferably more than 0 to 3 mN / m, and particularly preferably 0. Super-2 mN / m.

  The viscosity between the two phases in this method affects the average particle size and particle size distribution, and the smaller the viscosity ratio, the smaller the particle size distribution. When the viscosity ratio is defined as the polymer A solution phase / polymer B solution phase under the temperature conditions for carrying out the present invention, a preferable range is 0.1 or more and 10 or less, and a more preferable range is 0.1. 2 or more and 5 or less, more preferably 0.3 or more and 3 or less, particularly preferably 0.5 or more and 1.5 or less, and remarkably preferable range is 0.8 or more and 1.2 or less. is there.

  Using the phase-separating system thus obtained, resin fine particles are produced. The atomization is performed in a normal reaction tank. The temperature suitable for carrying out the present invention is in the range of −50 ° C. to 200 ° C., preferably −20 ° C. to 150 ° C., more preferably 0 ° C. to 120 ° C. from the viewpoint of industrial feasibility. More preferably, it is 10-100 degreeC, Most preferably, it is 20-80 degreeC, Most preferably, it is the range of 20-50 degreeC. From the viewpoint of industrial feasibility, the pressure suitable for carrying out the present invention is in the range of 100 atm from the reduced pressure state, preferably in the range of 1 to 5 atm, and more preferably in the range of 1 to 2 atm. Atmospheric pressure, particularly preferably atmospheric pressure.

  Under such conditions, an emulsion is formed by mixing the phase separation system state.

  That is, an emulsion is formed by applying a shearing force to the phase separation solution obtained above.

  In forming the emulsion, the emulsion is formed so that the polymer A solution phase becomes particulate droplets. Generally, when the volume of the polymer B solution phase is larger than the volume of the polymer A solution phase after phase separation. The emulsion in such a form tends to be easily formed. In particular, the volume ratio of the polymer A solution phase is preferably 0.4 or less with respect to the total volume 1 of both phases, 0.4 to 0.1 It is preferable to be between. When preparing the phase diagram, it is possible to set an appropriate range by simultaneously measuring the volume ratio in the concentration of each component.

  The resin fine particles obtained by this production method are fine particles having a small particle size distribution because a very uniform emulsion can be obtained at the stage of emulsion formation. This tendency is remarkable when a single solvent that dissolves both the polymers A and B is used. For this reason, in order to obtain a sufficient shearing force to form an emulsion, it is sufficient to use stirring by a conventionally known method, such as a liquid phase stirring method using a stirring blade, a stirring method using a continuous biaxial mixer, or a homogenizer. They can be mixed by a generally known method such as a mixing method or ultrasonic irradiation.

  In particular, in the case of stirring with a stirring blade, although depending on the shape of the stirring blade, the stirring speed is preferably 50 rpm to 1200 rpm, more preferably 100 rpm to 1000 rpm, still more preferably 200 rpm to 800 rpm, and particularly preferably 300 rpm to 600 rpm.

  Specific examples of the stirring blade include a propeller type, a paddle type, a flat paddle type, a turbine type, a double cone type, a single cone type, a single ribbon type, a double ribbon type, a screw type, and a helical ribbon type. However, it is not particularly limited as long as a sufficient shearing force can be applied to the system. Moreover, in order to perform efficient stirring, you may install a baffle plate etc. in a tank.

  In order to generate an emulsion, not only a stirrer but also a widely known device such as an emulsifier and a disperser may be used. Specifically, a batch emulsifier such as a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), Ebara Milder (manufactured by Ebara Seisakusho) , TK fill mix, TK pipeline homomixer (manufactured by Koki Kogyo Co., Ltd.), colloid mill (manufactured by Shinko Pantech Co., Ltd.), slasher, trigonal wet pulverizer (manufactured by Mitsui Miike Chemical Co., Ltd.), ultrasonic homogenizer, static For example, a mixer.

  The emulsion thus obtained is subsequently subjected to a step of precipitating target fine particles.

  In order to obtain the target resin fine particles, the target resin fine particles are deposited with a diameter corresponding to the emulsion diameter by bringing a poor solvent for the polymer A into contact with the emulsion produced in the above-described step.

  The contact method of the poor solvent and the emulsion may be a method of putting the emulsion in the poor solvent or a method of putting the poor solvent in the emulsion, but a method of putting the poor solvent in the emulsion is preferable.

  In this case, the method for introducing the poor solvent is not particularly limited as long as the resin fine particles produced in the present invention can be obtained, and any of a continuous dropping method, a divided addition method, and a batch addition method may be used. In order to prevent the particles from agglomerating, fusing and coalescing to increase the particle size distribution and to easily generate a lump with a size exceeding 1000 μm, the continuous dropping method and the divided dropping method are preferable. For practical implementation, the continuous dropping method is most preferred.

  The time for adding the poor solvent is from 10 minutes to 50 hours, more preferably from 30 minutes to 10 hours, and even more preferably from 1 hour to 5 hours.

  If it is carried out in a time shorter than this range, the particle size distribution may increase with the aggregation, fusion, and coalescence of the emulsion, and a lump may be generated. Moreover, when it implements in the time longer than this, when industrial implementation is considered, it is unrealistic.

  By performing within this time range, aggregation between particles can be suppressed when converting from emulsion to resin fine particles, and resin fine particles having a small particle size distribution can be obtained.

  The amount of the poor solvent to be added depends on the state of the emulsion, but is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and still more preferably, with respect to 1 part by weight of the total emulsion. Is 0.2 to 3 parts by weight, particularly preferably 0.2 to 1 part by weight, and most preferably 0.2 to 0.5 parts by weight.

  The contact time between the poor solvent and the emulsion may be a time sufficient for the fine particles to precipitate, but in order to cause sufficient precipitation and to obtain efficient productivity, 5 minutes to 50 minutes after completion of the addition of the poor solvent. Time, more preferably 5 minutes or more and 10 hours or less, still more preferably 10 minutes or more and 5 hours or less, particularly preferably 20 minutes or more and 4 hours or less, and particularly preferably 30 minutes or more and 3 hours or less. Within hours.

  The resin fine particle dispersion thus prepared is usually known in the art such as filtration, decantation, vacuum filtration, pressure filtration, centrifugation, centrifugal filtration, spray drying, acid precipitation method, salting out method, freeze coagulation method and the like. By performing solid-liquid separation by the method, the fine particle powder can be recovered.

  The resin fine particles separated by solid-liquid separation are purified by washing with a solvent or the like, if necessary, to remove attached or contained impurities and the like. In this case, the preferred solvent is the above poor solvent, and more preferably one or more mixed solvents selected from water, methanol, and ethanol.

  The obtained resin fine particles can be dried to remove the residual solvent. In this case, examples of the drying method include air drying, heat drying, reduced pressure drying, and freeze drying. The temperature for heating is preferably lower than the glass transition temperature, and specifically 50 to 150 ° C is preferable.

  In the method of the present invention, it is advantageous that recycling can be performed by utilizing the organic solvent and polymer B separated in the solid-liquid separation step performed when the resin fine particles are obtained.

  The solvent obtained by solid-liquid separation is a mixture of polymer B, an organic solvent and a poor solvent. By removing the poor solvent from this solvent, it can be reused as a solvent for forming an emulsion. The method for removing the poor solvent is usually performed by a known method, and specific examples include simple distillation, vacuum distillation, precision distillation, thin film distillation, extraction, membrane separation, and the like. This is a method by distillation or precision distillation.

  When performing distillation operations such as simple distillation and vacuum distillation, it is preferable to carry out in a state free from oxygen as much as possible because heat is applied to the system and the thermal decomposition of the polymer B and the organic solvent may be accelerated. Preferably, it is performed under an inert atmosphere. Specifically, it is carried out under nitrogen, helium, argon, carbon dioxide conditions.

Next, a method for producing the resin fine particle aqueous dispersion in the present invention will be described.
The resin fine particles obtained by the above method are dispersed in water as a dispersion medium by using a conventional mixing and dispersing machine (for example, a planetary mixer, three rolls, a mechanical stirrer, a self-revolving mixer, a homomixer, a ball mill, Any of the methods of a bead mill, a sand mill, a roll mill, a homogenizer, an attritor, a resolver, a paint shaker, etc. can be used, and several methods may be combined and adjusted. Moreover, you may perform heating and pressure increase / decrease as needed.

  The amount of the resin fine particles added to the water in the present invention is preferably adjusted according to the use for which the resin fine particle aqueous dispersion is used, but is preferably 80% by mass or less, more preferably 50% by mass or less. Yes, more preferably 30% by mass or less, particularly preferably 20% by mass or less. If it exceeds 80% by mass, the resin fine particles tend to be difficult to disperse, and it is necessary to disperse with a dispersant or the like. The lower limit is not particularly limited and may be set according to the purpose.

  Since the resin fine particles used in the present invention are excellent in dispersibility in water, the resin fine particles can be dispersed in water without using a dispersant as long as it is in the above preferred range.

  Therefore, in the present invention, since a dispersion of resin fine particles can be obtained substantially without using a dispersant, the occurrence of coloring, a decrease in heat resistance, a deterioration in water resistance, a base material due to the influence of the dispersant itself. It can also be used practically when there is a problem of reduced adhesion to the surface, bleed-out to the surface, stickiness, or the like. The aqueous dispersion containing the dispersant is usually used in the case of using the heat-resistant resin fine particles as in the present invention, and the heat treatment condition is usually high, so that coloring caused by the decomposition of the dispersant, etc. May become even more prominent, and adverse effects such as deterioration in design may become very large. Therefore, substantially not containing a dispersant is a great advantage in using the resin fine particle aqueous dispersion.

  The content of the dispersant is less than 1 part by weight, preferably less than 0.2 parts by weight, and most preferably not used, with respect to 100 parts by weight of the resin fine particles.

  The dispersant is not particularly limited as long as the resin fine particles are dispersed in water. For example, a polymer dispersant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant are exemplified. Agents and the like.

  Specific examples of the polymer dispersant include poly (vinyl alcohol) (which may be completely saponified or partially saponified poly (vinyl alcohol)), poly (vinyl alcohol-ethylene) copolymer (completely Saponified or partially saponified poly (vinyl alcohol-ethylene) copolymer), polyvinylpyrrolidone, poly (ethylene glycol), sucrose fatty acid ester, poly (oxyethylene fatty acid ester), poly ( Oxyethylene laurin fatty acid ester), poly (oxyethylene glycol monofatty acid ester), poly (oxyethylene alkylphenyl ether), poly (oxyalkyl ether), polyacrylic acid, sodium polyacrylate, polymethacrylic acid, polysodium methacrylate , Polystyrene sulfonic acid, polystyrene Sodium sulfonate, polyvinylpyrrolidinium chloride, poly (styrene-maleic acid) copolymer, aminopoly (acrylamide), poly (paravinylphenol), polyallylamine, polyvinyl ether, polyvinyl formal, poly (acrylamide), poly (methacrylic) Amide), poly (oxyethyleneamine), poly (vinyl pyrrolidone), poly (vinyl pyridine), polyaminosulfone, polyethylenimine, and other synthetic resins, disaccharides such as maltose, cellobiose, lactose, sucrose, cellulose, chitosan, hydroxyethyl cellulose , Hydroxypropylcellulose, methylcellulose, ethylcellulose, ethylhydroxycellulose, carboxymethylethylcellulose, carboxymethylcellulose Cellulose derivatives such as sodium carboxymethylcellulose and cellulose esters, amylose and derivatives thereof, starch and derivatives thereof, polysaccharides or derivatives thereof such as dextrin, cyclodextrin, sodium alginate and derivatives thereof, gelatin, casein, collagen, albumin, fibroin, keratin , Fibrin, carrageenan, chondroitin sulfate, gum arabic, agar, protein and the like, preferably poly (vinyl alcohol) (may be fully saponified or partially saponified poly (vinyl alcohol)), Poly (vinyl alcohol-ethylene) copolymer (may be fully or partially saponified poly (vinyl alcohol-ethylene) copolymer), polyethylene glycol, sucrose fatty acid ester , Poly (oxyethylene alkylphenyl ether), poly (oxyalkyl ether), poly (acrylic acid), poly (methacrylic acid), carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, ethylhydroxycellulose, carboxymethyl Cellulose derivatives such as ethyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, cellulose ester, and polyvinyl pyrrolidone, and more preferably poly (vinyl alcohol) (fully saponified or partially saponified poly (vinyl alcohol)). ), Poly (vinyl alcohol-ethylene) copolymer (fully saponified or partially saponified poly (vinyl alcohol-ethylene) copolymer ), Polyethylene glycol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, cellulose derivatives such as cellulose esters, and polyvinyl pyrrolidone.

  Specific examples of anionic surfactants include fatty acid sodium, fatty acid potassium, sodium alkylbenzene sulfonate, sodium alkyl naphthalene sulfonate, sodium alkyl sulfate, sodium alkyl sulfonate, sodium alkyl ether sulfate, monoalkyl phosphate, Examples include sodium polyoxyethylene alkyl ether phosphate, sodium fatty acid ester sulfonate, sodium fatty acid ester sulfate, sodium fatty acid alkylose amide sulfate, sodium fatty acid amide sulfonate, and the like.

  Specific examples of the cationic surfactant include alkyl methyl ammonium chloride, alkyl trimethyl ammonium chloride, dialkyl dimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, and alkyl pyridinium chloride.

Specific examples of the zwitterionic surfactant include alkylaminocarboxylates, carboxybetaines, alkylbetaines, sulfobetaines, phosphobetaines, and the like.
Specific examples of the nonionic surfactant include sucrose fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene lanolin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycol monofatty acid ester, polyoxyethylene alkylphenyl Ether, polyoxyethylene monobenzyl phenyl ether, polyoxyethylene dibenzyl phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene monostyryl phenyl ether, polyoxyethylene distyryl phenyl ether, polyoxyethylene tristyryl phenyl ether, Polyoxyethylene biphenyl ether, polyoxyethylene phenoxyphenyl ether, polyoxyethylene cumylf Vinyl ether, polyoxyethylene alkyl ethers, fatty acid alkanolamides, fatty acid monoethanolamide, fatty acid diethanolamide, fatty acid triethanol amide, polyoxyethylene fatty acid amides, isopropanolamides, alkylamine oxides, polyoxyethylene amines. In addition, if alkyl here is illustrated, a C1-C30 linear saturated hydrocarbon group or a branched saturated hydrocarbon group will be mentioned. A linear unsaturated hydrocarbon group or a branched unsaturated hydrocarbon group may be used instead of alkyl.

  In the resin fine particle aqueous dispersion of the present invention, various agents such as a leveling agent, an antifoaming agent, an anti-waxing agent, a pigment dispersant, an ultraviolet absorber and the like, and titanium oxide, as long as the purpose is not impaired In addition, pigments or dyes such as zinc and carbon black may be added.

  The resin fine particle water dispersion of the present invention is well dispersed in water even though it has high heat resistance, so that it can be dispersed well in water. High heat resistance can be imparted in paint applications such as adhesives, ink applications, binder or coating agent applications, and water-based cosmetic applications. In particular, in the case where a dispersant is not substantially used, coloring by a dispersant and a decrease in heat resistance, deterioration of water resistance, adhesion to a base material, bleeding out to the surface, and the occurrence of stickiness can be suppressed. Furthermore, since the dispersion medium is water, the organic solvent can be avoided, so that deterioration of the base material, environmental conservation, improvement of the workplace environment, and the like are possible.

  Next, the present invention will be described in more detail based on examples. The present invention is not limited to these examples. In the examples, the measurements used are as follows.

(1) Measurement of weight average molecular weight The weight average molecular weight was calculated by using a gel permeation chromatography method and comparing it with a calibration curve using polystyrene.
Apparatus: LC-10A series manufactured by Shimadzu Corporation Column: HFIP-806M × 2 manufactured by Showa Denko KK
Mobile phase: hexafluoroisopropanol Flow rate: 0.5 ml / min
Detection: differential refractometer column temperature: 25 ° C.

(2) Number-average particle size, volume average particle size, particle size distribution index calculation method-1
The particles were observed and the number average particle diameter was measured with a scanning electron microscope (scanning electron microscope JSM-6301NF manufactured by JEOL Ltd.). When the particles were not perfect circles, the major axis was measured as the particle diameter.

  The number average particle diameter (Dn) and the volume average particle diameter (Dv) were calculated from the average of 100 arbitrary particles according to the formulas (1) and (2). The particle size distribution index (PDI) was calculated according to Equation (3).

  Here, Di: particle size of each particle, n: number of measurement 100, Dn: number average particle size, Dv: volume average particle size, PDI: particle size distribution index.

(3) Number-average particle size, volume average particle size, particle size distribution index calculation method-2
After adjusting the fine particles to a slurry of 0.1% in ion-exchanged water and subjecting them to ultrasonic treatment that oscillates an ultrasonic wave of 25 kHz and about 100 W for 1 minute, a measurement sample is used, and a laser diffraction particle size distribution analyzer (SALD) -2100: manufactured by Shimadzu Corporation), and the volume average particle diameter and the number average particle diameter were calculated.

(4) Measurement of melting point Robot DSC RDC220 manufactured by Seiko Instruments Inc. was used to measure the top temperature of the melting peak when heated at a heating rate of 10 ° C./min in a nitrogen stream atmosphere.

(5) Evaluation of dispersibility (Dispersion evaluation 1)
The aqueous dispersions of Examples and Comparative Examples were filled in glass sample bottles and allowed to stand at 40 ° C. for 1 hour, and then the separation state of the compositions was visually observed and evaluated according to the following criteria.
○: Separation is not recognized.
X: Separated.
(Dispersion evaluation 2)
The aqueous dispersions of Examples and Comparative Examples were filled in glass sample bottles, and samples that were hardly separated in one minute after sonication were evaluated as “Good”. It was.

(6) Evaluation of coating film appearance (Coating evaluation 1)
The appearance of the coating film was evaluated according to the following criteria.
A: Coloring is not recognized.
○: Slight coloring is observed.
X: Coloring is recognized.
(Coating evaluation 2)
Moreover, the coating film was formed simultaneously and the external appearance was evaluated as follows.
5 g of the resin fine particle aqueous dispersion obtained above was applied to a polyester film (210 mm × 297 mm × 0.1 mm, manufactured by Toray Industries, Inc.) with a bar coater, and then dried with an air dryer at 150 ° C. for 30 minutes. A membrane was obtained. The appearance of the obtained coating film was visually confirmed. Good ones were marked with ◯, and poor ones with x.

(7) Resin used Toray Dupont Co., Ltd .: “Hytrel (registered trademark)” 7247
DuPont Co., Ltd .: “Hytrel (registered trademark)” 8238
Other resins used were polymerized according to the following reference examples.

[Reference Example 1]
10.0 parts of terephthalic acid, 14.0 parts of 1,4-butanediol and 70.0 parts of polytetramethylene glycol having a weight average molecular weight of about 3000, 0.01 parts of titanium tetrabutoxide and mono-n-butyl-monohydroxy 0.005 part of tin oxide was charged into a reaction vessel equipped with a helical ribbon stirring blade, and heated at 190 to 225 ° C. for 3 hours to carry out an esterification reaction while distilling the reaction water out of the system. After adding 0.06 part of tetra-n-butyl titanate to the reaction mixture and adding 0.02 part of “Irganox” 1098 (hindered phenol antioxidant manufactured by Ciba Japan Co., Ltd.), 245 ° C. Then, the pressure in the system was reduced to 30 Pa over 50 minutes, and polymerization was performed for 2 hours and 50 minutes under the conditions to obtain an aliphatic polyether-polyester copolymer. The melting point was 160 ° C., and the weight average molecular weight was 23,000.

[Reference Example 2]
37.3 parts of terephthalic acid, 32.7 parts of 1,4-butanediol and 30.0 parts of polytetramethylene glycol having a weight average molecular weight of about 3000, 0.01 parts of titanium tetrabutoxide and mono-n-butyl-monohydroxy 0.005 part of tin oxide was charged into a reaction vessel equipped with a helical ribbon stirring blade, and heated at 190 to 225 ° C. for 3 hours to carry out an esterification reaction while distilling the reaction water out of the system. After adding 0.06 part of tetra-n-butyl titanate to the reaction mixture and adding 0.02 part of “Irganox” 1098 (hindered phenol antioxidant manufactured by Ciba Japan Co., Ltd.), 245 ° C. Then, the pressure in the system was reduced to 30 Pa over 50 minutes, and polymerization was performed for 2 hours and 50 minutes under the conditions to obtain an aliphatic polyether-polyester copolymer. The melting point was 221 ° C. and the weight average molecular weight was 26,000.

[Reference Example 3]
42.7 parts of terephthalic acid, 37.3 parts of 1,4-butanediol and 20.0 parts of polytetramethylene glycol having a weight average molecular weight of about 3000, 0.01 parts of titanium tetrabutoxide and mono-n-butyl-monohydroxy 0.005 part of tin oxide was charged into a reaction vessel equipped with a helical ribbon stirring blade, and heated at 190 to 225 ° C. for 3 hours to carry out an esterification reaction while distilling the reaction water out of the system. After adding 0.06 part of tetra-n-butyl titanate to the reaction mixture and adding 0.02 part of “Irganox” 1098 (hindered phenol antioxidant manufactured by Ciba Japan Co., Ltd.), 245 ° C. Then, the pressure in the system was reduced to 30 Pa over 50 minutes, and polymerization was performed for 2 hours and 50 minutes under the conditions to obtain an aliphatic polyether-polyester copolymer. The melting point was 228 ° C., and the weight average molecular weight was 25,000.

(8) Production of resin fine particles Each resin fine particle was produced based on the following production example.

[Production Example 1]
In a 100 ml four-necked flask, 3.5 g of the aliphatic polyether-polyester copolymer (weight average molecular weight 23,000) prepared in Reference Example 1, 43 g of N-methyl-2-pyrrolidone as an organic solvent, polyvinyl alcohol (Japan Synthetic Chemical Industry Co., Ltd. 'GOHSENOL (registered trademark)' GL-05) (3.5 g) was added, heated to 90 ° C., and stirred until the polymer was dissolved. After returning the temperature of the system to 80 ° C., 50 g of ion-exchanged water as a poor solvent was dropped at a speed of 0.41 g / min via a liquid feed pump while stirring at 450 rpm. After the entire amount of water had been added, the mixture was stirred for 30 minutes, and the resulting suspension was filtered, washed with 100 g of ion-exchanged water, and vacuum-dried at 80 ° C. for 10 hours to obtain 3.1 g of a white solid. . When the obtained powder was observed with a scanning electron microscope, it was true spherical fine particles, and was polyether-polyester copolymer fine particles having a volume average particle size of 15.4 μm and a particle size distribution index of 1.17.

[Production Example 2]
Polyester elastomer “Hytrel (registered trademark)” 7247 (made by Toray DuPont Co., Ltd.), which is an aliphatic polyether-polyester copolymer, in a 1000 ml pressure-resistant glass autoclave (pressure-resistant glass industry, HyperGlaster TEM-V1000N) , Weight average molecular weight 29,000) 28 g, N-methyl-2-pyrrolidone (Kanto Chemical Co., Ltd.) 304.5 g, polyvinyl alcohol (Wako Pure Chemical Industries, Ltd. PVA-1500, weight average molecular weight 29,000: methanol 17.5 g of the sodium acetate content reduced to 0.05 mass% by washing with (2), and after nitrogen substitution, the mixture was heated to 180 ° C. and stirred for 4 hours until the polymer was dissolved. Thereafter, 350 g of ion-exchanged water as a poor solvent was dropped at a speed of 2.92 g / min via a liquid feed pump. After the entire amount of water has been added, the temperature is lowered while stirring, and the resulting suspension is filtered, washed with 700 g of ion exchange water and reslurried, and the filtered product is vacuum dried at 80 ° C. for 10 hours. 26.5 g of a white solid was obtained. When this white solid was observed with a scanning electron microscope, it had a volume average particle size of 5.5 μm and a particle size distribution index of 1.12. At the same time, the white solid was analyzed with a laser particle size distribution analyzer (SALD-2100, manufactured by Shimadzu Corporation). As a result, a polyether-polyester copolymer having a volume average particle size of 5.5 μm and a particle size distribution index of 1.12. It was fine particles.

[Production Example 3]
Polyester elastomer “Hytrel (registered trademark)” 7247 (produced by Toray DuPont Co., Ltd.), an aliphatic polyether-polyester copolymer, in a 1000 ml pressure-resistant glass autoclave (pressure-resistant glass industry, HyperGlaster TEM-V1000N) , 28 g of weight average molecular weight 29,000, 308 g of N-methyl-2-pyrrolidone (manufactured by Kanto Chemical Co., Inc.), PVA-1500 (manufactured by Wako Pure Chemical Industries, Ltd.), weight average molecular weight 29,000 in methanol After washing, 14 g of the sodium acetate content reduced to 0.05% by mass was replaced with nitrogen, heated to 180 ° C., and stirred for 4 hours until the polymer was dissolved. Thereafter, 350 g of ion-exchanged water as a poor solvent was dropped at a speed of 2.92 g / min via a liquid feed pump. After the entire amount of water has been added, the temperature is lowered while stirring, and the resulting suspension is filtered, washed with 700 g of ion exchange water and reslurried, and the filtered product is vacuum dried at 80 ° C. for 10 hours. 25.5 g of a white solid was obtained. When this white solid was observed with a scanning electron microscope, it had a volume average particle size of 8.6 μm and a particle size distribution index of 1.22. At the same time, as a result of analysis with a laser particle size distribution analyzer (SALD-2100, manufactured by Shimadzu Corporation), it was a polyether-polyester copolymer fine particle having a volume average particle size of 8.6 μm and a particle size distribution index of 1.22. .

[Production Example 4]
Polyester elastomer “Hytrel (registered trademark)” 7247 (produced by Toray DuPont Co., Ltd.), an aliphatic polyether-polyester copolymer, in a 1000 ml pressure-resistant glass autoclave (pressure-resistant glass industry, HyperGlaster TEM-V1000N) , Weight average molecular weight 29,000) 28 g, N-methyl-2-pyrrolidone (manufactured by Kanto Chemical Co., Inc.) 301 g, polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., PVA-1500, weight average molecular weight 29,000 in methanol) After washing, 10.5 g of the sodium acetate content reduced to 0.05% by mass was replaced with nitrogen, heated to 180 ° C., and stirred for 4 hours until the polymer was dissolved. Thereafter, 350 g of ion-exchanged water as a poor solvent was dropped at a speed of 2.92 g / min via a liquid feed pump. After the entire amount of water has been added, the temperature is lowered while stirring, and the resulting suspension is filtered, washed with 700 g of ion exchange water and reslurried, and the filtered product is vacuum dried at 80 ° C. for 10 hours. As a result, 26.0 g of a white solid was obtained. When this white solid was observed with a scanning electron microscope, it had a volume average particle size of 12.6 μm and a particle size distribution index of 1.22. At the same time, as a result of analysis with a laser particle size distribution analyzer (SALD-2100 manufactured by Shimadzu Corporation), it was a polyether-polyester copolymer fine particle having a volume average particle size of 12.5 μm and a particle size distribution index of 1.28. .

[Production Example 5]
Polyester elastomer “Hytrel (registered trademark)” 8238 (manufactured by DuPont Co., Ltd., weight) in a 1000 ml pressure-resistant glass autoclave (pressure-resistant glass industry, HyperGlaster TEM-V1000N). (Average molecular weight 27,000) 17.5 g, N-methyl-2-pyrrolidone (Kanto Chemical Co., Ltd.) 315 g, polyvinyl alcohol (Wako Pure Chemical Industries, Ltd. PVA-1500, weight average molecular weight 29,000 in methanol) 17.5 g) (sodium acetate content was reduced to 0.05% by washing) was replaced with nitrogen, heated to 180 ° C., and stirred for 4 hours until the polymer was dissolved. Thereafter, 350 g of ion-exchanged water as a poor solvent was dropped at a speed of 2.92 g / min via a liquid feed pump. After the entire amount of water has been added, the temperature is lowered while stirring, and the resulting suspension is filtered, washed with 700 g of ion exchange water and reslurried, and the filtered product is vacuum dried at 80 ° C. for 10 hours. 14.9 g of a white solid was obtained. When the obtained powder was observed with a scanning electron microscope, it was true spherical fine particles, and was polyether-polyester copolymer fine particles having a volume average particle size of 4.3 μm and a particle size distribution index of 1.25. At the same time, as a result of analysis with a laser particle size distribution analyzer (SALD-2100 manufactured by Shimadzu Corporation), it was a polyether-polyester copolymer fine particle having a volume average particle size of 5.4 μm and a particle size distribution index of 1.25. .

[Production Example 6]
Polyester elastomer “Hytrel (registered trademark)” 8238 (manufactured by DuPont Co., Ltd., weight) in a 1000 ml pressure-resistant glass autoclave (pressure-resistant glass industry, HyperGlaster TEM-V1000N). (Average molecular weight 27,000) 33.25 g, N-methyl-2-pyrrolidone (Kanto Chemical Co., Ltd.) 299.25 g, polyvinyl alcohol (Wako Pure Chemical Industries, Ltd. PVA-1500, weight average molecular weight 29,000: methanol 17.5 g of the sodium acetate content reduced to 0.05 mass% by washing with (2), and after nitrogen substitution, the mixture was heated to 180 ° C. and stirred for 4 hours until the polymer was dissolved. Thereafter, 350 g of ion-exchanged water as a poor solvent was dropped at a speed of 2.92 g / min via a liquid feed pump. After the entire amount of water has been added, the temperature is lowered while stirring, and the resulting suspension is filtered, washed with 700 g of ion exchange water and reslurried, and the filtered product is vacuum dried at 80 ° C. for 10 hours. As a result, 28.3 g of a white solid was obtained. When the obtained powder was observed with a scanning electron microscope, it was true spherical fine particles, and was polyether-polyester copolymer fine particles having a volume average particle size of 12.0 μm and a particle size distribution index of 1.23. At the same time, as a result of analysis by a laser particle size distribution meter (SALD-2100, manufactured by Shimadzu Corporation), it was a polyether-polyester copolymer fine particle having a volume average particle size of 14.7 μm and a particle size distribution index of 1.23. .

[Production Example 7]
In a 1000 ml pressure-resistant glass autoclave (pressure-resistant glass industry, Hyper Glaster TEM-V1000N), 17.5 g of the aliphatic polyether-polyester copolymer obtained in Reference Example 2 and N-methyl-2-pyrrolidone 315 0.0 g, 17.5 g of polyvinyl alcohol (PVA-1500, manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 29,000: sodium acetate content reduced to 0.05% by washing with methanol), After carrying out nitrogen substitution, it heated at 180 degreeC and stirred for 4 hours until the polymer melt | dissolved. Thereafter, 350 g of ion-exchanged water as a poor solvent was dropped at a speed of 2.92 g / min via a liquid feed pump. After the entire amount of water has been added, the temperature is lowered while stirring, and the resulting suspension is filtered, washed with 700 g of ion exchange water and reslurried, and the filtered product is vacuum dried at 80 ° C. for 10 hours. As a result, 17.0 g of a white solid was obtained. When the obtained powder was observed with a scanning electron microscope, it was true spherical fine particles, and was polyether-polyester copolymer fine particles having a volume average particle size of 11.4 μm and a particle size distribution index of 1.29.

[Production Example 8]
17.5 g of the aliphatic polyether-polyester copolymer obtained in Reference Example 3 and N-methyl-2-pyrrolidone 350 in a 1000 ml pressure-resistant glass autoclave (Pressure Glass Industrial Co., Ltd., Hyperglaster TEM-V1000N). 0.0 g, 17.5 g of polyvinyl alcohol (PVA-1500, manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 29,000: sodium acetate content reduced to 0.05% by washing with methanol), After carrying out nitrogen substitution, it heated at 180 degreeC and stirred for 4 hours until the polymer melt | dissolved. Thereafter, 350 g of ion-exchanged water as a poor solvent was dropped at a speed of 2.92 g / min via a liquid feed pump. After the entire amount of water has been added, the temperature is lowered while stirring, and the resulting suspension is filtered, washed with 700 g of ion exchange water and reslurried, and the filtered product is vacuum dried at 80 ° C. for 10 hours. As a result, 17.0 g of a white solid was obtained. When the obtained powder was observed with a scanning electron microscope, it was true spherical fine particles, and was polyether-polyester copolymer fine particles having a volume average particle size of 4.3 μm and a particle size distribution index of 1.30.

[Production Example 9]
In a 1000 ml pressure-resistant glass autoclave (Pressure Glass Industry Co., Ltd., Hyperglaster TEM-V1000N), 28.0 g of the aliphatic polyether-polyester copolymer obtained in Reference Example 3 and N-methyl-2-pyrrolidone 308 0.0 g, 17.5 g of polyvinyl alcohol (PVA-1500, manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 29,000: sodium acetate content reduced to 0.05% by washing with methanol), After carrying out nitrogen substitution, it heated at 180 degreeC and stirred for 4 hours until the polymer melt | dissolved. Thereafter, 350 g of ion-exchanged water as a poor solvent was dropped at a speed of 2.92 g / min via a liquid feed pump. After the entire amount of water has been added, the temperature is lowered while stirring, and the resulting suspension is filtered, washed with 700 g of ion exchange water and reslurried, and the filtered product is vacuum dried at 80 ° C. for 10 hours. As a result, 26.0 g of a white solid was obtained. When the obtained powder was observed with a scanning electron microscope, it was true spherical fine particles, and was polyether-polyester copolymer fine particles having a volume average particle size of 12.3 μm and a particle size distribution index of 1.31.

[Examples 1 to 10, Comparative Examples 1 to 4] <Adjustment and Evaluation of Resin Fine Particle Dispersion>
Using the resin fine particles obtained in Production Examples 1 to 9, the following typical examples were used to prepare resin fine particle dispersions and evaluate the characteristics.

Further, as a comparative example, in addition to the case where the medium was ethyl acetate, a resin fine particle dispersion was prepared using the resin fine particles shown below, and compared with the dispersion obtained in the examples.
<Resin fine particles used for comparison>
Nylon 12 fine particles (Orgasol, melting point 170 ° C by Arkema)

[Example 1]
20 parts by mass of the polyether-polyester block copolymer resin fine particles prepared in Production Example 1 were put into 80 parts by mass of water, and subjected to 25 KHz ultrasonic treatment for 1 minute to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was observed.

[Example 2]
20 parts by mass of the polyether-polyester block copolymer resin fine particles produced in Production Example 1 were added to 80 parts by mass of water, and 0.15 part by mass of Triton X-100 (manufactured by Aldrich) was added as a dispersant. Ultrasonic treatment was performed in the same manner as in Example 1 to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was observed.

[Example 3]
When a 40% by mass aqueous dispersion of the polyether-polyester block copolymer resin fine particles prepared in Production Example 2 was prepared, it was well dispersed. To 50 parts by mass of this aqueous dispersion, 50 parts by mass of water was added, and 25 KHz ultrasonic treatment was performed for 1 minute to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was observed.

[Example 4]
When a 40% by mass aqueous dispersion of the polyether-polyester block copolymer resin fine particles prepared in Production Example 3 was prepared, it was well dispersed. To 50 parts by mass of this aqueous dispersion, 50 parts by mass of water was added, and 25 KHz ultrasonic treatment was performed for 1 minute to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was observed.

[Example 5]
When a 40% by mass aqueous dispersion of the polyether-polyester block copolymer resin fine particles prepared in Production Example 4 was prepared, it was dispersed. To 50 parts by mass of this aqueous dispersion, 50 parts by mass of water was added, and 25 KHz ultrasonic treatment was performed for 1 minute to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was observed.

[Example 6]
When a 40% by mass aqueous dispersion of the polyether-polyester block copolymer resin fine particles prepared in Production Example 5 was prepared, it was dispersed. To 50 parts by mass of this aqueous dispersion, 50 parts by mass of water was added, and 25 KHz ultrasonic treatment was performed for 1 minute to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was observed.

[Example 7]
When a 40% by mass aqueous dispersion of the polyether-polyester block copolymer resin fine particles prepared in Production Example 6 was prepared, it was dispersed. To 50 parts by mass of this aqueous dispersion, 50 parts by mass of water was added, and 25 KHz ultrasonic treatment was performed for 1 minute to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was observed.

[Example 8]
When a 40% by mass aqueous dispersion of the polyether-polyester block copolymer resin fine particles prepared in Production Example 7 was prepared, it was dispersed. To 50 parts by mass of this aqueous dispersion, 50 parts by mass of water was added, and 25 KHz ultrasonic treatment was performed for 1 minute to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was observed.

[Example 9]
When a 40% by mass aqueous dispersion of the polyether-polyester block copolymer resin fine particles produced in Production Example 8 was prepared, it was dispersed. To 50 parts by mass of this aqueous dispersion, 50 parts by mass of water was added, and 25 KHz ultrasonic treatment was performed for 1 minute to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was observed.

[Example 10]
When a 40% by mass aqueous dispersion of the polyether-polyester block copolymer resin fine particles produced in Production Example 9 was prepared, it was dispersed. To 50 parts by mass of this aqueous dispersion, 50 parts by mass of water was added, and 25 KHz ultrasonic treatment was performed for 1 minute to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was observed.

[Comparative Example 1]
20 parts by mass of the polyether-polyester block copolymer resin fine particles prepared in Production Example 1 were added to 80 parts by mass of ethyl acetate, and subjected to ultrasonic treatment in the same manner as Example 1 to obtain a dispersion. As a result of evaluation of dispersibility, they were separated.

[Comparative Example 2]
20 parts by mass of commercially available nylon 12 fine particles (Orgasol, melting point 170 ° C., manufactured by Arkema Co., Ltd.) were added to 80 parts by mass of water, and 0.15 part by mass of Triton X-100 (manufactured by Aldrich) was added as a dispersant. In the same manner as above, ultrasonic treatment was performed to obtain an aqueous dispersion. As a result of evaluating water dispersibility, it was separated.

[Comparative Example 3]
20 parts by mass of commercially available nylon 12 fine particles (Orgasol, melting point 170 ° C., manufactured by Arkema Co.) were added to 80 parts by mass of water, and 1 part by mass of Triton X-100 (manufactured by Aldrich) was added as a dispersant. Was subjected to ultrasonic treatment to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was observed.

[Comparative Example 4]
20 parts by mass of commercially available nylon 12 fine particles (Orgasol, melting point 170 ° C., manufactured by Arkema Co., Ltd.) were added to 80 parts by mass of ethyl acetate and subjected to ultrasonic treatment in the same manner as in Example 1 to obtain a dispersion. As a result of evaluating dispersibility, almost no separation was observed.
The results of the above examples and comparative examples are shown in Table 1.

  In Comparative Example 1, ethyl acetate was used as a dispersion medium, but it was not dispersed and the dispersibility was poor.

  In Comparative Example 2, although the resin does not have an aliphatic polyether unit, the resin fine particles were not dispersed.

<Evaluation of dispersibility>
From Examples 1 to 10 and Comparative Example 1, it can be seen that the resin fine particles copolymerized with aliphatic polyether units are well dispersed in water even under a condition not containing a dispersant. On the other hand, it can be seen from Example 2 and Comparative Examples 2 to 4 that resin fine particles not containing an aliphatic polyether unit are dispersed only in water containing more organic solvent or dispersant.

<Evaluation of the appearance of the coating film>
By using the resin fine particle aqueous dispersion of the present invention from Examples 1 to 10 and Comparative Example 3, it is possible to obtain a coating film having a good appearance and prevented from being colored by the dispersant.

Claims (3)

Containing a resin fine particle comprising a copolymer containing 10 to 90% by mass of an aliphatic polyether unit, having a melting point of 120 ° C. or higher, a number average particle size of 1 μm to 100 μm, and a particle size distribution index of 1 to 3. An aqueous dispersion of fine resin particles characterized by   2. The resin fine particle aqueous dispersion according to claim 1, wherein the resin fine particle aqueous dispersion does not contain a dispersant or is contained in an amount of less than 1 part by mass with respect to 100 parts by mass of the copolymer. The resin according to claim 1 or 2 , wherein the copolymer containing 10 to 90% by mass of an aliphatic polyether unit is a copolymer comprising an aliphatic polyether unit and a crystalline polyester unit. Fine particle dispersion.