KR101372054B1 - Aqueous dispersion of fine resin particles - Google Patents

Abstract

According to the present invention, the number of fine resin particles is characterized by comprising a copolymer containing 10 to 90 mass% of aliphatic polyether units, and comprising a resin fine particle having a melting point of 120 ° C. or higher and an average particle diameter of 1 μm or more and 100 μm or less. Provide a dispersion. It is especially effective when a dispersing agent is less than 1 mass part with respect to 100 mass parts of copolymers, and does not contain a dispersing agent. Moreover, it is preferable that they are microparticles | fine-particles whose particle size distribution index is 1-3. According to this invention, it becomes possible to obtain the very practical aqueous dispersion containing the resin fine particle which consists of a copolymer with high heat resistance containing an aliphatic polyether unit.

Description

Resin Particulate Water Dispersion {AQUEOUS DISPERSION OF FINE RESIN PARTICLES}

This invention relates to the resin fine particle aqueous dispersion liquid which has heat resistance, and is suitable as a binder, such as a coating material and an adhesive agent, and a coating material.

Dispersions of resin particles having high heat resistance are used in paints, adhesives, binders or coatings as high-performance dispersions.

Heat-resistant resins such as polyarylene sulfide and polyamideimide generally tend to have low affinity with water, and in order to obtain these dispersions, organic solvents are used as a medium, or dispersants such as surfactants are used in water. The method of making it disperse is proposed (patent document 1, 2).

In recent years, the demand for changing the organic solvent conventionally used for a dispersion medium into highly stable water from a viewpoint of environmental conservation and labor safety has become very high.

On the other hand, the resin particle which consists of thermoplastic elastomers, such as an ether ester block copolymer, is disclosed by patent document 3, and what is used for a thermosetting resin, a photocurable resin, a varnish, etc. is described.

In addition, Patent Document 4 discloses a resin fine particle dispersion for forming a film. This patent document 4 especially discloses preferable microparticles | fine-particles from a viewpoint of a coating film external appearance and storage stability, The particle size suitable for it is 250 nm or less as an average particle diameter.

Japanese Patent Publication No. 2007-154166 Japanese Patent Publication No. 2009-67880 Japanese Patent Application Laid-Open No. 2008-239638 Japanese Patent Publication No. 2007-277497

In the aqueous dispersion of the resin fine particles, a surfactant is used for dispersion, and when mixed with a paint or a varnish, which is the next step in which the dispersion is used, dispersibility when the surfactant becomes a mixture when mixed is worsened. In some cases, the mixture may not be able to fully function. It is better that a surfactant etc. do not enter a dispersion liquid of resin fine particles as much as possible.

In addition, although depending on the use environment, when the particle size is small, dispersibility is ensured, but the problem that the specific surface area is increased and the viscosity of the dispersion is increased may be caused by the smaller particle size, and in order to reduce the influence, the particle size is 500 nm. Furthermore, an aqueous dispersion of resin fine particles having a dispersibility of 1 µm or more and having good dispersibility is required. In recent years, the improvement of the heat resistance of resin fine particles plays an important role in the development of new materials in various fields, and the improvement of the dispersion is one of the important problems.

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

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors discovered that the said objective can be achieved by the heat resistant resin microparticles | fine-particles which copolymerized an aliphatic polyether unit, and completed this invention.

That is, this invention has the following structure.

[1] A resin fine particle aqueous dispersion comprising a copolymer containing 10 to 90 mass% of aliphatic polyether units, the resin having a melting point of 120 ° C. or higher and a number average particle diameter of 1 μm or more and 100 μm or less. ,

[2] The aqueous resin fine particle dispersion according to [1], wherein the aqueous resin fine particle dispersion contains no dispersant or is less than 1 part by mass based on 100 parts by mass of the copolymer,

[3] The resin fine particle aqueous dispersion according to [1] or [2], wherein the particle size distribution index is fine particles having 1 to 3;

[4] The resin fine particle according to any one of [1] to [3], wherein the copolymer containing 10 to 90 mass% of aliphatic polyether units is a copolymer comprising an aliphatic polyether unit and a crystalline polyester unit. It is an aqueous dispersion.

According to this invention, it becomes possible to obtain the very practical aqueous dispersion containing the resin fine particle which consists of a copolymer with high heat resistance containing an aliphatic polyether unit. Moreover, since the resin fine particle which consists of a copolymer used by this invention disperse | distributes well to water, without including a dispersing agent substantially, it becomes possible to obtain the aqueous dispersion excellent in dispersibility, without using a dispersing agent. The resin fine particle aqueous dispersion obtained by the present invention can be used in the fields of paint, adhesives, binders or coatings, cosmetics, and can also be applied to aqueous solution aimed at reducing the environmental load of these applications. Moreover, since it can be set as the aqueous dispersion liquid with a good dispersibility, even if a dispersing agent is not used, it becomes possible to provide the high heat resistant resin fine particle aqueous dispersion which suppressed coloring and absorption by a dispersing agent.

Hereinafter, the present invention will be described in more detail.

The resin in the aqueous resin fine particle dispersion in the present invention is characterized by being a copolymer having a melting point of 120 ° C. or more and containing an aliphatic polyether unit. Especially by copolymerizing an aliphatic polyether unit, it turned out that the dispersibility to water is more favorable than an organic solvent also in the heat resistant resin which has low affinity with water generally, and discovered that the aqueous dispersion which was excellent in dispersibility was obtained. Since the dispersion medium is water, organic solvents can be avoided, which is preferable in terms of environmental preservation, and it is possible to improve the working environment for labor safety. In addition, the aqueous dispersion of the present invention has excellent heat dissipation without using a dispersant because of its excellent heat dissipation, even though it has high heat resistance. Therefore, when not using a dispersing agent, it is also possible to set it as the very practical aqueous dispersion which suppressed coloring by the dispersing agent, the fall of heat resistance, deterioration of water resistance, the fall of adhesiveness to a base material, the bleeding out to the surface, and stickiness.

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

The aliphatic polyether unit of this invention is represented by following General formula (1).

R represents a divalent aliphatic hydrocarbon group, and specific examples thereof include a straight chain saturated hydrocarbon group, a branched saturated hydrocarbon group, a straight chain unsaturated hydrocarbon group and a branched unsaturated hydrocarbon group. n is a repeating unit number and represents a positive number. As said linear saturated hydrocarbon group, branched saturated hydrocarbon group, linear unsaturated hydrocarbon group, and branched unsaturated hydrocarbon group, C1-C20 is preferable at the point which is more excellent in dispersibility to water, and it is especially preferable that it is C1-C10.

Specific examples of the aliphatic polyether units to be copolymerized include polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, polyhexamethylene glycol, copolymers of ethylene oxide and propylene oxide, and ethylene oxide addition of polypropylene glycol. Water, copolymers of ethylene oxide and tetrahydrofuran, and the like. It is especially preferable that carbon number of R, such as polyethyleneglycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, is 1-10 in order to provide hydrophilic property and to disperse | distribute to water easily.

As an amount of an aliphatic polyether unit, it is the range of 10-90 mass% in a copolymer, Preferably it is 15-90 mass%, More preferably, it is 20-80 mass%, More preferably, it is 20-70 mass%. If the aliphatic polyether unit is less than 10% by mass, the dispersibility of the resin in water is deteriorated, which is not preferable. When it exceeds 90 mass%, since the heat resistance of resin falls, it is unpreferable.

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

Melting | fusing point of this invention is 120 degreeC or more, Preferably it is 140 degreeC or more, More preferably, it is 150 degreeC or more, Especially preferably, it is 160 degreeC or more. If melting | fusing point is less than 120 degreeC, since heat resistance, such as a coating film, falls, it is unpreferable. Although there is no restriction | limiting in particular as an upper limit, From the point of dispersibility to water, it is preferable that it is 300 degrees C or less, and it is more preferable that it is 280 degrees C or less. In addition, melting | fusing point is melting | fusing point measured at 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 without particular limitation as long as the melting point is 120 ° C or higher. As another copolymerization component which may be copolymerized, a polyester unit, a polyamide unit, a polycarbonate unit, a polyarylene sulfide unit, a polyether ether ketone unit, a polyimide unit, the monomer unit which comprises these polymers, etc. are mentioned specifically, Can be. Especially, it is preferable that it is a block copolymer, and as a unit which comprises a block copolymer, a polyester unit and a polyamide unit are preferable. The polyester unit is preferable because the heat resistance is maintained even when the ratio of the polyether unit is increased, and particularly preferably, the polyester unit is a polymer unit of an aromatic dicarboxylic acid and a diol.

The polyester unit should just have an ester bond in a principal chain or a side chain, and it does not specifically limit, It can obtain by polycondensing 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-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like, and ester-forming derivatives thereof; and the like as the acid component containing a sulfonic acid group and a base thereof For example, sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, sulfo-p-xylylene glycol, 2-sulfo-1, Alkali metal salts such as 4-bis (hydroxyethoxy) benzene, alkaline earth metal salts, and ammonium salts can be used. Sums up.

The glycol component constituting the polyester unit is ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 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, neopentylglycol, 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 may be used, and these may be copolymerized using one kind or two or more kinds. do. These resin can use 1 type (s) or 2 or more types.

In this invention, the glycol polycondensate of aromatic dicarboxylic acid among the above is preferable at the heat resistant point of resin. Especially, polyethylene terephthalate, polybutylene terephthalate, etc. are preferable at the point of strength.

There is no restriction | limiting in particular as a weight average molecular weight of the copolymer containing the aliphatic polyether of this invention, Usually, it is 1,000-100,000, Preferably it is 10,000-80,000, More preferably, it is 10,000-50,000. In addition, a weight average molecular weight refers to the weight average molecular weight measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent, and converted into standard polystyrene.

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

As a specific example, the method of polycondensing the reaction product obtained by transesterifying the lower alcohol diester of dicarboxylic acid, the excess low molecular weight glycol, and the low melting polymer segment component in presence of a catalyst, and dicarboxylic acid, Any method, such as a method of polycondensing the reaction product obtained by esterifying an excess amount of glycol and a low melting-point polymer segment component in presence of a catalyst, may be taken.

Next, the resin fine particles in the aqueous resin fine particle dispersion of the present invention will be described.

The resin fine particle aqueous dispersion in this invention means that resin fine particle exists in the dispersion medium which uses water as a medium.

At this time, the resin fine particle aqueous dispersion is the best state in which resin fine particles are always suspended in the water which is a dispersion medium. However, in some cases, the fine particles of the resin precipitate with time, and in the present invention, the fine particles of the resin fine particles can be easily redispersed by mechanical redispersing. It is contained 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, and more preferably 1 to 20 µm. When the number average particle diameter is less than 1 µm, the fine particles tend to aggregate, and when the number average particle diameter exceeds 100 µm, the particles are precipitated in water, which is not preferable. In addition, the number average particle diameter of resin microparticles | fine-particles observes arbitrary 100 particle | grains with a scanning electron micrograph, measures a diameter, and calculates it from the following formula (1). In addition, when particle | grains are not round, the long diameter shall be 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, and more preferably 1.0 to 1.5. When the particle size distribution index exceeds 3.0, the coatability when used as a coating is deteriorated, which is not preferable. In addition, a particle size distribution index is computed by ratio of the volume average particle diameter with respect to a number average particle diameter according to following formula (3). A volume average particle diameter observes 100 arbitrary particle | grains with a scanning electron microscope photograph, measures a diameter, and computes it from the following formula (2). In addition, when particle | grains are not round, the long diameter shall be measured.

Di: particle size, n: measured number 100, Dn: number average particle size, Dv: volume average particle size, PDI: particle size distribution index.

It is preferable that the shape of resin microparticles | fine-particles is spherical shape, but elliptic spherical shape may be sufficient as it.

As a method of obtaining resin fine particles, it can be obtained by any known method. Among them, a method of obtaining fine particles by phase-separating a polymer solution to form an emulsion and adding a poor solvent (International Publication No. 2009/142231) is preferable.

For example, a solution phase containing a polymer A as a main component (hereinafter, a polymer A solution) is obtained by dissolving and mixing the resin (hereinafter polymer A) to be atomized, the polymer B dissolved in the poor solvent of the polymer A, and an organic solvent. After forming an emulsion in a system in which phases are separated into two phases, which are sometimes referred to as a phase) and a solution phase containing polymer B as a main component (hereinafter sometimes referred to as polymer B solution phase), the poor solvent of polymer A is It can obtain by the method of depositing polymer A by making it contact.

It demonstrates more concretely about the said method.

In the above, "the system which phase-separates the polymer A, the polymer B, and the organic solvent by dissolving, and phase-separating into two phases the solution phase which has polymer A as a main component, and the solution phase which has polymer B as a main component", and the polymer A and polymer B When it mixes with an organic solvent, it says the system isolate | separated into two phases the solution phase mainly containing polymer A, and the solution phase mainly containing polymer B.

By using such a system for phase separation, an emulsion can be formed by mixing and emulsifying under conditions for phase separation.

In addition, in the above, about whether or not a polymer is melt | dissolved, whether it melt | dissolves more than 1 mass% with respect to an organic solvent at the temperature which implements this method, ie, the temperature when polymer A and polymer B dissolve and mix, and separate two phases. Determine with.

In this emulsion, the polymer A solution phase becomes the dispersed phase, the polymer B solution phase becomes the continuous phase, and the polymer A precipitates from the polymer A solution phase in the emulsion to form the polymer A by contacting the poor solvent of the polymer A with this emulsion. Resin fine particles can be obtained.

In this method, although there is no restriction | limiting in particular in the combination as long as the resin microparticles | fine-particles of this method are obtained using the polymer A, the polymer B, the organic solvent which melt | dissolves these, and the poor solvent of the polymer A, The polymer A is a polymer polymer in this method. It is a synthetic polymer which does not exist in nature naturally, More preferably, it is a water-insoluble polymer.

In this method, it is preferable that the polymer A is insoluble in the poor solvent because the main point of the method is to precipitate fine particles when the method is in contact with the poor solvent, and a polymer which is not dissolved in the poor solvent described later is preferable. Particularly preferred are water-insoluble polymers.

Here, as a water-insoluble polymer, the solubility to water is 1 mass% or less, Preferably it is 0.5 mass% or less, More preferably, the polymer which is 0.1 mass% or less is shown.

Examples of the polymer B include thermoplastic resins and thermosetting resins, but are preferably dissolved in an organic solvent for dissolving the polymer A used in the present method and a poor solvent for the polymer A. Among them, the polymer B is dissolved in the organic solvent and is an alcohol solvent or water. It is more preferable in that it is excellent in industrial handleability, and it is particularly preferable to be dissolved in an organic solvent and dissolved in methanol, ethanol or water.

Specific examples of Polymer B include poly (vinyl alcohol) (which may be fully 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 (oxyethylenelaurin fatty acid ester), poly (oxyethylene Glycol monofatty acid ester), poly (oxyethylene alkylphenyl ether), poly (oxyalkyl ether), polyacrylic acid, sodium polyacrylate, polymethacrylic acid, sodium polymethacrylate, polystyrenesulfonic acid, polystyrenesulfonic acid sodium, polyvinyl pi Lolidinium chloride, poly (styrene-maleic acid) copolymer, aminopoly (acrylamide), poly (paravinylphenol), polyallylamine, polyvinyl Synthesis of le, polyvinyl formal, poly (acrylamide), poly (methacrylamide), poly (oxyethyleneamine), poly (vinylpyrrolidone), poly (vinylpyridine), polyaminosulphone, polyethyleneimine Disaccharides such as resin, maltose, cellobiose, lactose, sucrose, cellulose, chitosan, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, ethyl hydroxy cellulose, carboxymethyl ethyl cellulose, carboxymethyl cellulose, carboxymethyl Cellulose derivatives such as sodium cellulose 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, Arabia Radish, agar, protein and the like, and preferably poly (vinyl alcohol) (may be a 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, sucrose fatty acid ester, poly (oxyethylene alkylphenyl ether), poly (oxyalkyl ether), poly (acrylic acid), poly (methacryl) Acid), carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, ethyl hydroxy cellulose, carboxymethyl ethyl cellulose, carboxymethyl cellulose, carboxymethyl cellulose sodium, cellulose esters such as cellulose ester, poly Vinylpyrrolidone, and more preferably poly (vinyl alcohol) (completely saponified Partially saponified poly (vinyl alcohol)), poly (vinyl alcohol-ethylene) copolymer (completely saponified or partially saponified poly (vinyl alcohol-ethylene) copolymer), polyethylene glycol, carboxymethylcellulose, hydroxy Cellulose derivatives such as ethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, ethyl hydroxy cellulose, carboxymethyl ethyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, cellulose ester, polyvinylpyrrolidone, and particularly preferably Poly (vinyl alcohol) (may be fully saponified or partially saponified poly (vinyl alcohol)), poly (ethylene glycol), carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, Cells such as ethyl hydroxy cellulose Cellulose derivative, polyvinylpyrrolidone.

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

The weight average molecular weight here means the weight average molecular weight measured by the gel permeation chromatography (GPC) using water as a solvent, and converted into polyethyleneglycol.

When it cannot be measured by water, dimethylformamide is used, when it cannot be measured still, tetrahydrofuran is used, and when it cannot be measured, hexafluoroisopropanol is used.

As an organic solvent which melt | dissolves the polymer A and the polymer B, it is an organic solvent which can melt the polymer A and polymer B which are used, and is selected according to the kind 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-methyl Aromatic hydrocarbon solvents such as naphthalene, ester acetates such as ethyl acetate, methyl acetate, butyl acetate, butyl propionate and butyl butyrate, chloroform, bromoform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, 1,1, Halogenated hydrocarbon solvents such as 1-trichloroethane, chlorobenzene, 2,6-dichlorotoluene, hexafluoroisopropanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl butyl ketone, methanol, ethanol , Alcohol solvents such as 1-propanol and 2-propanol, N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), N, N-dimethyl Acetamide (DMA), propylenecarbone Aprotic polar solvents such as yttrate, trimethyl phosphoric acid, 1,3-dimethyl-2-imidazolidinone, sulfolane, formic acid, acetic acid, propionic acid, butyric acid, carboxylic acid solvents such as lactic acid, anisole, diethyl ether Ether solvents such as tetrahydrofuran, diisopropyl ether, dioxane, diglyme, dimethoxyethane, 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium hydrogen sulfate And ionic liquids such as 1-ethyl-3-imidazolium acetate and 1-ethyl-3-methylimidazolium thiocyanate or mixtures thereof. Examples of the polymer A component and the polymer B component used Is appropriately selected. Preferably, they are selected from aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, halogenated hydrocarbon solvents, alcohol solvents, ether solvents, aprotic polar solvents, and carboxylic acid solvents, and more preferably alcohol based solvents. Solvents, aprotic polar solvents, carboxylic acid solvents, and remarkably preferred are aprotic polar solvents, carboxylic acid solvents, and are readily available and can dissolve a wide range of polymers. Most preferably, N-methyl-2-pyrrolidone, dimethyl sulfoxide, from the point that it can be mixed uniformly with a solvent which can be used suitably as a poor solvent mentioned later, such as water and an alcohol solvent, N, N-dimethylformamide, N, N-dimethylacetamide, propylene carbonate, formic acid and acetic acid.

Two or more types of these organic solvents may be used, or may be mixed and used. However, a particle having a relatively small particle size and a small particle size distribution is obtained, and the trouble of the separation process during recycling of the used solvent is avoided, and the manufacturing process load is avoided. It is preferable that it is a single organic solvent from a viewpoint of reduction, and it is preferable that it is a single organic solvent which melt | dissolves both of the polymer A and the polymer B.

The poor solvent of the polymer A in this method means a solvent which does not dissolve the polymer A. To dissolve the solvent is that 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 still more preferably 0.1% by mass or less.

In this method, although the poor solvent of the polymer A is used, it is preferable that it is a poor solvent of the polymer A and the solvent which melt | dissolves the polymer B as such a poor solvent. Thereby, the polymer microparticles | fine-particles which consist of polymer A can be precipitated efficiently. Moreover, it is preferable that the solvent which melt | dissolves polymer A and the polymer B, and the poor solvent of polymer A are a solvent mixed uniformly.

The poor solvent in this method varies depending on the kind of the polymer A used, preferably both the polymers A and B used, specifically, pentane, hexane, heptane, octane, nonane, n-decane, n- Aliphatic hydrocarbon solvents such as dodecane, n-tridecane, tetradecane, cyclohexane, cyclopentane, aromatic hydrocarbon solvents such as benzene, toluene, xylene, 2-methylnaphthalene, ethyl acetate, methyl acetate, butyl acetate, propionic acid Ester solvents such as butyl and butyl butyrate, chloroform, bromoform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, chlorobenzene, 2,6-dichlorotoluene, hexafluoro Halogenated hydrocarbon solvents such as leusopropanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl butyl ketone, methanol, ethanol, 1-propanol, 2-prop Alcohol solvents such as panol, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, trimethyl phosphoric acid, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imida Aprotic polar solvents such as zolidinone and sulfolane, carboxylic acid solvents such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, anisole, diethyl ether, tetrahydrofuran, diisopropyl ether, dioxane, diglyme And solvents selected from at least one of ether solvents such as dimethoxyethane and water.

From the viewpoint of efficiently granulating the polymer A, an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, an alcohol solvent, an ether solvent, and water are most preferred, an alcohol solvent and water, and particularly preferably water.

In the present method, by appropriately selecting and combining the polymer A, the polymer B, the organic solvent which dissolves them, and the poor solvent of the polymer A, the polymer A can be efficiently precipitated and resin fine particles can be obtained.

At this time, the liquid which mixed and dissolved polymer A, B, and the organic solvent which melt | dissolves these needs to phase-separate into the two phases of the solution phase which has polymer A as a main component, and the solution phase which has polymer B as a main component.

Under the present circumstances, although the organic solvent of the solution phase which has a polymer A as a main component, and the organic solvent which has a polymer B as a main component may be same or different, it is preferable that they are substantially the same solvent.

The conditions for generating the state of two-phase separation differ depending on the kind of the polymers A and B, the molecular weight of the polymers A and B, the kind of the organic solvent, the concentration of the polymers A and B, the temperature and pressure at which the present method is to be carried out.

In order to obtain the conditions which tend to be in a phase separation state, it is preferable that the difference between the solubility parameters (hereinafter sometimes referred to as SP value) of the polymer A and the polymer B 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, still more preferably 3 (J / cm ³ ) ^1/2 or more , Particularly preferably 5 (J / cm ³ ) ^1/2 or more, very preferably 8 (J / cm ³ ) ^1/2 or more. If SP value is this range, it will become easy to phase-separate easily.

There is no restriction | limiting in particular if both polymer A and polymer B are melt | dissolved in an organic solvent, Preferably it is 20 (J / cm <^3> ) ^1/2 or less, More preferably, 15 (J / cm) as an upper limit of the difference of SP value. ³ ) ^1/2 or less, more preferably 10 (J / cm ³ ) ^1/2 or less.

The SP value here is calculated based on Fedor's estimation method, and is calculated based on the aggregation energy density and the molar molecular volume (hereinafter sometimes referred to as a calculation method) ("SP value basis"). ㆍ Application and Calculation Method ”by Yamamoto Hideki, Kabushi Kiisha Information Agency, issued March 31, 2005).

In the case where it cannot be calculated by this estimation method, the SP value is calculated (hereinafter sometimes referred to as an experimental method) by an experimental method by determining whether or not the solubility parameter is dissolved in a known solvent, and substituted it ( `` Polymer Handbook Fourth Edition '' J. Brand (J.Brand), published by Wiley, 1998).

In order to select the conditions under which the phases are separated, it is possible to distinguish the three-component phase drawing that 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 dissolving them is changed. .

In the preparation of the phase drawing, when the polymer A, B, and the solvent are mixed and dissolved at an arbitrary ratio, the determination is made as to whether an interface is formed, at least 3 or more, preferably 5 or more, more preferably 10 It is possible to confirm the conditions which become a phase separation state by carrying out by the above point and classifying the area | region separated into two phases and the area | region used as one phase.

At this time, in order to determine whether or not the phase separation state, the polymers A and B are adjusted to the ratio of the optional polymers A and B and the solvent at the temperature and pressure to implement the present invention, and then the polymers A and B are completely dissolved and dissolved. After making it stir enough, it is left to stand for 3 days and it confirms whether a phase separation is carried out macroscopically.

However, in the case of a sufficiently stable emulsion, macroscopic phase separation may not be performed even if left to stand for 3 days. In that case, phase separation is discriminated by microscopic phase separation using an optical microscope, phase difference microscope, or the like.

Phase separation is formed by separating a polymer A solution phase predominantly polymer A and a polymer B solution phase predominantly polymer B in an organic solvent. In this case, the polymer A solution phase is a phase in which polymer A is mainly distributed, and the polymer B solution phase is a phase in which polymer B is mainly distributed. In this case, the polymer A solution phase and the polymer B solution phase are the same as having a volume ratio according to the types and amounts of the polymers A and B used.

Although the state of phase separation is obtained and the density | concentration of the polymers A and B with respect to an organic solvent as an industrially enforceable density | concentration is assumed to exist in the range as far as possible in the organic solvent, Preferably it is more than 1 mass%-50 mass %, More preferably, it is more than 1 mass%-30 mass%, More preferably, it is 2 mass%-20 mass%.

The interfacial tension between the two phases of the polymer A solution and the polymer B solution in the present method is small because both phases are organic solvents, and therefore the interfacial tension is small and the emulsion produced by the property can be stably maintained. Is smaller than. 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 two phases in the present method is too small, the interfacial tension cannot be directly measured by a conventional method such as adding and measuring a heterogeneous solution to a commonly used solution. The interfacial tension can be estimated by estimating from the tension. When the surface tension of the air and on the angle of r _1, r _2, r ₁₂ The interfacial tension can be estimated as the absolute value of r ₁₂ = r ₁ -r _2. At this time, the preferable range of this r <_12> is more than 0-10mN / m, More preferably, it is more than 0-5mN / m, More preferably, it is more than 0-3mN / m, Especially preferably, it is more than 0-2mN / m.

The viscosity between two phases in this method affects an average particle diameter and particle size distribution, and the one with a smaller viscosity ratio tends to have a smaller particle size distribution. In the case where the viscosity ratio is defined as the polymer A solution phase / polymer B solution phase under the temperature condition to which the present invention is to be carried out, the preferred range is 0.1 or more and 10 or less, more preferably 0.2 or more and 5 or less, and even more preferably 0.3 or more. It is 0.5 or more and 3 or less as an especially preferable range, It is 0.8 or more and 1.2 or less as remarkably preferable range.

Resin fine particles are manufactured using the system of phase separation obtained in this way. In order to perform micronization, it implements in a normal reaction tank. The temperature suitable for practicing the present invention is in the range of -50 ° C to 200 ° C from the viewpoint of industrial feasibility, preferably -20 ° C to 150 ° C, more preferably 0 ° C to 120 ° C, and more preferably Is 10 ° C to 100 ° C, particularly preferably 20 ° C to 80 ° C, and most preferably 20 ° C to 50 ° C. The pressure suitable for carrying out the present invention is in the range of reduced pressure to 100 atmospheres, preferably in the range of 1 to 5 atmospheres, more preferably 1 to 2 atmospheres, especially from the viewpoint of industrial practicality. It is atmospheric pressure.

Under these conditions, an emulsion is formed by mixing the phase separation system states.

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

In the formation of the emulsion, an emulsion is formed such that the polymer A solution phase is in the form of droplets of particulate form. Generally, when phase separated, it is easy to form an emulsion of this type when the volume of the polymer B solution phase is larger than that of the polymer A solution phase. 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, and preferably between 0.4 and 0.1. In preparing the phase diagram, an appropriate range can be set by simultaneously measuring the volume ratio at the concentration of each component.

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

In particular, in the case of stirring by the stirring blade, the stirring speed is also dependent on the shape of the stirring blade, but the stirring speed is preferably 50 rpm to 1200 rpm, more preferably 100 rpm to 1000 rpm, even more preferably 200 rpm to 800 rpm, and particularly preferably 300 rpm to 600 rpm to be.

Specific examples of the stirring blades include propeller type, puddle type, flat puddle type, turbine type, double cone type, single cone type, single ribbon type, double ribbon type, screw type and helical ribbon type. If sufficient shearing force is applied, it will not be specifically limited to these. Moreover, in order to perform efficient stirring, you may install a baffle board etc. in a tank.

In addition, in order to generate an emulsion, not only a stirrer but also an apparatus generally widely known, such as an emulsifier and a disperser, can also be used. Specifically, batch type emulsifiers such as homogenizers (manufactured by IKA Corporation), polytron (manufactured by Kinematik Corporation), TK Auto Homo Mixer (manufactured by Tokushu Kikaka Kogyo Co., Ltd.), Ebara Milder (Ebara Seisakusho) TK Peel Mix, TK Pipeline Homo Mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), Colloid Mill (manufactured by Shinkoku Pantech Co., Ltd.), Slasher, Trigonal Wet Grinding Machine (Mitsui Miei Kakoku Co., Ltd.), Ultrasonic Homogenizer And static mixers.

The emulsion thus obtained is then provided to a step of depositing the target fine particles.

In order to obtain the target resin fine particles, the poor resin for the polymer A is brought into contact with the emulsion prepared in the above-mentioned step to precipitate the desired resin fine particles in a diameter corresponding to the emulsion diameter.

Although the method of contacting a poor solvent and an emulsion may be the method of putting an emulsion in a poor solvent, and the method of adding a poor solvent to an emulsion, the method of adding a poor solvent to an emulsion is preferable.

At this time, the method for introducing the poor solvent is not particularly limited as long as the resin fine particles produced in the present invention are obtained, and any of continuous dropping method, split addition method and batch addition method may be used. In order to prevent fusion and coalescence to increase the particle size distribution or to produce a mass of more than 1000 µm, the continuous dropping method and the split dropping method are preferable. to be.

Moreover, as time to add a poor solvent, it is 10 minutes or more and less than 50 hours, More preferably, it is 30 minutes or more and less than 10 hours, More preferably, they are 1 hour or more and less than 5 hours.

If it is carried out in a time shorter than this range, particle size distribution may become large according to aggregation, fusion, and coalescence of an emulsion, and a mass may be produced. In addition, when carrying out longer time, it is unrealistic when industrial implementation is considered.

By performing in this time range, when switching from an emulsion to resin fine particles, aggregation between particles can be suppressed and resin fine particles with a small particle size distribution can be obtained.

The amount of the poor solvent to be added also depends on the state of the emulsion, but is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, still more preferably 0.2 to 3 parts by mass with respect to 1 part by mass of the total weight of the emulsion, Especially preferably, it is 0.2 mass part-1 mass part, Most preferably, it is 0.2-0.5 mass part.

The contact time between the poor solvent and the emulsion may be sufficient time for the fine particles to be precipitated. To obtain efficient productivity while causing sufficient precipitation, it is 5 minutes to 50 hours after the completion of the poor solvent addition, and more preferably within 5 minutes to 10 hours. More preferably, it is 10 minutes or more and less than 5 hours, Especially preferably, it is 20 minutes or more and less than 4 hours, Remarkably preferably, it is 30 minutes or more and less than 3 hours.

The resin fine particle dispersion thus prepared is subjected to solid-liquid separation by the usual known methods such as filtration, decantation, reduced pressure filtration, pressure filtration, centrifugal separation, centrifugal filtration, spray drying, acid precipitation, salting out, and freeze coagulation. It can be recovered.

The resin fine particles separated in solid-liquid separation are purified by washing with a solvent or the like as necessary to remove impurities or the impurities contained therein. At this time, as a preferable solvent, it is the said poor solvent, More preferably, it is 1 type, or 2 or more types of mixed solvent chosen from water, methanol, and ethanol.

The obtained resin fine particles can be dried to remove residual solvent. At this time, as a drying method, air drying, heat drying, reduced pressure drying, freeze drying, etc. are mentioned. As for the temperature at the time of heating, temperature lower than glass transition temperature is preferable, and 50-150 degreeC is specifically, preferable.

In the method of this invention, it is advantageous that it is possible to recycle using the organic solvent and polymer B which were separated in the solid-liquid separation process performed when obtaining resin fine particles.

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 emulsion formation. As a method of removing the poor solvent, it is usually carried out by a known method, and specific examples include distillation, reduced pressure distillation, fine distillation, thin film distillation, extraction, membrane separation, and the like. It is a method by distillation.

However, when performing distillation operations such as distillation and vacuum distillation, heat may be applied to the system, which may promote thermal decomposition of the polymer B or the organic solvent. Therefore, the distillation operation such as distillation and reduced pressure distillation is preferably performed in the absence of oxygen, more preferably in an inert atmosphere. Under Specifically, it is carried out under nitrogen, helium, argon and carbon dioxide conditions.

Next, the method of manufacturing the resin fine particle aqueous dispersion in this invention is demonstrated.

The method of disperse | distributing the resin fine particle obtained by the said method to the water which is a dispersion medium is a conventional mixing disperser (for example, a planetary mixer, a triaxial roll, a mechanical stirrer, a revolving mixer, a homo mixer, ball mill, bead mill, sand) Mill, roll mill, homogenizer, attritor, dissolver, paint shaker, etc.) may be used, and several methods may be combined and adjusted. Moreover, it can also heat up or depressurize as needed.

Although it is preferable to adjust the addition amount of the resin fine particle with respect to the water in this invention according to the use which this resin fine particle aqueous dispersion is used, 80 mass% or less is preferable, More preferably, it is 50 mass% or less, More preferably Preferably it is 30 mass% or less, Especially preferably, it is 20 mass% or less. When it exceeds 80 mass%, it exists in the tendency for resin microparticles to disperse easily, and it is necessary to disperse | distribute with a dispersing agent etc .. The lower limit is not particularly limited and may be set according to the purpose.

Since the resin microparticles | fine-particles used by this invention are excellent in the dispersibility to water, as long as it is the said preferable range, it can disperse in water, without using a dispersing agent especially.

Therefore, in this invention, since the dispersion liquid of resin microparticles | fine-particles can be obtained without using a dispersing agent substantially, generation | occurrence | production of coloring, fall of heat resistance, deterioration of water resistance, deterioration of adhesiveness to a base material, and bleeding on the surface are influenced by a dispersing agent itself. It can also be used practically when out and stickiness are a problem. Aqueous dispersions containing dispersants are particularly common in applications where resin particles having high heat resistance, such as the present invention, have high heat treatment conditions, so that coloring due to decomposition of the dispersant is more pronounced, such as deterioration in designability. In some cases, the adverse effect is very large. Therefore, substantially including a dispersing agent is a big advantage in using the resin fine particle aqueous dispersion.

Content of a dispersing agent is less than 1 mass part with respect to 100 mass parts of resin fine particles, Preferably it is less than 0.2 mass part, Most preferably, it is not used.

The dispersant is not particularly limited as long as the dispersant is dispersed in water, and examples thereof include a polymer dispersant, an anionic surfactant, a cationic surfactant, an amphoteric ionic surfactant, and a nonionic surfactant.

Specific examples of the polymer dispersant include poly (vinyl alcohol) (which may be fully saponified or partially saponified poly (vinyl alcohol)) and 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 (oxyethylenelaurin fatty acid ester), poly (oxyethylene glycol monofatty acid Ester), poly (oxyethylene alkylphenyl ether), poly (oxyalkyl ether), polyacrylic acid, sodium polyacrylate, polymethacrylic acid, sodium polymethacrylate, polystyrenesulfonic acid, sodium polystyrene sulfonate, polyvinylpyrrolidinium chloride , Poly (styrene-maleic acid) copolymer, aminopoly (acrylamide), poly (paravinylphenol), polyallylamine, polyvinyl ether Synthetic resins such as polyvinyl formal, poly (acrylamide), poly (methacrylamide), poly (oxyethyleneamine), poly (vinylpyrrolidone), poly (vinylpyridine), polyaminosulfone, and polyethyleneimine Disaccharides such as, maltose, cellobiose, lactose, sucrose, cellulose, chitosan, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, ethyl hydroxy cellulose, carboxymethyl ethyl cellulose, carboxymethyl cellulose, carboxymethyl cellulose Cellulose derivatives such as sodium 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, Arabian Go , Agar, protein, and the like, preferably poly (vinyl alcohol) (which may be fully saponified or partially saponified poly (vinyl alcohol)), poly (vinyl alcohol-ethylene) copolymer (fully saponified 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 ), Carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, ethyl hydroxy cellulose, carboxymethyl ethyl cellulose, carboxymethyl cellulose, carboxymethyl cellulose sodium, cellulose ester such as cellulose ester, polyvinyl Pyrrolidone, and more preferably poly (vinyl alcohol) (completely saponified Powdered saponified poly (vinyl alcohol)), poly (vinyl alcohol-ethylene) copolymer (completely saponified or partially saponified poly (vinyl alcohol-ethylene) copolymer), polyethylene glycol, carboxymethyl cellulose, hydroxy Cellulose derivatives such as ethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, ethyl hydroxy cellulose, carboxymethyl ethyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, cellulose ester, and polyvinylpyrrolidone. .

Specific examples of the anionic surfactant include sodium fatty acid, potassium fatty acid, sodium alkylbenzene sulfonate, sodium alkylnaphthalene sulfonate, sodium alkyl sulfate ester sodium, sodium alkyl sulfonate, alkyl ether sulfate ester sodium, monoalkyl phosphate ester and polyoxyethylene alkyl ether phosphoric acid ester. Sodium, fatty acid ester sodium sulfonate, fatty acid ester sodium sulfate, sodium fatty acid alkylosamide sulfate ester, fatty acid sodium 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 amphoteric ionic 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 Monobenzylphenyl ether, polyoxyethylenedibenzylphenyl ether, polyoxyethylenetribenzylphenyl ether, polyoxyethylene monostyrylphenyl ether, polyoxyethylene distyrylphenyl ether, polyoxyethylene tristyrylphenyl ether, polyoxyethylene Biphenyl ether, polyoxyethylene phenoxyphenyl ether, polyoxyethylene cumylphenyl ether, polyoxyethylene alkyl ether, fatty acid alkanolamide, fatty acid monoethanolamide, fatty acid diethanolamide, fatty acid triethanolamide, polyoxyethylene fatty acid amide,And the like can be given small propanol amide, alkyl amine oxide, polyoxyethylene amines. Moreover, when alkyl is mentioned here, a C1-C30 linear saturated hydrocarbon group or a branched saturated hydrocarbon group is mentioned. Instead of alkyl, it may be a straight chain unsaturated hydrocarbon group or a branched unsaturated hydrocarbon group.

In the resin fine particle aqueous dispersion of this invention, various chemical agents, such as a leveling agent, an antifoamer, a lifting agent, a pigment dispersing agent, and an ultraviolet absorber, and pigments or dyes, such as a titanium oxide, zinc, and carbon black, as needed in the range which does not impair the objective. May be added.

The resin fine particle aqueous dispersion of the present invention is well dispersed in water even though the dispersant is not substantially used even though its heat resistance is high, so that it can be used for coating applications such as automobile interior and exterior coatings, home appliances and building materials, adhesive applications, ink applications, It is possible to impart high heat resistance in binder or coating applications and aqueous cosmetic applications. Particularly in the case where substantially no dispersant is used, it is possible to suppress coloring by the dispersant, deterioration of heat resistance and deterioration of water resistance, deterioration of adhesion to the substrate, bleeding out to the surface, and stickiness. For this reason, by avoiding an organic solvent, it becomes possible to deteriorate a base material, environmental conservation, improvement of a workplace environment, etc.

<Examples>

Next, the present invention will be described in more detail based on Examples. This invention is not limited only to these Examples. The measurement used in an Example is as follows.

(1) Measurement of the weight average molecular weight

The weight average molecular weight was calculated by comparing the calibration curve with polystyrene using gel permeation chromatography.

Apparatus: LC-10A series manufactured by Shimadzu Corporation

Column: Showa Denko Kabuki Kaisha HFIP-806M × 2

Mobile phase: hexafluoroisopropanol

Flow rate: 0.5ml / min

Detection: differential refractometer

Column temperature: 25 ° C

(2) Calculation method-1 of number average particle diameter, volume average particle diameter, particle diameter distribution index

The particle | grains were observed by the scanning electron microscope (the scanning electron microscope JSM-6301NF by a Nippon Denshi company), and the number average particle diameter was measured. In addition, when particle | grains are not round, the long diameter was measured as the particle diameter.

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

Di: particle size, n: measured number 100, Dn: number average particle size, Dv: volume average particle size, PDI: particle size distribution index.

(3) Calculation method-2 of number average particle diameter, volume average particle diameter, particle size distribution index

After adjusting microparticles | fine-particles to 0.1% of slurry in ion-exchanged water, what performed the ultrasonic processing which oscillates 25kHz and about 100W ultrasonic waves for 1 minute as a sample for a measurement, and laser diffraction type particle size distribution meter (SALD-2100: The volume average particle diameter and the number average particle diameter were calculated using Kaisha Shimadzu Corporation.

(4) measurement of melting point

The normal temperature of the melting peak at the time of heating at the temperature increase rate of 10 degree-C / min in nitrogen airflow atmosphere was measured using the robot DSC RDC220 by Seiko Instruments Co., Ltd ..

(5) evaluation of dispersibility

(Variance evaluation 1)

The aqueous dispersion of the Example and the comparative example was filled in the glass sample bottle, and it left to stand at 40 degreeC for 1 hour, and the separation state of the composition was visually observed and evaluated in accordance with the following criteria.

○: no separation confirmed

×: separated

(Variance evaluation 2)

The aqueous dispersion of the Example and the comparative example was filled into the glass sample bottle, and the thing which separation was hardly confirmed by the sample after 1 minute of ultrasonication was made into (circle), and the thing where separation was confirmed was x.

(6) Evaluation of coating film appearance

(Painting evaluation 1)

The appearance of the coating film was evaluated according to the following criteria.

◎: Coloring is not confirmed

○: Slightly colored

×: Coloring is confirmed

(Painting 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 x 297 mm x 0.1 mm manufactured by Toray Industries, Ltd.) with a bar coater, and then dried with a blow dryer for 150 ° C for 30 minutes to obtain a coating film. The external appearance of the obtained coating film was visually confirmed. (Circle) and the bad thing were made into x.

(7) used resin

Toray Dupont Co., Ltd .: "Hytrirel" 7247

Manufactured by DuPont Kabuki Shisha, "Hytrirel" 8238

About other used resin, it superposed | polymerized by the following reference example.

[Referential Example 1]

Helical ribbon stir blade 16.0 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 0.005 parts of mono-n-butyl-monohydroxytin oxide It injected into the reaction vessel provided, and it heated at 190-225 degreeC for 3 hours, and performed esterification reaction, flowing out reaction water out of the system. 0.06 parts of tetra-n-butyl titanate was further added to the reaction mixture, and 0.02 parts of "Irganox" 1098 (a hindered phenol-based antioxidant manufactured by Shiba Japan Co., Ltd.) was added, followed by heating to 245 ° C. 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. Melting point was 160 degreeC 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 0.005 parts of mono-n-butyl-monohydroxytin oxide It injected into the reaction vessel provided, and it heated at 190-225 degreeC for 3 hours, and performed esterification reaction, flowing out reaction water out of the system. 0.06 parts of tetra-n-butyl titanate was further added to the reaction mixture, and 0.02 parts of "Irganox" 1098 (a hindered phenol-based antioxidant manufactured by Shiba Japan Co., Ltd.) was added, followed by heating to 245 ° C. 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. Melting point was 221 degreeC and the weight average molecular weight was 26,000.

[Referential 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 0.005 parts of mono-n-butyl-monohydroxytin oxide It injected into the reaction vessel provided, and it heated at 190-225 degreeC for 3 hours, and performed esterification reaction, flowing out reaction water out of the system. 0.06 parts of tetra-n-butyl titanate was further added to the reaction mixture, and 0.02 parts of "Irganox" 1098 (a hindered phenol-based antioxidant manufactured by Shiba Japan Co., Ltd.) was added, followed by heating to 245 ° C. 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. Melting point was 228 degreeC, and the weight average molecular weight was 25,000.

(8) Preparation of Resin Fine Particles

About each resin fine particle, it manufactured based on the following manufacture examples.

[Production Example 1]

In a 100 ml four-necked flask, 3.5 g of an 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 (Nippon Kosei Chemical Co., Ltd.) 3.5 g of Gosenol (registered trademark) GL-05) manufactured by Kogyo Kogyo Co., Ltd. was added thereto, and the mixture was heated to 90 ° C. and stirred until the polymer was dissolved. After returning the temperature of the system to 80 degreeC, 50g of ion-exchange water was dripped at the speed | rate of 0.41g / min as a poor solvent via a liquid feed pump, stirring at 450 rpm. After adding the whole amount of water, the mixture was stirred for 30 minutes, and the obtained 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 the scanning electron microscope, it was a spherical microparticles | fine-particles, the polyether polyester fine particles of 15.4 micrometers of volume average particle diameters, and 1.17 particle size distribution index.

[Production Example 2]

Polyester elastomer "Hytrirel" which is an aliphatic polyether-polyester copolymer in 1000 ml pressure-resistant glass autoclave (hyperglaster TEM-V1000N of pressure-resistant glass high school Co., Ltd.) 7247 (made by Toray DuPont Co., Ltd.) 28 g of N-methyl-2-pyrrolidone (manufactured by Kanto Chemical Co., Ltd.), 304.5 g, polyvinyl alcohol (PVA-1500 manufactured by Wako Pure Chemical Industries, Ltd.), weight average molecular weight 29,000 : The sodium acetate content was reduced to 0.05 mass% by washing in methanol) 17.5 g was added, nitrogen-substituted, and it heated at 180 degreeC, and stirred for 4 hours until a polymer melt | dissolved. Thereafter, 350 g of ion-exchanged water was dropped as a poor solvent at a rate of 2.92 g / min via the liquid feed pump. After adding the whole amount of water, the mixture was cooled down and the resulting suspension was filtered, 700 g of ion-exchanged water was added, the slurry was washed, and the filtered fraction was vacuum dried at 80 ° C for 10 hours to obtain 26.5 g of a white solid. When this white solid was observed with the scanning electron microscope, the volume average particle diameter was 5.5 micrometers and the particle size distribution index was 1.12. At the same time, this white solid was analyzed by a laser particle size distribution analyzer (SALD-2100 manufactured by Shimadzu Corporation) and found to be polyether-polyester copolymer fine particles having a volume average particle diameter of 5.5 µm and a particle size distribution index of 1.12.

[Production Example 3]

Polyester elastomer "Hytrirel" which is an aliphatic polyether-polyester copolymer in 1000 ml pressure-resistant glass autoclave (hyperglaster TEM-V1000N of pressure-resistant glass high school Co., Ltd.) 7247 (made by Toray DuPont Co., Ltd.) 28 g of N-methyl-2-pyrrolidone (manufactured by Kanto Chemical Co., Ltd.), 308 g of polyvinyl alcohol (PVA-1500 manufactured by Wako Pure Chemical Industries, Ltd.), weight average molecular weight 29,000: After washing with methanol, 14 g of sodium acetate content was reduced to 0.05% by mass), followed by 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 was dropped as a poor solvent at a rate of 2.92 g / min via the liquid feed pump. The mixture was cooled, and then the temperature was lowered while stirring. The obtained suspension was filtered, 700 g of ion-exchanged water was added, the slurry was washed, and the filtered fraction was vacuum dried at 80 ° C. for 10 hours to obtain 25.5 g of a white solid. When this white solid was observed with the scanning electron microscope, the volume average particle diameter was 8.6 micrometers and the particle size distribution index was 1.22. Moreover, as a result of analyzing with a laser particle size distribution analyzer (SALD-2100 by Shimadzu Corporation), it was polyether-polyester copolymer microparticles | fine-particles whose volume average particle diameter is 8.6 micrometers and a particle size distribution index are 1.22.

[Production Example 4]

Polyester elastomer "Hytrirel" which is an aliphatic polyether-polyester copolymer in 1000 ml pressure-resistant glass autoclave (hyperglaster TEM-V1000N of pressure-resistant glass high school Co., Ltd.) 7247 (made by Toray DuPont Co., Ltd.) 28 g of N-methyl-2-pyrrolidone (manufactured by Kanto Chemical Co., Ltd.), 301 g of polyvinyl alcohol (PVA-1500 manufactured by Wako Pure Chemical Industries, Ltd.), weight average molecular weight 29,000: After washing with methanol, 10.5 g of sodium acetate content was reduced to 0.05% by mass), and nitrogen substitution was performed, followed by heating at 180 ° C and stirring for 4 hours until the polymer was dissolved. Thereafter, 350 g of ion-exchanged water was dropped as a poor solvent at a rate of 2.92 g / min via the liquid feed pump. After adding the whole amount of water, the mixture was lowered while stirring, the obtained suspension was filtered, 700 g of ion-exchanged water was added, the slurry was washed, and the filtered fraction was vacuum dried at 80 ° C for 10 hours to obtain 26.0 g of a white solid. When the white solid was observed with the scanning electron microscope, the volume average particle diameter was 12.6 micrometers and the particle size distribution index was 1.22. In addition, the result was analyzed by a laser particle size distribution analyzer (SALD-2100 manufactured by Shimadzu Corporation) and found to be polyether-polyester-copolymer fine particles having a volume average particle diameter of 12.5 µm and a particle size distribution index of 1.28.

[Production Example 5]

Polyester elastomer "Hytrirel", an aliphatic polyether-polyester copolymer, in a 1000 ml pressure-resistant glass autoclave (Hyperglass TEM-V1000N manufactured by Pressure-resistant Glass High-Grade Co., Ltd.) 8238 (manufactured by DuPont Industries, Ltd.) Average molecular weight 27,000) 17.5 g, N-methyl-2-pyrrolidone (manufactured by Kanto Chemical Co., Ltd.) 315 g, polyvinyl alcohol (PVA-1500 manufactured by Wako Pure Chemical Industries, Ltd.), weight average molecular weight 29,000: methanol 17.5 g of sodium acetate content was reduced to 0.05% by mass by addition, and then nitrogen-substituted. The mixture was heated at 180 ° C and stirred for 4 hours until the polymer was dissolved. Thereafter, 350 g of ion-exchanged water was dropped as a poor solvent at a rate of 2.92 g / min via the liquid feed pump. After adding the whole amount of water, the mixture was cooled down and the resulting suspension was filtered, 700 g of ion-exchanged water was added, the slurry was washed, and the filtered fraction was vacuum dried at 80 ° C. for 10 hours to obtain 14.9 g of a white solid. When the obtained powder was observed with the scanning electron microscope, it was a spherical microparticles | fine-particles, the polyether polyester fine particles of 4.3 micrometers of volume average particle diameters, and 1.25 particle size distribution index. Moreover, as a result of analysis by a laser particle size distribution analyzer (SALD-2100 by Shimadzu Corporation), it was polyether-polyester copolymer microparticles | fine-particles whose volume average particle diameter is 5.4 micrometers and a particle size distribution index is 1.25.

Production Example 6

Polyester elastomer "Hytrirel", an aliphatic polyether-polyester copolymer, in a 1000 ml pressure-resistant glass autoclave (Hyperglass TEM-V1000N manufactured by Pressure-resistant Glass High-Grade Co., Ltd.) 8238 (manufactured by DuPont Industries, Ltd.) Average molecular weight 27,000) 33.25 g, N-methyl-2-pyrrolidone (manufactured by Kanto Chemical Co., Ltd.) 299.25 g, polyvinyl alcohol (PVA-1500 manufactured by Wako Pure Chemical Industries, Ltd.), weight average molecular weight 29,000: After washing with methanol, 17.5 g of sodium acetate content was reduced to 0.05% by mass), followed by nitrogen substitution, followed by heating at 180 ° C. for 4 hours until the polymer was dissolved. Thereafter, 350 g of ion-exchanged water was dropped as a poor solvent at a rate of 2.92 g / min via the liquid feed pump. The mixture was cooled, and then the temperature was lowered while stirring. The obtained suspension was filtered, 700 g of ion-exchanged water was added, the slurry was washed, and the filtered fraction was vacuum dried at 80 ° C. for 10 hours to obtain 28.3 g of a white solid. When the obtained powder was observed with the scanning electron microscope, it was a spherical microparticle, the polyether-polyester copolymer microparticles whose volume average particle diameter is 12.0 micrometers, and a particle size distribution index are 1.23. In addition, the result was analyzed by a laser particle size distribution analyzer (SALD-2100 manufactured by Shimadzu Corporation), and the result was polyether-polyester copolymer fine particles having a volume average particle diameter of 14.7 µm and a particle size distribution index of 1.23.

[Production Example 7]

17.5 g of aliphatic polyether-polyester copolymer obtained in Reference Example 2, 315.0 g of N-methyl-2-pyrrolidone in a 1000 ml pressure-resistant glass autoclave (Hyper Glaster TEM-V1000N manufactured by Pressure-resistant Glass High-Grade Co., Ltd.) Nitrogen substitution was carried out by adding 17.5 g of polyvinyl alcohol (PVA-1500 manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 29,000: the sodium acetate content was reduced to 0.05% by mass by washing in methanol). It heated at 180 degreeC and stirred for 4 hours until a polymer melt | dissolved. Thereafter, 350 g of ion-exchanged water was dropped as a poor solvent at a rate of 2.92 g / min via the liquid feed pump. The mixture was cooled, and then the temperature was lowered while stirring. The obtained suspension was filtered, 700 g of ion-exchanged water was added, the slurry was washed, and the filtered fraction was vacuum dried at 80 ° C. for 10 hours to obtain 17.0 g of a white solid. When the obtained powder was observed with the scanning electron microscope, it was a spherical microparticles | fine-particles, the polyether-polyester-copolymer microparticles whose volume average particle diameter is 11.4 micrometers, and the particle size distribution index are 1.29.

[Production Example 8]

17.5 g of aliphatic polyether-polyester copolymer obtained in Reference Example 3, 350.0 g of N-methyl-2-pyrrolidone in a 1000 ml pressure-resistant glass autoclave (Hyper Glaster TEM-V1000N manufactured by Pressure-resistant Glass High-Grade Co., Ltd.) Nitrogen substitution was carried out by adding 17.5 g of polyvinyl alcohol (PVA-1500 manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 29,000: the sodium acetate content was reduced to 0.05% by mass by washing in methanol). It heated at 180 degreeC and stirred for 4 hours until a polymer melt | dissolved. Thereafter, 350 g of ion-exchanged water was dropped as a poor solvent at a rate of 2.92 g / min via the liquid feed pump. The mixture was cooled, and then the temperature was lowered while stirring. The obtained suspension was filtered, 700 g of ion-exchanged water was added, the slurry was washed, and the filtered fraction was vacuum dried at 80 ° C. for 10 hours to obtain 17.0 g of a white solid. When the obtained powder was observed with the scanning electron microscope, it was a spherical microparticles | fine-particles, the polyether polyester fine particles of 4.3 micrometers of volume average particle diameters, and 1.30 particle size distribution index.

[Production Example 9]

28.0 g of aliphatic polyether-polyester copolymer obtained in Reference Example 3, 308.0 g of N-methyl-2-pyrrolidone in a 1000 ml pressure-resistant glass autoclave (Hyper Glaster TEM-V1000N manufactured by Pressure-resistant Glass High-Grade Co., Ltd.) Nitrogen substitution was carried out by adding 17.5 g of polyvinyl alcohol (PVA-1500 manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 29,000: the sodium acetate content was reduced to 0.05% by mass by washing in methanol). It heated at 180 degreeC and stirred for 4 hours until a polymer melt | dissolved. Thereafter, 350 g of ion-exchanged water was dropped as a poor solvent at a rate of 2.92 g / min via the liquid feed pump. After adding the whole amount of water, the mixture was lowered while stirring, the obtained suspension was filtered, 700 g of ion-exchanged water was added, the slurry was washed, and the filtered fraction was vacuum dried at 80 ° C for 10 hours to obtain 26.0 g of a white solid. When the obtained powder was observed with the scanning electron microscope, it was a spherical microparticles | fine-particles, the polyether polyester fine particles of 12.3 micrometers in volume average particle diameters, and 1.31 of particle size distribution index.

[Examples 1-10, Comparative Examples 1-4] <Adjustment and evaluation of resin fine particle dispersion>

Using the resin fine particles obtained in Production Examples 1-9, the resin fine particle dispersion was adjusted using the following representative example, and the characteristic was evaluated.

In addition, the medium was made into ethyl acetate as a comparative example, and the resin fine particle dispersion liquid was used as the adjustment liquid using the resin fine particle shown below, and compared with the dispersion liquid obtained in the Example.

<Resin fine particles used for preparation>

Nylon 12 fine particles (Orgasol melting point 170 degrees Celsius made by Arkema Corporation)

Example 1

20 mass parts of polyether polyester block copolymer resin microparticles | fine-particles produced by the manufacture example 1 were put into 80 mass parts of water, and 25 KHz ultrasonic treatment was performed for 1 minute, and the aqueous dispersion was obtained. As a result of evaluating water dispersibility, almost no separation was confirmed.

[Example 2]

20 mass parts of polyether-polyester block copolymer resin microparticles | fine-particles produced by the manufacture example 1 were put into 80 mass parts of water, 0.15 mass part of Triton X-100 (made by Aldrich) was added as a dispersing agent, and it ultrasonically processed like Example 1 Was carried out to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was confirmed.

[Example 3]

When 40 mass% aqueous dispersion of the polyether polyester block copolymer resin microparticles | fine-particles produced in the manufacture example 2 was adjusted, it was well dispersed. 50 mass parts of water were added with respect to 50 mass parts of this aqueous dispersion, and 25 KHz ultrasonic treatment was performed for 1 minute, and the aqueous dispersion was obtained. As a result of evaluating water dispersibility, almost no separation was confirmed.

Example 4

When 40 mass% aqueous dispersion of the polyether polyester block copolymer resin microparticles | fine-particles produced in the manufacture example 3 was adjusted, it was well dispersed. 50 mass parts of water were added with respect to 50 mass parts of this aqueous dispersion, and 25 KHz ultrasonic treatment was performed for 1 minute, and the aqueous dispersion was obtained. As a result of evaluating water dispersibility, almost no separation was confirmed.

[Example 5]

When 40 mass% aqueous dispersion of the polyether polyester block copolymer resin microparticles | fine-particles produced in the manufacture example 4 was adjusted, it was dispersed. 50 mass parts of water were added with respect to 50 mass parts of this aqueous dispersion, and 25 KHz ultrasonic treatment was performed for 1 minute, and the aqueous dispersion was obtained. As a result of evaluating water dispersibility, almost no separation was confirmed.

[Example 6]

When 40 mass% aqueous dispersion of the polyether polyester block copolymer resin microparticles | fine-particles produced in the manufacture example 5 was adjusted, it was dispersed. 50 mass parts of water were added with respect to 50 mass parts of this aqueous dispersion, and 25 KHz ultrasonic treatment was performed for 1 minute, and the aqueous dispersion was obtained. As a result of evaluating water dispersibility, almost no separation was confirmed.

[Example 7]

When 40 mass% aqueous dispersion of the polyether polyester block copolymer resin microparticles | fine-particles produced in the manufacture example 6 was adjusted, it was dispersed. 50 mass parts of water were added with respect to 50 mass parts of this aqueous dispersion, and 25 KHz ultrasonic treatment was performed for 1 minute, and the aqueous dispersion was obtained. As a result of evaluating water dispersibility, almost no separation was confirmed.

[Example 8]

40 mass% aqueous dispersion of the polyether polyester block copolymer resin microparticles | fine-particles produced in the manufacture example 7 was adjusted, and was dispersed. 50 mass parts of water were added with respect to 50 mass parts of this aqueous dispersion, and 25 KHz ultrasonic treatment was performed for 1 minute, and the aqueous dispersion was obtained. As a result of evaluating water dispersibility, almost no separation was confirmed.

[Example 9]

When 40 mass% aqueous dispersion of the polyether polyester block copolymer resin microparticles | fine-particles produced in the manufacture example 8 was adjusted, it was dispersed. 50 mass parts of water were added with respect to 50 mass parts of this aqueous dispersion, and 25 KHz ultrasonic treatment was performed for 1 minute, and the aqueous dispersion was obtained. As a result of evaluating water dispersibility, almost no separation was confirmed.

[Example 10]

When 40 mass% aqueous dispersion of the polyether polyester block copolymer resin microparticles | fine-particles produced in the manufacture example 9 was adjusted, it was dispersed. 50 mass parts of water were added with respect to 50 mass parts of this aqueous dispersion, and 25 KHz ultrasonic treatment was performed for 1 minute, and the aqueous dispersion was obtained. As a result of evaluating water dispersibility, almost no separation was confirmed.

Comparative Example 1

20 mass parts of polyether polyester block copolymer resin microparticles | fine-particles produced by the manufacture example 1 were put into 80 mass parts of ethyl acetate, and it carried out similarly to Example 1, and obtained the dispersion liquid. As a result of evaluating dispersibility, it was isolate | separated.

[Comparative Example 2]

20 parts by mass of commercially available nylon 12 fine particles (170 ° C of Orgasol melting point manufactured by Arkema Co., Ltd.) was added to 80 parts by mass of water, 0.15 parts by mass of Triton X-100 (manufactured by Aldrich) was added as a dispersant, and ultrasonic waves were obtained in the same manner as in Example 1. The treatment was carried out to obtain an aqueous dispersion. As a result of evaluating water dispersibility, it was isolate | separated.

[Comparative Example 3]

20 parts by mass of commercially available nylon 12 fine particles (orgasol melting point, 170 ° C. manufactured by Arkema Co., Ltd.) was added to 80 parts by mass of water, 1 part by mass of Triton X-100 (manufactured by Aldrich) was added as a dispersant, and ultrasonic waves were obtained in the same manner as in Example 1. The treatment was carried out to obtain an aqueous dispersion. As a result of evaluating water dispersibility, almost no separation was confirmed.

[Comparative Example 4]

20 mass parts of commercially available nylon 12 microparticles | fine-particles (Argasol melting | fusing point 170 degreeC) were put into 80 mass parts of ethyl acetate, and it carried out similarly to Example 1, and obtained the dispersion liquid. As a result of evaluating dispersibility, almost no separation was confirmed.

Table 1 shows the results of the Examples and Comparative Examples.

In Comparative Example 1, ethyl acetate was used as the dispersion medium, but was not dispersed, resulting in poor dispersibility.

Moreover, in the comparative example 2, although it was resin which does not have an aliphatic polyether unit, this resin fine particle was not disperse | distributed.

<Evaluation of Dispersibility>

It was found from Examples 1 to 10 and Comparative Example 1 that the resin fine particles copolymerized with an aliphatic polyether unit were well dispersed in water even under a condition not containing a dispersant. On the other hand, from Example 2 and Comparative Examples 2-4, it turned out that resin microparticles | fine-particles which do not contain an aliphatic polyether unit are disperse | distributed only to the water containing more organic solvent or a dispersing agent.

<Appearance Evaluation of Coating Film>

By using the resin fine particle aqueous dispersion of this invention from Examples 1-10 and Comparative Example 3, it was possible to obtain the coating film with favorable external appearance which prevented coloring by a dispersing agent.

Claims (4)

It consists of a copolymer containing 10-90 mass% of aliphatic polyether units, Comprising: It contains resin fine particle whose melting | fusing point is 120 degreeC or more, number average particle diameter is 1 micrometer or more and 100 micrometer or less, and particle size distribution index is 1-3. Resin fine particle aqueous dispersion made into. The aqueous resin particulate dispersion according to claim 1, wherein the aqueous resin particulate dispersion contains less than 1 part by mass with respect to 100 parts by mass of the copolymer even if it contains or does not contain a dispersant. The aqueous resin fine particle dispersion according to claim 1 or 2, wherein the copolymer containing 10 to 90 mass% of aliphatic polyether units is a copolymer comprising aliphatic polyether units and crystalline polyester units. delete